Sustained Hydrotreatment of Biomass Pyrolysis … Hydrotreatment of Biomass Pyrolysis Bio –oil...
Transcript of Sustained Hydrotreatment of Biomass Pyrolysis … Hydrotreatment of Biomass Pyrolysis Bio –oil...
Sustained Hydrotreatment of Biomass Pyrolysis Bio –oil with Minimal Catalyst Deactivation
Zia Abdullah, PhD Versa Renewables, LLC
Rachid Taha, PhDBattelle Memorial Institute
Huamin Wang, PhDPacific Northwest National Laboratory
Created by Battelle and Equinox Chemicals
Bio-Chemicals & Products Drop-in Bio-Fuel
Our mission is to produce biomass-based renewable chemicals and fuels
which are cost-competitive with existing petroleum-based technologies.
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We are well equipped with pyrolysis, hydrotreatment, bio fuels & chemical production and analytical capabilities
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50 #/day bench scale auger Pyrolysis System (ABRI Tech)
1 ton/day Proprietary Downflow Pyrolysis System
Bench Scale Hydrotreatment System& Analytical Capabilities 1 gal/day Hydrotreatment Pilot System Bio oil to biochemical pilot reactors
Commercial Scale Fuels & Chemicals Production Capability
The industry’s bio oil upgrading problem
Upgrading
Biomass PyrolysisSulfided CatalystHydrotreatment
BiofuelBio Oil
Upgrading
Biomass PyrolysisSulfided CatalystHydrotreatment
BiofuelBio OilN.M. CatalystStabilization
Hypotheses:
• Noble Metal stabilization catalyst deactivates first because of coke formation
• Unstabilized bio oil rapidly deactivates the catalyst & plugs the reactor
• Non carbon supported stabilization catalysts along with a decoking procedure will solve the problem
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TiO2 supported stabilization catalysts and a regeneration procedure were developed
Catalyst Stage I: 3%Ru/TiO2
Stage II: 3%Ru/TiO2-ZSM5
LHSV - Total 0.2-1
LHSV – Stage I 0.4-2
LHSV – Stage II 0.4-2
Stage I temperature 150-200oC (170
oC)
Stage II temperature 200-400oC (380
oC)
Reactor Pressure 1,800 psig
H2/Bio-oil Ratio (L/L) 3,000
TOS (hrs.)~50 between regeneration cycles
PNNL Developed TiO2 Supported Catalysts Fresh catalyst
Hydrotreatment
In situ rinse with solvent
Hydrogen reduction at 400oC
Catalyst characterization
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Catalysts were still losing activity over 200 hrs. TOS
CH4OH Rinse + H2 Reduction @ 400oC Removes all Carbon
Some Loss of Acidity in Both Stage I and Stage II Catalyst Contaminated by Metals and S
Metal Dispersion Loss not Significant
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Metal poisoning was confirmed using synthetic bio oil with and without additives
Synthetic Bio oil Composition
Element(ppm)
Actual Bio oil
Synthetic bio oil
Aluminum 161 186
Calcium 84 113
Iron 130 117
Magnesium 17 101
Phosphorus 48 72
Potassium 29 103
Sodium 13 63
Zinc 18 58
Sulfur 50 6
Total 1309 819
Additives to Synthetic Bio oil to Simulate Poisons in Actual Bio oil
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An ion exchange resin treatment was used for bio oil cleanup
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• Filtration of bio-oil via 0.2 µm to remove resin • Blended bio-oil with 30% methanol to improve the
homogeneity of the bio-oil and enable use of fixed bed catalyst.
• No CH4 or unaccounted H2O produced in Stage I at steady state.
• Other solvents, including water are being considered.
• Bio-oil/Resin: 10• Reaction : 2 hrs. at 40oC• N2 at atmospheric
pressure• Mechanical stirring
Blended bio-oil with 30% methanol to improve
homogeneity
0 20 30
Mechanic Mixer
N2
relief valve
Thermocouple
Heating media
Mechanical Mixer
Relief Valve
Thermocouple
N2
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(ppm) Al Ca Fe K Mg Na Si S
Bio oil1 41 160 47 <10 <45 <.1 <50
Bio oil (present study)
5 18 16 57 5 4 11 10
Cleaned up Bio oil
<3 <3 <3 6 <3 3 1 9
Bio oil cleanup was integrated with hydrotreatment
Hydrocarbon Product
Ru/TiO2Catalyst
Zone I
0.2 µm filtration
Conventional sulfided catalyst
Ion Exchange
Zone II
Solventrecycle
Bio Oil
1 Diebold, J.P., “A Review of the chemical and physical mechanisms of the storage stability of bio oils”, in Fast Pyrolysis of Biomass: A Handbook, Vol 2., Bridgewater, A.V., IEA Bioenergy, 2002.
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This process was successful at hydrotreatment for 1,200 hrs. TOS
H/C Product yield: 60 gal./ton
%Wt.
Paraffins 24.1
Total aromatic 5.6
Napththelenes 67.9
Olefins 2.4
Total 100
RON ~70
Chain length C6-C14
Refineryexample
Battelle Results
Density (kg/m3) 0.8-0.9 0.81-0.85
BSW (wt%) 0.5 NA (<0.5)
Total S (wt%) 0.082 <0.005
Total N2 (wt%) 0.015 <0.05
TAN (mg KOH/g) 0.5 <0.5
Pour Point (oC) 21-36 NA(<<20)
Viscosity (cPs) 3-236 <2
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Summary
This project has enabled a commercially viable bio oil hydro-treatment process to produce renewable blend stock for transportation fuels.
• Novel, low cost bio oil cleanup process to enable long-term operation of a bio oil stabilization catalyst
• A non carbon supported catalyst and successful regeneration, allowing long-term hydrotreater operation
• New process has demonstrated stabilization and hydrotreatment catalysts for over 1,200 hrs. TOS
Acknowledgements
The experimental work was done at the Battelle Memorial Institute and the Pacific Northwest National Laboratories.
Financial Support was provided by Battelle and by the Department of Energy / EERE / BETO.
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