CONVERSION of PLASTICS to FUELS

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Fast pyrolysis of agricultural wastes
Characterization of pyrolysis products
Jale Yanik, Christoph Kornmayer, Mehmet
Saglam, Mithat Yüksel Department of Chemistry,
Faculty of Science, Ege University,
35100 Izmir,Turkey Institue for Technical
Chemistry Division of Chemical-Physical
Processing Forschungszentrum Karlsruhe,Germany
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Outline

• General Aspects of Pyrolysis
• Aim
• Materials and Methods
• Results
• Conclusion

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Concept for the use of biomass
ethanol, chemicals
fermentation
Biomass
pyrolysis
fuels, chemicals
gasification
synthesis
chemicals transport fuels
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Biomass Pyrolysis Products
Conditions yield, yield, yield,
liquid Char Gas
Carbonisation low temperature ,long residence time 30 35 35
Gasification high temperature ,long residence time 5 10 85
Fast pyrolysis moderate temperature, short residence time 75 12 13
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
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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MATERIALS
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 Oreganum stalk Straw
Proximate analysis (wt) Proximate analysis (wt) Proximate analysis (wt) Proximate analysis (wt)
Moisture 6.3 9.0 7.2
Ash 2.1 4.0 4.1
Ultimate analysis (dry wt) Ultimate analysis (dry wt) Ultimate analysis (dry wt) Ultimate analysis (dry wt)
C 42.90 42.50 43.89
H 6.40 6.00 6.54
N 0.60 0.70 0.42
S 0.29 0.29 0.51
K 2.4 5.2 3.5
Ca 0.1 1.4 1.2
Cl 0.59 1.15 1.88
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• Composition of lignocellulosic material (wt)

Corncob Oreganum stalk Straw
Cellulose 31.7 33.8 34.5
Lignin 31.7 10.9 12.2
Hemicellulose 3.4 9.3 14.2
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REACTOR
Fluidized bed reactor (ID 40 mm, length 300 mm)
Silica sand (450 µm) 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 ?C
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PROCESS
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
HMWL
Extractives, LMW
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 Oreganum stalk Corncob Straw
Gas 32 30 39
Aqueous phase 6 0.3 6 1.3 6 0.5
Oil 39 3.1 41 0.9 35 1.3
Char 23 1.9 23 1.5 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.
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Characterization of pyrolytic oil
The compounds detected by GC/MS, wt.
Corncob Corncob Oreganum Oreganum Straw Straw
AP WS AP WS AP WS
Acids
acetic 2.93 5.09 4.07 2.56 2.24 2.60
propanoic 0.20 0.44 0.31 0.32 0.11 0.29
Nonaromatic aldehydes
hydroxyacetaldehyde 1.94 2.23 0.82 - 4.63 4.40
propanal, 3-hydroxy 0.42 0.50 0.29 0.20 0.22 0.59
Nonaromatic ketones 2.46 6.89 5.54 7.37 1.89 5.12
Furans 0.13 1.45 0.66 1.30 0.03 1.25
Pyrans nd 0.04 nd nd 0.01 0.05
APaqueous phase WSwater soluble fractions
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Characterization of pyrolytic oil
Corncob Corncob Oreganum Oreganum Straw Straw
AP WS AP WS AP WS
Lignin derived phenols (phenol o-,p-,m-cresol) 0.02 0.44 0.09 0.29 nd 0.19
Guaiacols/methoxy phenols 0.01 0.30 0.21 0.56 nd 0.34
Syringols/dimethoy phenols nd 0.16 0.24 0.54 nd 0.40
Catechols (Hydroquinone benzene, 1,4-dihydroxy-Benzene, dihydroxy-methyl-) nd 0.21 0.21 0.28 nd 0.12
Sugars (a-d-Glucopyranose, 1,43,6-dianhydro Arabinofuranose, 1,5-anhydro) 0.29 2.28 0.68 0.47 0.15 1.50
APaqueous phase WSwater soluble fractions
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Characterization of pyrolytic oil
The concentration of some compounds detected by
HPLC and photometer, wt.
Corncob Corncob Oreganum Oreganum Straw Straw
AP WS AP WS AP WS
Acetone, v/v 7.3 5.0 2.4 1.0 3.3 14.7
Formic acid, wt. 0.34 1.22 0.03 0.15 0.46 1.78
Formaldehyde,wt 3.15 1.22 n.d n.d 2.52 6.21
Methanol, v/v 2.04 1.70 3.05 1.30 2.49 1.29
Total phenols, wt. 0.18 0.66 nil 12.54 0.08 13.50
APaqueous phase WSwater soluble fractions
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Fuel Characteristics of Pyrolysis Products
Properties of oil from pyrolysis of biomasses
CO OO SO
Water content, wt 14.32 6.18 4.68
C 45.01 53.70 48.34
H 8.48 5.78 6.16
N 1.10 2.64 1.25
S 0.15 0.44 0.27
O 45.26 37.57 43.99
from diference
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Fuel Characteristics of Pyrolysis Products
Properties of chars from pyrolysis of biomasses
CC OC SC
Ash, wt 10.1 14.9 38.4
GCV, kcal kg-1 25 24 19
Proximate analysis, wt Proximate analysis, wt Proximate analysis, wt Proximate analysis, wt
C 74.25 64.81 62.77
H 2.91 5.00 2.81
N 0.78 2.04 0.75
S 0.74 0.55 0.62
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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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Conclusions
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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Conclusions

• 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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Conclusions

• 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.