Tesi di Dottorato di MARCO TELLINI Matricola D01585

POLITECNICO DI MILANO

DIPARTIMENTO DI CHIMICA, MATERIALI E INGEGNERIA CHIMICA Giulio Natta

HYDROGEN FROM WASTE AND CO2 SEQUESTRATION

Dottorato di Ricerca in Chimica Industriale e Ingegneria Chimica (CII)

XVIII ciclo 2003 - 2006

Coordinatore: prof. Renato Rota Tutore: prof. Renato Del Rosso Relatore: prof. Paolo Cntola

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Acknowledgments

I refrain from making a long list of thanks, that might be interpreted as immodest selfappraisal to have worked with known men of science. I cannot however be silent on the advice and support that I received from professors P. Cntola and R. Del Rosso. I duly acknowledge Integrated Environmental Technologies, LLC that made possible my experimental work on their plasma pilot plant. Last but not least, I express my thanks to whomever will read this work.

Marco Tellini Matricola D01585 Politecnico di Milano Dipartimento di Chimica, Materiali e Ingegneria Chimica Giulio Natta (Academic Year 2004-2005)

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List of Publications
Publications and Presentations to Conferences

Tellini M., P. Cntola, R. Del Rosso and P. Gronchi, 2004, May. Hydrogen from Waste. Chemical Engineering Transactions, Vol. 4, (Pisa, Italy: AIDIC Hydrogen Conference Proceedings), ISBN 88-900775-3-0. Tellini M., P. Cntola, R. Del Rosso and P. Gronchi, 2004, June 28-July 1. Viable H2 Production from Carbon Waste by Dry Reforming. (Evora, Portugal: Renewables International Conference Proceedings). Tellini M., R. Del Rosso, P. Cntola, and P. Gronchi, 2004. "Solid Waste Thermal Characterisation." La Rivista dei Combustibili e dell'Industria Chimica, Vol. 58, No. 6. Tellini M., R. Del Rosso and P. Cntola, 2005. "Solid and Carbon Waste Generation Impact." Chemical Engineering Transactions, Vol. 7, (Naxos, Italy: PRES '05 8th International Conference Proceedings), ISBN 88-900775-8-1. Tellini M., R. Del Rosso and P. Cntola, 2005, October. Hydrogen from Fluff Destruction in a Plasma Reactor. Chemical Engineering Transactions, Vol. 8, (Palermo, Italy: AIDIC International Hydrogen Conference Proceedings), ISBN 88-901915-0-3. Tellini M., 2005. Hydrogen from Waste and CO2 Sequestration. (Milano, Italy: AIDIC, Associazione Italiana di Ingegneria Chimica), ISBN 88-900775-9-X. Tellini M., J. Batdorf, W. Quapp and P. Cntola, 2005. Automobile Shredder Residue Destruction in a Plasma Gasification Reactor. Article submitted, under referees evaluation. Tellini M., R. Del Rosso and S. Pierucci, 2005. Low Pressure CO2 Partial Absorption from Flue Gas in the New Carbon Tax Scenario. Article submitted, under referees evaluation. Tellini M., 2005, December 5. Syngas from Waste and CO2 in a Plasma Reactor. (San Paolo, Brazil: Sustainable Reuse, University of San Paolo CIRRA International Conference Proceedings). Tellini M., 2005, December 5. Municipal Wastewater Recovery System for Oil Refinery Uses. (San Paolo, Brazil: Sustainable Reuse, University of San Paolo CIRRA International Conference Proceedings). Tellini M. and A. Marques, 2005, December 5. Waste Impact and Characterisation. (San Paolo, Brazil: Sustainable Reuse, University of San Paolo CIRRA International Conference Proceedings).

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Table of Contents
TABLE OF CONTENTS LIST OF FIGURES LIST OF TABLES ABSTRACT (final report to the Faculty, in Italian) INTRODUCTION 1. SOLID WASTE GENERATION 1.1 1.2 Human and industrial activities generate waste Solid waste 1.2.1 Municipal waste 1.2.2 Assimilated municipal waste 1.2.3 Biomass waste 1.2.4 Industrial waste 1.2.5 Special waste and inerts Differentiated collection and means of waste reduction Regulations, laws and carbon tax 1.4.1 Carbon dioxide and global warming 1.4.2 Carbon tax References
I V IX

A/1 I-1 1 1 1 1 3 3 4 4 5 6 7 7 9 11 11 11 14 18 20 24 25 25 29 30 31 31 33 35

1.3 1.4

1.5

2. WASTE REDUCTION AND CHARACTERISATION 2.1 2.2 2.3 2.4 2.5 2.5 Reduction of municipal solid waste Block diagram of current treatment flows Characterisation of municipal waste Scenario of differentiated collection and heating values Fluff References

3. TRADITIONAL INCINERATION 3.1 3.2 Considerations common to incineration systems Grate furnaces 3.2.1 Air cooled grates 3.2.2 Water cooled grates Fluidised bed furnaces Rotary kilns References

3.3 3.4 3.5

ii

4. ALTERNATIVE THERMAL PROCESSES 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Gasification Pyrolysis ThermoselectTM Compact Power Continuous Melting ReactorTM Recycled Clean ProductsTM References

37 37 37 40 41 41 42 43 45 45 47 48 49 51 52 54 54 56 57 58 60 62 63 91 92 93 94 96 98 103 104

5. DIOXINS, FURANS AND RELATED COMPOUNDS 5.1 5.2 5.3 5.4 D/F formation mechanisms Dioxins control Dioxins analysis References

6. LOW PRESSURE CO2 PARTIAL ABSORPTION FROM FLUE GAS 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 General considerations and selection of amine Flue gas feed basis Selection of the process simulator and operating conditions Process flow diagram discussion and material balance Primary equipment list and estimates Investment offset Alternative for CO2 concentration References Appendix 6.1 7. PLASMA AND CO2 REFORMING POSSIBILITY TO GENERATE SYNGAS 7.1 7.2 7.3 7.4 7.5 7.6 7.7 Types of plasma generators Advantages of utilising a plasma process for treating waste Feasibility to use plasma for CO2 conversion Preliminary energy aspect for treating CO2 and waste Preliminary thermodynamic aspect for CO2 reforming Verification of the preliminary thermodynamic analysis References

Table of Contents

iii

8. APPROACH OF WASTE TO H2 AND CO IN A PLASMA REACTOR 8.1 8.2 8.3 8.4 8.5 8.6 Background and objective Combustion and oxidation Comparative material and heat balance of the model reaction via plasma conversion Comparison between conventional incineration and added plasma plant Promising means to develop a combined plant References

105 105 107 108 109 111 113 115 115 116 116 122 127 129 130 131 159 159 159 160 161 164 164 166 169 173 174 176 177 179 181 183 184

9. THERMOCHEMISTRY AND TEST PREPARATORY CALCULATIONS 9.1 9.2 9.3 9.4 9.5 9.6 9.7 Introduction Fluff, the feedstock of the process Thermochemical evaluation Heat losses and sensible heat compensation The issue of carbon black Testing objectives and summary of tests conditions References Appendices 9.1 to 9.5 10. PILOT TEST REPORTING AND DISCUSSION OF RESULTS 10.1 Introduction 10.2 Test apparatus description 10.3 Fluff feed 10.4 Plasma reactor 10.5 Testing procedure 10.6 Energy balance 10.7 Chemical analysis and material balance of inorganics 10.8 Syngas produced and operating input 10.9 Carbon balance and carbon black 10.10 Pseudo-order and rate of reaction 10.11 CSTR space time 10.12 Activation energy of the pseudo-reaction 10.13 Ash and vitrified material discharge 10.14 Coupling of CO2 emissions to the plasma plant 10.15 References Appendices 10.1 to 10.3

iv

11. WRAPPING IT ALL UP: RESEARCH AND PROCESS DEVELOPMENT PLAN 11.1 Research facility 11.1.1 Plasma pilot plant and laboratory 11.1.2 Laboratory services 11.1.3 Research funding through a foundation 11.2 Demonstration plant 11.2.1 Basis of design 11.2.2 Process description 11.2.3 Process flow diagram (PFD) and Equipment list 11.2.4 Plot plan and layout 11.3 Uses of syngas 11.4 Preliminary economics to continue the research 11.4.1 PyroPlasma Lab 11.4.2 Demonstration plant Appendices 11.1 to 11.3 12. CONCLUSIONS 12.1 Starting points validity confirmation 12.2 Experimentation and research findings 12.3 Avenues to continue the research and develop a plant

205 206 206 207 208 208 209 209 210 211 211 212 212 213 214 223 223 223 224

List of Figures
Chapter 2: Figure Figure Figure 1. 2. 3. Waste Reduction and Characterisation MSW in Italy Material flow of waste in Switzerland Waste to Swiss incinerators 11 12 13 14

Chapter 3: Figure Figure Figure Figure Figure Figure Figure Figure 1. 2. 3. 4. 5. 6. 7. 8.

Traditional Incineration Low Heating Value and constituents feed composition Calculation of adiabatic temperature for two cases Explanatory combustion diagram Power conversion typical yield, input basis = 100 Incineration plant block diagram Grate incineration/boiler conceptual layout Scheme of bubbling and circulating fluidised beds Incineration Conceptual rendering of a rotary kiln

25 26 27 28 28 29 30 32 34

Chapter 4: Figure Figure 1. 2.

Alternative Thermal Processes Scheme for ThermoselectTM Conceptual scheme for Romelt furnace

37 40 42

Chapter 6: Figure Figure Figure Figure Figure 1. 2. 3. 4. 5.

Low Pressure CO2 Absorption from Flue Gas Amine mole to weight concentrations CO2 Absorption with different amine combinations Amine absorption scheme Cryogenic absorption scheme Appendix 6 Simulator run scheme and balance of the preferred amine case

51 52 55 57 60

68

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Figure

6.

Appendix 6 Simulator run scheme and balance of the cryogenic case

70

Chapter 8: Figure Figure 1. 2.

Approach of Waste to H2 and CO in a Plasma Reactor Usable Energy referred to 1 kg input of waste Block diagram of the conventional incineration plus the added section that concentrates and converts CO2 to syngas

105 106

112

Chapter 9: Figure Figure Figure Figure Figure Figure Figure 1. 2. 3. 4. 5. 6. 7.

Thermochemistry and Test Preparatory Calculations Syngas from PVC: Energy from different O2 supplier Syngas from PVC: Feed (O2, H2O, CO2) and H2/CO ratios Syngas from Mix: Energy from different O2 supplier Syngas from Mix: Feed (O2, H2O, CO2) and H2/CO ratios Syngas versus feed energy on a triangular diagram for O2 supply Energy of syngas from PVC and PE, orthogonal plot Syngas from PVC: energy from different O2 supply with kW, P.Ox. & losses PVC Syngas: Feed (O2, H2O, CO2) and H2/CO ratios with kW, P.Ox & losses Syngas from Mix: Energy from different O2 supply with kW, P.Ox. & losses Mix syngas, (O2, H2O, CO2) feed and H2/CO ratios with kW, P.Ox. & losses Kp(T) of representative and water shift reactions Carbon conversion referred to temperature and carbon ratios with Kp(x,T). Appendix 9.1, Details of calculated charts and tables Appendix 9.4, Details of calculated charts and tables Appendix 9.5, Details of calculated charts and tables

115 119 119 119 120 120 121

125

Figure

8.

125

Figure

9.

126

Figure

10.

126 128

Figure Figure

11. 12.

128 131-134 136-153 154-157

Figures Figures Figures

--. --. --.

List of Figures

vii

Chapter 10: Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figures 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. --.

Pilot Test Reporting and Discussion of Results Block diagram Fluff as it was made available Fluff after fine shredding PEMTM Conceptual Scheme Hot section of the IET Plasma Pilot Plant Main streams and energy flows Cullet and inorganic materials leaving the reactor Syngas generation Offgas generation Oct 6, trial 1 Oct 6, trial 5 k(T) and activation constant determination Possible reuse products from poured glass Appendix10.2, Tables and figures of 13 trial tests.

159 159 160 161 162 163 165 168 169 170 171 171 177 180 187-201

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List of Tables
Chapter 1: Table Table Table Table 1. 2. 3. 4. Solid Waste Generation Municipal waste typical characterization Municipal waste production in Italy Special waste in Italy Differentiated waste collection by macro-areas in Italy 1 2 3 4 6

Chapter 2: Table Table Table Table Table Table Table Table Table Table Table Table 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12.

Waste Reduction and Characterisation Municipal waste management in the European Union MSW classification from referenced sources MSW composition and LHV from urban areas Comparison of reported and calculated LHV Base data for the waste simulation 30% differentiation, 2600 kcal/kg 30% differentiation, 1880 kcal/kg 40% differentiation, 3000 kcal/kg 35% differentiation, 2500 kcal/kg Upfront separation for RDF, 4000 kcal/kg Fluff average constituents (wt-%) Fluff average composition (wt-%)

11 13 15 15 17 18 19 19 19 21 21 22 23

Chapter 3: Table 1.

Traditional incineration Municipal waste material flows

25 25

Chapter 6: Table Table 1. 2.

Low Pressure CO2 Absorption from Flue Gas CO2/Acqueous amine reactions List of primary equipment in the absorption scheme

51 53 58

x Appendix 6: Summary table of various amine absorption trials Appendix 6: Simulator report tables for the amine case

Table

3.

64 71

Table

4.

Chapter 7: Table 1.

Plasma and CO2 Reforming Possibility to Generate Syngas Plasma conductivity compared to copper

91 92

Chapter 8: Table Table Table 1. 2. 3.

Approach of Waste to H2 and CO in a Plasma Reactor Thermodynamic reaction parameters. Potential use from the reactions. Comparison in MWh (1 t/h waste incineration @ 3500 kcal/kg yields 1 MWh)

105 107 109 110

Chapter 9: Table Table Table Table Table Table Table 1. 2. 3. 4. 5. 6. 7.

Thermochemistry and Test Preparatory Calculations Fluff average constituents (wt-%) . Elemental composition used for simulation (wt-%). Typical model reactions for Hi Heating values shown on the orthogonal plot Estimate of heat losses P.Ox. extra requirement of PVC for sensible heat and losses P.Ox. extra requirement of PVC for sensible heat and losses less DC power Cumulative reaction advancement and water gas shift Testing operating range Appendix 9.: Details of calculated charts and tables

115 116 117 117 121 122 123 123 127 129 131-134 135 135 136-153 154-157

Table Table Tables Table Table Tables Tables

8. 9. --.

A9.2. Appendix 9.: Conversion with sensible heat, no losses A9.3. Appendix 9.3: Conversion with sensible heat, no losses + DC --. --. Appendix 9.4: Details of calculated charts and tables Appendix 9.5, Details of calculated charts and tables

List of Tables

xi

Chapter 10: Table Table Table Table Table Table Table Table Table Table Table Table Tables Tables Tables 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. --. --. --. --. --.

Pilot Test Reporting and Discussion of Results Main streams and energy flows, heat and material balance Analysis of solids Cullet glass composition Main data pertinent to October 6th experimentation Electric power input vs. H2O and CO2 feed ratios Abatement of CO2 Average feed wt-ratios and temperatures in the reactor and TRC Cumulative stoichiometry and H of reaction @ 1300C Ash constituents (wt-%) UNI 10802_2002 limits and analysed leachate from residual glass Appendix 10.1, Inorganic materials balance Appendix 10.2, T61 test data extract Appendix10.2, Tables and figures of 13 trial tests Appendix10.3, Carbon balance @ 41 wt-% Appendix10.3, Carbon balance @ 54 wt-%

159 165 167 167 170 172 173 175 178 179 180 183 184 187-201 202 203

Chapter 11: Table Table Table 1. 2. 3.

Wrapping it all up: Research and Process Development Appendix 11.1, Process book index Appendix 11.2, Income Statement: Pyro Plasma Lab Foundation Appendix 11.3, Income Statement: Demonstration Plant

205 215-217 218 219-222

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Abstract
Motivazione del lavoro Lidea di questa ricerca inizi col mio precedente impiego nellincenerimento dei rifiuti, in cui si trattano enormi e crescenti quantit di rifiuti, remunerati dal conferimento degli stessi allimpianto (tariffa o tipping fee), ed al tempo stesso mi chiedevo come potesse essere ridotta lemissione di anidride carbonica che per questo tipo di impianti, e per le combustioni industriali in genere, assume portate di grande rilievo. Qualora lo smaltimento dei rifiuti, ancorch tossici, e la riduzione dellemissione di CO2 potessero avvenire o essere sfruttati con operazioni simultanee, o comunque una operazione potesse supportare ed integrarsi alla seconda, ne risulterebbe un accresciuto vantaggio ambientale, auspicabilmente sostenibile. Le mie considerazioni non avrebbero studiato, n ambto a qualificarsi per un contesto ecologico quantificabile in bilanci o soluzioni dellecosistema planetario, ben altri studi interdisciplinari relazionano limportanza dellanidride carbonica alleffetto serra. Stabilita comunque lesistenza grande o presunta del problema, da ingegnere chimico mi interessava come eventualmente ridurre le emissioni. Lattualit di una prossima tassazione sulle emissioni (carbon tax) era inoltre un incentivo per trovare possibili metodi ed applicazioni della ricerca. Va inoltre aggiunto che tutti gli incenerimenti di rifiuti mirano al recupero termico ed alla produzione di energia elettrica, energia che viene venduta a tariffe agevolate, premianti in Italia, motivo che induce interessi ancor pi forti a bruciare rifiuti e ad aumentare quindi le emissioni di anidride carbonica. Lanidride carbonica emessa con i fumi (trattati) circa in ragione del 10% in volume, diluita in una pari percentuale di umidit e di ossigeno in eccesso ed il resto costituito da azoto. La compressione di tali gas, emessi in volumi enormi, costituisce un problema di costo e non automatico dedurre che i fumi verranno smaltiti in cavit sotterranee o profondit marine in modo che lanidride carbonica resti intrappolata e gradualmente reagisca od evolva verso futuri equilibri ambientali. E dunque interessante porsi il problema di assorbire e concentrare la CO2 a basse pressioni, e rimane poi da chiedersi come si possa convertire o fissare il gas per farne qualcosa di conveniente o utile, a costi economicamente sostenibili per una dimensione industriale. Operando in un settore mirato a risolvere una problematica ecologica, era altres necessario porsi il problema che qualsiasi soluzione o processo risolutivo non fosse per cos dire unfriendly da generare altri e nuovi problemi ambientali, per esempio la generazione di gas tossici o sostanze o metalli dilavabili in acque o nel sottosuolo. La considerazione, a rigore banale, verr meglio compresa quando si proporr di convertire la CO2 a spese di un rifiuto tossico di matrice organica, che solo organico non , e contiene quindi metalli, cloro e sostanze eterogenee di vario tipo. Obiettivi e modalit Visti i presupposti e le motivazioni descritte, era imprescindibile analizzare macchine e processi correntemente in uso e pubblicazioni che almeno sul piano scientifico, sono da considerare di frontiera, giustificabili da un punto di vista teorico e speculativo, ancora non applicate o sperimentali dal punto di vista realizzativo. Non si doveva sottovalutare laspetto applicativo e tecnologico perch la dimensione dei problemi tale che piccoli impianti non attraggono alcun interesse e rimangono confinati a pubblicazioni pur validissime di uso accademico. Era giocoforza chiedersi se processi esistenti (varie tipologie di incenerimento e di assorbimento rigenerativo del gas) potevano rispondere ai quesiti iniziali e la risposta stata solo parzialmente affermativa. Sotto laspetto teorico, anche la modifica di processi esistenti avrebbe comportato un sostanziale re-design o problemi impiantistici nuovi. La mia analisi iniziale e

A/2 Relazione Finale sullAttivit di Tesi per il Collegio dei Docenti Rev.1 ricerca bibliografica sono state inevitabilmente diluite nellapprendere e tentare possibilit esistenti, poi abbandonate, e di caratterizzare i solidi eterogenei di partenza, sia per capire come poterli trattare ma anche per poterli rendere maneggiabili, alimentati e fruibili in modo affidabile per un sistema continuo. In estrema sintesi, il contenuto di carbonio ed il calcolo empirico del potere calorifico sono stati eletti a caratterizzazione del rifiuto solido per i riferimenti successivi. La possibile formazione di diossine, a causa di forte contenuto di cloro, precursori aromatici e superfici catalizzanti stata valutata per concludere lopportunit di parcellizzare lo scambio termico solo ad alta temperatura, fuori dalla finestra di temperature di formazione delle stesse. In tal senso, i primi capitoli della tesi sono speculativi e mirati a definire problematiche e fattibilit del processo che viene successivamente sperimentato. Il metodo procede per argomenti e gradi di complessit progressivi, una cinematica che risponde in modo veritiero allaffinamento per approssimazioni successive che ho seguito anche per i metodi previsionali di calcolo, completati alla fine con un simulatore termochimico per le reazioni e simulatori di processo per la parte di assorbimento della CO2. Per convertire la CO2, molecola molto stabile, e riformarla a CO, vengono generalmente usati processi catalitici, cosa che ho subito escluso nellottica di voler partire da rifiuti solidi, la cui disomogeneit e contaminazione sono molto elevate. La scelta sarebbe dunque diventata possibile con un reattore ad alta temperatura, in modo da spostare la conversione verso il CO, limitando o controllando la formazione di nerofumo. Oltre trenta societ al mondo, per non parlare di laboratori di ricerca, hanno o tentano di commercializzare processi al plasma, per le applicazioni pi svariate, ma nessuna pubblicizza il dry reforming di sostanze organiche. La cosa forse non interessava, costosa o comunque non erano ancora maturi i tempi per occuparsi della conversione della CO2.
Usable Energy referred to 1 kg input of waste (do not scale)
Energy input

Plasma + carbon 13501 CO 9598 Plus Carbon 7800 kcal/kg Waste Plasma 4876 1 kg Waste 3500 kcal/kg Waste Incineration CO 2112 H2 315 El. Power 2700 kcal/kg H2 1432 Plasma on flue gas 5371

CO2

El. Power 700 kcal/kg

El. Power 975 kcal/kg CO 2

El. Power 1074 kcal/kg

La prima analisi termochimica ha preso in considerazione il confronto di 3 casi con lincenerimento di rifiuti: trattamento al plasma su rifiuto tal quale, luso del plasma solo sui gas ed infine lintegrazione dellincenerimento con il trattamento al plasma del gas pi una fonte di carbonio (riquadri verdi). In questo modo si evidenziata la possibilit di ottenere energia chimica (CO + H2, curve viola) ed energia elettrica (curva nera) crescenti, sia pure a spese di materiale organico da smaltire (curva energetica nera superiore). Dopo aver analizzato ed escluso forme di processo esistenti, lobiettivo pi cogente e curioso da risolvere era quello se un reattore al plasma non avesse richiesto dispendi energetici tali da giudicarlo improponibile. Si quindi affrontata la possibilit di convertire i gas di combustione prodotti da un incenerimento

Hydrogen from Waste and CO2 Sequestration

A/3 Rev. 1

convenzionale (avevamo gi studiato ed escluso di agire sui rifiuti tal quali) in un reattore al plasma, alimentato a sua volta da una matrice organica, o per meglio dire da altri rifiuti (ancorch tossici o plastiche) con contenuto di carbonio nellintorno del 50% ponderale. Oltre alla validit di acquisire familiarit e sensibilit con lordine delle grandezze in gioco, i calcoli basati su consumi e recuperi energetici da letteratura hanno consentito di stabilire che il processo tandem fattibile e di questo abbiamo ampiamente pubblicato il confronto con lincenerimento tradizionale. In tal caso, la primissima critica che fu fatta al reattore allarco elettrico che i consumi sono elevati perch lo si raffronta allenergia netta che se ne pu ricavare (elettrica e/o termica).

La forza del nostro argomento non era ovviamente in disaccordo con questa posizione, ma la validit di dimostrare che la conversione fattibile e che lenergia nobile che se ne pu ricavare supera il 50% se si ragiona in termini di energia chimica, cio uso anzich combustione di H2 e di CO, ricavati da rifiuti e non diversamente ottenibili dallincenerimento convenzionale. Dimostrata a noi stessi la fattibilit, bisognava studiare la macchina ed in soccorso ci venuta la Integrated Environmental Technology (IET) americana, che interessata a proporre impianti in Italia e disponibile a sperimentare il dry reforming da me proposto sul loro impianto pilota, mi ha aperto strade insperate se avessimo voluto e potuto realizzare limpianto siffatto allinterno dellAteneo. Tempi e costi realizzativi, manodopera e costi operativi ci sono stati messi a disposizione gratuitamente ed abbiamo deciso di sperimentare con CO2 pura e con residuo di frantumazione di auto (ASR o fluff), sperando che alcuni imprenditori italiani avrebbero poi aderito a realizzare un impianto modulare in Italia. E comprensibile come IET avesse gi un modello di calcolo e di controllo del reattore, ma per non entrare in conflittualit di segretezza e per testare gli assunti iniziali, ho preferito sviluppare un modello autonomo durante la fase di programmazione, prima di avviare la sperimentazione. Sostanzialmente il modello ipotizza di superare in modo autotermico le temperature termodinamiche di equilibrio per la conversione a CO ed H2 e di convertire una parte del rifiuto

A/4 Relazione Finale sullAttivit di Tesi per il Collegio dei Docenti Rev.1 per ossidazione parziale a CO, in tal modo si riducono i consumi elettrici dellarco e si compensano le notevoli dissipazioni di calore, che in qualsiasi impianto pilota, corredato di decine di bocchelli, strumenti e variazioni di flusso non ottiene lefficienza e lisolamento di un impianto continuo industriale. Data leterogeneit del rifiuto, si sono ipotizzate delle composizioni di costituenti fittizi (PVC, PE, polistirene, gomma), in rapporti tali da ottenere la composizione elementare media analizzata nel rifiuto vero. A reagire con il carbonio sono stati considerati ossigeno, per lossidazione parziale, acqua per conversione a idrogeno (steam reforming) e CO2 per la conversione del gas inizialmente voluta (dry reforming). Lesempio sottoriportato limitato al caso del PVC ed il mix finale di calcolo dettagliato nella tesi.

Ovviamente la sostituibilit dimpiego dellossigeno usato sposta calcoli e condizioni operative verso diversi consumi e qualit del gas di sintesi prodotto. In tal modo stato calcolato il rapporto dei reagenti O/C, H2O/C, CO2/C e lenergia elettrica necessaria per le reazioni del modello. Si sono pertanto definiti dei parametri operativi da sperimentare e da verificare con la composizione dei gas uscente dal reattore pilota. Rimanendo sui calcoli del materiale e dei gas era necessario prevedere la possibile formazione di nerofumo e verificare sul campo che tale quantitativo fosse riciclabile al reattore e non costituisse, in quantit e qualit, un deterrente per leventuale caldaia a recupero da posizionare tra luscita del reattore ed il quenching/trattamento dei gas prodotti. Per non diluirsi in eccessivi dettagli, il trattamento gas, ampiamente sperimentato per altri tipi di alimentazione allo stesso impianto pilota (ad esempio per PCB e rifiuti farmaceutici), stato ignorato nel lavoro relativo alla tesi. Sono invece stati oggetto di ulteriore analisi sul campo tanto il modo pi sicuro per alimentare in continuo i materiali solidi quanto lanalisi del dilavamento delle scorie vetrificate scaricate dal reattore.

Hydrogen from Waste and CO2 Sequestration

A/5 Rev. 1

E altres peculiarit del reattore prescelto che inerti e sostanze non gassificate vengano inglobate in una matrice vetrosa che si forma da silicati e inorganici alimentati ma soprattutto dallaggiunta di vetro (rottame di vetro, glass cullet) al reattore per i vantaggi descritti nella tesi.La sperimentazione programmata si preposta dunque di verificare la possibilit di alimentare in continuo il fluff, ottenere quantit significative di CO e di H2, avere un riscontro sulle propriet di dilavamento del residuo vetrificato, raccogliere dati su ceneri e carbon black ottenuti, in modo da validare le ipotesi ed avere dati operativi utili per leventuale scale-up dellimpianto. Risultati, discussione Prima di trattare della sperimentazione sullimpianto pilota al plasma, conviene riassumere il Capitolo 6 della Tesi in cui si discute della fattibilit di assorbire lanidride carbonica dai fumi di combustione, tramite un processo rigenerativo amminico a bassa pressione.

La scelta dellammina ricaduta sulla MDEA con abbondante rapporto dacqua (10:1 molare), di per s termicamente sfavorevole ma tale da assicurare basse perdite di assorbente senza ricorrere a post-trattamenti di recupero. La MEA avrebbe presentato maggiore reattivit ma perdite superiori, tanto nellassorbitore, quanto nel rigeneratore. Temperatura, pressione e rapporto acqua/assorbente sono stati calcolati, a convergenza, con tre diversi simulatori di processo (C=Chemcad, P=ProII, H=Hysys). Non potendo infatti sperimentare anche questa sezione di impianto ho preferito arrivare ad un compromesso condivisibile da pi simulatori. Il processo di assorbimento con reazione non garantirebbe necessariamente la convergenza dei simulatori per condizioni operative arbitrarie, e bisognerebbe modificare i parametri di assorbimento (Hattas enhancement factors) con dati sperimentali o gi testati per simulazioni analoghe. Per il mio scopo stato sufficiente raggiungere risultati ottenibili con sistemi diversi ed il risultato finale stato quello di poter assorbire a 1.2 bar circa 63% dellanidride carbonica entrante, senza cio ricorrere a gravose compressioni del gas per lavorare in colonne in pressione. Nel diagramma riportato, il diametro ed il numero in alto della bolla indica il grado di assorbimento dellassorbente costituito dal rapporto acqua/ammina caratterizzato dal centro della bolla. Ciascuna bolla riporta una lettera (C, H, P) che evidenzia il simulatore usato e la temperatura di testa dellassorbitore, correlabile alla volatilit ed al quantitativo di ammina che si perderebbe. Risulta altres evidente che luso di meno acqua aumenta la tonalit dellassorbimento e le perdite di ammina, ma ottiene risparmi sul bilancio termico del sistema.

A/6 Relazione Finale sullAttivit di Tesi per il Collegio dei Docenti Rev.1 Analoghe considerazioni si applicano alluso di quantit diverse di ammina, da cui la necessit di ottimizzare le scelte operative.

Un separatore dacqua (apparecchio 4), posto dopo la compressione e raffreddamento del gas grezzo ed un cooler-flash-condenser (apparecchi 6, 7) con riciclo della MDEA sono stati introdotti allo schema classico di lavaggio amminico, sempre allo scopo di migliorare loperativit del sistema e ridurre le perdite. Il risultato migliorabile, per esempio anche attraverso luso di ammine miste, ma bastava qui dimostrare che forti compressioni (dai 7 ai 20 bar) possono essere evitate. Quanto al risparmio delleventuale carbon tax, in questo caso non sarebbe totale, ma pur sempre significativo, anche per lassorbimento parziale detto. La stima preliminare del costo di investimento del sistema alcanolamminico e dei costi di esercizio, ha permesso di calcolare che il sistema si ripagherebbe in due anni di esercizio, ovviamente se la CO2 poi convertita e se la carbon tax (ancora inesistente) avr una monetizzazione del tipo ipotizzato (Tesi: Cap. 6, Para. 6) confrontabile col valore dei cosiddetti Certificati Verdi. Veniamo ora alle prove sperimentali sul reattore al plasma. La sperimentazione condotta dopo aver stabilizzato il sistema avvenuta nellarco di tredici campagne di prove, rilevando i dati e le misure sia manualmente che tramite il DCS dellimpianto. Il solido stato alimentato a circa 6 kg/h costanti mentre il rapporto O/C, H2O/C, CO2/C variato come dal diagramma riassuntivo a bolle, per ottenere la conversione riportata nel seguito in due test tipici (Run #1 e Run #5). Ogni bolla rappresenta la frequenza di ottenimento della concentrazione media molare per H2 e CO, con il rapporto operativo di H2O e/o CO2 indicato. Nelle misurazioni, il gas prodotto fortemente diluito dallazoto iniettato per il quenching dei gas a valle del reattore; mentre le concentrazioni ottenute di H2 e di CO, riferite al secco, sono rispettivamente del 45 e 55 vol-%.
Syngas across all trials
25.00
Vol-% avg composition

Offgas generated in 13 trials

(Pure syngas basis: CO = 55.3 vol-% and H2 = 44.7 vol-% )
1861

23.00 21.00 19.00 17.00 15.00 13.00 11.00 9.00 7.00 0 1 2 3 4 5 6 7 8 9 10

CO2/C ratio: 1 to 4 = .2, .45, 1, 1.5 H2O/C ratio: 5 to 9 = .3, .45, 1, 1.5, 1.8 (overlapping ratios at points 3 to 6)

vol-% Avg; 19.6

1920 H2 CO

vol-% Avg; 54.1

vol-% Avg; 10.3

CO CO2 H2 N2

vol-% Avg; 16.1

Hydrogen from Waste and CO2 Sequestration

A/7 Rev. 1

Negli Stati Uniti il costo di ossigeno ed elettricit sono comparabili e non si potuto testarne lassoluta equivalenza in termini di apporto energetico per limpossibilit di superare la potenza installata di 14 kW. Questo ha limitato il campo di sperimentazione simultanea con H2O e CO2; ma si comunque stabilita la necessit di alimentare vapore per contenere la formazione di carbon black al 5%, nerofumo che estratto dai filtri a manica pu essere riciclato al reattore. Liniezione di vapore ha pure il pregio di produrre pi idrogeno e di costituire un volano termico per propria capacit termica e reazione di shift. Per alimentazione costante di solido (era troppo gravoso ed erratico cambiare e stabilizzare la portata del materiale) il valore medio di ossigeno e di acqua stato pari a circa 2/3 del contenuto di carbonio, mentre la CO2 convertita stata di circa 3 kg/kg fluff. Ragionando in termini di conversione della CO2, si riporta la tabella estratta dalle prove e si vede che circa il 90% dellanidride carbonica viene convertita (riga c-g), con un vantaggio sensibile rispetto allemissione della stessa ed alla trasformazione del carbonio del rifiuto in CO2, qualora questo potesse venire bruciato. Nella tabella sottoriportata le righe si riferiscono a tests diversi, tutti i test hanno avuto la portata di ossigeno (0.03 #mol) alimentazione e potenza elettrica costanti. Le altre variabili erano vapore ed anidride carbonica in entrata (righe c e c) mentre la combustione parziale per generare calore/CO stata della stessa entit. Per convertire pi CO2 nella riga c avremmo dovuto aumentare ossigeno o potenza elettrica. Il carbonio entrante (C + elettrodi + CO2) si ritrova come CO2, CO e frazione carbon black residua. A B B-A
C
#mol in

Abatement of CO2 CO2

# #mol in #

CO2
#mol out #

CO2
# combustion

Diff. 14.883 13.773 17.709 3.936 14.375 13.818 20.256 6.438

g c c-g g' c' c'-g'

0.4717 0.4717 0.4717 0.4717 0.4717 0.4717

5.66 5.66 5.66 5.66 5.66 5.66

0 0 0.1 0 0 0.2

0 0 4.4 0 0 8.8

0.133 0.159 0.169 0.145 0.158 0.211

5.870 6.980 7.445 0.464 6.379 6.936 9.297 2.362

20.753 20.753 25.153 11% 20.753 20.753 29.553 27%

70%

69%

Test T61 T63 T66 T62 T64 T65

#mol entranti H2O O2 .12 .03 .37 .03 .03 .03 .27 .03 .53 .03 .26 .03

CO2 .1 .2

riga sopra g riga g riga c riga sopra g riga g riga c

In termini di bilancio termico e di materia, la figura sottoriportata evidenzia che il processo non sarebbe certamente efficiente se si ragionasse in termini di incenerimento (cosa peraltro vietata per il fluff) ma considerando i recuperi energetici ed il valore intrinseco ottenibile dalluso di H2 e CO, lefficienza diventa molto superiore nel rispetto degli obiettivi iniziali, cio la termodistruzione sicura e la riduzione delle emissioni di CO2. Riferendoci al bilancio del reattore pilota, la colonna 1 di sinistra riporta i valori che caratterizzerebbero il solo ed eventuale incenerimento: tramutando la sostanza incenerita in energia equivalente, si otterrebbero 2.05 KW elettrici (20%). Lo stesso rifiuto, richiede ulteriore energia per fare il reforming al plasma e pensando di recuperare termicamente ed elettricamente energia, saremmo ancora a valori bassi, 8.19 kW (marcati in rosso nelle colonne 7 ed 8) contro i 24.56 immessi (33%). La bont del processo non va dunque ricercata quale metodo per trasformare energia o

A/8 Relazione Finale sullAttivit di Tesi per il Collegio dei Docenti Rev.1 produrre energia elettrica tramite un ciclo termico, ma si misura sulluso chimico del syngas e sulla validit di inertizzare sostanze tossiche diversamente inutilizzabili, oltre alla capacit di convertire CO2, anzich immetterla nellatmosfera. Per un confronto diretto, il riquadro azzurro, elenca la scala di energia immessa e fruibile dal processo.

Per mostrare la qualit del gas prodotto (ordinata di sinistra), in funzione delle variabili operative (ordinata di destra), vengono riportati i risultati di 2 test tipici. Il test #1 non alimenta
Oct 6, Run # 1
Plenum T=1080C, PEM T=820C, TRC T= 1050C, DC Feed = 14 kW

2.00 20.0 18.0 16.0 1.40 14.0 Vol-%, syngas 1.20 1.00 0.80 0.60 0.40 0.20 0.3 % 11.04.00 11.12.30 11.14.30 11.06.00 11.09.30 11.16.00 11.18.00 11.04.30 11.06.30 11.08.00 11.10.00 11.11.30 11.13.00 11.15.00 11.16.30 11.18.30 11.05.30 11.07.00 11.08.30 11.10.30 11.12.00 11.14.00 11.15.30 11.17.00 11.19.00 11.05.00 11.13.30 11.07.30 11.09.00 11.11.00 11.17.30 11.19.30 0.00 Wt-Ratios 12.0 10.0 8.0 6.0 4.0 2.0 0.0 11.5 % CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2 20.2% 18.2% 1.80 1.60

Solar time

Hydrogen from Waste and CO2 Sequestration

A/9 Rev. 1

CO2 ma realizza una conversione con solo vapore. A costanza di rifiuti solidi alimentati (circa 6 kg/h) e di energia elettrica (14 kW), lalimentazione di ossigeno per entrambi i casi di circa 1.7 O2/C ponderale. Il test #5 evidenzia un valore di H2O/C superiore (0.8) ed unimmissione di CO2/C pari a 1.4 ponderale, ottenendo percentuali di CO di oltre 3 punti pi alte rispetto al test #1. Le fluttuazioni della qualit del syngas sono essenzialmente da attribuire allalimentazione della coclea e del materiale eterogeneo; tramite interpolazione polinomiale delle curve si evidenzia landamento omotetico della generazione di H2 e CO: in corrispondenza a picchi di prodotto, si osservano gli avallamenti della curva della CO2.
%

Oct 6, Run # 5 Plenum T=1065C, PEM T=807C, TRC T= 1115C, DC Feed = 14 kW

26.0 24.7% 24.0

1.80 1.60

22.0 20.0 18.0 Vol-%, syngas 16.0 14.0 12.0 10.0 8.0 6.0 4.0 0.20 2.0 0.0 12.51.20 12.52.00 12.50.00 12.50.40 0.3 % 12.56.00 12.56.40 13.00.00 13.00.40 13.01.20 13.04.00 13.04.40 13.05.20 13.08.00 13.08.40 13.09.20 12.52.40 12.53.20 12.54.00 12.54.40 12.57.20 12.58.00 12.58.40 13.02.00 13.02.40 13.06.00 13.06.40 13.10.00 13.10.40 12.59.20 13.03.20 13.07.20 12.55.20 0.00 0.60 0.40 18.5% 1.20 15.7 1.00 0.80 Wt-Ratios 1.40 CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C O2/C Polinom. H2 Polinom. CO Polinom. CO2

Solar time

Le ceneri ottenute sono state inferiori all8% ponderale, anchesse possono essere riciclate e inglobate nel solido vetrificato, che per laggiunta di rottame di vetro risultato di circa 10% del fluff caricato. Il materiale vetrificato presenta caratteristiche di dilavamento compatibili con le norme US EPA/TCLP ed UNI 10802/2002, pertanto ipotizzabile che il materiale possa essere usato come riempitivo da costruzione, o nel peggiore dei casi, smaltibile in maniera compatta e sicura. Dal punto di vista cinetico non ci si attendevano sorprese, data lelevata temperatura e la turbolenza nella zona di reazione. Il calcolo a posteriori basato su prove avvenute a temperature controllate hanno permesso di determinare lordine della pseudoreazione ed una energia di attivazione di regime chimico, mentre il calcolo della velocit spaziale ha dato un tempo di permanenza nel reattore di poco superiore al secondo, compatibile con le reazioni di cracking termico. Nel bilancio globale il consumo medio di corrente continua allarco stato di 1.1 kW/kg di fluff e ci si attende che un impianto di grande scala avr meno dissipazioni termiche, unalimentazione pressoch costante del solido ed unefficienza migliore.

A/10 Relazione Finale sullAttivit di Tesi per il Collegio dei Docenti Rev.1

Conclusioni I risultati della ricerca illustrati vengono dettagliati nel Capitolo 10 della Tesi. Fondamentalmente si ottenuta la riprova che materiale eterogeneo, tipo rifiuti solidi, pu essere inertizzato e gassificato in un reattore al plasma autotermico, alimentato con anidride carbonica recuperata da fumi di combustione di un impianto congiunto. Le reazioni portano alla produzione di gas di sintesi la cui qualit pu essere ottimale per celle a combustibile, per separare idrogeno e/o per usarlo quale materia prima per sintesi chimiche. Sintesi di trasformazione potrebbero essere alcoli, aldeidi, colle, plastiche, combustibili Fisher Tropsch per esempio. I casi applicativi specifici andranno studiati in relazione al rifiuto usato per produrre il gas di sintesi (specifiche del gas) ed ai processi a valle, verosimilmente catalitici, per assicurare compatibilit e protezione da avvelenamento. Lintero discorso pu essere valorizzato in previsione di una tassa sulle emissioni e divieti pi severi circa lo smaltimento in discarica; diversamente, il motore economico della ricerca perderebbe possibilit attuative. Gi con i risultati della sperimentazione pilota, si possono fissare le dimensioni impressionanti del problema reale. Emissioni da 100'000 Nm3/h, valore assolutamente modesto per un inceneritore, per un forno industriale o per una centrale di potenza, significano circa 20 t/h di CO2, che sulla base della nostra sperimentazione possiamo convertire con 27 t/h di fluff (circa 143'000 t/anno) per generare 1.5 t/h di H2 e 25 t/h di CO. Questo dimostra che leventuale accoppiamento tandem ad una qualsiasi applicazione esistente prospetta un notevole esercizio di scale- up. In mancanza di una carbon tax (varie fonti Europee stanno speculando su prossimi valori che dal 2007 verranno applicati tra i 40 ed i 100 Euro/t di CO2 rispetto alle eccedenze di quota assegnate), i calcoli e le ipotesi che abbiamo fatto si attestano attorno ai 75 Euro/t (Capitolo 6). Questo significa che per una portata di 20 t/h la penalizzazione sui fumi di 207524 = 36'000 Euro/giorno ed i processi meno efficienti dovranno essere ripensati per compensare la perdita di remunerativit. Il Capitolo 11 della Tesi affronta con il piano di sviluppo e due modelli economici la possibilit di continuare la ricerca in due direzioni parallele, integrabili e non mutuamente escludibili: una ricerca di tipo accademico e di servizi, da svolgere e fruibili attraverso lUniversit, ed una ricerca applicata per arrivare ad un impianto modularizzato, dimostrativo. Alcuni industriali contattati sembrerebbero, almeno a parole, interessati ai risultati esposti e potrebbero essere pronti ad investire dopo aver visto un impianto esistente e funzionante, ma va detto di pi. La scala dei problemi (60 miliardi di tonnellate annue di CO2, 6 milioni di tonnellate annue di fluff, tanto per fissare gli ordini di grandezza) talmente grande che qualsiasi imprenditore pensa a grandi impianti, che non sono fattibili per rischio e per scale-up, se non per gradi e per miglioramenti successivi. E ancora prematuro sperare in una realizzazione impiantistica a breve, ma per il momento mi rimane la vera soddisfazione di aver vissuto questa intensa avventura di studio e di avere avuto il supporto di vari docenti, tra cui il prof. Cntola ed il prof. Del Rosso. Ringrazio anche lAIDIC che ha reso possibile la pubblicazione del mio libro, sostanzialmente codesta tesi di dottorato, Hydrogen from Waste and CO2 Sequestration, (ISBN 88-900775-9-X). Da ultimo doveroso riconoscere che solo linteresse, la collaborazione ed il supporto gratuito della Integrated Environmental Technology hanno reso possibile la sperimentazione pilota di questa ricerca. Marco Tellini

HYDROGEN FROM WASTE AND CO2 SEQUESTRATION

Marco Tellini

H2 CO

..

Introduction
The idea of this research started from my previous employment in waste incineration and when I wondered about means conducive to reduce carbon dioxide emissions. If the operations could be done simultaneously, or one at the expense of the destruction of waste, even toxic waste, the environmental advantage would be greater, perhaps economically sustainable. I started without direct aim, training nor specific knowledge on the measurable and definitive extent that CO2 bears for the greenhouse warming of our planet. The whole matter is far more complex and interdisciplinary, but given the problem, I thought that it becomes a chemical engineering challenge to study methods to reduce or eliminate the emissions. The side issue of upcoming taxation on emissions (Carbon Tax) was also the incentive to find a possible application of the research. A possibility that I considered was the feasibility of dry reforming organic matter with CO2 since I ignored the optimal conditions and existing equipment where such reaction could efficiently take place. I therefore started to scout possible furnaces and reactors, among which a conventional or modified incinerator could have merit. The initial analysis and bibliographic investigation was definitely diluted in learning and probing possibilities that were later abandoned, the dealing with heterogeneous solids evidenced handling difficulties, erratic characterisation and unreliable operation of the systems. To say the least, even the modification of existing processes would imply a redesign of the same and new engineering solutions. Types of organic waste exhibited characteristics unsuitable for use and the fact of having carbon dioxide dispersed in huge flue gas flowrates makes the CO2 sequestering attempt hard to apply in viable and economical terms for large and industrial installations. For these reasons, the first chapters of this dissertation can be seen as a wondering around to learn and condense what others have already studied or implemented. It is true that I learned by doing and spent a great amount of efforts in trying to accommodate existing technologies to my original scope. This gave me time and opportunities to study and re-analyse different notions and appreciate details that I had presumed to know, but that I actually learned when I studied them over and over and I made calculations to gain direct feeling with the numbers and the order of magnitude involved. The dissertation is written through progressive and thematic approach to the experimentation, prepared and reported under Chapters 9 and 10, and the sequencing shows how the work developed through the exclusion of a variety of alternatives. Some sections, that are found in Chapters 1, 2, 6, 7, 8 and 10, and the whole book which I published through AIDIC (ISBN 88-900775-9-X), have been laborious in their preparation because they were at that time singled out and considered for publication. Publishing became the tool for deeper investigation and critique by the referees; altogether, the exercise had the value for me to challenge, to discuss at conferences and to focus the subjects better, which was a gratifying and worthwhile learning practice. To summarise the evolution of my research, I became progressively aware and discarded avenues of treatment by fine tuning the method and goals to be achieved. The first chapters of this work are speculative and aim to make the subsequent operating decisions. Feasibilities were tested first from the theoretical and economical point of view, until arriving at a preferred case to test. I ultimately

I-2

abandoned the various forms of waste incineration to treat CO2 with sources of organic carbon. After familiarising with empirical methods, in order to characterise the waste, I resorted to elect the heating value and the carbon composition as indicative parameters of any potential treatment. I realised that municipal solid waste, large and important feedstock as it may be, is not the optimal waste to use, at least not directly as it is. Automobile shredder residue, or recycled plastics, or heavy organic sludge could be better sources of carbon; medical waste itself is also a good candidate to process, which brings the collateral benefit of being well paid for processing, advantage that enables a faster repayment of the investment in a commercial plant. Steam reforming of organic matter was planned to be partly substituted by dry reforming and I was intrigued from the start in developing a scheme to absorb CO2 at low pressure from flue gases (Chapter 6). The capture of CO2 from flue gases is in fact a crucial economic problem, it is a problem of concentrating the gas out of diluted and great streams of emissions. Once the gas is captured and compressed, it appears that most geophysicists have no concern on how the Earth will naturally neutralise it, but for me the advantage was to capture the gas at near atmospheric pressure and then find a possibility to use it or convert the CO2 at low pressure, avoiding thus heavy compression costs of the diluted emissions. Upon obtaining the gas at suitable pressure and concentration, the issue becomes on how to treat it. Due to the combined use of heterogeneous waste, I excluded catalytic processes and the initial analysis of a plasma reactor feasibility encountered diffused skepticism. Indeed a plasma process can be highly energy intensive, but the external energy input can be reduced via autothermal consumption of part of the waste and by limiting its operating temperature to the necessary level for conversion. To that effect, I presented thermochemical calculations at the 2004 Pisa H2 Convention and when the syngas product is not burnt, the ultimate chemical energy, or usefulness, of the syngas compensates for the overall energy balance of a plasma processing. The reactor was thus chosen to be a plasma reactor, which needed also to be safe and technologically reliable, resist to corrosion, erosion and thermal stress, aggravated by the use of waste of changing variety. Among all preliminary contacts and evaluations, I was blessed by the cooperation with Integrated Environmental Technologies (Richland, WA, USA), so that I could plan and execute the experimentation on their pilot unit. The quality of the syngas product demonstrated in line with pre-calculated predictions and is suitable for chemical use rather than burning the gas to produce electricity, operation that is widely spread and promoted in Italy and various Countries. The plasma brings several advantages in terms of destruction and non-formation of dioxins, it operates in reducing atmosphere and no air, so NOx are not formed, it generates safe and non leachable vitrified solids, compact enough to save on ultimate landfilling or reused as construction filler or inert material. When dealing with waste thermal treatments there is also a variety of related technologies, for instance De-SOx and auxiliary plants, which are deliberately ignored to avoid unnecessary branching of the work and because they are less pertinent to the main theme of this research.

Introduction

I-3

Last to be mentioned and yet no less important, finding resources external to the University took a considerable amount of time and documentation was prepared to promote and secure partners or sponsors for further research. The cooperation with other Universities was established, but no real investor has been found to date. The plan for possible later development is discussed under Chapter 11.

Hoping to assist in the reading of this thesis, the document is organised in four sections. The first section (Chapters 1 to 5) presents issues related to waste treatments and CO2 Human and industrial activities generate waste (Chapter 1) Waste is differentiated and reduced (Chapter 2) Aside from the type of treatment, a percentage of waste is sent to incineration (Chapter 3) Alternative thermal destruction processes (Chapter 4) Thermal processes open discussion concerning dioxins (Chapter 5)

The second section (Chapters 6 to 8) develops reasoning and calculations for absorbing CO2 at near atmospheric pressure and the feasibility to reuse the gas by feeding it to a plasma process to make H2 and CO CO2 absorption for dry reforming from flue gas at low pressure (Chapter 6) Among treatment alternatives, plasma is a viable pathway from waste to hydrogen and syngas, offering the potential saving of a Carbon Tax and greenhouse impact benefits (Chapters 7 to 8)

The third section (Chapters 9 and 10) is the preparation and the experimental work on the plasma reactor Thermodynamic conceptual design of a new process (Chapter 9) Pilot testing for the plasma core plant and results (Chapter 10)

The fourth section (Chapters 11 and 12) is the preliminary plan to continue the research in two main directions and drafts the conclusion of this work Experimental laboratory research and Demonstration plant (Chapter 11) Conclusions (Chapter 12).

..

1
1.1

SOLID WASTE GENERATION

Human and Industrial Activities Generate Waste

Waste is any substance, object, material derived from human activities or natural cycles that is abandoned or destined to be abandoned. Intrinsic inefficiency of activities and ways of life end up generating a portion of waste, be it damaged materials and equipment, refuse, contaminated or deteriorated substances, out of norm or defective products and last, but not least, a number of throw-away items because people discard non fashionable, useless or no longer cared objects and materials. In less evolved economies, the tendency is generally to delay disposal as long as possible and to recover objects, pieces or materials to the maximum extent, generating also opportunities of work for lower skill labour or even skilled recovery craftsmanship. The cost of labour and time, mass production, distributed spending power, fast technological substitution, marketing and taste that prevail in higher income economies have practically reduced selective recovery to the lowest level: an example is the duration and re-use of automobiles and parts in different Countries. This trend in the economic and social evolution generally disposes and dumps away in bulk, re-processes, recycles and recovers only what is utmost convenient, or easy, or dangerous to dispose. Industrial processing is more sophisticated in the sense that a process is born with a clear knowledge of waste and out of norm re-processing or inertisation, but even so, subtle convenience and regulated activities become the criteria to implement. Ultimately, without making an exaggerated generalisation, our economies dispose all that can be legally permitted and recover as little as regulations impose. The subject of waste practically covers all areas of livelihood, production and decay. Waste disposal and treatment constitutes a general public interest and is therefore regulated to ensure welfare, hygiene, safety of inhabitants and preservation and protection of natural flora and fauna. Public regulation and planning are often short-seen as hindrance or delay to activities themselves, but with the increase of social awareness, take noise reduction for instance, they become everyones assurance for the future.1 We can have a broad classification into solid, gaseous and liquid waste, but we shall only deal with solid waste here. Liquid waste, mainly wastewater from all sources, is a separate subject that will only concern us for the solids and sludge separated from their treatment. Gaseous waste will also be ignored with the exception of considering the carbon dioxide conspicuous fraction that comes from combustion processes.

1.2
1.2.1

Solid Waste

Municipal waste Since the seventies, it has been observed that there is a vast difference between the municipal waste quantity of industrialised economies and the waste of less developed Countries.

The general principles are found in ambient protection legislation, such as the Italian DPR 915/82, Art. 1.

Chapter 1

Data published in 2001 by Swiss statistics about OECD world indicators showed procapita annual production of waste at 380 kg in Italy, 450 kg in Switzerland, over 600 kg in USA and Canada, to list a few (Statistica Svizzera, 2001: pp. 20-23). The average waste production was about 500 kg/person-year in Europe. Figures and trends were confirmed by later sources: the trend is for a moderate increase which is however counterbalanced by the overall waste contraction due to higher recycling and differentiated collection. The waste is generally characterised by higher heating value, due to differentiated composition (vegetables and humid content separated from metals, glass, paper and plastics) and it is substantially increased by the amount of packing material (paper, plastic foils, bags and containers exceed 45 wt-% of the waste) that modern settlements generate. The issue of packing material is becoming a growing quantity and concern for its little or very slow decay features, the volume and the heating value of the plastic materials mainly. Rural and city settlements are also very different producers of waste. In the cities, paper, plastic and metals are approximately twice as relevant as their percentages referred to the countryside. An intuitive yet dramatic difference assessed by a French study was to indicate that 250 kg of packing were used in USA and 4 kg in Burundi (Atochem, 1990): their interest, at the time, was to pinpoint different packing consumptions, and we observe however that 4 kg of plastic uncontrolled dumping in a rural under-developed infrastructure constitute a progressive accumulation that, if unprepared to solve the problem, constitutes a relatively important environmental and ecological issue. Twenty years ago, the average Low Heating Value of municipal waste was around 2000 kcal/kg, today the LHV averages around 3500 kcal/kg which often imposes new technological means of treatment.2 According to several published data and national statistics often found as design basis for treatments of municipal waste, we can summarise reported figures (IRER, 2000: p. 11) in which the waste is typically characterised as per Table 1 below. Table 1: Municipal waste typical characterisation
Fractions Paper and cardboard Textiles Plastics Metals Organics Inerts Carbon Nitrogen Sulfur Chlorine wt-% min 12 1.4 4.1 2.3 16.1 3.4 wt-% max 44.7 9.4 21.4 6.9 51.8 16.5 wt-% avg

28.47 0.68 0.49 2.07

The same figures are consistent with the November 2003 report published by APAT, which also confirms their preliminary projections of 2002: incineration of waste is nationwide accounted for about 8.5 wt-%, with peaks of 18% in the North, where

Courtesy of Von Roll Environmental, Zrich -CH- about evolution of design data for air and water cooled grates incineration.

Solid Waste Generation

three Regions -Lombardia, Veneto and Emilia Romagna- incinerate over 70% of that (APAT, 2003: pp. 36, 51, 134). The quantity of waste produced in Italy is approaching 30 million tons per year with the broad classification reported in Table 2 below. Table 2: Municipal waste production in Italy
Waste production Production pro-capita in metropolitan areas Differentiated prod. Differentiated prod. Paper Organics Plastics(*) Glass Metals
(*)

[t/y 106 ] [kg/y] [kg/y] [t/y 106 ] [%] [t/y 103 ] [t/y 103 ] [t/y 103 ] [t/y 103 ] [t/y 103 ]

29 650 4.2 14.4 1308 1298 174.7 759 213

North +3.3% 514 3.25 24.4 957 1073 131.5 609 148

Centre +2.4% 557 0.7 11.4 266 173 27.5 106.7 53

South +0.3% 454 0.23 2.4 85 47 15.7 43 11

the plastics introduced with packaging are about 750000 t/year

The Italian Environmental Ministry recently issued the waste management report referred to the year 2002, in which, the 7th chapter provides a synthesis of most significant data (Ministero dellAmbiente, 2002: pp. 177-181). Similarly, up-to-date Swiss statistics reinforce the trend validity of differentiated collection and justify specific local variations: to have a comparison with Italy, 88% of the municipal waste in Switzerland is sent to incineration (Statistica Svizzera, 2002: pp. 130-137, 141). Assimilated municipal waste Reconcilable to municipal waste problems, in the sense that collection, treatment and safe disposal of end products is needed, are those industrial wastes that are generated by artisanship, small electro-mechanical industries and manufacturers, large commerce and storage facilities, natural product processing like edible oil manufacturing, food processing or wood sizing and preparation. Sanitary and hospital waste without risk of hazard or infections are found here. The packaging material is also an issue in this category. In general, the absence of relevant toxic substances enable to consider these waste as if they were originated by municipal settlements. Biomass waste Biomasses present an interesting instructive case, since they can be a viable source for energy recovery or constitute a substrate or a natural media useful for some other purpose, like nutrient irrigation/spread, for instance. Biomass wastes are also classified, take for example the CTI directive which lists their coding, composition, heating value and norms that apply for re-utilisation and dispatch to specific destinations after the substance full characterisation (CTI, 2003: pp. 3-53). With respect to the production of energy, the report identifies permissible constituents concentration and the various heating values that become interesting for planning a waste-to-energy recovery. 1.2.3 1.2.2

Chapter 1

Industrial waste The industrial waste scenario is highly mutable and varies within each industrial production, depending also on the size, the age, the technology, the legislation ruling at the time that a plant was constructed, implying also that environmentally minded and skilled operators can make a difference in the overall waste products. Going through each category may become a monumental task and would not modify the fundamental tenet that each industry, for instance the oil refining industry, has its own established means of treatment, recycling and safe disposal, because the technological know-how and the economic efficiency are also well spread and shared criteria. The novelties are often induced by technological breakthroughs and socio-political awareness, regulations and demand for efficiency or safety. For these reasons, specific industrial wastes and treatments are not discussed here, as they constitute a specific part in the overall process of any industry. Examples for type, quantity, recycling and treatment are easily found for all chemical plants. Special waste and inerts Special wastes, like toxic substances, have their own classification and regulated means of treatment. Here we can also identify the classification of packing materials, large or special waste like worn, obsolete or broken machinery and inerts, largely originated from civil construction and refurbishing industry. Table 3: Special waste in Italy
Economic activities
Agriculture and fishing Extraction industry Food industry Textile industry Garments, dye, furs Tanneries Wood industry, paper printing Oil refineries, coke and chemical industry Rubber industry and plastics Mining industry, non metals Metals and alloys Metal fabrication less machinery/plants Electronic and electrical fabrication Transport machinery fabrication Other manufacturing Electric power, water and gas Constructions Commerce, repairs, other services Transports, communications Finance, insurance, professional services Public administration, instruction, sanitary Waste treatment, waste water purification Various, non determined (N.D.) Totals [metric tons/year] 2000 Non-toxic 340,465 794,775 4,360,603 710,811 115,832 876,093 3,617,459 3,206,517 637,122 5,466,666 6,489,798 2,644,402 1,456,561 1,090,804 1,858,474 2,837,435 571,868 2,028,657 867,935 656,203 463,164 10,348,265 406,710 51,846,621 2000 Toxic 6,552 9,929 32,171 76,708 1,336 4,686 60,528 1,222,480 56,016 33,535 651,836 253,215 202,231 128,291 112,194 83,209 33,745 308,975 52,358 50,889 167,128 320,042 32,964 3,911,016 2001 Non-toxic 421,667 775,604 4,660,865 868,707 138,367 1,066,955 3,775,920 3,053,884 665,497 5,533,144 7,416,112 2,683,244 1,395,052 987,619 2,353,946 2,632,203 709,579 2,144,250 574,551 371,050 809,663 11,610,004 325,516 54,973,399 2001 Toxic 9,066 10,595 14,520 78,730 1,043 5,461 50,742 1,144,236 110,841 42,019 702,473 318,149 219,794 147,950 139,017 72,089 37,116 409,368 8,444 7,676 190,183 369,018 60,704 4,279,233

1.2.4

1.2.5

Table 3 data are extracted from the APAT report on waste (APAT, 2003: p. 368). Hospital waste, for the portion not assimilated to municipal waste is also treated as a special waste. The waste is segregated, catalogued and boxed. Exception made for

Solid Waste Generation

human limbs and surgery parts - to be buried - the materials are fed to authorised incinerators with prescribed precautions to avoid infections (Vercellis Province, 2004). Some materials are hard to classify or have dangerous concentrations of toxic constituents to enable their treatment blended with other materials. A peculiarity of the Italian law prohibits dilution or uncontrolled blending when constituents, like chlorine for instance, exceed tabulated values. The example of automobile demolition shredded plastics and textiles, fluff, is one case (WWF, 2004: pp. 3-8). Plastic of different type and origin represent over 15% of the disposed auto in which the thermoplastic portion varies around 50% of the material, but PVC is also heavily present with the frequent result that chlorine exceeds 3.5 wt-% of the fluff (ANPA, 2002: pp. 33-35, 45, 46). The technology of fluff disposal is an open matter that we shall address later.

1.3

Differentiated Collection and Means of Waste Reduction

The aim to differentiated collection is to separate voluminous waste, metal and highly polluting substances from normal household waste and also to recycle valuable materials. The trend in recent years indicates a certain progress and recoverable materials differentiated from households and small businesses with scrap paper, organic waste and glass accounting for the highest percentage. The relative quantities for other waste material is low, with salvage material collected from trade and industry that largely consists of metals. The recycling rate for paper, plastic-packaging and glass is still lower with respect to northern European Countries. It is not straightforward to elaborate on Italian statistic data due to the delay by which official data are published and because the huge amount of data available through newspapers and web-collection is somehow biased by the writing source. An example is the data of differentiated garbage collection. It seems that every politician jumped on the bandwagon to demonstrate that their town or electorate accomplished or exceeded the minimum target of differentiated collection. The target was set by the Legge Ronchi to reach 35% in the year 2003, in order to get Italy near European averages, mitigate the municipal garbage disposal problem without justifying a huge concession to build incinerators but also to prohibit new landfills and make a better use of the insufficient existing ones (Decreto Legislativo, 1997). We read about Milano, exceeding 39% and being the champion accomplisher, but we also read of several Veneto cities like Treviso (52%), Vicenza (49%), Padova (46%), Verona (36%), exceeding 40 to 50% in the differentiation (ANSA, 2004). Where is the truth? The matter is not so important if we stay out of local prize or quarrel. It is important to note that differentiation has progressed, and still can make relative progress, although it appears improbable that it will exceed the percentages of about 40% reached by northern European Countries, where we observe civic commitment, relatively scarce population with a proven background of differentiation exercise, monitored over decades. The latest official data available is found in the APAT-ONR 2002 Report on Waste sponsored by the Environmental Ministry (APAT, 2003: p.65) that we report in Table 4.

Chapter 1

Table 4: Differentiated waste collection by macro-areas in Italy

1999 (t) 2,969,455 547,404 190,705 3,707,564 % 23.1 9.0 2.0 13.1 2000 (t) 3,244,390 706,325 230,333 4,181,048 % 24.4 11.4 2.4 14.4 2001 (t) 3,833,462 835,084 446,250 5,114,795 2002 % (t) 28.6 4,165,810 12.8 953,069 4.7 575,022 17.4 5,693,900 % 30.6 14.5 6,0 19.1

North Centre South Italy

Out of the almost 30 million tons/year of municipal waste, the Italian nationwide percent of differentiated collection is currently reported slightly over 19%, registering the predominant percentage in the northern regions and metropolitan areas. Progress has been noticeable, in 1999 the production of waste was 28.4 million tons/year and the differentiated collection amounted to about 13% of the total. Aside from the obvious benefit of separating and not dumping waste as-is in one hypothetical site or method of treatment, segregation of waste leaves the real and effective recycling issue still open. Large quantities of paper are picked, but paper mills hardly tolerate this feed into their pure cellulosic production and machinery. Plastic poses a similar problem because it is not easily fractionated into homogeneous constituents and the reuse for any quality workcraft needs the respect, at least, of a minimum specification range. Electronic components, shredded circuit boards have high contents of valuable metals but represent in general a scarcely tapped source. Metals and glass appear to respond best to the purpose of recycling segregated waste.

1.4

Regulations, Laws and Carbon Tax

Prior to Legge Ronchi, landfilling was quite diffuse in Italy and classified by categories, depending on the waste. The first category was for municipal waste, assimilated waste and non toxic shovelable, stabilised sludge. The second category was divided into Class 2A, mainly suitable for inerts and non toxic minerals, while Class 2B was for special and toxic waste having less than 1/100th of prescribed toxic concentrations. Class 2C landfill could instead receive higher toxic waste, up to 10 times said tabulated concentrations and finally, third category landfills could receive materials of exceeding toxicity (DPR 915, 1982: attached Limit Concentration tables). This observation makes reference to current terminology and is for some respects obsolete, but it is the evidence of how public legislation detailed permissible dumps and alternatives to landfilling, addressing treatment with the same general classification for types of waste. The regulation of Legge Ronchi maintained in general terms the same concepts, adopting however a more specific classification of the wastes, labelled as per the European regulations, with D if they go to landfill, destruction or disposal (Attachment B), and R followed by a characterising number to imply recovery of some sort for the different types of waste (Attachment C).

Solid Waste Generation

Carbon dioxide and global warming A portion of waste is sent to incineration, less than 9% of the municipal waste and about 1% of the special waste to pinpoint figures for Italy (Ministero dellAmbiente, 2003: pp. 185, 191). Carbon dioxide is a greenhouse gas, it absorbs 21 times less infrared radiations than methane and 16000 times less than chlorofluorocarbons, but its massive emission to the atmosphere appears to represent one-half of the potential global warming (United Nations, 1995: p. 7). Discussion on whether the world is warming is still inconclusive and yet attempts are being proposed to reduce emissions, mainly CO2, because of its quantity and more is known about its sources, sinks and life cycle. The issue has therefore been moved to list major CO2 contributors, resulting in a dozen of Countries that account for nearly 80% of the emissions, USA and industrialised economies ahead, and check if a global policy can be implemented. While developed Countries have agreed to cut on emissions and underdeveloped Countries also agree, the underdeveloped Countries need to industrialise, generate fossil power and cannot penalise their development, delay or suffer a drop in their standard of living. After the Kyoto global session in Japan, broadly minded ambitious plans were to be implemented by the year 2010, interestingly enough to promote up to 22% of the power generation from renewable sources (European Commission, 1997: pp. 10-20). Presently, most factual results are still verbal and discussions are periodically adjourned or proposed again for the international new sessions. Facts remain controversial not simply because of complexity and the great number of scientific and social disciplines being involved. Measurements over extensive period of times, like temperature, to assess the alleged amount of global and persistent planetary warming is very problematic and tied to the territorial boundaries of investigation. Some global numbers are relatively simple to get and adjourn, like the yearly quantity of fossil fuels being extracted (5 billion tons of oil, plus the same of coal and about half that quantity in natural gas). Burning part of fossil fuels generates carbon dioxide for an approximate carbon equivalent of 6x10E9 t/y. Much harder becomes to establish how much of that CO2, subtracts from accumulating in the atmosphere, by absorption via plants, minerals, water bodies and oceans and to which extent all natural sinks affect the overall balance. From the social point of view, given a greenhouse effect problem and unbalance, which cannot be confined to the air of a given responsible contributor, the matter becomes on how to limit that someones contribution, without arresting social development, without damaging the development of others and who and how can control such matters. Carbon Tax Governments can promote the increase of carbon sinks, by planting forests for instance, and have a number of policy options to induce and enforce the reduction of CO2 emission. Energy price can be controlled, subsidy to environment damaging production can be removed, fuels and emissions can be taxed and new technologies can be sponsored to commercialisation. Without underestimating market inter-relations and competitive advantages among Countries, all options can be left to the autonomous free actions of each Nation. An overall measurable instrument to police the system is however needed. A brilliant idea 1.4.2

1.4.1

Chapter 1

was to fix quotas of CO2 emission for each Country and consider that permit tradeable among the same, so that one can exceed it indeed, but only if so counterbalanced with another Country that lowered emissions, in exchange for some other benefit (United Nations, 1995: pp. 9-21). One example of this Joint Implementation can be that a developed Country invests in machinery in an underdeveloped Country to reduce emissions or invests in reforestation in another Country as one way to offset its exceeded quota. Such an idea is not untested, it was already introduced by the Environmental Protection Agency in USA for limiting SO2 emissions since the seventies and later studied for NOx and other pollutants. The attribute tradeable opens indeed to a market of options, swaps, futures of the permit commodities and one credit can actually offset another penalty: in the global balance the targets should match. Although issues are not new, they are yet unresolved, mainly for political reasons. A relatively easy, even speculative solution to the above inaction can certainly be a tax on emissions. That means to ignore why and how we got there to pollute or to prevent pollution, it simply states that whoever pollutes pays. Dealing with CO2 emissions, mainly referred to fossil fuels, the name became carbon tax. Since we aimed at investigating possible means to reduce or re-utilise CO2 emissions from industrial combustion processes, it becomes therefore important to check the status and implications of such a tax, if yet applied or near to be applied in any part of the world. Contrary to the abundance of publications, the carbon tax is not applied anywhere yet. The scanning of legislation in those Countries where debate and green parties manifested higher urgency and interest shows that only Ireland, New Zealand, Australia, Canada have plans to apply the tax but no certain deadline. Few European Community members have kept discussions alive, the United States took a negative political approach in the international arena, but the economic and scientific community still debates over a possible future carbon tax. In essence, the political stands are not resolved, the future is not predictable, but studies and possible solutions are being investigated because the tax may eventually come and new technologies may then gain economic advantage and viability. In view of the carbon tax regulations, new technologies formerly neglected, mainly for costs, are likely to induce strong modifications, at least, at the level of industrial and power generation combustion (Tellini et al., 2005: pp. 363-368). This will also impact on the waste treatment sector, from collection to ultimate destination and special attention to waste having relevant carbon content. Segregation and reuse of materials like plastics and paper will become more efficient since partial recycle followed by combustion will not be economically competitive. Anaerobic biodigestion, dry reforming, arc or plasma in presence of CO2, for instance, may become challenging processes. Ultimately, it is likely that innovation will partially or totally offset the tax, or gain an equivalent credit, like green certificates in Italy, which can be correlated to the quantity of greenhouse gas sequestered.

Solid Waste Generation

1.5 References
ANPA, 2002, February. La Caratterizzazione del Fluff di Frantumazione dei Veicoli. Report 15/2002, (Roma: Agenzia Nazionale per la Protezione dellAmbiente). ANSA, 2004. via Internet, www.ecodallecitta.it/old/apr2003/rifiuti/noncrescono/ commentorifiuti.doc, and ANSA of Venice, Jan.7, 2004 notizie.msn.it/ ambiente/notizie/notiziari/ rifiuti/20040107155032805849.html. APAT, 2003, November. Rapporto Rifiuti. (Roma: Agenzia per la Protezione dellAmbiente e per i servizi Tecnici plus Osservatorio Nazionale sui Rifiuti). Atochem, 1990. Commercial flier on polyethylene and plastics used for packaging. CTI, 2003, April. Biocombustibili Specifiche e Classificazione - Raccomandazione SC 9, Fonti rinnovabili di energia, CTI R 03/1. (Milano: Comitato Termotecnico Italiano). Decreto Legislativo, 1997, February. Nr. 22/1997, also named as Legge Ronchi (Roma: Gazzetta Ufficiale). DPR, 1982. Decreto Presidente della Repubblica Nr. 915/1982, Art. 1, (Roma: Gazzetta Ufficiale). European Commission, 1997. Energy for the Future: Renewable Sources of Energy. White Paper for a Community Strategy and Action Plan. (Brussels: COM(97) Final Report). IRER, 2000, February. Leliminazione dei rifiuti mediante termodistruzione: effetti globali sullambiente. Final Report, (Milano: IRER). Ministero dellAmbiente, 2003, November. Rapporto Annuale sulla Gestione dei Rifiuti.(Roma: Osservatorio Nazionale sui Rifiuti). Statistica Svizzera, 2001. Lambiente in Svizzera. Statistiche e Analisi. (Neuchtel: UFAFP, Ufficio Federale Statistica). Statistica Svizzera, 2002. Lambiente in Svizzera. Statistiche e Analisi. (Neuchtel: UFAFP, Ufficio Federale Statistica). Tellini M., R. Del Rosso and P. Cntola, 2005. "Solid and Carbon Waste Generation Impact." Chemical Engineering Transactions, Vol. 7, (Naxos, Italy: PRES '05 8th Conference Proceedings), ISBN 88-900775-8-1. United Nations, 1995. Controlling Carbon Dioxide Emissions: the Tradeable Permit System. (Geneva: UNCTAD/GID/11). Vercellis Province, 2004. -January, Internet: www.provincia.vercelli.it/ organiz/tutamb/tut_ris_ambien/dwd/P_rif_Sez3.doc. WWF, 2000, October. Relazione Tecnica sui Rifiuti derivanti dalla Frantumazione delle Carcasse di Autoveicoli. (Torino: WWF Italia, Piemonte Val dAosta Regional Section).

..

WASTE REDUCTION AND CHARACTERISATION

2.1

Reduction of Municipal Solid Waste

In the previous chapter we focussed on a broad scenario of waste generation and collection. Among various wastes, it is reasonable to concentrate on municipal solid waste (MSW), due to the fact that other types of waste have a special, toxic or industrial nature which already involves or requires a peculiar, industrial type of processing. We shall deal with MSW and we now start from these tenets: There are substantial and growing quantities of waste Waste is classified and differentiated still insufficiently, < 20% in Italy Recycling is still unable to exploit all the differentiated waste Only about 1/10th of the waste is incinerated in Italy and generates CO2 Laws regulate and limit emissions. Since the days of unregulated landfill are fading away rapidly, treatment of waste is the pressing issue and all means of processing or recycling lead to reduce the initial quantities and volumes. Quantities recycled and readmitted to any natural cycle subtract from the ultimate portion delivered to waste treatment plants. The treatment is not normally limited to one form of processing and the differentiated collection implies a separation that justifies parallel and alternative processes, all integrated in a planned scheme for a given territory. In this chapter we aim at quantifying a balance of the possible streams of waste, their treatment destinations and pinpoint the flow to thermal degradation-incineration.

2.2

Block Diagram of Current Treatment Flows

The integration of various treatments exploits physical and chemical characteristics of the waste, ideally to its optimum valorisation and without generating harm or nuisance to people and to the environment. A small portion of MSW is differentiated and it is therefore hard to appreciate its reuse and massive reduction: a great portion of waste is still delivered to landfills as it can be seen from the weight percentages, all referred to 100 basis of MSW (Ministero dellAmbiente, 2003: pp. 177186). When referring to the flows of municipal waste in Figure 1, we look at the initial 86% passing through the right arrow: almost 84% of it goes straight to landfill, 10.5% is incinerated, less than 6% is to produce RDF. Adding the ultimate residues of incineration, we obtain the worrisome conclusion that material to landfills is subject to very limited reduction. This represents both a safe disposal problem and a simple loss of energy that could be recovered via incineration. If we assume a 3000 kcal/kg heating value of the waste and an overall conversion of 20% to electricity, we estimate to lose more than 20 million kWh every year, i.e. about 4% of all the power produced by ENEL (referred to a nominal capacity of 60 thousand MWhe).

12

Chapter 2

Figure 1: MSW in Italy

Year 2000 data: MSW = 29 x10e6 t/y Undifferentiated (24.8) + Differentiated collection (4.2) 8% 6% 86%

Recoverable material
Plastic, metals, glass, paper ...

Composting + biostabilisation
Organic + green

Residue

72%

5%

9%

Drying, fuel
High HV material

Incineration
Electric power

Raw material substitute, use

Compost, fertiliser

RDF

Landfill

Recoverable material follows a pattern of industrial substitution and addition to prime materials, sometimes with lower grade or lower cost reuse. Aerobic composting degrades the organic and the green portion of the waste: the resulting product is suitable to fertilise, to spread or dispose on agricultural and forest land. The degradation releases CO2 and water, so the final compost may be reduced to about 50% of the initial mass. Incineration degrades the waste thermally: in addition to heat recovery and/or power production, the resulting products are ashes, slag, inorganic salts and gas emissions. The thermal degradation releases CO2 and the final solids are reduced to about 25% of the initial mass.A potential development and declared target of Italy is to arrive to European average levels of incineration (Istituto per lAmbiente, 2002: p. 9). A low average means around 27% for Countries like France and Norway, while high levels of incineration are common to Denmark and Switzerland with percentages above 88%. Practically, incineration in Switzerland (Figure 2) covers the entire municipal waste production and landfills are not used as direct means of disposal but receive only classified streams of material, as reported by the copied figure taken from the Swiss Environmental Report (Statistica Svizzera, 2002: p. 142). The 2002 incineration relevant to about 4.8 million tons for households and commercial waste produced 1.1 million tons of material to landfills still. However, almost 2 million tons were

Waste Reduction and Characterisation

13

composted and disposed in environmentally safe manners. Out of the 6.4 millions tons of building and construction waste only 26% required landfilling. Figure 2: Material flow of waste in Switzerland (Environment Swiss Agency, Forest & Landscape)

Data published on the latest report of APAT are reproduced in Table 1 and refer to older statistics collected by ENEA, the validity of the table is for comparative assessment and it confirms that Italy is way behind the European percentages for waste incineration (APAT, 2003: p. 37). Table 1: Municipal waste management in the European Union Country
Austria Belgium Denmark Finland France Germany Greece Ireland Italy Luxembourg Holland Portugal Spain Sweden UK TOTAL

Year
1999 1999 1999 1999 1999 1998 1997 1998 2001 1999 2000 2000 1999 1998 1999

Landfill t/y %
1,551,936 1,486,800 361,352 1,465,440 13,268,925 14,113,804 3,565,580 1,765,732 20,002,859 60,060 1,221,528 3,409,318 17,490,936 1,300,656 26,785,341 107,849,267 35.0 27.7 10.8 61.1 41.7 35.5 91.4 91.4 67.1 21.6 12.6 75.3 71.5 32.5 80.8 54.0

Incinerator t/y %
452,658 1,356,112 1,673,910 196,080 9,966,437 9,682,726 10.2 25.8 50.2 8.2 31.4 24.3

Other t/y %
2,432,983 2,499,272 1,296,616 737,880 8,551,085 16,001,115 335,584 166,230 8,037,841 84,942 4,521,240 189,962 4,293,946 1,300,656 3,801,024 54,250,376 54.8 46.5 38.9 30.8 26.9 40.2 8.6 8.6 24.2 30.6 46.6 4.2 17.6 32.5 11.5 27.2

2,999,190 132,990 3,950,136 929,814 2,678,792 1,397,981 2,553,813 37,600,632

8.7 47.8 40.8 20.5 11.0 35.0 7.7 18.8

14

Chapter 2

Due to the nature of the modern waste and irrespective of the chain of treatments, a portion of the waste needs to be thermally treated. High percentages have sustainable validity, like it is shown in the picture below (Figure 3, copied from the referenced Swiss report) that exhibits the number of incinerators and the approximate flows of materials in Switzerland (Statistica Svizzera, 2002: p.142). In 2002, 28 incineration plants processed about 2.6 million tons, producing 580 thousand tons of material to landfills. In such heavy use of thermal treatment, the problem is eventually to decide the type of treatment and the level of overall emissions, discharges and efficiency that may result. Figure 3: Waste to Swiss incinerators (Environment Swiss Agency, Forest & Landscape)

2.3

Characterisation of Municipal Waste

We discussed how the predominant classification and the average composition of waste has changed over the years and how sampling of heterogeneous solids can be grossly inaccurate (World Bank, 1999: pp. 11-18). The natural organic fraction of waste is derived from households and food. The artificial organic and paper portions may come in small or larger quantities, depending on the differentiated collection. Each fraction exhibits also great variability in composition and humidity. For instance, paper humidity can range from 20 to 80%. Light plastic is mainly made of polyethylene, polypropylene and polystyrene originated by bottles, bags, sheets and films or packing: its heating value is high, moderately impoverished by weather humidity and water bound to transportation and storage. Heavy plastic is mostly made of high density polyethylene and co-polymers plus PVC: in addition to high heating value, this exhibits high concentrations of chlorine. Fabric and textiles, whether made by natural or artificial

Waste Reduction and Characterisation

15

fibres from clothing or carpeting, have high heating value but variable humidity for the same reasons. To characterise and study all possibilities, waste should be divided into various classes, but for historical and statistic convenience, the classification that is often found in Italy is reduced to the main categories that we used to summarise variations in Table 2 below (IRER, 2000: pp. 12-15). Table 2: MSW classification from referenced sources
Organic Undersieve Plastic Paper Textile, wood Metals Inert, glass %
Notes:
% $ &

North A% North B% Torino% 23,99 29,07 26,24 8,48 10,43 14,90 12,43 12,49 10,90 31,66 21,43 26,94 5,08 13,38 5,09 4,52 2,90 2,79 12,72 7,32 12,53 98,88 97,02 99,39

Carpi% IT-2000% IT-2003 CH-2002$ W. Bank& 9,42 16-52 31 30 32,40 4,42 n.a. n.a. n.a. n.a. 20,05 4-21,4 4 25 7,50 37,08 12-45 31 29 25,20 23,72 1,4-9,4 n.a. 2 n.a. 1,89 2,3-6,9 5 3 4,70 1,03 3,4-16,5 18 11 6,20 97,61

RANGE 9-32 8-15 4-25 12-32 1-23 1-7 1-18

IRER, 2000, op. cit. pp. 11-15 Ministero dell'Ambiente, 2003, op. cit., pp.177-181 Statistica Svizzera, 2002, op. cit., p. 139 World Bank Report, 1999, op. cit., p. 11

Things vary so much that even a single indicative parameter like the heating value is strongly affected by the different urbanisation where the waste originates from. Similarly, the analytical weight percent composition varies and can hardly be taken as a reference. For ease of comparison we indicated min-max ranges in Table 3. Table 3: MSW composition and LHV from urban areas
kcal/kg 2196 Milano 2232 Roma 1984 Palermo 2312 Reggio E. 2279 Carpi 2147 Parma RANGE 1980-2310 H2O 35.10 34.10 35.00 35.10 16.70 34.60 16-35 C 24.60 26.40 29.20 30.20 30.10 27.00 25-30 H 5.20 2.80 4.30 3.80 4.60 2.90 2.8-5.2 O 14.90 16.10 14.50 13.30 12.40 15.20 12-16 N 0.80 0.50 0.80 0.40 0.40 0.40 0.4-0.8 Cl 0.50 1.10 0.10 0.60 0.50 0.50 0.1-1.1 S 0.10 0.40 0.20 0.40 0.40 0.30 0.1-0.4

As it can be seen, the cases of Palermo and Carpi shown in the table appear incongruent. Palermo exhibits low heating value and high carbon content, Carpi has high water content and somehow higher HV with a good percent of carbon. Samples are not available to our analysis and the data, although good, might refer to slightly different grab samples or may refer to an average over various samples. In general, the variation range of the samples composition is erratic, depending on place, country, time, transport and weather conditions even the validity of a given sample or statistics is not necessarily reproduced. We therefore consider valid to assimilate the waste to a probable composition and avoid to characterise it or analyse it chemically in further details. In conclusion and irrespective of how recently these studies were reported, we can reasonably use these published statistics for the purpose of understanding the main variables and attempt a modelling of the same.

16

Chapter 2

Of all the properties of fuels or assimilated fuels, the net calorific value, or lower heating value, is the most important. The lower heating value of a fuel is defined as the energy content per unit weight released through total combustion (total oxidation of C, H and S, but no oxidation of N) with the exclusion of the latent heat of water condensation. The laboratory analyses of fuels are coded (for instance, ASTM D2015 or D3286 in USA and DIN 51900 in Europe are used for heating value determination in a bomb calorimeter) and may be complex or erroneous when applied to heterogeneous solids like waste. The theoretical calculations are based instead on the analytical knowledge of the combustible portion, ashes and constituents of the starting sample. The difficulty and the accuracy are clearly dependent on the availability of reproducible analysis and significance of the sample constituents. Various results, indicating the presumed burning potential of the material, may be plotted and confined within an area of a Tanner triangle diagram in which the vertex variables are the combustible, the ash and the moisture percentage of the sample. Furthermore, to overcome the difficulty and to quicken the determination of HV, empirical formulas have been proposed, such as Dulongs (a) or Francis and Lloyds (b) correlations (Black & Veatch, Drbal et al., 1996: p. 105). These formulas were mainly conceived for coal and natural combustibles which may be locally heterogeneous but they repeat on the average their bulk properties.

(a) (b)

HHV = 146 C + 620(H - 0.125 O) + 40.5 S HHV = 149 C + 530(H - 0.104 O) + 26.7 S

[BTU/#] [BTU/#]

We modified such correlations to obtain the formulas (c) and (d) below in order to calculate the LHV (with the water condensation subtraction term) in MJ/kg units.

(c) (d)

LHV = 33.96 C + 144.21(H - 0.125 O) + 9.42 S - 2.5 H2O LHV = 34.66 C + 123.28(H - 0.104 O) + 6.21 S - 2.5 H2O
(atomic species expressed in [kg/kg] and LHV in [MJ/kg])

The same formulas do not fit well the case of solid waste that does not have bulk homogeneity and repetitiveness. Even by averaging characteristics over several grab samples, mixed and ground, repetitiveness is seldom possible. It is also difficult to assimilate the composite waste to a pseudo-component, or a sum of pseudo-components. If this were possible, calculation could be attempted by simulating constituents rather than atomic components or via group contribution methods. For example, if we could make the hypothesis of dealing with benzene, phenol, polyethylene or a number of defined chemicals, calculations can be made, affected by good approximation. If we then refer to vegetables, organic food, wood and whatever composite materials come into the waste, the algorithms become increasingly laborious and the results break down. Various formulas were introduced, based on the weight percentage of elementary constituents, mainly C, H, S, O, N and H2O, but empirical correlations cannot account for the real energy released by combustion and lead to approximated results. In attempting to utilise the empirical criteria for municipal waste, M. Lemann reports a correlation that exceeds the heating values calculated from the thermochemical reaction of elementary constituents and the formula sometimes yields values lower than

Waste Reduction and Characterisation

17

the heat actually released by the combustion of complex organic species (Lemann, 1992: p. 68).

LHV = 34.8 C + 93.9 H + 10.5 S + 6.3 N - 10.8 O - 2.5 H2O

(atomic species expressed in [kg/kg] and LHV in [MJ/kg]) Normally, these calculations predict the heating values reported for published samples with a 5 to 10% accuracy. Chlorine, sometimes present in significant concentrations, does not actually bear a relevant heat contribution and is not included in the correlation. In view of the intrinsic empiricism of any formula, one may well drastically aim to work with a lower number of factors, say C and H only, plus the deduction due to humidity and oxygen already present in the weight analysis. Although no better prediction or simplification is obtained, one may also prefer to use the predictive formulas of any leading engineering/supplier company of incinerators, such as Von Roll Environmental, that modify their correlations periodically, depending on the experience derived from their reference plants and observations.1

LHV = 34.04 C + 101.74 H + 19.092 S + 6.28 N - 9.839 O - 2.5 H2O

(atomic species expressed in [kg/kg] and LHV in [MJ/kg]) Aiming to obtain a practical assessment of the LHV calculated with empirical formulas versus the experimental value for the same type and composition of waste already reported, we tabled the LHV calculated with formulas (c) and (d). Other comparisons reported in Table 4 are the thermal release column achievable by stoichiometric full combustion of the atomic constituents and the LHV calculated with Lemanns and VonRolls empirical formulas. Table 4: Comparison of reported and calculated LHV
LHV: Milano Roma Palermo Reggio E. Carpi Parma Reported kcal/kg 2196 2232 1984 2312 2279 2147 Calculated with approximated correlations (c) 2938 2218 3021 2986 3402 2335 (d) 2904 2320 3034 3009 3373 2422 Thermoch. 2657 2075 2775 2763 3131 2181 Lemann 2632 2221 2826 2826 3131 2310 VonRoll 2721 2271 2891 2881 3199 2356

In spite of the calculated variance, it appears that the formulas give acceptable and indicative values in as much as the chemical constituents of the waste are consistently and reasonably determined. We ignore whether the reported LHV of each city is indeed the exact and repetitive measurement associated with the given
1

Source: Von Roll Environmental, Zrich, CH, conceptual design indicative criteria provided to author.

18

Chapter 2

composition of waste, but we would face the same uncertainty if we were to make repetitive determinations of LHV and the corresponding chemical analyses. This observation is meant to annotate the operation limit and difficulty to characterise the waste so that formulas provide a practical tool of evaluation, sufficiently reliable when the starting composition is determined. A practical consequence of this reality is that any incinerator is designed and meant to operate within a combustion diagram and it is not realistic to pinpoint its throughput and efficiency as if it were a furnace fired with coal or gasoil.

2.4

Scenario of Differentiated Collection and Heating Values

It is now interesting to see how the heating value changes, starting from the same real or hypothetical waste source, as a function of the differentiation. Conversely, the fraction which is sent to incineration will be greatly affected by differentiation and the LHV of the feed will become a major advantage or concern for the applied technology (Tellini et al., 2004: pp. 242-250). For ease of discussion, we focus on the possible waste composition reported below in Table 5, which will be later used for several simulations. Table 5: Base data for the waste simulation

Firstly, we can make the hypothesis of 30% differentiation, so that 50% of the organic, 20% of the paper, 50% of the hazardous, 20% of the plastic plus 80% of inert is separated upstream. The portion that remains for incineration is characterised by a heating value around 2600 kcal/kg and by the composition of Table 6. We can otherwise make the hypothesis of 30% differentiation in another way so that 50% of the paper, hazardous and plastic plus 80% of inert is separated upstream. The portion that remains for incineration is characterised by a lower heating value, around 1880 kcal/kg and by the composition of Table 7. If we make an up-front mechanical separation, the portion to incineration results of greater heating value, above 3000 kcal/kg, since we can deplete the waste from most of the wet organic and under-sieve, say 85%, plus 50% of the metals, while leaving plastic, textiles and combustible materials to incineration as per Table 8 that follows.

Waste Reduction and Characterisation

19

Table 6: 30% differentiation, 2600 kcal/kg

Table 7: 30% differentiation, 1880 kcal/kg

Table 8: 40% differentiation, 3000 kcal/kg

20

Chapter 2

Coming closer to the Italian target of achieving the average European level of 35% differentiation, we can assume to separate upstream 40% of the organic, 50% of the paper and hazardous, 10% of the metals and plastic plus 80% of glass and inert. The portion that remains for incineration is characterised by a heating value around 2500 kcal/kg, and by the composition of Table 9. A variety of cases can therefore be simulated, with one interesting case that may actually be sought when we seek an efficient up-front separation to recover materials and send a rich portion for an RDF plant or palletise it for fluidised bed incineration. The end-result can be a differentiation leaving behind percentages of 90% for under-sieve and organic matter, 50% of the paper and hazardous, 80% of the metals and plastic plus 80% of glass and inert. The portions found in the incineration stream depends of the degree of reuse and it has a high heating value of about 4000 kcal/kg with the composition summarised in Table 10. We now have a numeric appreciation on how humidity and composition variables can change and how important is to define the type and range of waste for designing the treatment plant.

2.5

Fluff

A source of organic waste, important for its carbon content that can exceed 50% on a weight basis, is the shredded plastic originated from automobile demolition. This suggests that fluff can be a valuable source of energy, or chemicals, if it is looked at as a possible feedstock to make syngas. Automobile wrecks contain about 70% steel, 5% of odd materials and about 25% of textile, rubbers, glass and plastic components of different kind. This last portion, denominated fluff, is classified in Italy as non-conventional fuel, it contains high levels of metals, chlorine and contaminants which make it unsuitable for incineration as it is. The level of various leachable metals (Zn, Cu, Pb, Cd, Cr) make the fluff dangerous for aquifers. Under general terms the Italian law prohibits the use of high heating value substances as fuels when they are highly contaminated, with chlorine, for example. Such substances that could be considered for blending with cement or power plants fuels must however be treated only within plants authorised for waste disposal. Since we shall later consider fluff interesting for supplying carbon in a plasma process, we wish to familiarise better with this material even because fluff restrictions in Europe are set to progressively achieve the ultimate 2015 goal of putting only 5 wt-% of the fluff in safe landfills (European Community Directive, 2000). In addition to environmental issues, the average landfill costs are in the range of 160 $/t in Germany and Japan, 80 $/t in Italy to 50 $/t in USA: these costs become significant offsets for any treatment process (Zoboli et al., 2000). Internationally, fluff is also denominated Automobile Shredder Residue (ASR). The shredded material derived from automobile demolition-recycling represents a growing concern for all industrialised economies, where end-of-life vehicle recycling is prevalent.

Waste Reduction and Characterisation

21

Table 9: 35% differentiation, 2500 kcal/kg

Table 10: upfront separation for RDF, 4000 kcal/kg

22

Chapter 2

Although some fluff is derived from domestic appliances like refrigerators, the greatest quantity comes from shredded automobiles already stripped of most of their reusable metals. The vehicles that are deregistered every year are 80 to 90% of the new vehicle annual registrations or about 7% of the circulating stock (Development Bank of Japan, 2003). In the early years of this century the worldwide car production remains stable and close to 60 million vehicles, of which 20 millions in North America, the same in Europe and about 10 millions are manufactured in Japan (ACEA, 2003). Annual quantities of ASR were reported in the range of 4 million tons in 1999, about 22% of the ferrous scrap recovered from an estimate of 18 million deregistered automobiles in USA (Daniels, 1999). ASR quantities in Europe are estimated to exceed 2 million metric tons per year and about 800 thousand tons per year is the amount to be disposed in Japan (Development Bank of Japan, 2003: p. 32). The 10% fluff over scrap metal in Europe and Japan are nearly half the percent that is expected in USA and this can be explained with EoL auto export to nearby countries, higher degree of stripping and the fact that the USA market includes a greater percentage of large cars, SUVs, and light trucks with heavier engines, transmissions and bodies. For our purpose it is not essential to understand the real material flow of fluff but is enough to stress its worldwide abundance. Main indicative constituents for ASR are given in Table 11 below. Table 11: Fluff average constituents (wt-%) Data source: D. Bank Phillips of Japan classified as V = old cars % and N = new cars %
Glass and Inert Wood Paper Fabric Plastics to include PP PE PVC ABS PU PA Resin Rubber Aluminium Copper Iron Lead Zinc & related materials Total 16.1 7 3 2 15 50

WWF
(op. cit. pp. 3-8)

ANPA

(op. cit. pp. 33-35, 45)

44V 25N

17.1

38V 60N 10V 25N 1.5V 4.5N 10V 3.5N 5V 8N 5.5V 7.5N 1V 5N 15V 10N 1.5V 3N 1.5V 3N 1.52

0.14 0.50 0.84 24.90 13.86

39.3 8.7 5.1 4.4 8.0 0.2 1.1 100.0

6 5 4 8

22. 1.89 2.50

100

Waste Reduction and Characterisation

23

Vehicle demolition and recycling generates fluff of variable characterisation since the technological changes in the auto making affect the fluff relative quantities and composition evidenced by substantial differences in published data. ASR contains plastics, rubber, paper, wood, fabrics, sand, dirt, glass, teflon hoses, ferrous and nonferrous metal pieces and possibly automotive fluids and refrigerants. Subclasses of plastic-base materials and foams are polyurethanes, PP, PE, ABS, nylons, paints and acrylic varnishes, whereas the PVC content has decreased from 8 10% to about 3% in modern cars. Sheet molded composites and resins, polyesters and so called engineered plastics are also found since more and more structurally respondent plastics are used in the auto industry (Phillips, 1996). The chlorine content of the fluff is generally prohibitive for incineration and landfilling is currently the widespread method of disposal, while selective recovery of even valuable materials is practically impossible due to constituents mixing and the way of obtaining ASR from any junked vehicle. PVC is gradually being replaced in auto making and this explains how the chlorine concentration in modern cars fluff has decreased (ANPA, 2002: p. 46). As a summary indication, the chemical composition of ASR is reported in Table 12 constructed with data taken from the sources referenced above. Table 12: Fluff average composition (wt-%) Data source: Prelimin. Dev. Bank ANPA of Japan estimate
LHV [kcal/kg] Spec.Wt [kg/l] Carbon Hydrogen Oxygen Nitrogen Chlorine Fluorine Sulfur Inert Water Aluminum Arsenic Cadmium Chromium Copper Iron Lead Mercury Selenium Silicon Zinc 43004600 46.89 6.25 8.72 1.96 3.61 0.43 13.68 10.46 5.1 0.0006 0.0017 0.00004 0.62 0.178 0.0002 0.0001 0.35 0.0008 0.00005 0.56 0.28 4749 66.15 1.62.4 2.87 0.270.33 40 5 1 3.5 0.95

WWF

Last own Sample

6131 0.60 54.40 6.48 2.01 1.97 0.13 3.47

2 3 2

4.4 8 0.2

1.1

0.7

0.42 0.00038 0.0012 0.021 0.36 3.30 0.14 <0.00005 <0.00005 11.25 0.33

24

Chapter 2

2.6

References

ACEA, 2003.Auto Data, Automotive Production Historical Series 1995-2002, Brussels, Belgium. www.acea.be. ANPA, 2002. February. La Caratterizzazione del Fluff di Frantumazione dei Veicoli. Report 15/2002, (Roma: Agenzia Nazionale per la Protezione dellAmbiente). APAT, 2003, November. Rapporto Rifiuti. (Roma: Agenzia per la Protezione dellAmbiente e per i servizi Tecnici plus Osservatorio Nazionale sui Rifiuti). Black & Veatch, Drbal L. et al., 1996. Power Plant Engineering, (Norwell, Massa: Kluwer Academic Publishers). Daniels E., 1999. Recovering the Plastic in Junked Cars, Argonne National Laboratory. www.pprc.org/pprc/rpd/fedfund/doe/doe_oit/automobi.html. Development Bank of Japan, 2003, May. Prospects and Challenges for End-of-Life Vehicle Recycling. Research Report no. 41. European Community Directive 2000/53 on End-of-Life Vehicles, Official Journal of the European Community, October 21st, 2000. Lemann M., 1992. Abfalltechnik. (Dbendorf, CH: Dorema Texteam Verlag). IRER, 2000, February. Leliminazione dei rifiuti mediante termodistruzione: effetti globali sullambiente. Final Report, (Milano: IRER). Istituto per lAmbiente, 2002. Il ruolo della termovalorizzazione nella gestione integrata dei rifiuti. Corepla Report, (Milano: IPA). Ministero dellAmbiente, 2003, November. Rapporto Annuale sulla Gestione dei Rifiuti. (Roma: Osservatorio Nazionale sui Rifiuti). Phillips M., 1996, October. Plastic Growth in Auto Steadies. Recycling Today, www.recyclingtoday.com/articles. Statistica Svizzera, 2002. Lambiente in Svizzera. Statistiche e Analisi. (Neuchtel: UFAFP, Ufficio Federale Statistica). Tellini M., R. Del Rosso, P. Cntola, and P. Gronchi, 2004. "Solid Waste Thermal Characterisation." La Rivista dei Combustibili e dell'Industria Chimica, Vol. 58, No. 6. World Bank, 1999, August. Municipal Solid Waste Incineration. Technical Guidance Report, (Washington D.C.: The World Bank). WWF, 2000, October. Relazione Tecnica sui Rifiuti derivanti dalla Frantumazione delle Carcasse di Autoveicoli. (Torino: WWF Italia, Piemonte Val dAosta Regional Section). Zoboli R., et al., 2000. Regulation and Innovation in the Area of EoL Vehicles. (Milano, Italy: IDSE-CNR).

3
3.1

TRADITIONAL INCINERATION

Considerations Common to Incineration Systems

In the previous chapter we assessed that a portion of waste inevitably goes to incineration. Even the differentiation of garbage collection opens to various material balances which however bring a portion of waste to non recoverable material and such material can undergo incineration in order to have a substantial volume reduction other than being disposed in landfills. Indicative although approximated mass flows of possible MSW current treatments are compared in Table 1 and allow an appreciation of the relative quantities we are referring to. The elaboration is based on input data taken and consolidated from the IRER Report that simulates different venues of treatment (IRER, 2000: pp. 26-32, 103-118). Table 1: Municipal waste material flows
MATERIAL FLOW COMPARISON FOR VARIOUS COMBINATIONS OF TREATMENT Landfill Incineration Mechan. Different. Different. Different. Different. Different. as such as such Separation up to 30% up to 30% up to 35% up to 35% up to 35% 50% paper 20% paper gasification
50% plastic 10% plastic

TREATMENT MSW NO DIFFERENTIATION Recoveries Residue to incineration Composting Hazardous waste Compost product MECHANICAL SELECTION Recoveries Dry Wet BIOSTABILISATION INCINERATOR Air + Flue gas Water + Water Dust Slag Sludge To Landfill from differentiation To Landfill from incineration To Landfill from biostabilisation TOTAL to LANDFILL LHV of waste to incineration

[ dim.] kg 100 100 kg kg kg kg kg 100 1 64 35 35 100 1121 1215 143 120 3.3 28 1.6 64 713 773 91 76 2 18 1 71 793 860 101 85 2.3 20 1.1 1.5 23.5 25 1880 2618 64.3 721 781 92 77 2.1 18 1 2.2 21.2 23.4 2500 100 100 100 100 100 71 27.5 1.5 0.3 100 100 64.3 23.5 2.2 9.5 0.3 5.6 100 64.3 23.5 2.2 9.5 0.3 5.6 64.3 2 34.2 26 26 34.2 385 416 49 41 1.1 9.6 0.55 2.2 13.21 15.6 31 4000 100 64.3 23.5 2.2 9.5 0.3 5.6 64.3 2 34.2 26 26 34.2 96 128 49 41 1.1 9.6 0.55 2.2 13.21 15.6 31 4000

kg kg kg kg

kg kg kg kg kg kg kg kg kg kg kg kcal/kg

33 100 2180 33 2180

21 21 42 3030

Source of data: IRER 2/2000 Report

The differentiated garbage collection generates higher heating value waste due to the subtraction of green, humid, inert materials and for leaving large quantities of packaging and plastic residues. Historically, the incineration process could have been assimilated to a burning pit or to a household oven. Later concern about residual material, toxicity and gas emissions, as well as the advantage of recovering energy in some usable form of heat or electric power, brought to develop different methods, the most commercialised being today grate incineration, fluidised bed incineration and rotary kiln thermal destruction.

26

Charter 3

Essentially, all the processes seek to render the waste inert, reduce the ultimate volume of the portion being discharged from the processing, eliminate or segregate hazardous substances while reclaiming as much energy as possible as electric power. From the theoretical aspect, one incineration method equals the others, in the sense that the thermochemistry involved is the same: heat supplied from outside or self-generated by reaction, brings to free volatile components and humidity, the waste cracks into more gas and reactions proceed to partial or complete oxidation. Full oxidation is generally required as a sign of good combustion, avoidance of CO emissions and a diffused creed that high temperature plus excess oxygen in the flue gases prevent toxic substances emission. The energy input depends on the LHV of the waste that we learned how to characterise and to calculate, based on its major constituents. With variable components of the waste, like plastic, we would see higher percentages of H and C and a much higher heating value as evidenced by Figure 1. Figure 1: Low Heating Value and constituents feed composition Once we determine the heating value, we know the potential heat entering the H2O system. Based on the composition of C the waste, we can also calculate the H quantity of combustion air requirement O N and the quantity of flue gases exiting Cl the system. From composition and S physical properties of the exiting gases, 1803 2179 2516 4000 4200 an average specific heat is determined k c a l/k g for the gas, which enables also to determine the theoretical adiabatic temperature increase, upon oxidising dry material that contains mainly C, H, S, to CO2, H2O and SO2. Other reactions would obviously occur and yet these would not drastically modify the calculation. For instance, HCl is formed during the combustion, but its heating contribution is negligible. Analogously, from the heat subtraction point of view, cracking requires energy, but this is also neglected when speculating about the preliminary theoretical approach. In reality, it becomes merely speculative to make hypotheses about the cracking of species, due to the heterogeneous variability of the constituents in the waste. Finally, it is however true that the adiabatic temperature actually achieved accounts for the thermal impoverishment of endothermic reactions like cracking and the thermal losses that the closed system may have indeed. Failing to know or to have repetitive occurrence of any given model of reactions, we can simply disregard the single species and refer our thermal calculations to the cumulative LHV of the waste. The heat of reaction increases the exiting gas temperature and their specific heat Cp will vary. Simulation with various molar percentages of the main constituents (CO, CO2, O2, humidity) enables to consider an average Cp of 0.25 kcal/C-kg. A range between 0.25 and 0.3 is easily calculated from published physical data (Aerstin and Street, 1980: p. 227). Furthermore, by deducting an average 5% for heat losses and unburned material
45 40 35 30 25 20 15 10 5 0
%

F e e d c o m p o s itio n v s L H V

Traditional Incineration

27

we find the possible adiabatic gas temperature between 1100 and 1500 C. Even higher temperatures would result from highly organic materials, but limitations are set to prevent damages of the mechanical systems. The two examples calculated below (case of LHV = 2100 kcal/kg and LHV = 4000 kcal/kg) are indicative of what a high variance can signify on the systems and are exhibited in Figure 2. For simplicity the calculation is made for carbon and hydrogen conversion to CO2 and H2O, major constituents for the process. Since all plants are actually operated with a light under-pressure and are therefore under the ultimate suction of the tail ventilator, it is evident how a significant variation on the design conditions, or design operating point, can bring substantial inadequacy of the machinery when operation is attempted at different conditions. The induced fan ventilator, for instance, is normally designed with a 50% extra capacity, but the examples indicate that this margin would still be insufficient for the machinery. Figure 2: Calculation of adiabatic temperature for two cases
C + O2 = CO2 H2 + O2 = H2O Cases: waste @ 2100 and 4000 kcal/kg PCI C H O H2O Subtot. 13 2 12 63 90 2100 40 6 22 15 83 4000 Flue Gas (kg out / kg in) CO2 13 x 44/12= H2O 2 x 18/2= Air: Oxygen for reaction 13 x 32/12 + 2 x 16/2 = less oxygen in waste 12 O2 to feed with air O2 excess, + 80 wt-% N2 in air x 78/21 x 32/28 = 4.25 Umidity in waste Excess: 80 wt-% air on remaining waste
(depends on sizing, technology, grates, cooling ...)

C + O2 = CO2 H2 + O2 = H2O Cases: waste @ 2100 and 4000 kcal/kg Tot. PCI C H O H2O Subtot. 13 2 12 63 90 100 2100 40 6 22 15 83 100 4000 Out Flue Gas (kg out / kg in) 47.7 CO2 40 x 44/12= 18.0 H2O 6 x 18/2= Air: Oxygen for reaction 40 x 32/12 + 6 x 16/2 = less oxygen in waste 22 O2 to feed with air O2 excess, + 80 wt-% N2 in air x 78/21 x 32/28 = 4.25 Umidity in waste Excess: 80 wt-% air on remaining waste
(depends on sizing, technology, grates, cooling ...)

Other 10 17 In

Other 10 17 In

Tot. 100 100 Out 146.7 54.0

50.7 -12.0 38.7 30.933 295.8 73 131.4 496.8

30.9 295.8 63.0 131.4 586.8

154.7 -22.0 132.7 106.13 106.1 1014.9 1014.9 15.0 32 57.6 57.6 1311.3 1394.3

Assuming average Cp of gases = 0.25 kcal/kgC delta T adiabatic becomes: 2100 x 100/.25 / kg gas = 1431 C

Assuming average Cp of gases = 0.25 kcal/kgC delta T adiabatic becomes: 4000 x 100/.25 / kg gas = 1148 C

The excess air is to be seen as a peculiarity of the technology being used (Goerner, 2003: p. 10). A variable quantity of 20 to 80% air is normally found in all types of combustors but here we deal with heterogeneous, variable fuel, which contains also a variable and non-uniform quantity of water and inert materials, unevenly distributed in the overall mass fed to the furnace (Black & Veatch, 2001: p. 173) . With this regard, it is necessary to have an excess of air over the burning stoichiometry, but also an excess over the overall mass feed that may hinder or create preferential paths to the air that is used for the combustion. The method to assure that air is in excess and compliant to standard practices and law requirements for this industry is to impose that a minimum 6% oxygen content is measured in the flue gas after the combustion chamber. The variable feed (quantity and quality) demands to set a range of parameters acceptable for the intended system and machinery. A combustion diagram, shown in Figure 3, is the operating design tool that restricts mechanical and thermal inputs within the acceptable range of variance of the waste for a given system (Lemann, 1992: p. 69-72).

28

Charter 3

Figure 3: Explanatory combustion diagram Vertical right limit for max mechanical load Horizontal upper limit for max thermal load Diagonals = heating values Zone below the optimum requires air pre-heaters and auxiliary burners.

To provide an order of loading magnitude, grates accept about 300 kg/h-m2 of waste and about 1000 kW/m2 thermal input. Mechanical and thermal overloading can be tolerated temporarily and a 10% margin is acceptable. It is however important to note that such margin is evidently small if we recall how variable the waste can be and how inaccurate can be the determination of its heating value. Figure 4: Power conversion typical yield, input basis = 100 Regardless of the type of combustion method being utilised, the overall power conversion (net energy 96 obtained versus the energy input with 1 Thermal losses Furnace waste) is affected by various heat Flue gas losses and transformation efficiencies. 95 An overall 20% efficiency is obtained 13 Flue gas sensible heat Boiler by the energy balance that is practically affected by input-output 1 Mechanical losses 82 streams shown in Figure 4. When 57 Condenser heat Turbine cycle speaking in terms of chemical usable energy or possible heat reuse, the 1 Steam cycle auxiliaries 2 FGT auxiliaries 24 efficiency would become greater, but 1 Furnace auxiliaries ... Gross Elect. Gross it is customary to refer to achievable electric power generation, energy transferable at a noble level whereas 20 millions of kilocalories at low Net Elect. Energy temperature would not be indicative of a useful transformation. Different methods and technologies imply modifications and improvements but the present results are fairly consistent with the picture below. Given the same type of input, variations of the thermal treatment reflect on variations for emissions and a different extent in flue gas treatment, in handling the feed and discharge of solids. Since we are mainly concerned here on the combustion or hot
100 Energy in waste 4 Unburnt, slag

Traditional Incineration

29

portion of the processes -shaded box in Figure 5 - ancillary and downstream systems can be presently neglected as if they were conceptually alike for all the types of technology. Figure 5: Incineration plant block diagram

3.2

Grate Furnaces

In its very essence, the grate furnace does not conceptually differ from the early oven furnaces, but technologies have been applied for over 80 years and are regularly updated for changing requirements, legislation, operability and effectiveness. Waste is dumped into an air-tight feed hopper and a controlled ram feeder pushes the material to the grate, whether this be air or water cooled. The downward sloped grate is the footing of the combustion chamber as shown in the explanatory sketch, Figure 6. In a grate system the feed hopper and the pushing/feeding devices are also important to avoid air windage and fires upstream of the grate itself. The combustion primary air rising through the grate at the bottom of the furnace and the movement of the grate enable even distribution, homogenisation and travelling of the waste feed toward the solid exit. Homogeneous distribution and controlled even air paths are essential to obtain efficient combustion. Along with the sloping down of the grate, several phases take place: the material is dried, releases gases, is ignited, it cracks to release more gas, is incinerated and burnt out to non-reacting inert slag. The primary air source is fed through the grate for the purpose of being preheated, to stir and create turbulence in the burning material, but most importantly to cool the steel grate. Secondary air and also additional air used to cool the furnace sides adds to the air admitted through the grate. Air and waste have a pseudo co-current flow with a longer residence time that reduces the formation of CO, NOx and unburned organics. The furnace walls and the heat exchange sections recover radiant and convection heat to generate steam whereas particles disengagement, collection and

30

Charter 3

cleaning of the exchange surfaces is necessary to enable continuous operation of the boiler. The furnace walls are protected with refractory and tiles and the design features for membrane walls, the configuration of the chamber, the air swirl injection and control as well as the SNCR vary among different technologies or remain somehow subject to proprietary know-how. The SNCR (selective non catalytic reduction of nitrogen oxides) is conceptually done in the same manner, by feeding ammonia or urea to convert the oxides to nitrogen and water. The thermochemistry is well known but the mechanics to feed and control the process conditions are peculiar to each supplier. Figure 6: Grate incineration/boiler conceptual layout

Cleaned flue gas recirculation to the burning chamber was first introduced to increase thermal efficiency and reduce NOx formation due to lower oxygen content and lower flue gas generation. Some problems were found on the return lines where corrosive condensation was experienced but the method is excellent from the process point of view. For all grates, slag is extracted at the lower or exiting end of the furnace grate: it is dumped in a sealed water tank or sprayed with water to quench and disgregate the biggest pieces. 3.2.1 Air cooled grates Main constituents of grates operation are the hydraulic driven mechanisms and the mechanical moving parts. The grate provides simplicity but high heating value waste require higher air flowrates since this serves the process but also the metallurgical cooling requirements of the grate. The air quantity and means to control the grate skin temperature may also lead to higher NOx formation. Grates are divided into compartments, call them row or sectors, and have some sort of moving blocks or rolling cylinders that embody a controlled travelling- pushing method to rotate and move the waste material toward the exit in a uniform and planned

Traditional Incineration

31

way so that the residual material reaches the end with homogeneous air contact. The air flow through the grates is also controlled in each compartment. Water cooled grates The increased heating values and the flexibility in changing waste composition brought to develop different methods to cool the grates. The system mainly splits the cooling of the grate with air but also with a closed circuit coolant, normally a pressurised closed water piping loop, embedded in preferred grate blocks exposed to the direct flames. Only the hottest zones of the grate, having the highest thermal load, are normally water cooled, the rest being air cooled.1 The exchanged heat is recovered for district heating or to have higher efficiency in the thermal cycle by means of air preheating. Extended durability and lower parts replacements are obtained not simply for the reduced stress on mechanical parts but also because higher grade metallurgy is used to manufacture the components of the water cooled grates. By utilising a method that better protects from local overheating, these grates enable a better distribution of the waste load over their surface. Improved combustion enables also to slag out the residual material with a lower content of entrapped incombustible material. 3.2.2

3.3

Fluidised Bed Furnaces

This type of furnace is frequently used when the material fed to the reactor is pre-treated or has predictable reology like sludge, shredded or minute pieces. A large piece of organic material could also be fed indeed without damage and float until destroyed in the bed, the bed exhibits an upper level and behaves like a fluid. One problem would however occur when high density non homogeneous materials can fall to the bottom, accumulate or create problems with the air distribution that fluidises the particles bed. In fact, a number of nozzles sized to evenly distribute the air is placed at the bottom of the bed, this keeps the waste and the inert material, normally sand, in a homogeneous swirling medium, characterised by little wear, high resistance, high heat capacity and uniform distribution, simple design, flexible turn-down and operable conditions (Zenz, 1977: pp. 81-91). The bed is practically isothermal, temperature distribution is normally within 3 to 5C and this is important to control the temperature in highly exothermic reactions (McCabe and Smith, 1976: p.167). While on grate furnaces we can distinguish between different phases of degassing, cracking of the substance, release of gases and combustion of the same, in a fluidised bed the gases flash out of the substance and ignite immediately. The high turbulence created in the fluid-solid mixture leads to efficient mixing, full backmixing and heat transfer coefficients higher than those achievable in fixed bed, waste is therefore exposed to ideal burning conditions, resistant to upset conditions and unaffected by lumps or concentrated material hot spots that are damaging for conventional furnaces (Froment and Bischoff, 1979: pp. 662-669). Low fusion ash materials are less troublesome than they are in stationary or grate furnaces because the
Courtesy of Von Roll Environmental (Zrich, CH), evolution of design data for air and water cooled grates incineration.
1

32

Charter 3

overall temperature is evenly kept lower here, slagging and fouling are thus eliminated (Smith, 1985: pp. 27-31). The gasification and combustion occurs in a bubbling or circulating bed, depending on the gas velocity that leaves the bed stationary or sufficiently fast to travel out of the reactor and circulate the inert media back, Figure 7. The inert material is kept within the system to provide thermal capacity and exchange so that the bed behaves like a heat sink, slow to cool off when a temporary stop occurs. Fluidised beds allow extended residence time at temperatures above 850C.2 Stationary or circulating are chosen for the LHV and the heat sink tolerates and performs also with high heating values materials by keeping the quantity of non-combusted material around 0.5% versus averages of 2% for grate incinerators. The excess air through the bed is about 30-50% versus the excess of 80-100% for the grates, amounts that can be reduced in the grate plants by flue gas recirculation.

Figure 7: Scheme of bubbling and circulating fluidised beds (Courtesy from Von Roll)

The boiling reactor has a practical constant bed level and to integrate the fluidisation primary air feed a secondary air stream is injected over the bed for air control, added turbulence and staged combustion. In such a manner the bed temperature is kept well below the melting point of the ashes, since the ash sintering would create irregular fluidisation and problems at the bottom distributors. The circulating bed is not
2

The general principles are found in many ambient protection legislation, such as the Italian DPR 915/82 where residence time in excess of 2 seconds is to be guaranteed (Article 1).

Traditional Incineration

33

staged and the ashes are practically maintained in constant quantity due to solid recirculation. The gas separation and blow down of the ashes needs to be resolved prior to recycling and this solid classification is not easy due to the nature of waste. In generalised terms, it is preferable to use a boiling bed reactor, which by evidence is mechanically simpler, but the circulated bed enables to load higher heating value material. For circulating beds, the air flow fills the entire combustion reactor, it is necessary to trap the material blown out in a cyclone and return it to the system. The flue gas free from the largest part of entrained inert solids can then proceed to the heat exchange and flue gas treatment section. The technology is effective in generating lower volumes of flue gas, with low contaminant concentration. The reduced air flow and high uniform temperature generates lower NOx emissions: the quantity of NOx in a fluid bed is about half the oxides generated in a grate combustion, about 200 mg/Nm3 due to the lower operating temperature. Similarly, dioxins formation is lower but still high to require removal which is done by spraying activated carbon as adsorbent media, captured onto the tail end filter bags. The inert material can be easily mixed with some reactant, limestone or sodium bicarbonate for instance, to combine with acid gases like H2S, but since HCl is hard to capture, neutralising chemicals are generally added downstream in the flue gas treatment. Fluidised beds can reach 85% thermal efficiency (approximately 10% greater than grate systems) but the advantage is reduced by higher auto-consumption of power, mainly to move or recirculate the conspicuous inert material. Various provisions need to be tackled, the air distribution system must be uniform and depends on particles, air and nozzles, located on a plate stressed by high temperatures and great weight when the bed collapses or is no longer fluidised during outages (Pell, 2002: pp.72-75).

3.4

Rotary Kilns

The mass burning incineration is based on a rotating inclined cylinder in which the waste burns and moves downward as shown in Figure 8 (Statistica Svizzera, 2001: p. 36). The kiln is usually water wall cooled or refractory lined. The equipment was relatively simple and popular initially, similar to cement kilns; presently, its application is mainly for toxic and hospital waste. The systems have the peculiarity of being relatively small and compact, sturdy and maintenance free. They accept industrial or odd variable waste, coming in non homogeneous form and quantities but also with relatively high humidity. The residence time of material is generally high, in the order of hours, so cracking and gasification kinetics is not the controlling step for the design. When a high residence time and temperature is required for the exiting flue gas, an afterburner is found prior to the recovery boiler. Contrary to grates which are designed for a given feed homogeneity, the mechanical equipment can accept irregular loads: barrels of liquid waste can also be fed directly and this can favour the treatment of toxic materials, difficult or hazardous to handle. Toxic waste is also peculiar for discontinuous operation and while idle time is not convenient for grate and fluidised bed incinerators the discontinuities do not affect the rotary equipment operation.

34

Charter 3

Figure 8: Conceptual rendering of a rotary kiln (Courtesy from UFAFP)

Traditional Incineration

35

3.5

References

Aerstin F. and G. Street, 1980. Applied Chemical Process Design. 2nd ed., (New York: Plenum Press). Black & Veatch, Drbal L. et al., 2001. Power Plant Engineering. 5th ed., (Norwell, Massa: Kluwer Academic Publishers). DPR, 1982. Decreto Presidente della Repubblica Nr. 915/1982, Art. 1, (Roma: Gazzetta Ufficiale). Froment G. and K. Bischoff, 1979. Chemical Reactor Analysis & Design. (New York: John Wiley & Sons). Goerner K., 2003, July. Waste Incineration European State of the Art and new Developments. IFRF Combustion Journal, Nr. 2003-03. IRER, 2000, February. Leliminazione dei rifiuti mediante termodistruzione: effetti globali sullambiente. Final Report, (Milano: IRER). Lemann M., 1992. Abfalltechnik. (Dbendorf, CH: Dorema Texteam Verlag). McCabe W.and J. Smith, 1976. Unit Operations of Chemical Engineering. 3rd ed., (New York: McGraw-Hill). Pell M., 2002, August. Understanding the Design of Fluid-Bed Distributors., Chemical Engineering, No. 8. Smith D., 1985, October. Advances in Fluidised Bed Combustion and Cogeneration. Power Engineering, No. 10. Statistica Svizzera, 2001. Lambiente in Svizzera. Statistiche e Analisi. (Neuchtel: UFAFP, Ufficio Federale Statistica). Zenz F. A., 1977, December. How Flow Phenomena Affect Design of a Fluidized Beds. Chemical Engineering, No. 12.

..

ALTERNATIVE THERMAL PROCESSES

There is a number of alternative processes, some are novel or still referenced by very few commercial applications, others are conceptually clear but with no significant or repetitive reference at all. In the treatment of waste, which exhibits variable physical and chemical properties, it may also happen that due to relative simplicity, plants are sometimes manned by unskilled operating personnel. With this regard, the safe application of novel technologies is often seen as a hindrance to regular and efficient operation. End users, municipalities, local purpose companies and the banks that are present for project financed installations demand continuous trouble-free operation, normally between 7500 and 8000 hours per year, a risk hard to choose from when considering unproven processes. One feature common to alternative technologies is that pyrolysis, gasification, and thermal oxidation happen in distinct process equipment whereas they all take place in one reaction equipment, the furnace, for incineration. While mass burn incineration finds a most general and proven application, each alternative system attempts to improve the overall efficiency or reusability of products with valid arguments that ought to be taken in consideration for specific and selective applications. Among known cases, few technologies are summarised below as they exhibit points of innovation that will be later resumed or comparatively analysed in discussing the merit of the plasma process.

4.1

Gasification

Within a variety of high and low temperature possibilities, or system configurations, gasification of waste with air, but also with oxygen enriched air or pure oxygen, have been proposed for processes that are all designed to work under partial oxidation of the organic material. The majority of carbon is converted to syngas and water contributes to enrich the H2/CO ratio (Probstein and Hicks, 1982: pp.144-189). Residual solids are discharged as metal and ashes, one problem being that low melting point ashes may evaporate at the high operating temperatures of the gasifier and then escape to downstream treatments or clog in discharge chutes. Heavy metals are encapsulated in the glassy slag, with little or no risk of leaching out of the conglomerate. Another advantageous feature is the lower flue gas discharged from the plants. Starving air conditions reduce in fact the nitrogen dilution of the gases, resulting in lower volumes to treat, or higher heating value of the same, when they are meant to burn in downstream equipment like engines or gas turbines.

4.2

Pyrolysis

Pyrolysis is the chemical decomposition process induced by heat. The process is not new, town gas was formerly made by retorting of coal, a thermal degradation of organic material in the absence of oxygen (Shreve and Brink, 1977: pp. 65-70). Airless pyrolysis, or its arrangement in defect of O2, aims to crack decomposable materials at moderately low temperature and utilise the synthetic gases exiting the retort either for

38

Chapter 4

chemical uses or to burn them to recover heat and electricity produced in a combustion engine. Globally, it is an endothermic process where the organic material is distilled. Organic macromolecules like rubber, plastic, amid, cellulose etc. become thermally unstable and crack into smaller molecular constituents, gases and elementary carbon to yield: a solid residue, with a high carbon content of organic origin, char, plus metals, glass and inert contained in the waste. The char can be separated and used as fuel, while metals and glass can be recovered. a gas, incondensable phase, mainly made of hydrogen, low CHx, CO and CO2, that is generally burned within the process to integrate the energy requirement a separable condensable residue that can be described in three portions. A portion made with lower molecular weight organic fractions like aliphatic and aromatic hydrocarbons, alcohols, acids and ketones. A heavier portion made of naphtenes, oils, and tars that are difficult to use and a third watery portion of small and polar organic substances dissolved or emulsified in the water humidity freed by the pyrolysis.

Major variables are temperature and permanence time. The conventional pyrolysis operates within 300 and 500 C with slow heating rates of a few degrees per minute, ambient pressure and residence time in the order of hours. The long residence time is forgiving in terms of heterogeneous and variable capacity feed, the modest thermal gradient enables low cost and less troublesome technological solutions. Flash pyrolysis operates at temperatures around 1000 C, with high temperature gradients in the range of 200 C/sec and residence times of few seconds. This second process aims at the quasi-full gasification of the products at the expense of residual solids, generates more CO and H2: at first, this appears ideal for the treatment of waste. Its difficulty is however that the material needs to have greater homogeneity and finer particle sizes for handling and to enable the greater heat fluxes. Residence time of one hour is usually sufficient to carbonisation of the waste, i.e. the production of inert residues free from organic compounds with the objective to mineralise the waste, reduce its solid volume and recover materials that are thermally sterilised. The pyrolysis rate mainly depends upon the thermal diffusivity or the heated material property to increase its temperature. At equilibrium, gases reach a steady flow proportional to the quality and quantity of cracked material. The heat transport inside the material is favoured by mechanical mixing. The main pyrolytic steps are such that up to 150 C drying and water desorption occur, then, up to 250 C cracking begins, -COOH, CO, CO2 are released and cellulose is destroyed. Raising the temperature to 400 C organic substances undergo further cracking and coking, CH4 and C2 to C6 hydrocarbons are generated, HCl, HCN, H2S are released and NH-bonds are broken. At higher temperatures, up to above 600 C the full thermal cracking of aromatics can happen and some carbonates also decompose (Lemann, 1992: p. 74). Ultimately, the low cracking temperature does not enhance formation of cyclic compounds and aromatisation. Since flames are not generated here, there is no limit of reaching dangerous adiabatic temperatures and very high heating value waste can be accepted in the pyrolysis process. Upstream differentiated collection appears of marginal usefulness

Alternative Thermal Processes

39

since the pyrolysis accepts all types of waste and converts all organic material: plastic, fluff, compost suitable material, tires, hospital waste, paper and wood, varnish and paints, etc. About 60 to 80% of the acidic gaseous pollutants are formed during the pyrolysis, like HCl, HF, H2S. Quicklime may be added to the waste feed so to neutralise the flue gas from pyrolysis in situ, neutral salts can thus be discharged with the solid residues and the exiting flue gas will only need a reduced cleaning treatment downstream. Contrary to incinerators that burn solids and have their operation complicated by the need to have turbulence and high temperature, pyrolysis only generates gases which have a smoother operation if burned downstream. Forced convection thermal exchange is not used here, so particulate and fines are not carried in the gas phase. The pyrolysis gas is sent to hot cyclones that remove about 70% of the dust. The dust can be mixed with the pyrolysis coke, either recycled back or sent to some thermal disposal. Gases released by pyrolysis are less prone to dioxin formation than it can possibly occur while cooling gases cracked by direct combustion. Dioxins actually form, de novo, through carbon catalysis, enhanced by metals like Cu, between 200 and 500 C. The reaction time is fairly long while precursors like chlorophenols and chloro-benzene generate radicals that rapidly react within seconds in oxidising atmosphere and form dioxins in the temperature range of 200 to 650 C (Tuppurainen, et al., 2003: pp. 653654). The pyrolysis releases a quantity of tars and oils, these latter being a complex mix of condensable hydrocarbons (aliphatic HC, aromatics, alcohols, aldehydes, ketones, tars, oils, naphthenes) and char which are difficult to fractionate: local burning is however difficult and requires great handling caution to prevent clogging, odours and pollution. Due to the mild operating conditions, most inorganic material is not affected by the thermal cracking, solids and inert materials are found in the bottom char where porous charcoal, metals and inorganic salts are mixed. The char is quenched and sent to classification via magnetic field, a Foucault drum separator is used to separate nonferrous metals, gravimetric separation of carbon from glass and minerals is then made in water. Grinding is not necessary because no melting, no slag and no big blocks are generally formed. The pyrolysis of waste needs to assure mechanical continuity and the movement of the residual material, it is therefore most commonly made in rotating, sloped equipment. Kilns operate under a slight under-pressure. When the pyrolysis is made in a fluidised bed, the temperature control is very fine and uniformity is achieved by introducing inert materials like sand for quick heat transfer and flashing of pyrolysed substances. A concluding remark about pyrolysis is that the heating value of the waste that is not used up in compensating the endothermic reactions is ultimately found in the solids and in the syngas as chemical energy, usable or transportable for another use.

40

Chapter 4

4.3

Thermoselect Process

The process is a combination of pyrolysis and high temperature gasification. The waste is first compacted to high density, say 2 kg/cm3 by means of high compression in excess of 140 atm, so that the waste overall thermal conductivity is raised, the waste is freed from entrapped air and its initial volume is reduced to about 1/10th. The waste is then slowly pushed through a degassing tunnel, externally and coaxially heated indirectly by the hot gases obtained by burning a portion of the syngas developed within the same process. Heating up to about 600C for about 2 hours in defect of air releases humidity, gases and achieves the pyrolysis of organic constituents. This reduced mass is then gasified at over 2000 C in a reducing atmosphere by injecting CH4 or C3H8 and pure O2. Oxygen instead of air is used to reduce volumes, to reach high temperatures with the torches and to reduce NOx. The full destruction of organics at extreme temperatures is a sign of safety even when treating toxic substances. Carbon black, soot and fly ash are also minimised due to the higher temperature and smaller airflow compared to other combustors. The high temperature in the reactor enables both dry and steam reforming, conversion of CO2 and H2O with a carbon source to H2 and CO. Carbon is actually present in the compact mass fed to the reactor and the gases are stabilised at the mid height of the refractory lined reactor. Melted vitrified solids are water quenched and granulated from the bottom of the reactor, while the syngas (CO + H2) is cleaned from particulate and acidic contaminants like HCl prior to utilisation in a combustion engine or gas turbine to generate power. The first step in treating the gases exiting the reactor is a water quenching, down to about 90 C, as it is shown in Figure 1, taken from the the Swiss Report on Environment (Statistica Svizzera, 2001: p. 43). The rapid temperature decrease is conceptually conducive to prevent dioxins reformation. Gases are further scrubbed and treated with straightforward methods. Figure 1: Scheme for ThermoselectTM

Alternative Thermal Processes

41

4.4

Compact Power

In this process a pyrolysis is first made for the organic material, followed by a gasification and an ultimate oxidation at 1250C. A steam boiler recovers the waste heat from the gas engine exhaust, while the syngas is used as engine fuel (Compact Power, 2004, via internet). A preliminary evaluation shows that starting from a basis of 100 kg/h of waste, about 650 kg/h of air are introduced to obtain about 750 kg/h of flue gas. The syngas from pyrolysis is about 70 kg/h and the syngas from gasification is about 90 kg/h. The combined efficiency is claimed to be higher and easier to control, char is also expected to be less than it can be obtained in a simpler pyrolysis. The continuous combined process attempts to exploit the best from every piece of technology in a thoroughly integrated manner. The complexity of the system can also be viewed as a tolerance to feedstock variations and better controllability of each process stage.

4.5

CMR Continuous Melting Reactor

The process is proposed by the Italian firm Sogeni and is an example of incineration furnace able to accept various types of waste, metals included: it is derived from casting operations and enables to slag out high temperature inorganics, unleachable in their ultimate vitrified state, thus suitable to reuse or to safe disposal. Molten metals are periodically tapped out from the bottom ports and their relative separability enables differential recovery of constituents. In the case of scrap steel heavy loading, the furnace produces high grade cast iron, since iron oxides are reduced and low contents of Si, S, P remain in the sluiced product. A carbon source is fed either through the waste content itself or by pulverised coal addition. The furnace is very similar to blast ovens used in steel manufacturing, it is continuously loaded from the top and the high temperature is maintained by oxygen torches firing the organic material above the molten bottom bath. The bath has a great heat capacity that maintains the temperature uniform throughout the furnace geometry. The operation above 1600 C and the low oxygen reducing atmosphere promote the coking of the organic material that works as a reducing agent and with humidity generates syngas. The gas leaving the furnace at about 1200 C can either burn or be sent to outside engine burners after cleaning. The whole equipment is versatile and fairly simple, proven in steel manufacturing plant built according to the original invention of the Russian professor Romenets back in the 80s. An advantage of the equipment is that it has no moving parts, metals and slag stratify and overflow out of the system from different level siphons, as exhibited by the sketch of Figure 2. The thermochemistry is no different from other incinerators, although care is taken to introduce the reducing agent (carbon) rapidly, so that metal oxidation does not occur. The quantity of air is less than the amount required in traditional incinerators and the combination with the high temperature generates lesser NOx and destroys dioxins that may have eventually formed. Fly ash is entrapped and reprocessed in the

42

Chapter 4

high temperature metal bath, its removal with the slag is a substantial reduction in voluminous solid treatment and disposal. Figure 2: Conceptual scheme for Romelt furnace

4.6

RCP Recycled Clean Products

The process combines two thermal processes, a pyrolysis chamber above a water-cooled grate and gasification at high temperature in a secondary combustion chamber. The difficulty to feed heterogeneous waste to the gasifier is overcome by putting an upfront pyrolysis without pre-treatment, and the gasifier works on gases and not on a solid feed (VonRoll, 2004: via internet). The pyrolysis coke is oxidised in a smelting furnace so that the combustible material is fully depleted while inert components melt at temperatures exceeding 1400 C. Heavy metals (copper, iron alloys) are extracted from the molten liquid while volatile metals (zinc, cadmium, lead) transfer to the gas phase. The hot gases from the smelting bath pass through the fluidised bed second combustion chamber and are then mixed with sand which serves as a heat carrier for the steam generator (Pell, 2002: pp.72-75). The sand has also the purpose of homogenising the temperature and to prevent damaging hot spots (Froment and Bischoff, 1979: pp.662669). A similar process was developed by Noell and several companies are currently combining different features of gasification or traditional incineration to exploit and add separate advantages of each technology.

Alternative Thermal Processes

43

4.7

References

Compact Power Ltd., Avonmouth, 2004. Literature and internet commercial information at www.compactpower.co.uk. Froment G. and K. Bischoff, 1979. Chemical Reactor Analysis & Design. (New York: John Wiley & Sons). Lemann M., 1992. Abfalltechnik. (Dbendorf, CH: Dorema Texteam Verlag). Pell M., 2002, August. Understanding the Design of Fluid-Bed Distributors., Chemical Engineering, No. 8. Probstein R. and R.E. Hicks, 1982. Synthetic Fuels. (New York, NY: McGraw-Hill). Shreve R. and J. Brink, 1977. Chemical Process Industries. IV Ed., (New York, NY: McGraw-Hill). Statistica Svizzera, 2001. Lambiente in Svizzera. Statistiche e Analisi. (Neuchtel: UFAFP, Ufficio Federale Statistica). Tuppurainen K., et al., 2003. Perspectives on the Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans during Municipal Solid Waste (MSW) Incineration and other Combustion Processes. Accounts of Chemical Research, Vol. 36, No. 9. Von Roll Environmental, Zrich, 2004. RCP data available through their corporate web site: www.vonroll.ch.

..

DIOXINS, FURANS AND RELATED COMPOUNDS

Among various compounds and isomers, the following are the most often referenced because of their toxicity (TCDD is identified as the known most powerful chloracne producing compound since the 70s) and literature reports:

2,3,7,8-Tetrachlorodibenzo-p-dioxin (C12H4Cl4O2 = MW: 322)

Cl O Cl

Cl

Cl

2,3,7,8-Tetrachlorodibenzofuran (C12H4Cl4O = MW: 306)

Cl Cl

Cl

Cl

As many as 212 compounds can be identified in considering possible dioxins and furans formation. Equilibrium thermodynamics data base calculated with the group additivity approach and with computational molecular modelling methods minimise free energy to form dioxins within the 550 and 750 K window, stable at PO2 lower than 10-30 bar. While calculations appear to attribute higher stability to furans, practical observations do not seem to sustain such conclusion (Pengfu et al., 2001: pp.1870-1873). According to the same authors, the assumption that dioxins and furans do not noticeably interact with each other appears to be close to reality and their partial pressures in their stable existence temperature range are around 10-10 bar. To appreciate this result, we made the hypothesis of gas phase ideality and derived D/F partial pressure with the admissible D/F flue gas concentration. We calculated the D/F partial pressure at the imposed emission level of 0.1 ng/Nm3 and found an order of magnitude of 10-18 bar, a prescribed value well below the values that appear necessary to fall within the attainable stability range.

5.1

D/F Formation Mechanisms

Dioxins that are completely destroyed in the combustion chamber, form between 250 and 650 C or according to more recent evaluations between 250 and 400 C via three possible pathways, listed in ascending importance: - pyrosynthesis, i.e. high temperature formation in the gas phase - de novo i.e. formation from macromolecular carbon and chlorine - from various precursors.

46

Chapter 5

The D/F formation should be addressed simultaneously and not as if it may occur through a single independent pathway. D/F precursors formation is 102 to 105 faster than de novo synthesis, indicating that this route may dominate in the real incineration: radical/molecule reactions are actually an insignificant pathway in incinerators, compared with the condensation of two Clphenoxyl radicals. Thermodynamically stabilised dioxins do not find experimental evidence and this evidences that the PCDF isomers distribution is kinetically controlled other than thermodynamically controlled (Tuppurainen, et al., 2003: pp. 653-654). According to their model and pilot plant analysis, the authors found over 60 most probable paths to form D/F from phenol via oxy-chlorination whereas only marginal quantities appear to form during combustion (Tuppurainen, op. cit. p. 656). Kinetics is enhanced when precursors come into contact with fly ash which is also a way to justify D/F formation when residual carbon is negligible and de novo synthesis is thus irrelevant. The mechanisms are uncertain as to the ability to predict D/F formation, although they have been studied since the 70s: D/F already present in traces in the fuel cannot justify and account for the level in emissions, particularly when synthetic feed is made, with no starting D/F. Furthermore, the products decompose above 900C, they would be destroyed at the flame temperatures (Shaub and Tsang, 1983: p. 721). Gas-gas homogeneous reactions also play a minor role because the complexity of D/F formation must follow a multi-step formation kinetic, much greater than high temperature destruction kinetics. Various measurements of D/F right after the combustion chamber are demonstrated lower than concentrations measured downstream: formation by aggregation, condensation of D/F precursors must occur at lower temperatures, i. e. in the gas treatment sections. A recent study (Evans and Dellinger, 2003: pp. 1325-1330) analysed the kinetics of D/F formation and concluded that gasphase reactions of chlorinated phenols are fast enough to compete with surface-catalysed reactions. Experiments were conducted with a reaction time of 2 seconds over a temperature range of 300 to 1000C and differ from other reports related to longer reaction times between 10 and 100 seconds and temperatures below 700 C. The difference may indicate and support that extended pyrolysis generates less D/F, or at least that the gas phase formation mechanism is not so relevant for the pyrolytic process. Gas-solid heterogeneous condensation reactions between gas phase chloroaromatic precursors (existing or formed by incomplete combustion) and catalytic particles like particulate, metallic or divalent copper, appear to be significant. The temperature range can be within 200 and 400C (Kilgroe and Nelson et al., 1990: pp. 223-244). Fast reactions involving Cl-aromatics condensations may be expected to dominate in the boiler where temperatures range between 200 and 600 C and the residence time is in the range of seconds, feasible in less than 5 seconds for some authors (Gullett and Lemieux, 1994: pp. 107-118). The aromatic ring is chlorinated by molecular chlorine substitution, one may observe that molecular chlorine is not present, we rather have HCl, but the acid reacts with O2 in presence of metallic surfaces to generate Cl2. Once the aromatic ring has been chlorinated, the metal catalyst supports condensation reactions enhancing the kinetic by three orders of magnitude and D/F can form. Sulphur decreases D/F emissions. SO2 can oxidise with water to SO3 and reduce the Cl2 to HCl, impoverishing thus the molecular chlorine available for the ring chlorination. SO2 may also poison the catalytic particles or eliminate copper as CuSO4 to produce the same effect. Presently, we have no operating evidence of kinetic models capable to predict accurately the formation of D/F that may occur even for good combustion and any

Dioxins, Furans and Related Compounds

47

combination of Cl, C, H2, O2 (Altwicker, Ravi et al., 1990: pp. 1935-1944). In order to derive a reasonable fit with values of D/F measured in commercial plants, the same authors utilise a four steps D/F formation model and assume arbitrary factor modifications of the Arrhenius pre-exponential rates, previously published by Shaub and Tsang (op. cit. 1983: pp. 721-730). In all cases of industrial combustion, the measurement of low CO levels is taken to indicate that combustion is complete. Poor combustion can moreover increase the quantity of particulates, as well as soot, and generate organic precursors (Santoleri, 1995). Gas-solid heterogeneous reactions can also generate brand new D/F from inorganic chlorine and non-ring carbon compounds in dry pollution control equipment where the particulate residence time varies from seconds to dozens of minutes and activated carbon is observed as an effective catalyst (Dickson et al., 1992: pp. 18221827). Improvements may derive from rapid wet quenching (milliseconds) of the flue gas, in a venturi scrubber, to preclude D/F formation reactions (Doolittle et al., 2002: pp. 50-57). If a partially wet quencher is used, water saturation is not reached and temperatures are maintained above the dew point. D/F may form de novo in the equipment where the 200-400C temperature window exists, for instance in ductwork, ESP, cyclones, filters, and care should be exerted to keep the residence time very low in those potential forming spots. This is not clearly possible in equipment like filters. The reheater is also a case of potential formation: although the gas temperature is relatively low, say 130C, the metallic surface and some minor particulate hold-up may catalyse D/F formation.

5.2

Dioxins Control

The D/F control technologies are targeted to limit the conditions that form D/F. Failing prevention, activated carbon injection, carbon beds, catalytic oxidisers and inhibitors are used. The use of activated carbon, in fact, generates D/F in situ and reduces or removes the risk of downstream formation/leakage; D/F concentrations are therefore greater by far in the filtering beds due to the fact that D/F are artificially made and built up there, so great care needs to be taken in handling the carbon and the particles captured downstream onto the fabric filters. Inhibitors tend to eliminate one or more reacting effects. We discussed about SO2 presence to inhibit Cl2 by reducing it to HCl. Injection of Na2CO3 at the fuel feed side enhances the reaction with Cl2 and avoids to add excess sulphur that ultimately needs to be removed. Given the probability, the mechanism of formation and the modest prediction capability of current models, it is hard to exclude that one combustion process like incineration will not generate D/F. It is therefore useful to implement treatments that minimise the risk of emitting such toxic substances to the atmosphere. Leveraging upon the discussions above, it appears evident that D/F may form when the gases are treated or exchange heat in cooler equipment: metals as well as carbon particles are proven catalysts for D/F formation. One safe way to treat the gases is thus to enhance whatever possible formation of D/F in a controlled environment, to prevent the possibility that such potential formation occurs downstream. Activated carbon is an effective catalytic media to capture and form D/F prior to the bag-house filtration of particulates. D/F form and adsorb onto the carbon, they are then captured and disposed with the media itself. Means of ultimate disposal include combustion by recycling the media to the furnace or send the materials to authorised landfill.

48

Chapter 5

Studies on the adsorption of D/F on carbon demonstrate commercial plants removals to concentrations well below the prescribed European emission limits of 0.1 ng/Nm3 of flue gas. The methods include fixed bed activated carbon units and injection of small amount of adsorbent into the flowing gas, separated downstream before discharging the purified gas. The former method exhibits higher pressure drops but better efficiency, mainly to the distributed use and operability of the bed and longer contact time while the gas permeates through different bed layers. In both cases, the dioxin partitions between the gas and the solid phase as a function of temperature and partial pressure. Higher chlorine D/F have lower vapour pressure as compared to lower chlorine dioxins and exhibit greater tendency to condense onto the carbon. The adsorption kinetics fits well with the prediction based on Henrys law and relative pressure (partial pressure over the vapour pressure) in the range of 10-9 to 10-7. The trend is a corollary to saying that higher chlorine D/F heavier molecules are more efficiently adsorbed. Since dioxins are tightly adsorbed by activated carbon, other flue gas constituents such as HCl, volatile organics, and incomplete combustion products show no clear effect on the dioxins removal (Karademir et al., 2004: pp. 1201-1207). According to the same authors of the study, high humidity can negatively affect the adsorption on carbon by filling up the pores with condensed water.

5.3

Dioxins Analysis

The concentrations of D/F limits tolerated in emissions are so low that the reproducibility and accuracy of the analytical methods being adopted may sometimes become an issue. Detection limits have to be orders of magnitude below limits of pesticide residue analysis, i.e. below the level of 1 ppt (1 part in 1012 parts). Mass fragmentography is the exclusive use of the spectrometer for the mass specific recording of preselected ions. A mass fragmentogram is obtained by focussing on the masses where the ion abundance is expected and it achieves 10-12 grams sensitivities as opposed to a 10-7 gram sensitivity of mass chromatography. For D/F search the mass spectrometer is adjusted to monitor indicative ions where the highest sensitivity and selectivity is observed, like m/e values of 320, 322 and 324 peaks (Cattabeni et al., 1978: pp. 34-35). Any analysis is planned with the care to avoid co-eluting components and it is also complicated by the presence of interfering compounds. Furthermore, the mass spectrographic methods practically decompose the D/F to be measured and determine the initial D/F quantity from the measurement of fractioned particles like CO and Cl against a referenced, standardised graph of the method. This can eventually generate the suspicion that the fundamental constituents being measured do not come from D/F source but from other less lethal substances of the gas stream. For this reason, it is very important that the analysis be carried out by very experienced personnel and performed on accurately calibrated equipment.

Dioxins, Furans and Related Compounds

49

5.4

References

Altwicker, E., K. Ravi et al., 1990. The role of Precursors in Formation of Polychlorodibenzo-p.dioxins and Polychloro-dibenzofurans during Heterogeneous Combustion. Chemosphere, Vol. 20, No. 10-12. Cattabeni F., A. Cavallaro and G. Galli, 1978. Dioxin Toxicological and Chemical Aspects. (New York: Halsted Press Division of John Wiley & Sons). Dickson, L., D. Lenoir, and O. Hutzinger,1992. Quantitative Comparison of de novo and Precursor Formation of Polychlorinated Dibenzo-p-dioxins under Simulated Municipal Solid Waste Incinerator Postcombustion Conditions. Environmental Science and Technology, Vol. 26. Doolittle C., J. Woodhull and M.Venketesh, 2002, December. Managing Emissions during Hazardous Waste Combustion. Chemical Engineering, No. 12. Evans C. and B. Dellinger, 2003. Mechanisms of Dioxin Formation from the HighTemperature Pyrolysis of 2-Chlorophenol. Environmental Science and Technology, Vol. 37, No. 7. Gullett, B. and P. Lemieux, 1994. Role of Combustion and Sorbent Parameters in Prevention of Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofuran Formation during Waste Combustion. Environmental Science and Technology, Vol. 28. Karademir A. et al., 2004. Removal of PCDD/Fs from Flue Gas by a Fixed-Bed Activated Carbon Filter in a Hazardous Waste Incinerator. Environmental Science and Technology, Vol. 38, No. 4. Kilgroe, J., P. Nelson et al., 1990. Combustion Control of Organic Emissions from Municipal Waste Combustors. Combustion, Science and Technology, No.74. Pengfu T., I. Hurtado and D. Neuschtz, 2001. Thermodynamic Modeling of PCDD/Fs Formation in Thermal Processes. Environmental Science and Technology, Vol. 35, No. 9. Santoleri, J., 1995, May. Dioxin Emissions - Effect of Chlorine/Time/Temperature Relationship at 300 C. International Conference on Incineration and Thermal Treatment Technologies, (Bellevue, Washington: 2005 Conference Proceedings). Shaub, W.M. and W. Tsang, 1983. Dioxin Formation in Incinerators. Environmental Science and Technology, Vol. 17, No. 12. Tuppurainen K., et al., 2003. Perspectives on the Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans during Municipal Solid Waste (MSW) Incineration and other Combustion Processes. Accounts of Chemical Research, Vol. 36, No. 9.

..

LOW PRESSURE CO2 PARTIAL ABSORPTION FROM FLUE GAS

The capture and absorption of carbon dioxide from flue gases still attracts limited attention as do methods that separate CO2 and dispose it underground or under the sea. The recovery of CO2 has long been studied, indeed, by chemical firms who had a captive industrial use or reuse of the gas, but utilisation and interest has been orders of magnitude less consistent than the huge quantities regularly dumped freely to the atmosphere, under the general acceptance that CO2 was harmless prior to the modern acknowledgement that the gas bears greenhouse effects. Carbon dioxide used in the industry is also relatively cheap and of little concern for significant recovery. In simplified terms, we can say that CO2 is selectively captured and purified for specific chemical processing, or it is extracted and concentrated as a corollary effect of other gas operations, or it is just discharged. Operating conditions and plant complexity are clearly dependent on the chosen option and a fourth option of delivering the gas in some safe storage or natural depletion for environmental/ecological reasons is somehow derived or not yet detailed in economically feasible terms from existing methods. It does not therefore surprise that a flue gas compression under the sea is economically unacceptable or that the complete selective absorption of CO2 is discouraging. This scenario will however change in view of the most probable application of a carbon tax or the possibility to attract financial benefits from reducing CO2 emissions. The compelling drives for the partial if not total offset of the carbon tax will make acceptable even treatments that defect from reaching a premium removal efficiency. The treatment of flue gases traditionally deals with gas de-dusting and scrubbing of acidic constituents, while production plants, like for instance the Claus tail gas treatment of residual H2S, adopt selective and well studied solvent regenerated processes. The optimisation of amine absorption plants is mostly made at pressures exceeding 20 bar and the choice of the amine type and water concentration depends on the selectivity, efficiency, corrosion inhibition and various operating variables. CO2 is also absorbed but as a side effect, the plants are optimised to abate H2S selectively. In the case of carbon dioxide recovery from flue gas, the crucial variable is the possibility to operate at low pressure to avoid costly compression costs of the enormous flow rates of inert gas in which the CO2 is dispersed (mainly nitrogen) while good absorption percentages or selectivity are not necessarily as critical. Our study started from the direct scope to recover CO2 from flue gas and feed the concentrated gas to a downstream plasma dry reforming. The general aim was thus to keep the plant configuration as simple as possible and to verify the feasibility of the process. Based on the choices discussed below, a CO2 capture of about 63% is achievable with a modest loss of amine. The investment and operating costs estimated for the plant are lower than the equivalent loss in green certificate benefit for emitting that same CO2. A cryogenic alternative of separating water ice and then solid carbon dioxide (CO2 sublimates at low pressure) was also considered. Technological difficulties in exchanging heat between gas and solids appear to hinder the feasibility and the investment costs. Operation wise, the running costs of the low pressure cryogenic method are far greater than costs for an amine system.

52

Chapter 6

6.1

General Considerations and Selection of Amine

A variety of commercial methods is available for carbon dioxide absorption from gases and flue gases. Historically, the methods have been proven and optimised for working at moderate to high pressures. Membranes separate over 25 bar, hot potassium carbonate work at 7 bar or higher, various MEA, DEA, MDEA, DIPA, regenerable alkanolamine processes are encountered to work between 20 and 40 bar. Selectivity is very important for gas purification and recovery, like H2S for instance, and hindered amines are also used. CO2 absorption is controlled by mass transfer and is slow because, before reacting with the amine, CO2 must first react with water to form carbonic acid. Depending on the amine, the carbamate that may form is stable and takes 2 moles of amine for 1 mole CO2, RNHCOONH3R, but tertiary amines are unable to form carbamates and are generally easier to regenerate. MEA has the tendency to react with CO2 in the vapour phase to form carbamic salts. When the amine forms the carbamate, this can hydrolyse and form bicarbonate. For selective H2S absorption the amine structure would be chosen to impede carbamate formation and consequently CO2 absorption. Without thinking of using sterically hindered amines such as AMP or MDA, MDEA is a tertiary amine that ultimately achieves higher CO2 absorption (Kohl and Riesenfeld, 1985: p. 35). The graph of Figure 1 was made for an immediate correlation between molar and weight percentages of amine. Figure 1: Amine mole to weight concentrations MEA is very alkaline and highly reactive, it presents 70 greater corrosivity problems 60 particularly at concentrations in water exceeding 20 50 MEA wt-% and when the solution 40 MDEA is heavily loaded with 30 acidic gas. Mole weight: Several corrosion inhibitors 20 MEA = 61 MDEA = 119 are available. For instance, 10 Fluor describes how their 0 Econamine technology, that 0 5 10 15 20 25 mole-% is based on inhibited 30 wt-% MEA, can absorb CO2 satisfactorily near atmospheric pressure, utilising a carbon steel equipment process scheme, highly tolerant to O2 and SOx present in the flue gas (Chapel and Mariz, 1999). The cost of MEA is about half the cost of MDEA. Operation wise, the quantity of amine and H2O relate to the absorbed gas, primary amine capacity for CO2 is about 0.5 molar CO2/amine even at high PCO2. Our case of 1,000 kmol/h MDEA and 373 kmol/h CO2 feed, gives a ratio of 0.37 with an end result of 245 moles of CO2 in rich MDEA i.e. a mole ratio of 0.24. Typically, the molar
Molar to weight concentration in H2O
wt-%

Low Pressure CO2 Partial Absorption from Flue Gas

53

ratio of acid gas to MEA in the lean amine recycle is lower, CO2/MEA = 0.15 when moderate stripping is used (Kohl and Riesenfeld, 1985: pp. 33, 74). Although vapour pressures of alkanolamines are relatively low (MEA = 0.36 mmHg, MDEA = 0.01 mmHg as compared to 17.53 mmHg for water at 20C), vaporisation losses occur. Lowering the absorber top temperature around or below 80F = 27C to condense the amine is satisfactory unless stronger downstream captures are conceived with packed towers water wash or bauxite filter adsorption, methods that become expensive due to the high volume rates of the flue gas. According to the findings of Savage and associates, MDEA apparently acts as a base catalyst for hydration of CO2 so the operation in water abundance appears consistent and encouraging for flue gas absorption at atmospheric pressure (Savage et al., 1981: p. 3). MDEA shows selectivity and can be used, because of its low vapour pressure, in aqueous solution concentrations up to 60 wt-% without appreciable evaporation loss. The possibility of using a higher concentration without incurring in corrosion problems allows to decrease the required solution recirculation rate and therefore the cost of the plant. MDEA is highly resistant to thermal and chemical degradation, essentially non-corrosive, it has low specific heat and heat of reaction with CO2 of 475 btu/#-gas or 264 kcal/kg-gas, opposite to MEA having heat of reaction with CO2 of 825 btu/#-gas or 459 kcal/kg-gas (Kohl and Riesenfeld, 1985: pp. 42, 79). In reality, the heat of reactions should be down-rated and cannot be applied as such to the moles of CO2 absorbed because the reaction of carbon dioxide to carbamic acid is slow and a portion of the gas will be simply absorbed in water, without appreciable heat of reaction. The chemical equilibria in a CO2/H2S/Amine system are described by reactions of Table 1: Table 1: CO2/Acqueous amine reactions 1. RR'NH + H2O 2. CO2 + H2O 3. RR'NH + HCO34. HCO35. H2O 6. H2S 7. HSOHHCO3RR'NCOOCO3-H+ HSS-+ + + + + + + RR'NH2+ H+ H2O H+ OHH+ H+ K1 K2 K3 K4 K5 K6 K7

where R and R' represent CH2OH or C2H4OH alcohol groups. In our case, equations 6 and 7 do not apply and water is in such quantity that subtracts from the equilibrium. We therefore have 2 molecular and 6 ionic species, 8 equations need to be solved simultaneously to obtain the free concentration of CO2 with the partial pressure of CO2 that can be calculated by the Henry's constants and free concentration in the liquid phase. With respect to cases without chemical reaction, the absorption rate will be greater due to enhanced absorption and the enthalpy variation will also be significant since the reaction will be exothermic (Biardi, 2002). Conversely, in desorption, the release of CO2 from the amine will not be easy and hindrance to strip it off can be expected (Pacheco and Rochelle, 1998). Rather than setting up a solver method with experimental

54

Chapter 6

data and Hattas enhancement factor, the feasibility of low pressure absorption can be tested by running a process simulator. Several commercial simulators can be compared and ultimately choose one to elaborate process conditions that may fit them all. In spite of the fact that combustion flue gases arrive already scrubbed, their ultimate SO2 content can be as high as 300 ppmv. Even a small quantity of SO2 will complicate matters because it will readily dissolve in water and amines, will bind and degrade the amine and will not freely exit from the process recirculation loop. The process BSR/MDEA by Parsons, has provisions for water condensation and separation upstream of the amine section with caustic recirculation to protect against SO2 break through that would degrade the MDEA and induce corrosion (Keller et al., 2002 and Rameshi, 2000).

6.2

Flue Gas Feed Basis

Flue gases to the chimney of a combustion furnace or a waste incinerator are already treated to comply with emission regulations and vary depending upon the fuel, the equipment, the operating and ambient conditions. For the simulation design basis the parameters can be fixed on the average gas composition from an incinerator treating 250 t/d of MSW and producing the following: Flue Gas weight rate 107,500. kg/h molar rate 3,700. kmol/h T 60. C P atmospheric 10. vol-% CO2 9.5 vol-% H2O 71.1 vol-% N2 O2 9.3 vol-% .03 vol-% SOx

6.3

Selection of the Process Simulator and Operating Conditions

The analysis of different process simulators had the purpose to find a suitable tool and provide reproducible results on different systems to achieve convergence and compare the loss of absorbent, operability at low pressure, for a minimum extraction of CO2, say greater than 40% (> 150 kmol/h). The first step was to consider only a hypothetical absorber and see the kind of absoption that could be achieved at moderate pressures but with heavy quantities of amine and water. Trials at 6 bar, reduced to 1 bar were made, which would have reduced compression costs when feeding a flue gas. While the amine absorbs 100% of the CO2 at 40 bars, at 1 bara the capture remains high only with amine to CO2 molar ratio over 5. Water to amine molar ratio was first attempted above 6. The next step was to check the sensitivity to water quantity and the possibility to reduce both amine and water streams to the absorber. Trials to find a reasonable number of absorber stages were then made: whether the column operated with excess water or excess amine, a limited number of stages, ultimately decided to vary between 6 and 16, worked satisfactorily. The addition of substantial quantities of water did not improve CO2 absorption but has a good

Low Pressure CO2 Partial Absorption from Flue Gas

55

effect in lowering the absorber top temperature and reduce amine losses. The reaction of CO2 absorption is slow and controlled by liquid diffusion, but the higher absorption temperature did not bring significant improvements. On the contrary, a higher top temperature bears higher loss of amine and it was decided to keep it below 50C. The heat of reaction, greater when using MEA, does not generate large temperature differences due to the use of large quantities of water. As a trial, a strong concentration of amine in water was used, over 50 mol-% but it proved effective to use a more diluted amine and excess water (< 10 mol-%). This holds true even by using an amine to CO2 molar ratio of 3, the absorption was practically unchanged. Among possible choices, we tried three process simulators: SimSci PRO/II 6.0, HYSYS v3.1 and ChemCAD v5.2, software of Simulation Sciences Inc., Hyprotech LtdAspen Technologies and Chemstations Inc., respectively. Each one has merits of use and brings to the same fundamental results. The difficulty may actually be in the selection of the appropriate thermodynamic methods and data bank for calculating phase properties and enthalpies. The trials on the three simulators evidenced different absorption in relation to the quantity of water and amine fed to the absorber. Dozens of combinatory trials were made to select promising operating conditions. Major runs at 1.1 bara pressure are collected in the summary table under Appendix 6.1 at the end of this Chapter. Such trials enabled to condense results in the bubble chart of Figure 2 that shows the degree of CO2 absorption that was calculated with the various methods. Figure 2: CO2 Absorption with different amine combinations
CO2 absorption for a 373 kmole/h feed
( bubble size = %)

1600 1400
Kmole/h Amine

5000 kmole/h H2O = 90000 kCal/h-C

35
P-41

76
C-47

1200 1000 800 600 56 400

H-54

500 kmole/h MDEA = 12000 kCal/h-C

73
H-46

MEA

100
C-60 P-60

MDEA

70
H-48

35 57
H-55 C-46

28 48
H-50

42
C-45

30
P-45

P-40

200 3500

4500

5500

6500

7500
Kmole/h H2O

8500

9500

10500

11500

In the chart, the bubble diameter relates to the absorbed percent of carbon dioxide, indicated also in large digits, while the letter inside each bubble is indicative of the simulator used (C=ChemCad, H=Hysys or P=ProII), followed by the absorber column top temperature in Celsius. The loss of absorbent was high with MEA, due to heat of reaction and to higher volatility, but with the introduction of the absorber head cooler and flash separator the losses are reduced. MEA was also lost at the stripper (about 0.6

56

Chapter 6

kmol/h) whereas MDEA did not. Higher volatility and boiling point MEA resulted in losses at the stripper section even when operated at 60C. MEA has also the disadvantage of reacting to make irreversible salt with SOx and it exhibits high corrosive metal attack for the hot equipment, exalted by the presence of oxygen (Kohl and Riesenfeld, 1985: pp. 119-122). The conclusion of the absorber trials was that MDEA was preferable to MEA and the feed rates to be used for the system simulation were chosen to be 1,000 and 10,500 kmol/h for MDEA and H2O respectively. The selection of using ChemCad version 5.2 to simulate the whole system has been a matter of convenience. ChemCad5.2 practically resumes the main features of the other simulators, it allows to feed MEA and MDEA simultaneously and includes also a modifiable electrolyte package that calculates reactions equilibria to give credit to enhanced absorption occurring with strong polar components. Theoretically, the thermodynamic properties could be set for ideal vapour behaviour, but fearing numerical inconsistencies, the Amine package for K volatility and for enthalpies was adopted. The crucial equipment of the simulations are the columns (absorber and regenerator) which were defined as SCDS rigorous simultaneous multi-stage distillation, models that allow to specify Murphree efficiency by tray for key components. The amount of water and MDEA were fed at rates compatible with those that other simulators would also handle.

6.4

Process Flow Diagram Discussion and Material Balance

The scheme is a straightforward amine absorption-regeneration scheme with the topology shown in Figure 3 which is reported below to simplify the description. More details are attached under Appendix 6.1. Attempts were made with a rich amine split feed to the stripper and also with a top pumparound where the regenerator top 6 trays section worked like a contact cooler/condenser. Marginal advantages were obtained in terms of CO2 release and the column would become higher, so the simpler scheme was chosen. Similarly, a device for capturing or preventing SO2 from entering the system is necessary. Trials even at 10 ppmv would suggest that a chemical capture and blowdown is needed for the system convergence. To bring the whole system to convergence, the columns were first simulated separately, with a nominal start-up feed, before cut streams connections were made. The calculation is in fact easily offset if accumulation of a constituent builds up. Water coming from flue gas humidity, for instance, is condensed from the separator that operates at the absorber feed temperature and the recycle excess is drained off. Ideally, a higher absorber top temperature could be preferred because the purged offgas would then go to a chimney, most likely after pre-heating. That would also save on the trim cooler of the lean amine return, but higher absorber temperature means higher water evaporation and higher amine losses.

Low Pressure CO2 Partial Absorption from Flue Gas

57

Figure 3: Amine absorption scheme

The absorber has a loss of amine as it can be seen from stream Nr. 3 of the material balance reported in Appendix 6.1. Adding to concerns of not losing valuable absorbent, the idea of cooling and flashing the gas appeared viable and economical for recycling most of the amine to the circuit. The stripper was tested at various bottom temperatures up to 115C, with the initial desire to strip more CO2 or SO2 off the lean amine leaving the regenerator. The increase of bottom temperature lead to pinch the rich amine feed exchanger because the fluid currents have practically the same flow rates due to a small reflux and offgas rate in the stripper column. A higher reboiler duty reflecting also into greater cooling (stripper condenser and trim cooler) brings no advantages since the freedom is limited by the great quantity of water that sets the bottom boiling range. Pressure was clearly not a variable because the whole scope was to operate at the lowest compression costs. No amine is lost with the CO2 enriched gas leaving the stripper. In conclusion, the simulation evidenced a variety of viable schemes that for the purpose of this work need not to superimpose to the attached results but might be considered for detailed design. The absorber number of stages was optimised at 10 and the stripper was tried for a number of stages up to 30 but with no practical improvement over the final selection that was made for 16.

6.5

Primary Equipment List and Estimates

Based on the preliminary conceptual study major equipment can be constructed in carbon steel or S.S. AISI 304 and their +/- 30% FOB costs are summarised as follows to total the 1.3E6 Euro shown in Table 2 below: The FOB costs must be increased by all other itemised equipment costs, piping, instrumentation and electrical equipment, reinforced concrete and steel structures, paint, insulation plus engineering, construction and erection, indirect costs and contingencies. The cost of an estimate itself increases fivefold as the accuracy is increased from 30 to 10% (Chauvel, 1981: p. 85).

58

Chapter 6

Table 2: List of primary equipment in the absorption scheme Nr.

See PFD

Description
FG compressor Absorber Regenerator FG cooler Offgas cooler Amine exchanger Amine trim cooler Water separator Offgas flash separator MDEA Inventory

Data
0.3 barg, 860 kW D= 3.5 m, H= 8 m P=1.2 barg D= 1.2 m, H= 12 m P=1.2 barg

Wt
t

Duty
kcal/h 10E6

Area
m2

Estim
Eu 10E3

1 11 2 3 7 9 12 4 6 --

14 8 - 0.529 + 14.430 - 2.938 - 0.576 + 7.420 - 12.951 9 9 120 500 200 400 4500

210 35 25+ 70+ 160 50 110 120 310 25 25 160

D= 3.6 m, H= 3.5 m D= 3.6 m, H= 3.5 m

Rather than breaking down the details of such preliminary estimate, it is reasonable to utilise module factors that are common to the industry (Guthrie, 1974: pp. 108-118). The simplicity of the plant justifies to choose the factor 2.6 that multiplied by the bare module cost estimated above brings to a total investment of 3.4E6 Euro. Operating unit cost rates were derived from adjusting published averages (Peters and Timmerhaus, 1991: p. 815). The optimisation of heat flows and actual consumption has not been done as they will also depend on the selection of machinery and heat exchangers. Labour and utilities consumption over a period of 7,500 hours/year yields to running costs that are estimated as follows: Operators = 2 @ 35,000 Eu/y-person Electric power = 900 kW/h @ 7 Eu/kWh Amine make-up = 6 kg/h @ 1.5 Eu/kg Cooling water = 460 m3/h @ 1.5 Eu/m3 Low P. steam = 30 t/h @ 1.1 Eu/t Total operating costs = = = = = = 70,000 472,500 67,500 51,750 247,500 976,750 Eu/y Eu/y Eu/y Eu/y Eu/y Eu/y

6.6

Investment Offset

Investment and operating costs are recoverable against the saving of a future carbon tax and presently, in lack of that, it appears reasonable to make the tax equivalent to the monetary benefit of current Green Certificates in Italy (Tedeschi, 2004). Each one of such certificates corresponds to a clean power production of 100 MWh and is presently worth about 84 Euro/MWh. Certificates are traded on the financial market with a face value established by the Italian Electric Authority GRTN, in compliance to the 79/1999 "Bersani" Decree created for the gradual substitution of the CIP 6 government subsidy (Italian Law Decree D.L. 79, 1999). The decree enticed power producers to generate at least 2% of their production as green power, escalatable percentage that

Low Pressure CO2 Partial Absorption from Flue Gas

59

increased in 2004 to 2.35% because of the 239/2004 Law amendment. Producers that do not make green power are therefore forced to purchase the certificates from the market. On the long run, when all power producers will be sufficiently clean the market will disappear, but today is still unbalanced by far: in 2003, the demand of certificates was for 3.46 TWh and only 1.3 TWh were offered. For clarity, it is worth saying that a pure green power producer sees the full income benefit of the bonds related to its production; a conventional producer with no green power would now purchase certificates up to 2.35% of its production and would therefore dilute such cost in the overall production that he makes. This consideration enables to set boundary limits and each case needs to be weighted. In general terms, 14 kg of crude oil generate 44 kg of CO2. With an average heating value of 10,000 kcal/kg and an energy to electric power efficiency of 25%, the 44 kg of CO2 would be equivalent to 40.7 kWe or 1 ton of CO2 corresponds to 925 kWe, let us simply say 1tCO2 : 1MWe. Comparing to the certificates face value of 84Eu/MWh, 1tCO2 : 84Eu and by referencing to the average oil price of 40 Eu/barrel 250Eu/toil we get 1tCO2 : 0.3toil : 75Eu in fuel cost. Aside from approximations, this means that a sole green producer (100% credit) gets a CO2 bonus about equal to the fuel cost that a sole fossil power producer has, whereas the big fossil power producer perspective is to dilute the tax to 2.35% of its production, that translated into fuel cost is 1tCO2 : (84 0.0235+75) = 77Eu. All numbers are subjective and any consideration would need to be framed in an econometric model; nonetheless, all matters may become a serious concern for environmental reasons but also for the economics forced by the enormous hourly rates of power generation and flue gas emissions. For this same consideration, even a partial CO2 recovery, useless or unattractive for other industrial segments, would become very important. The ancillary plant that we considered has a CO2 partial recovery of 63% and was considered coupled to a municipal waste-to-energy incinerator of 250 t/d, having a potential net power average export of 8.5 MWh. The certificates equivalent benefit would therefore be 8.5 7500 0.63 = 40,000 MWh/y or 400 certificates, which means 3.36E6 Euro per year. By all means, whichever the calculation method, it is moreover evident that the rich CO2 stream must be sent to a downstream plant for reuse and the conversion, use of the gas will bear its own costs and economic analysis. The syngas will not be burnt to produce electricity or the carbon tax offset will void the whole exercise. The penalisation/benefit that we discussed can be considered excessively prudent, as any political drive could bear a reducing or power leverage effect. For instance, the green certificate criteria is a positive incentive for clean power, it is not reasonable to think that the disincentive will be of the same magnitude. Punishment is generally calibrated on a lower damaging scale in the industry. Nonetheless, this is pure speculation, the fines for traffic rules violation, for instance, go with the opposite trend. The new laws could also call for a gradual application of any tax to be, or could consider a grace period of non-application or even establish that the tax is applied for a limited number of years. The fines may also apply for such quotas that exceed an authorised limit that any given producer has declared and obtained permission from the Authorities. This last mechanism, in fact, appears the method adopted by the European Directive, after the Kyoto decisions, (European Directive Nr. 2003/87/CE, 2003), and the legislation of the local Governments (Italian Law 316, 30/12/2004, 2005). According to

60

Chapter 6

such laws, a limit of 40 Euro/t CO2 is talked about, increased to 100 Euro/t of emitted CO2, from 2007 to 2012. Many fail to reckon however that these fines are not applied yet. The Italian law established that all producers declare their emissions and the Authority makes a list and quotas to allow such emission. Should one exceed the authorised quota, then the fines come into play. Things are also scheduled to allow improvements/revamping of the plants and meanwhile mechanisms of trading the permits, across companies and States of the European Community, so it is still unclear what the real cost of these emissions will be. Aside from fault and misbehaviour, no matter how big is the fine, its importance appears strongly related to the amount and to the percent of emissions exceeding a pre-established limit. Certainty is, that in a matter of few years, some form of carbon tax will affect operators having substantial greenhouse gas emissions.

6.7

Alternative for CO2 Concentration

A possibility of concentrating CO2 from flue gas via cryogenic separation can also be considered. The gas has the peculiarity of solid to vapour sublimation; at atmospheric pressure the melting point is -78.6C and the boiling point is -56C. Since low temperature must be reached to make CO2 separable from the other gas, the first step would obtain the ice separation of water humidity. A detailed calculation of the cryogenic cycle and the crystallisation equipment were not simulated because the heat exchange solid-gas, refrigeration efficiency and the details of the crystallisers require specialised experience from systems manufacturers. For illustrative purposes, the scheme with the features that enabled the simulation is reported in Figure 4 below. Figure 4: Cryogenic absorption scheme

Low Pressure CO2 Partial Absorption from Flue Gas

61

Both operating and investment costs of refrigeration systems increase dramatically with the lowering of the refrigerant level temperature. Base-price estimates increase with a fourfold factor if the refrigerant level drops from 0 to -50C (Chauvel, op. cit.: p. 381). Technological difficulties would affect the ice separation, freezing of lines, the refrigerating loop and exchangers. Additional details are grouped under Appendix 1 that exhibits the possible flow scheme and the preliminary heat/material balance for the major streams. It is however evident that to overcome the higher pressure drops through the circuit, higher power requirements are necessary to compress the flue gases and higher cooling is necessary to remove the compression heat. Refrigerated streams returns (offgas and CO2) are used to recover and balance the enthalpy for cooling. The cost of refrigeration is operatively obtained by multiplying by 3 the subtracted heat to convert it to electric power, and divide it by 500 kcal/kg to assimilate it to a steam consumption. The comparison with the amine flowsheet brings to the higher operating costs presented below. As a first approximation, the investment costs were assumed to be equivalent for both methods, but the investment for crystallisers and low temperature heat transfer is likely to exceed the estimate for the amine plant. Two advantages are however obtainable from a cryogenic CO2 system: the first advantage is the elimination and potential loss of amine, the second advantage is the full recovery of CO2, which means the full benefit of non paying the carbon tax. Operators = 2 @ 35,000 Eu/y-person Electric power = 1600 kW/h @ 7 Eu/kWh Cooling water = 150 m3/h @ 1.5 Eu/m3 Low P. steam = 100 t/h @ 1.1 Eu/t Total operating costs = 70,000 = 840,000 = 20,000 = 830,000 = 1,760,000 Eu/y Eu/y Eu/y Eu/y Eu/y

Should we pro-rate the cryogenic operating costs to the 63% CO2 capture considered for the amine system, we would get 1.1E6 as opposed to 0.98E6 Euro/year, a close difference. On the other hand, the annual saving or green certificates calculated for the amine system increase from 3.36E6 Euro to 5.4E6 Euro. Indeed, this second advantage proves to be the crucial balancing factor when more complicated systems or operations are compared. Notwithstanding the detailed method for capturing and concentrating the CO2 from flue gas, we identified a viable system that may serve the purpose of feeding the concentrated gas to the dry reforming converter that will be discussed in later chapters and potential savings will largely depend on the level of a future tax on CO2 emissions.

62

Chapter 6

6.8

References

Biardi, G., Academic Year 2002-2003. Absorption Columns with Chemical Reaction. Chemical Engineering Post-Graduate Lectures at Politecnico di Milano. Chapel D. and Carl Mariz (Fluor Daniel), 1999, October 4-6. Recovery of CO2 from Flue Gases: Commercial Trends. Canadian Society of Chemical Engineers, (Saskatoon, Canada: Annual Meeting Proceedings). Chauvel A. et al., (Istitut Franaise du Ptrole), 1981. Manual of Economic Analysis of Chemical Processes. (New York: McGraw-Hill Co.). D.L. 79, (Italian Law Decree), dated 03/16/1999. (Roma: Gazzetta Ufficiale 75). European Directive Nr. 2003/87/CE, 2003. Emission Trading on Quotas for Greenhouse Gases. (Luxembourg: 13/10/2003). Guthrie K., 1974. Process Plant Estimating Evaluation and Control. (Solana Beach, Cal: Craftsman Book Company of America). Italian Law 316, dated 30/12/2004, 2005. Disposizioni urgenti per lapplicazione della direttiva 2003/87/CE in materia di scambio di quote di emissione dei gas ad effetto serra nella Comunit Europea. (Roma: Gazzetta Ufficiale 2, 4/1/2005). Keller A. et al., 2002, September. US Patent No. 20020134706. Kohl A. and F. Riesenfeld, 1985. Gas Purification. 4th ed., (Houston: Gulf Publishing). Pacheco M. and G. Rochelle, 1998. Rate-Based Modeling of Reactive Absorption of CO2 and H2S into Acqueous Methyldiethanolamine. Ind. Eng. Chem. Research, 37, 4107-4117. Peters M. and K. Timmerhaus, 1991. Plant Design and Economics for Chemical Engineers. 4th ed., (New York: McGraw-Hill Co.). Rameshi M. (Parsons Energy & Chemicals Group), 2000, November. State of the Art in Gas Treating. (San Francisco: British Sulphur 2000 Convention). Savage D. et al., 1981, April 5. Selective Absorption of H2S and CO2 into Acqueous Solutions of Methyldiethanolamine. (Houston: AIChE Meeting). Tedeschi E., 2004. Dal CIP N. 6/1992 ai certificati verdi. Via internet: www.ambientediritto.it/dottrina. Tellini M., R. Del Rosso and S. Pierucci, 2005. Low Pressure CO2 Partial Absorption from Flue Gas in the new Carbon Tax Scenario. Article submitted, under referees evaluation.

Low Pressure CO2 Partial Absorption from Flue Gas

63

Appendix 6.1 to Chapter 6

Table 3:

Summary of various amine absorption trials

Figure 5:

Simulator run scheme and balance of the preferred amine case

Figure 6:

Simulator run scheme and balance of the cryogenic case

Table 4:

Simulator report for the amine case

64

Chapter 6

Appendix 6.1, Table 3

All cases at 1.1 bar abs FG and 1.05 bar Amine feed
Offgas Wet FG Dry FG

Flash 2
H2O

3 Absorber 5
Rich Am.

Amine

4
Amine make-up (w/o stripper losses)

1
H2O DFG Off Amine Rich Am.

Differen.

Excess H2O

1 Case A HYSYS C H2O MEA MDEA CO2 Total kg/h Case A HYSYS 38 2436

2 38 3869

3 47 6228 21 0.4 8442 99440

4 35 162135 21358 11916

5 44 159776 21358 11915 7981 201034

(4 - 5)

(1 - diff.)

2359

77

16424 105043

195431

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

47 345.73 0.35 0 191.83 3513

35 9000 350 100

44 8869 349.65 100 181.35 9500

131

4.23

48.6%

9450

Case A ChemCAD C H2O MEA MDEA CO2 Total kmol/h Case B HYSYS

38 135.23

38 214.76

373.2 3563

46.6 328.28 0.01 0.01 205.48 3513

35 9500 350 100

41.6 9387.35 349.99 99.99 167.7 9500

112.65

22.58

44.9%

9950

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

48 343 0.64 0 114.4 3433

35 10500 740 0

51 10371.7 739.36 0 258.79 11370

128.3

6.93

69.3%

11240

Case B PRO II

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

50.4 376.56 0.684 0 0 3352

35 10500 740 0

52.5 10338.2 739.32 0 373.19 11451

161.8

-26.57

100.0%

11240

Low Pressure CO2 Partial Absorption from Flue Gas

65

H2O

DFG

Off

Amine

Rich Am.

Differen.

Excess H2O

1 Case B ChemCAD C H2O MEA MDEA CO2 Total kmol/h Case B' ChemCAD C H2O MEA MDEA CO2 Total kmol/h Case C HYSYS 38 135.23

2 38 214.76

3 50.1 371.59 0.7 0 0 3347.56

(4 - 5)

(1 - diff.)

373.2 3563

35 54 10500 10344.05 739.3 740 0 0 373.19 11240 11456.6

155.95

-20.72

100.0%

38 135.23

38 214.76

373.2 3563

61.8 634.02 3.75 0 0

35 4000 740 0

45.3 3581.6 736.25 0 373.19

418.4

-283.17

100.0%

3613.1 4740 4691.1 strong water evaporation and Amine losses 50 400 0.594 0 195.15 3571 35 6500 350 0 43 6315 349.4 0 178 6842

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

185

-49.77

373.2 3563

47.7%

6850

Case D HYSYS

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

36.4 194.39 0 0.007 348.72 3518

35 6500 0 350

39.2 6520 0 349.99 24.47 6895

-20

155.23

6.6%

6850

Case D PRO II

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

41 246.5 0 0.007 304.5 3526

35 6500 0 350

39 6468 0 349.99 68.75 6887

32

103.23

18.4%

6850

Case D ChemCad

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

45 300 0 0.01 262.5 3538

35 6500 0 350

40 6414.7 85.3 49.93 0 349.99 (w/o electrolyte package) 110.7 29.7% 6876

6850

66

Chapter 6

H2O

DFG

Off

Amine

Rich Am.

Differen.

Excess H2O

1 Case D' ChemCad C H2O MEA MDEA CO2 Total kmol/h Case D'' ChemCad 38 135.23

2 38 214.76

3 45.5 302.75 0 0.01 272.82 3551

4 35 4500 0 350

5 40 4412.89 0 349.99 100.36 4863.31

(4 - 5)

(1 - diff.)

87.11

48.12

373.2 3563

26.9%

4850

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2

46.2 286.5 0 0.03 292

35 2000 0 350

40.7 1929.12 0 349.97 81.19

70.88

64.35

21.8%

3563 3554 2350 2360.35 no more heat, no more reaction of CO2

Case E HYSYS

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

35.3 175 0 0.01 348.37 3498

35 10500 0 1000

38.2 10540 0 1000 24.82 11565

-40

175.23

6.7%

11500

Case E PRO II

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

41.1 233.4 0 0.01 249.2 3457

35 40.8 10500 10481.37 0 0 1000 1000 124 11500 11606

18.63

116.6

33.2%

Case F PRO II

C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

40.8 242.9 0 0.006 267.6 3485.2

35 10500 0 500

40 10607.1 0 500 105.5 11213

-107.1

242.33

28.3%

11000

Case F ChemCAD C H2O MEA MDEA CO2 Total kmol/h

38 135.23

38 214.76

373.2 3563

44.7 296.8 0 0.01 216.66 3488.8

35 10500 0 500

41.6 10418.8 0 499.99 156.5 11075.5

81.2

54.03

41.9%

11000

Low Pressure CO2 Partial Absorption from Flue Gas

67

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68

Chapter 6

Low Pressure CO2 Partial Absorption from Flue Gas

69

70

Chapter 6

Low Pressure CO2 Partial Absorption from Flue Gas

71

Appendix 6.1 Table 4: Simulator report for the amine case

Name: ASSORBITORE RIGENERATORE MDEA Rev3 Date: 04/05/2005 Time: 13:15:59
Calculation mode : Sequential Flash algorithm : Electrolyte Equipment Calculation Sequence 1 3 4 15 11 7 6 5 13 9 2 12 16 14 8 Equipment Recycle Sequence 11 7 6 5 13 9 2 12 16 14 8 Recycle Cut Streams 11 16 Recycle Convergence Method: Direct Substitution Max. loop iterations 40 Flash Damping factor 0.30 Recycle Convergence Tolerance Flow rate 1.000E-003 Temperature 1.000E-003 Pressure 1.000E-003 Enthalpy 1.000E-003 Vapor frac. 1.000E-003 Recycle calculation has converged. COMPONENTS ID # Name 1 46 Nitrogen 2 49 Carbon Dioxide 3 62 Water 4 47 Oxygen 5 744 C1-2Ethanolamine THERMODYNAMICS K-value model : Amine Enthalpy model : Amine Liquid density : Library ELECTROLYTE DATA INPUT Electrolyte model: Pitzer ID # Species 1 1005 H2O 2 1002 H+ 3 1004 OH4 1058 CO2 5 1059 CO3-6 1060 HCO37 1025 SO2 8 1026 SO3-9 1030 HSO310 744 C1-2Ethanolamine 11 1622 MDEA+ No. of reactions 6 Reaction Stoichiometrics and Parameters: Reaction Ln K = A + B / T + C Ln T + D * T + E * T * T; T, deg K Reaction 1 A 1.4093e+002 Species 1 2 3 Reaction 2 A 2.3548e+002 Species 4 1 Base = Molal B C D -1.3446e+004 -2.2477e+001 0.0000e+000 Stoichiometrics Form -1.0 H2O 1.0 H+ 1.0 OHBase = Molal B C D -1.2092e+004 -3.6782e+001 0.0000e+000 Stoichiometrics Form -1.0 CO2 -1.0 H2O

E 0.0000e+000

E 0.0000e+000

72

Chapter 6

2 6 Reaction 3 A 2.2007e+002 Species 6 2 5 Reaction 4 A -1.9621e+000 Species 7 1 2 9 Reaction 5 A -2.1274e+001 Species 9 2 8 Reaction 6 A -2.1224e+000 Species 11 10 2

1.0 H+ 1.0 HCO3Base = Molal B C D -1.2432e+004 -3.5482e+001 0.0000e+000 Stoichiometrics Form -1.0 HCO31.0 H+ 1.0 CO3-Base = Molal B C D 6.3740e+002 0.0000e+000 -1.5134e-002 Stoichiometrics Form -1.0 SO2 -1.0 H2O 1.0 H+ 1.0 HSO3Base = Molal B C D 1.3334e+003 0.0000e+000 0.0000e+000 Stoichiometrics Form -1.0 HSO31.0 H+ 1.0 SO3-Base = Molal B C D -5.1299e+003 0.0000e+000 0.0000e+000 Stoichiometrics Form -1.0 MDEA+ 1.0 C1-2Ethanolamine 1.0 H+

E 0.0000e+000

E 0.0000e+000

E 0.0000e+000

E 0.0000e+000

Henry's Constants:

Ln H = A + B / T + C Ln T + D * T H = kg-atm/mole; T, deg K A B C D 2 Carbon Dioxide 9.4491e+001 -6.7890e+003 -1.1452e+001 -1.0454e-002 4 Oxygen 1.0459e+001 -1.0854e+003 0.0000e+000 0.0000e+000

Pitzer Interaction Parameters: Id1 Id2 Eq. form B0a B0b 1002 1004 0 0.2080 0.0000 1002 1058 0 0.0330 0.0000 1002 1059 0 0.0860 0.0000 1002 1060 0 0.0710 0.0000 1002 1026 0 0.1030 0.0000 1002 1030 0 0.0850 0.0000 1004 1058 1 0.2600 -0.0016 1058 1058 2 -0.4922 149.2000 1058 1026 0 0.0680 0.0000 1058 1030 0 -0.0300 0.0000 1059 1622 0 0.0035 0.0000 1060 744 0 -0.0453 0.0000 1060 1622 2 1.1132 -366.7140 1025 1025 0 0.0275 0.0000 Overall Mass Balance Nitrogen Carbon Dioxide Water Oxygen C1-2Ethanolamine Total

B0c 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

B1 0.6545 0.0000 0.2812 0.2352 0.3332 0.2781 0.0000 0.0000 0.0000 0.0000 0.0122 0.1500 -0.0716 0.0000

B2 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

kmol/h Input Output 2630.952 2631.065 373.184 373.200 350.793 350.518 343.330 343.330 0.050 0.049 3698.309 3698.163

kg/h Input Output 73703.484 73706.667 16423.844 16424.527 6319.543 6314.578 10986.204 10986.207 5.958 5.873 107439.037 107437.860

Low Pressure CO2 Partial Absorption from Flue Gas

73

EQUIPMENT SUMMARIES Equip. No. Name Pressure out bar Type of Compressor Efficiency Actual power kW Cp/Cv Theoretical power kW Ideal Cp/Cv Calc Pout bar Motor RPM Calc. mass flowrate Compressor Summary 1 1.3000 3 0.8000 861.4009 1.3732 683.6613 1.3701 1.3000 1 107433 (kg/h)

Scds Rigorous Distillation Summary Equip. No. 2 11 Name No. of stages 16 10 1st feed stage 6 1 2nd feed stage 0 10 Condenser type 1 0 Condenser mode 3 0 Condenser spec. 60.0000 Reboiler mode 3 0 Reboiler spec. 111.0000 Cond press drop bar 0.1000 Colm press drop bar 0.2000 0.1000 Est. dist. rate 1000.0000 11700.0000 (kmol/h) Est. reflux rate 800.0000 (kmol/h) Est. stage 1 T C 55.0000 45.0000 Est. bottom T C 105.0000 50.0000 Est. stage 2 T C 70.0000 40.0000 Top pressure bar 1.1000 1.1000 Cond duty kcal/h -528649.3125 Reblr duty kcal/h 1.4454e+007 Iterations 150 0 Damping factor 1.0000 Reflux mole kmol/h 48.2389 11685.3301 Tray Efficiency Profile 2 2 Reflux ratio 0.1664 Reflux mass kg/h 869.3550 312997.2500 Tray type 3 3 Column diameter m 1.9812 3.6576 Tray space m 0.6096 0.6096 Thickness (top) cm 0.1587 0.1587 Thickness (bot) cm 0.3175 0.1587 No of sections 1 1 No of passes (S1) 1 1 Weir side width cm 36.8300 65.4050 Weir height cm 5.0800 5.0800 System factor 1.0000 1.0000 Component/Tray Efficiency Specification for Equip. 2 Tray # Component Efficiency 1 Nitrogen 1 1 Carbon Dioxide 1 2 Nitrogen 1 2 Carbon Dioxide 0.2 5 Nitrogen 1 5 Carbon Dioxide 0.3 6 Nitrogen 1 6 Carbon Dioxide 0.2

74

Chapter 6

15 Nitrogen 1 15 Carbon Dioxide 0.7 16 Nitrogen 1 16 Carbon Dioxide 1 Component/Tray Efficiency Specification for Equip. Tray # Component Efficiency 1 Nitrogen 1 1 Carbon Dioxide 0.2 1 Oxygen 1 10 Nitrogen 1 10 Carbon Dioxide 0.21 10 Oxygen 1 Heat Exchanger Summary 3 7 0.1000 0.1000 38.0000 35.0000 -2.9384e+006 -575686.0000

11

Equip. No. Pressure drop 1 bar Pressure drop 2 bar T Out Str 1 C Calc Ht Duty kcal/h LMTD (End points) C LMTD Corr Factor Str1 Pout bar Str2 Pout bar Shell and tube Design pressure bar

1.2000 0

1.0000 0

9 12 0.2000 0.1000 0.1500 75.0000 35.0000 7.4199e+006 -1.2951e+007 35.9138 1.0000 1.1000 1.1500 1.2500 2 0 2.0000

Equip. No. Output pressure bar Pressure increase bar Efficiency Calculated power kW Calculated Pout bar Head m Vol. flow rate m3/h Mass flow rate kg/h

Pump Summary 5 1.1500 0.1500 0.8000 0.0039 1.1500 1.4448 0.7442 787.9258 Flash Summary 6 1 3.6576 3.3599 0.6350 0.6350 5.0800 7833.4126 1.113E+005 6.174 0.057 55613.570 8.772E-004

13 0.1000 0.7566 1.3000 0.8687 272.1846 319490.0000

Equip. No. Type Diameter m Length m Vessel thickness cm Head thickness cm Straight flange cm Metal density kg/m3 K values: Nitrogen Carbon Dioxide Water Oxygen C1-2Ethanolamin STREAM PROPERTIES Stream

FG properties: Overall Vapor Temperature deg C 60.000 Pressure bar 1.030 Std sp. gr. * air = 1 1.003 Enthalpy kcal/h -5.441E+007 -5.441E+007 Molar flow kmol/h 3698.259 3698.259 Mass flow kg/h 107433.076 107433.076 Avg. mol. wt. 29.050 29.050

Liquid

Solid

0.000E+000 0.000 0.000 0.000

0.000E+000 0.000 0.000 0.000

Low Pressure CO2 Partial Absorption from Flue Gas

75

Actual dens kg/m3 Actual vol m3/h Cp kcal/kmol-C Cp/Cv Flowrates in kg/h Nitrogen Carbon Dioxide Water Oxygen C1-2Ethanolamine Stream 2

1.081 99374.327

1.081 99374.327 7.356 1.373 73703.4871 16423.8444 6319.5428 10986.2039 0.0000

0.000 0.000 0.000

0.000 0.000 0.000

73703.4871 16423.8444 6319.5428 10986.2039 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

Compr. FG properties: Overall Vapor Temperature deg C 87.251 Pressure bar 1.300 Std sp. gr. * air = 1 1.003 Enthalpy kcal/h -5.367E+007 -5.367E+007 Molar flow kmol/h 3698.259 3698.259 Mass flow kg/h 107433.076 107433.076 Avg. mol. wt. 29.050 29.050 Actual dens kg/m3 1.261 1.261 Actual vol m3/h 85190.652 85190.652 Cp kcal/kmol-C 7.385 Cp/Cv 1.371 Flowrates in kg/h Nitrogen 73703.4871 73703.4871 Carbon Dioxide 16423.8444 16423.8444 Water 6319.5428 6319.5428 Oxygen 10986.2039 10986.2039 C1-2Ethanolamine 0.0000 0.0000 Stream Abs head properties: Overall Vapor Temperature deg C 41.494 Pressure bar 1.100 Std sp. gr. * air = 1 0.982 Enthalpy kcal/h -2.525E+007 -2.525E+007 Molar flow kmol/h 3332.065 3332.065 Mass flow kg/h 94753.334 94753.334 Avg. mol. wt. 28.437 28.437 Actual dens kg/m3 1.197 1.197 Actual vol m3/h 79189.966 79189.966 Cp kcal/kmol-C 7.175 Cp/Cv 1.386 Flowrates in kg/h Nitrogen 73704.4864 73704.4864 Carbon Dioxide 6001.4536 6001.4536 Water 3975.5041 3975.5041 Oxygen 10985.5731 10985.5731 C1-2Ethanolamine 86.3174 86.3174 Stream Rich amine properties: Overall Vapor Temperature deg C 75.000 Pressure bar 1.100 Std sp. gr. * air = 1 0.938 Enthalpy kcal/h -8.463E+008 -6.190E+004 Molar flow kmol/h 11766.476 0.854 Mass flow kg/h 319490.000 29.397 Avg. mol. wt. 27.153 34.429 Actual dens kg/m3 1050.465 1.315 Actual vol m3/h 304.141 22.358 Cp kcal/kmol-C 9.061 Cp/Cv 1.293 4 3

Liquid

Solid

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-8.462E+008 11765.622 319460.430 27.152 1133.708 281.784 23.272

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

76

Chapter 6

Latent heat kcal/kmol Flowrates in kg/h Nitrogen 2.1602 Carbon Dioxide 10774.8041 Water 189545.3369 Oxygen 0.6288 C1-2Ethanolamine 119167.0000 Stream 5

10966.5610 1.9778 21.7661 4.8576 0.5398 0.2555 0.1824 10753.0388 189540.4607 0.0890 119166.6535 0.0000 0.0000 0.0000 0.0000 0.0000

MDEA makeup properties: Overall Vapor Temperature deg C 20.000 Pressure bar 1.150 Std sp. gr. * air = 1 4.114 Vpress bar 0.00 Enthalpy kcal/h -5.725E+003 0.000E+000 Molar flow kmol/h 0.050 0.000 Mass flow kg/h 5.958 0.000 Avg. mol. wt. 119.164 0.000 Actual dens kg/m3 1038.024 0.000 Actual vol m3/h 0.006 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0000 0.0000 Carbon Dioxide 0.0000 0.0000 Water 0.0000 0.0000 Oxygen 0.0000 0.0000 C1-2Ethanolamine 5.9582 0.0000 Stream Cooled FG properties: Overall Vapor Temperature deg C 38.000 Pressure bar 1.200 Std sp. gr. * air = 1 1.003 Enthalpy kcal/h -5.661E+007 -4.611E+007 Molar flow kmol/h 3698.259 3544.012 Mass flow kg/h 107433.076 104654.081 Avg. mol. wt. 29.050 29.530 Actual dens kg/m3 1.407 1.371 Actual vol m3/h 76334.148 76331.345 Cp kcal/kmol-C 7.303 Cp/Cv 1.378 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 73703.4871 73703.4517 Carbon Dioxide 16423.8444 16423.4564 Water 6319.5428 3540.9724 Oxygen 10986.2039 10986.1941 C1-2Ethanolamine 0.0000 0.0000 Stream Condensate properties: Overall Vapor Temperature deg C 34.976 Pressure bar 1.150 Std sp. gr. * air = 1 0.926 Vpress bar 0.26 Enthalpy kcal/h -8.301E+008 -2.735E+003 Molar flow kmol/h 11514.962 0.000 Mass flow kg/h 308801.093 2.821 Avg. mol. wt. 26.817 24.495 Actual dens kg/m3 1004.249 1.105 Actual vol m3/h 307.494 2.553 Cp kcal/kmol-C 8.418 Cp/Cv 1.359 7 6

Liquid

Solid

-5.725E+003 0.050 5.958 119.164 1038.024 0.006 74.382 22531.9354 0.0000 0.0000 0.0000 0.0000 5.9582

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-1.050E+007 154.247 2778.995 18.017 992.518 2.800 18.009 10365.6370 0.0330 0.3882 2778.5638 0.0098 0.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-8.176E+008 11514.962 308798.272 26.817 1012.649 304.941 23.012

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

Low Pressure CO2 Partial Absorption from Flue Gas

77

Latent heat kcal/kmol Flowrates in kg/h Nitrogen 3.1827 Carbon Dioxide 341.1288 Water 189284.0251 Oxygen 0.0049 C1-2Ethanolamine 119172.7770 Stream 8

11412.3719 1.8906 0.0141 0.8406 0.0022 0.0732 1.2921 341.1148 189283.1888 0.0026 119172.6919 0.0000 0.0000 0.0000 0.0000 0.0000

Dry FG properties: Overall Vapor Temperature deg C 38.000 Pressure bar 1.200 Std sp. gr. * air = 1 1.020 Enthalpy kcal/h -4.611E+007 -4.611E+007 Molar flow kmol/h 3544.016 3544.016 Mass flow kg/h 104654.136 104654.136 Avg. mol. wt. 29.530 29.530 Actual dens kg/m3 1.371 1.371 Actual vol m3/h 76331.472 76331.472 Cp kcal/kmol-C 7.303 Cp/Cv 1.378 Flowrates in kg/h Nitrogen 73703.4517 73703.4517 Carbon Dioxide 16423.4741 16423.4741 Water 3541.0213 3541.0213 Oxygen 10986.1950 10986.1950 C1-2Ethanolamine 0.0000 0.0000 Stream FG to flash properties: Overall Vapor Temperature deg C 35.000 Pressure bar 1.000 Std sp. gr. * air = 1 0.982 Enthalpy kcal/h -2.583E+007 -2.309E+007 Molar flow kmol/h 3332.065 3292.501 Mass flow kg/h 94753.334 93965.418 Avg. mol. wt. 28.437 28.539 Actual dens kg/m3 1.124 1.115 Actual vol m3/h 84303.500 84302.757 Cp kcal/kmol-C 7.152 Cp/Cv 1.388 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 73704.4864 73704.4793 Carbon Dioxide 6001.4536 5989.7962 Water 3975.5041 3279.6974 Oxygen 10985.5731 10985.5704 C1-2Ethanolamine 86.3174 5.8726 Stream Flash drain properties: Overall Vapor Temperature deg C 35.000 Pressure bar 1.150 Std sp. gr. * air = 1 0.688 Vpress bar 0.31 Enthalpy kcal/h -2.737E+006 0.000E+000 Molar flow kmol/h 39.564 0.000 Mass flow kg/h 787.926 0.000 Avg. mol. wt. 19.915 0.000 Actual dens kg/m3 1058.692 0.000 Actual vol m3/h 0.744 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h 10 9

Liquid

Solid

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-2.737E+006 39.564 787.916 19.915 1058.694 0.744 19.009 10593.8837 0.0080 11.6581 695.8050 0.0024 80.4446

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-2.737E+006 39.564 787.926 19.915 1058.692 0.744 19.008 10593.8816

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

78

Chapter 6

Nitrogen Carbon Dioxide Water Oxygen C1-2Ethanolamine Stream 11

0.0080 11.6578 695.8131 0.0024 80.4446

0.0000 0.0000 0.0000 0.0000 0.0000

0.0080 11.6578 695.8131 0.0024 80.4446

0.0000 0.0000 0.0000 0.0000 0.0000

To absorber properties: Overall Vapor Temperature deg C 34.975 Pressure bar 1.150 Std sp. gr. * air = 1 0.925 Vpress bar 0.26 Enthalpy kcal/h -8.329E+008 -2.744E+003 Molar flow kmol/h 11554.527 0.000 Mass flow kg/h 309589.040 2.831 Avg. mol. wt. 26.794 24.498 Actual dens kg/m3 1004.429 1.105 Actual vol m3/h 308.224 2.562 Cp kcal/kmol-C 8.416 Cp/Cv 1.359 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 3.1925 1.8963 Carbon Dioxide 352.7867 0.0147 Water 189980.0000 0.8431 Oxygen 0.0075 0.0034 C1-2Ethanolamine 119253.2187 0.0731 Stream Offgas properties: Overall Vapor Temperature deg C 35.000 Pressure bar 1.000 Std sp. gr. * air = 1 0.985 Enthalpy kcal/h -2.309E+007 -2.309E+007 Molar flow kmol/h 3292.501 3292.501 Mass flow kg/h 93965.402 93965.402 Avg. mol. wt. 28.539 28.539 Actual dens kg/m3 1.115 1.115 Actual vol m3/h 84302.735 84302.735 Cp kcal/kmol-C 7.152 Cp/Cv 1.388 Flowrates in kg/h Nitrogen 73704.4793 73704.4793 Carbon Dioxide 5989.7962 5989.7962 Water 3279.6886 3279.6886 Oxygen 10985.5713 10985.5713 C1-2Ethanolamine 5.8725 5.8725 Stream properties: Overall Vapor Temperature deg C 35.000 Pressure bar 1.000 Std sp. gr. * air = 1 0.688 Vpress bar 0.31 Enthalpy kcal/h -2.737E+006 0.000E+000 Molar flow kmol/h 39.564 0.000 Mass flow kg/h 787.926 0.000 Avg. mol. wt. 19.915 0.000 Actual dens kg/m3 1058.692 0.000 Actual vol m3/h 0.744 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0080 0.0000 13 12

Liquid

Solid

-8.203E+008 11554.527 309586.209 26.794 1012.839 305.662 22.994 11409.5931 1.2962 352.7720 189979.0137 0.0041 119253.1479

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-2.737E+006 39.564 787.926 19.915 1058.692 0.744 19.008 10593.8816 0.0080

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000

Low Pressure CO2 Partial Absorption from Flue Gas

79

Carbon Dioxide Water Oxygen C1-2Ethanolamine Stream 14

11.6578 695.8131 0.0024 80.4446

0.0000 0.0000 0.0000 0.0000

11.6578 695.8131 0.0024 80.4446

0.0000 0.0000 0.0000 0.0000

properties: Overall Vapor Temperature deg C 47.802 Pressure bar 1.200 Std sp. gr. * air = 1 0.938 Vpress bar 0.43 Enthalpy kcal/h -8.537E+008 0.000E+000 Molar flow kmol/h 11766.476 0.000 Mass flow kg/h 319490.000 0.000 Avg. mol. wt. 27.153 0.000 Actual dens kg/m3 1173.798 0.000 Actual vol m3/h 272.185 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 2.1602 0.0000 Carbon Dioxide 10774.8041 0.0000 Water 189545.3369 0.0000 Oxygen 0.6288 0.0000 C1-2Ethanolamine 119167.0000 0.0000 Stream CO2 Gas properties: Overall Vapor Temperature deg C 60.000 Pressure bar 1.100 Std sp. gr. * air = 1 1.356 Enthalpy kcal/h -2.524E+007 -2.524E+007 Molar flow kmol/h 289.812 289.812 Mass flow kg/h 11385.228 11385.228 Avg. mol. wt. 39.285 39.285 Actual dens kg/m3 1.568 1.568 Actual vol m3/h 7260.203 7260.203 Cp kcal/kmol-C 9.259 Cp/Cv 1.282 Flowrates in kg/h Nitrogen 2.1602 2.1602 Carbon Dioxide 10434.4522 10434.4522 Water 947.9865 947.9865 Oxygen 0.6288 0.6288 C1-2Ethanolamine 0.0000 0.0000 Stream Recycle properties: Overall Vapor Temperature deg C 111.000 Pressure bar 1.400 Std sp. gr. * air = 1 0.927 Vpress bar 1.40 Enthalpy kcal/h -8.071E+008 0.000E+000 Molar flow kmol/h 11476.520 0.000 Mass flow kg/h 308103.326 0.000 Avg. mol. wt. 26.846 0.000 Actual dens kg/m3 955.230 0.000 Actual vol m3/h 322.544 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0000 0.0000 Carbon Dioxide 341.0399 0.0000 Water 188594.2812 0.0000 16 15

Liquid

Solid

-8.537E+008 11766.476 319490.000 27.153 1173.798 272.185 23.014 11274.4302 2.1602 10774.8041 189545.3369 0.6288 119167.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-8.071E+008 11476.520 308103.326 26.846 955.230 322.544 23.777 10518.6113 0.0000 341.0399 188594.2812

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000

80

Chapter 6

Oxygen C1-2Ethanolamine Stream 17

0.0000 119168.0001

0.0000 0.0000

0.0000 119168.0001

0.0000 0.0000

properties: Overall Vapor Temperature deg C 47.779 Pressure bar 1.300 Std sp. gr. * air = 1 0.938 Vpress bar 0.43 Enthalpy kcal/h -8.537E+008 0.000E+000 Molar flow kmol/h 11766.476 0.000 Mass flow kg/h 319490.000 0.000 Avg. mol. wt. 27.153 0.000 Actual dens kg/m3 1173.833 0.000 Actual vol m3/h 272.177 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 2.1602 0.0000 Carbon Dioxide 10774.8041 0.0000 Water 189545.3369 0.0000 Oxygen 0.6288 0.0000 C1-2Ethanolamine 119167.0000 0.0000 Stream properties: Overall Vapor Temperature deg C 83.606 Pressure bar 1.250 Std sp. gr. * air = 1 0.927 Vpress bar 0.51 Enthalpy kcal/h -8.146E+008 0.000E+000 Molar flow kmol/h 11476.520 0.000 Mass flow kg/h 308103.326 0.000 Avg. mol. wt. 26.846 0.000 Actual dens kg/m3 978.480 0.000 Actual vol m3/h 314.879 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0000 0.0000 Carbon Dioxide 341.0399 0.0000 Water 188594.2812 0.0000 Oxygen 0.0000 0.0000 C1-2Ethanolamine 119168.0001 0.0000 Stream 19 Cool recycle properties: Overall Vapor Temperature deg C 35.000 Pressure bar 1.150 Std sp. gr. * air = 1 0.927 Vpress bar 0.05 Enthalpy kcal/h -8.275E+008 0.000E+000 Molar flow kmol/h 11476.520 0.000 Mass flow kg/h 308103.326 0.000 Avg. mol. wt. 26.846 0.000 Actual dens kg/m3 1012.688 0.000 Actual vol m3/h 304.243 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0000 0.0000 Carbon Dioxide 341.0399 0.0000 Water 188594.2812 0.0000 Oxygen 0.0000 0.0000 18

Liquid

Solid

-8.537E+008 11766.476 319490.000 27.153 1173.833 272.177 23.014 11274.6873 2.1602 10774.8041 189545.3369 0.6288 119167.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-8.146E+008 11476.520 308103.326 26.846 978.480 314.879 23.443 10867.7523 0.0000 341.0399 188594.2812 0.0000 119168.0001

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-8.275E+008 11476.520 308103.326 26.846 1012.688 304.243 23.029 11415.4828 0.0000 341.0399 188594.2812 0.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000

Low Pressure CO2 Partial Absorption from Flue Gas

81

C1-2Ethanolamine Stream 20

119168.0001

0.0000

119168.0001

0.0000

H2O back properties: Overall Vapor Temperature deg C 38.000 Pressure bar 1.200 Std sp. gr. * air = 1 0.622 Vpress bar 0.51 Enthalpy kcal/h -1.050E+007 0.000E+000 Molar flow kmol/h 154.244 0.000 Mass flow kg/h 2778.941 0.000 Avg. mol. wt. 18.017 0.000 Actual dens kg/m3 992.525 0.000 Actual vol m3/h 2.800 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0330 0.0000 Carbon Dioxide 0.3708 0.0000 Water 2778.5275 0.0000 Oxygen 0.0098 0.0000 C1-2Ethanolamine 0.0000 0.0000 Stream Recycle properties: Overall Vapor Temperature deg C 35.008 Pressure bar 1.150 Std sp. gr. * air = 1 0.926 Vpress bar 0.26 Enthalpy kcal/h -8.301E+008 0.000E+000 Molar flow kmol/h 11514.912 0.000 Mass flow kg/h 308795.168 0.000 Avg. mol. wt. 26.817 0.000 Actual dens kg/m3 1012.617 0.000 Actual vol m3/h 304.948 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 3.1824 0.0000 Carbon Dioxide 341.1289 0.0000 Water 189284.0393 0.0000 Oxygen 0.0049 0.0000 C1-2Ethanolamine 119166.8236 0.0000 Stream H2O back properties: Overall Vapor Temperature deg C 38.000 Pressure bar 1.200 Std sp. gr. * air = 1 0.622 Vpress bar 0.51 Enthalpy kcal/h -2.614E+006 0.000E+000 Molar flow kmol/h 38.394 0.000 Mass flow kg/h 691.727 0.000 Avg. mol. wt. 18.017 0.000 Actual dens kg/m3 992.525 0.000 Actual vol m3/h 0.697 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0082 0.0000 Carbon Dioxide 0.0923 0.0000 Water 691.6239 0.0000 Oxygen 0.0024 0.0000 C1-2Ethanolamine 0.0000 0.0000 26 23

Liquid

Solid

-1.050E+007 154.244 2778.941 18.017 992.525 2.800 18.009 10365.6348 0.0330 0.3708 2778.5275 0.0098 0.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-8.301E+008 11514.912 308795.168 26.817 1012.617 304.948 23.002 11411.9867 3.1824 341.1289 189284.0393 0.0049 119166.8236

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

Liquid

Solid

-2.614E+006 38.394 691.727 18.017 992.525 0.697 18.017 10365.6348 0.0082 0.0923 691.6239 0.0024 0.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

82

Chapter 6

Stream

Water Bleed properties: Overall Vapor Temperature deg C 38.000 Pressure bar 1.200 Std sp. gr. * air = 1 0.622 Vpress bar 0.51 Enthalpy kcal/h -7.887E+006 0.000E+000 Molar flow kmol/h 115.850 0.000 Mass flow kg/h 2087.214 0.000 Avg. mol. wt. 18.017 0.000 Actual dens kg/m3 992.525 0.000 Actual vol m3/h 2.103 0.000 Cp kcal/kmol-C 0.000 Latent heat kcal/kmol Flowrates in kg/h Nitrogen 0.0248 0.0000 Carbon Dioxide 0.2785 0.0000 Water 2086.9036 0.0000 Oxygen 0.0074 0.0000 C1-2Ethanolamine 0.0000 0.0000

27

Liquid

Solid

-7.887E+006 115.850 2087.214 18.017 992.525 2.103 18.018 10365.6348 0.0248 0.2785 2086.9036 0.0074 0.0000

0.000E+000 0.000 0.000 0.000 0.000 0.000 0.000

0.0000 0.0000 0.0000 0.0000 0.0000

FLOW SUMMARIES Stream No. 1 Stream Name FG Temp C 60.0000 Pres bar 1.0300 Enth kcal/h -5.4415E+007 Vapor mole fraction 1.0000 Component mole fractions Nitrogen 0.7114 Carbon Dioxide 0.1009 Water 0.0949 Oxygen 0.0928 C1-2Ethanolamine 0.0000 Total kmol/h 3698.259 Flowrates in kmol/h Nitrogen 2630.952 Carbon Dioxide 373.184 Water 350.793 Oxygen 343.330 C1-2Ethanolamine 0.000 Electrolytes: H2O 0.000 H+ 0.000 OH0.000 CO2 0.000 CO3-0.000 HCO30.000 C1-2Ethanolamine 0.000 MDEA+ 0.000 Total kg/h 107433.076 Component mass fractions Nitrogen 0.6860 Carbon Dioxide 0.1529 Water 0.0588 Oxygen 0.1023 C1-2Ethanolamine 0.0000 Stream No. Stream Name Temp C Pres bar 5 MDEA makeup 20.0000 1.1500

2 Compr. FG 87.2507 1.3000 -5.3674E+007 1.0000 0.7114 0.1009 0.0949 0.0928 0.0000 3698.259 2630.952 373.184 350.793 343.330 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 107433.076 0.6860 0.1529 0.0588 0.1023 0.0000 6 Cooled FG 38.0000 1.2000

3 Abs head 41.4941 1.1000 -2.5253E+007 1.0000 0.7896 0.0409 0.0662 0.1030 0.0002 3332.067 2630.988 136.366 220.677 343.310 0.724 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 94753.334 0.7779 0.0633 0.0420 0.1159 0.0009 7 Condensate 34.9759 1.1500

4 Rich amine 75.0000 1.1000 -8.4632E+008 7.2564E-005 0.0000 0.0208 0.8942 0.0000 0.0850 11766.574 0.077 244.826 10521.529 0.020 1000.024 10278.455 0.000 0.011 1.538 33.525 209.269 723.694 276.329 319490.000 0.0000 0.0337 0.5933 0.0000 0.3730 8 Dry FG 38.0003 1.2000

Low Pressure CO2 Partial Absorption from Flue Gas

83

Enth kcal/h -5725.0 Vapor mole fraction 0.00000 Component mole fractions Nitrogen 0.0000 Carbon Dioxide 0.0000 Water 0.0000 Oxygen 0.0000 C1-2Ethanolamine 1.0000 Total kmol/h 0.050 Flowrates in kmol/h Nitrogen 0.000 Carbon Dioxide 0.000 Water 0.000 Oxygen 0.000 C1-2Ethanolamine 0.050 Electrolytes: H2O 0.000 H+ 0.000 OH0.000 CO2 0.000 CO3-0.000 HCO30.000 C1-2Ethanolamine 0.000 MDEA+ 0.000 Total kg/h 5.958 Component mass fractions Nitrogen 0.0000 Carbon Dioxide 0.0000 Water 0.0000 Oxygen 0.0000 C1-2Ethanolamine 1.0000

-5.6612E+007 0.95829 0.7114 0.1009 0.0949 0.0928 0.0000 3698.259 2630.952 373.184 350.793 343.330 0.000 154.236 0.000 0.000 0.009 0.000 0.000 0.000 0.000 107433.076 0.6860 0.1529 0.0588 0.1023 0.0000

-8.3014E+008 4.7146E-023 0.0000 0.0007 0.9125 0.0000 0.0868 11514.962 0.114 7.751 10507.023 0.000 1000.074 10499.205 0.000 0.068 0.000 6.019 1.732 986.236 13.838 308801.093 0.0000 0.0011 0.6130 0.0000 0.3859

-4.6111E+007 1.0000 0.7424 0.1053 0.0555 0.0969 0.0000 3544.016 2630.951 373.176 196.560 343.329 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 104654.136 0.7043 0.1569 0.0338 0.1050 0.0000

Stream No. 9 10 11 12 Stream Name FG to flash Flash drain To absorber Offgas Temp C 35.0000 35.0000 34.9754 35.0000 Pres bar 1.0000 1.1500 1.1500 1.0000 Enth kcal/h -2.5829E+007 -2.7373E+006 -8.3288E+008 -2.3091E+007 Vapor mole fraction 0.98813 0.00000 3.9257E-032 1.0000 Component mole fractions Nitrogen 0.7896 0.0000 0.0000 0.7991 Carbon Dioxide 0.0409 0.0067 0.0007 0.0413 Water 0.0662 0.9762 0.9127 0.0553 Oxygen 0.1030 0.0000 0.0000 0.1043 C1-2Ethanolamine 0.0002 0.0171 0.0866 0.0000 Total kmol/h 3332.067 39.564 11554.527 3292.501 Flowrates in kmol/h Nitrogen 2630.988 0.000 0.114 2630.987 Carbon Dioxide 136.366 0.265 8.016 136.101 Water 220.677 38.624 10545.648 182.053 Oxygen 343.310 0.000 0.000 343.310 C1-2Ethanolamine 0.724 0.675 1000.749 0.049 Electrolytes: H2O 38.360 38.360 10537.566 0.000 H+ 0.000 0.000 0.000 0.000 OH0.000 0.000 0.067 0.000 CO2 0.001 0.001 0.000 0.000 CO3-0.023 0.023 6.191 0.000 HCO30.241 0.241 1.825 0.000 C1-2Ethanolamine 0.388 0.388 986.475 0.000 MDEA+ 0.287 0.287 14.274 0.000 Total kg/h 94753.334 787.926 309589.040 93965.402 Component mass fractions Nitrogen 0.7779 0.0000 0.0000 0.7844

84

Chapter 6

Carbon Dioxide Water Oxygen C1-2Ethanolamine

0.0633 0.0420 0.1159 0.0009

0.0148 0.8831 0.0000 0.1021 14 47.8023 1.2000 -8.5374E+008 0.00000 0.0000 0.0208 0.8942 0.0000 0.0850 11766.574 0.077 244.826 10521.529 0.020 1000.024 10276.968 0.000 0.009 0.274 61.729 182.822 693.734 306.290 319490.000 0.0000 0.0337 0.5933 0.0000 0.3730 18 83.6063 1.2500 -8.1457E+008 0.00000 0.0000 0.0007 0.9122 0.0000 0.0871 11476.520 0.000 7.749 10468.736 0.000 1000.034 10460.867 0.000 0.128

0.0011 0.6137 0.0000 0.3852 15 CO2 Gas 60.0000 1.1000 -2.5237E+007 1.0000 0.0003 0.8181 0.1816 0.0001 0.0000 289.812 0.077 237.093 52.622 0.020 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 11385.228 0.0002 0.9165 0.0833 0.0001 0.0000 19 Cool recycle 35.0000 1.1500 -8.2752E+008 0.00000 0.0000 0.0007 0.9122 0.0000 0.0871 11476.520 0.000 7.749 10468.736 0.000 1000.034 10460.920 0.000 0.068

0.0637 0.0349 0.1169 0.0001 16 Recycle 111.0000 1.4000 -8.0715E+008 0.00000 0.0000 0.0007 0.9122 0.0000 0.0871 11476.520 0.000 7.749 10468.736 0.000 1000.034 10460.872 0.000 0.151 0.036 1.663 6.050 990.506 9.527 308103.326 0.0000 0.0011 0.6121 0.0000 0.3868 20 H2O back 38.0003 1.2000 -1.0501E+007 0.00000 0.0000 0.0001 0.9999 0.0000 0.0000 154.244 0.001 0.008 154.234 0.000 0.000 0.000 0.000 0.000

Stream No. 13 Stream Name Temp C 35.0000 Pres bar 1.0000 Enth kcal/h -2.7373E+006 Vapor mole fraction 0.00000 Component mole fractions Nitrogen 0.0000 Carbon Dioxide 0.0067 Water 0.9762 Oxygen 0.0000 C1-2Ethanolamine 0.0171 Total kmol/h 39.564 Flowrates in kmol/h Nitrogen 0.000 Carbon Dioxide 0.265 Water 38.624 Oxygen 0.000 C1-2Ethanolamine 0.675 Electrolytes: H2O 38.360 H+ 0.000 OH0.000 CO2 0.001 CO3-0.023 HCO30.241 C1-2Ethanolamine 0.388 MDEA+ 0.287 Total kg/h 787.926 Component mass fractions Nitrogen 0.0000 Carbon Dioxide 0.0148 Water 0.8831 Oxygen 0.0000 C1-2Ethanolamine 0.1021 Stream No. 17 Stream Name Temp C 47.7786 Pres bar 1.3000 Enth kcal/h -8.5374E+008 Vapor mole fraction 0.00000 Component mole fractions Nitrogen 0.0000 Carbon Dioxide 0.0208 Water 0.8942 Oxygen 0.0000 C1-2Ethanolamine 0.0850 Total kmol/h 11766.574 Flowrates in kmol/h Nitrogen 0.077 Carbon Dioxide 244.826 Water 10521.529 Oxygen 0.020 C1-2Ethanolamine 1000.024 Electrolytes: H2O 10276.968 H+ 0.000 OH0.009

Low Pressure CO2 Partial Absorption from Flue Gas

85

CO2 0.274 CO3-61.756 HCO3182.796 C1-2Ethanolamine 693.707 MDEA+ 306.317 Total kg/h 319490.000 Component mass fractions Nitrogen 0.0000 Carbon Dioxide 0.0337 Water 0.5933 Oxygen 0.0000 C1-2Ethanolamine 0.3730 Stream No. 23 Stream Name Recycle Temp C 35.0079 Pres bar 1.1500 Enth kcal/h -8.3013E+008 Vapor mole fraction 0.00000 Component mole fractions Nitrogen 0.0000 Carbon Dioxide 0.0007 Water 0.9125 Oxygen 0.0000 C1-2Ethanolamine 0.0868 Total kmol/h 11514.912 Flowrates in kmol/h Nitrogen 0.114 Carbon Dioxide 7.751 Water 10507.024 Oxygen 0.000 C1-2Ethanolamine 1000.024 Electrolytes: H2O 10499.309 H+ 0.000 OH0.068 CO2 0.000 CO3-6.018 HCO31.733 C1-2Ethanolamine 986.197 MDEA+ 13.837 Total kg/h 308795.168 Component mass fractions Nitrogen 0.0000 Carbon Dioxide 0.0011 Water 0.6130 Oxygen 0.0000 C1-2Ethanolamine 0.3859

0.008 3.186 4.555 988.978 11.055 308103.326 0.0000 0.0011 0.6121 0.0000 0.3868 26 H2O back 38.0003 1.2000 -2.6139E+006 0.00000 0.0000 0.0001 0.9999 0.0000 0.0000 38.394 0.000 0.002 38.392 0.000 0.000 38.392 0.000 0.000 0.002 0.000 0.000 0.000 0.000 691.727 0.0000 0.0001 0.9999 0.0000 0.0000

0.000 6.021 1.728 986.196 13.837 308103.326 0.0000 0.0011 0.6121 0.0000 0.3868 27 Water Bleed 38.0003 1.2000 -7.8873E+006 0.00000 0.0000 0.0001 0.9999 0.0000 0.0000 115.850 0.001 0.006 115.843 0.000 0.000 115.842 0.000 0.000 0.006 0.000 0.000 0.000 0.000 2087.214 0.0000 0.0001 0.9999 0.0000 0.0000

0.000 0.000 0.000 0.000 0.000 2778.941 0.0000 0.0001 0.9999 0.0000 0.0000

SIEVE TRAY SIZING Vapor load is defined as the vapor from the tray below. Liquid load is defined as the liquid on the tray. Equip. 2 Tray No. 1 Tray Loadings Vapor Liquid 12254.582 kg/h 869.355 kg/h 8064.921 m3/h 0.885 m3/h Density 1.519 kg/m3 982.235 kg/m3 Tower internal diameter, m ................ 1.067 Tray spacing, cm ................ 60.960 No. of tray liquid passes ................ 1 Downcomer dimension, Width cm Length cm Area m2 Side 19.685 82.765 0.113 Avg. weir length cm ................ 82.765 Weir height, cm ................ 5.080

86

Chapter 6

Flow path length cm ................ 67.310 Flow path width cm ................ 99.104 Tray area, m2 ................ 0.894 Tray active area m2 ................ 0.667 % flood ................ 72.065 Fractional entrainment ................ 0.537 Aeration factor ................ 0.562 Minimum (Weeping) vapor flow kg/h ........... 4130.734 Tray press loss, cm ................ 12.312 Tray press loss, bar ................ 0.012 Downcomer clearance cm ................ 4.445 Downcomer backup cm ................ 17.690 Downcomer residence time, sec ................ 81.582 Liquid holdup m3 ................ 0.040 Liquid holdup kg ................ 39.506 Design pressure, bar ................ 1.100 Joint efficiency ................ 0.850 Allowable stress bar ................ 944.582 Corrosion allowance cm ................ 0.079 Column thickness cm ................ 0.159 Bottom thickness cm ................ 0.318 Equip. 2 Tray No. 2 omissis Equip. 2 Tray No. 5 Tray Loadings Vapor Liquid 12328.325 kg/h 943.098 kg/h 7750.115 m3/h 0.906 m3/h Density 1.591 kg/m3 1040.625 kg/m3 Tower internal diameter, m ................ 1.067 Tray spacing, cm ................ 60.960 No. of tray liquid passes ................ 1 Downcomer dimension, Width cm Length cm Area m2 Side 19.685 82.765 0.113 Avg. weir length cm ................ 82.765 Weir height, cm ................ 5.080 Flow path length cm ................ 67.310 Flow path width cm ................ 99.104 Tray area, m2 ................ 0.894 Tray active area m2 ................ 0.667 % flood ................ 72.463 Fractional entrainment ................ 0.514 Aeration factor ................ 0.563 Minimum (Weeping) vapor flow kg/h ........... 4586.515 Tray press loss, cm ................ 11.435 Tray press loss, bar ................ 0.012 Downcomer clearance cm ................ 4.445 Downcomer backup cm ................ 16.817 Downcomer residence time, sec ................ 75.743 Liquid holdup m3 ................ 0.039 Liquid holdup kg ................ 40.886 Design pressure, bar ................ 1.243 Joint efficiency ................ 0.850 Allowable stress bar ................ 944.582 Corrosion allowance cm ................ 0.079 Column thickness cm ................ 0.159 Bottom thickness cm ................ 0.318 Equip. 2 Tray No. 6 Tray Loadings Vapor Liquid 13473.970 kg/h 321577.287 kg/h 8361.365 m3/h 280.706 m3/h Density 1.611 kg/m3 1145.602 kg/m3 Tower internal diameter, m ................ 1.981 Tray spacing, cm ................ 60.960 No. of tray liquid passes ................ 1 Downcomer dimension, Width cm Length cm Area m2

Low Pressure CO2 Partial Absorption from Flue Gas

87

Side Avg. weir length cm Weir height, cm Flow path length cm Flow path width cm Tray area, m2 Tray active area m2 % flood Fractional entrainment Aeration factor Minimum (Weeping) vapor flow Tray press loss, cm Tray press loss, bar Downcomer clearance cm Downcomer backup cm Downcomer residence time, sec Liquid holdup m3 Liquid holdup kg Design pressure, bar Joint efficiency Allowable stress bar Corrosion allowance cm Column thickness cm Bottom thickness cm Total column pressure drop = Equip. 11

36.830 154.147 ................ ................ ................ ................ ................ ................ ................ ................ ................ kg/h ........... ................ ................ ................ ................ ................ ................ ................ ................ ................ ................ ................ ................ ................ 0.071 bar

0.395 154.147 5.080 124.460 184.182 3.083 2.292 73.762 0.001 0.645 24397.796 10.635 0.012 4.445 47.076 2.386 0.408 467.891 1.257 0.850 944.582 0.079 0.159 0.238

Tray No. 1 Vapor Liquid 98159.657 kg/h 312997.248 kg/h 83066.614 m3/h 301.358 m3/h Density 1.182 kg/m3 1038.624 kg/m3 Tower internal diameter, m ................ 3.505 Tray spacing, cm ................ 60.960 No. of tray liquid passes ................ 1 Downcomer dimension, Width cm Length cm Area m2 Side 63.500 270.006 1.192 Avg. weir length cm ................ 270.006 Weir height, cm ................ 5.080 Flow path length cm ................ 223.520 Flow path width cm ................ 325.051 Tray area, m2 ................ 9.650 Tray active area m2 ................ 7.266 % flood ................ 78.785 Fractional entrainment ................ 0.024 Aeration factor ................ 0.573 Minimum (Weeping) vapor flow kg/h ........... 54567.112 Tray press loss, cm ................ 13.067 Tray press loss, bar ................ 0.013 Downcomer clearance cm ................ 4.445 Downcomer backup cm ................ 32.957 Downcomer residence time, sec ................ 4.693 Liquid holdup m3 ................ 0.887 Liquid holdup kg ................ 920.966 Design pressure, bar ................ 1.100 Joint efficiency ................ 0.850 Allowable stress bar ................ 944.582 Corrosion allowance cm ................ 0.079 Column thickness cm ................ 0.159 Bottom thickness cm ................ 0.159 Equip. 11 Tray No. 2 omissis Equip. 11 Tray No. 10 Tray Loadings Vapor Liquid 105608.352 kg/h 319492.000 kg/h 80583.432 m3/h 272.186 m3/h Tray Loadings

88

Chapter 6

Density 1.311 kg/m3 1173.797 kg/m3 Tower internal diameter, m ................ 3.505 Tray spacing, cm ................ 60.960 No. of tray liquid passes ................ 1 Downcomer dimension, Width cm Length cm Area m2 Side 63.500 270.006 1.192 Avg. weir length cm ................ 270.006 Weir height, cm ................ 5.080 Flow path length cm ................ 223.520 Flow path width cm ................ 325.051 Tray area, m2 ................ 9.650 Tray active area m2 ................ 7.266 % flood ................ 78.834 Fractional entrainment ................ 0.026 Aeration factor ................ 0.572 Minimum (Weeping) vapor flow kg/h ........... 61780.377 Tray press loss, cm ................ 12.232 Tray press loss, bar ................ 0.014 Downcomer clearance cm ................ 4.445 Downcomer backup cm ................ 30.183 Downcomer residence time, sec ................ 4.759 Liquid holdup m3 ................ 0.834 Liquid holdup kg ................ 978.362 Design pressure, bar ................ 1.200 Joint efficiency ................ 0.850 Allowable stress bar ................ 944.582 Corrosion allowance cm ................ 0.079 Column thickness cm ................ 0.159 Bottom thickness cm ................ 0.159 Total column pressure drop = 0.134 bar HEATING CURVES SUMMARY Eqp # 2 Unit type : SCDS Unit name: Condenser NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 73.2 1.2 5.29E+005 12255 2 71.7 1.2 4.52E+005 12124 3 70.3 1.2 3.80E+005 12004 4 68.8 1.2 3.14E+005 11893 5 67.3 1.2 2.52E+005 11791 6 65.9 1.1 1.95E+005 11697 7 64.4 1.1 1.41E+005 11610 8 62.9 1.1 9.11E+004 11529 9 61.5 1.1 4.41E+004 11455 10 60.0 1.1 6.05 11385 Reboiler NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 109.1 1.4 0.000 0 2 109.3 1.4 1.20E+006 2419 3 109.5 1.4 1.66E+006 3253 4 109.7 1.4 2.27E+006 4415 5 109.9 1.4 3.05E+006 5930 6 110.2 1.4 4.08E+006 7942 7 110.4 1.4 5.47E+006 10735 8 110.6 1.4 7.41E+006 14680 9 110.8 1.4 1.03E+007 20526 10 111.0 1.4 1.45E+007 29319 Eqp # 3 Unit type : HTXR Unit name: Stream 2 NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 87.3 1.3 2.94E+006 107433

Liquid kg/h 0 131 251 362 463 558 645 725 800 869 Liquid kg/h 337367 334948 334114 332952 331438 329426 326632 322688 316841 308049

Vap mole frac. 1.0000 0.9785 0.9588 0.9406 0.9239 0.9085 0.8942 0.8810 0.8687 0.8573 Vap mole frac. 0.0000 0.0087 0.0117 0.0160 0.0216 0.0291 0.0395 0.0543 0.0761 0.1088

Vap mass frac. 1.0000 0.9893 0.9795 0.9705 0.9622 0.9545 0.9474 0.9408 0.9347 0.9291 Vap mass frac. 0.0000 0.0072 0.0096 0.0131 0.0176 0.0235 0.0318 0.0435 0.0608 0.0869

Liquid kg/h 0

Vap mole frac. 1.0000

Vap mass frac. 1.0000

Low Pressure CO2 Partial Absorption from Flue Gas

89

2 81.8 1.3 2.79E+006 107433 3 76.3 1.3 2.64E+006 107433 4 70.8 1.3 2.49E+006 107433 5 65.4 1.3 2.34E+006 107433 6 59.9 1.2 2.19E+006 107433 7 54.4 1.2 2.04E+006 107433 8 48.9 1.2 1.90E+006 107433 9 43.5 1.2 8.65E+005 105892 10 38.0 1.2 8.06 104654 Eqp # 7 Unit type : HTXR Unit name: Stream 3 NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 41.5 1.1 5.76E+005 94753 2 40.8 1.1 5.11E+005 94645 3 40.1 1.1 4.63E+005 94582 4 39.3 1.1 4.08E+005 94509 5 38.6 1.1 3.47E+005 94428 6 37.9 1.0 2.81E+005 94340 7 37.2 1.0 2.13E+005 94249 8 36.4 1.0 1.42E+005 94155 9 35.7 1.0 7.12E+004 94060 10 35.0 1.0 14.1 93965 Eqp # 9 Unit type : HTXR Unit name: Stream 17 NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 47.8 1.3 0.000 0 2 50.8 1.3 8.19E+005 0 3 53.8 1.3 1.64E+006 0 4 56.9 1.2 2.46E+006 1 5 59.9 1.2 3.28E+006 1 6 62.9 1.2 4.11E+006 2 7 65.9 1.2 4.93E+006 3 8 69.0 1.1 5.76E+006 4 9 72.0 1.1 6.58E+006 9 10 75.0 1.1 7.42E+006 29 Stream 16 NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 111.0 1.4 7.42E+006 0 2 108.0 1.4 6.59E+006 0 3 104.9 1.4 5.76E+006 0 4 101.9 1.3 4.93E+006 0 5 98.8 1.3 4.11E+006 0 6 95.8 1.3 3.28E+006 0 7 92.7 1.3 2.46E+006 0 8 89.7 1.3 1.64E+006 0 9 86.7 1.3 8.19E+005 0 10 83.6 1.2 0.000 0 Eqp # 11 Unit type : SCDS Unit name: Eqp # 12 Unit type : HTXR Unit name: Stream 18 NP Temp Pres Del H Vapor C bar kcal/h kg/h 1 83.6 1.2 1.30E+007 0 2 78.2 1.2 1.15E+007 0 3 72.8 1.2 1.01E+007 0 4 67.4 1.2 8.61E+006 0 5 62.0 1.2 7.17E+006 0 6 56.6 1.2 5.73E+006 0 7 51.2 1.2 4.29E+006 0 8 45.8 1.2 2.86E+006 0 9 40.4 1.2 1.43E+006 0

0 0 0 0 0 0 0 1541 2779

1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 0.9769 0.9583

1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 0.9857 0.9741

Liquid kg/h 0 108 172 244 325 413 505 599 694 788

Vap mole frac. 1.0000 0.9987 0.9979 0.9968 0.9956 0.9942 0.9927 0.9912 0.9897 0.9881

Vap mass frac. 1.0000 0.9989 0.9982 0.9974 0.9966 0.9956 0.9947 0.9937 0.9927 0.9917

Liquid kg/h 319490 319490 319490 319489 319489 319488 319487 319485 319481 319461 Liquid kg/h 308103 308103 308103 308103 308103 308103 308103 308103 308103 308103

Vap mole frac. 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 Vap mole frac. 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

Vap mass frac. 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 Vap mass frac. 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

Liquid kg/h 308103 308103 308103 308103 308103 308103 308103 308103 308103

Vap mole frac. 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

Vap mass frac. 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000

90

Chapter 6

10

35.0

1.1

64.5 FG Viscosity cP 0.018 0.000 Schedule 10 Compr. FG Viscosity cP 0.020 0.000 Schedule 10 Abs head Viscosity cP 0.018 0.000

308103

0.0000

0.0000

Line Sizing for Stream 1 Flowrate kg/h Vapor 107433.076 Liquid 0.000 Total 107433.076 Pipe ID Nominal Dia. cm cm 71.125 71.125 Line Sizing for Stream 2 Flowrate kg/h Vapor 107433.076 Liquid 0.000 Total 107433.076 Pipe ID Nominal Dia. cm cm 60.325 60.325 Line Sizing for Stream 3 Flowrate kg/h Vapor 94753.334 Liquid 0.000 Total 94753.334 Pipe ID Nominal Dia. cm cm 44.450 45.720 Line Sizing for Stream 4 Flowrate kg/h Vapor 29.400 Liquid 319460.400 Total 319490.000 Pipe ID Nominal Dia. cm cm 34.290 35.560 Line Sizing for Stream 5 Flowrate kg/h Vapor 0.000 Liquid 5.958 Total 5.958 Pipe ID Nominal Dia. cm cm 1.712 1.270

Density 1.081 0.000 1.081 Total Press psi/100 0.1931 Density 1.261 0.000 1.261 Total Press psi/100 0.3834 Density kg/m3 kg/m3 kg/m3 Drop ft kg/m3 kg/m3 kg/m3 Drop ft

Velocity m/sec 69.4369

Velocity m/sec 82.7464

1.197 kg/m3 0.000 kg/m3 1.197 kg/m3 Schedule Total Press Drop Velocity psi/100 ft m/sec 10 1.4982 141.6713 Rich amine Viscosity Density cP 0.016 1.315 kg/m3 0.631 1133.708 kg/m3 1050.457 kg/m3 Schedule Total Press Drop Velocity psi/100 ft m/sec 10 0.0938 0.9143 MDEA makeup Viscosity Density cP 0.000 0.000 kg/m3 108.334 1038.024 kg/m3 1038.024 kg/m3 Schedule Total Press Drop Velocity psi/100 ft m/sec 10 0.3623 0.0069

PLASMA AND CO2 REFORMING POSSIBILITY TO GENERATE SYNGAS

Plasma, the 4th state of matter, is for about 99% the most common form of matter in the visible universe and, closer to us, is found in the highest atmosphere layers where solar UV radiations strip electrons from air molecules and create a mix of ions and free electrons. Plasma is the state of gaseous matter in which a mixture of ionic particles or electrically charged particles co-exist (Alonso and Finn, 1969: Vol. I, p. 5). Although its local characterisation is influenced by particles charge, plasma is electrically neutral in its overall undisturbed equilibrium. Excitation and gas ionisation processes depend on local gas density and electric properties, being influenced by the gas propensity to yield outer electrons free. The motion of charges implies denser, immediately followed by thinner distribution due to repulsion, with harmonic oscillations that evidence the plasma frequency footprint, inversely proportional to the mass of the participating particles. Among charges, electrons are thousands of times lighter and faster than the other particles: heavier atoms and ions oscillations become therefore relatively irrelevant (Feynman, 1964: Vol. II, p. 7-3). Oscillations are also associated to electromagnetic radiations and indicate the state of plasma, starting from the moment in which the gas glows and increases its electric conductivity. Matter and energy are necessary to produce a gas plasma. Conversely, plasma becomes a source of matter and energy or, from this point of view, it becomes a transducer, vector for matter and energy (Kirk-Othmer, 1998: Vol. IXX, pp. 232-233). Artificial plasma is normally generated by electric discharge and by maintaining an electric current flow that ionises the gas. The main transport of charge is tied to the flow of electrons, accelerated by the electric field. When electromagnetic energy is applied to a gas, a rapid temperature increase is obtained, molecules are brought to partial or total dissociation into ions and atoms, radicals and electrons that interact and randomly move (Kirk-Othmer, op. cit. 1998: Vol. XVII, p. 226). The energy content of plasma is superior by far than the energy content of the originating gas because the plasma possesses ionisation energy that adds to translational, vibrational and dissociation energy (Ullmann, 1992: Vol. A20, pp. 427-437). Ignoring gravitational effects, we can assume that the energy variation supplied to the gas is found as potential and kinetic energy of the plasma, the potential energy being described in terms of gas correlations in an electric field with k=Boltzmanns constant qV = f(T, ne, k, ) and the kinetic energy expressed through the particles mean velocity (Kirk-Othmer, 1984: Supplement, p. 599).

E = Ek + Ep = mv2 + qV | mv2 | = | qV | and

for an isolated system E=0

vavg = f( T/Atomic weight)

where the atomic weight pertains to species that generate the plasma. If the plasma is therefore reached at a certain minimum energy, it is reached at a particle velocity that for lighter particles has a small denominator and quadratically greater temperatures. To bring a metal or a heavy gas to the plasma state, we can expect that the temperature be raised to greater values than if we were to make an hydrogen plasma. Having a variety of

92

Chapter 7

species, the plasma will not be in equilibrium and thermal uniformity. The fastest particles will exhibit hotter temperatures and the heavier particles will be relatively colder. Indicatively, Telectrons 20,000 K >> Tions > Tatoms 6,000 K (Artsimovich, 1978: p. 16). By increasing the pressure of the system, collisions and probability that electrons collide with heavier particles (ions) will increase or the electric discharge potential will decrease. Slightly above atmospheric pressure, a thermal uniformity local thermodynamic equilibrium (LTE) is reached and the plasma is often referred to as thermal plasma (Venugopalan, 1971: Vol. 1, pp. 8, 10). For industrial applications, the objective is not to conceive a partial or total state of plasma for all the species in the region where the use of plasma is planned: the plasma is rather made with a light gas, for instance methane or argon and the materials of interest are brought to react within the plasma stream. It is not the plasmatic gas that influences the reaction but the high temperature and the heat transfer rate that become crucial for the plasma chemical reactions. In order to have an appreciation on how properties are magnified in plasma conditions we report few indicative values in Table 1: Table 1: Plasma conductivity compared to copper
Property Thermal conductivity [W/m K] Electrical conductivity [S/m] affecting transfer of Energy Charge N2 gas 0.03 @ 373K 0.15 @ 1500K Copper @ 373K 385 6,250 N2 Plasma @ 8,000 K 5,000 2,000

--

7.1

Types of Plasma Generators

They are classified according to the interaction between the discharge and the substance that receives the arc discharge. In non-transferred arc generators the electrodes do not participate to the process, they could, but it is normally better they do not consume or erode, they have the function to conduct the electric arc that generates the plasma. The reaction substances are injected and carried in the plasma gas in between the electrodes. The electrodes maintain the electric flux, the reaction occurs between the electrodes or downstream the arc generator. A strong electrodes cooling is to be foreseen to avoid their rapid wear. A transferred arc generator has at least one electrode made by the substance to be treated. The thermal flux at the point of the arc attack is extremely high and concentrated, which easily brings to the fusion of the treated material. Normally, the electrode of the material to be treated is the anode (examples of metal fabrication, CaC2 synthesis, bulk processes). Voltage is kept low in such processes and the electric amperage is maximised. The cathode or the negative electrode emitting electrons, can be C or W, water cooled, unless the cathode is also chosen as a consumable substance such as graphite that supplies also carbon to the reaction. When materials like sludge or RDF are used directly, they may require calcining or additives to make them conductors. Dielectric materials, like plastics, can be possibly put inside conductor crucibles or sunk in a conducting bath where molten metals or conductive salts will close the arc and keep

Plasma and CO2 Reforming Possibility to Generate Syngas

93

the temperature uniform. The electrode(s) consumption implies the substitutive advancement to replenish the worn part and importantly, to maintain the design distance between electrodes. To achieve good direction and avoid the trembling or flickering of the arc, the carrier gas is often injected tangentially, and it is further confined along and around the main axis of the equipment by means of a magnetic field that creates a ring type, a cylinder shaped stabilisation of the reaction zone. An inert plasma carrier gas like argon enables electrodes duration because it prevents metal oxidation and subsequent embrittlement of the electrodes. The gas can also be a reactive gas like carbon dioxide (Inaba, Nagano and Endo, 1999: pp. 73, 74). In spite of the greater work to excite CO2, the gas may become a convenient carrier when it participates to the reactions and either the corrosion is prevented or electrodes are made of a wearable material (Blair, 1978: pp. 533-653).

7.2

Advantages of Utilising a Plasma Process for Treating Waste

For comparatively equal results, the high energy intensity of a thermal plasma allows to treat equal amounts in smaller plants. The high energy flux, for instance, 4.5 kW/cm2 with an argon jet, are 15 times greater than the energy flux of an oxygen-fuel free flame which is in the order of 0.3 kW/cm2 (Hooke,1992: p. 3). The high temperature is normally synonymous for higher reaction velocity and readiness to reach thermodynamic equilibrium. Verification of probable reaction mechanisms and thermodynamic equilibria, extended over a wide temperature spectrum, indicate that high temperature kinetics will not be the governing variable. This reflects in smaller permanence and contact time, equilibria are attained more rapidly in smaller equipment and better controlled. In the case of batch processes, faster means also quasi-continuous processes with start-up or shut-downs that are also quicker. When plasma is applied to treat waste or toxic waste there are advantages of slagging out inert materials, vitrified metals and minerals are practically encapsulated in a non-leachable glassy matrix, and gases are released at high temperature with limited risk to generate undesired pollutants. Dioxins and furans, for instance, would not form and would destroy at the plasma conditions, the peculiarity of quenching the gases after the reaction section are also a safe protection against dioxin condensation from precursors onto cold surfaces or formation onto catalytic centers like soot, which is not formed, or moderately formed, at the high temperature of plasma. All combustions and conventional incineration of waste operate in oxidising atmosphere. The plasma process can also be made in reducing or inert atmosphere. The reducing atmosphere (CO + H2) and the null or reduced amount of air introduced into the system drastically reduce NOx formation. The non-use of air also reflects in smaller volumes to treat: gas cleaning equipment are therefore more compact and cheaper (Inaba, op. cit.: p. 73). The high temperature gradient between plasma and surrounding circulating gas, outside the plasma shroud, enables the rapid quench of the products of reaction. Having the purpose to reduce the quantity of CO2 dumped to the atmosphere and to use recoverable materials or plastics that are certainly abundant, like PET or used paper,

94

Chapter 7

which are valid carbon sources otherwise unutilised or unwanted, the plasma processing at high temperatures, (above 1500 K), makes possible to reduce CO2 with a C donor. CO2 + C CO2 + CH4 = 2CO = 2CO + 2H2 H 40 kcal/mole H 62.3 kcal/mole, favoured @ T > 973K (G = 62354 64.05T cal/mole)

7.3

Feasibility to Use Plasma for CO2 Conversion

The following considerations are developed by progressive approximation of the order of magnitude as the method makes the analysis easier and treatable by simple mathematics. By removing approximations as the study develops, the comprehension improves, but remains rooted on the previous learning and the figures that were experienced. The first feasibility step pertains to conversions and the energetic aspect for reactions below 1500K, starting from a treated flue gas. We have already seen that flue gas has an average percent of CO2 around 10 vol-% and we aim to see if the thermodynamic conversion can be energetically and economically sustained. As a first approximation we may think to convert a gas with the same number of moles of CO2 and H2O and reduce it to CO and H2. Flue Gas CO2 O2 N2 H2O H2 CO Total: mol-% 12-10 6-5 75-60 6-25 100 Base 100: mol in 10 5 75 10 100 Q = -38.5 Q = -28.1 Q = -66.5 mol out 5 75 10 30 120 kcal kcal kcal

= 2CO CO2 + C(s) = CO + H2 H2O + C(s) -----------------------------------------------CO2 + H2O + 2C(s) = 3CO + H2

The global heat of reaction is negative, i.e. the highly endothermic reaction will force us to work at high temperature (Meneghini, 1966: Vol. I, pp. 100-103). Enthalpies of formation are approximated. Literature values are not always consistent, owing to the conditions they refer to. Practically, the reference state for state variables is just a matter of convenience. Any reference state and the path to lead to the final products agree with the same physical observation, i.e. G= 0 at the same equilibrium temperature. From the starting CO2 and H2O, we can calculate the necessary C, source that is assumed to be carbon but may well become organic material, refuse plastics, carbon black, methane, graphite electrodes or any carbon rich material.

Plasma and CO2 Reforming Possibility to Generate Syngas

95

We can also have simultaneous counter-reactions that would regress the process, the presence of oxygen could reform water and carbon dioxide: CO2 + H2 2CO + O2 2H2 + O2 = CO + H2O = 2CO2 = 2H2O Q = Q = Q = -10.4 68.08 114.6 kcal kcal kcal

Due to starving O2 conditions and excess steam, we can momentarily make the assumption that these exothermal reactions be shifted towards the syngas formation as we also have already assumed to operate at high temperature. We can pinpoint a raw flue gas rate of 100,000 Nm3/h and ignore kinetic and thermodynamic figures just to start.1 We shall later remove such initial simplifications. 100,000 (0.1) /22.414 = 446.15 kmol/h of H2O and CO2 446.15 (18) = 8.03 t/h H2O 446.15 (44) = 19.63 t/h CO2 by first ignoring the process efficiency, the stoichiometric consumption requires 2 kmol C/kmol CO2 446.15 2 = 892.3 kmol/h C 892.3 12 = 10.707 t/h of carbon to produce 1 kmol of H2 and 3 kmol of CO 446.15 2 = 0.892 t/h H2 446.15 3 (12+16 = 28) = 37.477 t/h of CO 2C CO2, H2O Flue G. Conversion (base 100000 Nm3/h) kmol/h 446.15 446.15 892.30 1338.45 446.15 t/h 19.630 8.030 10.707 37.477 0.892 3CO, H2 LHV2mix = kcal/Nm3

CO2 H2O C CO H2

3017 2550

966 with N2

We can now have two cases: a gas without nitrogen (after the absorption and concentration of CO2) or the case of flue gas, as such, with N2. For the first case, the
1

Flow rate pro-rated from municipal incineration plants -Uppsala, Alkmaar, Trezzo(Courtesy of Von Roll Environmental - Zrich, CH). 2 D. Meneghini, op. cit., p. 38.

96

Chapter 7

Low Heating Value (LHV) is similar to the water-gas (H2:CO 1:1 @ 2300 kcal/Nm3), with a marginal enrichment to about 2400 kcal/Nm3 due to its ratio H2 : 3CO. In the second case, the LHV will be lower, like it is for air-syngas, (CO 30 vol-%, H2 5 vol-%, LHV 950 kcal/m3):3 [(3017) + (2550)] 40/120 + (0 80/120) = 2900 0.333 = 966 kcal/m3 LHV

to make a preliminary conservative calculation, we can assume to have this kind of poor fuel LHV (nitrogen ignored) (37.477 / 28 + 0.892 / 2) 22.414 = 40,000 Nm3/h 40,000 966 / 10,000 kcal equivalent to 1 kg oil = 3864 kg/h oil 3864 / 0.92 / 159 l/barrel = 26.4 barrels/hr 26.4 35 Eu/barrel = 925 Euro/hr 925 24 320 day/year = 7.1 106 Euro/year Thinking about investing half the equivalent revenue, we get 3.5E6 Eu/year to repay the investment in 10 years or 35E6 Euro to spend. The investment would need to cover the CO2 absorption/concentration and the plasma plant capable to convert the gas with the organic feed to syngas. In reality, the available figure could be much greater, in consideration of saving on the carbon tax and considering tipping fee revenues. These preliminary considerations have not clearly solved the feasibility query but they provide a rock-bottom indication that a substantial investment can be justified if a plant technically viable and reliable can be made.

7.4

Preliminary Energy Aspect for Treating CO2 and Waste

We have not so far checked the energetic convenience to burn the municipal waste but we have only addressed the conversion of the derived gas. Differently, we would have to start with a thermal balance upstream and from data that result in the flue gas quantity that we have used. 500 t/d / 24 8000 hrs 3500 kcal/kg-waste / 860 = 678,300 MW 17.5 MW 8000 = 140,000 MW power export/year

the efficiency order of magnitude is thus 140,000 / 678,300 = 20% a kg-waste possesses the energy content of 3500/860 = 4 kW and after a conventional valorisation yields 0.8 kW.

D. Meneghini, op. cit., pp. 103-106.

Plasma and CO2 Reforming Possibility to Generate Syngas

97

MSW 4 kW

Conventional El. 0.8 kW

Cumulative efficiency

20%

The flue gas originated from this reference incinerator are100,000 Nm3/h : 500,000/24 = 4.8 Nm3/kg waste, that when expressed in terms of calories obtained from syngas would be 4.8 40/100 966 = 1855 kcal / 860 = 2.15 kW. The balance so far would appear positive, but we also consumed the carbon feed, i.e. 10707 kg 4.8/100000 8000 = 4111/860 = 4.78 kW. In total, we get 0.8 + 2.15 - 4.78 - 4 = - 5.83 kW. The count is definitely negative, but we can consider that even the carbon is fed as a waste, plastics for instance, in such a case it is not energy added to the process, but energy re-valued from being thrown away. The plasma process consumes electric energy also, we can claim that the extra safety or the non-production of toxic by-products is a premium for the process, yet we are likely to have a specific power consumption of about 1 kW/kg, data derived from Westinghouse information, that will be later verified with other literature sources and with the experimental tests on the plasma pilot plant. The heat recovery with a turbine cycle would be likely to remain the same, although at higher temperature the efficiency can be higher. We can conclude that the specific generation of power equals about 1 kW/kg-waste. The specific electricity consumption of the plasma process applied to flue gas are not identified here, but we can assimilate them to the specific mass consumption that we would have on solids as such. In that case, the mass feed rate with the flue gas is 27.66 t/h which is like obtaining a specific consumption of 1.1 kW/kg. Summing up the above calculations, the preliminary comparison results as follows: C 4.78 kW El. 1.1 kW MSW 4 kW Conventional Plasma El. 1.0 kW Cumulative efficiency 20% 29% syngas 2.15 kW

98

Chapter 7

C 4.78 kW El. 1.0 kW MSW 4 kW Plasma syngas 2.15 kW El. 1.0 kW Cumulative efficiency 32%

In view of this preliminary reasoning, one could be encouraged to think that the direct treatment on the waste itself would exhibit a higher efficiency and, as a minimum, it would eliminate the complication of the equipment for the extra section of the plant. This should be further investigated, not simply for the energy balance but also for its technological feasibility and to consider that the direct plasma on the waste generates untreated syngas, while the two steps operation with the CO2 conversion generates a clean current of syngas ready for export (Tellini et al., 2004).

7.5
Species C(s) CH4 C2H2 C2H6 CO CO2(g) H2 H2O(g) H2O(l) O2(g) N2 (g)

Preliminary Thermodynamic Aspect for CO2 Reforming

Hf=298
[kcal/mol]

Gf=298
[kcal/mol]

S
[cal/K-mol]

Cp
[cal/K-mol]

0 -17.889 54.190 -20.236 -26.420 -94.050 0 -57.796 -68.315 0 0

0 -12.140 50.000 -7.860 -32.810 -94.260 0 -54.634 -56.687 0 0

1.361 44.520 48.000 54.760 47.300 51.070 31.211 45.104 16.710 49.003 45.770

2.066 8.540 10.500 12.540 6.970 8.870 6.892 8.025 17.995 7.016 6.961

HT = Hf + H(T) T GT = Gf + G(T) T Calculating the free energy of reaction G react. we made use of tabled Gf to have a first hand feeling on the feasibility of the reaction with standard conditions (Lange, 1979: Table 9-1). The same data were checked to agree with other sources: Pasquon, Rossini, Perry 3-137). Since we operate far from 298K, we shall equal to zero the free energy and calculate the minimum temperature over which the reaction can take place: GT = H TS GT = 0 TGT=0 = H / S 1000

(multiplier 1000 for [S] )

Plasma and CO2 Reforming Possibility to Generate Syngas

99

In which S react.@298 = i ni Si is calculated with the respective stoichiometric coefficients. In spite of the approximation, it is verified that GT calculated at 298K effectively is the Greact. obtained with the tabled Gformation . By increasing the temperature, G is influenced more by the S. For very negative H we have very exothermic reactions, the fact that S is also negative signifies the reactions are subject to equilibrium. When the sign are the same, the reaction goes to equilibrium in which the greater addendum makes the reaction thermodynamically possible or impossible (Natta and Pasquon, 1966: Vol I, p. 29). very favoured reaction not very favoured reaction favoured, equilibrium reaction not favoured, equilibrium reaction Desired reactions: VF NF FE NE [Kcal] Hreac.@298 41.21 31.376 72.586 9.834 -188.1 135.26 -52.84 H<0 H>0 H<0 H>0 [Kcal] Greac.@298 28.64 21.824 50.464 6.816 -188.52 122.9 -65.62 & & & & S>0 S<0 S<0 S>0

[cal/K-mol] [K] Sreac.@298 T(G0) 42.169 32.046 74.215 10.123 977 979 978 971

NE CO2 + C(s) = 2CO NE H2O + C(s) = CO + H2 -------------------------------------NE CO2 + H2O + 2C(s) = 3CO + H2 NE CO2 + H2 = CO + H2O VF 2C + 2O2 = 2CO2 = 2CO + O2 NE 2CO2 ------------------------------------VF 2C + O2 = 2CO

1.412 -133215 41.463 3262 42.875 -1232

The partial oxidation of carbon is shifted to the right due to low pressure and high temperature; another way to look at the desired reactions is: VF C + O2 = CO2 NE 2CO2 = 2CO + O2 -----------------------------------NE C(s) + CO2 = 2CO -94.05 135.26 41.21 -94.26 122.9 28.64 0.706 -133215 41.463 3262 42.169 977

The last reaction is endothermic and occurs with moles increase: it will be shifted to the right by low pressure and high temperature. Undesired reactions: FE 2CO + O2 = 2CO2 FE 2H2 + O2 = 2H2O NE C + 2H2O = CO2 + 2H2 -135.26 -115.6 21.542 -122.9 -109.268 15.008 -41.463 -21.217 21.921 3262 5448 983

100

Chapter 7

Other reactions: FE FE NE NE NE C + 2H2 = CO + 3H2 =4 CO2 + CH4 =5 2CH4 = 3CH4 + H2O =

[Kcal] Hreac.@298 CH4 CH4 + H2O 2CO + 2H2 C2H2 + 3H2 C2H2 + CO + 6H2 -17.889 -49.265 59.099 89.968 139.233

[Kcal] Greac.@298 -12.14 -33.964 41.78 74.28 108.244

[cal/K-mol] [K] Sreac.@298 T(G0) -19.263 -51.309 61.432 52.593 103.902 928 960 962 1710 1340

The case of H < 0 and S > 0 maintains G always < 0 and makes it zero for T<0. This is not physically possible since T > 0, i.e. the reaction is always favoured. At the temperature of nullifying the free energy the tendency inverts, or a thermodynamically favoured reaction FE will gradually revert with further increase of the temperature beyond TGT= 0 . Conversely, a non favoured reaction NE will start to generate the written products as the temperature creeps over the limit of TGT= 0 . From the calculation of the table above, it becomes evident that a reaction FE becomes NE (for instance 2CO2 2CO + O2 not favoured to the right, favoured to the left). FE and NE are two ways to look at the same limiting condition. For convenience of graphical representation all FE reactions below are inverted to become NE. The trick is banal but is introduced to make the graph homogeneous and all reactions are therefore written above their limiting temperature Ti,GT= 0 . In this manner, we can easily identify along the direction of increasing temperatures the tendency and the existence of a given equilibrium, condition generally verified for obtaining acceptable yields from exothermic reactions (Natta and Pasquon, op. cit.: p. 93). Before we refine the thermodynamic analysis with correlations related to high temperatures, let us look at the reaction fields determined so far. Reactions are all written above their Ti,GT=0. Under the line, the reaction does not occur or it is not thermodynamically relevant. By referencing to all the equilibrium non favoured reactions, NE, their advancement will occur only for temperatures above the indicated temperature limit. Although we have not made kinetic considerations yet, the above picture seems to encourage to operate not above 1300K and to remain between the two bold line temperature frontiers for the following reasons: unless necessary, to limit the thermal expenditures avoid undesired reactions that bring to ethyne and unsaturated compounds methane that eventually forms near 900K will degrade with CO2 above 1000K. We observe also that even by limiting the analysis to few constituents and equilibria, the characterising temperatures are very far from each other. That means that once an operating temperature range is set, to maintain and to control the temperature becomes very important to control the selectivity and the end-products.

4 5

Inverse reaction of steam reforming. Dry reforming reaction.

Plasma and CO2 Reforming Possibility to Generate Syngas

101

TK 5448 3262 1340

Reactions VF

Reactions NE

Reactions NE from FE 2H2O 2CO2 2H2 + O2 2CO + O2

2CH4 3CH4 + H2O C+ 2H2O CO2 + H2 C(s) + CO2 C(s) + H2O CO2 + H2O + 2C(s)

C2H2 + 3H2 C2H2 + CO + 6H2 CO2 + 2H2 CO + H2O 2CO CO + H2 3CO + H2 2CO+ 2H2 CH4 + H2O CH4
cumulative reaction of interest

960 928 900 2C + O2 C + O2

CO2+ CH4 CO + 3H2 C + 2H2 2CO these VF reactions CO2 are very favoured

The simple scale reported below compacts the reactions that we considered around their feasible temperatures and it becomes quite evident that a plasma reactor, capable of reaching very high temperatures needs to be controlled and could represent a technological challenge by itself. 930 1230 980 1710 1340 3260 5450 T [K]

Cumulatively, the overall reaction of the example involves carbon dioxide conversion and water becomes determinant for shifting the equilibrium to the right. The reaction doubles the number of moles and will be favoured by low pressure. One method to reduce the reagents pressure is to reduce their partial pressure by means of injecting a diluent gas, that in this case can be steam. CO2 + H2O + 2C(s) 3CO + H2

Let us calculate the maximum thermodynamic conversion, without recycles, that we can expect at the equilibrium temperature T= 978K at which Greaction = 0, i.e. Keq = 1. We can then consider the same equilibrium, but with a strong water steam excess. Keq = [CO]3 [H2] / [CO2] [H2O] equilibrium concentrations are in between brackets, the concentration of C(s) in the gas

102

Chapter 7

phase is ignored due to activity = In 1 1 2 Out 3x x 1-x 1-x 2+ 2x Mol calc. 1.581 0.527 0.473 0.473 3.054 [fract. ] mol-% 0.517 51.7 0.173 17.3 0.155 15.5 0.155 15.5 1. 100.0

CO H2 H2O CO2 Tot.

Keq = 1 = (3x)3/(2+ 2x)3 x/(2+ 2x) (2+ 2x)/(1-x) (2+ 2x)/(1-x) = 33x4/4(1+ x)2(1-x)2 = { 33 x2 / (2 (1+ x) (1-x)) }2 1 = 33 x2 / (2 (1+ x) (1-x)) 2.598 x2 = (1-x2) 3.598 x2 = 1 x = (1 / 3.6)1/2 = 0.527

upon finding x , we can calculate the other moles at the equilibrium and the molar percent tabled above. Let us now repeat the calculation with a strong water excess to have a mass drive to the right with steam. To develop sensitivity, let us triple the water moles. CO H2 H2O CO2 Tot. Keq = 1 In 3 1 4 Out 3x x 3-x 1-x 4+ 2x Mole calc. 2.469 0.823 2.177 0.177 5.646 [fract. ] 0.437 0.146 0.386 0.031 1. mol-% 43.7 14.6 38.6 3.1 100.0

= (3x)3/(4+ 2x)3 x/(4+ 2x) (4+ 2x)/(3-x) (4+ 2x)/(1-x) = 33x4/(4+ 2x)2(3-x)(1-x) x = 0.823 via numerical solution.

We note that the hydrogen yield has dramatically increased from 52.7 to 82.3%, while the non converted CO2 is reduced from 47.3% to 17.7%. Similarly, we could triple carbon dioxide. CO H2 H2O CO2 Tot. Keq = 1 In 1 3 4 Out 3x x 1-x 3-x 4+ 2x Mole calc. 2.469 0.823 0.177 2.177 5.646 [fract. ] mol-% 0.437 43.7 0.146 14.6 0.031 3.1 0.386 38.6 1. 100.0

= (3x)3/(4+ 2x)3 x/(4+ 2x) (4+ 2x)/(1-x) (4+ 2x)/(3-x) = 33x4/(4+ 2x)2(3-x)(1-x) x = 0.823 with identical numerical solution.

In this case, we note that the hydrogen yield has increased from 52.7 to 82.3% as it was for the case of using three times the quantity of steam.

Plasma and CO2 Reforming Possibility to Generate Syngas

103

On the contrary, the non converted CO2 goes from 47.3% to 72.5%. The use of extra CO2, that implies also compression/absorption costs and poses more difficulties for the recycle, does not appear convenient. We could furthermore analyse the thermodynamic equilibria kp in terms of partial pressures pi. The gases are reasonably assumed to have ideal behaviour due to low pressure and high temperatures. PV = nRT [ai] = ni/V = Pi/RT Keq = [CO]3 [H2] / [CO2] [H2O] kp = pCO3 pH2 / pCO2 pH2O Keq = kp / R2T2 pCO + pH2 + pCO2 + pH2O = P It does not however appear useful to continue on the elaboration of absolute partial pressure values, since we already have gas volume (molar) compositions and by fixing T and P, we do not introduce further data to improve our understanding of the problem (keq = cost . kp).

7.6

Verification of the Preliminary Thermodynamic Analysis

The thermodynamic variables used so far were taken at the reference conditions of P = 1 atm e T=298K, they should be corrected for temperature. ((H)/T)P = i ni Cp,i ((S)/T)P = i ni Cp,i /T For free energy, Van Krevelen-Chermin offer relatively simple interpolations, accurate from 600 < T < 1500K (Natta and Pasquon, op. cit.: pp. 40-53). Let us check if the table already prepared is significantly modified with new correlations. Species G f=298
[kcal/mole]

Kirchhoffs

Gf1500K = A + BT/100
[kcal/mole]

C(s) CH4 CO CO2(g) H2O(g)

0. -12.140 -32.810 -94.260 -54.634

A 0. -21.161 -26.582 -94.234 -59.138

B 2.587 -2.122 -0.035 1.316

By reconsidering some of the written reactions we obtain that even wider application correlations (600 < T < 1500K) do not improve our earlier accuracy and the zeroing of Greaction . It is therefore possible to confirm the temperature limits that were calculated for the equilibria with the first reasoning based on the thermodynamic properties at standard conditions.

104

Chapter 7

T Precedent [Kcal] [K] T Greact.@298 NE CO2 + C(s) = 2CO NE H2O + C(s) = CO + H2 -------------------------------------NE CO2 + H2O + 2C(s) = 3CO + H2 VF 2C + O2 = 2CO 28.64 21.82 50.46 -65.62 -122.9 -109.27 977 979 978 -1232

T Recalculated [K] A B TG=0 41.07 -4.21 32.55 -3.44 73.63 -7.65 -53.16 -4.24 4.17 2.63 976 947 962 -1253 3241 4493

FE 2CO + O2 = 2CO2 FE 2H2 + O2 = 2H2O

3262 -135.30 5448 -118.27

7.7

References

Alonso M. and E. Finn, 1969. Fundamental University Physics. (Reading, Massachusetts: Addison Wesley). Artsimovich L., 1978. A Physicists ABC on Plasma. (Moscow: MIR Publishers). Blair D., 1978. Electrical Breakdown of Gases. (New York: Wiley) Feynman R., 1964. Lectures on Physics. (Reading, Massachusetts: Addison Wesley). Hooke W., 1992. Some Implications of the Cariplo International Workshop on Plasma Destruction of Hazardous Wastes. (Como: Italian Phys. Society, Conference Proceedings). Inaba T., M. Nagano and M. Endo, 1999. Investigation of Plasma Treatment for Hazardous Wastes such as Fly Ash and Asbestos. Electrical Engineering in Japan, Vol. 126, No. 3. Kirk-Othmer Encyclopedia of Chemical Technology, 1998. 4th ed. (New York: Wiley). Kirk-Othmer Encyclopedia of Chemical Technology, 1984. 3rd ed. Supplement. (New York: Wiley). Langes Handbook of Chemistry, 1979. 12th ed. (New York: Wiley). Meneghini D., 1966. Chimica Applicata e Industriale. (Milano: Casa Editrice Vallardi). Natta G. and I. Pasquon, 1966. Principi della Chimica Industriale. Vol. I. (Milano: Tamburini). Tellini M., P. Cntola, R. Del Rosso and P. Gronchi, 2004, June 28-July 1. Viable H2 Production from Carbon Waste by Dry Reforming. (Evora, Portugal: Renewables International Conference Proceedings). Ullmanns Encyclopedia of Industrial Chemistry, 1992. 5th ed. (Basel: VCH VerlagsAG). Venugopalan M., 1971. Reactions under Plasma Conditions. (NY: Wiley-Interscience).

APPROACH OF WASTE TO H2 AND CO IN A PLASMA REACTOR

The growing concern about fuels progressive depletion demands alternative sources compatible with the environment. Within this frame, waste valorisation other than simple incineration may offer a solution if enhanced recovery of energy is coupled with the production of electric energy or steam or district heat distribution. The use of high energy plasma is targeted to accomplish a high level of energy available through the production of syngas plus conventional energy recovery and a safer degradation of materials. This chapter aims to discuss the energy differential scenario when a plasma-to-waste approach is compared to conventional burning, and consider the reaction of used oxygen bound to carbon dioxide and water to produce hydrogen.

8.1

Background and Objective

Following differentiated collection of the garbage and classification of materials with partial recovery, a variety of treatments exist, and yet a large portion, ranging between 70 to 30% of the waste, is sent to incinerators. Incineration with heat recovery is the most used and quickest way to reduce the volume of the ultimate fraction of waste while the overall scheme of waste treatment possibilities returns approximately 25 to 40% of the material to authorised dumps (IRER, 2002: pp. 101-116). The processing via incineration is quite extensive and is often referred to as thermo-valorisation, implying that materials otherwise useless or noxious are upgraded to the value of a usable form or energy. The process is also enticed in Countries like Italy where there is a premium revenue for the electricity exported to the grid. Essentially, incineration yields low grade heat, useful for heating and or electricity, the latter being in the range of 20% of the total power input carried by the waste. The process is far from what one would consider efficient and produces corollary side effects, like NOx and dioxins generation, acidic and pollutant laden gases which all require treatment prior to ultimate release to the ambient. Another unresolved issue for incinerators is the total loss of valuable materials, electronic circuit board metals for instance, and their difficulty to cope with the growing calorific value of the modern waste feed (Hairston, 2002: pp. 27-28). Alternate routes to decompose materials via thermal destruction at high temperatures exist. In a plasma reactor we would have fast reactions in smaller volumes, metastable products attained with rapid quenching, high heat fluxes and reduced gas flow and relevant treatment (Pfender, 1999: p. 21), since the excess air used in a normal combustor is not necessary. In addition to safety, improved kinetic and process favourable operation, the flue gas volume of sealed pyrolysis or plasma treatment is tenfold less than the volume of conventional waste incinerators and its treatment is thus more efficient and uses smaller equipment. The melted residues recover molten metals and safely dispose vetrified unleachable materials.

106

Chapter 8

The use of plasma would put more energy into the process and recover some of it in the same unattractive manner. However, when the greater energy input allows higher grade energy recovery or products permissible with that energy expense, the recovery is greater by far. Hydrogen carries a high heat content, if not otherwise considered for chemical industry uses. The subsequent topic of this study is to couple the plasma reaction with a water and waste carbon injection so to obtain more CO and H2 via reforming. Hydrogen is obtained from the same feed mass and the process burns the used oxygen from inexpensive sources of water and carbon dioxide as it is explained in the following pages: the added energy output or usefulness of CO and H2 compensates for the additional electric power input. The first option (white boxes) is to burn waste, obtain electric power and discharge CO2. In a second option we could make the same process, enhanced at greater temperature, in a plasma reactor (blue boxes). A third possibility (addition of the green boxes) is to make the process in two sections as shown in Figure 1: conventional incineration followed by concentration of the CO2 discharged from the first section and utilise another cheap source of carbon like plastic waste, not otherwise usable, in a CO2 plasma reforming to produce syngas. This apparently simple thermochemical comparative study did rapidly bring to discard the usefulness to use a plasma process directly on waste, as such, but it also had the advantage to show that the conversion is viable, in spite of diffused criticism and unsustainable energy consumptions attributed to a plasma reactor (Tellini et al., 2004: pp. 143-150). Figure 1: Usable Energy referred to 1 kg input of waste (not to scale)
Energy referred to 1 kg input of waste
14000 12000 10000 kCal 8000 6000 4000 2000 0 Std. Plasma Plasma Plasma Incin- on waste on gas on gas + C eration

Energy in Energy out CO energy out H2 energy out

Plasma on CO2 gas + C

CO
Carbon addition

Plasma on waste, direct

Plasma on CO2 flue gas

1 kg Waste 3500 kcal/kg

Waste Incineration
Electricity

CO

Electricity
Electricity

H2
H2

Electricity
CO2
CO2

Approach of Waste to H2 and CO in a Plasma Reactor

107

8.2

Combustion and Oxidation

From the chemical point of view, conventional combustion may take a variety of forms, depending on the feedstock and it generally involves large volumes of air, rarely enriched air or pure oxygen. To simplify this analysis we may think of reacting carbon, to avoid discussion of collateral reactions, by-products and pollutants and we shall limit ourselves to the thermodynamic and stoichiometric aspects of desired reactions. Some combustions exhibit very favoured equilibria and some others are favoured at any temperature. The combustion of H2 and CO is favoured, runs up to equilibrium, and reverses above the calculated temperature (Lange, 1979, Table 9-1). The reactions with O2 supplied by H2O and CO2 (H>0 & S>0) are equilibrium endothermic reactions, unfavoured, but they can happen above the calculated temperature (Natta and Pasquon, 1966: Vol I, p. 29). Without gain nor prejudice from kinetic considerations, let us say that they may well happen above 1000K (Rostrup et al., 1975: pp. 21-25). Since we aim at burning waste, or at the carbon portion of the waste, in Table 1 we also report as a model the cumulative reaction of carbon with water and carbon dioxide.
Table 1: Thermodynamic reaction parameters

H@298 G@298 S@298 T(G=0)

[Kcal] [Kcal] [cal/K-mol] [K]

Combustion reactions: 2C(s) + O2 = 2CO (partial ox.) 2CO + O2 = 2CO2 2H2 + O2 = 2H2O Oxidation with O2 supplied by H2O: H2O + C(s) = H2 + CO H2O + CH4 = 3H2 + CO Oxidation with O2 supplied by CO2 CO2 + C(s) = 2CO CO2 + CH4 = 2CO + 2H2 Conversion of Carbon Waste CO2 + C(s) = 2CO H2O + C(s) = CO + H2 CO2 + H2O + 2C(s) = 3CO + H2

-52.84 -135.26 -115.60 31.37 49.26 41.21 59.10

-65.62 -122.90 -109.27 21.82 33.96 28.64 41.78

42.87 -41.46 -21.22 32.04 51.31 42.17 61.43

-1232 3262 5448 979 960 977 962

72.58

50.46

74.21

978

From the model reaction, if a greater injection of steam is chosen we can obtain a greater quantity of hydrogen, possibility not so attractive if we are interested to dispatch the syngas as fuel because of the relative heating values of the gases. H2 has in fact a Low Heating Value (LHV) of approximately 2,550 kcal/Nm3 whereas CO has a LHV of 3,017 kcal/Nm3. For a reaction with an overall gas H2:3CO volume ratio and a marginal heating

108

Chapter 8

value difference of about 15% the production of CO is desirable. On a weight basis, the heating values of the gases are 28,577 and 2,415 kcal/kg for H2 and CO respectively.

8.3

Comparative Material and Heat Balance of the Model Reaction via Plasma Conversion

While oxygen combustion generates heat, the reactions or assimilated combustions that we have seen require heat to produce valuable or usable compounds. By comparing ideal reactions, a kilomole of C releases +94,050 kcal, whereas the same kilomole requires 31,376 kcal to react with water or 41,210 kcal to react with CO2. Energy wise, the latter two possibilities immediately exhibit a net energy deficit. Let us consider each material with the energy input of its heating value. This is not the H of that substance, but its energy usefulness if it were alternatively burned to completion in a conventional combustion. CO2 and H2O enthalpy are considered in calculating the heat of reaction, but have no heating value -LHV- in our considerations, neither as input nor as end product of the process. The first process, i.e. the actual combustion, brings the end result of dumping CO2 and to recover a fraction of the combustion energy, say 20% via heat transfer, steam generation and production of electricity.1 In other words, we get 94,050/860 = 109 x .2 = 22 kW/kmole-C. (109 kW) C O2 Combustion (Q = -H = + 109 kW) Usable 20% kW CO2 22. 0.0 22.0 kW

The H2O oxidation of C generate no CO2 and absorb heat; however, the reaction products are not a waste, do not have a spent energy content, so to speak. Being able to partially oxidise C with CO2, we obtain 2 moles of CO, that for a later thermal use are equivalent to 157.2 kW. The cumulative sum of the two partial reactions, referred to carbon, is thus as follows: (218 kW) 2C CO2 + H2O Conversions (Q = -H = -84.4 kW) Usable (303-84.4)/218 = 100% H2 3CO 67.2 235.8 303. kW

To carry our analysis further, we must deplete the balance by the input of other useful energy, mainly the electric power input, necessary to react the materials at high

1 Most waste-to-energy plants burn the waste; through a thermal cycle, coupled to a steam turbine, plants have an overall power generation of about 20%.

Approach of Waste to H2 and CO in a Plasma Reactor

109

temperature in a plasma reaction. Preliminarily, we may assume that a plasma process has a specific electric power consumption of about 1 kW/kg.2,3 Different cases calculated above are summarised in Table 2 below. Exiting the plasma, there will also be heat recovery to mitigate the power consumption. Experimental data are reported in the range of 80-90% heat recovery based on heat transport analysis and quantity of heat measured on the experimental reactor cooling water (Iwata and Shibuya, 1998: pp. 10, 14). Under these conditions, it is reasonable to assume that the heat recovery from the thermal cycle coupled to the reactor would reasonably recover about 20 % electric power of the plasma input, proportional to the treated mass, percentage already stated for a conventional waste-to-energy incinerator. Table 2: Potential use from the reactions
H react kW in 109 -36,50 -47,90 -42,20 kW out 145,80 157,20 151,50 Plasma 80% thermal 20% electr kW 1 kW/kg recovery 22 -30 24 5 -56 45 9 -62 50 10 Net kW 22 84 62 57 Usable Effic. % 20 77 57 52

C + O2 C + H2O C + CO2 C + H2O + CO2

Reheating of flue gas and downstream processing of syngas, like H2 enriched via PSA (Pressure Swing Absorption) for instance, are not detailed here. Another skepticism about plasma reactors refers to high electrode consumptions. It must be recognised that for the chemical conversion that we aim at, it is not necessary to push the plasma operating temperature higher than 3,000 K (to lower also power consumption) since it only suffices to start and maintain the arc and to stay above the material limiting temperature for electrons emission. By the same token, electrodes can be consumable materials like graphite, or tungsten electrodes, having a melting temperature in excess of 3,660 K, with consequent lower wear in a low temperature plasma (Iwata and Shibuya, 1998: p. 15). In all cases, the plasma gas consumption, air or a noble gas like Argon, is fairly limited and is reported to be less than 1% of the total gas flow (Fox et al., 2001: pp. 6-9).

8.4

Comparison between Conventional Incineration and Added Plasma Plant

To consider transformation efficiency, a 20.3 t/h conventional incineration plant generates about 20 MWh (depending on the heating value of the waste) and a flue gas of

Commercial information of Westinghouse. The Canadian company Pyrogenesis indicates a consumption of 0.26 kW/kg-waste, value that we calculated for raising adiabatically the temperature of reactants above 1000 K. 3 For a semi industrial pilot plant used in a SITE program soil remediation in USA consumption for plasma is reported at 1.2 kW/kg (Retech Inc., 1992: p. 22). Other sources triple the consumption (Lemann, 1992: p. 192).
2

110

Chapter 8

about 100,000 Nm3/h.4 Assuming that CO2 and H2O represent each 10 vol-% of the gas, we have 19.6 t/h and 8. t/h of the respective constituents for a total of 27.6 t/h and a mass ratio between suitable gas outlet and charge of 1.36. Based on published information, a plasma for solid has a mass specific consumption between 0.22 and 1.6 kW/kg, (Fox et al., 2001) or even lower consumption of 0.1 kW/kg-waste.5 If we were to make a plasma on the waste as such, we would therefore consume power for an order of magnitude between 0.22 and 1.6 MW/t. Let us now consider to process the suitable gases coming from the conventional incineration in a plasma reactor, adding the necessary carbon, to perform our model reaction: (CO2 + H2O) + 2C = H2 + 3CO The total feed to the gases from the CO2 humid concentrator has a stoichiometric mass ratio of 86/62 = 1.387 that multiplied by the 1.36 ratio calculated above gives a factor of 1.886. In this manner, a comparative equivalence can be made with the power feed of the conventional incinerator above and results are summarised in Table 3. The cumulative plasma power input becomes thus 1.6 x 1.886 = 3 MW/t of waste feed or 0.41 MW/t if we use the lower 0.22 specific consumption referenced above. C = 0.886 Waste = 1. Incinerator 1.36 Plasma 1.886 mass ratios

Table 3: Comparison in MWh (1 t/h waste incineration @ 3500 kcal/kg yields 1 MWh)
Incinerator Plasma only 1. Conventional incinerator 2. Plasma on waste as such (max) 3. 4. Conventional incinerator 5. Plasma on waste as such (max) 6. 7. Plasma on flue gas 8. (min) (max) (min) (min) 1. 2.96 1. 1. -1.6 -0.22 -3. -0.41 Plasma -3. -0.41 20% Total +1. -1.28 -0.18 +2.96 -2.4 -0.33 -1.4 0.67 +LHV 0 n.a. n.a. 0 11. 11. 11. 11. 0.32 0.04 0.6 0.08 0.6 0.08 Grand Total +1. -1.28 -0.18 +2.96 +8.6 +10.67 +9.6 +11.67 on Waste on Gas Recovery

For lines 1, 2 and 3 above, the feed is 1 t/h of waste. For lines 4, 5, and 6 the feed is increased by the waste carbon source (as if plastic were processed together with the waste).

4 5

Indicative data from reference plants of Von Roll Environmental, Zrich, 2003. Divulgative material for plants made by Hitachi Metals, Japan, 2001.

Approach of Waste to H2 and CO in a Plasma Reactor

111

Carbon equivalent addition is 7800/3500(.88) = 1.96. For lines 7 and 8 the feed is increased by the waste carbon source and plasma treated with the gases originated by the incinerator. Associated to the table above, we have the potential use or the heating value of the gases that we generate: 3CO and H2. From the scheme of cumulative conversions calculated in our previous paragraph, we derived a LHV syngas content of 303 kW for every two kg-moles of C feed, or 303 / 24 = 12.6 kW/kg, for 0.88 t/h of carbon feed, we get a LHV of 11 MW/t. At lines 2 and 3 a small portion of CO2 is converted to CO and H2 (Wen and Jiang, 2001: p. 666), but for our comparison the exact quantity (n.a.) is only marginal and it is not shown.

8.5

Promising Means to Develop a Combined Plant

In this chapter we did not try to couple in details an existing technology, like an incinerator, and a plasma reactor to accomplish the dry reforming of a carbonaceous source. The purpose was still speculative, to start gaining an appreciation of where things are feasible and where inconsistencies need to be addressed in a specific analysis. We discussed the feasibility to burn substances by supplying oxygen already used up in a stable molecule (CO2 or H2O). We can also supply the necessary organic or plastics waste. CO2 is produced everywhere and dumped to the atmosphere. Residue Derived Fuels (rich of carbon) are also produced in large quantities and hardly reutilised. Practically, we can state that we have abundant and cheap feedstocks to process safely. The energy balance, unfavourable in general terms, becomes favourable when we bench mark it to usable energy/products obtained from a waste or even harmful inputs. Specific sections of the process that is being integrated here have been demonstrated or have current applications. We discussed about carbon dioxide absorption at low pressure, which appeared to be viable, and it appears that the direct destruction of waste in a plasma reactor are claimed by various firms (Fnfshilling, 1993: pp. 89-100). These facts are encouraging reasons to initiate a specific research project and match the various aspects of a process scheme. We have shown that based on the preliminary consumption of a plasma plant the ultimate usable efficiency for the overall model reaction can reach beyond 50%. Results can be sustained or helped when the source of carbon is a no cost waste material and its energy input can be regarded as a free add on. Concluding our considerations, the process that we propose, shown in Figure 2, exhibits chemical processing potential and allows to see things from a new perspective if we want to get rid of waste, of CO2 and of unusable plastics or organic materials.

112

Chapter 8

Figure 2: Block diagram of the conventional incineration plus the added section that concentrates and converts CO2 to syngas.
kW

T u rb in e

C le a n F . G .
S team
dust HCl HF H2S SO 2

B oiler

S tac k

W a s te
C O N V E N T IO N A L P L AN T

C o n ve n tio n a l In c in e r a tio n

FG

C o n ve n tio n a l F .G .T .

R eh eat

C le a n
P artial reh eat, if an y Z ero S O 2
E tO H m ak e-u p

C O 2 + re s id u al S O 2

H 2O

AD D - O N P L AN T

CO2 A b s o r p tio n

CO2 S tr ip p in g
S team

- S O 2, w a s h & n e u tr a l is a tio n

kW Ar C
P la s m a C o n v e rt e r

CO2

B oiler

T u rb in e

H 2O

kW

u se a )

Fuel U se
CO

CO + H2

u se b )

C o m p re s s io n

PSA

H2

R e fe r e n c e : M u n ic ip a l W a s te = 2 0 .8 t/h C O 2 in F G = 1 0 '0 0 0 N m 3 /h C f e e d = 1 0 .7 t/h

F lu e G a s = 1 0 0 '0 0 0 N m 3 /h C O 2 = 1 9 .6 t/h C O ( g ) = 3 7 .5 t/h H 2 (g ) = 0 .9 t/h

Approach of Waste to H2 and CO in a Plasma Reactor

113

8.6

References

Fox C., et al., 2001. In situ Plasma Remediation of Contaminated Soils. Remediation Journal, Vol. 11, Issue 4, Autumn. Fnfschilling M., et al., 1993. Test Results with the Plasma Centrifugal Furnace at Muttenz, Switzerland. Vol. 37, (Bologna: Societ Italiana di Fisica, Plasma Technologies for Hazardous Waste Destruction Conference Proceedings), ISBN 88-7794-052-2. Hairston D., 2002. Pyrolysis gets All Fired up. Chemical Engineering, No. 3. IRER, 2002, February. Leliminazione dei rifiuti mediante termodistruzione: effetti globali sullambiente. Final Report, (Milano: IRER). Iwata M. and M. Shibuya, 1998. Effects of Arc Current and Electrode Size on Electrode Erosion in AC Plasma Torches. Electrical Engineering in Japan, Vol. 124, N.4. Langes Handbook of Chemistry, 1979. 12th ed. (New York: Wiley). Lemann M., 1992. Abfalltechnik. (Dbendorf, CH: Dorema Texteam Verlag). Meneghini D., 1966. Chimica Applicata e Industriale. (Milano: Casa Editrice Vallardi). Natta G. and I. Pasquon, 1966. Principi della Chimica Industriale. Vol. I. (Milano: Tamburini). Pfender E., 1999. Thermal Plasma Technology: Where Do We Stand and Where Are We Going? Plasma Chemistry & Plasma Processing, Vol.19, N. 1. Retech, Inc., 1992, Plasma Centrifugal Furnace. Applications Analysis Report, U.S. Environmental Protection Agency, (Cincinnati, OH: June) EPA/540/A5-91/007. Rostrup J., Nielsen, 1975. Steam Reforming Catalysts. (Copenhagen: Teknisk Forlag A/S). Tellini M., P. Cntola, R. Del Rosso and P. Gronchi, 2004, May. Hydrogen from Waste. Chemical Engineering Transactions, Vol. 4, (Pisa, Italy: AIDIC Hydrogen Conference Proceedings), ISBN 88-900775-3-0. Wen Y., Jiang X., 2001, December. Decomposition of CO2 Using Pulsed Corona Discharges Combined with Catalyst. Plasma Chemistry and Plasma Processing, Vol. 21, N.4.

..

THERMOCHEMISTRY AND TEST PREPARATORY CALCULATIONS

Based on the considerations and studies of the previous chapters, we have come to the planning of the experimental work. The source of CO2 from flue gas will not be tested since a regenerable amine pilot plant is not in the scope of this research, but the experimental work will test the conversion and dry reforming of the organic source of carbon in a plasma reactor. The chosen waste organic source will be automobile shredder material.

9.1

Introduction

Shredded material derived (ASR) from automobile demolition/recycling has a good quantity of organics, the carbon content can exceed 50% on a weight basis. This suggests that fluff can be a valuable source of energy, or chemicals, if it is looked at as a possible feedstock to make syngas. The plasma reactor product gas after treatment, i.e. quenching, scrubbing and dust cleaning can be used as clean syngas fuel or feedstock to downstream chemical processes. The electric energy demand of the plasma process is reduced by consuming part of the fluff feed in an oxygen starved combustion, achieve a quasi auto-thermal process and still allow CO and H2 generation. Starting from fluff, hydrogen production is enhanced by steam reforming and carbon conversion to CO with minimal formation of carbon black and consumption of the plasma electrodes are accounted. A promising feasibility is also the fluff carbon portion conversion by dry reforming, by means of CO2 fed to the reactor. Due to the power optimization requirements, oxygen is used to make the process quasi autothermal and the cracking of the organic source with O2 is difficult to control: starving O2 brings to elementary carbon deposition and high O2 implies fast kinetics, CO2 formation and overheating. In such a context, the high temperature thermodynamic comparison of ternary equilibrium systems C-CO2-O2 and C-H2O-O2, where C stands for any organic source, is less energy intensive for steam reforming and it is yet feasible and controllable when CO2 is used alone or in combination with water. When choosing from different sources of spent or reacted oxygen, dry reforming exhibits higher HR than steam reforming. For methane reforming, for instance, both reactions are endothermic, HR = 49 kcal/mol and HR = 59 kcal/mol for H2O and CO2 respectively. The use of water brings three substantial advantages. The first advantage is that hydrogen is supplied and this is important when low hydrogen feedstocks are used and hydrogen is the ultimate product. The second advantage is that a water excess is introduced. This acts as a beneficial operating tool to control and stabilize the temperature due to the water thermal capacity and through the parallel reactions of water-gas shift (moderately exothermic) and steam reforming (endothermic). The third advantage is that the formation of carbon soot is limited, or easier to control: the CO concentration of the shift reaction limits the parallel Boudouard carbon equilibrium.

116

Chapter 9

9.2

Fluff, the Feedstock of the Process

Fluff or ASR quantity, type and concerns were already discussed under Chapter 2 and the summary table is repeated here for ease of discussion. Table 1 below gives main indicative constituents for ASR, with data that are taken from referenced sources: Development Bank of Japan, 2003: p. 32, Phillips, 1996, WWF, 2000: pp. 3-8 and ANPA, 2002: pp. 33-35, 45. Table 1: Fluff average constituents (wt-%) Data source: D. Bank Phillips of Japan classified as V = old cars % and N = new cars % Glass and Inert 16.1 7 Wood 3 Paper 2 Fabric 17.1 15 Plastics to include 50 PP PE PVC ABS PU PA Resin 39.3 Rubber 8.7 6 Aluminium 5.1 5 Copper 4.4 4 Iron 8.0 8 Lead 0.2 Zinc & related materials 1.1 Total 100.0 100

WWF
(op. cit. pp. 3-8)

ANPA

(op. cit. pp. 33-35, 45)

44V 25N

38V 60N 10V 25N 1.5V 4.5N 10V 3.5N 5V 8N 5.5V 7.5N 1V 5N 15V 10N 1.5V 3N 1.5V 3N 1.52

0.14 0.50 0.84 24.90 13.86

22. 1.89 2.50

Because of the difficulty to make calculations on heterogeneous and variable solid mixtures, a set of simulating constituents were chosen, with the evident advantage of referring to something repetitive, best if significantly close to the possible real cases.

9.3

Thermochemical Evaluation

A series of preparatory calculations were performed to evaluate high temperature syngas formation, starting from model constituents reacting with oxygen, water and carbon dioxide or a combination thereof. The model constituents (organics) were chosen among a variety of reacting materials commonly reported in the fluff: polystyrene, polyethylene, polypropylene, PVC, polycarbonates, rubber, polyurethanes.

Thermochemistry and Test Preparatory Calculations

117

Materials that do not react in the plasma reactor gasifier to produce syngas, or materials that exit as glass, metals, silica and inert, were not modelled. The four selected constituents relative mix was then adjusted to approach the elemental composition actually analysed in the shredded, mixed, homogenized fluff sample. Simulated compositions of PVC, PE, rubber, polystyrene and mix are shown in Table 2. Table 2: Elemental Composition used for simulation (wt-%) Simulant and Fluff PVC PE Isoprene rubber Polystyrene Analysed Fluff sample Mix @ 25% for each type** Mix @ % Factor**
&&

C 38.00 85.00 78.80 92.20 54.40 51.45 59.38

H 5.90 15.00 10.70 7.80 6.48 6.90 6.46

Cl 56.10

10.50

% Factor 5 9 30 56 100

1.97 9.82 1.96

3.40&& 1.84 2.21

2.01

determined as total sulphur

** factored for the 30% sample inert content allowance

Calculations were meant to provide preliminary operating ranges and compositions for the tests. Model reactions of the type described in Table 3 were considered at 1300 and 1100C, but ultimately the 1100C case was dropped. Only thermodynamic data at 1300C were considered since this is the core reactor temperature experimented in the pilot plant later. Table 3: Typical model reactions for Hi (Stoichiometry not shown) Set 1 Case/Index i=1 i=2 i=3 i=4 i=5 i=6 i=7 CxHy + zS + tiO2 = CO + zH2S + H2 CxHy + zS + tiO2 + riH2O = CO + zH2S + H2 CxHy + zS + tiO2 + riH2O = CO + zH2S + H2 CxHy + zS + tiO2 + siCO2 = CO + zH2S + H2 CxHy + zS + tiO2 + siCO2 + riH2O = CO + zH2S + H2 CxHy + zS + tiO2 + siCO2 + riH2O = CO + zH2S + H2 CxHy + zS + tiO2 + siCO2 + riH2O = CO + zH2S + H2

Each set of model reactions was studied to allow an intrinsic heat and material balance and the overall result was then factored to match the ultimate feed composition of the fluff sample. Assumptions for the calculations were that all gas-phase molecules behave ideally, pressure is practically atmospheric or slightly negative and plasma kinetics are non influential since temperatures are well above the minimum equilibrium temperatures that minimise Gibbs free energy. The decision to limit the number of sample constituents to the selected four sets was therefore justified, although a more realistic modelling would involve hundreds of species.

118

Chapter 9

Our purpose was to run the reactions near auto-thermal conditions, to furnish as much energy as possible by means of auto-combustion with pure oxygen (partial oxidation to CO) and so avoiding high consumptions of electric power. For this reason, the great variety of CO2 or H2O combinatory feeds was also limited and reactions of extremely endothermic stoichiometry were simply ignored. Given a fixed electric power input, the quantity of O2 starved combustion was calculated for various feed input of H2O and CO2. On such a basis, molar balances and gas compositions were calculated. In spite of narrowing the spectrum of reagent feeds, enough data were collected to obtain a relative appreciation of the specific weight energy input versus the energy derived from the syngas generated for given O2 amounts to sustain the endothermic reactions. The initial energy input was practically the heat of reaction, whereas the syngas output energy is made up with the specific enthalpy that can be derived from 1 gram of CO and H2, i.e. 2.4 kcal/g and 29.7 kcal/g respectively. The conspicuous extent of calculations was resolved by running each model reaction through a thermochemical simulator, the HSC program that utilises data taken from JANAF Thermochemical Tables (Chase, 1985 plus previous editions and Roine, 1999). Qr and specific quantities were registered in a spreadsheet for the additional numerical elaboration that followed in order to table results and make diagrams. The exact species (speaking of polymers like PVC, PE ) were not available in the simulator data bank, so constituents were assimilated to a similar sub-structure polymer to make calculations easy. The simplification was however checked: PVC, for instance, assimilated to a vinyl trimer of -CH=CHCl gives an error < 0.8% on hydrogen that already vanishes with the vinyl pentamer. Polyethylene, to take another case, assimilated to a C20 paraffin, gives no appreciable error. The data-base similitude constituents are identified in the tables of Appendix 9.1 to this Chapter with the graphs of all runs for all sets. The case of rubber was integrated with 0.25 mol of reticulating sulphur, although this addition did not significantly change the ultimate effect (gas or heat) of the simulation. To shorten our discussion here, we refer to the Appendix 9.1 and we present 4 diagrams below for one of the constituents, Polyvinylchloride, and for the combined mix of all four simulated species. The abscissa number identifies the reaction considered for the set. As initially expected, the energy associated to syngas (HV/gram) is always greater than the required energy input (Q/gram), Figure 1 and Figure 3, while quantities of CO and H2 are clearly dependent on operating parameters (CO2/C and H2O/C), i.e. the degree of dry or steam reforming, Figure 2 and Figure 4.

Thermochemistry and Test Preparatory Calculations

119

Figure 1: Syngas from PVC: Energy from different O2 supplier

Syngas from PVC

200 175 150 125 100 75 50 25 0 1 2 3 4 5 6 7 PVC Reactions 5.00 4.00 3.00 2.00 1.00 0.00 -1.00 Syngas Grams

CO gr kCal/g H2 gr HV/gr-syn Q/gr

Figure 2: Syngas from PVC: Feed (O2, H2O, CO2) and H2/CO ratios

Syngas from PVC

0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 PVC Reactions 1.40 1.20 1.00 0.80 0.60 0.40 Gas in: wt-ratio Gas out: molar ratio O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

Figure 3: Syngas from Mix: Energy from different O2 supplier

Syngas from Mix

350 Syngas Grams 250 150 50 -50 1 2 3 4 5 6 Mix Reactions 7 4.90 2.90 0.90 -1.10 kCal/g CO gr H2 gr HV/gr-syn Q/gr

120

Chapter 9

Figure 4: Syngas from Mix: Feed (O2, H2O, CO2) and H2/CO ratios

Syngas from Mix

0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 Mix Reactions 1.40 Gas out: molar ratio 1.20 1.00 0.80 0.60 0.40 0.20

Gas in: wt-ratio

O/C wt-ratio

CO2/C wt-ratio

H2O/C wt-ratio

H2/CO molar

The idea of using a triangular base three-dimensional graph was long but uselessly pursued in order to present specific weight energy surfaces (process input and syngas output) to compare the demand and possible gain of reactions directly from the reactants coordinates located on the triangular base. In this manner each point of the base triangle would be a mix and the O2 vertex would represent pure combustion, the CO2 vertex would signify dry reforming and the H2O vertex stand for steam reforming. Trials were made in many ways and with AutocadTM but suitable software capable of running threedimensional triangular based diagrams do not exist commercially, and became too laborious to generate a vectorial one similar to the trial drawing prepared and shown on the right side of Figure 5 below. Figure 5: Syngas versus feed energy on a triangular diagram for O2 supply

Thermochemistry and Test Preparatory Calculations

121

Ultimately, it was decided to make orthogonal the triangular base plot. While the ordinate remains indicative of energy variables, the 90 base axes became X=CO2/(O2+H2O), direction of dry reforming, and Y=H2O/(O2+H2O), direction of steam reforming. In such a way, the energy surface diagrams were made plottable, although graphs turned out to be hardly useful and legible, as it can be seen from the graph for PVC and PE specific weight energy reported in Figure 6 below, having the transformed coordinates given in Table 4. Figure 6: Energy of syngas from PVC and PE, orthogonal plot
kcal/g 12 10 8 6 4 2 0 -2 DQ/g-PVC HV-PVC/g-syngas HV-PVC/g-PVC DQ/g-PE HV-PE/g-syngas HV-PE/g-PE

0.6 0.7 0.4 0.5 0.1 0.2 0.3 0.4 0.2 0.3 0.5 0.6 0.7 0.8 0.90 0.1 Y = H2O/(O2+H2O) X = CO2/(O2+H2O)

Table 4: Heating values shown on the orthogonal plot X PVC 0 0.000 0.000 0.400 0.400 0.400 0.400 0.000 0.000 0.000 0.857 0.857 0.500 0.667 Y 0 0.333 0.667 0.000 0.600 0.200 0.360 0.000 0.400 0.600 0.000 0.143 0.250 0.100 Q/gsubstance 0.776 0.309 -0.323 0.588 -0.360 0.272 0.019 1.488 -0.207 -1.055 0.067 -0.357 -0.307 -0.014 HV/gsyngas 3.643 4.226 4.784 3.472 4.226 3.728 3.930 4.311 4.973 5.291 3.893 4.027 4.297 4.054 HV/gsubstance 3.386 4.018 4.649 3.739 4.687 4.055 4.308 9.194 10.889 11.737 10.618 11.041 10.991 10.698

PE

122

Chapter 9

9.4

Heat Losses and Sensible Heat Compensation

Prior to calculating the operating ranges of experimental feed rates, it is necessary to account for two important energy dissipation sources: the heat losses of the pilot plant, that given topology, heavy instrumentation, nozzles, penetrations and limited insulation make it inevitably greater than any industrial plant would have, but also the sensible heat to supply for bringing reactants to 1300C. Supported by earlier experimentation, we derived an empirical correlation for thermal losses in relation to the size of the plant: ln(kW) = ln(#/h feed)/(1.23 + (#/h feed)/164000) with the feed in lbs/h Another way to look at thermal losses is to account them between 10 and 30% of the sensible heat given to the reacting inlet material, which for the geometry and conditions of our hot reactor can be estimated by natural convection air dissipation in Table 5 which is based on a basic calculation procedure of Roine, op. cit. given in their chapter 10.1: Table 5: Estimate of heat losses Heat loss = (6.8 + 0.046 * T2) * (T2 - T1) * A 2677 3.1 8.74 kcal/h kW use 8 60 25

A = m2 reactor surface, say 1 m diam, L = < 2.m T2 = surface outer temperature of reactor C T1 = room temperature C

The same loss for processing about 20 #/h comes to 0.3 kcal/gram feed, or as a percent of sensible heat supplied to the feed (PE max Qsens case) as a percent of sensible heat supplied to the feed (PVC min Qsens case)

7.6% 26.8%

Heat losses are essentially tied to geometry and lagging. When feeding material with low heat of reaction, since the adiabatic temperature is kept at 1300, more sensible heat is to be supplied and the loss becomes more significant in relation to the quantity of feed or heat loss referred to inlet substance. The sensible heat to furnish to the gas is eventually recoverable, in a boiler or in a gas pre-heater, for instance, but we need to determine the heat input here to make the reactions happen. The heat can either come from electric power, which is normally more expensive and limited in the specific case of a pilot plant operation or chemical energy from the combustion of a portion of the feed. This latter method is typical of auto-thermal processes and we shall study it by limiting the combustion of the organic material to CO (partial oxidation), the heat evolved will thus be lower than burning to CO2, but the ultimate constituent is already the product gas. An abstract from Appendix 9.2 is presented here for PVC only: the sensible heat deficiency can be covered by adiabatic partial oxidation (reaction 1 of each set of reactions) of the substance; therefore, the quantity that needs to be fed to the reactor is increased according to its heat generating capability. Figures are referred to grams of simulating substance, since a molar base would be misleading when the real

Thermochemistry and Test Preparatory Calculations

123

species or mix are considered. The first reaction is the substance oxidation exothermic reaction and needs no modifications. Calculations refer to the exact reactions already written for each simulated set and the sensible heats were derived with Cp taken from thermochemical tables. We deducted the heat of reaction from the products total heat and introduced a quantity of disposable extra feed for supplying the unbalance of heat via partial oxidation. The results show that even more than twice the original reacted quantity may be needed, Table 6. Table 6: P.Ox. extra requirement of PVC for sensible heat and losses
B = A - Q Sensible heat to supply to feed (if>0) A= B/g = heat Extra Sensible heat deficiency for gr-feed for of products at gram of 100% Q, effect of 1300 substance reaction 1 Total substance feed

Q reaction

PVC
(simulated via HSC 111TCH g) Mol. Wt.

189.512

Cases 1 2 3 4 5 6 7

kCal/g-mol 147.000 58.553 -61.209 111.383 -68.260 51.502 3.597

kCal/g-mol -11.771 96.551 236.187 34.594 244.049 104.413 160.268

kCal/g-mol kCal/g-feed 135.229 n.a. 155.104 -0.509 174.978 -1.246 145.977 -0.183 175.789 -1.288 155.915 -0.551 163.865 -0.846

0.657 1.607 0.235 1.660 0.710 1.090

g 1.000 1.657 2.607 1.235 2.660 1.710 2.090

The plasma reactor receives also a DC power input (14 kW max) which deducted by estimated losses yields a net input of +6 kW. This energy amount is the maximum capability that was exploited for running the tests with the average feed rate of 6 kg/h fluff. The same cases described above were therefore calculated and are presented under Appendix 9.3: for some reactions, it is quite evident that the power input still requires substance to be consumed by partial oxidation in order to reach the equilibrium temperature, Table 7. Table 7: P.Ox. extra requirement of PVC for sensible heat and losses less DC power
B = A - Q Sensible heat to supply to feed (if>0) (B-DC)/g = heat deficit Extra A= Sensible heat every gram of gr-feed for 100% Q, effect of of products at substance reaction 1 1300

Q reaction

Total substance feed

PVC
(simulated via HSC 111TCH g) Mol. Wt.

189.512

Cases 1 2 3 4 5 6 7

kCal/g-mol 147.000 58.553 -61.209 111.383 -68.260 51.502 3.597

kCal/g-mol -11.771 96.551 236.187 34.594 244.049 104.413 160.268

kCal/g-mol kCal/g-feed 135.229 n.a. 155.104 0.351 174.978 -0.386 145.977 0.677 175.789 -0.428 155.915 0.309 163.865 0.014

0.498 0.551

g 1.000 1.000 1.498 1.000 1.551 1.000 1.000

The calculation of CO, H2 quantities or operating ratios resulting from the thermochemical analysis is straightforward and simple but very laborious, so we ran the

124

Chapter 9

model reactions with the same method already described and the stoichiometry for each case was fed to the Heat and Material Balance subroutine of the HSC program. Quantities are referred to kmol and kg as compared to the tables that were previously used. The desired base reaction was entered as per the previous analysis and an add-on partial oxidation reaction of the same species was separately superimposed to evidence the material quantity required for reaching auto-thermal conditions with gases exiting the reactor at the ultimate adiabatic temperature of 1300. Thermal losses were set to 8 kW = 6,880 kcal/h. The electric power input was constrained to 14 kW DC. It will also be seen that the pilot plant accepts AC power, but we can consider that the principal purpose of alternate current is to maintain warm the reactor and the molten glass bath by joule effect. Although the pilot plant consumption of graphite electrodes is limited to about half a kg/h, such input has been considered for its partial oxidation contribution: 2CO. The contribution is not marginal, for the case of simulated PVC the 2C + O2 graphite corresponds to about 0.5 kmoles of substance. Correspondence between substance to be oxidised and input DC power is also possible: for instance, 1.8 kmol of simulated PVC correspond to a power input of 14 kW. Considerations and checks of this type validated the figures calculated with the two methods and enable sufficient confidence for establishing the operating ranges of the experiments. Under Appendix 9.4 calculations for each simulation case are presented for reactions 2 through 7. The Appendix is introduced with two summary tables that enable to trace how operating variables affect H2 and CO generation in respect of extra partial oxidation material and graphite electrodes that are being consumed. Graphs of the same type already presented above are copied below and give an appreciation on how the new conditions make the parameters move. The new CO and H2 productions, both for simulated PVC (Figure 7 and Figure 8) and for the mix (Figure 9 and Figure 10) are greater, the reactants to carbon (O/C, CO2/C and H2O/C) increase three to five folds and the H2/CO molar ratio remains practically unchanged. An interesting consideration is also to ascertain the extent of chemical energy input (via partial oxidation of some of the organic feedstock) compared to the DC power supplied to the system. The exercise has been calculated in steps, moving from the first approximation model reactions and mix of Appendix 9.1 to the more accurate predictions of Appendix 9.4, calculations that take into consideration heat dissipation, electrodes, DC power and sensible heat. The table that compares initial base values with the revised calculation exhibits that the O/C ratio creeps to 0.8, four to five times higher, having introduced more CO2 (CO2/C about 3 times more) and more H2O (H2O/C about 5 to 6 times more). The net DC power input, estimated to be 6 kW for a 6 kg/h feed, equals to 0.860 kcal/g-substance and is smaller by a factor of 2.4 when compared to 2.132 kcal/g, generated by the POx heat of reaction. If the 0.2 O/C factor calculated with the base case is applied as POx and we downrate it for the 83% carbon content of the mix that we simulated, we conclude that our modeling is for an operation in which the POx energy contribution is (2.132)(0.166):0.86 = 0.41 or say 40% of the DC useful input.

Thermochemistry and Test Preparatory Calculations

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Figure 7: Syngas from PVC: energy from different O2 supply with kW, P.Ox. & losses

Syngas from PVC with kW, P. Ox., Losses & Electrodes

250 225 200 175 150 125 100 75 50 25 0 1 2 3 4 5 6 7 PVC Reactions 5.00 4.00 3.00 2.00 1.00 0.00 -1.00 kCal/g CO gr H2 gr HV/gr-syn Q/gr

Figure 8: PVC Syngas: Feed (O2, H2O, CO2) and H2/CO ratios w/ kW, P.Ox & losses

Syngas Grams

Syngas from PVC with kW, P. Ox., Losses & Electrodes

1.20 Gas in: wt-ratio Gas out: molar ratio 1.00 0.80 0.60 0.40 0.20 0.00 1 2 3 4 5 6 7 PVC Reactions 0.60 0.40 1.20 1.00 0.80 O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

126

Chapter 9

Figure 9: Syngas from Mix: Energy from different O2 supply w/ kW, P.Ox. & losses

Syngas from Mix with kW, P. Ox., Losses & Electrodes

500 450 400 Syngas Grams 350 300 250 200 150 100 50 0 1 2 3 4 5 6 7 Mix Reactions 4.90 4.40 3.90 3.40 2.90 2.40 1.90 1.40 0.90 0.40 -0.10 -0.60 -1.10

CO gr kCal/g H2 gr HV/gr-syn Q/gr

Figure 10: Mix syngas, (O2, H2O, CO2) feed and H2/CO ratios w/ kW, P.Ox. & losses

Syngas from Mix with kW, P. Ox., Losses & Electrodes

1.30 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 Mix Reactions 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40

Gas out: molar ratio

Gas in: wt-ratio

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

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9.5

The Issue of Carbon Black

The last, yet important, issue to be addressed before setting the operating ranges of the experiments was to find the limitations that minimise or exclude the formation of carbon black. From the preliminary thermochemical aspect of reforming given under Chapter 7, and the heat/products calculations of Appendix 9.2, we observed that when the heat supplied as electric power or as quantity burned to furnish chemical energy exceed the thermodynamic equilibrium limit, the adiabatic temperature exceeds 1300C and reactions go to the right. On the contrary, if the temperature remains too low, parallel and counter-reactions become more influential and we can expect a considerable portion of unconverted C, noticeable as carbon soot or carbon black. Simultaneous competing reactions are certainly numerous and the variety of the feedstock can expand them to hundreds or even thousands when hydrocarbon precursors and intermediates are considered, as it could be simulated with the thermodynamic model available at the Politecnico di Milano (Dente, Ranzi et al., 2002: pp. 919-927; Ranzi et al., 2001: pp. 99139). For the purposes of our discussion, we considered few reactions, which can be added together to make a cumulative reaction, and the parallel shift reaction under the hypothesis of reaching thermodynamic equilibrium. Kp constants were written for an arbitrary advancement producing methane or gaseous carbon constituents. Kps calculated by means of thermochemical data were tabled against temperature and the Kp would enable to calculate a limiting advancement x. Based on the advancement, we could predict the trend and the value of non-reacted carbon. In reality, things proved not so accurate, because the calculated thermodynamic equilibrium (G=0) of reactions do not necessarily converge to the same temperature and the analysis could only determine a temperature range, around 725C, at which Kp is read and the x is calculated, Figure 11. Table 8 and the diagrams below are extracted from Appendix 9.5 where the cumulative carbon reaction and the shift reaction are considered in terms of x, the mole advancement of methane formation. Table 8: Cumulative reaction advancement and water gas shift

128

Chapter 9

Figure 11: Kp(T) of representative and water shift reactions

Kp(T)

5 4.5 4 3.5
A

3
Kp

2.5 2 1.5 1 0.5 0

Shift

Cumul.

T C

Figure 12: Carbon conversion referred to temperature and carbon ratios with Kp(x,T)

Shift vs. Cumulative Carbon Reaction

1.40 1.30 1.20
CO/(CO+CO2) and Kp(x,T)

1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 x = CH4
Equil. T C

1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00

CO/(CO+CO2) Kp shift Kp cum T shift T cum Potenza (Kp shift) Potenza (T cum) Poli. (T shift)

Thermochemistry and Test Preparatory Calculations

129

As it is shown in Figure 12, a value of x = 0.54 (corresponding to a CO/(CO + CO2) ratio = 0.7) relates to a unitary Kpshift and a thermodynamic equilibrium temperature around 800C. This means that a higher concentration of x, makes a greater Kp value and the reaction is shifted to the right. Having little CO, the cumulative simultaneous carbon reaction is hindered or moved to the left, thus carbon black formation. The formation or non-reaction of carbon can actually be influenced by having a greater quantity of steam, which again is like saying that CO partial pressure is lowered. Conversely, if x is low, Kpshift is low, we would have a large quantity of CO that does not react with water. This effect on the cumulative carbon reaction is that C is being transformed, thus little carbon black is to be expected. The addition of CO2 for the tests of dry reforming will therefore influence the ratio of CO/(CO + CO2) with the subsequent potential formation of carbon soot. From the theoretical point of view it will prove effective to limit such an operating ratio below 0.7 and test the physical quantity of carbon that forms within a low percent, indicatively, below 5% of the total carbon feed rate (Tellini et al., 2005).

9.6

Testing Objectives and Summary of Test Conditions

The key objectives that were set for the test are to demonstrate the following: consistent, controllable, and reliable feeding of the fluff efficient conversion to syngas possibility of dry reforming within power input capability limitation of carbon black formation ascertain the possibility to recover waste heat in a conventional boiler permissible leach characteristics of the discharged glass. At the end of preparatory calculations, the operating ranges to be tested were set according to the table below: Table 9: Testing operating range Fluff feed rate: Reaction temperature: DC power input to electrodes: H2O/C wt-ratio Max to substance H2O/C wt-ratio CO2/C wt-ratio Max to substance CO2/C wt-ratio O/C wt-ratio Max to substance O/C wt-ratio 6 kg/h > 850C 14 kW 0 0.9 (0.2 central) 0.5 0 1.2 (0.3 central) 0.6 0 1.1 (0.2 central) 0.6

Testing, instrumentation as well as the analytical work had been planned and limited for the purposes above. It is obviously recognised that the quality and the extent of syngas treatment are clearly important, but they had already been widely demonstrated in previous tests on chlorinated organics and similar waste (Quapp et al., 2003).

130

Chapter 9

Routine testing were not taken into specific consideration. Similarly, the dolomite neutralising and coating agent which is preloaded to the bag filter for particles screening affects the composition of the ashes (discharged or recycled to the reactor), but such details were not part of our experimentation and were only considered for reporting results, analyses and making the material balance. Results and discussion of the tests are reported under Chapter 10.

9.7.

References

ANPA, 2002, February. La Caratterizzazione del Fluff di Frantumazione dei Veicoli. Report 15/2002, (Roma: Agenzia Nazionale per la Protezione dellAmbiente). Chase M.W., et al., 1985. JANAF Thermochemical Tables Supplement. J. of Phys. and Chem. plus previous editions. Dente M., E. Ranzi, et al., 2002. Applied Thermal Engineering. No. 22, Issue 8, pp. 919927. Development Bank of Japan, 2003, May. Prospects and Challenges for End-of-Life Vehicle Recycling. Research Report No. 41. Phillips M., 1996, October. Plastic Growth in Auto Steadies. Recycling Today, www.recyclingtoday.com/articles. Quapp W., et al. 2003, May. Waste Gasification - Test Results from Plasma Destruction of Hazardous, Electronic and Medical Wastes-. IT3 2003 Florida Conference. Ranzi E., M. Dente, G. Bozzano, et al., 2001. Lumping Procedures in Detailed Kinetic Modeling of Gasification, Pyrolysis, Partial Oxidation and Combustion of Hydrocarbon Mixtures. Progress in Energy and Combustion Science, 27. Roine A., et al., 1999. HSC Chemistry for Windows version 4.0, Outokumpu Research Oy, Pori, Finland. Tellini M., R. Del Rosso and P. Cntola, 2005, October. Hydrogen from Fluff Destruction in a Plasma Reactor. Chemical Engineering Transactions, Vol. 8, (Palermo, Italy: AIDIC Hydrogen Conference Proceedings), ISBN 88-901915-0-3. WWF, 2000, October. Relazione Tecnica sui Rifiuti derivanti dalla Frantumazione delle Carcasse di Autoveicoli. (Torino: WWF Italia, Piemonte Val dAosta Regional Section).

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131

Chapter 9: APPENDIX 9.1

Thermodynamic simulation of full conversion to syngas at 1300 C
(calculations were made at 1100 and 1300C, results are reported for 1300C only)

The first step of the study is referred to individual sample species, then results are combined for a possible mix of feed constituents. We refer to PVC, Polyethylene, Isoprene (plus 0.25S) and Polystyrene (n1).

Notes to the tables below: n1 Since gas is formed @ high T by destruction of constituents, it is assumed that results are additive, i.e. there is no interaction in the mixture syngas, as if individual species were separately decomposed and syngas added together. Reactions fully to CO and H2. All the oxygen is assumed to come from O2, from CO2 and from H2O, the reagent oxygen fractional sum is = 1 in all case reactions. The heat of reaction is referred to 1 gram of the simulated formula, which is stoichiometrically similar to the feed constituent. Simulation for ease of calculation from available data bank formulas. Higher chain MW does not change order of magnitude. We assumed that all C, even added as CO2, is converted to CO. Some C will actually convert to CO2, depending also on the pure O2 feed. Heating value of syngas referred to unit weight of substance feed (calculated at 2.393 kcal/g for CO and 29.7 kcal/g for H2). Heating value of syngas referred to unit weight of syngas produced (water as non condensed steam). Weight ratios of oxygen reagents versus carbon in the material feed.

n2 n3

n4 n5 n6 n7

First Constituent: PVC (n2) Case 1 C6H11Cl3 + 3O2 = 3HCl + 6CO + 4H2 2 C6H11Cl3 + 2O2 + 2H2O = 3HCl + 6CO + 6H2 3 C6H11Cl3 + O2 + 4H2O = 3HCl + 6CO + 8H2 4 C6H11Cl3 + 2.5O2 + CO2 = 3HCl + 7CO + 4H2 5 C6H11Cl3 + O2 + 3H2O + CO2 = 3HCl + 7CO + 7H2 6 C6H11Cl3 + 2O2 + H2O + CO2 = 3HCl + 7CO + 5H2 7 C6H11Cl3 + 1.6O2 + 1.8H2O + CO2 = 3HCl + 7CO + 5.8H2 8 C6H11Cl3 + 3H2O + 3CO2 = 3HCl + 9CO + 7H2 9 C6H11Cl3 + H2O + 5CO2 = 3HCl + 11CO + 5H2 (n3) H reaction Q reaction Q/gr kcal kcal kcal/gr 147.00 58.55 -61.21 111.38 -68.26 51.50 3.60 -202.12 -188.02 0.776 0.309 -0.323 0.588 -0.360 0.272 0.019 -1.067 -0.992 (n4) CO gr 168.062 168.062 168.062 196.073 196.073 196.073 196.073 252.094 308.114

wt-% within feed C in Cl in H in 0.380 0.562 0.059 unchanged

Syngas mol-% ratio HVsyngas HCl out H2 out CO out H2/CO kcal/gr 0.231 0.308 0.462 0.667 3.643 0.200 0.400 0.400 1.000 4.226 0.176 0.471 0.353 1.334 4.784 0.214 0.286 0.500 0.571 3.472 0.176 0.412 0.412 1.000 4.226 0.200 0.333 0.467 0.713 3.728 0.190 0.367 0.443 0.828 3.930 0.158 0.368 0.474 0.777 3.840 0.158 0.263 0.579 0.454 3.258

At 1300 C

H2 gr 8.063 12.095 16.126 8.063 14.111 10.079 11.692 14.11 10.08

(n5) (n6) Oxygen portion in Wt-ratios in (n7) CO2 H2O O/C CO2/C H2O/C Syngas HV/gr-sub. HV/gr-syn O2 gr kcal/gr kcal/gr
(gas to substance) (syngas prod.)

Case 1 -147.00 2 -58.55 via HSC H2O+O2 3 61.21 111TCH g) O2+CO2 4 -111.38 H2O+O2+CO2 5 68.26 Mol. Wt. O2+H2O+CO2 6 -51.50 189.512 Autothermal 7 -3.60 H2O+CO2 8 202.12 H2O+CO2 9 188.02
+Oxygen mix O2

PVC

(simulated

O2+H2O

176.125 180.157 184.188 204.136 210.184 206.152 207.765 266.205 318.193

3.386 4.018 4.649 3.739 4.687 4.055 4.308 5.395 5.470

3.643 4.226 4.784 3.472 4.226 3.728 3.930 3.840 3.258

1.000 0.667 0.333 0.714 0.286 0.571 0.457

0.286 0.286 0.286 0.286 0.333 0.909

0.444 0.333 0.296 0.667 0.148 0.317 0.429 0.127 0.143 0.254 0.257 0.203 0.667 0.091

0.083 0.167 0.190 0.190 0.190 0.190 0.222 0.606 0.107 0.036 0.064 0.167 0.023

Syngas from PVC

200 175 150 125 100 75 50 25 0 1 2 3 4 5 6 7 PVC Reactions 5.00 4.00 3.00 2.00 1.00 0.00 -1.00 0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 Gas in: wt-ratio Syngas Grams

Syngas from PVC

1.40 1.20 1.00 0.80 0.60 0.40 5 6 7 PVC Reactions Gas out: molar ratio

CO gr H2 gr HV/gr-syn Q/gr

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

kCal/g

132

Chapter 9

Second Constituent: PE (n2) Case 1 C20H42 + 2 C20H42 + 3 C20H42 + 4 C20H42 + 5 C20H42 + 6 C20H42 + 7 C20H42 + 10O2 = 20CO + 21H2 6O2 + 8H2O = 20CO + 29H2 4O2 + 12H2O = 20CO + 33H2 7O2 + 6CO2 = 26CO + 21H2 6O2 + 2H2O + 6CO2 = 26CO + 23H2 6O2 + 4H2O + 4CO2 = 24CO + 25H2 6.75O2 + 1.5H2O + 5CO2 = 25CO + 22.5H2 (n4) CO gr 560.208 560.208 560.208 728.270 728.270 672.250 700.260

wt-% within feed C in H in 0.850 0.150 unchanged

Syngas mol-% ratio HVsyngas H2 out CO out H2/CO kcal/gr 0.512 0.488 1.049 4.311 0.592 0.408 1.451 4.973 0.623 0.377 1.653 5.291 0.447 0.553 0.808 3.893 0.469 0.531 0.883 4.027 0.510 0.490 1.041 4.297 0.474 0.526 0.901 4.054

At 1300 C

(n3) H reaction Q reaction Q/gr kcal kcal kcal/gr 420.51 -58.54 -298.06 18.92 -100.84 -86.74 -3.97 1.488 -0.207 -1.055 0.067 -0.357 -0.307 -0.014

H2 gr 42.332 58.458 66.521 42.332 46.363 50.395 45.356

(n5) (n6) Oxygen portion in Wt-ratios in (n7) Syngas HV/gr-sub. HV/gr-syn O2 CO2 H2O O/C CO2/C H2O/C gr kcal/gr kcal/gr
(gas to substance) (syngas prod.)

Case 1 -420.51 (simulated O2+H2O 2 58.54 via HSC H2O+O2 3 298.06 EIC g) O2+CO2 4 -18.92 H2O+O2+CO2 5 100.84 Mol. Wt. O2+H2O+CO2 6 86.74 7 3.97 282.552 Autothermal
+Oxygen mix O2

PE

602.540 618.666 626.729 770.602 774.633 722.645 745.616

9.194 10.889 11.737 10.618 11.041 10.991 10.698

4.311 4.973 5.291 3.893 4.027 4.297 4.054

1.000 0.600 0.400 0.538 0.462 0.500 0.540

0.462 0.462 0.333 0.400

0.133 0.400 0.080 0.600 0.053 0.072 0.077 0.062 0.167 0.067 0.060 0.072

0.030 0.045 0.092 0.092 0.067 0.080 0.006 0.013 0.005

Syngas from PE
800 700 600 500 400 300 200 100 0 1 2 3 4 5 6 7 PE Reactions 5.00 4.00 kCal/g 3.00 2.00 1.00 0.00 -1.00 Gas in: wt-ratio CO gr H2 gr HV/gr-syn Q/gr 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 1 2 3 4

Syngas from PE
1.70 1.60 1.50 1.40 1.30 1.20 1.10 1.00 0.90 0.80 0.70 5 6 7 PE Reactions

Gas out: molar ratio

Syngas Grams

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

Third Constituent: Isoprene (n2)

wt-% within feed C in S in H in Case 0.788 0.105 0.106 1 C5H8 + 0.25S + 2.5O2 = 5CO + 0.25H2S + 3.75H2 unchanged 2 C5H8 + 0.25S + 1.5O2 + 2H2O = 5CO + 0.25H2S + 5.75H2 3 C5H8 + 0.25S + 0.5O2 + 4H2O = 5CO + 0.25H2S + 7.75H2 4 C5H8 + 0.25S + 1.5O2 + 2CO2 = 7CO + 0.25H2S + 3.75H2 5 C5H8 + 0.25S + 0.75O2 + 1.25CO2 + 2.25H2O = 6.25CO + 0.25H2S + 6H2 6 C5H8 + 0.25S + O2 + 2CO2 + H2O = 7CO + 0.25H2S + 4.75H2 7 C5H8 + 0.25S + 1.3O2 + 2CO2 +0.4H2O = 7CO + 0.25H2S + 4.15H2 (n3) H reaction Q reaction Q/gr kcal kcal kcal/gr 156.98 37.22 -82.54 23.12 -61.42 -36.77 -0.84 2.062 0.489 -1.084 0.304 -0.807 -0.483 -0.011 (n4) CO gr 140.052 140.052 140.052 196.073 175.065 196.073 196.073

Syngas mol-% ratio HVsyngas H2S ou H2 out CO out H2/CO kcal/gr 0.028 0.417 0.556 0.750 3.791 0.023 0.523 0.455 1.149 4.480 0.019 0.596 0.385 1.548 5.133 0.023 0.341 0.636 0.536 3.407 0.020 0.480 0.500 0.960 4.158 0.021 0.396 0.583 0.679 3.664 0.022 0.364 0.614 0.593 3.510

At 1300 C

H2 gr 7.559 11.591 15.622 7.559 12.095 9.575 8.366

(n5) (n6) Oxygen portion in Wt-ratios in Syngas HV/gr-sub. HV/gr-syn O2 CO2 H2O O/C CO2/C H2O/C gr kcal/gr kcal/gr
(gas to substance) (syngas prod.)

Case 1 -156.98 2 -37.22 via HSC H2O+O2 3 82.54 2M13B g O2+CO2 4 -23.12 plus 0.25S) H2O+O2+CO2 5 61.42 Mol. Wt. O2+H2O+CO2 6 36.77 7 0.84 76.133 Autothermal
+Oxygen mix O2

Isoprene

(simulated

O2+H2O

147.611 151.643 155.674 203.632 187.160 205.648 204.439

7.351 8.924 10.496 9.112 10.221 9.898 9.427

3.791 4.480 5.133 3.407 4.158 3.664 3.510

1.000 0.600 0.200 0.429 0.240 0.286 0.371

0.571 0.400 0.571 0.571

0.533 0.400 0.320 0.800 0.107 0.229 0.360 0.128 0.143 0.152 0.057 0.198

0.120 0.240 0.457 0.320 0.457 0.457 0.108 0.043 0.017

Syngas from Rubber

200 175 150 125 100 75 50 25 0 1 2 3 4 5 6 7 Rubber Reactions 4.90 3.90 kCal/g 2.90 1.90 0.90 -0.10 -1.10 Gas in: wt-ratio CO gr H2 gr HV/gr-syn Q/gr 0.60 0.50 0.40 0.30 0.20 0.10 0.00 1 2 3

Syngas from Rubber

1.50 1.30 1.10 0.90 0.70 0.50 4 5 6 7 Rubber Reactions

Gas out: molar ratio

Syngas Grams

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

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Appendix 9.1, cont.d:

Fourth Constituent: Polystyrene (n2) Case 1 C8H8 + 4O2 = 8CO + 4H2 2 C8H8 + 2O2 + 4H2O = 8CO + 8H2 3 C8H8 + O2 + 6H2O = 8CO + 10H2 4 C8H8 + 2O2 + 4CO2 = 12CO + 4H2 5 C8H8 + 2O2 + 2CO2 + 2H2O = 10CO + 6H2 6 C8H8 + 2O2 + 3CO2 + H2O = 11CO + 5H2 7 C8H8 + 2.1O2 + 3CO2 + 0.8H2O = 11CO + 4.8H2 (n3) H reaction Q reaction Q/gr kcal kcal kcal/gr 249.34 9.81 -109.95 -18.39 -4.29 -11.34 0.64 2.394 0.094 -1.056 -0.177 -0.041 -0.109 0.006 (n4) CO gr 224.083 224.083 224.083 336.125 280.104 308.114 308.114 wt-% within feed C in H in 0.922 0.077 unchanged Syngas mol-% ratio HVsyngas H2 out CO out H2/CO kcal/gr 0.333 0.667 0.499 3.341 0.500 0.500 1.000 4.226 0.556 0.444 1.252 4.647 0.250 0.750 0.333 3.033 0.375 0.625 0.600 3.523 0.312 0.688 0.453 3.258 0.304 0.696 0.437 3.224

At 1300 C

H2 gr 8.063 16.126 20.158 8.063 12.095 10.079 9.676

(n5) (n6) Oxygen portion in Wt-ratios in (n7) Syngas HV/gr-sub. HV/gr-syn O2 CO2 H2O O/C CO2/C H2O/C gr kcal/gr kcal/gr
(gas to substance) (syngas prod.)

Case 1 -249.34 2 -9.81 via HSC H2O+O2 3 109.95 STY g) O2+CO2 4 18.39 H2O+O2+CO2 5 4.29 Mol. Wt. O2+H2O+CO2 6 11.34 7 -0.64 104.151 Autothermal
+Oxygen mix O2 (simulated O2+H2O

Polystyrene

232.146 240.209 244.241 344.188 292.199 318.193 317.790

7.448 9.747 10.897 10.022 9.885 9.953 9.839

3.341 4.226 4.647 3.033 3.523 3.258 3.224

1.000 0.500 0.250 0.333 0.400 0.364 0.382

0.667 0.400 0.545 0.545

0.333 0.500 0.167 0.750 0.083 0.111 0.200 0.133 0.091 0.121 0.073 0.127

0.094 0.141 0.333 0.200 0.273 0.273 0.038 0.017 0.014

Syngas from Polystyrene

350 Syngas Grams 300 250 200 150 100 50 0 1 2 3 4 5 6 7 Polystyrene Reactions 4.90 3.90 kCal/g 2.90 1.90 0.90 -0.10 -1.10 Gas in: wt-ratio CO gr H2 gr HV/gr-syn Q/gr

Syngas from Polystyrene

1.20 1.00 0.80 0.60 0.40 0.20 1 2 3 4 5 6 7 Polystyrene Reactions

Gas out: molar ratio

0.40 0.30 0.20 0.10 0.00

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

The figure that follows in the next page represents the starting base case, calculated for the reactions (1 through 7) of each constituent. The identified boxes for the pro-rated mix composition have the following meaning: A (specific HV of syngas), B (specific heat of reaction), and C (O/C wt-ratio). Specific values are referred to 1 gram of substance since we used simulated species (moles may not correspond) and it is useful to refer to units of carbon feed. While the energy of the products is comprehensively characterized by the specific heating value of the syngas (3.2 to 4.9 kcal/gram-syngas), the heats of reaction for the mix depend on the constituents and are kept low (negative to +0.2 kcal/g) near the autothermal level, by consuming substance and burning O2 to CO. By looking at the O/C ratios, we estimated an appreciable consumption of oxygen (O/C = 0.1 to 0.2 or 10 to 20 wt-% of the organic carbon source). This consumption relates to the partial oxidation of the substance since we attribute all H2O and CO2 transformation to CO and H2. Given this amount of partial oxidation we can observe that the smaller amount of POx is required when no CO2 is fed. At combined or apportioned feed of CO2 and H2O, POx is always needed to sustain the endothermic reactions. CO grams were between 226 and 323, H2 was between 11 and 23 grams, starting from the organic carbon feed mix of 97 grams.

134

Chapter 9

We now take the mix that was suggested from the chemical analysis of fluff & maintain the same model reactions pro-quota for each constituent: Basecase: elaboration from reactions 1 through 7, carbon downrating for inerts is not applied yet. PVC 5% H2/CO 1 2 3 4 5 6 7 H2O/C 1 2 3 4 5 6 7 CO2/C 1 2 3 4 5 6 7 O/C 1 2 3 4 5 6 7 0.0222 0.0148 0.0074 0.0159 0.0063 0.0127 0.0102 0.0120 0.0072 0.0048 0.0065 0.0055 0.0060 0.0065 0.1600 0.0960 0.0320 0.0686 0.0384 0.0457 0.0594 0.1867 0.0933 0.0467 0.0622 0.0747 0.0679 0.0713 0.3809 0.2113 0.0909 0.1531 0.1250 0.1323 0.1473 0.0000 0.0000 0.0000 0.0095 0.0095 0.0095 0.0095 0.0000 0.0000 0.0000 0.0083 0.0083 0.0060 0.0072 0.0000 0.0000 0.0000 0.1371 0.0960 0.1371 0.1371 0.0000 0.0000 0.0000 0.1867 0.1120 0.1527 0.1527 0.0000 0.0000 0.0000 0.3416 0.2258 0.3054 0.3066 0.0000 0.0042 0.0083 0.0000 0.0054 0.0018 0.0032 0.0000 0.0027 0.0041 0.0000 0.0005 0.0011 0.0004 0.0000 0.0360 0.0720 0.0000 0.0324 0.0129 0.0051 0.0000 0.0525 0.0788 0.0000 0.0210 0.0095 0.0076 0.0000 0.0954 0.1631 0.0000 0.0593 0.0253 0.0164 0.40 0.0333 0.0500 0.0667 0.0286 0.0500 0.0357 0.0414 0.0944 0.1306 0.1487 0.0727 0.0795 0.0937 0.0811 0.2250 0.3448 0.4644 0.1608 0.2880 0.2038 0.1779 0.2796 0.5600 0.7013 0.1867 0.3360 0.2540 0.2446 0.6323 1.0854 1.3811 0.4488 0.7535 0.5871 0.5450 PE 9% ISO 30% STY 56% Mix (sum) 100% -wt

Syngas from Mix

1.40 1.30 1.20 1.00 0.90 0.20 0.80 0.70 0.60 0.10 0.50 0.40 0.30 0.00 1 2 3 4 5 6 7 Mix Reactions 0.20 Gas out: molar ratio 1.10 Gas in: wt-ratio 0.30

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

Box C

PVC 5% grams CO 1 2 3 4 5 6 7 grams H2 1 2 3 4 5 6 7 kcal/g HV-syn 1 2 3 4 5 6 7 kcal/g Q/gr 1 2 3 4 5 6 7 0.0388 0.0154 -0.0161 0.0294 -0.0180 0.0136 0.0009 0.1822 0.2113 0.2392 0.1736 0.2113 0.1864 0.1965 0.4032 0.6048 0.8063 0.4032 0.7056 0.5040 0.5846 8.4031 8.4031 8.4031 9.8037 9.8037 9.8037 9.8037

PE 9%

ISO 30%

STY 56%

Mix (sum) 100% -wt

50.4187 50.4187 50.4187 65.5443 65.5443 60.5025 63.0234

42.0156 42.0156 42.0156 58.8219 52.5195 58.8219 58.8219

125.4865 125.4865 125.4865 188.2300 156.8582 172.5438 172.5438

226.3239 226.3239 226.3239 322.3999 284.7257 301.6719 304.1928 350

Syngas from Mix

Syngas Grams

150 100 50 0 1 2 3 4 5 6 7 Mix Reactions

1.90 0.90 -0.10 -1.10

0.3880 0.4476 0.4762 0.3504 0.3625 0.3868 0.3649

1.1374 1.3441 1.5400 1.0220 1.2473 1.0993 1.0531

1.8712 2.3667 2.6022 1.6983 1.9731 1.8245 1.8057

Box A

3.5788 4.3697 4.8576 3.2443 3.7941 3.4969 3.4202

0.1339 -0.0186 -0.0949 0.0060 -0.0321 -0.0276 -0.0013

0.6186 0.1467 -0.3253 0.0911 -0.2420 -0.1449 -0.0033

1.3406 0.0528 -0.5912 -0.0989 -0.0231 -0.0610 0.0034

Box B

2.1319 0.1962 -1.0275 0.0276 -0.3152 -0.2199 -0.0002

kCal/g

3.8099 5.2612 5.9869 3.8099 4.1727 4.5356 4.0820

2.2677 4.5153 3.4773 9.0306 4.6866 11.2885 2.2677 4.5153 3.6285 6.7732 2.8725 5.6442 2.5098 5.4186

10.9960 18.3738 22.7683 10.9960 15.2799 13.5562 12.5950

300 250 200

4.90 3.90 2.90 CO gr H2 gr HV/gr-syn Q/gr

Thermochemistry and Test Preparatory Calculations

135

Chapter 9: APPENDIX 9.2

Thermodynamic simulation of full conversion to syngas at 1300 C with sensible heat (no losses)
B = A - Q A= B/g = heat Extra grSensible heat Sensible heat of deficiency for feed for Q, effect of to supply to products at gram of 100% reaction 1 feed (if>0) 1300 substance

Q reaction

Total substance feed

Stoichiometric O2

O2 addition

Total O2

O2/feed wt-ratio

PVC
(simulated via HSC 111TCH g) Mol. Wt.

189.512 PE
(simulated via HSC EIC g) Mol. Wt.

Cases 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7

kCal/g-mol 147.000 58.553 -61.209 111.383 -68.260 51.502 3.597 420.512 -58.535 -298.058 18.922 -100.840 -86.738 -3.968 156.980 37.217 -82.544 23.116 -61.418 -36.765 -0.837 249.335 9.812 -109.950 -18.391 -4.290 -11.340 0.636

kCal/g-mol -11.771 96.551 236.187 34.594 244.049 104.413 160.268 3.137 561.683 840.956 469.217 524.489 593.130 496.265 -61.905 77.733 217.369 93.456 192.288 163.274 121.384 -123.600 155.673 295.310 187.119 171.397 179.258 165.294

kCal/g-mol kCal/g-feed 135.229 n.a. 155.104 -0.509 174.978 -1.246 145.977 -0.183 175.789 -1.288 155.915 -0.551 163.865 -0.846 423.649 503.148 542.898 488.139 423.649 506.392 492.297 95.075 114.950 134.825 116.572 130.870 126.509 120.547 125.735 165.485 185.360 168.728 167.107 167.918 165.930 -0.011 -1.988 -2.976 -1.661 -1.856 -2.099 -1.756 n.a. -1.021 -2.855 -1.228 -2.526 -2.145 -1.594 n.a. -1.495 -2.835 -1.797 -1.646 -1.721 -1.587

0.657 1.607 0.235 1.660 0.710 1.090 0.007 1.336 2.000 1.116 1.247 1.410 1.180

g 1.000 1.657 2.607 1.235 2.660 1.710 2.090 1.007 2.336 3.000 2.116 2.247 2.410 2.180 1.000 1.495 2.385 1.595 2.225 2.040 1.773 1.000 1.624 2.184 1.750 1.687 1.719 1.663

g 0.5066 0.3377 0.1689 0.4221 0.1689 0.3377 0.2702 1.1325 0.6795 0.4530 0.7928 0.6795 0.6795 0.7645 1.0508 0.6305 0.2102 0.6305 0.3152 0.4203 0.5464 1.2290 0.6145 0.3072 0.6145 0.6145 0.6145 0.6544

g 0.3327 0.8139 0.1192 0.8410 0.3598 0.5523 0.0084 1.5127 2.2649 1.2637 1.4126 1.5974 1.3366

g 0.5066 0.6704 0.9828 0.5413 1.0099 0.6975 0.8225 1.1410 2.1923 2.7179 2.0565 2.0921 2.2770 2.1010 1.0508 1.1508 1.6652 1.2561 1.6024 1.5132 1.3589 1.2290 1.3818 1.7628 1.5368 1.4593 1.4981 1.4692

282.552 Isoprene
(simulated via HSC 2M13B g plus 0.25S) Mol. Wt.

76.133 Polystyrene
(simulated via HSC STY g) Mol. Wt.

0.495 1.385 0.595 1.225 1.040 0.773

0.5203 1.4550 0.6256 1.2871 1.0929 0.8125

104.151

0.624 1.184 0.750 0.687 0.719 0.663

0.7673 1.4556 0.9223 0.8448 0.8836 0.8147

0.5066 0.4046 0.3770 0.4382 0.3796 0.4078 0.3935 0.370.5 1.1325 0.9386 0.9060 0.9720 0.9310 0.9446 0.9637 0.91.13 1.0508 0.7697 0.6983 0.7873 0.7202 0.7418 0.7664 0.71.05 1.2290 0.8507 0.8070 0.8779 0.8648 0.8715 0.8835 .81.23

minMax

minMax

minMax

minMax

Chapter 9: APPENDIX 9.3

Thermodynamic simulation of full conversion to syngas at 1300 C with sensible heat (+DC-losses)
(B-DC)/g = grheat deficit Extra A= B = A - Q Sensible heat Sensible heat of every gram of feed for Q, 100% products at to supply to effect of substance 1300 feed (if>0) reaction 1

Q reaction

Total substance feed

Stoichiometric O2

O2 addition

Total O2

O2/feed wt-ratio

PVC
(simulated via HSC 111TCH g) Mol. Wt.

189.512 PE
(simulated via HSC EIC g) Mol. Wt.

Cases 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7

kCal/g-mol 147.000 58.553 -61.209 111.383 -68.260 51.502 3.597 420.512 -58.535 -298.058 18.922 -100.840 -86.738 -3.968 156.980 37.217 -82.544 23.116 -61.418 -36.765 -0.837 249.335 9.812 -109.950 -18.391 -4.290 -11.340 0.636

kCal/g-mol -11.771 96.551 236.187 34.594 244.049 104.413 160.268 3.137 561.683 840.956 469.217 524.489 593.130 496.265 -61.905 77.733 217.369 93.456 192.288 163.274 121.384 -123.600 155.673 295.310 187.119 171.397 179.258 165.294

kCal/g-mol kCal/g-feed 135.229 n.a. 155.104 0.351 174.978 -0.386 145.977 0.677 175.789 -0.428 155.915 0.309 163.865 0.014 423.649 503.148 542.898 488.139 423.649 506.392 492.297 95.075 114.950 134.825 116.572 130.870 126.509 120.547 125.735 165.485 185.360 168.728 167.107 167.918 165.930 0.849 -1.128 -2.116 -0.801 -0.996 -1.239 -0.896 n.a. -0.161 -1.995 -0.368 -1.666 -1.285 -0.734 n.a. -0.635 -1.975 -0.937 -0.786 -0.861 -0.727

0.498 0.551

g 1.000 1.000 1.498 1.000 1.551 1.000 1.000 1.000 1.758 2.422 1.538 1.669 1.833 1.602 1.000 1.078 1.968 1.178 1.808 1.623 1.356 1.000 1.265 1.825 1.391 1.328 1.360 1.304

g 0.5066 0.3377 0.1689 0.4221 0.1689 0.3377 0.2702 1.1325 0.6795 0.4530 0.7928 0.6795 0.6795 0.7645 1.0508 0.6305 0.2102 0.6305 0.3152 0.4203 0.5464 1.2290 0.6145 0.3072 0.6145 0.6145 0.6145 0.6544

0.2523 0.2794

g 0.5066 0.3377 0.4211 0.4221 0.4482 0.3377 0.2702 1.1325 1.5378 2.0635 1.4020 1.4377 1.6225 1.4466 1.0508 0.7125 1.2269 0.8178 1.1641 1.0750 0.9207 1.2290 0.9403 1.3213 1.0953 1.0178 1.0566 1.0277

282.552 Isoprene
(simulated via HSC 2M13B g plus 0.25S) Mol. Wt.

0.758 1.422 0.538 0.669 0.833 0.602

0.8583 1.6104 0.6093 0.7581 0.9430 0.6821

76.133 Polystyrene
(simulated via HSC STY g) Mol. Wt.

0.078 0.968 0.178 0.808 0.623 0.356

0.0821 1.0168 0.1873 0.8489 0.6547 0.3742

104.151

0.265 0.825 0.391 0.328 0.360 0.304

0.3258 1.0141 0.4808 0.4033 0.4421 0.3732

0.5066 0.3377 0.2811 0.4221 0.2889 0.3377 0.2702 0.270.5 1.1325 0.8748 0.8520 0.9116 0.8612 0.8853 0.9028 0.851.13 1.0508 0.6609 0.6236 0.6941 0.6439 0.6623 0.6789 0.621.05 1.2290 0.7433 0.7240 0.7873 0.7663 0.7771 0.7883 .721.23

minMax

minMax

minMax

minMax

136

Chapter 9

APPENDIX 9.4: Summary and notes

1 2 3 4 5 6 7 8 9 This summary tables all cases reaching 1300C, PVC cases are omitted because numerous and used to check parameters All cases involve 14 kW DC power in, 8 kW estimated heat losses Graphite electrodes input is considered, proportional to experiment, 1/2 Kg for a 6 Kg substance feed The comparison is made with the calculation of extra power originated by partial oxidation (no electrodes) of Appendix 9.3 The quantity of C in column H is always greater because it is proportional to the feed and extra substance to partial oxidation When the extra substance is high (PE2, PE3, PE5, ISO5) the electrodes, proportional to substance, make a great difference When the extra substance is little, the electrode C is significant (PSTY2, ISO4) or very significant (ISO2), which means that the difference of calculation is little or the methods are comparable The calculation sheets of Appendix 9.4 are detailed and provide results consistent with those of Appendix 9.3 (gram based) Mass ratios and molar syngas ratios are calculated with all contributions (substance, p.ox. electrodes)

Reaction filename.BAL PE2 PE3 PE4 PE5 PE6 PE7 ISO2 ISO3 ISO4 ISO5 ISO6 ISO7 PSTY2 PSTY3 PSTY4 PSTY5 PSTY6 PSTY7

Extra substance Kmol (base = 1 Kmol) 0.773 1.659 0.538 0.981 0.911 0.614 0.035 1.07 0.197 0.912 0.715 0.404 0.156 0.734 0.338 0.247 0.292 0.234

C in

C Katom a

C % = tot. C previoulsly =C electrodes electrodes Katom calculated Katom b H =a+b E

C Katom H-E

C% extra

x 20

x5

x8

15.460 33.180 10.760 19.620 18.220 12.280 0.175 5.350 0.985 4.560 3.575 2.020 1.248 5.872 2.704 1.976 2.336 1.872

3.479 5.117 3.018 3.887 3.750 3.167 0.490 0.979 0.566 0.904 0.811 0.664 0.836 1.254 0.968 0.902 0.934 0.893

23% 15% 28% 20% 21% 26% 280% 18% 57% 20% 23% 33% 67% 21% 36% 46% 40% 48%

18.939 38.297 13.778 23.507 21.970 15.447 0.665 6.329 1.551 5.464 4.386 2.684 2.084 7.126 3.672 2.878 3.270 2.765

0.758 1.422 0.538 0.669 0.833 0.602 0.078 0.968 0.178 0.808 0.623 0.356 0.265 0.825 0.391 0.328 0.360 0.304

15.157 3.782 28.440 9.857 10.759 3.019 13.388 10.119 16.653 5.317 12.046 3.401 0.390 0.275 4.838 1.491 0.891 0.660 4.039 1.425 3.115 1.271 1.781 0.903 2.121 -0.037 6.601 0.525 3.130 0.542 2.625 0.253 2.878 0.392 2.430 0.335

25% 35% 28% 76% 32% 28% 70% 31% 74% 35% 41% 51% -2% 8% 17% 10% 14% 14%

Case
PVC2 PVC3 PVC4 PVC5 PVC6 PVC7 PE2 PE3 PE4 PE5 PE6 PE7 ISO2 ISO3 ISO4 ISO5 ISO6 ISO7 PSTY2 PSTY3 PSTY4 PSTY5 PSTY6 PSTY7

extra gmol species

0 0.163 0 0.209 0 0 0.773 1.659 0.538 0.981 0.911 0.614 0.035 1.07 0.197 0.912 0.715 0.404 0.156 0.734 0.338 0.247 0.292 0.234

tot tot gmol g species species 1.000 189.512 1.163 220.402 1.000 189.512 1.209 229.120 1.000 189.512 1.000 189.512 1.773 500.965 2.659 751.306 1.538 434.565 1.981 559.736 1.911 539.957 1.614 456.039 1.035 70.502 2.070 141.004 1.197 81.537 1.912 130.242 1.715 116.822 1.404 95.638 1.156 120.399 1.734 180.598 1.338 139.354 1.247 129.876 1.292 134.563 1.234 128.522

tot CO g 168.062 195.457 196.073 231.198 196.073 196.073 993.249 1489.593 1029.662 1277.834 1182.599 1044.228 144.954 289.908 223.663 302.792 296.210 252.654 259.040 388.560 411.865 335.453 373.547 360.550

tot H2 g 12.095 17.441 8.063 15.796 10.079 11.692 91.181 136.750 65.106 87.891 88.959 71.347 11.855 23.711 9.048 18.989 14.980 11.420 17.384 26.076 10.789 14.086 12.433 11.563

O/C-sub wt 0.890 0.569 1.111 0.597 0.890 0.711 1.032 1.032 1.074 1.064 1.054 1.064 0.819 0.819 0.888 0.845 0.867 0.878 0.756 0.756 0.835 0.798 0.817 0.820

CO2/C-sub H2O/C-sub H2/C-sub H2/CO wt wt wt molar 0.000 0.000 0.611 0.505 0.611 0.611 0.000 0.000 0.716 0.556 0.384 0.569 0.000 0.000 1.225 0.479 0.855 1.044 0.000 0.000 1.370 0.736 1.064 1.114 0.500 0.861 0.000 0.621 0.250 0.450 0.339 0.339 0.000 0.075 0.157 0.069 0.580 0.580 0.000 0.353 0.175 0.085 0.650 0.650 0.000 0.301 0.145 0.122 0.168 0.208 0.112 0.181 0.140 0.162 0.214 0.214 0.176 0.185 0.194 0.184 0.191 0.191 0.126 0.166 0.146 0.136 0.157 0.157 0.084 0.118 0.100 0.098 1.000 1.240 0.571 0.949 0.714 0.829 1.276 1.276 0.879 0.956 1.045 0.949 1.136 1.136 0.562 0.871 0.703 0.628 0.933 0.933 0.364 0.584 0.463 0.446

Thermochemistry and Test Preparatory Calculations

137

Appendix 9.4, cont.d: The summary table just exhibited collects data that were run by individual sheets for the significant reactions of each simulated component, in near to autothermal conditions. To appreciate how such calculations were made, sheets for Polyethylene and for Isoprene like rubber are attached hereunder, prior to presenting the tables that enable to graph feed ratios and outputs.

138

Chapter 9

Thermochemistry and Test Preparatory Calculations

139

140

Chapter 9

Thermochemistry and Test Preparatory Calculations

141

142

Chapter 9

Thermochemistry and Test Preparatory Calculations

143

Appendix 9. 4: ISOPRENE LIKE, second reaction

144

Chapter 9

Appendix 9. 4: ISOPRENE LIKE, third reaction

Thermochemistry and Test Preparatory Calculations

145

Appendix 9. 4: ISOPRENE LIKE, fourth reaction

146

Chapter 9

Appendix 9. 4: ISOPRENE LIKE, fifth reaction

Thermochemistry and Test Preparatory Calculations

147

Appendix 9. 4: ISOPRENE LIKE, sixth reaction

148

Chapter 9

Appendix 9. 4: ISOPRENE LIKE, seventh reaction

Thermochemistry and Test Preparatory Calculations

149

Appendix 9.4, cont.d: In analogy to Appendix 9.1, we used the HSC calculated data for the same reactions and constituents and utilised the same graphs. Only the bold data in the framed yellow boxes are valid and are the data summarised in the opening page of this Appendix. The other numbers are shaded in light colours because they are not necessarily used in these graphs. The frames were simply utilised for making the graphs.

Thermochemical data calculated with HSC were inputed to the same identical frames of Appendix 9.1, simply to exploit the same graphs. New and solely valid data in dark boxes. First Constituent: PVC (n2) Case 1 C6H11Cl3 + 3O2 = 3HCl + 6CO + 4H2 2 C6H11Cl3 + 2O2 + 2H2O = 3HCl + 6CO + 6H2 3 C6H11Cl3 + O2 + 4H2O = 3HCl + 6CO + 8H2 4 C6H11Cl3 + 2.5O2 + CO2 = 3HCl + 7CO + 4H2 5 C6H11Cl3 + O2 + 3H2O + CO2 = 3HCl + 7CO + 7H2 6 C6H11Cl3 + 2O2 + H2O + CO2 = 3HCl + 7CO + 5H2 7 C6H11Cl3 + 1.6O2 + 1.8H2O + CO2 = 3HCl + 7CO + 5.8H2 8 C6H11Cl3 + 3H2O + 3CO2 = 3HCl + 9CO + 7H2 9 C6H11Cl3 + H2O + 5CO2 = 3HCl + 11CO + 5H2 (n3) H reaction Q reaction Q/gr kcal kcal kcal/gr 147.00 58.55 -61.21 111.38 -68.26 51.50 3.60 -202.12 -188.02 0.776 0.309 -0.323 0.588 -0.360 0.272 0.019 -1.067 -0.992 (n4) CO gr 168.062 168.062 195.457 196.073 231.198 196.073 196.073 252.094 308.114 wt-% within feed C in Cl in H in 0.380 0.562 0.059 unchanged HVsyngas Syngas mol-% ratio HCl out H2 out CO out H2/CO kcal/gr 0.231 0.308 0.462 0.667 3.643 0.200 0.400 0.400 4.226 1.000 0.176 0.471 0.353 4.630 1.240 0.214 0.286 0.500 3.472 0.571 0.176 0.412 0.412 4.139 0.949 0.200 0.333 0.467 3.728 0.714 0.190 0.367 0.443 3.930 0.829 0.158 0.368 0.474 0.777 3.840 0.158 0.263 0.579 0.454 3.258 Wt-ratios in (n7) CO2/C H2O/C

At 1300 C

H2 gr 8.063 12.095 17.441 8.063 15.796 10.079 11.692 14.111 10.079

(n5) (n6) Oxygen portion in Syngas HV/gr-sub. HV/gr-syn O2 CO2 H2O gr kcal/gr kcal/gr
(gas to substance) (syngas prod.)

O/C

Case 1 -147.00 2 -58.55 via HSC H2O+O2 3 61.21 111TCH g) O2+CO2 4 -111.38 H2O+O2+CO2 5 68.26 Mol. Wt. O2+H2O+CO2 6 -51.50 189.512 Autothermal 7 -3.60 H2O+CO2 8 202.12 H2O+CO2 9 188.02
+Oxygen mix O2 O2+H2O

PVC

(simulated

176.125 180.157 212.898 204.136 246.994 206.152 207.765 266.205 318.193

3.386 4.018 5.201 3.739 5.395 4.055 4.308 5.395 5.470

3.643 4.226 4.630 3.472 4.139 3.728 3.930 3.840 3.258

1.000 0.667 0.333 0.714 0.286 0.571 0.457

0.333 0.667 0.286 0.286 0.286 0.286 0.333 0.909 0.429 0.143 0.257 0.667 0.091

0.444 0.890 0.569 1.111 0.597 0.890 0.711

0.000 0.000 0.611 0.505 0.611 0.611 0.222 0.606

0.500 0.861 0.000 0.621 0.250 0.450 0.167 0.023

Syngas from PVC with kW, P. Ox., Losses & Electrodes

250 225 200 175 150 125 100 75 50 25 0 1 2 3 4 5 6 7 PVC Reactions 5.00 4.00 3.00 kCal/g 2.00 1.00 0.00 -1.00 Gas in: wt-ratio CO gr H2 gr HV/gr-syn Q/gr 1.20

Syngas from PVC with kW, P. Ox., Losses & Electrodes

0.80 0.60 0.40 0.20 0.00 1 2 3 4 5 6 7 PVC Reactions

1.00 0.80 0.60 0.40

Gas out: molar ratio

1.00

1.20

Syngas Grams

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

All other graphs that follow are generated in the same manner.

150

Chapter 9

Syngas from Rubber with kW, P. Ox., Losses & Electrodes

300 275 250 225 200 175 150 125 100 75 50 25 0 1 2 3 4 5 6 7 Rubber Reactions

Syngas from Rubber with kW, P. Ox., Losses & Electrodes

1.40 1.20

4.90

Gas in: wt-ratio

Syngas Grams

3.90
kCal/g

2.90 1.90 0.90 -0.10 -1.10

CO gr H2 gr HV/gr-syn Q/gr

1.00 0.80 0.60 0.40 0.20 0.00 1 2 3 4 5 6 7 Rubber Reactions

1.00 0.90 0.80 0.70 0.60 0.50

Gas out: molar ratio

1.20

1.10

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

Syngas fromPE w kW P. O Losses & Electrodes ith , x.,

1600 1400 1200 1000 800 600 400 200 0 1 2 3 4 5 6 7 5.00 4.00 3.00 2.00 1.00 0.00 -1.00
COgr H2 gr HV/gr-syn Q /gr
1.20 1.00 0.80 0.60 0.40 0.20 0.00 1

Syngas fromPE w kW P. O Losses & Electrodes ith , x.,

1.40 1.30 1.20 1.10 1.00 0.90 0.80 0.70 2 3 4 5 6 7
O w /C t-ratio C 2/Cw O t-ratio H /Cw 2O t-ratio H Om 2/C olar

Syngas from Polystyrene with kW, P. Ox., Losses & Electrodes

450 400
Syngas Grams

Syngas from Polystyrene with kW, P. Ox., Losses & Electrodes

1.40 1.30 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 Polystyrene Reactions 1.00
Gas out: molar ratio

3.90

0.90 0.80 0.70 0.60 0.50 0.40 0.30

300 250 200 150 100 50 0 1 2 3 4 5 6 7 Polystyrene Reactions

2.90 1.90 0.90 -0.10 -1.10

kCal/g

Gas in: wt-ratio

350

CO gr H2 gr HV/gr-syn Q/gr

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

Thermochemistry and Test Preparatory Calculations

151

Syngas from Mix with kW, P. Ox., Losses & Electrodes

500 450 400 Syngas Grams 350 300 250 200 150 100 50 0 1 2 3 4 5 6 7 Mix Reactions 4.90 4.40 3.90 3.40 2.90 1.90 1.40 0.90 0.40 -0.10 -0.60 -1.10 kCal/g 2.40 CO gr H2 gr HV/gr-syn Q/gr

Syngas from Mix with kW, P. Ox., Losses & Electrodes

1.30 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 Mix Reactions 1.20 1.10 Gas out: molar ratio 1.00 0.90 0.80 0.70 0.60 0.50 0.40

Gas in: wt-ratio

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

152

Chapter 9

In analogy to the table prepared for the base case, the recalculated summary follows:

We now take the mix that was suggested from the chemical analysis of fluff & maintain the same model reactions (1 through 7) pro-quota for each constituent. Data elaborated from HSC simulations, carbon downrating for inerts is not applied yet. PVC 5% H2/CO 1 2 3 4 5 6 7 H2O/C 1 2 3 4 5 6 7 CO2/C 1 2 3 4 5 6 7 O/C 1 2 3 4 5 6 7 0.0222 0.0445 0.0284 0.0555 0.0299 0.0445 0.0355 0.0120 0.0929 0.0929 0.0966 0.0958 0.0948 0.0958 0.1600 0.2456 0.2456 0.2663 0.2534 0.2602 0.2633 0.1867 0.4235 0.4235 0.4678 0.4472 0.4575 0.4593 0.3809 0.8064 0.7904 0.8863 0.8262 0.8570 0.8539 0.0000 0.0000 0.0000 0.0305 0.0253 0.0305 0.0305 0.0000 0.0000 0.0000 0.0644 0.0500 0.0345 0.0512 0.0000 0.0000 0.0000 0.3675 0.1437 0.2565 0.3133 0.0000 0.0000 0.0000 0.7673 0.4119 0.5960 0.6240 0.0000 0.0000 0.0000 1.2298 0.6309 0.9175 1.0190 0.0000 0.0250 0.0430 0.0000 0.0311 0.0125 0.0225 0.0000 0.0305 0.0305 0.0000 0.0068 0.0141 0.0063 0.0000 0.1740 0.1740 0.0000 0.1059 0.0525 0.0255 0.0000 0.3639 0.3639 0.0000 0.1683 0.0814 0.0680 0.0000 0.5935 0.6115 0.0000 0.3121 0.1605 0.1223 0.0333 0.0500 0.0620 0.0286 0.0475 0.0357 0.0415 0.0944 0.1148 0.1148 0.0791 0.0860 0.0941 0.0854 0.2250 0.3408 0.3408 0.1686 0.2613 0.2109 0.1884 0.2796 0.5225 0.5225 0.2038 0.3270 0.2593 0.2498 0.6323 1.0281 1.0401 0.4801 0.7218 0.5999 0.5650 1.30 1.20 1.10 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 Mix Reactions PE 9% ISO 30% STY 56% Mix (sum) 100% -wt

Syngas from Mix with kW, P. Ox., Losses & Electrodes

1.20 1.10 Gas out: molar ratio 1.00 0.90 0.80 0.70 0.60 0.50 0.40

Gas in: wt-ratio

O/C wt-ratio CO2/C wt-ratio H2O/C wt-ratio H2/CO molar

Box C

PVC 5% grams CO 1 2 3 4 5 6 7 grams H2 1 2 3 4 5 6 7 kcal/g HV-syn 1 2 3 4 5 6 7 kcal/g Q/gr 1 2 3 4 5 6 7 0.0388 0.0154 -0.0161 0.0294 -0.0180 0.0136 0.0009 0.1822 0.2113 0.2315 0.1736 0.2070 0.1864 0.1965 8.4031 8.4031 9.7729 9.8037 11.5599 9.8037 9.8037

PE 9%

ISO 30%

STY 56%

Mix (sum) 100% -wt

50.4187 89.3924 134.0634 92.6696 115.0051 106.4339 93.9805

42.0156 43.4862 86.9724 67.0989 90.8376 88.8630 75.7962

125.4865 145.0624 217.5936 230.6444 187.8537 209.1863 201.9080

226.3239 286.3441 448.4022 400.2165 405.2562 414.2869 381.4884

Syngas from Mix with kW, P. Ox., Losses & Electrodes

500 450 400 Syngas Grams 350 300 250 200 150 100 50 0 1 2 3 4 5 6 7 Mix Reactions 4.90 4.40 3.90 3.40 2.90 1.90 1.40 0.90 0.40 -0.10 -0.60 -1.10 kCal/g 2.40 CO gr H2 gr HV/gr-syn Q/gr

0.4032 3.8099 0.6048 8.2063 0.8721 12.3075 0.4032 5.8595 0.7898 7.9102 0.5040 8.0063 0.5846 6.4212

2.2677 4.5153 3.5565 9.7350 7.1133 14.6026 2.7144 6.0418 5.6967 7.8882 4.4940 6.9625 3.4260 6.4753

10.9960 22.1026 34.8954 15.0189 22.2849 19.9667 16.9071

0.3880 0.4220 0.4220 0.3615 0.3735 0.3873 0.3725

1.1374 1.3372 1.3373 1.0364 1.2013 1.1122 1.0722

1.8712 2.3018 2.3018 1.7304 1.9563 1.8327 1.8153

Box A

3.5788 4.2723 4.2926 3.3020 3.7382 3.5186 3.4565

0.1339 -0.0186 -0.0949 0.0060 -0.0321 -0.0276 -0.0013

0.6186 0.1467 -0.3253 0.0911 -0.2420 -0.1449 -0.0033

1.3406 0.0528 -0.5912 -0.0989 -0.0231 -0.0610 0.0034

Box B

2.1319 0.1962 -1.0275 0.0276 -0.3152 -0.2199 -0.0002

Thermochemistry and Test Preparatory Calculations

153

The comparison between the first calculated base case and the mixed case is reported below:
C o m p a ris o n o f b a s e c a s e w ith s im u la tio n o f re a c tio n s th a t in c lu d e s k W , lo s s e s a n d s e n s ib le h e a t (H S C ) B ase P. Ox. O /C 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 1 2 3 4 5 6 7 0 .3 8 0 9 0 .2 1 1 3 0 .0 9 0 9 0 .1 5 3 1 0 .1 2 5 0 0 .1 3 2 3 0 .1 4 7 3 0 .0 0 0 0 0 .0 9 5 4 0 .1 6 3 1 0 .0 0 0 0 0 .0 5 9 3 0 .0 2 5 3 0 .0 1 6 4 0 .0 0 0 0 0 .0 0 0 0 0 .0 0 0 0 0 .3 4 1 6 0 .2 2 5 8 0 .3 0 5 4 0 .3 0 6 6 2 2 6 .3 2 3 9 2 2 6 .3 2 3 9 2 2 6 .3 2 3 9 3 2 2 .3 9 9 9 2 8 4 .7 2 5 7 3 0 1 .6 7 1 9 3 0 4 .1 9 2 8 1 0 .9 9 6 0 1 8 .3 7 3 8 2 2 .7 6 8 3 1 0 .9 9 6 0 1 5 .2 7 9 9 1 3 .5 5 6 2 1 2 .5 9 5 0 3 .5 7 8 8 4 .3 6 9 7 4 .8 5 7 6 3 .2 4 4 3 3 .7 9 4 1 3 .4 9 6 9 3 .4 2 0 2 2 .1 3 1 9 0 .1 9 6 2 -1 .0 2 7 5 0 .0 2 7 6 -0 .3 1 5 2 -0 .2 1 9 9 -0 .0 0 0 2 HSC sa m e 0 .8 0 6 4 0 .7 9 0 4 0 .8 8 6 3 0 .8 2 6 2 0 .8 5 7 0 0 .8 5 3 9 0 .0 0 0 0 0 .5 9 3 5 0 .6 1 1 5 0 .0 0 0 0 0 .3 1 2 1 0 .1 6 0 5 0 .1 2 2 3 0 .0 0 0 0 0 .0 0 0 0 0 .0 0 0 0 1 .2 2 9 8 0 .6 3 0 9 0 .9 1 7 5 1 .0 1 9 0 sa m e 2 8 6 .3 4 4 1 4 4 8 .4 0 2 2 4 0 0 .2 1 6 5 4 0 5 .2 5 6 2 4 1 4 .2 8 6 9 3 8 1 .4 8 8 4 sa m e 2 2 .1 0 2 6 3 4 .8 9 5 4 1 5 .0 1 8 9 2 2 .2 8 4 9 1 9 .9 6 6 7 1 6 .9 0 7 1 sa m e 4 .2 7 2 3 4 .2 9 2 6 3 .3 0 2 0 3 .7 3 8 2 3 .5 1 8 6 3 .4 5 6 5 sa m e sa m e sa m e sa m e sa m e sa m e sa m e In c re a s e n -f o ld 3 .8 8 .7 5 .8 6 .6 6 .5 5 .8

P. Ox. H 2 O /C

6 .2 3 .7 5 .3 6 .3 7 .5

P. Ox. C O 2 /C

3 .6 2 .8 3 .0 3 .3

P. Ox. g ra m s CO

1 .3 2 .0 1 .2 1 .4 1 .4 1 .3

P. Ox. g ra m s H2

1 .2 1 .5 1 .4 1 .5 1 .5 1 .3

P. Ox. k c a l/g H V -s y n

1 .0 0 .9 1 .0 1 .0 1 .0 1 .0

P. Ox. k c a l/g Q /g r

154

Chapter 9

CARBON EQUILIBRIUM STUDY We can start by considering the following simultaneous reactions, with Kp(T) and a proper advancement Kp(T) at 500 525 550 560 570 580 590 600 610 620 630 640 650 660 670 680 690 700 750 A B C D a b c shift a+b+c
A+B+C+D
C+2H2=CH4 C+2H2O=CO2+2H2 C+H2O=CO+H2 C+CO2=2CO CH4+2O2=CO2+2H2O CH4+CO2=2CO+2H2 CH4+H2O=CO+3H2 H2O+CO=CO2+H2 3CH4+2O2=2CO+CO2+6H2 4C+3H2O=CH4+3CO+H2

775 0.06 6.1 5.26 4.5

800 0.048 8 7.6 7.1 1.00E+41 210 205

850 0.03 13.4 15 17

900 0.02 21 28 36

1000 0.009 49 82 139 1.00E+32 10000 860

1200 0.003 187 470 1179

1300C 0.002 323 1000 10000

2.21 1.45 0.97 0.84 0.72 0.62 0.54 0.47 0.4 0.35 0.31 0.27 0.24 0.21 0.19 0.17 0.15 0.13 0.08 0.1 0.17 0.26 0.31 0.37 0.44 0.51 0.6 0.7 0.82 0.95 1.1 1.27 1.5 1.69 1.9 2.2 2.5 4.6 0.02 0.04 0.07 0.1 0.12 0.15 0.19 0.23 0.29 0.35 0.43 0.52 0.64 0.77 0.93 1.1 1.33 1.58 3.59 0.01 0.02 0.03 0.04 0.05 0.07 0.09 0.11 0.15 0.2 0.25 0.31 0.4 0.5 0.64 0.8 1 2.8

800 655 0.89 0.77

1.00E+06 1.00E+05 0.4 0.341

4.2

3.5 3.31 3.11

2.9 2.76

2.6 2.47 2.34 2.22

2.1

1.9

1.8 1.73 1.65 1.58 1.28

1.16

1 1.00E+43

0.6 1.00E+40

0.001 0.002 0.003 0.006 0.009 0.015 0.025 0.040 0.06 0.100 0.150 0.230 0.350 0.53 3.61 8.800

20

100

426

5448 3.00E+05

1.60E+06

reactions a) and a+b+c) could be ignored because their high Kp indicates they are fully driven to the right we want to write the other reactions, cumulatively, with a degree of advancement, if we use only stoichiometric factors it would be like implying they already are at the equilibrium, which may be not true if reactions are simultaneous, given infinite activity of solid carbon and availability of reactants, we can state y=1-w we can write all equations for x to find the T that satisfies the equilibria x=w z=2w z=2x 1-x=y s=1-x s=y y=1-x

CHAPTER 9 APPENDIX 9.5

A B C D shift
A+B+C+D

C+2H2=CH4 C+2H2O=CO2+2H2 C+H2O=CO+H2 C+CO2=2CO H2O+CO=CO2+H2 4C+3H2O=CH4+3CO+H2

mol IN H2 H2O CO2 2 2 1 1 1 1 3

mol OUT CO CH4 Total H2 H2O CO2 2 2-2x 2 2y 2-2y y 1 z 1-z 1 1-w s 1-s x 3-3x s

CO CH4 Total Kp= x 2-x x(2-x)/(2(1-x))^2 2+y y(2y)^2/((2+y)(2(1-y))^2) z 1+z z^2/(1-z^2) 2w 1+w (2w)^2/(1-w^2) 1-s 3x (1-s)^2/s^2 x 3+2x 27x^5/(3+2x)^2/(3-3x)^3

if we now combine the cumulative and the shift reaction in terms of x

xH2O + xCO = (1-x)CO2 + (1-x)H2 4xC + (3-3x)H2O = xCH4 + 3xCO + xH2

i.e.

4xC + (3-2x)H2O = xCH4 + 2xCO + H2 + (1-x)CO2

and we can express the ratio

CO/(CO+CO2) = 2x/(1+x)

Thermochemistry and Test Preparatory Calculations

155

Appendix 9.5, cont.d:

Kp(T)

5 4.5 4 3.5
A

3 Kp 2.5 2 1.5 1 0.5 0

B C D Shift Cumul.

T C

156

Chapter 9

x=w= s=y= z=

Trials: 0.83 0.17 1.66

0.49 0.51 0.98

0.41 0.59 0.82

0.39 0.61 0.78

0.22 0.78 0.44

0.49 0.51 0.98

0.485 0.515 0.97

0.48 0.52 0.96

0.475 0.525 0.95

0.47 0.53 0.94

0.465 0.535 0.93

0.46 0.54 0.92

0.455 0.545 0.91

0.45 0.55 0.9

0.445 0.555 0.89

0.44 0.56 0.88

0.435 0.565 0.87

0.43 0.57 0.86

0.425 0.575 0.85

0.42 0.58 0.84

KpA KpB KpC KpD

8.401 0.711 0.003 0.220 -1.570 24.253 8.858 1.264

0.468 0.472 2.053 0.808

0.422 0.572 1.554 0.718

0.161 3.527 0.240 0.203

0.711 0.220 24.253 1.264

0.693 0.231 15.920 1.230

0.675 0.242 11.755 1.198

0.657 0.254 9.256 1.165

0.640 0.266 7.591 1.134

0.623 0.279 6.402 1.104

0.607 0.293 5.510 1.074

0.592 0.307 4.817 1.044

0.576 0.322 4.263 1.016

0.562 0.338 3.810 0.988

0.547 0.354 3.433 0.960

0.533 0.372 3.114 0.934

0.519 0.390 2.840 0.907

0.506 0.409 2.604 0.882

0.493 0.429 2.397 0.857

Kpshift 23.837 Kpcum 3.692 x=w= s=y= z= 0.415 0.585 0.83

0.923 0.013 0.41 0.59 0.82

0.483 0.004 0.405 0.595 0.81

0.409 0.003 0.4 0.6 0.8

0.080 0.000 0.395 0.605 0.79

0.923 0.013 0.39 0.61 0.78

0.887 0.012 0.385 0.615 0.77

0.852 0.012 0.38 0.62 0.76

0.819 0.011 0.375 0.625 0.75

0.786 0.010 0.37 0.63 0.74

0.755 0.009 0.365 0.635 0.73

0.726 0.009 0.36 0.64 0.72

0.697 0.008 0.355 0.645 0.71

0.669 0.007 0.35 0.65 0.7

0.643 0.007 0.345 0.655 0.69

0.617 0.006 0.34 0.66 0.68

0.593 0.006 0.335 0.665 0.67

0.569 0.005 0.33 0.67 0.66

0.546 0.005 0.325 0.675 0.65

0.524 0.005 0.32 0.68 0.64

KpA KpB KpC KpD

0.481 0.450 2.214 0.832

0.468 0.472 2.053 0.808

0.456 0.495 1.908 0.785

0.444 0.519 1.778 0.762

0.433 0.545 1.660 0.739

0.422 0.572 1.554 0.718

0.411 0.600 1.456 0.696

0.400 0.630 1.367 0.675

0.390 0.661 1.286 0.655

0.380 0.694 1.210 0.634

0.370 0.729 1.141 0.615

0.360 0.766 1.076 0.596

0.351 0.805 1.017 0.577

0.342 0.846 0.961 0.558

0.333 0.889 0.909 0.540

0.324 0.935 0.860 0.523

0.315 0.983 0.815 0.506

0.307 1.034 0.772 0.489

0.299 1.088 0.732 0.472

0.291 1.146 0.694 0.456

Kpshift Kpcum x=w= s=y= z=

0.503 0.004 0.315 0.685 0.63

0.483 0.004 0.31 0.69 0.62

0.463 0.004 0.305 0.695 0.61

0.444 0.003 0.3 0.7 0.6

0.426 0.003 0.295 0.705 0.59

0.409 0.003 0.29 0.71 0.58

0.392 0.003 0.285 0.715 0.57

0.376 0.002 0.28 0.72 0.56

0.360 0.002 0.275 0.725 0.55

0.345 0.002 0.27 0.73 0.54

0.330 0.002 Trials:

0.316 0.002 0.49 T

0.303 0.002 0.49 0.51 0.98

0.290 0.001 0.41 T

0.277 0.001 0.41 0.59 0.82

0.265 0.001 0.39 T

0.254 0.001 0.39 0.61 0.78

0.243 0.001 0.22 T

0.232 0.001 0.22 0.78 0.44

0.221 0.001

KpA KpB KpC KpD

0.283 1.206 0.658 0.441

0.275 1.271 0.624 0.425

0.268 1.339 0.593 0.410

0.260 1.412 0.562 0.396

0.253 1.489 0.534 0.381

0.246 1.570 0.507 0.367

0.239 1.658 0.481 0.354

0.232 1.750 0.457 0.340

0.226 1.849 0.434 0.327

0.219 1.955 0.412 0.315

570 530 870 725

0.711 0.220 24.253 1.264

600 580 720 690

0.468 0.472 2.053 0.808

605 595 695 685

0.422 0.572 1.554 0.718

685 725 725 725

0.161 3.527 0.240 0.203

Kpshift Kpcum

0.211 0.001

0.202 0.001

0.193 0.001

0.184 0.001

0.175 0.000

0.167 0.000

0.159 0.000

0.151 0.000

0.144 0.000

0.137 0.000

800 665

0.923 0.013

1100 595

0.483 0.004

1200 590

0.409 0.003

1400 560

0.080 0.000

Thermochemistry and Test Preparatory Calculations

157

Kp versus x
4.000 3.500 3.000 2.500 Kp 2.000 1.500 1.000 0.500 0.000 0.41 0.42 0.43 0.44 0.45 0.46 0.47 0.48 0.49 x
2.000 1.800 1.600

Kp versus x

1.400 1.200

B
Kp

1.000 0.800 0.600 0.400 0.200 0.000

Shift

Shift

0.5

0.3

0.32

0.34 x

0.36

0.38

0.4

..

10

PILOT TEST REPORTING AND DISCUSSION OF RESULTS

10.1

Introduction

The planning of the test was based on the waste organic source characterized in Chapter 9 and the plasma reactor processing of the automobile shedder material was made in a series of thirteen tests. Successful tests were conducted to demonstrate that the material, heterogeneous and irregular in form as it may arrive to the processing plant, can be made flowable and suitable for continuous and controllable feed. The product gas after quenching, scrubbing and dust cleaning can be used as clean syngas fuel or feedstock to downstream chemical processes. Hydrogen and carbon monoxide were obtained in the range between 20 and 22 vol-% respectively, or 45 and 55 vol-% dry basis, when corrected for nitrogen dilution specific to the pilot plant. The composition was most dependent on the selected operating conditions and use of steam versus dry reforming. Starting from 6.5 wt-% hydrogen content in the fluff, hydrogen production is enhanced by steam reforming. Concerning the aspect of dry reforming, conversion levels depend on the power input and averaged to exceed 3 kg of CO2 per kg of fluff feed. The leach rate (of toxic compounds) from the solid products is well beneath limits set by UNI 10802_2002, or equivalent methods, and allow to consider the ultimate vitrified material safely disposable or a filler for road and construction works. The electric energy demand of the plasma process can be reduced in two ways. A boiler can fit after the plasma reactor to recover waste heat in the product gas and steam would be generated to produce electric energy via a thermal cycle turbine generator. The other substantial method to reduce the electric power input is obtained by consuming part of the fluff feed in an oxygen starved combustion, achieve a quasi auto-thermal process and still allow CO and H2 generation.

10.2

Test Apparatus Description

The pilot plant main sections of interest for these experiments are the solid feed and the plasma reactor. The quench and gas scrubbing, dust removal, carbon purification adsorption of the gases and the feed of gases and utilities like steam and nitrogen purge need not to be detailed as they are regular ancillary parts of the existing system. A simplified block diagram is shown in Figure 1 below.

Feed

Figure 1: Block diagram

Syngas

Plasma

Thermal Resident Chamber

Quench

Baghouse

Scrubber

Carbon filter

Glass

Ash

160

Chapter 10

The solid feed-rate was standardised and maintained for the duration of the test as well as the supply of DC and AC power, H2O, CO2, O2 and N2 were manually recorded at regular intervals. The offgas was continuously measured throughout the test to read the vol-% of H2, CO, CO2, O2, N2 and CH4. Main variables were measured by local instruments and all gases were measured with rotameters, calibrated prior to the beginning of the experiments. Main variables measurements like temperature and pressure at various points, as well as gas feeds and utilities were also measured with online instruments and recorded in the process computer tied to the main control system. The off gas volumetric composition was automatically measured by a process gas analyzer, manufactured by NOVA, in which the product gas sample was drawn through a series of heated particulate filters and then dried by passing the syngas over a semipermeable membrane that allows for transport of water in the sample to a dry nitrogen stream. The resulting clean, dry syngas is analyzed by several different detectors. Simultaneous measurement of carbon monoxide, carbon dioxide, and methane is accomplished with a high stability infra red detector. Hydrogen is detected with a methane compensated thermal conductivity cell. Oxygen is detected with a long-life electrochemical fuel-cell sensor. Calibration gases are used at the start of each test to ensure measurement accuracy.

10.3

Fluff Feed

Heterogeneous materials, variable in size, quality and physical properties are typically difficult to feed (Figure 2). Ideally, the material should be finely divided and homogenized before processing. An auger or belt or feed device can then be calibrated to obtain constant, controllable, reproducible and reliable federates. Otherwise, the testing would be erratic and hard to interpret. Figure 2: Fluff as it was made available

Pilot Test Reporting and Discussion of Results

161

After adequate shredding (courtesy of Shredding Systems Inc., Portland, Oregon) and mixing (Figure 3), the pieces of fluff had an apparent uniform size of about one-half centimetre and the mechanical auger feed ran flawless for the whole weight calibration test (several hours at variable speeds) and then for the tests, which altogether lasted several days. Figure 3: Fluff after fine shredding

5 mm

10.4

Plasma Reactor

The pilot plant of Integrated Environmental Technologies (IET) has been used for the tests, thanks to their support and active participation in this research. This plasma reactor accomplishes two distinct operations simultaneously, gasification and vitrification. Organic material is gasified in a chemically reducing environment and inorganic materials (metals and minerals) are melted and incorporated into the glassy product. With regard to product gas emissions, the system had already been demonstrated to produce very low values of dioxin, certainly due to destruction of precursors, lack of free chlorine (the raw syngas contains HCl not Cl2), minimal catalysing metals such as copper, and temperatures well above the dioxin formation window followed by quenching of the gases to below 200C in a fraction of a second (Tuppurainen, 2003: pp. 652-658). Extensive testing on the destruction of PCBs using this exact technology was conducted by Kawasaki Heavy Industries in Japan in 2003 with the result that the Japanese government approved the use of this technology for treatment of PCBs (Quapp, et al., 2004). NOx compounds are not formed because the

162

Chapter 10

plasma operates in a high temperature reducing environment. Under these conditions oxygen in the system reacts preferentially with excess hydrogen, with CO and other organic compounds. Chlorine in the process reacts with hydrogen to form hydrogen chloride, which is easily scrubbed from the synthesis gas. Thus the offgas has low concentrations of chlorine (in any form), this non-corrosive characteristic becomes important for any subsequent utilisation. Copper and metals present in the electronic scrap remain in the molten glass bath. A small quantity of glass, carbon particles, and other materials will exit the plasma reactor with the gases. These materials form a particulate that is readily removed in the baghouse filter.

Figure 4: PEMTM

Conceptual Scheme

The patented Plasma Enhanced Melter (PEM) system, outlined here just for its process features and shown in Figure 4, has been previously described and its emissions are reported while treating hazardous waste, electronic scrap and medical waste (Quapp, et al., 2003). The process chamber is the heart of the system, it is contained in a doublewalled vessel having the sides and the lid cooled with forced air, while the floor is water cooled. The interior of this vessel is lined with layers of refractory materials to contain the molten product, resist to the glass contact and insulate the shell from the high process temperatures. The PEM system is operated with a molten glass pool in the bottom of the process vessel. Two drains are located in the process chamber, one in the side wall of the glass pool for normal glass product removal and one in the center of the floor for removal of molten glass or metal. The bottom of the glass pool is fabricated from graphite, covered by an electrically conductive refractory, thus allowing the furnace floor to be used as an electrode in the power supply system. Glass is heated by AC joule-effect to a temperature exceeding 1200C while the zone above the bath, in vicinity and between the arc electrodes, can reach 1300 to 1500C, depending on the power input. The DC plasma arc is produced by a pair of graphite electrodes, which arc to the surface of the molten glass and produce heat for the endothermic gasification reactions.

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Organic materials are reacted above the glass surface with steam and a small amount of oxygen. Inorganic materials are typically dissolved into the glass pool as oxides. Nonoxidized metals sink to the bottom of the vessel where they melt and alloy together to form a pool of molten metal at the bottom of the glass pool. The PEM is a very energy efficient waste plasma processor since the DC and the AC electrodes require minimal cooling water (total losses to electrode holders are less than 5%). There are also small losses on the DC side due to rectifier losses and transformer impedance losses on the AC side. It should be noted that in this plasma system heat is not just added to the top but is added throughout the glass bath in a tri-dimensional manner. Figure 5: Hot section of the IET Plasma Pilot Plant

The single heating from the top used in other systems often results in glass overheating with possible damages of the refractory and volatilisation of the lighter parts of the glass, like Na2O which are important instead as fluxing agent and keep uniform bath viscosity

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and temperature. The proprietary electrode design, cooling and replenishment advancement enables trouble-free and continuous operation, qualities that are also exploited in the laboratory scale pilot plant (Figure 5). As with most small-scale test units, the efficiency is less than a full-scale system due to the relative sizes of nozzles, un-insulated flanges, and the high heat losses with respect to material processing rate. The small scale pilot system uses a proportionately larger quantities of nitrogen for purges and atomization. This increases the relative amount of nitrogen and thus decreases the concentration of hydrogen and other product gases.

10.5

Testing Procedure

The key objectives of the test were to demonstrate consistent, controllable, and reliable feeding of the ASR material, demonstrate efficient conversion to a syngas, evaluate waste heat recovery, and demonstrate permissible leach characteristics of the discharged glass. The quality and treatability of the syngas are also important but they had already been widely demonstrated in previous tests on chlorinated organics and similar waste. After bringing reactor and extended residence chamber to about 900C, fluff and oxygen were brought to react under a nominal power input of 14 kW to the plasma. The process variables were steam, oxygen and carbon dioxide addition, at constant fluff feed rate. Each run had the duration of about 15 to 20 minutes of stable operation, while approximately 10 minutes were allowed between operating conditions changes, to avoid upsets or erroneous readings. The volume of the pilot plant reactor is such that negligible and yet repetitive lag is observed between variations, hydrogen is faster to displace than carbon monoxide and sufficient time was used to flush the system with nitrogen between heavy CO2 dosages to avoid misinterpretations. About 10 vol-% CO2 was allowed to remain in the syngas, which was achieved by controlling the steam injection with the ultimate result to measure a CO/(CO+CO2) ratio of about 0.7. The procedure was explained for establishing a degree of water-shift-reaction and simultaneous carbon Boudouard equilibria to yield and limit the carbon black formation to about 5% of the total feed rate. The testing feed rate was held constant at 6.3 kg/h for all the selected tests except for the last few runs, which were operated at double capacity feed. Solid glass and ashes were taken out, batch-wise, at the end of each day run, and they are therefore homogeneous averages of the day.

10.6

Energy Balance

In terms of heat balance, the process would not be efficient if we were to reason in terms of a single conversion in a type of incinerator, thing which is incidentally prohibited when treating ASR. If we are however to consider the recovery of valuable products, H2 and CO, the conversion content is very high and the comparison is marked by the blue box reported below. The same waste, requires more energy input in a plasma converter and if only thermal power recovery is then considered, a higher value is obtained, due to the greater input that has been used. The balance described below is based on the quantities and fluxes of the pilot plant, figures that cannot be rated as

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optimal for an industrial case, but enough to appreciate the relative efficiency of the intended use, application of Figure 6 below. Looking at column 5 of Table 1, the power input of the pilot plant appears to penalize the possible application of the process; in reality, 8 of the 14 kWh shown on the table are estimated to be attributable to heat dissipation. A larger system could easily offset the high relative thermal losses of the experimental equipment; nonetheless, it is possible to foresee an efficient application of this study, particularly for the feed stocks that are noxious, or cheap or even a source of revenue -tipping fee- for being treated (Tellini et al., 2004:pp. 143-150). The end result of the left column 1 would obtain 2.05 kWe (20%) and the red value of column 7 and 8 would get 8.19 kWe, against the 24.56 fed to the system (33%). The system is not however meant to transform and extract electric power, so the input and output scale of energies in the blue frame, colour coded as per Table 1, is only meant to fix the relative figures of the discussion. Figure 6: Main streams and energy flows
AC and DC Power Electrodes Glass O2, N2, H2O, CO2

Steam, kW 7 CO = 18 vol-% H2 = 22 vol-%

2 3 4 5

Fluff feed

Reactor

Boiler (expected)

FGT

Syngas

C recycle

Table 1: Main streams and energy flows, heat and material balance (hourly base)

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The efficiency of producing electricity through an incinerator is stated at 20% of the total thermal input as it would be exceeded only with additional heat recovery like district heating, heat pumps or thermo-compression (Chapter 3). The efficiency of the heat recovery was taken higher, as 25% which is justified by higher operating temperatures of the thermal cycle, while the genset can reach 35% or higher efficiency, depending on the combustion engine. The comparison of alternative efficiencies, calculated from the pilot plant operation (bottom line of the table) is favourable to the plasma process, due to the HV of the syngas, 6.62+1.57=8.19 kWhe as opposed to 2.05 kWhe that could be obtained from conventional incineration, but insufficient if we were to subtract the power input of about 14.3 kWh. Understanding that a commercial plasma plant would not have such heavy losses, most of the wasted 8 kW would be spared and the overall balance would close or be slightly positive (6.62+1.57-6)= 2.19 kWhe, value that compares to incineration. In this case, the only advantage of the plasma treatment would need to be sought in plant and emission safety, as well as operating and investment costs or advantages that may derive from CO2 abatement tied to the application of a carbon tax. The greater efficiency would however be gained if the syngas is used as such and it is not thermally down-rated to burn and produce electricity via a thermal engine. The compared efficiency would thus increase to (18.9+1.57)/(14.3+10.26)83%, depending on losses and other accounts like electrodes, reheats or ancillary utilities.

10.7

Chemical Analysis and Material Balance of Inorganics

Fluff feed as well as vitrified solid discharge and FGT ash were analysed as reported in Table 2. The analyses were made on samples taken from the bulk of solids, with the miners method, i.e. after mixing the solid, a pile of one quart of the material was segregated, the material mixed again and a fourth of that pile segregated again. The operation was repeated until a small pile of sample was obtained, from which a grab sample was taken for chemical analysis. The procedure is clearly affected by the starting heterogeneity, but we can say that each sample was fairly representative of the initial solids. The sample of fluff was taken from the finely shredded material: inaccuracy may occur if a piece of metal is included or excluded from the sample, the same can be said for a tiny rock and glass, but data were reproducible on the average of several determinations. Initially, the resolution of a dozen independent equations linear system was attempted to balance the same number of constituents. Even by using robust algorithms, the system did not converge. We introduced an error compensation for each constituents (physically, that could mean that a constituent was taken in or out by some unit operation or was not correctly accounted, as it could be due to erroneous chemical analysis). The method works and is intrinsically justifiable, but the accuracy of results is merely a mathematical consistency. We then preferred to impose the balance of silicon and the mass flowrate ratio derived accordingly. Silicon is introduced with fluff, is also introduced with a nominal initial charge of glass cullet (used as aid to control the viscosity of the bath), it is drawn from the system with the pouring of the vitrified slag and with the ash.

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Table 2: Analysis of solids

1 Plasma 2 Stream Spec. Weight Cl (total) F (total) S (total) Al Ca Cu Fe Mg Pb Zn Si K Na Hg Sn P B Ba Be Cd Co Cr Mn Mo Ni As Sb Se V units Kg/l ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm 1 0.6 19,700 0 34,763 4,227 16,135 3,635 33,090 2,036 1,378 3,338 112,530 653 880 < 0.5 55.9 465 110 692 < 0.09 11.9 16.2 210 304 39.2 90.6 3.8 140 < 0.5 15.1 2 2.2 201 370 < 29 60.7 24,311 50.9 97.4 < 247 1.5 167 288,490 29.4 614 < 0.5 < 2.5 12.2 2.7 10.9 < 0.1 < 0.5 < 0.1 9.4 34.6 < 2.5 0.6 < 0.5 < 0.5 < 0.5 < 0.2 3 0.3 82,080 1,368 24,082 1,920 7,610 3,580 3,370 3,040 10,660 25,140 119,200 14,900 171,540 7.4 824 349 461 508 0.1 61.3 3.6 63.7 322 79.1 43.9 22.5 260 28.9 4.1 Baghouse 3

The poured molten glass contains silicon of the slag but also the unbalance of silicon coming from the reactor glass pool, having quality assimilated to ordinary glass, Table 3. Table 3: Cullet glass composition Since the system was started afresh, it is reasonable to make the hypothesis SiO2 70.5 as Si 33.0 that the extra glass lining input Al2O3 1.9 as Al 1.0 contribution had the same composition Fe2O3 0.4 as Fe 0.28 of the cullet, while the glass pool portion had the same CaO 13 as Ca 9.3 exiting composition of the poured glass. We Na2O 12 as Na 8.9 99.7 54.08 had measured the quantity of fluff introduced in the repetitive tests, not simply by calibrating the auger feed, but by difference of all the material weighted in a starting bucket and in the final leftover bin (28.6 kg for the October 6th tests).
K2O wt-% 1.9 as K wt-% 1.6

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Similarly, we knew the quantity of cullet (4.5 kg) and the quantity of poured glass (20 kg at the end of the tests). It is not known how much glass remained inside the reactor (a quantity of molten glass is always left inside, even during idle conservation of the equipment), we can assume about 1/4th of the reactor useful volume, say 7 liters or 15 kg at the end of the tests. The quantity of ash (2.1 kg after drying the water off) was measured and was also affected by the quantity of dolomite, MgCO3CaCO3, which was actually added to pre-coat the baghouse filter at the start of operation (0.7 kg). We considered that only about one third of the dolomite, 0.25 kg, exited as Ca and Mg with the ash, but this contribution plays a marginal role in the overall balance indeed. The material balanced for silicon, which may well be considered inert, relevant to a 28.6 kg fluff feed and 20 kg residual glass pouring is reported under Appendix 10.1. To conclude considerations on the material balance of inorganics, the metals and species that are not accounted in the analyses of solids are abated in the scrubber section of the gas cleaning system and are exhibited in the material balance as exiting stream Off, whereas gases and organics are discussed in separate sections of this Chapter. Figure 7: Cullet and inorganic materials leaving the reactor
7 Dolomite Inorganic materials Balance (dry) 1 Feed Plasma 6 Cullet+molten inside 2
Slag - kg Cullet - kg Off - kg Q1/Q2

4 Baghouse 3
Q1/Q6

To scrubber

5
Adjustment

15 20 25 29 35 40

4.15 8.5 13 16 22 26

3.4 4.1 5 5.5 6.5 7.3

1.9 1.4 1.1 1 0.8 0.7

6.9 3.4 2 1.8 1 1

Mass balance at 28.6 kg fluff feed

30 25 20 Kg 15 3 10 5 0 15 20 25 29 35 40 Glass slag, kg 2 1 0 7 6 5 4 Cullet, kg Off, kg Q1/Q2 Q1/Q6 Ratios

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Referring to the table of Appendix 10.1 and to Figure 7, the unbalance of 4.1 kg is not necessarily to constitute the whole load to the scrubbing system. There can be pieces of metals, steel for instance, having a melting point >1570C, that might have sunk to the bottom of the glass bath and were not extracted, therefore it escaped the analysis used as base of the material balance. Similarly, there may be some metal oxides and pieces of rock that did not melt and remained on the bottom of the bath of the pilot plant. Such problems would not occur with a continuous industrial reactor blow-down and would be items to consider for a scale-up design.

10.8

Syngas Produced and Operating Input

It is reasonable to assume that all gas-phase molecules behave ideally, pressure is practically atmospheric or slightly negative, kinetics are non influential since the temperatures are well above the minimum equilibrium temperatures that minimise Gibbs free energy. On such basis, molar balances and gas compositions were calculated. The mass feed ratios of O/C, H2O/C and CO2/C were varied between 0.2 and 2.0 and the resulting syngas composition is shown on the gas diagrams reported below. Given the 14 kW DC power feed limitations of the experimental unit, the first issue was to feed sufficient pure oxygen to establish a quasi auto-thermal process when it is well known that most gasification reactions are endothermic. Oxygen feed ratios were varied with the main criteria to sustain the fluff conversion and syngas generation, depending on the water or carbon dioxide feed to the reactor. The power consumption is also affected by thermal dissipation, but since there is equivalence between electric power and oxygen supply, the choice becomes a matter of relative cost: performance of the process and the attained temperatures are interchangeable irrespective of the power source. Figure 8: Syngas generation Experimental water to carbon feed ratio, or to that effect, CO2 to carbon feed ratio ranged from 0.2 to 1.8 and the amount of CO and H2 is shown in Figure 8. Each bubble represents the gas average concentration for a given operating parameter. The size of the bubbles is proportional to the number of repetitive measurements at the indicated feed ratios. The maximisation of the H2 concentration and bubble frequency was obtained for the higher steam to carbon ratios whereas excessive steam injection did not significantly improve the hydrogen production, although it increased the power input need. The mid points (3 to 6) have dual feed of H2O and CO2. As the water increases, with lower CO2 feed, H2 increases and the CO production diminishes.

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Figure 9: Offgas generation Repeatability for the CO and H2 production in 13 selected (Pure syngas basis: CO = 55.3vol-% and H2 = 44.7vol-%) trials is shown in Figure 9. vol-% Avg; The trials were characterised 19.6 by stable run-lengths of about 20 minutes, and the operating CO vol-% Avg; vol-% Avg; variables (O2, H2O, CO2) were CO2 54.1 10.3 ratioed to the carbon feed. The N2 H2 CO, H2, CO2 measured in the N2 syngas were manually taken vol-% Avg; 16.1 every 5 minutes whereas the vol-% process instrumentation recorded every 2 seconds. The diagram shows that the product gas is strongly diluted by nitrogen. The reactor is not fed with nitrogen nor air, but N2 is largely utilised with water injection in the quenching of the gases, downstream the plasma reactor. On the basis of the process computer recordings, all significant trials of October 6th are reported and diagrammed in Appendix 10.2 to this chapter. For convenience of discussion, we report under Table 4 the exiting gas composition with main reagents input of the experiments performed on that day, followed by Figure 10 and Figure 11 relevant diagrams of two significant runs (Tellini et al., 2005).
Offgas generated in 13

Table 4: Main data pertinent to October 6th experimentation

Averages report for each run of October 6 Exiting gas vol-% Stable Trials T61 T62 T63 T64 T65 T66 T67 CO 18.2 19.0 17.9 17.5 22.4 19.6 24.6 CO2 10.2 9.7 11.0 11.5 13.4 13.8 7.6 CH4 0.4 0.7 0.5 0.4 0.4 0.0 0.0 H2 16.2 19.7 19.7 21.1 15.4 9.3 19.1 wt-ratio CO (CO+CO2) 0.6 0.7 0.6 0.6 0.6 0.6 0.8 feed wt-ratios H2O/C CO2/C

O2/C

0.3 0.8 1.2 1.7 0.8 0.0 0.9

0.0 0.0 0.0 0.0 1.4 0.9 0.0

1.7 1.7 1.8 1.8 1.7 1.7 2.1

Fluctuations are explainable with the variable composition of the heterogeneous fluff and by the irregularities in feeding the solid with an auger, although the auger had been previously calibrated. Results would clearly be much smoothened out for a commercial plant where the large solid feed-rate is likely to resemble continuity and homogeneity. For practical purposes, the gas measurements are also superimposed with a 6th degree polynomial interpolation and it becomes quite evident that the H2 production develops homothetically with the CO production. Correspondent to syngas peaks, we note diagram valleys for the CO2 that also exits with the product gas.

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Figure 10: Oct 6, trial 1

Oct 6, Run # 1
Plenum T=1080C, PEM T=820C, TRC T= 1050C, DC Feed = 14 kW

20.0 18.0 16.0

20.2% 18.2% 17.7

2.00 1.80 1.60 1.40 CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2

14.0 Vol-%, syngas 11.5 % 1.00 0.80 0.60 0.40 0.20 0.3 % 11.04.00 11.04.30 11.05.00 11.05.30 11.06.00 11.06.30 11.07.00 11.07.30 11.08.00 11.08.30 11.09.00 11.09.30 11.10.00 11.10.30 11.11.00 11.11.30 11.12.00 11.12.30 11.13.00 11.13.30 11.14.00 11.14.30 11.15.00 11.15.30 11.16.00 11.16.30 11.17.00 11.17.30 11.18.00 11.18.30 11.19.00 11.19.30 0.00 Wt-Ratios 12.0 10.0 8.0 6.0 4.0 2.0 0.0 1.20

Solar time

Figure 11: Oct 6, trial 5

Oct 6, Run # 5 Plenum T=1065C, PEM T=807C, TRC T= 1115C, DC Feed = 14 kW
26.0 24.7% 24.0 1.60 22.0 20.0 18.0 Vol-%, syngas 16.0 14.0 12.0 10.0 8.0 6.0 4.0 0.20 2.0 0.0 12.50.00 12.50.40 12.51.20 12.52.00 0.3 % 12.52.40 12.53.20 12.54.00 12.54.40 12.55.20 12.56.00 12.56.40 12.57.20 12.58.00 12.58.40 12.59.20 13.00.00 13.00.40 13.01.20 13.02.00 13.02.40 13.03.20 13.04.00 13.04.40 13.05.20 13.06.00 13.06.40 13.07.20 13.08.00 13.08.40 13.09.20 13.10.00 13.10.40 0.00 0.60 0.40 14.9% 18.5% 1.20 15.7 1.00 0.80 Wt-Ratios 1.40 CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C O2/C Polinom. H2 Polinom. CO Polinom. CO2 1.80

Solar time

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Test # 1 had no CO2 feed, but H2O. At constant material and power feed , the oxygen to carbon weight ratio was kept at 1.7 for both tests. Test #5 exhibits a greater H2O/C (0.8) and an admission of CO2/C of 1.4 weight ratio, yielding a CO percent of about 3 points greater. The limitation effect of electric power feed versus the possibility to obtain a satisfactory dry reforming was one aspect of the experiments. In preparatory tests it has been possible to run experiments to crash, in the sense to obtain no better output or no output for a given feed ratio of CO2/C and H2O/C as opposed to O2/C. In other words, a test was visibly satisfactory when syngas was analysed by the process instruments (CO and H2 above 10. vol-% plus O2 nil, evidence of reducing atmosphere), with limited carbon black formation (indicated by no increase of pressure drops in the baghouse, as compared to the normal operating level of P 1 psi that maintained the measured reactor pressure slightly negative or atmospheric), and temperature stable above 900 C in the reactor. The test crashed when missing said objectives as the water and carbon dioxide feed combination was increased. The footing for energy is the burning or partial oxidation of the carbon, ideally this consumes no electric power, it releases thermal power. As water and CO2 to carbon ratios are increased, without feeding oxygen, electric power must be increased or cracking and gasification would not occur or stop. The attempt was to draw a tri-dimensional power envelope (ordinate z) dependent upon steam and dry reforming characterised by H2O/C and CO2/C axes (x, y), as initially planned and explained under Chapter 9. Losses and available power input limitations allowed few points of measurements that are summarised in Table 5 and easily allow the equation of a limiting useful power plane. Feed combinations exceeding the power of the plane require oxygen, or conversely, for a given useful power input only permissible combinations of water and CO2 to carbon ratios would be possible. Table 5: Electric power input vs. H2O and CO2 feed ratios z = kW (net of losses) 4.3 8. 9. x = H2O/C 0.2 1. 0.2 y = CO2/C 0 0 1.

x y z .2 0 4.3 1 0 8 .2 1 9

1 1 =0 1 1

z = 3.375 + 4.625 x + 4.7 y [kW] In a tri-dimensional graph, the plane cuts the permissible boundary region of feed combinations, for example at z = 9 kW x = 0.5, y = 0.7 or x = 0.8, y = 0.4, while x 0, y = 1.5 is a non permissible locus. The result is more speculative than useful, with additional experimental data in a wider power range, a surface intersection boundary could be determined, but even that case would mainly offer a graphic representation rather than a tool for operation.

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10.9

Carbon Balance and Carbon Black

From the quality of measured syngas we have seen that methane production was marginal, non detectable or below 0.3 vol-%. From the ash analysis, carbon black was generated, particularly when only CO2 was fed to the reactor, experience that was attempted with the preliminary tests. As we have already discussed, we had the need to use O2 to compensate for lack of electrical power. This could have been avoided by feeding a relatively smaller rate of fluff (higher power intensity input), but we would have then suffered a discontinuous feed of the solids, bridging inside the feed bin and unreliable calibration of the auger feed. The use of extra oxygen may actually generate CO2 because the combustion has very rapid kinetics and the reaction is not necessarily controllable to stop short at partial oxidation. We have seen that water introduction brings control benefits and reduces soot or carbon black formation. All considerations enable to conclude that a large reactor, starved with oxygen and with steam reforming sustained by adequate power feed would work satisfactorily and the dry reforming would actually convert CO2 plus carbon to greater concentration of syngas. Based on measured results taken from the pilot plant size and type of experimentation, the carbon balance for the significant tests of October 6th is reported under Appendix 10.3 to this Chapter. The gas vol-% are those taken from the experiments and the consistency has been verified for two fluff feed carbon concentrations. The quantities of carbon, are the same that are exhibited in the run sheets of Appendix 10.2, tables that are placed in front of each exhibited diagram. Conversions are expressed with and without recycle of the residual carbon black. Concerning the CO2 abatement, it is interesting to observe Table 6 below, which reports plasma results but also the amount of CO2 that would be generated in a full combustion of the carbon source plus the CO2 intended as plasma reagent. Table 6: Abatement of CO2
C
#mol in

Abatement of CO2 CO2

# #mol in #

CO2
#mol out #

CO2
# combustion

Diff. 14.883 13.773 17.709 3.936 14.375 13.818 20.256 6.438

g c c-g g' c' c'-g'

0.4717 0.4717 0.4717 0.4717 0.4717 0.4717

5.66 5.66 5.66 5.66 5.66 5.66

0 0 0.1 0 0 0.2

0 0 4.4 0 0 8.8

0.133 0.159 0.169 0.145 0.158 0.211

5.870 6.980 7.445 0.464 6.379 6.936 9.297 2.362

20.753 20.753 25.153 11% 20.753 20.753 29.553 27%

70%

69%

A Test T61 T63 T66 T62 T64 T65 #mol entering O2 H2O .12 .03 .37 .03 .03 .03 .27 .03 .53 .03 .26 .03 CO2 .1 .2

B-A

line above line g line g line c line above line g line g line c

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The carbon enters as organic fraction of the material, graphite electrodes and CO2 and it exits as CO2, CO and residual carbon black fraction. It is clear that allowing oxygen and also the degree of CO2 formation already explained, even the plasma reactor generates CO2 with a converted quantity of input CO2 greater when higher power to carbon feed is available. The CO2 introduced into the plasma process, as a reagent, is mostly converted. Furthermore, the CO2 that would be generated in a conventional burning of the fluff would be much greater. By reading the balance (lbs and lbs-mol/h) of lines g and c, that start with the same carbon content and have CO2 added for line c, the ultimate quantity of CO2 that leaves the system is only 11 wt-% of the CO2 that was introduced. In a combustion process all carbon and CO2 would go to CO2, and the difference that we read is 70%. Based on other tests data ( T64 and T65) we read different percentages due to different operating parameters, but the end result is always that a substantial percent of the CO2 is taken out from emissions. Carbon calculations were based from the beginning of the experiments on the 41 wt-% carbon content that was firstly analysed; later carbon analysis indicated a higher carbon content up to 54 wt-%, difference that might be attributable to two major facts. The latter sample, taken from the same shredded material, needed very fine grinding for the laboratory microanalysis and it is possible that some heavy solids like scrap metals or rocks were not included or even that the material first analysed had greater humidity. All variations are likely to occur again with any processing of fluff and for that reason we remained with the initial carbon concentration of 41 wt-%. Compared to the same gas results and to the same feed of reagents (CO2, O2 and H2O), a greater carbon concentration in the fluff would reduce the conversion and increase the carbon black recycling. A table was generated for the forms of carbon of each run (C input, carbon black, graphite from electrodes, CO, CO2, CH4) and significant tables are reported for the October 6th tests under Appendix 10.2. The initial percent of carbon black was estimated to vary between 7 and 15 % of the feed that justifies to recycle it back in a commercial reactor. During the tests, a lower residual portion of carbon black was found, 12.9 wt-% of the total ash quantity accumulated for all tests in one day. The quantity of dry ash of that day was 2. kg as opposed to the total fluff feed of 28.6 kg, i.e. 2.2 wt-% of the incoming fluff carbon.

10.10 Pseudo-order and Rate of Reaction

When considering high temperatures reactions, the chemical states of combination are very fast and the chemistry kinetics is not the controlling variable, the study is essentially thermodynamic and the reactions can be considered at their equilibrium. The problem can be studied with macroscopic balances at the inlet and outlet of the system, without the need to analyse the evolution with local temperature or concentrations profiles. We made the hypothesis that reactions go on irreversibly until the reactants are exhausted because we operate above the equilibrium temperature. Starting from heterogeneous material this implies that all the reacting material is decomposed and/or converted to the gas phase.

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We can ascertain if the two hypotheses hold true or if the hindrance to gasification can prevent that reactions reach the equilibrium. -r = k(T) f(CA, CB, ) the kinetic constant is independent from concentrations and generally depends on temperature, catalyst, pressure and/or less importantly, on phase variables for liquid systems. The constant can easily be expressed in the form of Arrhenius formula in which the pre-exponential factor is an indication of the collision frequency and the minimum energy to react is given by the activation term E. k(T) = A exp(-E/RT) or in log form ln k = ln A E/R (1/T)

constants are found for most species, but we dealt with an unidentified solid mixture so we derive the values from our experimental data. We only use data measured at fairly homogeneous temperatures. Firstly, we determine the pseudo-order of reaction for the gas reactants -r = k CAa CBb CCc for a cumulative order of reaction n= a+b+c

exponents that are not necessarily linked to the pseudo-reaction stoichiometry. Since the reactor volume was fixed, we can simply write concentrationsVolume=moles |r| = k(T) [O2]a [H2O]b [CO2]c the rate becomes moles of carbon consumed in 1 hour for a reaction volume V in m3. Table 7: Average feed wt-ratios and temperatures in the reactor and TRC chamber Test T51 T52 T53 T54 T55 T56 T61 T62 T63 T64 T65 T66 T67 H2O/C CO2/C 0.20 0.43 0.12 0.09 0.19 0.41 0.30 0.82 1.18 1.71 0.78 0.93 PEM C 1010 1070 1050 1090 1080 1095 1080 1062 1080 1075 1075 1100 1150 TRC C 990 1050 1080 1085 1110 1130 1045 1065 1090 1110 1115 1135 1150

1.41 0.95

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Chapter 10

We utilise the reactions tests of Table 7 that indicates main feed ratios and operating temperatures. Mole rates are in #mole/h and details are reported in Appendix 10.3. T62 T64 T65 T67 0.399 = k62 (.03+.29)a (.27)b 0.421 = k64 (.03+.3)a (.53)b 0.558 = k65 (.03+.27)a (.26)b (.2)c 0.81 = k67 (.06+.34)a (.32)b

passing to logarithms, for the same average temperature Tavg=1071C, we have identical ln k for all reactions T62 T64 T67 0.9188 + ln k = 1.1394 a + 1.3093 b 0.8651 + ln k = 1.10866 a + 0.63488 b 0.2107 + ln k = 0.9163 a + 1.1394 b

solving and substituting into T65, we get a= 3.13, b= -0.05, c= -0.334 and n= 2.75 plus k= 13.2 The same pseudo-order of reaction introduced into T61 and T63 yield k61= 13.71 and k63= 13.47, while things are not as good for reaction T66: this is explained by the fact that we ran the reaction without practical addition of H2O other than humidity and the molecular water of the substance. Water is important, even when dry reforming is made because both reforming reactions are endothermic, HR = 49 kcal/mol and HR = 59 kcal/mol for H2O and CO2 respectively. The water excess acts to control and stabilize the temperature due to its thermal capacity and through the parallel reactions of watergas shift (moderately exothermic) and steam reforming (endothermic) with the additional advantage that hydrogen is supplied and this is a further help when using low hydrogen feedstocks (Natta and Piontelli, 1937: pp. 177-182). We also verified the pseudo-constants for reactions of the series T5. Reaction T55(1095C) gave k=18., T52(1060C) gave k=14.78 and T54 (1088C) gave k=15.35. In consideration and adjusting for different temperatures, the fit was however moderately consistent because we ran those tests with little or no steam. Notwithstanding these considerations, it appears that we are within the order of magnitude of the calculated rate constant.

10.11 CSTR Space Time

The reactor behaves like a backmixed reactor. One doubt could be that if a plug flow reactor fits the data, we would obtain a significantly smaller reactor volume, but these considerations cannot apply to the turbulent chamber where the plasma is generated. In other types of plasma reactors, the reaction is confined to an annular cylinder but even within such region, where for example gases are conveyed and constrained by a magnetic field, turbulence and local temperature uniformity allow to consider the reaction volume fully mixed. The objection could possibly hold in the thermal residence chamber (TRC) of our apparatus, where the gases transit without

Pilot Test Reporting and Discussion of Results

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catalyst or additional reagent, just to prolong their residence time at high temperature, or in special cases, are assisted by a flame when low heating value feedstock are used. This last case did not apply to our experiments: we had the potential post-combustion disabled. We therefore assimilate the whole available reaction volume to a continuous stirred tank reactor, practically operated to exceed the thermodynamic equilibrium temperature, and we can apply the integral design formula of a CSTR: V = FA0 X /(-r)exit or t = CA0 X /(-r)exit

written to obtain the volume or the reactor space time for a given feed-rate FA0 or initial concentration CA0 in terms of conversion X and exiting rate of reaction. Reactions consumed fluff at the rate of 13 lbs/h, having the average carbon content of 41 wt-%, in a volume of reaction that can be estimated from visual physical dimensions as follows: a molten glass overhead space of about one third of a cubic foot plus a TRC volume of about 90 liters, for a total of say 100 liters (detailed size and internals of the reactor are not disclosed as they are proprietary information of IET, owner of the pilot plant). This means that we obtain a reactor space time calculated as follows: 13(0.41)/12 = 0.4441 #mol 13.2/0.100 = 132. #mol/h/m3 0.4441/132 = 0.0033 h = 11.8 s converted carbon moles rv rate, 100 l reactor space time in seconds

The residence time calculated from such apparent geometry appears to be consistent with the 10 to 15 seconds lag that we observed between gas displacement readings during the experiments. Speculating on the TRC, which is actually seen as an additional safety for operating a system that treats (variable quality) waste, one may infer that if we limit our space time to the volume of the plasma zone itself, the time reduces to one tenth, approximately 1.2 seconds, which compares to literature values found for the thermal cracking of hydrocarbons.

10.12 Activation Energy of the Pseudo-reaction

The next calculation is E, the energy of activation in Arrhenius formula, Figure 12: k(T) and activation constant determination k(T) = A exp(-E/RT)

178

Chapter 10

we can ratio two constants, at different operating temperatures (Figure 12), and ln k2 = A + (-E/RT2) ln k1 = A + (-E/RT1) ln k1 - ln k2 = -E/R(1/T1 - 1/T2) (2.6 2.58)/((7.3-7.44)10-4) = - E/1.987 E = 2838 cal/g-mol = 2.84 kcal/g-mol The order of magnitude of 3 kcal/g-mol seems to support the hypothesis that we are in chemical regime and it makes sense because we operate at high temperature with minute solid pieces and turbulence in the plasma gasification volume. The rate of reaction often follows the rule of thumb to double for every 10C temperature increase, but it also becomes more sensitive as the activation energy becomes larger. A possibility to verify the value that we obtained is the relation of activation energy with the heat of reaction, through the empirical method of PolanyiSemenov (Fogler, 1992: p. 102). E = C (-HR) with C = 48 kJ/mol and = -0.75 for endothermic reactions (we aim to convert to CO and H2)

The gasification/conversion reaction(s) of our carbonaceous solid mix may be quite involved, as we also burn some carbon with O2 to supply heat. To carry out this type of check let us write the hypothetical reaction with the moles measured at the balance of the experiment test T65, subtracting the moles of non reacted C and found as carbon black, and ignoring methane which is in nominal quantity (0.005 #mol/h or less), we obtain a cumulative, hypothetical stoichiometry as per Table 8: Table 8: Cumulative stoichiometry and H of reaction @ 1300C C C C 0.354 ultimately 0.342 referred 1. +H2O = = +O2 = 0.2 0.27 = to correlate the ni to 0.057 = entering mol of C we 0.1666 = +CO2 CO 2CO 0.342 calculate 0.342 get 1. +H2 CO2 0.211 +4.2 kcal/g-mol 12.28 kcal/g-mol

0.29 we have 0.228 to one 0.6666

0.228 the HR 0.228 0.6666

The quantity of H2 was derived from the ratio with CO obtained for the experiment T65 in which H2/CO 1/1.5. E = 11.47 - 0.75(+12.28) = 2.26 kcal/g-mol This value is 20% smaller than we calculated, but we know that we had significant heat losses (it is like saying that our operation converted less C and burned it to supply heat, so the end result was like forcing a greater HR that reflects in a smaller E).

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10.13 Ash and Vitrified Material Discharge

Ashes were collected after quenching, at the bottom of the bag filter. Their quality was checked, not for disposable characteristics, but to investigate the possibility to design a conventionally rapped waste heat boiler for the offgas downstream the plasma reactor. Table 9: Ash constituents (wt-%) Specific weight Carbon Chlorine Fluorine Sulfur (as total) Cadmium Chromium Copper Mercury Zinc [kg/l] 0.3 12.90 8.20 0.13 3.47 0.0061 0.0064 0.36 0.00074 2.51 The amount of carbon black and ashes are suitable to be recycled back to the reactor and the inert portion is purged with the molten glass. Constituents of the ash are marginally affected by the dolomitic neutralising and coating agent as already explained. Major ash constituents are reported in Table 9.

The testing had been planned for the gasification purposes above and further analytical work was beyond the purposes of this test. Only gaseous effluents were measured whereas the glass leaching test and the analysis of the ashes were done afterward. No analysis was made for the ultimate gases released by the system nor the constituents of the scrubbed water were investigated. In previous tests, dealing with high chlorine waste (PCBs) and mercury hospital wastes, it had been ascertained that contaminants released by the plasma reactor as HCl, HF, or Cd, Pb, Zn and Hg for the metallic treatment case, can be captured safely and neutralised without fear to release them to the atmosphere (Batdorf et al., 2005). As to the water cooling, water effluent quality and treatment, no investigations were planned since the topics are fully studied and applied already in plasma plants commercialised by IET. The discharged glass well compares to the glass scoured from the reactor in similar tests. Leaching tests were performed according to the Italian method UNI 10802_2002, a water leaching test that recently homogenised European norms set for disposable or safe reusable solids. Similar favourable testing can be obtained according to EPA TCLP 1311. The comparison of the sample analysis and the permissible values are given in Table 10.

180

Chapter 10

Table 10: UNI 10802_2002 Limits and Analysed Leachate from residual glass
Species pH TDS DOC Phenol Index Arsenic (As) Barium (Ba) Cadmium (Cd) Chromium (Cr) Copper (Cu) Lead (Pb) Mercury (Hg) Molibdenum (Mo) Nickel (Ni) Antimonium (Sb) Selenium (Se) Silver (Ag) Zinc (Zn) Chlorides (Cl) Fluorides (F) Sulphates (SO4) US / EPA TCLP Test Limit (ppm) UNI 10802_2002 Test Limit (mg/l) 400 50 0.1 0.05 2 0.004 0.05 0.2 0.05 0.001 0.05 0.04 0.006 0.01 Not Applicable 0.4 80 1 100 Leach Analysis (mg/l) 9.83 100 <1 < 0.01 < 0.001 0.05 < 0.001 0.001 0.003 0.002 < 0.001 < 0.001 0.001 < 0.001 < 0.001 0.01 3.4 < 0.1 <1

Not Applicable 5.0 100.0 1.0 5.0 Not Applicable 5.0 0.2 Not Applicable Not Applicable Not Applicable 1.0 5.0 Not Applicable Not Applicable Not Applicable Not Applicable

Figure 13: Possible reuse products from poured glass Value and possible reuse of the glass discharge will greatly vary on location and use. From tests and reuse studies in USA, the glass matrix can be modified to make grit blasting media, low density aggregates, roofing tiles, bricks and blocks (Surma et al., 2001). The recycle concept uses the coarse fraction of the crushed glass for grit blasting media and the finer fraction for low density foam glass products (Figure 13). While the glass density is between 2.3 and 2.8 g/cm3, the density of the foam glass tiles and bricks can be adjusted between 0.4 and 1 g/cm3, or depend upon the strength of the required material.

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10.14 Coupling of CO2 Emissions to the Plasma Plant

On the basis of utilising the results of the pilot plant tests, it is possible to extrapolate to a possible plant the results in order to have an appreciation of the key figures that we should deal with. The scaling up of the plant will clearly modify the parameters; nonetheless, higher efficiency, the possibility to feed higher specific power and achieve better conversion with lower recycling will enable to exceed the minimum base results that we can summarise below. Let us start from some fundamental figures to trace the minimum achievements of the possible plant that couples an emission gas treatment with a plasma dry reformer. 100,000 Nm3/h of flue gas with an average content of 10 vol-% CO2 = 20 t/h CO2 Using a CO2/C wt-ratio = 1.5, we need 13.3 t/h C or 27 t/h fluff, which already gives the impressive capacity of 648 t/day or say 142,560 t/year. Based on the material conversion of the pilot plant, and ignoring for the moment the recycling, we can express the balance in terms of C t-moles/h and such a plant would have 1.54 t-mol/h entering C, found at the end of the process in 0.15 t-mole/h of carbon black, the same of un-reacted CO2 and 1.23 t-mole/h of CO for an overall yield of 34.5 t/h CO and about 2 t/h H2 in product gases. These orders of magnitude can better be visualised for the exact balance, constructed on the flow apportionment of the experiments: The product gas was diluted to 50 vol-% by the quenching nitrogen introduced after the reactor in the FGT The vol-% of the CO2 bleed was 10% of the gas exiting the system The carbon black formation was about 10 wt-% of the raw carbon fed as CO2 and fluff The dry syngas ratios were 55 vol-% for CO and 45 vol-% for H2 Given that we wish to start with 20 t/h = 0.455 t-mole/h CO2 and use a CO2/C wt-ratio of 1.5, the equations and the solutions are as follows:
z = C O 2 re c yc .

x = CO2 y= C R e a c to r

t = CO r = H2

s = C re c yc .

Overall C mole balance CO2 recycle Carbon black recycle Syngas quality

x+y=z+t+s z (0.1) 2 (z + t + r) s 0.1 (44 x + 12 y) /12 t = 0.55 (t + r)

182

Chapter 10

Given x = 0.455 Given 44 x / 12 y = 1.5 or x / y = 0.41 molar Solving for the variables, the values become as follows: t-mol/h 0.455 1.11 0.885 0.402 0.278 0.724 t/h 20. 13.32 24.78 17.67 3.34 1.45

x y t z s r

If we were to consider a 5% bleed and recycle of CO2, which is likely to be achieved with higher power to the electrodes, the results would be as follows: t-mol/h 0.455 1.11 1.05 0.238 0.278 0.909 t/h 20. 13.32 29.4 10.47 3.34 1.81

x y t z s r

18 % greater than 24.78 40 % lower than 17.67 25 % higher than 1.45

These order of magnitude are a clear sign of the necessity of a substantial scale-up and the necessity of a major investment to accomplish it.

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10.15 References
Batdorf J., D. Lamar and W. Quapp, May 9-13, 2005. Demonstration of Mercury Capture Efficiency during Medical Waste Processing in a PEMTM. 24th Int.l Conf. on Incineration and Thermal Treatment Technologies, Galverston, Texas. Fogler S., 1992. Elements of Chemical Reaction Engineering. 2nd ed., (Englewood Cliffs, NJ: Prentice Hall). Natta G. and R. Piontelli, April, 1937. Sullutilizzazione del metano per la produzione di idrogeno. La Chimica e lIndustria, XV, Anno XIX, No. 4. Quapp W. and D. Lamar, May 12-16, 2003. Waste Gasification - Test Results from Plasma Destruction of Hazardous, Electronic, and Medical Wastes. IT3 Conference, Florida. Quapp W., J.Batdorf, D. Lamar et al., May 10-14, 2004. Destruction of Electrical Equipment and PCB Oil in a PEMTM. IT3 Conference, Arizona. Surma J., W. Quapp and R. Dejaiffe, 2001. Production of Recycled Products from Coal Ash Using a PEMTM. International Ash Utilisation Symposium, Paper # 101, Center for Applied Energy Research, University of Kentucky. Tellini M., P. Cntola, R. Del Rosso and P. Gronchi, 2004, May. Hydrogen from Waste. Chemical Engineering Transactions, Vol. 4, (Pisa, Italy: AIDIC Hydrogen Conference Proceedings), ISBN 88-900775-3-0. Tellini M., J. Batdorf, W. Quapp and P. Cntola, 2005. Automobile Shredder Residue Destruction in a Plasma Gasification Reactor. Article submitted, under referees evaluation. Tuppurainen K., A. Asikainen, P. Ruokojarvi and J. Ruuskanen, 2003. Perspectives on the Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans during Municipal Solid Waste (MSW) Incineration and other Combustion Processes. Acc. Chem. Res., 36 (9).

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Chapter 10

Appendix 10.1:

Balance of Inorganics

Appendix 10.2:

Syngas Diagrams and Balances

Appendix 10.3:

Balance of Carbon

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185

7 Dolomite 1 Inorganic materials Balance (dry) Feed 6 Plasma Cullet+molten inside 2 units Kg/l ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm g/t
g

4 Baghouse 3 5

To scrubber

Adjustment
in-out [g]

Stream Spec. Wt. Cl (total) F (total) S (total) Al Ca Cu Fe Mg Pb Zn Si K Na Hg Sn P B Ba Be Cd Co Cr Mn Mo Ni As Sb Se V Sum

M.W. 35.5 19 32 27 40 63.5 55.8 24.3 207 65.4 28 39 23 200.6 118.7 31 11 137.3 9 112.4 59 52 55 96 58.7 75 121.7 79 51

(concentrations, ppm can be seen as wt-ratios) +1 -2 -3 +6 0.6 2.2 0.3 19,700 201 82,080 0 370 1,368 34,763 29 24,082 4,227 60.7 1,920 10000 16,135 24,311 7,610 93000 3,635 50.9 3,580 33,090 97.4 3,370 2800 2,036 247 3,040 1,378 1.5 10,660 3,338 167 25,140 112,530 288,490 119,200 330,000 653 29.4 14,900 16000 880 614 171,540 89000 0.5 0.5 7.4 55.9 2.5 824 465 12.2 349 110 2.7 461 692 10.9 508 0.09 0.1 0.1 11.9 0.5 61.3 16.2 0.1 3.6 210 9.4 63.7 304 34.6 322 39.2 2.5 79.1 90.6 0.6 43.9 3.8 0.5 22.5 140 0.5 260 0.5 0.5 28.9 15.1 0.2 4.1 234,520
6,708

+7 2.86

1+6+7-2-3 384 -10 942 201 804 95 961 80 17 38 -1 122 403 0 0 12 2 18 0 0 0 6 7 1 2 0 3 0 0 n.a.
4,091

delta g-mole 10.8 -0.5 (-) 29.4 69 7.4 94 25 20.1 (+) 1.5 17.2 drop, melt.point >1500C 3.3 and FeS2 pyrite, melts @ 1171 0.1 0.6 0.0 must balance 3.1 17.5

217000

132000

Appendix 10.1

314,747
-6,295

471,529
-1,006

540,800
4,597

349,000
87

in/out in kg

6+1 trials 28.602 measured

1 batch 1dry batch 20 2.134 measured

1 batch 1dry batch 8.5 0.250 4.091 measured calculated

1.4

3.4

186

Chapter 10

Date Time 6/10 every 2" (solar) 4.00.00 6.00.00 10.00.02 T61 11.06.02 T61 11.06.04 T61 11.06.06 T61 11.06.08 T61 11.12.12 T61 11.12.14 T61 11.12.16 T61 11.14.20 T61 11.14.22 T61 11.14.24 T61 11.14.26 T61 11.14.28 T61 11.14.30 T61 11.14.32 T61 11.14.34 T61 11.15.36 T61 11.15.38 T61 11.15.40 T61 11.15.42 T61 11.15.44 T61 11.15.46 T61 11.15.48 T61 11.15.50 T61 11.15.52 T61 11.15.54 T61 11.15.56 T61 11.15.58 T61 11.16.00 T61 11.16.02 T61 11.16.34 T61 11.16.50 T61 11.16.52 T61 11.16.54 T61 11.18.02 T61 11.18.04

TI-0115

TI-0119

TI-0674 CO (CO+CO2) H2O/C feed O2/C feed

CO 0.2 0.6 0.3 18.5 18.4 18.3 18.2 19.4 19.3 19.3 18.4 18.4 18.3 18.2 18.1 18.1 18.0 18.1 18.1 18.0 17.9 17.8 17.7 17.6 17.5 17.5 17.5 17.5 17.4 17.4 17.5 17.4 18.0 18.4 18.5 18.5 18.9 18.9

CO2 CH4 vol-% 0.3 0.0 6.9 0.0 1.6 0.0 10.3 0.4 10.3 0.4 10.4 0.4 10.4 0.4 9.5 0.5 9.5 0.5 9.6 0.5 10.8 0.5 10.9 0.4 10.9 0.4 10.8 0.4 10.8 0.4 10.8 0.4 10.9 0.4 10.9 0.4 10.9 0.3 10.8 0.3 10.7 0.2 10.6 0.2 10.5 0.2 10.4 0.2 10.4 0.2 10.3 0.3 10.2 0.3 10.1 0.3 10.0 0.2 10.0 0.3 9.9 0.3 9.9 0.2 9.3 0.3 9.3 0.3 9.4 0.3 9.4 0.3 9.9 0.3 9.9 0.3

H2 Plenum Offgas 0.3 0.1 0.4 17.0 16.9 16.8 16.8 16.9 16.9 16.8 16.4 16.4 16.4 16.4 16.4 16.5 16.5 16.5 16.4 16.2 16.1 16.0 15.9 15.8 15.7 15.6 15.5 15.5 15.4 15.4 15.3 15.3 15.5 15.8 15.9 15.9 17.0 17.1 704 843 1059 1085 1085 1085 1085 1080 1080 1080 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1068 1074 1074 1080 1080 1080 1080 1080

Inside after PEMTRC

Carbon Fluff O2 PEM O2 PEM O2 TRC TRC TRC Tot O2 O2 O2 feed #/h feed #/h Steam Steam Steam O2 PEM PSI SCFM #/hr PSI SCFH #mol/hr PSI SCFH #mol/hr #/hr @ carbon % 41

500 593 752 824 824 824 824 824 824 824 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818 818

533 752 986 1034 1034 1034 1034 1040 1040 1040 1052 1052 1052 1052 1046 1046 1046 1046 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052 1052

0.64 0.64 0.64 0.64 0.67 0.67 0.67 0.63 0.63 0.63 0.63 0.63 0.63 0.62 0.62 0.62 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.63 0.64 0.64 0.64 0.64 0.66 0.66 0.66 0.66 0.66 0.66

0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049 0.3049

1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189 1.7189

5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248 5.248

12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8

15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15

10.5 10.5 10.5 10.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5

1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 Chapter 10,40 Appendix 10.2 1.6 4 0.113 Test T61 40 1.6 4 0.113 1.6 40 4 0.113 Some central data for main 1.6 40 4 0.113 variables 40 1.6 4 0.113 (more than 40 lines were 1000 1.6 4 0.113 1.6 40 4 recorded for each run) 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113 1.6 40 4 0.113

45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45 45

18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18 18

0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169 0.169

9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021 9.021

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187

Offgas generated in 13 trials

(Pure syngas basis: CO = 55.3 vol-% and H2 = 44.7 vol-%)

19.6

54.1

10.3

CO CO2 H2 N2

16.1

188

Chapter 10

1 Nitrogen flow rate 1 6 Gas measurement is dry SCFM 1.70 scfh 7 Gas Composition 1.5 2.68 O2 0.0% 21 88.0 psig 4.6 scfm P correct to air SCFM CO 19.0% 3 0.7 lbmols/hr 1 air#mole @SC =379 ft CO2 10.1% 2 Material feed rate CH4 0.4% 16.3% 0% Error term H2 12.8 lb/hr lbmol/hr subtotal 45.8% 5.21 0.43 N2 54.2% C 40.7% 5.4% 0.69 0.35 100.0% H2 7.6% 0.97 0.0304 8 Flow rate calculation based on nitrogen O2 H2O 4.0% 0.51 0.03 Offgas 8.4 scfm 9 Carbon in offgas 3 Steam flow rate C in CO 0.25 lbmols/hr 1.6 lb/hr 0.09 lbmols/hr C in CO2 0.13 lbmols/hr C in CH4 0.01 lbmols/hr 4 Oxygen flow rate - PEM 40.0 scfh subtotal 0.39 lbmols/hr 4.73 lb/hr 4.0 psig 0.7 scfm 10 Hydrogen and methane by ratio 0.11 lbmols/hr H2 0.22 lbmols/hr CH4 0.01 lbmols/hr 5 Oxygen flow rate - TRC 11 Oxygen in offgas 45.0 scfh 18.0 psig O2 lbmols/hr 1.1 scfm 0.17 lbmols/hr 5a Carbon dioxide flow rate - PEM Appendix 10.2 scfh 3.0 psig October 6th, Test number 1 scfm Material balance on manual lbmols/hr average readings 2a Carbon from electrodes 0.5 lb/hr

11 Carbon solid by difference C(s) 0.98 lb/hr 8% of feed 12 Water from Equilibrium Calculation T (C) 1,069 Factor 0.49 H2O 0.23 lbmols/hr 13 Composition CO 0.25 lbmols/hr CO2 0.13 lbmols/hr H2 0.22 lbmols/hr CH4 0.01 lbmols/hr H2O 0.23 lbmols/hr N2 0.72 lbmols/hr Total 0.96 lbmols/hr 14 Oxygen Balance O2 In 0.37 lbmols/hr O2 Out 0.38 lbmols/hr Delta (0.0081) -2% 15 Hydrogen balance H2 In 0.46 H2 Out 0.46 Delta 0.0000 16 Combined Delta Delta 0.0081

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189

Oct 6, Run # 1
Plenum T=1080C, PEM T=820C, TRC T= 1050C, DC Feed = 14 kW

20.0
O2/C

20.2% 18.2% 16.3

2.00 1.80 17.7 1.60 1.40 CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2

18.0 16.0 14.0 Vol-%, syngas 11.5 %

10.0 8.0 6.0 4.0 2.0 0.0 11.04.00 11.04.30 11.05.00 11.05.30 11.06.00 0.3 % 11.06.30 11.07.00 11.07.30 11.08.00 11.08.30 11.09.00 11.09.30 11.10.00 11.10.30 11.11.00 11.11.30 11.12.00 11.12.30 11.13.00 11.13.30 11.14.00 11.14.30 11.15.00 11.15.30 11.16.00 11.16.30 11.17.00 11.17.30 11.18.00 11.18.30 11.19.00 11.19.30
H2O/C

1.00 0.80 0.60 0.40 0.20 0.00

Solar time

Wt-Ratios

12.0

1.20

190

Chapter 10

1 Nitrogen flow rate 1 1.70 scfh 88.0 psig 4.6 scfm 0.7 lbmols/hr 2 Material feed rate 0% Error term lb/hr lbmol/hr 12.8 C 40.7% 5.21 0.43 H2 5.4% 0.69 0.35 O2 7.6% 0.97 0.0304 H2O 4.0% 0.51 0.03 3 Steam flow rate 4.3 lb/hr 0.24 lbmols/hr 4 Oxygen flow rate - PEM 40.0 scfh 5.0 psig 0.7 scfm 0.12 lbmols/hr 5 Oxygen flow rate - TRC 45.0 scfh 18.0 psig 1.1 scfm 0.17 lbmols/hr 5a Carbon dioxide flow rate - PEM scfh 6.0 psig scfm lbmols/hr 2a Carbon from electrodes 0.5 lb/hr

6 Gas measurement is dry 7 Gas Composition 1.5 2.57 O2 20 0.0% CO 18.4% CO2 10.8% CH4 0.5% H2 17.0% subtotal 46.7% N2 53.3% 100.0% 8 Flow rate calculation based on nitrogen Offgas 8.6 scfm 9 Carbon in offgas C in CO 0.25 lbmols/hr C in CO2 0.15 lbmols/hr C in CH4 0.01 lbmols/hr subtotal 0.40 lbmols/hr 4.84 lb/hr 10 Hydrogen and methane by ratio H2 0.23 lbmols/hr CH4 0.01 lbmols/hr 11 Oxygen in offgas O2 lbmols/hr

11 Carbon solid by difference C(s) 0.87 lb/hr 7% of feed 12 Water from Equilibrium Calculation T (C) 1,215 Factor 0.37 H2O 0.37 lbmols/hr 13 Composition CO 0.25 lbmols/hr CO2 0.15 lbmols/hr H2 0.23 lbmols/hr CH4 0.01 lbmols/hr H2O 0.37 lbmols/hr N2 0.72 lbmols/hr Total 1.09 lbmols/hr 14 Oxygen Balance O2 In 0.45 lbmols/hr O2 Out 0.46 lbmols/hr Delta (0.0069) -2% 15 Hydrogen balance H2 In 0.61 H2 Out 0.61 Delta 0.0000 16 Combined Delta Delta 0.0069

Chapter 10, Appendix 10.2 October 6th, Test number 2 Material balance on manual average readings

Pilot Test Reporting and Discussion of Results

191

Oct 6, Run # 2 Plenum T=1060C, PEM T=812C, TRC T= 1060C, DC Feed = 14 kW

24.0 22.0 20.0 18.0 16.0 14.0 12.0 10.0 8.0 0.60 6.0 0.40 4.0 2.0 0.3 % 0.0 11.23.00 11.23.44 11.24.28 11.25.12 11.25.56 11.26.40 11.27.24 11.28.08 11.28.52 11.29.36 11.30.20 11.31.04 11.31.48 11.32.32 11.33.16 11.34.00 11.34.44 11.35.28 11.36.12 11.36.56 11.37.40 11.38.24 11.39.08 11.39.52 11.40.36 11.41.20 11.42.04 11.42.48 11.43.32 11.44.16 11.45.00 11.45.44 11.46.28 0.00 0.20
H2O/C

23.4% 22.6 21.4%

O2/C

2.00 1.80 1.60 1.40 1.20 12.0% 1.00 0.80 Wt-Ratios, feed CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2

18.6

Vol-%, syngas

Solar time

192

Chapter 10

1 Nitrogen flow rate 1 1.70 scfh 88.0 psig 4.6 scfm 0.7 lbmols/hr 2 Material feed rate 0% Error term lb/hr lbmol/hr 12.8 C 40.7% 0.43 5.21 H2 0.35 5.4% 0.69 O2 7.6% 0.97 0.0304 0.03 4.0% 0.51 H2O 3 Steam flow rate 6.2 lb/hr 0.34 lbmols/hr 4 Oxygen flow rate - PEM 40.0 scfh 8.0 psig 0.8 scfm 0.12 lbmols/hr 5 Oxygen flow rate - TRC 45.0 scfh 18.0 psig 1.1 scfm 0.17 lbmols/hr 5a Carbon dioxide flow rate - PEM scfh 4.0 psig scfm lbmols/hr 2a Carbon from electrodes 0.5 lb/hr

6 Gas measurement is dry 7 Gas Composition 1.5 2.56 O2 20 0.0% CO 17.5% CO2 11.7% CH4 0.3% H2 17.8% subtotal 47.3% N2 52.8% 100.0% 8 Flow rate calculation based on nitrogen Offgas 8.7 scfm 9 Carbon in offgas C in CO 0.24 lbmols/hr C in CO2 0.16 lbmols/hr C in CH4 0.00 lbmols/hr subtotal 0.40 lbmols/hr 4.85 lb/hr 10 Hydrogen and methane by ratio H2 0.24 lbmols/hr CH4 0.00 lbmols/hr 11 Oxygen in offgas O2 lbmols/hr

11 Carbon solid by difference C(s) 0.86 lb/hr 7% of feed 12 Water from Equilibrium Calculation T (C) 1,241 Factor 0.35 H2O 0.47 lbmols/hr 13 Composition CO 0.24 lbmols/hr CO2 0.16 lbmols/hr H2 0.24 lbmols/hr CH4 0.00 lbmols/hr H2O 0.47 lbmols/hr N2 0.72 lbmols/hr Total 1.19 lbmols/hr 14 Oxygen Balance O2 In 0.51 lbmols/hr O2 Out 0.51 lbmols/hr Delta (0.0030) -1% 15 Hydrogen balance H2 In 0.72 H2 Out 0.72 Delta 0.0000 16 Combined Delta Delta 0.0030

Chapter 10, Appendix 10.2 October 6th, Test number 3 Material balance on manual average readings

Pilot Test Reporting and Discussion of Results

193

Oct 6, Run # 3 Plenum T=1080C, PEM T=812C, TRC T= 1090C, DC Feed = 14 kW

24.3% 22.6 20.7% 18.3 1.40 1.20 1.00 0.80 0.60 0.40 4.0 2.0 0.3 % 0.0 11.51.00 11.51.42 11.52.24 11.53.06 11.53.48 11.54.30 11.55.12 11.55.54 11.56.36 11.57.18 11.58.00 11.58.42 11.59.24 12.00.06 12.00.48 12.01.30 12.02.12 12.02.54 12.03.36 12.04.18 12.05.00 12.05.42 12.06.24 12.07.06 12.07.48 12.08.30 12.09.12 12.09.54 12.10.36 12.11.18 12.12.00 12.12.42 12.13.24 0.00 0.20 Wt-Ratios, feed
H2O/C

2.00
O2/C

24.0 22.0 20.0 18.0 16.0 Vol-%, syngas 14.0

1.80 1.60 CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2

12.0% 12.0 10.0 8.0 6.0

Solar time

194

Chapter 10

1 Nitrogen flow rate 1 1.70 scfh 87.0 psig 4.6 scfm 0.7 lbmols/hr 2 Material feed rate 0% Error term lb/hr lbmol/hr 12.8 C 40.7% 0.43 5.21 H2 0.35 5.4% 0.69 O2 0.03 7.6% 0.97 0.03 4.0% 0.51 H2O 3 Steam flow rate 9.0 lb/hr 0.50 lbmols/hr 4 Oxygen flow rate - PEM 40.0 scfh 9.0 psig 0.8 scfm 0.13 lbmols/hr 5 Oxygen flow rate - TRC 45.0 scfh 18.0 psig 1.1 scfm 0.17 lbmols/hr 5a Carbon dioxide flow rate - PEM scfh 4.0 psig scfm lbmols/hr 2a Carbon from electrodes 0.5 lb/hr

6 Gas measurement is dry 7 Gas Composition 1.5 2.31 O2 18 0.0% CO 17.7% CO2 10.9% CH4 0.5% H2 21.7% subtotal 50.8% N2 49.3% 100.0% 8 Flow rate calculation based on nitrogen Offgas 9.2 scfm 9 Carbon in offgas C in CO 0.26 lbmols/hr C in CO2 0.16 lbmols/hr C in CH4 0.01 lbmols/hr subtotal 0.42 lbmols/hr 5.10 lb/hr 10 Hydrogen and methane by ratio H2 0.32 lbmols/hr CH4 0.01 lbmols/hr 11 Oxygen in offgas O2 lbmols/hr

11 Carbon solid by difference C(s) 0.61 lb/hr 5% of feed 12 Water from Equilibrium Calculation T (C) 1,229 Factor 0.36 H2O 0.54 lbmols/hr 13 Composition CO 0.26 lbmols/hr CO2 0.16 lbmols/hr H2 0.32 lbmols/hr CH4 0.01 lbmols/hr H2O 0.54 lbmols/hr N2 0.72 lbmols/hr Total 1.26 lbmols/hr 14 Oxygen Balance O2 In 0.59 lbmols/hr O2 Out 0.56 lbmols/hr Delta 0.0316 5% 15 Hydrogen balance H2 In 0.87 H2 Out 0.87 Delta (0.0000) 16 Combined Delta Delta 0.0316

Chapter 10, Appendix 10.2 October 6th, Test number 4 Material balance on manual average readings

Pilot Test Reporting and Discussion of Results

195

Oct 6, Run # 4 Plenum T=1060C, PEM T=810C, TRC T= 1110C, DC Feed = 14 kW

2.00 24.0 22.0 20.0 18.0 16.0 Vol-%, syngas 1.20 14.0 13.0% 12.0 10.0 8.0 6.0 0.40 4.0 2.0 0.0 12.19.00 12.19.40 12.20.20 12.21.00 0.3 % 12.21.40 12.22.20 12.23.00 12.23.40 12.24.20 12.25.00 12.25.40 12.26.20 12.27.00 12.27.40 12.28.20 12.29.00 12.29.40 12.30.20 12.31.00 12.31.40 12.32.20 12.33.00 12.33.40 12.34.20 12.35.00 12.35.40 12.36.20 12.37.00 12.37.40 12.38.20 12.39.00 12.39.40 0.20 0.00 1.00 0.80 0.60 24.2%
H2O/C

23.5 22.9

O2/C

1.80 1.60 1.40 Wt-Ratios, feed CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2

19.5%

Solar time

196

Chapter 10

1 Nitrogen flow rate 1 1.70 scfh 87.0 psig 4.6 scfm 0.7 lbmols/hr 2 Material feed rate 0% Error term lb/hr lbmol/hr 12.8 5.21 0.43 C 40.7% 0.69 0.35 H2 5.4% 0.97 0.03 O2 7.6% 4.0% 0.51 0.03 H2O 3 Steam flow rate 4.1 lb/hr 0.23 lbmols/hr 4 Oxygen flow rate - PEM 25.0 scfh 42.0 psig 0.8 scfm 0.12 lbmols/hr 5 Oxygen flow rate - TRC 40.0 scfh 18.0 psig 0.9 scfm 0.15 lbmols/hr 5a Carbon dioxide flow rate - PEM 40.0 scfh 42.0 psig 1.1 scfm 0.2 lbmols/hr 2a Carbon from electrodes 0.5 lb/hr

6 Gas measurement is dry 7 Gas Composition 1.5 3.07 O2 24 0.0% CO 22.2% CO2 13.7% CH4 0.3% H2 14.8% subtotal 50.9% N2 49.1% 100.0% 8 Flow rate calculation based on nitrogen Offgas 9.3 scfm 9 Carbon in offgas C in CO 0.33 lbmols/hr C in CO2 0.20 lbmols/hr C in CH4 0.00 lbmols/hr subtotal 0.53 lbmols/hr 6.36 lb/hr 10 Hydrogen and methane by ratio H2 0.22 lbmols/hr CH4 0.00 lbmols/hr 11 Oxygen in offgas O2 lbmols/hr

11 Carbon solid by difference C(s) 1.36 lb/hr 11% of feed 12 Water from Equilibrium Calculation T (C) 1,238 Factor 0.35 H2O 0.38 lbmols/hr 13 Composition CO 0.33 lbmols/hr CO2 0.20 lbmols/hr H2 0.22 lbmols/hr CH4 0.00 lbmols/hr H2O 0.38 lbmols/hr N2 0.72 lbmols/hr Total 1.10 lbmols/hr 14 Oxygen Balance O2 In 0.60 lbmols/hr O2 Out 0.55 lbmols/hr Delta 0.0471 8% 15 Hydrogen balance H2 In 0.60 H2 Out 0.60 Delta 0.0000 16 Combined Delta Delta 0.0471

Chapter 10, Appendix 10.2 October 6th, Test number 5 Material balance on manual average readings

Pilot Test Reporting and Discussion of Results

197

Oct 6, Run # 5 Plenum T=1065C, PEM T=807C, TRC T= 1115C, DC Feed = 14 kW

26.0 24.0 22.0 20.0 18.0 Vol-%, syngas 16.0 14.0 12.0 10.0 8.0 6.0 4.0 0.20 2.0 0.0 12.50.00 12.50.40 12.51.20 12.52.00 0.3 % 12.52.40 12.53.20 12.54.00 12.54.40 12.55.20 12.56.00 12.56.40 12.57.20 12.58.00 12.58.40 12.59.20 13.00.00 13.00.40 13.01.20 13.02.00 13.02.40 13.03.20 13.04.00 13.04.40 13.05.20 13.06.00 13.06.40 13.07.20 13.08.00 13.08.40 13.09.20 13.10.00 13.10.40 0.00 0.60 0.40
H2O/C O2/C

1.80 24.7% 1.60 1.40 18.5% 14.9% 17.9 15.7 1.00 0.80 Wt-Ratios 1.20

CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C O2/C Polinom. H2 Polinom. CO Polinom. CO2

Solar time

198

Chapter 10

1 Nitrogen flow rate 1 1.70 scfh 87.0 psig 4.6 scfm 0.7 lbmols/hr 2 Material feed rate 0% Error term lb/hr lbmol/hr 12.8 C 40.7% 5.21 0.43 0.69 0.35 H2 5.4% 0.97 0.03 O2 7.6% 4.0% 0.51 0.03 H2O 3 Steam flow rate lb/hr lbmols/hr 4 Oxygen flow rate - PEM 29.0 scfh 31.0 psig 0.8 scfm 0.13 lbmols/hr 5 Oxygen flow rate - TRC 40.0 scfh 19.0 psig 1.0 scfm 0.15 lbmols/hr 5a Carbon dioxide flow rate - PEM 30.0 scfh 31.0 psig 0.7 scfm 0.1 lbmols/hr 2a Carbon from electrodes 0.5 lb/hr

6 Gas measurement is dry 7 Gas Composition 1.5 4.18 O2 33 0.0% 17.2% CO CO2 14.8% CH4 0.0% H2 7.8% subtotal 39.8% N2 60.2% 100.0% 8 Flow rate calculation based on nitrogen Offgas 7.6 scfm 9 Carbon in offgas C in CO 0.21 lbmols/hr C in CO2 0.18 lbmols/hr C in CH4 lbmols/hr subtotal 0.38 lbmols/hr 4.60 lb/hr 10 Hydrogen and methane by ratio H2 0.09 lbmols/hr CH4 lbmols/hr 11 Oxygen in offgas O2 lbmols/hr

11 Carbon solid by difference C(s) 2.47 lb/hr 19% of feed 12 Water from Equilibrium Calculation T (C) 1,368 Factor 0.29 H2O 0.28 lbmols/hr 13 Composition CO 0.21 lbmols/hr CO2 0.18 lbmols/hr H2 0.09 lbmols/hr CH4 lbmols/hr H2O 0.28 lbmols/hr N2 0.72 lbmols/hr Total 1.00 lbmols/hr 14 Oxygen Balance O2 In 0.44 lbmols/hr O2 Out 0.42 lbmols/hr Delta 0.0181 4% 15 Hydrogen balance H2 In 0.37 H2 Out 0.37 Delta 0.0000 16 Combined Delta Delta 0.0181

Chapter 10, Appendix 10.2 October 6th, Test number 6 Material balance on manual average readings

Pilot Test Reporting and Discussion of Results

199

Oct 6, Run # 6 Plenum T=1100C, PEM T=800C, TRC T= 1135C, DC Feed = 14 kW

23.8%
O2/C

1.80 1.60 1.40 1.20

24.0 22.0 20.0 18.0

14.0 12.0 10.0 8.0 6.0 4.0 2.0 0.0 13.30.00 13.30.42 13.31.24 13.32.06 13.32.48 13.33.30 13.34.12

14.8% 1.00 12.6% 12.9 0.80 0.60 0.40 0.20 0.0% 0.00 13.34.54 13.35.36 13.36.18 13.37.00 13.37.42 13.38.24 13.39.06 13.39.48 13.40.30 13.41.12 13.41.54 13.42.36 13.43.18 13.44.00 13.44.42 13.45.24 13.46.06 13.46.48 13.47.30 13.48.12 13.48.54 13.49.36 13.50.18 13.51.00 13.51.42 13.52.24

8.1

Solar time

Wt-Ratios, feed

16.0 Vol-%, syngas

CO CO2 CH4 H2 CO/(CO+CO2) H2O/C (n.a.) CO2/C O2/C Polinom. H2 Polinom. CO Polinom. CO2

200

Chapter 10

1 Nitrogen flow rate 1 1.70 scfh 87.0 psig 4.6 scfm 0.7 lbmols/hr 2 Material feed rate 0% Error term lb/hr lbmol/hr 24.0 0.81 9.77 C 40.7% 0.65 5.4% 1.30 H2 0.06 7.6% 1.82 O2 0.05 4.0% 0.96 H2O 3 Steam flow rate 4.9 lb/hr 0.27 lbmols/hr 4 Oxygen flow rate - PEM 50.0 scfh 18.0 psig 1.2 scfm 0.19 lbmols/hr 5 Oxygen flow rate - TRC 40.0 scfh 19.0 psig 1.0 scfm 0.15 lbmols/hr 5a Carbon dioxide flow rate - PEM scfh 4.0 psig scfm lbmols/hr 2a Carbon from electrodes 0.5 lb/hr

6 Gas measurement is dry 7 Gas Composition 1.5 7.51 O2 31 0.0% CO 25.4% CO2 6.8% CH4 0.0% H2 21.0% subtotal 53.2% N2 46.8% 100.0% 8 Flow rate calculation based on nitrogen Offgas 9.7 scfm 9 Carbon in offgas C in CO 0.39 lbmols/hr C in CO2 0.10 lbmols/hr C in CH4 lbmols/hr subtotal 0.50 lbmols/hr 5.95 lb/hr 10 Hydrogen and methane by ratio H2 0.32 lbmols/hr CH4 lbmols/hr 11 Oxygen in offgas O2 lbmols/hr

11 Carbon solid by difference C(s) 4.32 lb/hr 18% of feed 12 Water from Equilibrium Calculation T (C) 1,500 Factor 0.24 H2O 0.36 lbmols/hr 13 Composition CO 0.39 lbmols/hr CO2 0.10 lbmols/hr H2 0.32 lbmols/hr CH4 lbmols/hr H2O 0.36 lbmols/hr N2 0.72 lbmols/hr Total 1.08 lbmols/hr 14 Oxygen Balance O2 In 0.56 lbmols/hr O2 Out 0.48 lbmols/hr Delta 0.0776 14% 15 Hydrogen balance H2 In 0.97 H2 Out 0.69 Delta 0.2873 16 Combined Delta Delta 0.3649

Chapter 10, Appendix 10.2 October 6th, Test number 7 Material balance on manual average readings

Pilot Test Reporting and Discussion of Results

201

Oct 6, Run # 7 Plenum T=1150C, PEM T=800C, TRC T= 1140C, DC Feed = 14 kW

26.5%
O2/C

2.50

26.0 24.0 22.0 20.0 18.0 16.0 14.0 12.0 10.0 8.0 6.0 4.0 2.0 9.4%

23.5 23.4% 2.00 19.5 Wt-Ratios, feed CO CO2 CH4 H2 CO/(CO+CO2) H2O/C CO2/C (n.a.) O2/C Polinom. H2 Polinom. CO Polinom. CO2

Vol-%, syngas

1.50

H2O/C

1.00

0.50

0.2% 0.0 14.00.00 14.00.32 14.01.04 14.01.36 14.02.08 14.02.40 14.03.12 14.03.44 14.04.16 14.04.48 14.05.20 14.05.52 14.06.24 14.06.56 14.07.28 14.08.00 14.08.32 14.09.04 14.09.36 14.10.08 14.10.40 14.11.12 14.11.44 14.12.16 14.12.48 14.13.20 14.13.52 14.14.24 14.14.56 14.15.28 14.16.00 14.16.32 0.00

Solar time

202

Chapter 10

#mol/h IN
1087
Subst. C

**
CO2
Electr. C

Sum
Sum C N2
Subst.O2

#mol/ha-b OUT
C black Conv.'d

(a-b)/c to CO to CO2 to CH4 Process conv. C% CO

H2O

CO2

O2 mol O2

T61 T63 T66

1071

0.43 0.43 0.43 0.43 0.43 0.43 0.81

0.042 0.472 0.042 0.472 0.1 0.042 0.572 0.042 0.042 0.2 0.042 0.042 0.472 0.472 0.672 0.852

0.72 0.72 0.72 0.72 0.72 0.72 0.72

0.03 0.12 0.03 0.37 0.03 0.03 0.03 0.03 0.03 0.06 0.27 0.53 0.26 0.32

0.1

0.28 0.370 0.29 0.505 0.28 0.425 No steam addition 0.29 0.3 0.27 0.7 0.455 0.595 0.630 0.920

0.082 0.390 0.251 0.133 0.005 0.072 0.400 0.237 0.159 0.004 0.206 0.366 0.197 0.169 0.000 0.073 0.051 0.113 0.360 0.399 0.421 0.558 0.492 0.247 0.256 0.342 0.388 0.145 0.158 0.211 0.104 0.007 0.007 0.005 0.000

53.2 50.3 34.4 52.4 54.3 51.0 45.5 Process conversion expressed as CO to total C feed

T62 T64 T65 T67

0.2

Gas vol-% OUT as per process analyser

1087 H2 N2 CO CO2 CH4

vol-% dry C in gas

ultimate C conversion CO CO2 CH4

(No carbon black, separated upstream or recycled) Conversion expressed here as CO to total gasified C. If the total C black is recycled, it is like stating that all C is converted to gases.

T61 T63 T66

1071

16.3 17.8 7.8 17 21.7 14.8 19.1

54.2 52.8 60.2 53.3 49.3 49.1 46.8

19.0 17.5 17.2 18.4 17.7 22.2 25.4 **

10.1 0.400 11.7 0.300 14.8 0.000 10.8 10.9 13.7 6.8 0.500 0.500 0.300 0.000

64.4 59.3 53.8 62.0 60.8 61.3 78.9

34.2 39.7 46.3 36.4 37.5 37.8 21.1

1.4 100.0 1.0 100.0 0.0 100.0 1.7 1.7 0.8 0.0 100.0 100.0 100.0 100.0

Appendix 10.3
41 wt-% Carbon content of fluff

T62 T64 T65 T67

Graphite electrodes consumed @ 0.5 #/h

CO2 C

PEM + electrodes

Separator

CO CO2 CH4

C black recycle .

Trial T61, material balances: .473 moles C in = .082 C 0 combined O2 .251 CO 0.126 .133 CO2 0.133 .005 CH4 0 0.471 0.259 We started with .37 moles, .37-.259=.111 extra oxygen, must be in H2O due to reducing environment, recombination with H2 and nil measurements .111x2=.222 H2O out, which is separated and not measured by NOVA .222-.12=.102 H2O generated or about .05 moles O2 Exiting water from shift reaction=.22(.13)/.25/.0247exp(4020/TK)=.23, ok H2in=.34+.12=.46 and H2out=.22H2+.01CH4+.23H2O=.46 ok

Pilot Test Reporting and Discussion of Results

203

#mol/h IN
1087
Subst. C

**
CO2
Electr. C

Sum
Sum C N2
Subst.O2

#mol/ha-b OUT
C black Conv.'d

(a-b)/c to CO to CO2 to CH4 Process conv. C% CO

H2O

CO2

O2 mol O2

T61 T63 T66

1071

0.571 0.571 0.571 0.571 0.571 0.571 1.075

0.042 0.612 0.042 0.612 0.1 0.042 0.712 0.042 0.042 0.2 0.042 0.042 0.612 0.612 0.812 1.116

0.72 0.72 0.72 0.72 0.72 0.72 0.72

0.03 0.12 0.03 0.37 0.03 0.03 0.03 0.03 0.03 0.06 0.27 0.53 0.26 0.32

0.1

0.28 0.370 0.29 0.505 0.28 0.425 No steam addition 0.29 0.3 0.27 0.7 0.455 0.595 0.630 0.920

0.223 0.389 0.250 0.133 0.005 0.213 0.399 0.237 0.158 0.004 0.348 0.364 0.196 0.168 0.000 0.214 0.193 0.256 0.626 0.398 0.420 0.556 0.491 0.247 0.255 0.341 0.387 0.145 0.157 0.211 0.104 0.007 0.007 0.005 0.000

40.9 38.6 27.5 40.3 41.7 42.0 34.7 Process conversion expressed as CO to total C feed

T62 T64 T65 T67

0.2

Gas vol-% OUT as per process analyser

1087 H2 N2 CO CO2 CH4

vol-% dry C in gas

ultimate C conversion CO CO2 CH4

(No carbon black, separated upstream or recycled) Conversion expressed here as CO to total gasified C. If the total C black is recycled, it is like stating that all C is converted to gases.

T61 T63 T66

1071

16.3 17.8 7.8 17 21.7 14.8 19.1

54.2 52.8 60.2 53.3 49.3 49.1 46.8

19.0 17.5 17.2 18.4 17.7 22.2 25.4 **

10.1 0.400 11.7 0.300 14.8 0.000 10.8 10.9 13.7 6.8 0.500 0.500 0.300 0.000

64.4 59.3 53.8 62.0 60.8 61.3 78.9

34.2 39.7 46.3 36.4 37.5 37.8 21.1

1.4 100.0 1.0 100.0 0.0 100.0 1.7 1.7 0.8 0.0 100.0 100.0 100.0 100.0

T62 T64 T65 T67

54 wt-% Carbon content of fluff

Graphite electrodes consumed @ 0.5 #/h

CO2 C

PEM + electrodes

Separator

CO CO2 CH4

C black recycle .

Trial T61, material balances: .612 moles C in = .223 C 0 combined O2 .251 CO 0.126 .133 CO2 0.133 .005 CH4 0 0.612 0.259 We started with .37 moles, .37-.259=.111 extra oxygen, must be in H2O due to reducing environment, recombination with H2 and nil measurements .111x2=.222 H2O out, which is separated and not measured by NOVA .222-.12=.102 H2O generated or about .05 moles O2 Exiting water from shift reaction=.22(.13)/.25/.0247exp(4020/TK)=.23, ok H2in=.34+.12=.46 and H2out=.22H2+.01CH4+.23H2O=.46 ok

..

11

WRAPPING IT ALL UP: RESEARCH AND PROCESS DEVELOPMENT PLAN

It becomes natural, after describing the experimentation, to capitalise on main results and wonder if additional activities can be planned. Activities may be planned on two levels, one parallel to the other, and without mutual exclusion. The first activity is to continue the research, both theoretical and experimental. The second activity is to scale-up the plant (in steps) to commercialise the type and size of plants that will remunerate investors, but also sizeable and visible enough to resolve an existing problem into appreciable applications. Both avenues are synergistic, one may learn from the other and feed substantial benefits and information back to the other. Actually, the making of sole research confined to university work will certainly improve the understanding and the results accomplished so far, but the limited scale of a pilot plant plus the human and tangible resources to deploy would still be an enormous investment for any university. The end result may be further publications and accomplishments of students, but we presently do not have the possibility to set up a dedicated Pilot Plant with annexed Laboratory that would cost in the range of half a million Euros. On the other hand, it would be hard to propose and difficult to gain from additional experimental research sponsored by IET, because these former MIT and Battelle researchers are already promoting their technology and they wish to protect their knowhow from disclosing facts to competitors. From the applied research side, the needs to treat fluff or to knock out appreciable amounts of CO2 are so vast that the few investors that were contacted do not intend to initiate a journey of applied research for a small industrial plant (certain or doubtful as it may prove): their needs are indeed ten fold bigger than we can aim at building with a first prototype. For instance, the largest fluff treatment ever attempted (in Japan) has a capacity of 165 t/d.1 A first demonstration plant of our type could have a capacity of about 30 t/d and we found one local investor having a fluff accumulating capacity (treatment plant availability) of 750 t/d or greater. Other potential investors with fluff disposal problems, in Italy and in Europe, are looking for medium to long term solutions and plant capacities of similar magnitude. In all cases, the order of magnitude for building a Demonstration Plant is expected in the range of 15 to 20 million Euros. It is evident that a lot remains to be done, the crucial issue is to assemble the team that can sustain the expenses for applied research and development of a demonstration plant, further scalable or modularised to the desired capacity. To recap the research that was presented, the results come from a series of thirteen stabilised tests in which fluff was continuously treated in a plasma reactor in different feed matrices. The tests demonstrated the effectiveness of the chemically reducing environment of the plasma reactor to destroy fluff and to produce syngas. The ashes collected from the test enable to approach the design of a waste heat boiler located between the plasma reactor and the quench/flue gas treatment. The clean syngas can be used to produce electric power in an internal combustion engine generator or for production of hydrogen or chemical syntheses from CO. Leaching data on the
1

Hitachi Metals, mixed waste feed plant (municipal solid waste plus 2 lines for fluff treatment, each one having a design capacity of 82.5 t/d), Utashinai Project, Japan.

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discharged vitrified solids were determined below the appropriate regulatory standards and allow to consider their possible utilisation. There are economic advantages associated to the treatment of the fluff, which can be considered and tailored to the specific reality of the Country where a plant is to be built. From the energetic point of view, the overall balance closes if consideration is given to produce base chemicals (CO + H2). Fluff is voluminous, leachable, hard to treat and landfills are not going to remain its preferred means of disposal. The saving on land and associated costs justifies a tipping fee for the materials, becoming thus a revenue for the processing plant operator. Recycling of usable solid material is also to be compared against the necessity of disposing to a landfill the solid ashes, dusts or materials that would be generated by an alternative process. Glass aggregate can be used for construction or blasting grit or brick blocks, or tiles. Another use is to fill excavations and road works or the ultimate saving can be to dispose such materials in cheaper class landfills, in much smaller volumes than a conventional incineration slag and ash disposal would need. The above results are also expressed quantitatively and from such data we can extrapolate costs and goals for the possible new research and for the research applied to an external demonstration plant. The first can be structured in the form of a Foundation, in which the University and Private Investors join to build and operate a pilot unit. Personnel would mainly come from the University in order to limit costs and fulfil academic goals aimed at research and education. The foundation will also transpose know-how and services to third parties so to gain revenues re-invested in the foundation laboratory. The off-premises Demonstration Plant would be run by industry personnel and built in an industrial area, given the size, the continuous operation, the extent of raw feed, products and effluents as well as the ancillary and utility units with permits and regulations to be observed. The size, funding and management of such investment would be structured and planned with the Foundation, but it is a private exercise to be detailed upon concluding the detailed engineering of the plant. Ultimately, revenues for the Foundation but also for the Demonstration Plant Investors will be royalties from licensing out the technology of new plants. The small demonstration plant is going to require the implementation steps, design, planning and construction, of any full scale plant. The basic design and the process guarantees of the demonstration plant will be developed within the Foundation on the basis of the research in what the industry could assimilate to a so called Process Package or a UOP Schedule A design package. From such information, any qualified contractor could bid and build the plant. For both lines of activities foreign institutions or partners are also possible and yet, redundant as it may sound, nothing will start without investors. The following paragraphs are organised for attracting possible interest and outline the work that may then follow, both in the areas of University activities and Demonstration Plant activities.

11.1
11.1.1

Research Facility

Plasma pilot plant and laboratory Building a pilot test unit identical or similar to the one where this experimentation was made may appear redundant or inefficient. In reality, making a

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solid waste processing system at the Politecnico di Milano (Dipartimento di Chimica, Materiali e Ingegneria Chimica), having about 10 kg/h nominal capacity, is an effort that will treat a variety of waste and involve several researchers and students with obvious educational and innovation purposes. The continuous analysis monitoring on the gaseous products is an effective tool to gain a deeper knowledge on various tests and to provide validation for specific tests that may be commissioned by third parties. The hot temperature laboratory would be controlled and have adequate instrumentation to investigate heat losses and kinetics for different materials, while heat conservation and recovery, lining, refractory tests and gas purification would enhance the experimentation. Nothing prevents cooperation with external firms and entities, but since the laboratory is on university premises it is likely to exploit cooperation with other research institutions in terms of specialised topics to be developed by a selected entity and results to promote common goals plus joint publications. The method is conducive to mobilise more scholars, located in several research centres, even foreign institutions. The method may assure higher efficiency and quality of results with the potential benefit of becoming more visible and capable to attract European funds or a greater number of sponsors. Some sponsors may actually become interested due to the return on professionality and training of their personnel that might involve with the research projects. The starting goals of the research centre are deducible from the basic tenets of this research that with moderate expansion can be summarised as follows: Waste to hydrogen Carbon dioxide sequestering Production and export of CO and syngas Response and contacts with the need of small communities and chemical/power producers in view of the starting waste (organics, plastics, toxic waste, CO2) or materials to valorise or make inert Safety and ambient concern Non-conventional waste-to-energy plants Scale-up and assistance to the Demonstration Plant. Laboratory services The research centre and laboratory, that for simplicity we shall call Pyro Plasma Lab, would develop services for third parties and for the Demonstration Plant. Services will vary from testing on new feeds and materials to process engineering and procedures for optimisation and start-up. A certain amount of analytical work can also be envisioned, particularly in the area of hot gases. Once the laboratory is affirmed, the comparative analysis of alternative hot treatments may be requested by clients (even via multi-clients studies) and this serves the purpose of wider investigations or improvement of the proprietary process. Based on the success of the Demonstration Plant, the staff of the laboratory may become the instrument or part of the team that makes the technology available to new users. Such availability may take the form of a license or a joint venture. We have actually developed schemes of licensing and base contracts of cooperation which however are still premature and would bring no further clarity if detailed here. 11.1.2

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Research funding through a foundation The Pyro Plasma Lab will not be possible without an upfront contribution from various investors and financial contributors. In fact, it appears presently unrealistic to hope for exclusive university or governmental funds to start a new laboratory. Many industrialists who contact universities allure the idea that a good project would be funded from the beginning by university or public funds, so that they can later join and somehow participate to commercialising the project. Quite the contrary appears to be realistic instead, and a pool of Private Corporate Participants (PCP) and sponsors, together with the university that takes the lead, can raise sufficient operating money to make things happen. As it happens in all tests, the risk may fail but the starting entities have the freedom and flexibility to start, at their own pace. It is also likely that PCPs would inject entrepreneurship into the initiative and if the group is well assorted with interests and business diversification, it is possible that some immediate returns are paid back to the participants. For the PCPs the benefits are of fiscal nature, direct knowledge and/or participation in scientific works with possible training of their own selected personnel, exposure to sector conferences, advertising as nominated sponsor/member of the initiative and secure the ultimate benefits of commercialising the program to which they decided to adhere in the first place. In other words, these matters are likely to be complementary to their own activity since they showed active interest and participation. For the University, which would take and govern the initiative, yet with a limited participation of say 20% of the starting capital, the benefits are far more wider since a group of researchers can work and the investment goes in laboratory, modern equipment and advanced instrumentation for the starting purposes, but also for collateral research uses. In terms of human return, the research laboratory would gain higher visibility with other universities and research centres, stimulate personnel even by larger participation to symposia and expert panels, generate and support undergraduate and graduate research. As the people get trained and proficiently organised they may develop synergistic processes or improvements, possibly candidates for patents or know-how. The organisation or formal structure of this funding tool would be a non-profit foundation, in which all financial gains are re-invested to acquire tools and equipment or to expand scope and number of the research staff.

11.1.3

11.2

Demonstration Plant

In order to make a demonstration plant that starts from the experimental results and later research development it is necessary to make a basic engineering design followed by a detailed engineering and construction project. Only the basic engineering activities will be practically executed by the research team and will be embodied in a Process Book. The preliminary index of the Process Book is attached at the end of this Chapter, under Appendix 11.1, while major guidelines concerning its content are described hereunder.

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Basis of design Fluff with the characteristics listed under Chapters 3 and 9 will be chosen as major feedstock for the plant, having a 1 t/h minimum continuous processing capacity. Upon detailing the engineering of the plant, further analytical work may vary the initial constituent composition and it will be appropriate to design for a range of material characteristics. In the most probable case that a continuum of variability cannot be found, the system design will be done for points, or through a limiting envelope of minmax operating points as it is customarily utilised for the combustion diagrams of incinerators (Chapter 3). This technique will furthermore become necessary because fluff will be mixed with a portion of medical waste, so to gain higher remuneration and faster repayment of the investment. The treatment of municipal waste, as such, is not foreseen due to low heating value and heterogeneity and because MSW does not generally justify the deployment of plasma destruction. At the beginning of the design work, it is necessary to be clear on all design parameters and expected performance of the plant. The process engineering activities will embody the design philosophy that in our case is derived from the previous experimental experience. Design parameters will be detailed and grouped by category: Site and ambient conditions Capacity and quality, influent streams and outflows Operating and design temperature and pressure Availability or requirement of utilities and chemicals Mode of operation and required controls Battery limits and interfaces Storage and hold-up Codes and applicable standards Safety requirements. Process description The planning and execution of the described experimentation make possible to trace the guidelines that will characterise the design of the Demonstration Plant. We learned unique advantages, features and optimisations that will be considered in developing the process scheme. While a description of the main features is already found under Chapters 6 through 10, a brief process features recap is given below. The raw solid waste, practically inodorous, but yet to be stored in respect of handling, water leaching and emissions precautions, is admitted to a two step shredding system, consisting of a gross breaking and blending machine, followed by a shredder capable to reduce particles to a minute 5 mm average apparent size. This flowable material is mixed with other shredded solids, that could be medical waste, and is transported by means of belt conveyors to the tight sealed plasma reactor feed hopper. A feed auger or a coclea type conveyor would then take the solids to the chute of the plasma reactor controlled by adequate no-clog and weight calibration valve. The reactor, operating in slight depression and equipped with nitrogen purge, sees the controlled admission of pure oxygen and steam plus the desired flow of carbon dioxide, coming from the adjoined flue gas adsorption/concentration system. The multi-layer refractory 11.2.2

11.2.1

210

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lined reactor is periodically loaded with glass cullet, introduced to replenish the molten lining bath, that is periodically discharged to blow-down inert and residual metal oxides. Among the reactor entering streams, carbon laden solids are recycled from the gas cleaning system and from the boiler ash hoppers. The syngas leaving the reactor is passed through a waste heat boiler to recover the heat of the gas down to approximately 400C to prevent dioxins formation. Quenching of the syngas is then followed by particulate removal and scrubbing. An activated carbon filter is also foreseen for mercury adsorption prior to the tail end induced fan that keeps the depression throughout the process. The syngas is ultimately delivered to CO/H2 separation or to downstream users. The waste heat, recovered as steam, is utilised for the closed thermal cycle power generation that integrates the plasma electric power consumption. Ancillary plant systems (N2, O2, plant and instrument air, demineralised water, scrubbed water treatment and reuse, the steam-power cycle details, glass and vitrified solids handling, filtration, storage and dilution of MDEA ) are not described here for simplicity and they can yet represent a significant part of the plant, if the same is to be a stand-alone or grass root installation. The absorption and concentration of CO2, taken from a nearby flue gas emission source, is part of the on-site units instead. By recalling the study described under Chapter 6, the system is characterised by low operating pressure to offset unnecessary compression costs. The absorber will follow an SO2 scavenging unit and an inlet flash contactor to reduce the cooled compressed gas to equilibrium humidity and eliminate excess water; part of which is being recirculated with MDEA and maintain the amine to water operating ratio that we experimented. The flue gas leaving the absorber is disposed to the chimney after cooling and passing through a top absorber flash drum to minimise absorbent losses. The absorber bottom rich amine/water solution goes to the stripper. The stripper overhead wet gas, rich of CO2, goes then to the plasma reactor, while the bottom reboiled lean amine/water solution is cooled with the stripper feed stream and in a water trim cooler prior to recycling back to the absorber. Process Flow Diagram (PFD) and Equipment List The above process description is simple enough to be followed without drafting a comprehensive PFD and Equipment List, even because the main sections are already reported under Chapters 6 and 9. The PFD(s) will be prepared with tagged items, major control loops and major interconnecting piping during the basic engineering of the Demonstration Plant. For all major equipment, a process specification or a duty specification, at least, will be prepared to enable further definition, design and procurement of the items. There will be proprietary items, such as the plasma reactor and related patented features like the electrodes advancement system or the molten glass exiting ports, for instance, for which the process specification will identify the intended scope and the design/supply that will be performed by the proprietary technology owner. The normal operating or nominal capacity overall material and heat balance will be prepared for the Demonstration Plant. A basic difference exists between production plants and waste treatment plants. In a production plant the target is the net end production and quality. The balance is generally worked backwards, so the net flow plus the intermediate streams are accounted to calculate the necessary inputs. A waste plant 11.2.3

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211

material balance is generally calculated from upstream, because the major concern is to ensure the treatment capacity of the delivered waste. The two concepts go hand in hand, due to recycles and re-use around specific blocks. The balances will be developed during the engineering phase with specific attention to peak and minimum values or transitory conditions for start-up or upset studies that ensure the safe operation of the plant. For the purpose of running a first preliminary economic model of the investment, the major assumption and variables on capacity and consumption are summarised in the first pages of the model. A combined Equipment List will be generated to detail the equipment shown on the PFDs, mainly to group and guide the process design work, while all details will be defined during the detailed engineering phase and upon choosing the equipment for the project. 11.2.4 Plot Plan and layout A detailed study needs to be done for the final size of the plant. The addition of the plant to existing facilities or the grass-root settlement of the plant involve a variety of utilities and sub-units, all affecting the ultimate distribution and layout of the equipment. A preliminary study for the on-site equipment of the 30 t/d plasma treatment can well be affected by the off-sites and can only be prepared when battery limits and location of the plant are defined. On a preliminary basis, the plot area is anticipated in the range of 2000 m2.

11.3

Uses of Syngas

The plasma plant gaseous products, after scrubbing and particulate removal, constitute building blocks for chemical syntheses. In many Countries, Italy in particular, there are strong incentives for producing electricity and the syngas is commonly burnt. Hydrogen can be separated instead and CO sent to processing. The separation of hydrogen, for instance with Pressure Swing Absorption (PSA) membranes, requires pressurisation, but the volume and concentration of the gaseous products are however limited and the compression costs become acceptable. Lower purity purge hydrogen from PSA can be used as fuel, when only partial recovery is tolerated. For CO, the possibilities are numerous and in some industrialised areas, like central Germany for instance, there are gas pipelines distributing the gas. For local uses, methanation of CO with hydrogen to yield methane, or a Fisher Tropsch synthesis would produce low molecular weight hydrocarbons and gasoline. CO can produce formic acid and formaldehyde, methanol and higher alcohols, or make acetic acid via carbonylation. With ethanol and acetylene CO makes acrylates and there is a variety of plastics, fibers and glues that can be derived. Hydroformylation of alkenes or chlorination to phosgene or caprolactam with butadiene are few examples that open a variety of applications. It would be long to describe and it is well documented by all Organic Chemistry books that numerous syntheses derive from alcohols, aldehydes or just from the few referenced intermediates obtainable from CO. Notwithstanding the production of chemicals and intermediates is the kind of activity that power plant or solid waste treatment plant personnel or managers are not

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prepared to start readily, it is however conceivable that, in terms of integrated economies and technologies, the drive for optimisation and profitability may combine different types of useful processing to end products, starting from the treatment and conversion of solid waste.

11.4

Preliminary Economics to Continue the Research

The modelling and planning of activities needs to be tailored to specific cases and will largely depend on the influence and number of the participating partners. On a preliminary basis, the following considerations and income statements are foreseen. Approximate as they may be, the figures provide the order of magnitude and the targets that appear realistic for producing a commercial result. Although it is not simple wishful thinking that one affluent investor be readily available and interested to fund the project alone, the working hypothesis is that a pool of investors is found. On the account of fluff spread availability that was discussed under Chapter 2, it appears conceivable to aggregate few European end users. Based on leads or signs that a study will generate a potential agreement and development, it would be necessary to prepare a business plan, set schedule and milestones, seek additional sources of European grants or CNR funding and corporate supporters. Preparatory work would also be needed for setting preliminary contracts, legal advice and protecting intellectual property rights, as well as increasing on going cooperation with foreign universities, but the more one speculates about undertaking a serious and multi-facet approach, the more evident becomes that a team is necessary and the team will only exist if initial support or funding becomes available. Pyro Plasma Lab As we explained above, the foundation would start with limited scope and personnel to reduce the initial money outlay. Captive services will be first sold to the partners or sponsors of the initiative, in order to plan for guaranteed sources of income, that will immediately help in acquiring equipment and instrumentation for the laboratory. Key figures that help to understand the five-years plan presented under Appendix 11.2 are summarised below: Politecnico di Milano annual minimum grant of 20E3 Eu/y, for 5 years 5 PCP initial participants at a minimum of 17E3 Eu/y each, for 5 years Annual turnover in billable research/services, 200E3 Eu to 600E3 Eu ( 5th year) Equipment/apparatus 70E3 Eu initial to over 650E3 Eu ( 5th year) Offices of 30 m2 and laboratory of 100 m2 Gradual increase of personnel, starting from 2, with contract assistantships Full reinvestment of profits Working capital limited to cover 3 months operation Royalties starting after the 3rd year From the foundation point of view, although everything is reinvested, the payback period of the project is about four years. 11.4.1

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213

Demonstration Plant The scaling up for a commercial plant requires to be executed in steps of progressive size and the core part of the first size (plasma hot section), nominally of 30 t/d, can constitute a module to expand from. This method of risk reduction is also necessary to learn by doing and to model the system under a variety of real case problems still untested. For preliminary purposes, the cost figures of the model presented under Appendix 11.3 to this chapter were provided by IET and we pro-rated ancillary systems from similar cases. The ultimate configuration of the plant and the size of investment will be established during the engineering phase. Conferring the waste to be treated will generate tipping fee revenues and we assimilated the fluff gain equivalent to treating MSW. A portion of the material is anticipated to be medical waste, which commands a much higher fee and helps to repay the investment more rapidly. For the demonstration unit, which has high relative costs, compared to capacity and productivity, it is possible to envision that a large percent, say 30% of the capacity, will be used for the medical waste. Personnel, chemicals and utilities are among the variables found and detailed in the first pages of the model report. Although the plant would produce syngas, the model makes the assumption that the chemical energy has a commercial value like if it produced electric power. The revenue from using broken bottles or recycled glass (cullet) is presently ignored as well as the revenue that is likely to come from the treatment of CO2 from the sequestering of flue gas. These are precautionary assumptions to investigate if the plant can be sustainable with a reduced number of favourable economic inputs. As it is customary when referring to energy intensive projects, an important factor that is going to weigh the financial impact and payback period of the Demonstration Plant is the crude oil price. A sensitivity analysis will provide an accurate evaluation at the stage of detailing the engineering and the financial model with actual design figures and estimates. There are many variables in the financial model and the ultimate return on investment depends on their inter-relation. Assumptions used for the ten-years plan are summarised in the first pages of the model and key figures are reported below: Plant capacity 30 metric ton/day Fluff processing capacity in excess of 7100 t/y Medical waste processing capacity about 30 wt-% Fluff tipping fee 8 cent/kg, medical waste tipping fee 80 cent/kg Base investment in excess of 16 million Euros Self-financing of 80% with a 20% possible zero interest grant Debt financing rate at 4% Cash flow is discounted at 3% for an IRR exceeding 7%. In conclusion, the projects of continuing the research and the possible commercialisation of the plant via a demonstration size installation stand a good possibility of repayment. Prior to undertaking the final investment decisions, further support can be gained from specific feasibility studies so that the limited commitment to

11.4.2

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detail further the process and the economics can reduce the risks of a larger scale investment.

Appendix 11.1

Process Book

Appendix 11.2

Income Statement: Pyro Plasma Lab Foundation

Appendix 11.3

Income Statement: Demonstration Plant

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APPENDIX 11.1:
INTRODUCTION SECTION 100 101 102 103 104 105

PROCESS BOOK INDEX

(General) BASIS OF DESIGN BATTERY LIMIT CONDITIONS EQUIPMENT LIST LIST OF MAIN DUTY SPECIFICATIONS LIST OF DATA SHEETS AND FORMS

SECTION

200 201 202 203 204 205 206 207

(Flows) DESCRIPTION OF THE PLANT PROCESS FLOW DIAGRAMS MASS / ENERGY BALANCE NORMAL OPERATION CO RELIEF AND FLARE START-UP SHUT-DOWN

SECTION

300 301 302 303 304 305

(Analyses and Specifications) WASTE COMPOSITION AND ANALYSIS SYNGAS AND PRODUCTS SPECIFICATION INCOMING WATER ANALYSIS NEUTRALISATION OF WASTEWATER REJECTS AND BLOWDOWNS

SECTION

400 401 402 403 404 405 406 407

(Tankage and Plasma System) VESSELS, TANKS, DRUMS AND FLASH DRUMS REACTORS COLUMNS AND SCRUBBERS ASH HOPPERS AIR FILTERS AND ELECTROSTATIC PRECIPITATORS LININGS AND INSULATION REFRACTORIES

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SECTION

500 501 502 503 504 505 506

(Heat Transfer) SHELL AND TUBE EXCHANGERS ELECTRIC HEATERS AND PLASMA ELECTRODES AIR COOLERS CONDENSERS COOLING TOWERS WASTE HEAT BOILERS

SECTION

600 601 602 603 604 605 606 607 608 609

(Machinery) CENTRIFUGAL PUMPS METERING PUMPS COMPRESSORS BLOWERS FANS MIXERS AND AGITATORS SHREDDERS AND GRINDERS CONVEYORS TURBINES

SECTION 700

700 701 702 703 704 705 706 707 708

(Instrumentation and Controls) CONTROL VALVES CONTROLLERS RELIEF AND SAFETY VALVES INDICATORS AND TOTALIZERS ANALYSERS ALARMS AND INTERLOCKS DCS ESD

SECTION

800 801 802 803 804

(Chemical Feed Systems) CAUSTIC SODA HYDROCHLORIC ACID OXYGEN FEED SYSTEM COATINGS AND GLASS CULLET FEED

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217

805 806

MDEA BOILER ADDITIVES

SECTION

900 901 902 903 902 904

(Other Systems) PLANT AND INSTRUMENT AIR NITROGEN DISTRIBUTION ION EXCHANGERS CARBON ADSORBERS DEAERATORS

SECTION

1000 1001 1002 1003

(Piping) LINE LIST LINE CLASSIFICATION LINE SPECIFICATIONS

SECTION

1100 1101 1102 1103

(Electrical Equipment) USER LIST MOTORS SINGLE LINE DIAGRAM

SECTION

1200

(Miscellanea)

-------

SECTION

2000

(Safety)

-------

SECTION

3000 3001 3002

(Process Guarantees) PERFORMANCE GUARANTEES PERFORMANCE TEST AND DURATION

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Simplified Income Statement for the first 5 years operation of Pyro Plasma Lab APPENDIX 11.2
(Euro x 1000 unless differently noted)
Line

1 2 3 4 5 6 7

Sales of services Margin on services Total sales of Engin'g services Reworks, discounts, allowances Pilot tests, paid develop. technol Feasibility Studies Basic License Package design NET SALES

1 2 3 4 5 120 170 180 190 200 50% 60 85 90 95 100 180 255 270 285 300 5% -9 -13 -14 -14 -15 25 40 60 60 70 incl 20 30 30 40 incl incl 100 150 200 ---------------- ---------------- ---------------- ---------------- ---------------196 302 447 511 595 40 45 60 120 180 30 31 32 50 75 100 120 140 150 150 30 31 32 35 45 25 26 27 28 29 20 20 22 25 30 7 15 17 18 19 3 4 6 7 8 20 25 30 35 40 ---------------- ---------------- ---------------- ---------------- ---------------275 317 366 468 576 -79 -40.3% -15 -4.9% 80 17.9% 43 8.3% 19 3.2%

5 years

---------2051 663

8 9 10 11 12 13 14 15 18

Depreciable equipment Analytical equipment Salaries, staff directly hired Officers, advisors compensation Outside professionals (for contracts) Outside consultants, legal licensing Travels Office consummables Research unpaid expenses TOTAL COSTS

---------2003 47 2.3%

19

GROSS OPERATING MARGIN % of net sales DEPRECIATION NET OPERATING INCOME FINANCIAL BURDEN (**)

20 21 22 23 24

Not considered here, we'll see how it works in a foundation -79 -3 -82 0 -15 -4 -101 0 80 -5 -26 0 43 -6 0 -5 19 -7 0 -5 -10 12 ===== 47 -25

CUMULATIVE RESIDUAL LOSS TAXES

(46%, reinvested in lines 8,9)

NET PROFIT -82 -19 75 32 6 ========================== == ============== ========= ========= ========= ========= 25 26 27 28 29 PAYBACK PERIOD: three to four years CAPITAL PAID-IN INVESTMENT Politecnico Grant @ kEu 5 sponsors, PCP @ kEu CNR or EU or else 620 Euros (000) or more if other grants are obtained 20 20 20 20 20 85 85 85 85 85 15 15 20 20 25 120 120 125 125 130 69 79 92 117 144

20 17

620

30 31

WORKING CAPITAL

(&&)

3 months

Short term debt with banks -31 22 109 40 -8 ========================== = ==== ========= ========= ========= ========= ========= 32 Personnel Tech/Assist. 1/1= 1/2= 1/2= 1/3= 1/3= # total staff 2 3 3 4 4 Calculated @ 5% on entire working capital. Does NOT consider positive interests on financial short term investments Notes (**) (&&) Exposure with Banks on operating expenses, NOT on orders or procurement delays between buy/sell of goods

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A 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37

D
1000 x Euro

Income statement first 10 years of operation Constant Eu Fluff Medical waste Plant productivity Export capacity Green certificates Power current price CH4 post-combustion, start-up N2 O2 Electrodes Glass sales Personnel Salary increase/year Chemicals Fly-ash disposal Wastewater and salts Leasing and various Ordinary maintenance Consumable materials Depreciable investments Additional investments Zero interest grant from institutions Own resource financing or via j.v. Financing rate Duration of financing Net profit portion to repay debt Discount rate Salvage value hypothesis Financing entity(ies) Taxation of profits

APPENDIX 11.3
30 (metric t/d total) 8 (tipping fee) 80 (tipping fee)

Main hypotheses of model @ capacity of t/day= t/y t/y h/y MWh h/y h/y m3/y kg/h kg/h Eu/h t/y 1000/y percent 1000/y t/y t/y percent/y percent/y percent/y million Eu percent/y percent/y percent/y percent/y years percent percent percent 7150 2100 7400 1.80 7400 7400 222000 33 350 5.6 0 315 0.5% 594 0 0 0 1% 1% 16 0 20% 80% 4% 15 90% 3% 0 TBA 46.34% c/kg c/kg

say 30%

including thermal recovery c/kwh 8.4 Green C. c/kwh 7.5 c/m3 7 c/kg 20 c/kg 15 from 7 $/h see prospect or input (percent over inflation) see prospect or input c/kg 0 0 c/kg on turnover or actual value on investment or actual value on investment or actual value see prospect or input

poliannual financial burdens are calculed on this portion only duration to optimise with taxes and cash-flow less possible new investments (approximates legal reserves and TFR)

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A 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 PERSONNEL DETAILS # Managers Supervisors External analysis laboratory Switchboard, services, storage Guards, reception Total administrative personnel Daily maintenance Shift maintenance Shift operators Control room Boiler, gas treatment, power gen. General duty daily operators Others Utilities, demi, chemicals included above Waste loading and operation Weigh scale, included above

E req. *

F Unit Cost 50 25 10 20 15

G Eu x 1000 /year 0 25 10 20 30 -------------85 40 0 -------------40

nomin. shifts

APPENDIX 11.3

0 0 1 1 0 1 1 1 2 2 -------------- -------------4 5 2 1 1 0 2 2 0 0 -------------- -------------2 2

20 20

3 5 17 85 1 1 15 15 1 1 15 15 0 0 15 0 0 0 15 0 3 5 15 75 0 0 15 0 -------------- --------------------------8 12 190 ======== ======== PERSONNEL, TOTAL 19 315 Eu x 1000 * For shifts, inclusive of vacations, weekends, absenteism (5%) (7/5)(1.05)(1+1/12) = 1.6 / person 363.636 CHEMICALS CONSUMPTION DETAILS H2SO4 NaOH HCl O2 N2 Glass cullet (could become a revenue) Biocides and additives Oil Water Bag house additives Others (Fuel, separate) t/y 10 222 100 2590 244 336 3 1 2000 25 0 Eu/kg Euro 0.05 500 0.1 22200 0.15 15000 0.15 388500 0.2 48840 0.03 10091 1 3000 2 2000 0.05 100000 0.15 3750 0 0 -------------593,881 Euro/y

1 1 1 0 1 1 1

3 1 1 0 0 3 0

Wrapping it all up: Research and Process Development Plan

221

A 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106

APPENDIX 11.3
DEPRECIABLE INVESTMENTS INITIAL Buildings Light constructions, insulation Machinery, equipment Specific units: Switchgears, transformers Distribution grid, power netw. Boiler, gas treatment Lines and piping Instrumentation and various Computers, CPU Controls Furniture Office machines initial base around 23 million $ => 16.1 % depreciation (1/2 1st year) 4 10 8 7 8 9 4 10 20 12 20 MM Eu million initial 1 1 6 mixed product 4 10 48

0.5 3.5 0.5 4 2 18 2 8 1 10 1 20 0.5 6 0.5 10 --------------------------16 141.5 8.84% 12.31 years 13 rounded off

Depreciation weighed, yearly percent Lifetime of depreciable goods (based on depreciation in Italy) year= 1/(% legal)+1, half rate for 1st and pertaining last year

222

Chapter 11

A 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160

D
1

E
2

F
3

G
4

H
5

I
6

J
7

K
8

L
9

M
10

Prelim inary Incom e Statem ent Sales Fluff tipping fee hypothesis Medical waste tipping fee Electric power green certificates Exported electric power equivalent Secondary products (like CO2, glass cautiously put=0) TOTAL REVENUES (Eu x 1000) Salaries Fuels Ordinary m aintenance Maintenance consum able m aterial Chem icals Electrodes Ash disposal and salts New deductible investm ents Leasing and others TOTAL COSTS GROSS OPERATING MARGIN
% on turnover

APPENDIX 11.3

572 572 572 572 572 572 572 572 572 572 1680 1680 1680 1680 1680 1680 1680 1680 1680 1680 1119 1119 1119 1119 1119 1119 1119 1119 1119 1119 999 999 999 999 999 999 999 999 999 999 0 0 0 0 0 0 0 0 0 0 -------------- --------------------------- -------------- ------------- --------------------------- ---------------------------- -------------4370 4370 4370 4370 4370 4370 4370 4370 4370 4370 315 317 318 320 321 323 325 326 328 329 16 16 16 16 16 16 16 16 16 16 160 160 160 160 160 160 160 160 160 160 160 160 160 160 160 160 160 160 160 160 594 594 594 594 594 594 594 594 594 594 41 41 41 41 41 41 41 41 41 41 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 -------------- --------------------------- -------------- ------------- --------------------------- ---------------------------- -------------1286 1287 1289 1291 1292 1294 1295 1297 1299 1300 3084
71%

43699

0.5% 1.0% 1.0%

0% 0%

12930 30768

3082
71%

3081
71%

3079
70%

3078
70%

3076
70%

3074
70%

3073
70%

3071
70%

3070
70%

DEPRECIATION (on initial value) New Depreciable Investm ents Depreciation on new investm ents CUMULATIVE DEPRECIATION NET OPERATING INCOME

667 0 0 667 2417 -1151 0 -1151 0 -587

1333 0 0 1333 1749 -1151 166 42 20 -922 0 -383

1333 0 0 1333 1748 -1151 261 56 13 -821 0 -429

1333 0 0 1333 1746 -1151 328 58 15 -751 0 -461

1333 0 0 1333 1744 -1151 395 59 16 -681 0 -493

1333 0 0 1333 1743 -1151 466 60 17 -609 0 -526

1333 0 0 1333 1741 -1151 539 61 18 -533 0 -560

1333 0 0 1333 1739 -1151 615 62 19 -455 0 -595

1333 0 0 1333 1738 -1151 693 64 21 -373 0 -632

1333 0 0 1333 1736 -1151 776 65 22 -289 0 -671 -5337 18102

FINANCIAL BURDENS, POLIANNUAL 4.0% interest credit, not paid for anticipated repaym ent interests on advanced repaym ents (###) INTERESTS/BURDENS ON PREVIOUS PROFIT TOTAL BURDENS AND INTERESTS CUMULATIVE RESIDUAL LOSS FISCAL BURDENS 46.34%

could be elim inated for the 1st year

6180 NET OPERATING PROFIT (NOP) 679 444 497 534 571 609 648 689 732 777 ==================================================== ======== ================ ================ ======== ======== ======== ======== CASH FLOW (NOP + DEPRECIATION) 1346 1777 1831 1867 1904 1942 1981 2023 2066 2110 ACCELERATED REPAY of INITIAL INVEST 90% 1211 1599 1648 1680 1713 1748 1783 1820 1859 1899 (% NOP + 100% DEPRECIATION) YEAR END RESIDUAL DEBT TO PAY 10949 9896 9157 8405 7624 6812 5968 5089 4176 3226 ==================================================== ======== ================ ================ ======== ======== ======== ======== year 1 2 3 4 5 6 7 8 9 10 (###) for the advanced repaym ent of initial the financing, an interest can be negotiated with the bank for instance, equal to the discount rate plus half the spread with the poliannual interest rate IRR CALCULATED ON THE TOTAL INVESTMENT AS OW N DEBT 5,220 Eu x 1000 Discount of NET PROFITS, @ 3% 3,054 " with Inv. = 16,000 initial Eu x 1000 having own financing = 12,800 Eu x1000 Discount of CASH FLOW , (NPVc) 7.3% IRR (% ) (cash flow on total invested capital)

12

CONCLUSIONS

The conclusions of this work, condensed in a bullet-type list, are derived from the pilot plant experimental data and can therefore be optimised during scale-up. Details of the experimental results were exhibited under Chapter 10 and the possible avenues to continue this research, both theoretical and applied for a demonstration plant, are found under Chapter 11.

12.1

Starting Points Validity Confirmation

a) Abundant organic-based waste (among which ASR), abundant and near-tobe-taxed emissions of CO2 suggest the need to find a treatment solution. b) The calculation of a scheme to capture and concentrate CO2 from flue gases, at nearly atmospheric pressure with MDEA, is feasible. It needs further development and optimisation to accomplish a capture rate higher than the achieved 63%. The scheme appears fairly economical and it can have a few years payback time (depending on the carbon tax level). c) The use of a plasma converter is a viable possibility to recover usable energy (more than it is fed to the system) provided that the syngas is used chemically and not burnt/transformed into electric power. d) The carbon tax will be offset by the conversion of CO2, economics will clearly depend on the tax. By similitude, we modelled a tax derived from Green Certificates (about 75 Eu/t-CO2); current speculations, in Europe, indicate that the emissions tax may vary between 40 and 100 Eu/t-CO2.

12.2

Experimentation and Research Findings

a) Experiments proved that an autothermal plasma process, operating at fairly low temperatures, near 1300C, and equipped with anti-corrosion, energy minded technological features can be used. The autothermal partial combustion was made with pure O2. The continuous feed reliability of the solids has been demonstrated. Steam reforming was compared to dry reforming, and it is generally convenient to inject a quantity of steam to reduce carbon black formation (recyclable) and enhance H2 production. Water steam consumption varied between 0.2 and 1.8 kg/kg-C or 0.1 and 0.9 kg/kg-fluff. Oxygen consumption was practically held constant at about 0.9 kg/kg-fluff. CO2 conversion was approximately 3 kg/kg-fluff. The conversion rate reached 90% of the gas feed, depending on operating conditions and on the available DC power level. The DC power to the electrodes was practically held constant at 14 kW for an average input to the arc of about 1.1 kW/kg-fluff. The average electrode consumption was limited to 0.05 kg/kg-fluff. The solid vitrified end-product exhibited leaching releases below norm and it can be used or disposed in safe and very compact volumes.

b) c) d)

e) f) g)

h)

i)

224

Chapter 12

j)

Ashes discharged from the bag-house were in the range of 0.08 kg/kg-fluff and can be recycled to the reactor. k) The syngas obtained from the plasma reactor has promising quantities of CO and H2, about 55-45 vol-%, dry basis, and it is likely to be used for chemical syntheses. Its actual suitability will depend on the downstream specification, particularly if the product gas is used in a catalytic process.

12.3

Avenues to Continue the Research and Develop a Plant

A variety of applications can apply to the product syngas: organic syntheses, Fisher-Tropsch fuels, fuel cells, formaldehyde, alcohols, acetic acid, glues, plastics, hydrogen by itself, to name a few. b) The research within the University can also have a monetary payback (as sunk re-investment) in terms of services and royalties obtained from external users, not necessarily from captive services requested by the initial subscribers to the initiative. A universities-third parties foundation type mechanism has been considered for starting up funds and generate a nonprofit academic institution. c) The pilot plant experimentation exhibited a variety of issues, among which, thermal losses, scale-up of the reactor, heat recovery, layout optimisation, O2 vs. power feed, recycling, vitrified discharge use that will need to be addressed in the design of a commercial but also for a demonstration plant. d) The size of the CO2 and waste generation is very big, the worldwide order of magnitude for emitted CO2 is 60 billion t/year and fluff generation amounts to about 6 million t/year (almost a third in Europe). Aside from cost of oil/energy acceleration and the application of a carbon tax, any meaningful plant is likely to be considered after being able to exhibit or reference a sizable demonstration plant. e) For our purposes, we focussed on the possibility to arrive at a demonstration plant of 30 t/day, fluff feed basis, but also in a mix of multifeeds that are to exploit the best tipping fees from the supply of waste. The demonstration plant would thus have a repay period below 10 years with a safe IRR of about 7%. Such economic model would obviously need to be tailored on energy and financial burdens, during detailed design. f) Given the case of treating 100,000 Nm3/h emissions (about 20 t/h CO2, which is a modest rate for any industrial combustion), we could adjoin the CO2 treatment in a plasma plant fed with 27 t/h of fluff, to generate 1.5 t/h H2 and 25 t/h CO. Even this plant size represents a 20 fold scale-up of the possible demonstration plant size given under point e) above. a)

It becomes quite evident that major activities of research and engineering will be necessary, but these can only happen if adequate financial funding will be found. Furthermore, funds will be necessary to secure additional human resources since the new scale of operation requires a multidisciplinary team, acting beyond the scheme and the limits of a doctoral work.