Sustained Hydrotreatment of Biomass Pyrolysis Bio oil with Minimal Catalyst Deactivation Zia Abdullah, PhD Versa Renewables, LLC Rachid Taha, PhD Battelle Memorial Institute Huamin Wang, PhD Pacific Northwest National Laboratory
Created by Battelle and Equinox Chemicals Our mission is to produce biomass-based renewable chemicals and fuels which are cost-competitive with existing petroleum-based technologies. Bio-Chemicals & Products Drop-in Bio-Fuel 2
We are well equipped with pyrolysis, hydrotreatment, bio fuels & chemical production and analytical capabilities 50 #/day bench scale auger Pyrolysis System (ABRI Tech) 1 ton/day Proprietary Downflow Pyrolysis System Commercial Scale Fuels & Chemicals Production Capability Bench Scale Hydrotreatment System & Analytical Capabilities 1 gal/day Hydrotreatment Pilot System Bio oil to biochemical pilot reactors 3
The industry s bio oil upgrading problem Upgrading Biomass Pyrolysis Bio Oil Sulfided Catalyst Hydrotreatment Biofuel Upgrading Biomass Pyrolysis Bio Oil N.M. Catalyst Stabilization Sulfided Catalyst Hydrotreatment Biofuel 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 4
TiO 2 supported stabilization catalysts and a regeneration procedure were developed PNNL Developed TiO 2 Supported Catalysts Fresh catalyst Stage I: 3%Ru/TiO 2 Catalyst Stage II: 3%Ru/TiO 2 -ZSM5 LHSV - Total 0.2-1 LHSV Stage I 0.4-2 LHSV Stage II 0.4-2 Stage I temperature 150-200 o C (170 o C) Stage II temperature 200-400o C (380 o C) Reactor Pressure H 2 /Bio-oil Ratio (L/L) TOS (hrs.) 1,800 psig 3,000 ~50 between regeneration cycles Hydrotreatment In situ rinse with solvent Hydrogen reduction at 400 o C Catalyst characterization 5
Catalysts were still losing activity over 200 hrs. TOS Metal Dispersion Loss not Significant CH 4 OH Rinse + H 2 Reduction @ 400 o C Removes all Carbon Some Loss of Acidity in Both Stage I and Stage II Catalyst Contaminated by Metals and S 6
Metal poisoning was confirmed using synthetic bio oil with and without additives Synthetic Bio oil Composition Additives to Synthetic Bio oil to Simulate Poisons in Actual Bio oil Element (ppm) Actual 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 Synthetic bio oil 7
An ion exchange resin treatment was used for bio oil cleanup Bio-oil/Resin: 10 Reaction : 2 hrs. at 40 o C N 2 at atmospheric pressure Mechanical stirring N 22 Relief relief valve Valve Mechanical Mixer Mechanic Mixer Thermocouple Blended bio-oil with 30% methanol to improve homogeneity Heating media 0 20 30 8 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 CH 4 or unaccounted H 2 O produced in Stage I at steady state. Other solvents, including water are being considered. 8
Bio oil cleanup was integrated with hydrotreatment Bio Oil 0.2 µm filtration Ion Exchange (ppm) Al Ca Fe K Mg Na Si S Bio oil 1 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 Solvent recycle Conventional sulfided catalyst Zone I Zone II Ru/TiO 2 Catalyst Hydrocarbon Product 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. 9
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 Refinery example 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 ( o C) 21-36 NA(<<20) Viscosity (cps) 3-236 <2 10
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. 11