advances in thermo- chemical conversion of biomass ... · hindustan pencils – jammu a – plus...
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Advances in Thermo-chemical conversion of
biomass – Hydrogen and Biofuel
S Dasappa
Indian Institute of Science
Bangalore 560 012
Presented at the EU-India Conference on advance Biofuels – Delhi 11-13 March 2019
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• Established in1909 as a Trust (Charitable Endowments Act 1890) • Deemed University from 1957 • Funded by MHRD since 1993
Conceived in 1896 by the inspired vision of the pioneering industrialist Jamsetji Tata
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Founder’s mandate: Institute designed to promote original investigations in all branches of learning and to utilise them for the benefit of India.
Vision
21st century: to be among the world’s foremost academic institutions through the pursuit of excellence and the promotion of innovation.
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Composition of biomass
Element
Mass fraction
(%)
Carbon 52.02
Nitrogen 0.12
Sulphur 0.42
Hydrogen 6.55
Oxygen 41.43
Chemical
Composition CH1.4O0.6
Molecular weight 27.89 kg kmol-1
For liquid fuels – increase the Hydrogen to carbon ratio
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Biomass conversion process
Thermo-chemical conversion platform
Combustion, pyrolysis , gasification
Bio-chemcial conversion platform
Hydrolysis and fermentation
Fuels, Chemicals and other by-
products
Combined heat and
power Biomass
Residues
By products
CO, H2, Bio-oil
Sugar, Lignin
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•DOI: 10.1371/journal.pone.0022113
Biological and Thermo-chemical conversion process
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Natural available substances with Hydrogen as an element
•Water (H2O) •Electrolysers
• 2H2O 2H2 +O2
• Theoretical H2 yield is about 100 g/kg of water
•Biomass (C1.0 0.7(H2O)) •Bio-chemical and •Thermo-chemical
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Thermo-chemical conversion -Overall process chemistry for liquid fuels
• C1.0 0.7(H2O) C: H 1:1.4
• Air gasification CO : H2 1:1
• Oxy-Steam gasification CO : H2 1:3
• CH3OH C:H 1:4
• C2H5OH C:H 1: 3
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Possible routes from Biomass to biofuels • Biological conversion
• Biogas – biomethane – hydrogen - Methanol
• Thermo-chemical conversion • Biomass – Producer gas – Electricity – Electrolyser
CO2+H2
• Biomass – syngas – methanol
• Energy intensive of adding hydrogen
• Electrolyser > Biological ~ Thermo-chemical
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Thermo-chemical conversion • Gasification
• Biomass to mixture of gas and separating hydrogen
• C1.0 0.7(H2O) + 0.2 O2 + H2O 1.7H2 + CO2 • Theoretical limit 150 g of H2/kg of biomass
• Air gasification • C1.0 0.7(H2O) + 02+3.76 N2 0.2 H2+ 0.2 CO+0.02 CH4
+0.12CO2+0.46N2 • Here about 40 – 45 g of hydrogen per kg of biomass
• Oxy-steam • C1.0 0.7(H2O) + x02+ y H2O 0.25-502 H2+0.12 – 0.25 CO
+0.04 – 0.05CH4+ 0.15 - 0.25CO2
• Up to 100 g of hydrogen per kg of biomass
Challenges - Establishing clean gas and scale-up
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Brief history on the gasification technology at IISc
• Gasification research commenced in 1980’s • Emphasis was on 5 hp diesel pump sets
• Over 450 Man-Years of R&D effort
• Evolved State-of-the art technology
• Undergone critical third party evaluation – by various groups
• Licensed the technology in India and abroad
• At IISc (Open top down draft technology - distinctly different
from other designs) • Multi-fuel capability • Power range 5 – 2000 kWe • Both power and high quality thermal applications • Over 450,000 hours of operational experience • Annual operational hours ~ 7000 hours • Gas cleaning system for turbo-charged engines • Developed indigenous engines for producer gas operation
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Open top Dual air down draft – The IISc design
R and D started early 1980’s
Approx 500 man year’s of effort
Over 10,000 components
Cyclone Cooler Scrubber - 1 Scrubber-2
Flare
EngineFabric filterReactor
Char/ash
Air
Gas
Air
• Technology transfer executed South to North • Probably the best in the capacity across the globe • Engine manufacturers provide guarantee and warranty on the product
• Features • 0.9 – 1.2 kg/kWh • 7000 hours of annual operation
• Engine • Indigenous engines developed for
producer gas 10 kW to 400 kWe
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CHP
Biomass
Liquid fuels
Activated carbon
Heat (domestic)
Heat (industrial) Power
Hydrogen Chemicals
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Glimpses of the power projects ..
Beach Mineral Corporation – Tamil Nadu 1.5 MW
Hindustan pencils – Jammu
A – Plus – Thailand 1.2 MW Wood Power - Switzerland
Gomathy mills – 1MW
Ndola, Zambia
Cocodrilo - Cuba
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R and D at IISc – beyond power from biomass
•Improve H2 to CO ratio Oxy-steam gasification •Hydrogen rich syn-gas
•Hydrogen • Liquid fuels • Fuels for Fuel cells
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Air gasification – Oxy-steam gasification
Air gasification Oxy-Steam gasification
Yield limited by H2 content in biomass ~ 60 g/kg of biomass
Single stage process
H2 yield enhanced by using H2O as a
reactant
Gasification
Low volume fraction (~20% H2, ~45% N2) makes it economically
non-viable for separation
Use of O2 instead of air enhances the H2
yield to 45-55%
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Oxy-steam gasification results
SBR 0.75 1 1.4 1.5 1.8 2.4 2.7
ER 0.21 0.18 0.21 0.23 0.27 0.28 0.3
H2 yield (g kg-1 of biomass)
66 68 71 73 94 99 104
H2 yield (volume fraction, %) on dry basis 41.8 45.2 43.1 45.2 49.6 51.6 50.5
CO yield (volume fraction, %) on dry basis 27.6 24.9 26.5 24.9 17 12.4 13
H2/CO 1.5 1.8 1.6 1.8 2.9 3.8 3.9
LHV (MJ Nm-3) 8.9 8.6 8.8 8.7 8 7.4 7.4
Hydrogen efficiency (%) 73.7 63.2 67.2 63.5 70.5 61 63.7
Gasification efficiency (%)
85.8 76.8 80.8 77 79.5 70.5 71.5
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Syngas to fuel cell
Source: Ref. 17, P.L. Spath and D.C.Dayton
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Syngas from oxy-steam gasification of biomass
Particulate and tar removal
Cooling Wet scrubbing
Contaminants removal
Water Gas Shift Reactor
Syngas enrichment compression
Conditioned gas
Liquid fuel for separation
• Methanol • Ethanol • DME
Hydrogen separation
Catalytic reactor
Biochemical reactor
Oxy-steam gasification process 99.999 % hydrogen
Syn-gas CO and H2
mixture
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Importance of syngas chemistry
•R for methanol synthesis should range from 2 to 2.1 and values are % in volumes • There are two routes of adjusting the R
ratio • CO2 Separation
• Water gas shift reaction to convert CO to H2 and CO2, followed by CO2 removal by absorption
• Addition of Hydrogen to adjust the stoichiometry
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Fuel type Wood chips Coconut shells Corn cobs
Dimension of the
fuel used (mm) 24 × 25 × 40 mm 4 × 25 × 40 mm 25 X 30 x 40 mm
Density (kg/m3) 650 ± 10 1100 ± 100 400 Bulk density (kg/m3) 400 (400-450) 250 Moisture content
(%) 11 8 10
Ash content (%) < 3 < 1.5 <4
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0 0.2 0.4 0.6 0.8 1 1.2
0
0.2
0.4
0.6
0.8
1
1.2
0
10
20
30
40
50
60
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
VO
L.%
SBR
SBR vs. Cold Gas Composition
CO-Exp CO2-exp CH4-Exp H2-Exp
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Contaminant(s) Gas Phase
Specification
Contaminants observed for different biomass materials
Casuarina wood chips Coconut shells Corncob
Tar (Styrene – A) Below dew point Catalyst poisoning
compounds <
1 ppmV
< 0.50 ppmV (A) < 0.50 ppmV (A) < 0.50 ppmV (A)
Organic compounds
(includes Benzene – B,
Toluene – T)
Below dew point < 1.60 ppmV(B) (B) (B) < 0.10 ppmV (B) < 0.20 ppmV
(B)
3.5 ppmV (T) < 0.50 ppmV (T) < 0.40 ppmV
(T)
Halide compounds
(HCl – A HF – C)
< 10 ppbV < 0.25 ppmV (A) < 0.17 ppmV (A)
< 0.13 ppmV
(A)
< 0.25 ppmV (C) < 0.17 ppmV (C)
< 0.17 ppmV
(C)
Nitrogen compounds
(NH3 – A)
Total N < 1 ppmV 14 ppmV (A) 25 ppmV (A) 47 ppmV (A)
Sulphur compounds
(H2S – A)
Total S < 1 ppmV < 0.1 ppmV (A) < 0.1 ppmV (A) < 0.1 ppmV
(A)
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Acknowledgements
The work carried out on the biomass gasification technology has received significant funding from the MNRE and DBT for the support
……….Thank you
[email protected] http://cgpl.iisc.ernet.in/dasappa/