CNVERSIN F CRP IL T ARMATICS VER DPED ZSM-5 CATALYSTS Presented by: Swapnil Fegade Department of Chemical Engineering University of North Dakota Contributors: Swastika Bithi Dr. Brian Tande Dr. Wayne Seames Dr. Darrin Muggli Dr. Alena Kubátová Dr. Evguenii Kozliak
Background on cracking and reforming of crop oil Replace existing petroleum-derived chemicals with identical molecules from crop oils. BioFuel + Thermal Cracking H H Crop ils Catalytic Cracking H H H H Short Chain Fatty Acids + Zeolites and metals such as Pt, Zn, Ga are suitable catalysts + Benzene Toluene Aromatics
Why Aromatics? Aromatics are primary building blocks in petrochemical industry Applications of toluene and xylenes Solvent Paint thinner Monomer preparation (for PET) Present in Gasoline 95% of toluene consumption is for the production of benzene 99% of ethylbenzene produced is consumed for styrene production BTEX world demand 155 million tons CMAI Ref: SL003305 (Chemical Market Associates, Inc.)
Zeolite catalysts Widely used for catalytic cracking process Aluminosilicates (Si-Al) Microporus structure ZSM-5: zeolite type catalysts Pentasil structure http://chemelab.ucsd.edu/aeronex02/background.html
Literature Review lefin aromatization pathway over HZSM-5 catalyst Dmitri B. Lukyanov N. Suor Gnep, and Michel R. Guisnet, Ind. Eng. Chem. Res. 1994,33, 223-234.
Literature Review Reaction scheme for the aromatization of propene over zeolites lefins are converted to oligomers ligomers converted to higher oligomers and lower olefins Lower olefins and higher oligomers converted into aromatics via dehydrogenation Lower olefins converted to alkanes via hydrogenation V.R. Choudhary et al. / Applied Catalysis A: General 231 (2002) 243 251
Renewable sources for chemicals and fuels production Potential feedstocks Triglyceride oils, such as palm oil, soybean oil, canola oil - by thermal cracking - by catalytic cracking crops such as corn, wheat, barley, sugar crops - by pyrolysis ther biomass such as wood - by pyrolysis [1] Bhatia, S.; Mohamed, A. R.; Shah, N. A. A. Chem. Eng. J. 2009, 1-2, 347-354. [2] Maher, K. D.; Bressler, D. C. Bioresour. Technol. 2007, 12, 2351-2368 [3] Sai Katikaneni, John Adjaye, Raphael Idem, Narendra Bakhshi, Journal of the American il Chemists' Society, 1998, 75, 381-391.
Hypothesis Aromatic compounds such as benzene, toluene, ethylbenzene and xylenes (BTEX) can be produced by cracking of soybean oil by using doped zeolite (ZSM-5) catalysts.
Methodology Catalyst preparation Calcination of ZSM-5 to get its H-ZSM-5 form Doping of HZSM-5 with metals (Zn, Ga) Catalyst activation Cracking and catalytic conversion of soybean oil Products separation and analysis Statistical design analysis
Experimental setup for catalytic conversion of soybean oil H 2 ut T Catalyst Bed Temperature Display Catalyst Thermocouple Heater H 2 In Condenser il heated continuously Vapors passed through catalyst bed Products condensed Coke collected after cooling Products analyzed by GC-FID Reactor FI Product Rotameter T il Temperature Display Nitrogen Soybean il Heating Mantle
Fractional factorial experimental design A two level, resolution-iv fractional factorial screening design (16 run design) Factors: Dopant identity (A); Dopant concentration (B); Reaction temperature (C); Initial oil charge (D); Nitrogen flow rate (E); Reaction time (F)
Experimental design analysis for toluene yield Surprisingly dopant type was not a significant factor Dopant concentration, reaction temperature and initial oil charge were the significant factors.
Experimental design analysis for xylene yields Initial oil charge was the only significant factor
Experimental design analysis for total BTEX yield Surprisingly dopant type was not a significant factor Dopant concentration, reaction temperature and initial oil charge were the significant factors
Conclusions Bio-based aromatic compounds can be produced from crop oil via catalytic cracking process Dopant identity did not show a significant effect on aromatization Reaction temperature, dopant concentration and the amount of initial oil charged to the reactor (oil to catalyst ratio) were the most significant factors for the overall aromatics yield Crop oil could be very efficiently used as a renewable resource for manufacturing bio-based aromatic compounds
Acknowledgements We thank USDA (grant # 2008-35504-04515), the ND Soybean Council, the ND Department of Commerce Centers of Excellence Program and Bayer Crop Science for financial support
Thanks Sustainable Energy Research Initiative and Supporting Education