Ege University

Fast pyrolysis of agricultural wastes: Characterization of pyrolysis products

Jale Yanik, Christoph Kornmayer*, Mehmet Saglam, Mithat Yksel
Department of Chemistry, Faculty of Science, Ege University, 35100 Izmir,Turkey *Institue for Technical Chemistry Division of Chemical-Physical Processing ChemicalForschungszentrum Karlsruhe,Germany
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General Aspects of Pyrolysis  Aim  Materials and Methods  Results  Conclusion

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Concept for the use of biomass

fermentation
ethanol, chemicals

Biomass

pyrolysis

fuels, chemicals

gasification

synthesis

chemicals transport fuels

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Biomass Pyrolysis Products

Conditions liquid Carbonisation low temperature ,long residence time Gasification high temperature ,long residence time 30 5 75 yield, % Char 35 10 12 Gas 35 85 13

Fast pyrolysis moderate temperature, short residence time

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http://www.pyne.co.uk

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Fast Pyrolysis Liquid

Bio-oil consists of many oxygenated organic chemicals and is water miscible.  dark brown liquid  combustible  not miscible with hydrocarbons  heating value ~ 17 MJ/kg  density ~ 1.2 kg/l  pH ~ 2.5  pungent odour  viscosity increases with time

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Applications of Bio-Oil
Electricity Heat Transport fuels Bulk chemicals Fine chemicals diesel, turbine CHP and boiler upgrading, emulsions Resins, fertilizers,e.g Levoglucosan e.g

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Co-Products
Gas (COx, H2, light hydrocarbons) can be used to heat pyrolysis reactor Char - process heat - activated carbon - soil amendment

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Concept for the use of biomass

Pyrolysis of biomass in a local plants
char + oil

Entrained flow gasification in large central plant

Syngas (CO + H2)

chemical synthesis

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Forschungszentrum Karlsruhe in der Helmholtz-Gemeinschaft

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Aim

to determine the yields and composition of products from fast pyrolysis of three agricultural wastes

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corncob, wheat straw and oreganum stalk.

Oregano is an aromatic and medical plant. Turkey is one of the worlds largest suppliers of oregano. Oreganum stalks are abundant agricultural wastes from harvest

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Corncob Proximate analysis (wt%) Moisture Ash C H N S K Ca Cl 6.3 2.1 42.90 6.40 0.60 0.29 2.4 0.1 0.59

Oreganum stalk 9.0 4.0 42.50 6.00 0.70 0.29 5.2 1.4 1.15

Straw

7.2 4.1 43.89 6.54 0.42 0.51 3.5 1.2 1.88

Ultimate analysis (dry wt%)

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Composition of lignocellulosic material (wt%)

Corncob Cellulose Lignin Hemicellulose 31.7 31.7 3.4 Oreganum stalk 33.8 10.9 9.3 Straw 34.5 12.2 14.2

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Fluidized bed reactor (ID: 40 mm, length 300 mm)

Silica sand (450 m) with a static bed depth of 37 mm Gas velocities: 0.25-0.30 m/s Residence time of gas: 1-2 s Feed: 100 g Temperature: 500 rC

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BigPower Project BioGasTech Workshop 9-11 April 2008, Gebze/Trkiye

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BigPower Project BioGasTech Workshop 9-11 April 2008, Gebze/Trkiye

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gas

BIOMASS

coke

oil

aqueous phase

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Aqueous phase and oily compounds collected in traps were weighed. Heat exchanger, electro filters and cotton wool were first washed out with CH2Cl2 and then with methanol. CH2Cl2 solubles were added into the oily compounds received from the traps. The methanol solution was filtered, methanol solubles were weighed as high molecular weight lignin (HMWL).

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oil yield = oil phase received in traps + recovered by CH2Cl2 and CH3OH washing.

coke yield = coke collected in the charpot + methanol unsolubles

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Fractionation of Oils
Oil Water solubles Water insolubles

Extractives, LMW

HMWL

According to K. Sipila, E. Kuoppala, L. Fagernas, A. Oasmaa, Characterization of biomass-based flash pyrolysis oils, Biomass Bioenergy 14 (1998) 103113.
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Analysis of oil elemental analysis water content Analysis of water-soluble fraction GC-MS (60m x 0.25 mm chrompack DB 1 701) HPLC Photometer Gas Product Analysis GC-FID, TCD
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Product distributions from pyrolysis of agricultural wastes, wt%

Feed Gas* Aqueous phase Oil Char Oreganum stalk 32 6 0.3 39 3.1 23 1.9 Corncob 30 6 1.3 41 0.9 23 1.5 Straw 39 6 0.5 35 1.3 20 0.4

* Calculated from mass balance ;

Oil yields----------- 13-17 wt% from rapeseed 14 wt% from sugarcane bagasse, coconut shell 57 wt% (containing 43 wt% waer) from rice straw 66 wt% (containing 20 wt% water) from pine sawdust
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Characterization of pyrolytic oil

Composition of oil obtained from pyrolysis of agricultural wastes.
100 90 80 0 0 wt 0 0 0 20 10 0 orega stalk cor cob straw

W e tracti es W water a water sol bles

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Characterization of pyrolytic oil

The compounds detected by GC/MS, wt.%
Corncob AP
Acids acetic propanoic Nonaromatic aldehydes hydroxyacetaldehyde propanal, 3-hydroxy 3Nonaromatic ketones Furans 1.94 0.42 2.46 0.13 2.23 0.50 6.89 1.45 0.82 0.29 5.54 0.66 nd 0.20 7.37 1.30 nd 4.63 0.22 1.89 0.03 0.01 4.40 0.59 5.12 1.25 0.05 2.93 0.20 5.09 0.44 4.07 0.31 2.56 0.32 2.24 0.11 2.60 0.29

Oreganum AP WS

Straw AP WS

WS

Pyrans nd 0.04 AP:aqueous phase; WS:water soluble fractions

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Characterization of pyrolytic oil

Corncob AP
Lignin derived phenols (phenol; o-,p-,m-cresol) o-,p-,mGuaiacols/methoxy phenols Syringols/dimethoy phenols Catechols
(Hydroquinone; benzene, 1,41,4dihydroxy-Benzene, dihydroxydihydroxydihydroxymethyl-) methyl-

Oreganum AP
0.09 0.21 0.24 0.21

Straw AP
nd nd nd nd

WS
0.44 0.30 0.16 0.21

WS
0.29 0.56 0.54 0.28

WS
0.19 0.34 0.40 0.12

0.02 0.01 nd nd

Sugars
( -d-Glucopyranose, 1,4:3,61,4:3,6dianhydro ; Arabinofuranose, 1,51,5-anhydro)

0.29

2.28

0.68

0.47

0.15

1.50

AP:aqueous phase; WS:water soluble fractions

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Characterization of pyrolytic oil

The concentration of some compounds detected by HPLC and photometer, wt.%
Corncob AP Acetone, v/v % Formic acid, wt.% Formaldehyde,wt% Methanol, v/v% Total phenols, wt.% 7.3 0.34 3.15 2.04 0.18 WS 5.0 1.22 1.22 1.70 0.66 Oreganum AP 2.4 0.03 n.d 3.05 nil WS 1.0 0.15 n.d 1.30 12.54 Straw AP 3.3 0.46 2.52 2.49 0.08 WS 14.7 1.78 6.21 1.29 13.50

AP:aqueous phase; WS:water soluble fractions

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Fuel Characteristics of Pyrolysis Products

Properties of oil from pyrolysis of biomasses
CO Water content, wt % C H N S O*
*from diference
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OO 6.18 53.70 5.78 2.64 0.44 37.57

SO 4.68 48.34 6.16 1.25 0.27 43.99

14.32 45.01 8.48 1.10 0.15 45.26

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Fuel Characteristics of Pyrolysis Products

Properties of chars from pyrolysis of biomasses
CC Ash, wt% 10.1 OC 14.9 24 64.81 5.00 2.04 0.55 SC 38.4 19 62.77 2.81 0.75 0.62

GCV, kcal kg-1 25 Proximate analysis, wt% C 74.25 H 2.91 N 0.78 S 0.74

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Fuel Characteristics of Pyrolysis Products

Pyrolysis of agricultural wastes produced a gas rich in carbon oxides (about 8490 v/v%, mainly CO2) The methane amount were about 68 v/v% where as C2 C4 gases were minor.

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fast pyrolysis of three biomass species (corncob, oreganum stalks and straw) was carried out at 500 C.
 gas products obtained with a yield around 3040 % were composed of mostly carbon oxides.  aqueous phase and oil phase were separately obtained as pyrolysis liquids.  oil yield from biomass species ranged from 35 to 41%.
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 oils were fractionated as water-soluble and water-unsoluble fractions. The oil containing 68% of water-soluble fraction was obtained from corncob, whereas the fraction of water soluble was around 52% in the case of both straw and oreganum stalk.  carboxylic acids, mainly acetic acid, nonaromatic ketones, mainly acetone, methanol and phenols are the main organic compounds of the water-soluble fraction.

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 Although,pyrolysis yields did not significantly change with the type of biomass, the composition of oil varied depending on the feedstock.  oil was found to be highly oxygenated. Therefore, it was concluded that the oil obtained from biomasses needs to be upgraded for use as a fuel.  chars from pyrolysis can be used to produce smokeless briquettes.

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