2015 North Central Regional Sun Grant Center Annual Meeting March 18 2015 Stephen Gent PhD Assistant Professor Mechanical Engineering Dept South Dakota State University Gregory Michna PhD ID: 1040389
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1. Fast Pyrolysis of Oilseed Byproduct Feedstocks2015 North Central Regional Sun Grant Center Annual MeetingMarch 18, 2015Stephen Gent, Ph.D.Assistant ProfessorMechanical Engineering Dept.South Dakota State UniversityGregory Michna, Ph.D.Assistant ProfessorMechanical Engineering Dept.South Dakota State University1Graduate Student Contributors: W. Sonnek, J. Harris, B. Lawburgh, J. LawburghUndergraduate Student Contributor: Z. Parks
2. Pathways for Nonfood Oilseeds2OilseedRenewable DieselMEALOILLubricantsRenewable PlasticsRenewable Jet FuelBeefDairySwineAquacultureProtein Supplement(low concentration)
3. Where we fit in…3OilseedRenewable DieselMEALOILLubricantsRenewable PlasticsRenewable Jet FuelBeefDairySwineAquacultureProtein Supplement(low concentration)Upgrade Bio-Oil via HydrotreatmentBio-OilFastPyrolysisof Meal
4. Project ScopeCharacterize the properties of meals from Ethiopian mustard (Brassica carinata) and camelina (Camelina sativa) as feedstocks for fast pyrolysisProduce bio-oils via fast pyrolysis from these meals and characterize bio-oil propertiesInvestigate use of catalysts and hydrogenation for upgrading4http://www.aero-news.net/images/content/commav/2006/Cessna-CitationMustang-0906b.jpg
5. Biofuels LaboratoryEquipmentFast Pyrolysis Fluidized Bed ReactorFast Pyrolysis Auger ReactorAnalytical EquipmentGas chromatograph mass spectrometers, CHNS-O elemental analyzer, calorimeters, rheometer, viscometer, volumetric Karl Fischer titrator, volumetric potentiometric titrator CapabilitiesProduce bio-oil from cellulosic feedstocksAnalyze bio-oil properties: elemental analysis, energy content, etc.5
6. Thermochemical Processes6Energy &Water VaporGASIFICATIONPYROLYSISTORREFACTIONFEEDSTOCKCOMBUSTIONGas(Bio-gas)Liquids (Bio-oils)Solids (Bio-char)Waste HeatPyrolysis: Reaction at Temps of 400-650°C in absence of oxygenFast Pyrolysis: Heating rate of 10-100+ C/s; resident time on order of seconds
7. Fluidized Bed Reactor7
8. Carinata (Brassica carinata)Supplier: Agrisoma Biosciences, Ltd., Saskatchewan, CanadaHexane extracted oilsFine, nearly powder consistency 8http://www.africa.upenn.edu/faminefood/category3/cat3_Brassica_carinata.htm
9. Camelina (Camelina sativa)Supplier: Willamette Biomass, Rickreall, ORCold-press extracted oils9http://www.oilseedcrops.org/
10. Project ProgressCalorimetry and physical properties of meals feedstock completedas received and driedunground and groundProduction of bio-oils from both meals using fluidized bed and auger reactorsAnalysis of bio-oilsYieldEnergy contentWater contentTANViscosityAging Effects10
11. Feedstock Characterization11
12. Oilseed MealFormBulk Density(kg/m3)Average ParticleSize (mm)CarinataUnground, Undried6700.726Unground, Dried6500.921Ground, Undried7300.543Ground, Dried7600.207CamelinaUnground, Undried5301.380Unground, Dried5100.890Ground, Undried5600.563Ground, Dried5500.520Results of digital microscope tests to determine particle size ranges.Feedstock Characterization (2)SpeciesFormCalorific Value (kJ/kg)CarinataUndried Meal17,700Dried Meal19,500CamelinaUndried Meal21,300Dried Meal22,700
13. Fast Pyrolysis Parametric Study13Independent VariablesSet Values Reactor Temperature (°C)400, 450, 500, 550, 600Condenser Temperature (°C)20, 40Zeolite Catalyst Present550°C Reactor, 40°C CondenserFeedstock TypeCarinata Meal, Camelina Meal
14. Bio-Oil Analysis14Dependent VariablesMeasured PropertiesBio-Oil YieldDigital scale measurement of bio-oil from set quantity of feedstockBio-Oil Energy ContentBomb calorimeter energy content Bio-Oil Water ContentKarl Fischer measurement of water contentBio-Oil TANTitrator measurement of mg KOH/g oilBio-Oil ViscosityRheometer measurement of dynamic viscosity (Pa-s)
15. Ranges of energy content, yield, water content, TAN, and dynamic viscosity of bio-oils from carinata meal.NOTE: Two consistencies of bio-oil were collected: 1) a lower viscosity bio-oil (LVBO) from condenser 1, and 2) a higher viscosity bio-oil (HVBO) from the rest of the condensersSummary of Results of Bio-Oil from Carinata MealPropertyValue RangeBio-Oil Yield12-20% (LVBO)4-22% (HVBO)Bio-Oil Energy Content7,600-8,600 kJ/kg (LVBO)26,900-30,030 kJ/kg (HVBO)Bio-Oil Water Content56-63% (LVBO)12.5-17.2% (HVBO)Bio-Oil TAN75.7-107.8 (LVBO)13.7-64.8 mg KOH/g (HVBO)Bio-Oil Viscosity0.006-0.01 Pa-s (LVBO)0.53-3.60 Pa-s (HVBO)
16. Results: Carinata Meal Yield16Measured Yield (Mass Fraction)ProductLVBOHVBOCharCondenser (°C) Condenser (°C) Condenser (°C) Reactor (°C)2040204020404000.12--0.04--0.68--4500.190.190.100.130.480.485000.190.220.110.200.470.355500.210.190.120.180.310.426000.210.200.210.200.320.31500 CAT--0.19--0.12--0.51Measured mass fractions of the bio-oil and char products created from carinata mealHigher reactor temperature reduced char yield and increased bio-oil yields
17. Results: Carinata Bio-Oil Water Content17Water Content (% H2O)ProductHVBOLVBOCondenser (°C) Condenser (°C) Reactor (°C)2040204040017.2------45012.612.062.561.350013.112.260.060.155013.912.760.059.060011.714.560.956.9500 CAT--12.5--62.0Measured water content of the high viscosity and low viscosity bio-oils on the days in which they were producedHigher reactor temperature and low condenser temperature minimized water content in HVBO
18. Results: Carinata Bio-Oil Calorific Values18Day171428Condenser (°C)Condenser (°C)Condenser (°C)Condenser (°C)Reactor (°C)204020402040204040025,080--------------45027,80028,21630,03729,31730,05728,83829,25329,27250027,32827,15527,97426,88628,65727,28128,97827,94455027,55827,37527,97927,32129,01527,78629,43727,79160027,90426,78628,78927,51529,33227,17629,36427,317500 CAT--27,651--27,584--28,607--28,701Measured energy content (kJ/kg) of the high viscosity bio-oils for the different pyrolysis conditions and comparison of agingOverall, energy value of HVBO was between 27,000 and 30,000 kJ/kg.Energy contents with aging are constant for first month.
19. Results: Carinata Bio-Oil TAN19Day171428Condenser (°C)Condenser (°C)Condenser (°C)Condenser (°C)Reactor (°C)204020402040204040064.8--------------45020.218.717.622.018.921.519.219.050015.824.619.320.213.724.218.026.255014.224.515.819.017.120.519.122.860017.214.518.519.914.320.716.918.1500 CAT--13.7--18.6--13.4--15.7Measured total acid numbers (TAN in mg KOH/g oil)) of the high viscosity bio-oils for the different pyrolysis conditions and the effects of agingOverall, TAN values of HVBO are consistent and relatively stable over one month. Long-term tests are ongoing.
20. Results: Carinata Bio-Oil Viscosity20Day171428Condenser (°C)Condenser (°C)Condenser (°C)Condenser (°C)Reactor (°C)20402040204020404000.49--------------4500.340.860.631.270.501.670.931.945000.360.940.841.501.103.632.303.535500.360.930.892.101.572.513.603.106000.481.451.020.981.131.061.581.30500 CAT--0.72--1.42--1.84--3.12Measured dynamic viscosity (Pa-s) of the high viscosity bio-oils for the different pyrolysis conditions and how the bio-oils compare with agingOverall, viscosity of HVBO increases with aging (2-3 times over 1 month period). Long-term tests are ongoing.
21. Ranges of energy content, yield, water content, TAN, and dynamic viscosity of bio-oils from camelina meal.Preliminary Results of Bio-Oil from Camelina MealPropertyValue RangeBio-Oil Yield30-46%464-692 g from 1.5 kg feedstockBio-Oil Energy Content28,200-29,000 kJ/kg Bio-Oil Water Content16.5-18.9%Bio-Oil TAN41.4-43.6 mg KOH/gBio-Oil Viscosity0.03-0.18 Pa-s
22. Ongoing and Future WorkContinue investigation of camelina meal for bio-oil productionContinue in situ upgrading of bio-oils with zeolite catalystsInvestigate hydrotreatment of bio-oils22
23. Dissemination Sonnek, W., Michna, G., and Gent, S. (2015). Investigation of Fast Pyrolysis of Brassica Carinata in an Auger Type Reactor. Proceedings of the ASME Power & Energy Conference, PowerEnergy2015-49376, June 28-July 3, San Diego, CA (accepted for publication)Harris, J., Lawburgh, B., Lawburgh, B., Michna, G., and Gent, S. (2014). Properties of Brassica Carinata and Camelina Sativa Meals and Fast Pyrolysis Derived Bio-Oils. Proceedings of the ASME 2013 8th Energy Sustainability Conference, ESFuelCell2014-6387, June 30-July 2, Boston, MA. (published)23
24. Special Thanks to:South Dakota Oilseed InitiativeMechanical Engineering Department24This study was supported by the US Department of Transportation, Office of the Secretary, Grant No. DTOS59-07-G-00054.
25. Thank youStephen Gent, PhDStephen.Gent@sdstate.edu605-688-5337Gregory Michna, PhDGregory.Michna@sdstate.edu605-688-639525