Biosystems Engineering South Dakota State University March 2015 Catalytic Fast Pyrolysis of Ag amp Forest Residues for Aromatic Fuel Additives Lin Wei James Julson Final report Background ID: 1041936
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1. Department of Agricultural & Biosystems Engineering South Dakota State UniversityMarch 2015 Catalytic Fast Pyrolysis of Ag & Forest Residues for Aromatic Fuel AdditivesLin Wei, James JulsonFinal report
2. Background Funded by DOE through NC Sun Grant InitiativeStarted in Oct. 1st , 2010 and ended up in Sept. 30th, 2014 The goal is to convert Ag & Forest Residues to Aromatic Fuel Additives using catalytic fast pyrolysis (CFP)Develop an effective CFP processDevelop appropriate catalysts for the CFP process Preliminarily evaluate technical and economic feasibility of CFP Specific objectives
3. Catalytic fast pyrolysis (CFP ) BiomassHeatSyngas Bio-oil Bio-char Sizing and drying No air400 - 600oCBiomassCatalyst Biomass Breakdown Catalysis Hydrocarbons
4. SDSU Proprietary Pyrolysis Reactor FeaturesHigh heating rateNo carried gases needAtmospheric pressure Easy scaling up Simple structure with low costReliable…Operating conditions: Temperature: 450 – 600oC, Heating rate: 500 – 1000oC/min Processing time: 10 – 30 s Pressure: ≈ 1 atm, Feeding rate: 1 – 3 kg/h, Bio-oil yield rate: 50 – 65 %
5. Two-step pyrolysis for drop-in fuelsSDSUHDO reactor SDSUPyrolysis reactor Crude bio-oilPyrolysis HDO upgrading Crude bio-oil Sawdust Hydrocarbons(drop in fuel) Water Forest residues Corn stover
6. GCMS Analysis of Raw Bio-oil o-Xylene 1.60%2-Cyclopenten-1-one, 2-methyl- 3.07%2-Furancarboxaldehyde, 5-methyl- 5.13%2-Cyclopenten-1-one, 2,3-dimethyl- 1.92%2-Cyclopenten-1-one, 2,3-dimethyl- 1.92%13-Octadecenal, (Z)- 9.88%n-Hexadecanoic acid 9.04% Cyclotetradecane 3.03 %4-Methyl-dodec-3-en-1-ol 1.02%Crude bio-oil
7. GCMS analysis of upgraded bio-oilo-Xylene 38.02% p-Xylene 14.85% Ethylbenzene 4.15% Benzene, 1-ethyl-3-methyl- 4.65% Naphthalene, 1-methyl- 5.62%Benzene, 1,2,3-trimethyl- 14.46% Naphthalene, 2,7-dimethyl- 2.13%Upgraded bio-oilUpgraded bio-oilOver 80% of Aromatics(38.02 + 14.85 + 14.46 +4.15 + 4.65 + 5.62 + 2.13+…)
8. Properties of raw bio-oil and upgraded bio-oil and petroleum-derived gasoline and diesel* the lowest temp. we can get in our labsPropertiesRaw bio-oilDrop-in fuelGasolineDiesel Freezing point, oC ~0< -15*- 30- 5 pH value 2.8 – 3.25.0 – 5.6 Viscosity cSt @ 20 oC30 – 50 1.20 – 1.880.40 – 0.801.90 – 4.10Density, Kg/L0.98 – 1.06 0.80 – 0.850.740.83Heating Value, MJ/kg16-2541 – 484342Carbon Content, % w.t.2584.59 – 85.1285 – 8887Hydrogen Content, % w.t.109.90 – 11.2612 – 1513Oxygen Content, % w.t.390.40 – 0.7200Water Content, % w.t.40< 0.2%00The HDO upgraded bio-oil is compatible with petroleum hydrocarbons Comparison of bio-oil, drop-in fuel to Petroleum-derived fuels
9. Catalyst Development ZSM-5Alumina oxide Activated carbonSupports/carriersActivated carbon Alumina oxide ZSM-5 StepsPrepare support materialsImpregnating precursors to the supportsDried and calcined at 350 – 650℃ for 5 – 8 hr Active metalsPt, Pd, Ru, Cu, Mo, Ni, Co, etc.
10. Bifunctional Mo-Cu catalyst samples Development of Bifunctional Catalysts Better selectivity and activity to light hydrocarbon (gasoline ranged), lower cost, long lifetime, etc. Used catalystFresh catalyst
11. Characterization of CatalystsCatalysts BET Surface area (m2/g)Langmuir Surface area (m2/g)Total Pore volume(cm3/g)HZSM-5432.18517.440.37Mo/HZSM-5364.33433.840.32#1 Mo-Cu/HZSM-5122.77157.510.24#2 Mo-Cu/HZSM-5166.45229.640.28#3 Mo-Cu/HZSM-5206.45263.380.29Cu/HZSM-5372.87426.060.35Surface and Microstructure CatalystsThe BET surface is calculated from the size and number of the adsorbed gas molecules (N2, Argon, Krypton), which is forming a monolayer on the surface of the catalyst samples at standard temperature and pressure.Langmuir surface area is determined by maximum amount of adsorbate adsorbed per gram of adsorbent for forming a monolayer.
12. Characterization of CatalystsFresh HZSM-5 HZSM-5 used in CFP at 400 °C HZSM-5 used in CFP at 500 °CHZSM-5 used in CFP at 600 °CThere is no significant difference in the spectra patterns Investigate bulk structure (crystallite structure and size) using X-ray diffraction (XRD):
13. Characterization of CatalystsSurface active sites (or concentration) of active intermediates using FTIR
14. SEM images of CatalystsFresh ZSM-5Used ZSM-5Fresh Zn-ZSM-5Used Zn-ZSM-5100nm100nm100nm100nm
15. TEM images of CatalystsFresh ZSM-5Used ZSM-5Fresh Zn-ZSM-5Used Zn-ZSM-5100nm100nm100nm100nm
16. In-situ CFP Method Different CFP ApproachesBio-oil yield and quality improvement depending on catalyst/biomass (C/B) ratio. Higher C/B, better quality and yield Increase hydrocarbon contentsHigher water content (phase separation )High catalyst consumption. Difficult to regenerate catalyst
17. Pyrolysis reactor Catalyst Catalytic cracking reactor Quality Bio-oil Heater Biomass Heater Condenser Syngas Coolant N2 Ex-situ CFP SystemEx-situ CFP Method Better bio-oil yield and quality. Easy to separation biofuelsBetter activity and selectivityLow catalyst consumption. Longer lifetime Easy to regenerate catalyst
18. Ex-Situ CFP of Sawdust No.Reaction conditionssawdust, gcatalyst, g1Py 500oC only 5002Py500oC+Cracking400oC50203Py500oC+Cracking500oC50204Py500oC+Cracking600oC5020Temperatures, feedstocks, and catalysts used in the test runs
19. Effect of temperature on Ex-situ CFPProportions of syngas, bio-oil, and bio-char produced in sawdust CFP at different reaction conditions
20. Ex-situ CFP bio-oil properties Oil phase aqueous phases
21. Ex-situ CFP bio-oil properties Reaction Temperature, C Oil phase Aqueous phaseHeating values, MJ/kgViscosity, cPNo catalyst29.292.0240022.372.13550023.802.0260022.891.99
22. What we have doneFiled a U.S. patent application for the proprietary pyrolysis reactors and process.Successfully convert corn stover, sawdust, switchgrass, etc.) to crude bio-oil and upgraded the bio-oils to drop-in fuel (additives aromatic hydrocarbons)Developed appropriate catalysts for CFP and bio-oil upgrading processes. Designed the second generation CFP systemSupport 3 postdoc and 4 PhD studentsPublished 5 journal papers and 12 conference presentations/papers
23. Catalyst system Catalyst deactivation Coking and alkali metal deposition Lifetime Catalyst cost, selectivity, and activity Operation Syngas applications (heating, F-T synthesis, etc.)Bio-char applications (activated carbon, soil amendment ,)Condensation efficiency Issues need to be addressed
24. Second generation CFP reactors Second generation reactor First generation reactor New Generation Technologies Combine pyrolysis and upgrading two steps in one continuous processScale up CFP process Catalysts screening for commercialization Improve catalyst selectivity and activity with low costsProject Progress attracted Congress senator and Representative visited the labsMade connections with national and international companies Established a start-up companyProvide education to more students and public
25. Plans for Next Publish research results an provide proper information to the community and publicProvide more bio-refinery education and training for the communityLooking for new funding to move on the researchImprove the second generation technologies for high drop-in fuel yield and qualityExploring any collaboration opportunity to scale up the process for commercialization
26. Conclusions The CFP system can produce quality bio-oils that can be upgraded to aromatics or fuel additives (drop-in fuels). Catalyst implementation and reaction conditions (heating rate, temperature, pressure, etc.) played critical roles in the yield and quality of bio-oils and drop-in fuels.It is tech-economic feasible if improve the CFP system and catalysts.
27. AcknowledgmentFunding supported by DOE: Award #: DE-FG36-08GO88073Research teams: Postdoc: Zhongyi Ma, Yang Gao, Chunkai ShiGraduate students: Wangda Qu, Yinbin Huang, Shouyun Cheng, Zhongwei Liu, Xianhui Zhao Thank you for your attention !GCMS analyses helped by Dr. Douglas Raynie, Ms. Shanmugapriya Dharmarajan, Mr. John Kiratu, and Ms. Changling Qiu in the Chemistry Dept. SDSUXRD analysis helped by Dr. Qiquan Qiao and Mr. Ashish Dubey. The XRD equipment is supported by the NSF MRI grant (Award No. 1229577). TEM analysis helped by Dr. Phil Ahrenkiel. BET measurement helped by Dr. Zhengrong Gu, Yuhe Cao, Ms. Xiaomin Wang for the