Fuel 90 (2011) 14021407

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Fuel
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The Gibbs Free Energy Gradient Method for RDF gasication modelling
D. Barba a, M. Prisciandaro b,, A. Salladini c, G. Mazziotti di Celso d
a

University Campus Biomedico of Rome, Via lvaro del Portillo, 21, 00128 Roma, Italy Department of Chemistry, Chemical Engineering and Materials, University of LAquila, Campo di Pile, Zona Industriale di Pile, 67100 LAquila, Italy c Processi Innovativi, Corso Federico II, 67100 LAquila, Italy d Department of Food Science, University of Teramo, 64023 Mosciano S. Angelo, Teramo, Italy
b

a r t i c l e

i n f o

a b s t r a c t
Starting from an equilibrium model for gasication, this research group has devised a new mathematical model, the so called Gibbs Free Energy Gradient Method Model (GMM). This model permits to bypass the semi-qualitative view, typical of equilibrium models, which assume very restrictive hypotheses such as equilibrium state for all the reactions involved in gasication process, complete conversion of carbon matter, gasication products in gas phase only. GMM model overcomes these limitations providing a quantitative point of view, even though the hypothesis of no tar production affects both models. GMM model has been applied to RDF gasication, supplying reliable results in the gasication process analysis. Model computations in terms of gas yield, gas composition, low heating value and H2 yield, have been compared with literature results, showing that computed data are in good agreement with experimental ones. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 1 April 2010 Received in revised form 9 December 2010 Accepted 19 December 2010 Available online 1 January 2011 Keywords: RDF Gasication Model Equilibrium Free energy

1. Introduction The growing demand for clean gaseous fuels as well as chemical feedstock, has led to an increasing attention to gasication processes in the past two decades [1]. The mechanism of gasication has been extensively studied and it is well documented [2,3]: briey, thermochemical gasication is a process for converting solid fuels into gaseous phase. The chemical energy of the solid fuel is converted into both thermal and chemical energy of the gas. The chemical energy contained within the gas is a function of its chemical composition; thus the chemical composition of the product gas determines its quality as a fuel. Biomass is potentially an attractive feedstock for producing transportation fuels as its use in small plants (about 510 MW) contributes a little to carbon dioxide increase in the atmosphere [4,5]. This is particularly true if small plants are provided with biomass plantation in close proximity, as CO2 emission due to biomass transport must not be taken into account [4]. Thermochemical gasication of biomass is a well-known technology; however, biomass gasication is not reaching a commercial scale because of several reasons: rst there are some technical problems not yet solved, like tar production, whose formation can cause lter clogging and malfunctions to gas turbine [6,7]; secondly it must be taken into account non-technical barriers, mainly the cost of the biomass

Corresponding author. Tel.: +39 0862 434202; fax: +39 0862 434203.
E-mail address: marina.prisciandaro@univaq.it (M. Prisciandaro). 0016-2361/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2010.12.022

and the fact that it is not concentrated in one location, but spread over a wide area [8]. These two problems are overcome with refuse-derived fuel (RDF) from municipal solid waste (MSW). It is paid for the disposal of the RDF (it has a negative cost) and it is available in big amounts from MSW disposal plants. Moreover, the heterogeneous composition of RDF restricts the class of possible secondary users (such a cement works, steelworks, etc.) that would prefer more selective incoming uxes. Thus the opportunity to use RDF to produce fuel gas through gasication appears promising, even if it arises some problems: one is RDF possible high content in chlorine [9], both inorganic (i.e. NaCl) and organic (i.e. PVC) [10]; therefore the raw gasication-gas would not only contain the typical impurities of tar and NH3 but also some chlorine both inorganic (HCl and Cl2) and organic (chlorinated organics). So, a de-acidication treatment of produced gases would be necessary. As far as gasication modelling, recent efforts include the application of an equilibrium model to predict the performance of commercial gasiers, as well as several kinetic models for particular reactor types. Such methods are limited to small numbers of reactions and species with clearly dened mechanisms, while for more complex systems, the reaction mechanisms often require extensive study. Although kinetic models provide essential information on mechanisms and rates, equilibrium models are valuable because they can predict thermodynamic limits as a guide to process design, evaluation and improvement [11,12]. However, a literature analysis has shown that, generally, equilibrium models fail in matching experimental results; particularly, these models are

D. Barba et al. / Fuel 90 (2011) 14021407

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unsuccessful for methane and hydrogen estimated content in the gas [13,14]. To improve the ability of equilibrium models to t experimental data, in particular as regards the content of methane, hydrogen and carbon residue, several researchers have made some changes entering corrective correlations in their models [11,15]; this method on one hand improves the approaching of theoretical results to experiments, on the other hand makes the models unpredictive, thus missing the possibility to be employed in the development of industrial processes. A different approach is that of using a non-equilibrium temperature, i.e. to consider that equilibrium among chemical reactions takes place at a temperature lower than actual reaction temperature [11,16]. Starting from an equilibrium model, this research group has devised a new mathematical model, the so called Gibbs Free Energy Gradient Method Model (GMM). This model allowed to bypass the semi-qualitative view, typical of equilibrium models, for a quantitative view, providing reliable results in gasication process analysis. The novelty and the power of this approach stands in its capability of modelling experimental results, on which the simulation itself is based. It is thus an adaptive model, more than a predictive one. In this paper the GMM has been applied to RDF gasication process; results obtained are in good agreement with experimental ones, showing that this model is a very useful tool in process analysis of a RDF gasication process. There are two general approaches to equilibrium modelling: stoichiometric, and non-stoichiometric. The former employs equilibrium constants of all constituent reactions, while the latter minimizes the Gibbs free energy subject to mass balance and nonnegativity constraints. As shown by Smith and Missen [17], the two approaches are essentially equivalent. In general, thermodynamic equilibrium models assume that residence time is high enough to reach equilibrium for all involved reactions; complete carbon conversion; absence of TAR; perfect mixing with subsequent absence of thermal gradients; adiabatic process. Among these hypotheses, the less veried is the equilibrium attained for all reactions: there is a good agreement among researchers in saying that below 1000 C reforming reaction between carbon, steam and CO2 are kinetically limited [18]. Moreover, the inuence of gasier type is to be taken into account. This research group has devised an equilibrium model that simulate gasication with steam as gasifying medium. The model combines atomic species conservation laws and thermodynamic equilibrium laws, considering the global gasication reaction that leads from feed to gaseous nal products. In this way a tool able to predict the nal composition of the gas, once known proximate and ultimate analysis of the feed and operating conditions (pressure, temperature, steam/feed ratio), is obtained. 2. Theory 2.1. The Gibbs Free Energy Gradient Method Model The model is based on the following assumptions: all considered reactions are at equilibrium; carbon is completely gasied and it is not present among reaction products, that are CO, CO2, H2O, H2, CH4, N2 all in gas phase, with the exception of solid ashes; as said above, the presence of TAR is not considered. The total gasication reaction is thus the following:

solved is made of the four mass balances on C, H, N and O, and of the following two chemical reactions at equilibrium:

CO H2 O $ CO2 H2 CH4 H2 O $ CO 3H2

Watergas shift Steam reforming

2 3

An Arrhenius type equation has been used to express the dependence of kinetic constants on temperature in Eqs. (2) and (3). With respect to the previous analysis, the new non-equilibrium approach starts from removing the assumptions made of all reactions at thermodynamic equilibrium, of all the carbon gasied, and of all reaction products in gas phase, while the hypothesis of the absence of TAR still remains. So, the model becomes able to analyze experimental results of a real gasier with nite residence times and efuents both in gas and in solid phase, with a carbonaceous unreacted residue with ashes. To simulate the process, the following mass and energy balances have been carried out. 2.1.1. Mass balance The gas and solid phase entering and leaving the reactor have been so characterized:  Reactor outlet: gas phase formed by CO, CO2, H2O, H2, CH4, N2, H2S; solid phase formed by unreacted carbonaceous residue and ashes.  Reactor inlet: gas phase formed by gasifying medium air and/or steam; solid phase formed by RDF, with composition specied by its brute formula. Considering that RDF brute formula has been changed with respect to Eq. (1), to take into account also for H2S formation, the gasication process has been modeled in two steps:  a rst step, in which RDF is decomposed at high temperature to produce a carbonaceous residue and a primary gas, which undergoes gasication reactions, represented by the following equation:

m r  CH4 rH2 S CHm Op Nq Sr ! pCO 4 2  m r q 1 p C N2 4 2 2

CHm Op Nq wH2 O ! aCO bCO2 cH2 dCH4 eH2 O f N2 1

In this equation CHmOpNq is the RDF brute formula, deducible from its ultimate analysis, on mist and ash free basis, and stoichiometric coefcient a, b, c, d, e, f are unknown. The system of equations to be

 a second step, in which the gas previously produced modies its composition due to the occurrence of water shift (see Eq. (2)) and steam reforming (see Eq. (3)) reactions, becoming the nal syngas. The gasication model so conceived gives birth to a solid carbonaceous residue that, on the basis of the chemical reactions chosen for the second step, it is not further consumed, and, as a matter of fact, constitutes the unreacted process solid carbonaceous residue. However that quantity is insensitive to process operating conditions, particularly to reaction temperature and to gasifying medium/RDF ratio, since it is determined by Eq. (4) stoichiometry only. Consequently there is the need of introducing two adjustable parameters, d and c, that vary RDF decomposition reaction stoichiometry (Eq. (4)) with varying process conditions. These two parameters have been linked to the effect of two chemical reactions in which solid carbon takes place in the real gasication process, both with air and with steam. For the parameter d, the Boudouard reaction, in which CO from RDF decomposition produces solid carbon, is considered:

dCO $

d d C CO2 2 2

where d are the CO moles that participate in this transformation.

1404

D. Barba et al. / Fuel 90 (2011) 14021407

For the parameter c, the Carbon reforming reaction, in which solid carbon increases gas yield, is chosen:

3 c cC cH2 O ! cCO CH4 2 2

in which c are water moles that gasify solid carbon. The effect of two parameters is that of increasing the mole number of solid carbon as for d, which is linked to CO partial conversion, and of decreasing the mole number of solid carbon as for c, which is linked to steam gasication. Including Eqs. (5) and (6) in Eq. (4), RDF global decomposition reaction becomes:

where lo T represents the standard chemical potential of the comi ponent i at the temperature T, R is the gas universal constant; Pi is the partial pressure of the component i. The standard chemical potential of the component i at the generic temperature T, starting from the reference state T0 = 298 K is given by the following relation:

lo T lo T 0 i i

T T T0

hi T T2

dT

13

T0

m r c  d CH4 CO2 CHm Op Nq Sr cH2 O ! p-d cCO 4 2 2 2   m r 3c d q rH2 S 1 7 C N2 p 4 2 2 2 2

When air the gasifying medium, the methane combustion reaction is also to be considered:

CH4 2O2 ! CO2 2H2 O

Taking into account that not all methane is consumed by combustion since gasication takes place with under-stoichiometric air quantity, being oxygen the limiting agent if x are oxygen moles fed for RDF mole, the decomposition global reaction becomes:

CHm Op Nq Sr cH2 O xO2 3:76N2 ! p d cCO   m r c x  d x CH4 CO2 rH2 S 4 2 2 2 2 2   q  m r 3c d C 3:76x N2 xH2 O p 1 4 2 2 2 2

Through the adjustable parameters c and d it is possible to manage both unreacted carbonaceous residue and primary gas composition coming from RDF decomposition reaction. Once noted the moles out owing from rst reaction step (Eq. (4)), it is possible to describe the system evolution as a function of the reaction coordinates of the two chemical reactions (Eqs. (2) and (3)), chosen for modelling the second gasication stage. Differently from the behaviour of equilibrium model, chemical reactions are not independent towards gas nal composition, since CO is present in both of them. For mass balance formulation, the reaction coordinate of the watergas shift reaction, a, has been referred to total CO, taking into account also for steam reforming reaction; the reaction coordinate of the steam reforming reaction, b, has been referred to CH4. On the basis of reaction stoichiometry, indicating with ni the initial moles of the i-component, where i = CO, CO2, H2O, H2, CH4, N2, H2S, for each species it is possible to write:

where hi is the standard molar enthalpy of the component i. Once chemical potentials of the system components have been dened, and at a xed temperature, it is possible to study the total free energy of the system using Eq. (11). The total free energy is a function of two independent variables, the reaction coordinates a and b: it is represented as a spatial surface, characterized by the presence of a minimum that exactly corresponds to the equilibrium conditions of the system. The new modelling approach uses the thermodynamic principle which states that a system always evolves from initial conditions to equilibrium conditions reducing, through the path, its energetic content, that reaches the minimum value in the point where the reactions are simultaneously at equilibrium. This equilibrium condition is actually reached when the residence time is innite. It is well known that residence time in industrial equipments is limited and so the system will reach the lowest energy level compatibly with the actual residence time that may be found in the equipment according to the reactor geometry and operating conditions. Among the innite routes between the initial point (in which a = b = 0) and the equilibrium point (in which a = aeq and b = beq) the system chooses the path that offers the maximum slope in the surface G(a, b), i.e. the maximum gradient grad[G(a, b)]. This route is the one that point by point best takes advantage of the driving force of the process, that is the Gibbs free energy variation. The experimental knowledge of the residence time stops this route in the point that corresponds to the real reactor outlet conditions. From a mathematical point of view the direction in which the punctual variation of the function G results in its maximum value is that indicated by the gradient vector, whose components coincide with the partial derivatives of the same function:

G0a

  @Ga; b ; @a bcos t

G0b

  @Ga; b @b acos t

14

ni a; b f no i

10

where ni is the number of moles of the component i. In order to observe the evolution of the system from the initial conditions towards equilibrium conditions, it is necessary to refers to the Gibbs free Energy state function (G), that at temperature and pressure constant, only depends on reaction coordinates a and b and can be expressed as:

Ga; bjT;P

X
i

ni a; b li a; b; T

11

In this equation ni is the number of moles of the component i in gaseous phase, while li represents the chemical potential of the component i in gaseous phase at the temperature T of the system. Components in both considered reactions are in the gaseous phase, so the chemical potential of the generic component can be expressed with the following relation:

li lo T RT ln Pi i

12

In the plane dened by the axes a and b, the direction of the gradient vector is given, point by point, by the ratio of both derivatives. These two progress parameters have been used to nd the minimum value for the G function. The computational strategy chosen is based on the conjugated gradient method, which solve the model system equation by means of the Built-in-Unit of MathCAD software, called minimize. This method allows to free the model from time step parameter. So the model calculates numerically the subsequent states of the system towards the point characterized by the compositions that better approximate the experimental composition of the outgoing gas. Through a set of experiments it is possible to adjust the model dening the optimum values for adaptive constants. This ne tuning phase is constituted of two steps: in the rst period the model has been solved with experimental data of a gasication process, in order to nd suitable adaptive constants (c, d), together with the progress parameters, which are able to minimize the difference between experimental and computed data. In the second period adaptive constants and progress parameters found are used to predict gas phase composition of a gasication process, whose characteristics are similar to the one used in the rst step.

D. Barba et al. / Fuel 90 (2011) 14021407

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ferred to the system from the outside, which tends to zero in the case of autothermic gasication with only air/oxygen.

3. Results and discussion 3.1. Comparison between model and experimental results from literature The model proposed has been validated by using literature results. Two experimental works have been used for the comparison. The rst is the one published by Lv and coworkers [19]. Authors have injected biomass (pine wood blocks) in a self-heated uidized bed using airsteam as gasication medium. They have performed experimental runs to investigate the effects of reactor temperature (from 700 C up to 900 C), steam to biomass ratio (steam rate from 0 to 1.8 kg/h), and equivalence ratio (from 0.19 up to 0.27) on gas composition and gas yield. Table 1 reports the ultimate analysis of pine wood blocks. Table 2 reports the experimental conditions used by Lv et al. [19]. The second paper considered for the comparison is the one published by Li et al. [20], which have injected sawdust material in a circulating uidized bed gasier, using air as uidization mean. The gasication temperature has been kept in the 700850 C range, while total air supplied varied between 135 and 310 N m3. Table 3 reports the ultimate analysis of sawdust material, while Table 4 shows the experimental conditions used by Li et al. selected for the comparison with computed data. By using the GMM model described above, from the minimization of the Gibbs free energy for the considered system the surface trend of total free energy, visualized both as spatial representation (Fig. 2) and iso-level curves (Fig. 3) is obtained. In particular Fig. 2 shows the minimum value of Gibbs free energy (z-axis), as a function of steam reforming reaction progress (b, y-axis) and water gas shift reaction progress (a, x-axis). Fig. 4 shows the comparison between computed ad experimental data [19] of gas yield and LHV as a function of RDF feeding rate. For both parameters the agreement is quite good for all the RDF feeding rate examined. More precisely computed gas yield overestimates experimental data: this behaviour is probably due to the fact that the model developed in this paper does not take into account tar production. However, tar yields detected by Lv et al. [19] are not sufcient to ll the gap between experimental and computed data of Fig. 4. It is necessary to keep in mind that experimental results obtained from Lv et al. [19] are relative to gasication of biomass. The gap should be compared with tar yields from a gasication plant fed with RDF, for example with the data obtained by Cioni et al. [21]: as expected tar yields detected from these authors strongly decrease the gap between experimental and computed data of Fig. 4. As for LHV, computed data are in good agreement with experimental ones [19]. This behaviour is conrmed by Fig. 5, too, which shows gas composition data and experimental results as a function

Fig. 1. Scheme for the energy balance.

2.1.2. Energy balance The following total energy balance is carried out, referring to the scheme reported in Fig. 1:

X  X  Q1 Q2 H H
IN

OUT

15

where Q1 and Q2 are the heat in kJ/h released to the outside in the rst and second stage, respectively (see Fig. 1), and:

X  Hair HRDF Hsteam H X IN Hgas HAshChar H

OUT

16 17

in which HRDF is enthalpy of RDF at the inlet temperature Ti, and it is given by:

HRDF H0 RDF

Ti

C p;RDF dT

18

298;15

The RDF enthalpy of formation H0 , because of its complex chemRDF ical structure, can be estimated as:

H0 LHVRDF RDF

X
iprod-comb

mi H0 i

19

where LHVRDF represents the Low Heating Value, H0 is the molar eni thalpy of formation, mi is the stoichiometric coefcient of each of the products obtained by the complete combustion of a single mole of RDF. The goodness of the process efciency is evaluated through the calculation of the efciency at 25 C (cold efciency), dened as:

gcold
where:

LHVgas G LHVRDF M 1 e

20

Q steam Q 1 Q 2 gcomb LHVRDF M

21

In this equation LHV is the gas and RDF low heating value in kJ/ N m3 and kJ/kgRDF, respectively; G is the produced gas owrate, in N m3/h; M is the RDF owrate, kg/h; Qsteam is the heat necessary to produce the steam owrate used as gasifying medium, kJ/h; (Q1 + Q2) is the heat released to the outside in the rst and second stage, respectively (see Fig. 1), kJ/h; e, dened in Eq. (21), is the RDF fraction to be burned to develop the heat amount (Q1 + Q2); gcomb is the RDF combustion efciency. Actually the correct thermodynamic denition of efciency in an energetic optimization study of the system, must consider both the net heat supply to the system and the fact that the products that derive from the combustion of the gas and those that derive by the direct combustion of RDF are discharged to stack at a temperature not below 120140 C. For this reason the hot efciency (ghot) has been dened as:

Table 1 Proximate and ultimate analysis of pine wood blocks. Moisture: 8 wt.% wet basis; Higher heating value: 20.54 kJ/kg [19]. Proximate analysis (wt.% dry basis) Volatile matter Fixed carbon Ash 82.29 17.16 0.55 Ultimate analysis (wt.% dry basis) C H O N S 50.54 7.08 41.11 0.15 0.57

ghot

LHVgas G DHgas LHVfuel M Q req DHfuel

22

where DH represents the loss of enthalpy of the combustion products of the gas and the fuel, and Qreq is the net amount of heat trans-

1406 Table 2 Experimental conditions [19]. Test N Temperature (C) Biomass (kg/h) ER 1 870 7.2 0.24 2 930 7.89 0.25 3 1015 10.76 0.27 4

D. Barba et al. / Fuel 90 (2011) 14021407

5 1108 11.36 0.25

1093 11.2 0.28

Table 3 Ultimate analysis of sawdust material [20]. All ultimate analyses, heating values and stoichiometric air volumes are on dry basis. SPF = spruce, pine and r mixed sawdust. Fuel type Carbon (wt.%) Hydrogen (wt.%) Oxygen (wt.%) Nitrogen (wt.%) Sulphur (wt.%) Ash (wt.%) Moisture content (wt.%) Higher heating value (MJ/kg) Stoichiometric air (NM3/kg) Dry bulk density (kg/m3) Mean particle diameter (mm) Cypress 51.6 6.20 40.4 0.65 0.46 0.70 9.722.0 20.3 5.36 136 1.49 Hemlock 51.8 6.20 40.6 0.60 0.38 0.40 8.815.0 20.3 5.36 128 0.92 SPF 50.4 6.25 41.6 0.62 0.34 0.70 10.0 19.8 5.20 119 0.82 Mixed 48.9 7.86 40.3 0.21 0.07 2.69 4.26.7 21.7 5.56 465 0.43

Fig. 3. Iso-level curves.

3
Table 4 Experimental conditions [20] selected for comparison. Run number Sawdust species Total gasication run time (h) Sawdust consumption (kg) Moisture content in sawdust (%) Total air supplied (N m3) Mean suspension temp. (C) Mean gas composition (dry basis) H2 (%) CO (%) CH4 (%) CO2 (%) Mean dry gas heating value (MJ/N m3) Gas yield (N m3/kg) 2 Cyp. 4.53 103.8 9.7 255 718 3.1 11.0 1.9 15.9 2.96 2.92 3 SPF 3.00 80.7 10.5 177 766 3.2 10.7 1.9 17.1 2.92 2.48 4 Hem. 4.23 110.6 10.0 281 815 3.0 9.6 1.9 17.1 2.75 3.10 7 Hem. 2.62 88.1 11.7 142 718 5.5 16.6 3.4 15.0 4.82 2.34 15 Mixed 3.55 55.2 4.2 135 805 5.9 10.0 1.2 18.3 2.54 3.24
LHV gas, exp. data LHV gas, model results Gas yield, model results Gas yield, exp. data

10

Gas yield, Nm3/kg

2 6

4 1 2

0 7 8 9 10 11 12

RDF feeding rate, kg/h

Fig. 4. Gas yield and LHV as a function of feeding rate: comparison between GMM previsions and experimental results [19].

60

40

vol

30

H2, CH4, CO,

20 10

0 850 900 950 1000 1050 1100 1150

Temperature, C
CO2, exp. data CO2, model results CO, exp. data CO, model results CH 4, model results CH 4, exp. data

Fig. 2. Spatial representation of Gibbs free energy as a function of steam reforming (b) and water gas shift (a) reaction progress.

H2, model results H2, exp. data

Fig. 5. Gas composition (% vol, dry basis inert free) as a function of temperature: comparison between GMM previsions and experimental results [19].

of gasication temperature: the agreement between experimental and computed data is very satisfactory. Fig. 6 reports the H2 yield and ow rate as a function of RDF feeding rate. Computed data are in good agreement with experi-

mental ones. Little model underestimate is probably due to the fact that it doesnt take into account, for example, chlorine specie (HCl).

CO2,

20

vol

40

LHV gas, MJ/Nm3

D. Barba et al. / Fuel 90 (2011) 14021407

1407

50

0.4

H2 yield, gH2/kgRDF

30

0.2

H2 flow rate, kg/h

40

0.3

tained by Li et al. [20]. Fig. 7 reports gas yield and HHV as a function of RDF ow rate. Also here the model little overestimates gas yield experimental data. The reasons of this behaviour are the same of those above: inability of the model to consider tar production and use of biomass instead of RDF. Finally Fig. 8 shows that the comparison between gas composition computed and experimental as a function of gasication temperature is satisfactory. 4. Conclusions Gibbs Free Energy Gradient Method Model (GMM) results have been compared with literature experimental data, proving that GMM is a very useful tool for process analysis of a gasication process. Of course, as this model is not able to predict tar content in gas phase coming from biomass gasication process, the best results can be obtained considering technologies which allow small tar production (uidized bed, downdraft gasiers) and biomass with low cellulose content. With this advice the model can be applied to analyze experimental results of a real gasier such as nal produced gas composition, gas heating value and overall gasifying efciency. The model enables a scaling up of experimental data supporting the design of the industrial gasifying plant. References
[1] McKendry P. Energy production from biomass (part 3): gasication technologies. Bioresour Technol 2002;83:5563. [2] Bridgwater AV. Renewable fuels and chemicals by thermal processing of biomass. Chem Eng J 2003;91:87102. [3] Bridgwater AV. The technical and economic feasibility of biomass gasication for power generation. Fuel 1995;74:631. [4] McKendry P. Energy production from biomass (part 1): overview of biomass. Bioresour Technol 2002;83:3746. [5] Giltrap DL, McKibbin R, Barnes GRG. A steady state model of gaschar reactions in a downdraft biomass gasier. Solar Energy 2003;74:8591. [6] McKendry P. Energy production from biomass (part 2): conversion technologies. Bioresour Technol 2002;83:4754. [7] Milne TA, Abatzoglou N, Evans RJ. Biomass gasier tars: their nature, formation and conversion. NREL/TP-570-25357, National Renewable Energy Laboratory, Golden, Colorado, USA; 1998. [8] Caputo AC, Palumbo M, Pelagagge PM, Scacchia F. Economics of biomass Energy utilization in combustion and gasication plants: effects of logistic variables. Biomass Bioenergy 2005;28:3551. [9] Corella J, Toledo JM, Molina G. Performance of CaO and MgO for the hot gas clean up in gasication of a chlorine-containing (RDF) feedstock. Bioresour Technol 2008;99:753944. [10] Borgianni C, De Filippis P, Pochetti F, Paolucci M. Gasication process of wastes containing PVC. Fuel 2002;81:182733. [11] Li X, Grace JR, Watkinson AP, Lim CJ, Ergudenler A. Equilibrium modelling of gasication: a free energy minimization approach and its application to a circulating uidized bed coal gasier. Fuel 2001;80:195207. [12] Ni Q, Williams A. A simulation study on the performance of an entrained ow coal gasier. Fuel 1995;74:10210. [13] Melgar A, Perez JF, Laget H, Horillo A. Thermochemical equilibrium modelling of a gasifying process. Energy Convers Manage 2007;48:5967. [14] Schuster G, Lofer G, Weigl K, Hofbauer H. Biomass steam gasication an extensive parametric modelling study. Bioresour Technol 2001;77:719. [15] Jarungthammachote S, Dutta A. Thermodynamic equilibrium model and second law analysis of a downdraft waste gasier. Energy 2007;32:16609. [16] Kersten SRA, Prins W, van der Drift B, van Swaij WPM. Principles of a novel multistage circulating uidized bed reactor for biomass gasication. Chem Eng Sci 2003;58:72531. [17] Smith WR, Missen RW. Calculating complex chemical equilibria by an improved by reaction-adjustment method. Can J Chem Eng 1968;46(4): 269272. [18] Prins MJ, Ptasinski KJ, Janssen F. From coal to biomass gasication: comparison of thermodynamic efciency. Energy 2007;32:124859. [19] Lv P, Yuan Z, Ma L, Wu C, Chen Y, Zhu J. Hydrogen-rich gas production from biomass air and oxygen/steam gasication in downdraft gasier. Renew Energy 2007;32:217385. [20] Li XT, Grace JR, Lim CT, Watkinson AP, Chen HP, Kim JR. Biomass gasication in a circulating uidized bed. Biomass Bioenergy 2004;26:17193. [21] Cioni M, La Marca C, Riccardi J. RDF gasication in circulating uidized bed gasier: characterization of syngas and ash. Enel produzione spa, Research Department, Italy.

20

H2 flow rate, model results H2 f low rate, exp. data H2 yield, exp. data H2 yield, model results

0.1

10 9

0 11 12

10

RDF feeding rate, kg/h

Fig. 6. Hydrogen yield and ow rate as a function of RDF feeding rate: comparison between GMM and experimental results [19].

5
HHV gas, exp. data HHV gas, model results Gas yield, model results Gas yield, exp. data

12

Gas yield, Nm3/kg

8 3

2 4 1

0 12 16 20 24 28 32

RDF feeding rate, kg/h

Fig. 7. Gas yield and HHV as a function of feeding rate: comparison between GMM previsions and experimental results [20].

20

H2, CH4, CO, CO2, % vol

16

12 8

0 700 720 740 760 780 800 820

Temperature, C
CO2, exp. data CO2, model results H2, model results H2, exp. data CO, exp. data CO, model results CH4, model results CH4, exp. data

Fig. 8. Hydrogen yield and ow rate as a function of RDF feeding rate: comparison between GMM and experimental results [20].

Similar considerations can be applied to Figs. 7 and 8, which show the comparison between model and experimental data ob-

HHV gas, MJ/Nm3