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-cd9895bd7-8ctnn Total loading time: 0 Render date: 2024-12-26T03:07:58.128Z Has data issue: false hasContentIssue false

5 - Spray Reactor-Based Terephthalic Acid Production as a Greener Alternative to the Mid-Century Process

Published online by Cambridge University Press:  15 September 2022

Bala Subramaniam
Bala Subramaniam
Affiliation:
University of Kansas
Get access

Summary

Terephthalic acid (TPA) is a commodity chemical made by treating p-xylene (pX) with oxygen (O2) via the so-called Mid-Century (MC) process. TPA is a key ingredient to make polyethylene terephthalate plastic used in water bottles. The MC process uses a stirred reactor in which O2 is dispersed through an acetic acid solution of pX and catalyst (Co/Mn/Br). However, O2 starvation in the liquid phase causes incomplete oxidation necessitating product purification in a catalytic hydrogenation unit that accounts for nearly 50%, 16% and 33% of the overall capital investment, operating costs and greenhouse gas emissions, respectively. To mitigate O2 starvation, an alternate reactor technology is presented wherein the continuous and dispersed phases are reversed by spraying the liquid phase as fine droplets into a vapor phase containing O2 to increase the gas–liquid interfacial area. As a result, the spray reactor produces polymer-grade TPA in one step, eliminating the hydrogenation unit. Life cycle assessment confirms that the spray process without the hydrogenation unit significantly lowers global warming, acidification and other harmful emissions when compared to the MC process.

Keywords

terephthalic acidspray reactorlife cycle assessmentMid-Century process
Type
Chapter
Information
Green Catalysis and Reaction Engineering
An Integrated Approach with Industrial Case Studies
 , pp. 89 - 122
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

Landau, R. and Saffer, A., Process for the preparation of terephthalic acid, U.S. patent 2,833,818A. 1958-05-06.Google Scholar
Tomás, R. A. F., Bordado, J. C. M. and Gomes, J. F. P., p-Xylene oxidation to terephthalic acid: A literature review oriented toward process optimization and development. Chem. Rev., 113 (2013), 7421–69.Google Scholar
Energy with Purpose. BP Annual Report and Form 20-F (2019). Available at: www.bp.com/content/dam/bp/business-sites/en/global/corporate/pdfs/investors/bp-annual-report-and-form-20f-2019.pdf, last accessed Apr 17, 2020.Google Scholar
Raghavendrachar, P. and Ramachandran, S., Liquid-phase catalytic oxidation of p-xylene. Ind. Eng. Chem. Res., 31 (1992), 453–62.Google Scholar
Partenheimer, W., Methodology and scope of metal/bromide autoxidation of hydrocarbons. Catal. Today, 23 (1995), 69–158.Google Scholar
Sheehan, R. J., Terephthalic acid, dimethyl terephthalate, and isophthalic acid. In Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim: Wiley-VCH, 2012), pp. 17–28.Google Scholar
Weissermel, K. and Arpe, H.-J., Industrial Organic Chemistry, 3rd ed. (Weinheim: Wiley-VCH, 1997).Google Scholar
Abrams, K. J., Process for Preparing Aromatic Carboxylic Acids with Efficient Energy Recovery by the Oxidation of Aromatic Hydrocarbon Feedstocks, U.S. patent 5,723,656A. 1998-03-03.Google Scholar
Tashiro, Y., Iwahama, T., Sakaguchi, S. and Ishii, Y., A new strategy for the preparation of terephthalic acid by the aerobic oxidation of p-xylene using N-hydroxyphthalimide as a catalyst. Adv. Synth. Catal., 343 (2001), 220–25.Google Scholar
Hashmi, S. M. A. and Al-Luhaidan, S., Process for Preparing Purified Terephthalic Acid. EP 1671938 A1. 2006-06-21.Google Scholar
Ure, A. M. and Parker, D., Methods, Processes, and System for Treating and Purifying Crude Terephthalic Acid and Associated Process Streams, International patent application WO 2010/122304 A1. 2010-10-28.Google Scholar
Meyer, D. H., Fiber-grade Terephthalic Acid by Catalytic Hydrogen Treatment of Dissolved Impure Terephthalic Acid, U. S. patent 3,584,039. 1971-06-08.Google Scholar
Li, M., Niu, F., Zuo, X., Metelski, P. D., Busch, D. H. and Subramaniam, B., A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid. Chem. Eng. Sci., 104 (2013), 93–102.Google Scholar
Squeezing Profitability from the PTA/PET Value Chain: Impact of the Latest Technology Advances (White Plains, New York: Nexant, 2005).Google Scholar
Zuo, X., Niu, F., Snavely, W. K., Subramaniam, B. and Busch, D. H., Liquid phase oxidation of p-xylene to terephthalic acid at medium-high temperatures: Multiple benefits of CO2 expanded liquids. Green Chem., 12 (2010), 260–67.Google Scholar
Lin, R., De Vreede, M., Sluijmers, J. W., de Boer, M. and Woodruff, T. E., Method for Oxidizing a Slurry Composition in a Post Oxidation Zone in the Presence of Added Steam, U.S. patent 7,342,128 B2. 2008-3-11.Google Scholar
Dunn, J. B. and Savage, P. E., Terephthalic acid synthesis in high-temperature liquid water. Ind. Eng. Chem. Res., 39 (2002), 4460–65.Google Scholar
Dunn, J. B., Urquhart, D. I. and Savage, P. E., Terephthalic acid synthesis in supercritical water. Adv. Synth. Catal., 344 (2002), 385–92.Google Scholar
Hamley, P. A., Ilkenhans, T., Webster, J. M., Garcia-Verdugo, E., Venardou, E., Clarke, M. J., Auerbach, R., Thomas, W. B., Whiston, K. and Poliakoff, M., Selective partial oxidation in supercritical water: The continuous generation of terephthalic acid from para-xylene in high yield. Green Chem., 4 (2002), 235–38.Google Scholar
Garcia-Verdugo, E., Fraga-Dubreuil, J., Hamley, P. A., Thomas, W. B., Whiston, K. and Poliakoff, M., Simultaneous continuous partial oxidation of mixed xylenes in supercritical water. Green Chem., 7 (2005), 294–300.Google Scholar
Fraga-Dubreuil, J. and Poliakoff, M., Organic reactions in high-temperature and supercritical water. Pure Appl. Chem., 78 (2006), 1971–82.Google Scholar
Li, K.-T. and Li, S.-W., CoBr2-MnBr2 containing catalysts for catalytic oxidation of p-xylene to terephthalic acid. Appl. Catal. A: Gen., 340 (2008), 271–77.Google Scholar
Subramaniam, B., Busch, D. H. and Niu, F., Spray Process for Selective Oxidation, U.S. patent 9,238,608 B2. 2016-01-19.Google Scholar
Santacesaria, E., Di Serio, M. and Iengo, P., Mass transfer and kinetics in ethoxylation spray tower loop reactors. Chem. Eng. Sci., 54 (1999), 1499–504.Google Scholar
Cussler, E. L., Diffusion: Mass Transfer in Fluid Systems, 3rd ed. (New York: Cambridge University Press, 2009).Google Scholar
Cao, G., Pisu, M. and Morbidelli, M., A lumped kinetic model for liquid-phase catalytic oxidation of p-xylene to terephthalic acid. Chem. Eng. Sci., 49 (1994), 5775–83.Google Scholar
Cao, G., Servida, A. and Pisu, M., Kinetics of p-xylene liquid-phase catalytic oxidation. AIChE J., 40 (1994), 1156–66.Google Scholar
Cincotti, A., Orrù, A. and Cao, G., Effect of catalyst concentration and simulation of precipitation processes on liquid-phase catalytic oxidation of p-xylene to terephthalic acid. Chem. Eng. Sci., 52 (1997), 4205–13.Google Scholar
Wang, Q., Li, X., Wang, L., Cheng, Y. and Xie, G., Kinetics of p-xylene liquid-phase catalytic oxidation to terephthalic acid. Ind. Eng. Chem. Res., 44 (2005), 261–66.Google Scholar
Yan, X., Data mining macrokinetic approach based on ANN and its application to model industrial oxidation of p-xylene to terephthalic acid. Chem. Eng. Sci., 62 (2007), 2641–51.Google Scholar
Lange, N., Lange’s Handbook of Chemistry, 15th ed. (New York: McGraw-Hill, 1999).Google Scholar
Aspen HYSYS®, Version 7.1 (Calgary, Alberta, Canada: Aspen Technologies, 2009).Google Scholar
Hilmen, E. K., Separation of azeotropic mixtures: Tools for analysis and studies on batch distillation operation. PhD dissertation, Norwegian University of Science and Technology (2000).Google Scholar
Melhem, G. A., 1997. A detailed method for estimating mixture flammability limits using chemical equilibrium. Process Saf. Prog., 16 (1997), 203–18.Google Scholar
Rajagopalan, B., Investigation of dense CO2 as a solvent medium for the catalytic oxidation of hydrocarbons. PhD dissertation, University of Kansas (2007).Google Scholar
Krag, P. W. and Henson, H. R., 1993. Materials selection for sulfide pressure oxidation autoclaves. Flammability and Sensitivity of Materials in Oxygen-Enriched Atmospheres: 6th Volume ASTM STP 1197 (Philadelphia: American Society for Testing and Materials, 1993).Google Scholar
Osada, M. and Savage, P. E., Terephthalic acid synthesis at higher concentrations in high-temperature liquid water. 1. Effect of oxygen feed method. AIChE J., 55 (2009), 710–16.Google Scholar
Roffia, P., Callni, P. and Motta, L., Byproduct identification in the terephthalic acid production process and possible mechanisms of their formation. Ind. Eng. Res. Prod. Res. Develop., 23 (1984), 629–34.Google Scholar
Li, M., A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid. PhD dissertation, University of Kansas (2013).Google Scholar
Schwarz, J., Beloff, B. and Beaver, E.. Use sustainability metrics to guide decision-making. Chem. Eng. Sci., 98 (2002), 58–63.Google Scholar
Dunn, J. B. and Savage, P. E., Economic and environmental assessment of high-temperature water as a medium for terephthalic acid synthesis. Green Chem., 5 (2003), 649–55.Google Scholar
Li, M., Ruddy, T., Fahey, D. R., 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
Aspen HYSYS®, Version 7.3 (Calgary, Alberta, Canada: Aspen Technologies, 2013).Google Scholar
Piras, L., Chiarelli, M., Schena, S. and Soro, L., Process for the Recovery of Purified Terephthalic Acid, U.S. patent 6,639,104 B2. 2003-10-28.Google Scholar
Donaldson, P. A., Gardner, M. W., Hollins, A. M., Milne, I. P., Usher, G. W. and Ward, P. N., Production of Aromatic Carboxylic Acids, European patent application EP0937026 A1. 1999-08-25.Google Scholar
Hsu, Y. and Lin, C., Process for Producing Highly Pure Aromatic Carboxylic Acids, U.S. patent 6,245,939 B1. 2001-06-12.Google Scholar
Parten, W. D. and Ure, A. M., Dehydration of Acetic Acid by Azeotropic Distillation in the Production of an Aromatic Acid, U.S. patent 5,980,696. 1999-11-09.Google Scholar
Peters, M. S., Timmerhaus, K. D. and West, R. E., Plant Design and Economics for Chemical Engineers, 5th ed. (Boston, MA: McGraw Hill, 2004).Google Scholar
Walas, S. M., Chemical Process Equipment: Selection and Design (Stoneham, MA: Butterworth Publishers, 1988).Google Scholar
Lozowski, D., Business news. Chem. Eng., 119 (2012), 63–64.Google Scholar
U.S. Energy Information Administration. Available at: www.eia.gov, last accessed May 25, 2020.Google Scholar
U.S. Bureau of Labor Statistics. Available at: www.bls.gov/oes/, last accessed May 25, 2020.Google Scholar
ICIS. Available at: www.icis.com/explore/commodities/chemicals/xylenes/ , last accessed Jan 2013.Google Scholar
GaBi, Version 6 (Germany: PE International, 2012).Google Scholar
Bare, J. C., Hofstetter, P., Pennington, D. W. and Udo de Haes, H. A., Life cycle impact assessment workshop summary: midpoints versus endpoints: The sacrifices and benefits. Int. J. Life Cycle Assess., 5 (2000), 319–26.Google Scholar
Bare, J. C., Developing a Consistent Decision-making Framework by Using the U.S. EPA’s TRACI (Cincinnati, OH: US Environmental Protection Agency, 2002). Available at: https://clu-in.org/conf/tio/lcia/AICHE2002paper.pdf, last accessed June 2, 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
Curran, M. A., The status of life-cycle assessment as an environmental management tool. Environ. Prog., 23 (2004), 277–83.Google Scholar
Baitz, M., Colodel, C. M., Kupfer, T., Pflieger, J., Schuller, O., Hassel, F., Kokborg, M., Köhler, A. and Stoffregen, A., GaBi Database & Modelling Principles 2012: Quantifying Uncertainty in GaBi (Germany: PE International, 2012).Google Scholar
Partenheimer, W. A., Chemical model for the Amoco “MC” oxygenation process to produce terephthalic acid. In Catalysis of Organic Reactions, ed. Blackburn, D. W. (New York: Marcel Dekker, Inc., 1990), pp. 321–46.Google Scholar
Royall, D. J., Bartlett, J. A. and Fairhurst, R. G., Production of Aromatic Carboxylic Acids and Recovery of Co/Mn Catalyst from Ash, U.S. patent 6,255,510 B1. 2001-07-03.Google Scholar
Turner, J. A. and Jeffery, I. C., Effluent Gas Treatment, WO patent application 96/39595. 1996-12-12.Google Scholar
Romanenko, A. V., Likholobov, V. A., Timofeeva, M. N., Hva, J. S. and Seok, P. J., Catalytic Composition, Method for Manufacturing Thereof and Method for the Purification of Terephthalic Acid, U.S. patent 6,753,290 B1. 2004-06-22.Google Scholar
BASF Catalysts – Metal Prices. Available at: http://apps.catalysts.basf.com/apps/eibprices/mp/, last accessed May 27, 2020.Google Scholar
TRI Explorer. Available at: https://enviro.epa.gov/triexplorer/tri_release.chemical, last accessed May 27, 2020.Google Scholar
GHG Data Publication Tool. Available at: https://ghgdata.epa.gov/ghgp/main.do, last accessed May 27, 2020.Google Scholar
Burgess, A. A. and Brennan, D. J., Application of life cycle assessment to chemical processes. Chem. Eng. Sci., 56 (2001), 2589–604.Google Scholar
Schaich, J. R., Estimate fugitive emissions from process equipment. Chem. Eng. Prog., 87 (1991), 31–35.Google Scholar
Siegell, J. H., Improve VOC emission predictions. Hydrocarb. Process., 76 (1997), 119–21.Google Scholar
Shonnard, D. R. and Hiew, D., Comparative environmental assessments of VOC recovery and recycle design alternatives for a gaseous waste stream. Environ. Sci. Technol., 34 (2000), 5222–28.Google Scholar
Allen, D. T. and Shonnard, D. R., Green Engineering: Environmentally Conscious Design of Chemical Processes (Upper Saddle River, NJ: Prentice-Hall, Inc., 2002).Google Scholar
BP. Annual Report and Form 20-F 2011. Available at: bp.com/annualreport, last accessed May 27, 2020.Google Scholar
Bode, C. J., Chapman, C., Pennybaker, A. and Subramaniam, B., Developing students’ understanding of industrially relevant economic and life cycle assessments. J. Chem. Educ., 94 (2017), 1798–801.Google Scholar
Chang, C.-C., Green, S. K., Williams, C. L., Dauenhauer, P. J. and Fan, W., Ultra-selective cycloaddition of dimethylfuran for renewable p-xylene with H-BEA. Green. Chem., 16 (2014), 585–88.Google Scholar
Pang, J., Zheng, M., Sun, R., Wang, A., Wang, X. and Zhang, T., Synthesis of ethylene glycol and terephthalic acid from biomass for producing PET. Green. Chem., 18 (2016), 342–59.Google Scholar
Volanti, M., Cespi, D., Passarini, F., Neri, E., Cavani, F., Miszey, P. and Fozer, D., Terephthalic acid from renewable resources: early-stage sustainability analysis of a bio-PET precursor. Green Chem., 21 (2019), 885–96.Google Scholar
Bozell, J. J. and Petersen, G. R., Technology development for the production of biobased products from biorefinery carbohydrates: The US Department of Energy’s “Top 10” revisited. Green Chem., 12 (2010) 539–54.Google Scholar
Sajid, M., Zhao, X. and Liu, D., Production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): Recent progress focusing on chemical-catalytic routes. Green Chem., 20 (2018), 5427–53.Google Scholar
Eerhart, A. J. J. E., Faaij, A. P. C. and Patel, M. K., Replacing fossil based PET with biobased PEF; process analysis, energy and GHG balance. Energy Environ. Sci., 5 (2012), 6407–22.Google Scholar
Zuo, X., Venkitasubramanian, P., Busch, D. H. and Subramaniam, B., Optimization of Co/Mn/Br-catalyzed oxidation of 5-hydroxymethylfurfural to enhance 2,5-furandicarboxylic acid yield and minimize substrate burning. ACS Sustain. Chem. Eng., 4 (2016), 3659–68.Google Scholar
Zuo, X., Venkitasubramanian, P., Martin, K. J. and Subramaniam, B., Facile production of 2,5-furandicarboxylic acid via oxidation of industrially sourced crude 5-hydroxymethylfurfural. ChemSusChem (2021). https://doi.org/10.1002/cssc.202102050Google Scholar
Zuo, X., Chaudhari, A. S., Snavely, K. W., Niu, F., Zhu, H., Martin, K. J. and Subramaniam, B., Kinetics of 5-hydroxymethylfurfural oxidation to 2,5-furandicarboxylic acid with Co/Mn/Br catalyst. AIChE J., 62 (2017) 162–71.Google Scholar
Subramaniam, B., Zuo, X., Busch, D. H. and Venkitasubramanian, P., Process for Producing both Biobased Succinic Acid and 2,5-Furandicarboxylic Acid, WO patent application 2013/033081 A3. 2013-03-07.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
×