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8 - A Greener Higher Olefin Hydroformylation Process

Published online by Cambridge University Press:  15 September 2022

Bala Subramaniam
Affiliation:
University of Kansas
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Summary

Higher olefin hydroformylation with syngas to produce linear aldehydes uses cobalt-based catalyst complexes, which requires rather high temperatures (>180°C) and pressures (~20 MPa). Further, it entails substantial solvent usage to recover and recycle the cobalt complex. Rh-based catalysts are known to operate at milder conditions (<100°C and a few MPa) and are much more active and selective toward the linear aldehyde. However, Rh is three orders of magnitude more expensive than cobalt and requires near-quantitative recovery for economic viability. A new 1-octene hydroformylation process that uses carbon-dioxide expanded liquid (CXL) as solvent medium and a nanofiltration membrane to substantially retain the Rh-catalyst complex in the reactor was demonstrated by researchers at the University of Kansas Center for Environmentally Beneficial Catalysis to outperform the cobalt-based process, with capital investment being 30% lower than the Co-based process. Gate-to-gate life cycle assessments show that the CXL process is environmentally friendlier than the conventional process in most impact categories such as ecotoxicity, greenhouse gas emissions and smog formation.

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Chapter
Information
Green Catalysis and Reaction Engineering
An Integrated Approach with Industrial Case Studies
, pp. 167 - 188
Publisher: Cambridge University Press
Print publication year: 2022

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References

Billig, E. and Bryan, D. R., Oxo process. In Kirk-Othmer Concise Encyclopedia of Chemical Technology (Hoboken, NJ: Wiley-Interscience, 2000), pp. 117.Google Scholar
Frohning, D. D., Kohlpaintner, C. W. and Bohnen, H. W., Hydroformylation. In Applied Homogeneous Catalysis with Organometallic Compounds, ed. Cornils, B. and Herrmann, W. A. (Weinheim: Wiley-VCH, 2002), pp. 31103.Google Scholar
Cornils, B., In New Syntheses with Carbon Monoxide, Reactivity and Structure, Concepts in Organic Chemistry, Vol. 11, ed. Falbe, J. (Berlin: Springer-Verlag, 1980), chapter 1, pp. 1225.Google Scholar
van Leeuwen, P. W. N. M., Homogeneous Catalysis: Understanding the Art, (New York: Springer-Verlag, 2004).Google Scholar
Desset, S. L., Reader, S. W. and Cole-Hamilton, D. J., Aqueous-biphasic hydroformylation of alkenes promoted by “weak” surfactants. Green Chem., 11 (2009), 630–37.Google Scholar
Tran, D. N., Legrand, F.-X., Menuel, S., Bricout, H., Tilloy, S. and Monflier, E., Cyclodextrin-phosphane possessing a guest-tunable conformation for aqueous rhodium-catalyzed hydroformylation. Chem. Commun., 48 (2012), 753–55.Google Scholar
Kunna, K., Müller, C., Loos, J. and Vogt, D., Aqueous-phase hydroformylation of 1-octene: styrene lattices as phase-transfer agents. Angew. Chem. Int. Ed., 45 (2006), 7289–92.Google Scholar
Hamerla, T., Rost, A., Kasaka, Y. and Schomäcker, R., Hydroformylation of 1-dodecene with water-soluble Rhodium catalysts with bidentate ligands in multiphase systems. ChemCatChem, 5 (2013), 1854–62.Google Scholar
Chen, S.-J., Wang, Y.-Y., Yao, W.-M., Zhao, X.-L., Vo-Thanh, G., and Liu, Y., An ionic phosphine-ligated rhodium(III) complex as the efficient and recyclable catalyst for biphasic hydroformylation of 1-octene. J. Mol. Catal. A: Chem., 378 (2013), 293–98.Google Scholar
Brunsch, Y. and Behr, A., Temperature-controlled catalyst recycling in homogeneous transition-metal catalysis: minimization of catalyst leaching. Angew. Chem. Int. Ed., 52 (2013), 1586–89.Google Scholar
Schäfer, E., Brunsch, Y., Sadowski, G. and Behr, A., Hydroformylation of 1-dodecene in the thermomorphic solvent system dimethylformamide/decane. Phase behavior–reaction performance–catalyst recycling. Ind. Eng. Chem. Res., 51 (2012), 10296–306.Google Scholar
Behr, A., Vorholt, A. J. and Seidensticker, T., An old friend in a new guise: Recent trends in homogeneous transition metal catalysis. ChemBioEng Rev., 2 (2015), 621.Google Scholar
Neves, Â. C. B., Calvete, M. J. F., Pinho e Melo, T. M. V. D. and Pereira, M. M., Immobilized catalysts for hydroformylation reactions: A versatile tool for aldehyde synthesis. Eur. J. Org. Chem., 32 (2012), 6309–20.Google Scholar
Solinas, M., Jiang, J., Stelzer, O. and Leitner, W., A cartridge system for organometallic catalysis: Sequential catalysis and separation using supercritical carbon dioxide to switch phases. Angew. Chem. Int. Ed., 44 (2005), 2291–95.Google Scholar
Bronger, R. P. J., Bermon, J. P., Reek, J. N. H., Kamer, P. C. J., van den Broeke, L. J. P., Carter, D. N., Licence, P. and Poliakoff, M., The immobilisation of phenoxaphosphine-modified xanthene-type ligand on polysiloxane support and application thereof in the hydroformylation reaction. J. Mol. Catal. A: Chem., 224 (2004), 145–52.Google Scholar
Kunene, T. E., Webb, P. B. and Cole-Hamilton, D. J., Highly selective hydroformylation of long-chain alkenes in a supercritical fluid ionic liquid biphasic system. Green Chem., 13 (2011), 1476–81.Google Scholar
Webb, P. B., Sellin, M. F., Kunene, T. E., Williamson, S., Slawin, A. M. Z. and Cole-Hamilton, D. J., Continuous flow hydroformylation of alkenes in supercritical fluid–ionic liquid biphasic systems. J. Am. Chem. Soc., 125 (2003), 15577–88.Google Scholar
Chen, D., Schmitkamp, M., Franciò, G., Klankermayer, J. and Leitner, W., Enantioselective hydrogenation with racemic and enantiopure binap in the presence of a chiral ionic liquid. Angew. Chem., Int. Ed. Engl., 47 (2008), 7339–41.Google Scholar
Hintermair, U., Francio, G. and Leitner, W., A fully integrated continuous-flow system for asymmetric catalysis: enantioselective hydrogenation with supported ionic liquid phase catalysts using supercritical CO2 as the mobile phase. Chem. Eur. J., 19 (2013), 4538–47.Google Scholar
Hintermair, U., Gong, Z., Serbanovic, A., Muldoon, M. J., Santini, C. C. and Cole-Hamilton, D. J., Continuous flow hydroformylation using supported ionic liquid phase catalysts with carbon dioxide as a carrier. Dalton Trans., 39 (2010), 8501–10.Google Scholar
Riisager, A., Fehrmann, R., Haumann, M. and Wasserscheid, P., Supported ionic liquid phase (SILP) catalysis: an innovative concept for homogeneous catalysis in continuous fixed-bed reactors. Eur. J. Inorg. Chem., 4 (2006), 695706.Google Scholar
Schönweiz, A. and Franke, R., Supported ionic liquid phase (SILP) materials in hydroformylation catalysis. In Supported Ionic Liquids: Fundamentals and Applications, ed. Fehrmann, R., Riisager, A. and Haumann, M. (Weinheim: Wiley, 2014), pp. 307–26.Google Scholar
Liu, D., Hydroformylation of C3 and C8 olefins in hydrocarbon gas-expanded solvents. PhD dissertation, University of Kansas (2018).Google Scholar
Janssen, M., Wilting, J., Müller, C. and Vogt, D., Continuous rhodium-catalyzed hydroformylation of 1-octene with polyhedral oligomeric silsesquioxanes (POSS) enlarged triphenylphosphine. Angew. Chem. Int. Ed. Engl., 49 (2010), 7738–41.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), 294301.Google Scholar
Jana, R. and Tunge, J. A., A homogeneous, recyclable rhodium(I) catalyst for the hydroarylation of Michael acceptors. Org. Lett., 11 (2009), 971–74.Google Scholar
Jessop, P. G. and Subramaniam, B., Gas-expanded liquids. Chem. Rev., 107 (2007), 2666–94.Google Scholar
Scurto, A. M., Hutchenson, K. W. and Subramaniam, B., Gas-expanded liquids: Fundamentals and applications. In Gas-Expanded Liquids and Near-Critical Media, Vol. 1006, eds. Hutchenson, K. W., Scurto, A. M. and Subramaniam, B. (Washington, DC: American Chemical Society, 2009), pp. 337.Google Scholar
Subramaniam, B., Gas expanded liquids for sustainable catalysis. In Innovations in Green Chemistry and Green Engineering, eds. Anastas, P. T. and Zimmerman, J. B. (New York: Springer, 2013), pp. 536.Google Scholar
Xie, Z., Fang, J., Maiti, S. K., Snavely, W. K., Tunge, J. A. and Subramaniam, B., Enhanced hydroformylation by carbon dioxide-expanded media with soluble Rh complexes in nanofiltration membrane reactors. AIChE J., 59 (2013), 4287–96.Google Scholar
Fang, J., Jin, H., Ruddy, T., Pennybaker, K., Fahey, D. R. and Subramaniam, B., Economic and environmental impact analyses of catalytic olefin hydroformylation in CO2-expanded liquid (CXL) media. Ind. Eng. Chem. Res., 46 (2007), 8687–92.Google Scholar
Xie, Z. and Subramaniam, B., Development of a greener hydroformylation process guided by quantitative sustainability assessments. ACS Sustain. Chem. Eng., 2 (2014), 2748–57.Google Scholar
Vargas, J. M., Hydrogenation catalyst for oxo alcohol process. U.S. patent 5,306,848. 04-26-1994.Google Scholar
Roussel, P. B., Process for preforming cobaltous salts using shell-type preformer catalysts. U.S. patent 5,600,031. 1997-02-04.Google Scholar
Hill, R. R. and Roussel, P. B., Reactivation or regeneration of cobalt preformer catalyst for oxo process. U.S. patent 5,434,318. 1995-07-18.Google Scholar
Beadle, S. W. and Poulin, C. A., Use of stripper reactor reflux as an initiator for preforming reaction of cobaltous salts to cobalt carbonyls. U.S. patent 5,457,240. 1995-10-10.Google Scholar
Summerlin, W. H., Method for removing hydroformylation catalyst. U.S. patent application WO 93/24438. 1993-12-09.Google Scholar
Beadle, S. W., Summerlin, W. H. and Van Driessche, E. T. A., Airless cobalt demetalling in the cobalt flash combination catalyst cycle. U.S. patent 5,410,090. 1995-04-25.Google Scholar
Hanin, J. A. A., Production of alcohols. European patent application 0343819 A1. 12-05-1989.Google Scholar
Peters, M. S., Timmerhaus, K. D. and West, R. E., Plant Design and Economics for Chemical Engineers, 5th ed. (New York: McGraw-Hill, 2003).Google Scholar
Anonymous, Economic indicators. Chem. Eng., 120 (2013), 68.Google Scholar
Carnegie Mellon University Green Design Institute. Economic Input–Output Life Cycle Assessment. Available at: www.eiolca.net/, last accessed June 11, 2020.Google Scholar
Li, M., Ruddy, T., Fahey, D., Busch, D. H. and Subramaniam, B., Terephthalic acid production via greener spray process: comparative economic and environmental impact assessments with Mid-Century process. ACS Sustain. Chem. Eng., 2 (2014), 823–35.Google Scholar
Ghanta, M., Fahey, D. R., Busch, D. H. and Subramaniam, B., Comparative economic and environmental assessments of H2O2-based and tertiary butyl hydroperoxide-based propylene oxide technologies. ACS Sustain. Chem. Eng., 1 (2013), 268–77.Google 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), 1829.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), 4978.Google Scholar
Lappin, G. R., Nemec, L. H., Sauer, J. D. and Wagner, J. D., Higher olefins. In Kirk-Othmer Encyclopedia of Chemical Technology (Weinheim: Wiley-VCH, 2010), pp. 120.Google Scholar
de Klerk, A., Fischer–Trøpsch process. In Kirk-Othmer Encyclopedia of Chemical Technology (Weinheim: Wiley-VCH, 2013), pp. 136.Google Scholar
Drury, D. J., Formic acid. In Kirk-Othmer Encyclopedia of Chemical Technology (Weinheim: Wiley-VCH, 2013), pp. 19.Google Scholar
Ozokwelu, E. D., Toluene. In Kirk-Othmer Encyclopedia of Chemical Technology (Weinheim: Wiley-VCH, 2000), pp. 133.Google Scholar
Pierantozzi, R., Carbon dioxide. In Kirk-Othmer Encyclopedia of Chemical Technology (Weinheim: Wiley-VCH, 2003), pp. 803–22.Google Scholar
Graedel, T. E., Barr, R., Chandler, C., Chase, T., Choi, J., Christoffersen, L., Friedlander, E., Henly, C., Jun, C., Nassar, N. T., Schechner, D., Warren, S., Yang, M.-Y. and Zhu, C., Methodology of metal criticality determination. Environ. Sci. Techol., 46 (2011), 1063–70.Google Scholar
Graedel, T. E., Harper, E. M., Nassar, N. T. and Reck, B. K., On the materials basis of modern society. Proc. Natl. Acad. Sci., 112 (2013) 6295–300.Google Scholar
NIST/SEMATECH e-Handbook of Statistical Methods. Available at: www.itl.nist.gov/div898/handbook/pmd/section2/pmd213.htm, last accessed June 12, 2020.Google Scholar
Hendrickson, C. T., Lave, L. B. and Matthews, H. S., Environmental Life Cycle Assessment of Goods and Services: An Input–Output Approach (Baltimore, MD: Resources for the Future Press, 2006).Google Scholar
US Census Bureau. Consumer Price Indexes. Available at: www.census.gov/library/publications/2011/compendia/statab/131ed/prices.html, last accessed June 12, 2020.Google Scholar
Rhodium price. Available at: www.kitco.com/charts/rhodium.html, last accessed June 12, 2020.Google Scholar
Cobalt price. Available at: www.infomine.com/investment/metal-prices/cobalt/, last accessed June 12, 2020.Google Scholar
Kramer, J., Nöllen, E., Buijs, W., Driessen, W. L. and Reedijk, J., Investigations into the recovery of Wilkinson’s catalyst with silica-immobilized P-donor ligands. React. Funct. Polym., 57 (2003), 111.Google Scholar
Kramer, J., Scholten, A., Driessen, W. L. and Reedijk, J., Recovery of rhodium-containing catalysts by silica-based chelating ion exchangers containing N and S donor atoms. Inorg. Chim. Acta, 315 (2001), 183–90.Google Scholar
Yousif, A. M., Nishioka, M., Wakui, Y. and Suzuki, T. M., Rapid adsorption of Rh(III) by polyamine-functionalized cellulose fiber combined with microwave irradiation. Chem. Lett., 39 (2010), 1317–18.Google Scholar
EPA Toxics Release Inventory Explorer. Available at: https://enviro.epa.gov/triexplorer/tri_release.chemical, last accessed June 12, 2020.Google Scholar
EPA Greenhouse Gas Emission Report Inventory. Available at: http://ghgdata.epa.gov/ghgp/main.do, last accessed June 12, 2020.Google Scholar
Allen, D. T. and Shonnard, D. R., Green Engineering: Environmentally Conscious Design of Chemical Processes (Upper Saddle River, NJ: Prentice Hall PTR, 2002).Google Scholar
Cornils, B., Herrmann, W. A., Wong, C.-H. and Zanthoff, H.-W., eds., Catalysis from A to Z : A Concise Encyclopedia, 4th ed., 4 vols (Weinheim: Wiley-VCH, 2013).Google Scholar
Gelest Website. Available at: www.gelest.com/gelest/forms/Home/home.aspx, last accessed July 4, 2020.Google Scholar
Mark, J. E., Overview of siloxane polymers. In Silicones and Silicone-Modified Materials, eds. Clarson, S. J., Fitzgerald, J. J., Owen, M. J. and Smith, S. D. (Washington, D.C.: American Chemical Society, 2000), Vol. 729, pp. 110.Google Scholar
Keller, F., Weinmann, H. and Schurig, V., Chiral polysiloxane-fixed metal 1,3-diketonates (chirasil-metals) as catalytic lewis acids for a hetero Diels-Alder reaction: Inversion of enantioselectivity upon catalyst–polymer binding. Chem. Ber., 130 (1997), 879–85.Google Scholar
Cypryk, M., Pospiech, P., Strzelec, K. and Sobczak, J. W., Soluble akylthiopolysiloxane-supported palladium catalysts for the Heck reaction. Phosphorus Sulfur Silicon Relat. Elem., 184 (2009), 1586–98.Google Scholar
DeClue, M. S. and Siegel, J. S., Polysiloxane-bound ligand accelerated catalysis: A modular approach to heterogeneous and homogeneous macromolecular asymmetric dihydroxylation ligands. Org. Biomol. Chem., 2 (2004), 2287–98.Google Scholar
Xie, Z., Akien, G. A., Sarkar, B. R., Subramaniam, B. and Chaudhari, R. V., Functionalized polydimethylsiloxane-attached Rh-complexes as nanofilterable homogeneous hydroformylation catalysts. Ind. Eng. Chem. Res., 54 (2015), 10656–60.Google Scholar

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