Book contents
- Green Catalysis and Reaction Engineering
- Cambridge Series in Chemical Engineering
- Green Catalysis and Reaction Engineering
- Copyright page
- Dedication
- Contents
- Preface
- Acknowledgments
- 1 Sustainability Challenges of the Chemical Industry
- 2 Multiphase Catalytic Processes and Sustainability Challenges
- 3 Ethylene Production from Diverse Feedstocks and Energy Sources
- 4 Ethylene Epoxidation in Gas-Expanded Liquids with Negligible CO2 Formation as a Byproduct
- 5 Spray Reactor-Based Terephthalic Acid Production as a Greener Alternative to the Mid-Century Process
- 6 Sustainability Assessments of Hydrogen Peroxide-Based and Tertiary Butyl Hydroperoxide-Based Propylene Oxide Technologies
- 7 Separation of Propane/Propylene Mixture by Selective Propylene Hydroformylation in Gas-Expanded Liquids
- 8 A Greener Higher Olefin Hydroformylation Process
- 9 Solid Acid-Catalyzed Olefin/Isoparaffin Alkylation in Supercritical Carbon Dioxide
- 10 Epilogue
- Index
- References
9 - Solid Acid-Catalyzed Olefin/Isoparaffin Alkylation in Supercritical Carbon Dioxide
Published online by Cambridge University Press: 15 September 2022
Book contents
- Green Catalysis and Reaction Engineering
- Cambridge Series in Chemical Engineering
- Green Catalysis and Reaction Engineering
- Copyright page
- Dedication
- Contents
- Preface
- Acknowledgments
- 1 Sustainability Challenges of the Chemical Industry
- 2 Multiphase Catalytic Processes and Sustainability Challenges
- 3 Ethylene Production from Diverse Feedstocks and Energy Sources
- 4 Ethylene Epoxidation in Gas-Expanded Liquids with Negligible CO2 Formation as a Byproduct
- 5 Spray Reactor-Based Terephthalic Acid Production as a Greener Alternative to the Mid-Century Process
- 6 Sustainability Assessments of Hydrogen Peroxide-Based and Tertiary Butyl Hydroperoxide-Based Propylene Oxide Technologies
- 7 Separation of Propane/Propylene Mixture by Selective Propylene Hydroformylation in Gas-Expanded Liquids
- 8 A Greener Higher Olefin Hydroformylation Process
- 9 Solid Acid-Catalyzed Olefin/Isoparaffin Alkylation in Supercritical Carbon Dioxide
- 10 Epilogue
- Index
- References
Summary
Alkylation of 1-butene with isobutane is employed industrially to produce C8 alkylates (such as trimethylpentane) as high-octane motor fuel. Such alkylates supply roughly up to 15% of the U.S. gasoline pool. However, the process uses large quantities of sulfuric acid (as catalyst) generating acid waste whose handling poses health and environmental hazards. The main pollutants are sulfur dioxide (SO2) emissions (which causes acid rain) and acid leakage in the alkylation unit. This chapter presents an alternate process that uses a solid catalyst (Nafion® supported on silica) in dense CO2 media to produce C8 alkylates (solid acid/CO2 process). Although the environmental concerns with SO2 emissions and acid leakage are eliminated, the activity of the solid acid catalyst is lower than sulfuric acid resulting in an approximately 30% higher capital investment than the conventional process. For C8 alkylate productivity, capital investments and operating costs to be nearly identical, the required olefin throughput in the solid acid/CO2 process must be four-fold higher. Such analyses establish performance targets for the solid acid/CO2 process to be commercially viable.
- Type
- Chapter
- Information
- Green Catalysis and Reaction EngineeringAn Integrated Approach with Industrial Case Studies, pp. 189 - 204Publisher: Cambridge University PressPrint publication year: 2022
References
Corma, A. and Martinez, A., Chemistry, catalysts, and processes for isoparaffin-olefin alkylation: Actual situation and future trends. Catal. Rev. Sci. Eng., 35 (1993), 483–570.Google Scholar
Albright, L. F., Alkylation of isobutane with C3−C5 Olefins to produce high-quality gasolines: Physicochemical sequence of events. Ind. Eng. Chem. Res., 42 (2003), 4283–89.Google Scholar
Albright, L. F., Alkylation-industrial. In Encyclopedia of Catalysis, vol. 1, ed. Horváth, I. T. (Hoboken, NJ: John Wiley, 2003), pp 262–81.Google Scholar
Albright, L. F. and Ryan, J. M., Alkylation processes to produce high-quality gasolines. In Encyclopedia of Chemical Processing, Vol. 1, ed. Lee, S. (New York: Taylor & Francis, 2006), pp. 57–66.Google Scholar
Albright, L. F., Kranz, K. E. and Masters, K. R., Alkylation of isobutane with light olefins. Yields of alkylates for different olefins. Ind. Eng. Chem. Res., 32 (1993), 2991–96.Google Scholar
Minnick, D., Kore, R., Lyon, C. J., Subramaniam, B., Shiflett, M. B. and Scurto, A. M., Understanding sulfur content in alkylate from sulfuric acid-catalyzed C3/C4 alkylations. Energy Fuels, 33 (2019), 4659–70.Google Scholar
Van Zele, R. L. and Diener, R., On the road to HF mitigation. Hydrocarb. Proc., 69 (1990), 92.Google Scholar
Garwood, W. E., Leaman, W. K., Myers, C. G. and Plank, C. J., Isoparaffin-olefin alkylation using crystalline zeolite catalyst. U.S. patent 3,251,902. 1966-05-17.Google Scholar
Kirsch, F. W., Potts, J. D. and Barmby, D. S., Isoparaffin-olefin alkylations with crystalline aluminosilicates: I. Early studies: C4-olefins. J. Catal., 27 (1972), 142–50.CrossRefGoogle Scholar
Weitkamp, J. and Traa, Y., Isobutane/butene alkylation on solid catalysts. Where do we stand? Catal. Today, 49 (1999), 193–99.Google Scholar
Chauvin, Y., Hirschauer, A. and Olivier, H., Alkylation of isobutane with 2-butene using 1-butyl-3-methylimidazolium chloride: Aluminium chloride molten salts as catalysts. J. Mol. Catal., 92 (1994), 155–65.Google Scholar
Yoo, K., Namboodiri, V. V., Varma, R. S. and Smirniotis, P. G., Ionic liquid-catalyzed alkylation of isobutane with 2-butene. J. Catal., 222 (2004), 511–19.Google Scholar
Hallett, J. P. and Welton, T., Room-temperature ionic liquids: Solvents for synthesis and catalysis. Chem. Rev., 111 (2011), 3508–76.Google Scholar
Wang, H., Meng, X., Zhao, G. and Zhang, S., Isobutane/butene alkylation catalyzed by ionic liquids: a more sustainable process for clean oil production. Green Chem., 19 (2017), 1462–89.Google Scholar
Tang, S. W., Scurto, A. M. and Subramaniam, B., Improved 1-butene/isobutane alkylation with acidic ionic liquids and tunable acid/ionic liquid mixtures. J. Catal., 268 (2009), 243–50.CrossRefGoogle Scholar
Timken, H. K., Luo, H., Chang, B.-K., Carter, E. and Cole, M., ISOALKY™ technology: Next-generation alkylate gasoline manufacturing process technology using ionic liquid catalyst. In Commercial Applications of Ionic Liquids, ed. Shiflett, M. B. (Switzerland: Springer Nature, 2020), pp. 33–47.Google Scholar
Lyon, C. J., Sarsani, V. S. R. and Subramaniam, B., 1-Butene plus isobutane reactions on solid acid catalysts in dense CO2-based reaction media: Experiments and modeling. Ind. Eng. Chem. Res., 43 (2004), 4809–14.Google Scholar
Hyprotech HYSYS® 3.1 (Calgary, Canada: Hyprotech Ltd., 2002).Google Scholar
Albright, L. F., Alkylation will be key process in reformulated gasoline era. Oil Gas J., 88 (1990), 79–92.Google Scholar
Albright, L. F., H2SO4, HF processes compared, and new technologies revealed. Oil Gas J., 88 (1990), 70–77.Google Scholar
Gong, K., Chafin, S., Pennybaker, K., Fahey, D. R. and Subramaniam, B., Economic and environmental impact analyses of solid-acid catalyzed isoparaffin/olefin alkylation in supercritical carbon dioxide. Ind. Eng. Chem. Res., 47 (2008), 9072–80.Google Scholar
Meyer, D. W., Chapin, L. E. and Muir, R. F., Cost benefits of sulfuric acid alkylation. Chem. Eng. Prog., 79 (1983), 59–65.Google Scholar
Branzaru, J., Introduction to Sulfuric Acid Alkylation Unit Process Design (Kansas: Stratco Inc., 2001).Google Scholar
Lyon, C., Subramaniam, B. and Pereira, C. J., Enhanced isooctane yields for 1-butene/isobutane alkylation on SiO2-supported Nafion® in supercritical carbon dioxide. In Catalyst Deactivation 2001. Studies in Surface Science and Catalysis, Vol. 139, eds. Spivey, J. J., Roberts, G. W. and Davis, B. H. (Amsterdam: Elsevier, 2001), pp. 221–28.Google Scholar
Lyon, C. J., Optimization of activity and selectivity by pressure-tuning during solid-acid catalyzed isoparaffin/olefin alkylation in supercritical carbon dioxide. Ph.D. thesis, University of Kansas (2002).Google Scholar
Peters, M. S., Timmerhaus, K. D. and West, R., Plant Design and Economics for Chemical Engineers, 5th ed. (New York: McGraw-Hill, 2003).Google Scholar
Walas, S. M., Chemical Process Equipment: Selection and Design (Boston: Butterworths, 1988).Google Scholar
Gary, J. H. and Handwerk, G. E., Petroleum Refining: Technology and Economics. 4th ed. (New York: Marcel Dekker, 2001).Google Scholar
Allen, D. T. and Shonnard, D. R., Green Engineering: Environmentally Conscious Design of Chemical Processes (Upper Saddle River, NJ: Prentice Hall, 2002).Google Scholar
Chen, H. and Shonnard, D. R., Green engineering, process aafety and inherent safety: A new paradigm. In Green Engineering Tutorial: Environmentally-Conscious Design of Chemical Processes, Safety and Chemical-Engineering Education (SAChE) Faculty Workshop, Baton Rouge, LA (2003).Google Scholar
Energy Facts, 1992. USDOE Energy Information Administration, Washington, DC (United States). Available at: www.osti.gov/servlets/purl/10104478, last accessed June 14, 2020.Google Scholar
EPA. Compilation of Air Pollutant Emission Factors: Volume 1: Stationary Point and Area Sources; AP-42, 5th ed. (Research Triangle Park, NC: U.S. Environmental Protection Agency, 1995). Available at: www3.epa.gov/ttn/chief/ap42/toc_kwrd.pdf, last accessed June 16, 2020.Google Scholar
Mackay, D., Multimedia Environmental Models: The Fugacity Approach, 2nd ed. (Boca Raton, FL: Lewis Publishers, 2001).Google Scholar
SRC Chemfate. Available at: www.srcinc.com/what-we-do/environmental/scientific-databases.html, last accessed June 16, 2020.Google Scholar
EPI Suite™-Estimation Program Interface. Available at: www.epa.gov/tsca-screening-tools/epi-suitetm-estimation-program-interface, last accessed June 16, 2020.Google Scholar
Goedkoop, M., The Eco-Indicator 95 (Amersfoort, Netherlands: Pré Consultants, 1995). Available at: www.pre-sustainability.com/download/EI95FinalReport.pdf, last accessed June 16, 2020.Google Scholar