skip to main content

Thermodynamic Study of One-step Production from Isobutene to Methyl Methacrylate

1School of Energy and Chemical Engineering, Xiamen University Malaysia, Jalan Sunsuria, Bandar Sunsuria, 43900 Sepang, Selangor Darul Ehsan, Malaysia

2Kelip-kelip! Center of Excellence for Light Enabling Technologies, School of Energy and Chemical Engineering, Xiamen University Malaysia, Jalan Sunsuria, Bandar Sunsuria, 43900 Sepang, Selangor Dahrul Ehsan, Malaysia.

3College of Chemistry and Chemical Engineering, Xiamen University, 361005 Xiamen, China

4 Department of Petroleum Technology and Alternative Fuels, Faculty of Environmental Technology, UCT, Prague, Technická 5, 160 00 Praha 6-Dejvice, Czech Republic

5 Department of Chemical Education, Universitas Mulawarman, Kampus Gunung Kelua, Samarinda, 75119, East Kalimantan, Indonesia

View all affiliations
Received: 17 Aug 2022; Revised: 10 Sep 2022; Accepted: 10 Sep 2022; Available online: 21 Sep 2022; Published: 30 Sep 2022.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2022 by Authors, Published by BCREC Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.

Citation Format:
Cover Image

Methyl methacrylate (MMA) has emerged as an essential industrial monomer. However, the toxic by-production and shortage supply of MMA in the global market has gained great attention. Herein, a one-step synthesis to produce MMA from isobutene via a direct oxidative esterification process has been demonstrated to curb the aforementioned downsides. Thermodynamic analysis via Gibbs free energy minimization method proved the feasibility of this route via the equilibrium constant. Despite tert-butanol and isobutane showed higher equilibrium constant than isobutene, they should be avoided. Isobutane is highly flammable while the precursor of tert-butanol is exorbitant. Thus, isobutene was selected for the equilibrium compositions screening. Isobutene conversion was 90% and 15% MMA yield at 700 °C and IBN: O2: MeOH ratio with 1:7:1. This route is mainly limited by the generation of side reactions from the reaction of CH3OH and O2. By varying the feedstock ratio at 1:2:1, the MMA yield increased to ~25%. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (


Fulltext View|Download
Keywords: Thermodynamic Analysis; Sustainable; One-step Production; Methyl Methacrylate; Isobutene
Funding: Hengyuan International Sdn. Bhd. under contract EENG/0003; Xiamen University Malaysia Research Fund under contract XMUMRF/2019-C4/IENG/0019; Xiamen University Malaysia Research Fund under contract XMUMRF/2020-C5/IENG/0029

Article Metrics:

  1. Nagai, K. (2001). New developments in the production of methyl methacrylate. Applied Catalysis A: General, 221(1–2), 367–377. DOI: 10.1016/S0926-860X(01)00810-9
  2. Darabi Mahboub, M.J., Dubois, J.L., Cavani, F., Rostamizadeh, M., Patience, G.S. (2018). Catalysis for the synthesis of methacrylic acid and methyl methacrylate. Chemical Society Reviews, 47(20), 7703–7738. DOI: 10.1039/c8cs00117k
  3. Nagai, K., Ui, T. (2004). Trends and Future of Monomer-MMA Technologies. Sumitomo Kagaku, 1–12
  4. Schunk, S.A., Brem, N. (2011). Routes to methacrylic acid via partial oxidation. In: Hess, C., Schlögl, R. (eds) Nanostructured Catalysts: Selective Oxidation. London: Royal Society of Chemistry (RSC)
  5. Rostamizadeh, M., Taeb, A. (2016). Synthesis and Characterization of HZSM-5 Catalyst for Methanol to Propylene (MTP) Reaction. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 46(5), 665–671. DOI: 10.1080/15533174.2014.988825
  6. Rostamizadeh, M., Taeb, A. (2015). Highly selective Me-ZSM-5 catalyst for methanol to propylene (MTP). Journal of Industrial and Engineering Chemistry, 27, 297–306. DOI: 10.1016/j.jiec.2015.01.004
  7. Gogate, M.R., Spivey, J.J., Zoeller, J.R. (1997). Synthesis of methyl methacrylate by vapor phase condensation of formaldehyde with propionate derivatives. Catalysis Today, 36, 243–254. DOI: 10.1016/S0920-5861(96)00241-6
  8. Merger, F., Foerster, H.-J. (1983). Preparation of alpha-alkylacroleins. 4408079
  9. Guo, X., Huang, C., Chen, B. (2008). One-step synthesis of methylmethacrylate from methacrolein over Keggin-type heteropoly compounds. Korean Journal of Chemical Engineering, 25(4), 675–680. DOI: 10.1007/s11814-008-0111-5
  10. Jing, F., Katryniok, B., Dumeignil, F., Bordes-Richard, E., Paul, S. (2014). Catalytic selective oxidation of isobutane to methacrylic acid on supported (NH4)3HPMo11VO40 catalysts. Journal of Catalysis, 309, 121–135. DOI: 10.1016/j.jcat.2013.09.014
  11. Spivey, J.J., Gogate, M.R., Zoeller, J.R., Colberg, R.D. (1997). Novel Catalysts for the Environmentally Friendly Synthesis of Methyl Methacrylate. Industrial and Engineering Chemistry Research, 36(11), 4600–4608. DOI: 10.1021/ie970139r
  12. Ballarini, N., Cavani, F., Degrand, H., Etienne, E., Pigamo, A., Trifirò, F., Dubois, J.L. (2007). The Oxidation of Isobutane to Methacrylic Acid: An Alternative Technology for MMA Production. IN: Tundo, P., Perosa, A., Zecchini, F. (Eds.) Methods and Reagents for Green Chemistry: An Introduction, 265–279. DOI: 10.1002/9780470124086.ch14
  13. Guan, Y., Ma, H., Chen, W., Li, M., Qian, G., Chen, D., Zhou, X., Duan, X. (2020). Methyl methacrylate synthesis: Thermodynamic analysis for oxidative esterification of methacrolein and aldol condensation of methyl acetate. Industrial and Engineering Chemistry Research, 59(39), 17408–17416. DOI: 10.1021/acs.iecr.0c02017
  14. Cavani, F., Mezzogori, R., Pigamo, A., Trifirò, F., Etienne, E. (2001). Main aspects of the selective oxidation of isobutane to methacrylic acid catalyzed by Keggin-type polyoxometalates. Catalysis Today, 71(1–2), 97–110. DOI: 10.1016/S0920-5861(01)00435-7
  15. Okuhara, T., Mizuno, N., Misono, M. (2001). Catalysis by heteropoly compounds-recent developments. Applied Catalysis A: General, 222(1–2), 63–77. DOI: 10.1016/S0926-860X(01)00830-4
  16. Cavani, F., Trifirò, F. (1999). Selective oxidation of light alkanes: Interaction between the catalyst and the gas phase on different classes of catalytic materials. Catalysis Today, 51(3–4), 561–580. DOI: 10.1016/S0920-5861(99)00041-3
  17. Abe, T. (1999). New process for methylmethacrylate MGC’s New ACH Process for MMA. Studies in Surface Science and Catalysis, 121(C), 461–464. DOI: 10.1016/S0167-2991(99)80119-0
  18. Drent, E., Arnoldy, P., Budzelaar, P.H.M. (1994). Homogeneous catalysis by cationic palladium complexes . Precision catalysis in the carbonylation of alkynes. Journal of Organometallic Chemistry, 475, 57–63. DOI: 10.1016/0022-328X(94)84007-5
  19. Mizuno, M., Seo, T., Suzuta, T. (2009). Production method of methyl methacrylate. 1–6
  20. Liu, C., Sun, J., Smith, C., Wang, Y. (2013). A study of ZnxZryOz mixed oxides for direct conversion of ethanol to isobutene. Applied Catalysis A: General, 467, 91–97. DOI: 10.1016/j.apcata.2013.07.011
  21. Leeuwen, B.N.M.v., Wulp, A.M.v.d., Duijnstee, I., Maris, A.J.A.., Straathof, A.J.J. (2012). Fermentative production of isobutene. Applied Microbiology and Biotechnology, 93, 1377–1387. DOI: 10.1007/s00253-011-3853-7
  22. Gao, J., Fan, G., Yang, L., Cao, X., Zhang, P., Li, F. (2017). Oxidative esterification of methacrolein to methyl methacrylate over gold nanoparticles on hydroxyapatite. ChemCatChem, 9(7), 1230–1241. DOI: 10.1002/cctc.201601560
  23. Song, N., Rhodes, C., Bartley, J.K., Taylor, S.H., Chadwick, D., Hutchings, G.J. (2005). Oxidation of isobutene to methacrolein using bismuth molybdate catalysts: Comparison of operation in periodic and continuous feed mode. Journal of Catalysis, 236(2), 282–291. DOI: 10.1016/j.jcat.2005.10.008
  24. Weber, D., Weidler, P., Kraushaar-Czarnetzki, B. (2017). Partial oxidation of isobutane and isobutene to methacrolein over a novel Mo–V–Nb(–Te) mixed oxide catalyst. Topics in Catalysis, 60(17–18), 1401–1407. DOI: 10.1007/s11244-017-0830-0
  25. Kurimoto, I., Hashiba, H., Onodera, H., Aoki, Y. (1992). Catalyst for the production of methacrylic acid. 5153162
  26. Wilczynski, R., Jerrick Juliette, J. (2007). Methacrylic acid and derivatives. Kirk-Othmer Encyclopedia of Chemical Technology. Wiley-VCH Verlag GmbH & Co. KGaA
  27. Li, H., Tan, Y., Chen, X., Yang, W., Huang, C., Li, J., Ding, Y. (2021). Efficient synthesis of methyl methacrylate by one step oxidative esterification over Zn-Al-mixed oxides supported gold nanocatalysts. Catalysts, 11(2), 1–16. DOI: 10.3390/catal11020162
  28. Shreiber, E.H., Mullen, J.R., Gogate, M.R., Spivey, J.J., Roberts, G.W. (1996). Thermodynamics of methacrylate synthesis from methanol and a propionate. Industrial and Engineering Chemistry Research, 35(7), 2444–2452. DOI: 10.1021/ie9507134
  29. Yaws, C.L. (1999). Chemical properties handbook: Physical, thermodynamics, environmental transport, safety & health related properties for organic. McGraw-Hill Education, 1999
  30. Li, Y., Zhang, Z., Wang, J., Ma, C., Yang, H., Hao, Z. (2015). Direct dehydrogenation of isobutane to isobutene over carbon catalysts. Chinese Journal of Catalysis, 36(8), 1214–1222. DOI: 10.1016/S1872-2067(15)60914-7
  31. Zhang, L., Paul, S., Dumeignil, F., Katryniok, B. (2021). Selective oxidation of isobutane to methacrylic acid and methacrolein: A critical review. Catalysts, 11(7), 769. DOI: 10.3390/catal11070769
  32. Anonymous (2021). Propylene oxide market, in Propylene oxide market by application (polyether polyols, propylene glycols),production process (chlorohydrin, styrene monomer, cumene based), end-use industry (automotive, building & construction), and geography - Global foreca. In: 2 July 2021.
  33. Bohre, A., Avasthi, K., Novak, U., Likozar, B. (2021). Single-Step Production of Bio-Based Methyl Methacrylate from Biomass-Derived Organic Acids Using Solid Catalyst Material for Cascade Decarboxylation-Esterification Reactions. ACS Sustainable Chemistry and Engineering, 9(7), 2902–2911. DOI: 10.1021/acssuschemeng.0c08914
  34. Wang, G., Cai, G. (2021). Cooperative catalytic effects between Brønsted and Lewis acid sites and kinetics for production of methyl methacrylate on SO42−/TiO2-SiO2. Chemical Engineering Science, 229, 116165. DOI: 10.1016/j.ces.2020.116165
  35. Ran, R., Li, J., Wang, G., Li, Z., Li, C. (2019). Esterification of Methacrylic Acid with Methanol: Process Optimization, Kinetic Modeling, and Reactive Distillation. Industrial and Engineering Chemistry Research, 58(6), 2135–2145. DOI: 10.1021/acs.iecr.8b03842
  36. Harilal, A., Dasireddy, V.D.B.C., Friedrich, H.B. (2018). Effect of water and methanol in the production of methyl methacrylate over iron phosphate catalysts. Reaction Kinetics, Mechanisms and Catalysis, 124(1), 265–277. DOI: 10.1007/s11144-017-1331-7
  37. Li, B., Yan, R., Wang, L., Diao, Y., Li, Z., Zhang, S. (2014). SBA-15 supported cesium catalyst for methyl methacrylate synthesis via condensation of methyl propionate with formaldehyde. Industrial and Engineering Chemistry Research, 53(4), 1386–1394. DOI: 10.1021/ie403422s
  38. Jiang, L., Diao, Y., Han, J., Yan, R., Zhang, X., Zhang, S. (2014). MgO-SBA-15 supported Pd-Pb catalysts for oxidative esterification of methacrolein with methanol to methyl methacrylate. Chinese Journal of Chemical Engineering, 22(10), 1098–1104. DOI: 10.1016/j.cjche.2014.08.002

Last update:

No citation recorded.

Last update:

No citation recorded.