Skip to main content Accessibility help

We use cookies to distinguish you from other users and to provide you with a better experience on our websites. Close this message to accept cookies or find out how to manage your cookie settings.

Close cookie message
×
Hostname: page-component-cd9895bd7-mkpzs Total loading time: 0 Render date: 2024-12-26T02:19:02.005Z Has data issue: false hasContentIssue false

4 - Ethylene Epoxidation in Gas-Expanded Liquids with Negligible CO2 Formation as a Byproduct

Comparative Sustainability Analysis with Conventional Process

Published online by Cambridge University Press:  15 September 2022

Bala Subramaniam
Bala Subramaniam
Affiliation:
University of Kansas
Get access

Summary

Ethylene oxide (EO) is a commodity chemical made by treating ethylene with oxygen over a silver-based catalyst. One of its major applications is for making polyethylene terephthalate (PET) plastics used in water bottles. In the conventional process, up to 15% of the ethylene is simply burned as CO2. This chapter discusses an alternative process that employs methyltrioxorhenium (MTO) as a catalyst and hydrogen peroxide (H2O2) as an oxidant to produce EO with no CO2 as a byproduct. While the capital costs for both processes are similar, the EO production cost for the alternative process is competitive only if the MTO catalyst remains stable for at least one year and the Re leaching is <0.7 ppm. Unexpectedly, cradle-to-gate life cycle assessments (LCA) reveal that the overall environmental impacts on greenhouse gas emissions, air quality and water quality are similar for both processes. In the alternate technology, the carbon footprint associated with H2O2 production reduces the gains made in converting ethylene to EO avoiding CO2 as a byproduct. Direct H2O2 synthesis technology and effective H2O2 utilization are essential to reduce the environmental footprint of the alternate technology.

Keywords

cradle-to-gate LCAethylene oxideepoxidationmethyltrioxorheniumhydrogen peroxide
Type
Chapter
Information
Green Catalysis and Reaction Engineering
An Integrated Approach with Industrial Case Studies
 , pp. 67 - 88
Publisher: Cambridge University Press
Print publication year: 2022

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Rebsdat, S. and Mayer, D., Ethylene oxide. In Ullmann’s Encyclopedia of Industrial Chemistry (New York: Wiley-VCH, 2012), pp. 547–572.Google Scholar
Weissermel, K. and Arpe, H.-J., Industrial Organic Chemistry, 4th ed. (Weinheim: Wiley-VCH, 2003).CrossRefGoogle Scholar
Buffum, J. E., Kowaleski, R. M. and Gerdes, W. H., Ethylene Oxide Catalyst. U.S. patent 5,145,824. 1992-09-08.Google Scholar
Zabetakis, M. G., Flammability Characteristics of Combustible Gases and Vapors (Washington, D.C.: U.S. Department of Interior, US Bureau of Mines, 1965).Google Scholar
Hess, L. G. and Tilton, V. V., Ethylene oxide: Hazards and methods of handling. Ind. Eng. Chem., 42 (1950), 1251–58.CrossRefGoogle Scholar
Ghanta, M., Ruddy, T., Fahey, D. R., Busch, D. H. and Subramaniam, B., Is the liquid-phase H2O2-based ethylene oxide process more economical and greener than the gas-phase O2-based silver-catalyzed process? Ind. Eng. Chem. Res., 52 (2013), 18–29.Google Scholar
Lee, H.-J., Ghanta, M., Busch, D. H. and Subramaniam, B., Towards a CO2-free ethylene oxide process: Homogeneous ethylene oxide in gas-expanded liquids. Chem. Eng. Sci., 65 (2010), 128–34.CrossRefGoogle Scholar
Lee, H.-J., Shi, T.-P., Busch, D. H. and Subramaniam, B., A greener, pressure intensified propylene epoxidation process with facile product separation. Chem. Eng. Sci., 62 (2007), 7282–89.CrossRefGoogle Scholar
Subramaniam, B., Busch, D. H., Lee, H.-J., Ghanta, M. and Shi, T.-P., Process for Selective Oxidation of Olefins to Epoxides. U.S. patent 8,080,677 B2. 2011-12-20.Google Scholar
Ohgaki, K., Nishii, H., Saito, T. and Katayama, T., High-pressure phase equilibria for the methanol-ethylene system at 25°C and 40°C. J. Chem. Eng. Japan, 16 (1983), 263–67.Google Scholar
Ghanta, M., Lee, H.-J., Busch, D. H. and Subramaniam, B., Highly selective homogeneous ethylene epoxidation in gas (ethylene)-expanded liquid: Transport and kinetic studies. AIChE J., 59 (2013) 180–87.Google Scholar
Pujado, P. R. and Hammerman, J. I., Integrated Process for the Production of Propylene Oxide. U.S. patent 5,599,956. 02-04-1997.Google Scholar
Aspen HYSYS 7.1 (Calgary, Canada: Aspen Technologies, 2009).Google Scholar
Peters, M. S. and Timmerhaus, K. D., Plant Design and Economics for Chemical Engineers, 4th ed. (New York: McGraw Hill Inc, 1991).Google Scholar
Chilton, C. H., Popper, H. and Norden, R. B., Modern Cost Engineering: Methods and Data, Vol. I (New York: McGraw-Hill, 1978).Google Scholar
Walas, S. M., Chemical Process Equipment: Selection and Design (Boston: Butterworth-Heinemann, 1990).Google Scholar
Matley, J., Modern Cost Engineering: Methods and Data, Vol. II (New York: McGraw-Hill, 1984).Google Scholar
McCain, J. H., Naumann, A. W. and Wang, W.-Y., Thermal Process for Removal of Contaminants From Process Streams. U.S. patent 5,563,282. 10-8-1996.Google Scholar
Golubev, Y. D., Dementeva, L. and Vlasov, G. M., Solubility of ethylene oxide in C1–4 alcohols. The Soviet Chemical Industry, 8 (1971), 536–38.Google Scholar
Stoukides, M. and Pavlou, S., Ethylene oxidation on silver catalysts: Effect of ethylene oxide and of external transfer limitations. Chem. Eng. Commun., 44 (1986), 53–74.Google Scholar
Tosh, E., Mitterpleininger, J. K. M., Rost, A. M. J., Veljanovski, D., Herrmann, W. A. and Kuhn, F. E., Methyltrioxorhenium revisited: improving the synthesis for a versatile catalyst. Green Chem., 9 (2007), 1296–98.CrossRefGoogle Scholar
Vezzosi, S., Ferre, A. G., Crucianelli, M., Crestini, C. and Saladino, R., A novel and efficient catalytic epoxidation of olefins with adducts derived from methyltrioxorhenium and chiral aliphatic amines. J. Catal., 257 (2008), 262–69.Google Scholar
Bracco, L. L. B., Juliarena, M. P., Ruiz, G. T., Feliz, M. R., Ferraudi, G. J. and Wolcan, E., Resonance energy transfer in the solution phase photophysics of ‒Re(CO)(3)L+ pendants bonded to poly(4-vinylpyridine). J. Phys. Chem. B, 112 (2008), 11506–16.Google Scholar
Fang, J., Jana, R., Tunge, J. A. and Subramaniam, B., Continuous homogeneous hydroformylation with bulky rhodium catalyst complexes retained by nano-filtration membranes. Appl. Catal. A: Gen., 393 (2011), 294–301.CrossRefGoogle Scholar
Vora, B. V. and Pujado, P. R., Process For Producing Propylene Oxide. U.S. patent 5,599,955. 02-04-1997.Google Scholar
Fischer, M., Kaibel, G., Stammer, A., Flick, K., Quaiser, S., Harder, W. and Massonne, K., Process for the Manufacture of Hydrogen Peroxide. U.S. patent 6,375,920 B2. 04-23-2002.Google Scholar
Chemical Engineering Plant Cost Index (CEPCI). Chem. Eng., 117 (2010), 68.Google Scholar
ICIS. Chemicals. Available at: www.icis.com/explore/commodities/chemicals/, last accessed Feb 9, 2020.Google Scholar
U.S. Energy Information Administration-Crude Oil. Available at: www.eia.doe.gov/, last accessed Feb 9, 2020.Google Scholar
U.S. Bureau of Labor Statistics. Consumer Price Index. Available at: www.bls.gov/cpi/, last accessed Feb 9, 2020.Google Scholar
Engineering News Record. : Cost Indexes, Wages and Prices. Available at: www.enr.com, last accessed Feb 8, 2020.Google Scholar
Baitz, M., Colodel, C. M., Kupfer, T., Florin, J., Schuller, O., Hassel, F., Kokborg, M., Köhler, A., Thylmann, D., Stoffregen, A., Schöll, S., Görke, J. and Rudolf, M., GaBi Database & Modelling Principles (2013). Available at: www.gabi-software.com/uploads/media/GaBi_Modelling_Principles_2013.pdf, last accessed Feb 9, 2020.Google Scholar
Bare, J. C., Norris, G. A., Pennington, D. W. and McKone, T., TRACI: The tool for the reduction and assessment of chemical and other environmental impacts. J. Ind. Ecol., 6 (2002), 49–78.Google Scholar
Bare, J. C., Hofstetter, P., Pennington, D. W. and Udo de Haes, H. A., Midpoints versus endpoints: The sacrifices and benefits. Int. J. LCA, 5 (2000), 319–26.Google Scholar
Allen, D. T. and Shonnard, D., Sustainable Engineering Concepts, Design, and Case Studies, 1st ed. (New York: Prentice Hall, 2012).Google Scholar
Kalnes, T. N., Koers, K. P., Marker, T. and Shonnard, D. A., A technoeconomic and environmental life cycle comparison of green diesel to biodiesel and syndiesel. Environ. Prog. Sustain., 28 (2009), 111–120.CrossRefGoogle Scholar
Kargbo, D. M., Wilhelm, R. G. and Campbell, D. J., Natural gas plays in the Marcellus Shale: Challenges and potential opportunities. Environ. Sci. Techol., 44 (2010), 5679–84.Google Scholar
Processing Natural Gas. Natural Gas. Available at: www.naturalgas.org, last accessed Feb 9, 2020.Google Scholar
Zimmermann, H. and Walzl, R., Ethylene. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2012), pp. 465–529.Google Scholar
Windmeier, C. and Barron, R. F., Cryogenic technology. In Ullmann’s Encylcopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2013), pp. 1–71.Google Scholar
Freilich, M. B. and Petersen, R. L., Potassium compounds. In Kirk-Othmer Encyclopedia of Chemical Technology (New York: Wiley-VCH, 2005), pp. 1–42.Google Scholar
Rebsdat, S. and Mayer, D., Ethylene Glycol. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2012), pp. 531–44.Google Scholar
Hussey, D. F., Foutch, G. L. and Ward, M. A., Water, Ultrapure. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2008), pp. 1–20. 2Google Scholar
Ott, J., Gronemann, V., Pontzen, F., Fiedler, E., Grossman, G., Kersebohm, D. B., Weiss, G. and Witte, C., Methanol. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2012), pp. 1–27.Google Scholar
Goor, G., Glenneberg, J. and Jacobi, S., Hydrogen peroxide. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2007), pp. 393–427.Google Scholar
Lauermann, G., Häussinger, P., Lohmuller, R. and Watson, A. M., Hydrogen. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2012), pp. 1–15.Google Scholar
Welch, V. A., Fallon, K. J. and Gelbke, H.-P., Ethylbenzene. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2005), pp. 451–64.Google Scholar
Austin, G. T., Shreve’s Chemical Process Industries, 5th ed. (New York: McGraw Hill, 1985).Google Scholar
Shimizu, S., Watanabe, N., Kataoka, T., Shoji, T., Abe, N., Morishita, S. and Ichimura, H., Pyridine and pyridine derivatives. In Ullmann’s Encyclopedia of Industrial Technology (Weinheim: Wiley-VCH, 2000), pp. 557–89.Google Scholar
Schrödter, K., Bettermann, G., Staffel, T., Wahl, F., Klein, T. and Hofmann, T., Phosphoric acid and phosphates. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2012), pp. 679–724.Google Scholar
BASF/Dow/Solvay HPPO Plant. Available at: www.chemicals-technology.com/projects/basf-hppo/, last accessed Feb 9, 2020.Google Scholar
Toxic Release Inventory – BASF Corporation. Available at: https://enviro.epa.gov/triexplorer/release_fac_profile?TRI=70734BSFCRRIVER&TRILIB=TRIQ1&FLD=&FLD=RELLBY&FLD=TSFDSP&OFFDISPD=&OTHDISPD=&ONDISPD=&OTHOFFD=&YEAR=2011, last accessed Feb 9, 2020.Google Scholar
Greenhouse gas data – BASF Corporation. Available at:  https://ghgdata.epa.gov/ghgp/service/facilityDetail/2011?id=1004208&ds=E&et=PE&popup=true, last accessed Feb 9, 2020.Google Scholar
Ranganathan, S. and Sieber, V., Recent advances in the direct synthesis of hydrogen peroxide using chemical catalysis: A review. Catalysts, 8 (2018), 379.Google Scholar
Abou Shama, M. A. and Xu, Q., Optimal design of gas-expanded liquid ethylene oxide production with zero carbon dioxide byproduct. Ind. Eng. Chem. Res., 57 (2018), 5351–58.Google Scholar
Foster, G., Low-carbon futures for bioethylene in the United States. Energies, 12 (2019), 1958.Google Scholar
Lu, X., Zhou, W.-J., Wu, H., Liebens, A. and Wu, P., Selective synthesis of ethylene oxide through liquid-phase epoxidation of ethylene with titanosilicate/H2O2 catalytic systems. Appl. Catal. A: Gen., 515 (2016), 51–59.Google Scholar
Yan, W., Ramanathan, A., Patel, P. D., Maiti, S. K., Laird, B. B., Thompson, W. H. and Subramaniam, B., Mechanistic insights for enhancing activity and stability of Nb-incorporated silicates for selective ethylene epoxidation. J. Catal., 336 (2016), 75–84.Google Scholar

Save book to Kindle

To save this book to your Kindle, first ensure [email protected] is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about saving to your Kindle.

Note you can select to save to either the @free.kindle.com or @kindle.com variations. ‘@free.kindle.com’ emails are free but can only be saved to your device when it is connected to wi-fi. ‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

Available formats
×

Save book to Dropbox

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Dropbox.

Available formats
×

Save book to Google Drive

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Google Drive.

Available formats
×