Skip to main content
SpringerLink
Log in

Waste-Reducing Catalytic Oxidation of m-Xylene to m-Toluic Acid

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

Catalytic performances of soluble Co, Co/Mn, Co/Mn/Br, and Co/Mn/Ce catalysts for m-xylene (MX) oxidation without acetic acid (HAc) solvent were studied, comparing with Co/HAc catalysts. In m-toluic acid (MTA) production, a Ce-salt promoter could effectively substitute for bromide salts and the recycle alcohol/aldehyde liquid mixture acts as a more efficient promotor than either peroxides or MTA itself. The Co/Mn/Ce system, free of acetic acid and Br−, was a superior catalyst in terms of activity and selectivity to MTA. Just as for p-xylene oxidation using Co/Mn/Br catalysts, both the MX reaction rate and the MTA selectivity increased with temperature when using Co/Mn/Ce catalysts. Unlike p-xylene oxidation however, MX oxidation resulted in more coupling products. For MX oxidation catalyzed by a supported Co-imide complex in supercritical CO2, the activity was lower by more than an order of magnitude, but the MTA selectivity was greater.

Graphical Abstract

The selectivity behavior of the catalyst systems indicate that the Co/Mn/Ce system, free of acetic acid solvent and corrosive Br−, was a superior catalyst, both in terms of overall activity and selectivity for MTA.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Scheme 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Raghavendrachar P, Ramachandran S (1992) Liquid-phase catalytic oxidation of p-xylene. Ind Eng Chem Res 31:453–462

    Article  CAS  Google Scholar 

  2. Partenheimer W (2014) The influence of pH in metal/bromide catalyzed homogeneous aerobic oxidation. Part 1. Effect on activity and selectivity of p-xylene oxidation. Appl Catal A 481:183–189

    Article  CAS  Google Scholar 

  3. Li K-T, Li S-W (2008) CoBr 2-MnBr2 containing catalysts for catalytic oxidation of p-xylene to terephthalic acid. Appl Catal A 340:271–277

    Article  CAS  Google Scholar 

  4. Chavan SA, Halligudi SB, Srinivas D, Ratnasamy P (2000) Formation and role of cobalt and manganese cluster complexes in the oxidation of p-xylene. J Mol Catal A Chem 161:49–64

    Article  CAS  Google Scholar 

  5. Falcon H, Campos-Martin JM, Al-Zahrani SM, Fierro JLG (2010) Liquid-phase oxidation of p-xylene using N-hydroxyimides. Catal Commun 12:5–8

    Article  CAS  Google Scholar 

  6. Tomás RAF, Bordado JCM, Gomes JFP (2013) p-Xylene oxidation to terephthalic acid: a literature review oriented toward process optimization and development. Chem Rev 113:7421–7469

    Article  Google Scholar 

  7. Grane HR (1974) Method for the production of phthalic and toluic acids by the catalytic oxidation of xylenes, US Patent Application 05/316,186., Atlantic Richfield Company, USA, p 3

  8. Golubev GS, Aleksandrov VN, Gitis SS, Savinova VV, Zabelina GV (1971) Some reactions accompanying auto-oxidation of m-xylene. Pet Chem USSR 11:152–156

    Google Scholar 

  9. Longland G (1974) Integration of para-or meta-xylene oxidation to terephthalic acid or isophthalic acid and its purification by hydrogen treatment of aqueous solution, US Patent 3839436 A, Standard Oil Co., USA

  10. Marsh DR, Stark LE (1980) Apparatus for iso- or terephthalic acid production in and recovery from benzoic acid-water solvent system, US Patent 4185073 A., Standard Oil Co., USA

  11. Jhung SH, Lee KH, Park Y-S (2002) Liquid Phase oxidation of xylenes: effects of water concentration and alkali metals. Bull Korean Chem Soc 23:59–64

    Article  CAS  Google Scholar 

  12. Long X-L, Wang Z-H, Wu S-Q, Wu S-M, Lu H-F, Yuan W-K (2014) Production of isophthalic acid from m-xylene oxidation under the catalysis of the H3PW12O40/carbon and cobalt catalytic system. J Ind Eng Chem 20:100–107

    Article  CAS  Google Scholar 

  13. Acharyya SS, Ghosh S, Bal R (2015) Fabrication of three dimensional (3D) hierarchical Ag/WO3 flower-like catalyst materials for the selective oxidation of m-xylene to isophthalic acid. Chem Commun 51:5998–6001

    Article  CAS  Google Scholar 

  14. Hirose I, Yamamoto K, Okitsu H (1982) Process for preparing benzenecarboxylic acids, US Patent 4,354,037., Teijin Ltd., JP

  15. Partenheimer W (2001) The structure of metal/bromide catalysts in acetic acid/water mixtures and its significance in autoxidation. J Mol Catal A: Chem 174:29–33

    Article  CAS  Google Scholar 

  16. Albarran G, Munguia JS (2014) Radiolytic oxidation of xylenes by.OH radicals. Radiat Phys Chem 97:90–94

    Article  CAS  Google Scholar 

  17. Xu B, Qi R, Zhong W, Du W, Qian F (2013) Optimization of p-xylene oxidation reaction process based on self-adaptive multi-objective differential evolution. Chemom Intell Lab Syst 127:55–62

    Article  CAS  Google Scholar 

  18. Hanotier J, Hanotier-Bridoux M (1981) Mechanism of the liquid phase homogeneous oxidation of alkylaromatic hydrocarbons by cobalt salts. J Mol Catal 12:133–147

    Article  CAS  Google Scholar 

  19. Cao G, Servida A, Pisu M, Morbidelli M (1994) Kinetics of p-xylene liquid-phase catalytic oxidation. AIChE J 40:1156–1166

    Article  CAS  Google Scholar 

  20. Chavan SA, Srinivas D, Ratnasamy P (2001) A novel, zeolite-encapsulated μ3-oxo Co/Mn cluster catalyst for oxidation of para-xylene to terephthalic acid. Chem Commun 12:1124–1125

    Article  Google Scholar 

  21. Nakaoka K, Miyama Y, Matsuhisa S, Wakamatsu S (1973) Preparation of terephthalic acid using paraldehyde promotor ind. Eng Chem Prod Res Develop 12:150–155

    Article  CAS  Google Scholar 

  22. Li M, Niu F, Zuo X, Metelski PD, Busch DH, Subramaniam B (2013) A spray reactor concept for catalytic oxidation of p-xylene to produce high-purity terephthalic acid. Chem Eng Sci 104:93–102

    Article  CAS  Google Scholar 

  23. Patton JW, Seppi NF (1970) Terephthalic Acid from p-Xylene. Ind. Eng. Chem. Prod. Res. Develop. 9:521–524

    Article  CAS  Google Scholar 

  24. Murphy EF, Schmid L, Burgi T, Maciejewski M, Baiker A (2001) Nondestructive sol-gel immobilization of metal(salen) catalysts in silica aerogels and xerogels. Chem Mater 13:1296–1304

    Article  CAS  Google Scholar 

  25. Musie GT, Wei M, Subramaniam B, Busch DH (2001) Autoxidation of substituted phenols catalyzed by cobalt schiff base complexes in supercritical carbon dioxide. Inorg Chem 40:3336–3341

    Article  CAS  Google Scholar 

  26. Song Y, Hart K, Dooley K (2004) Waste-reducing catalysis for acylation of a secondary amine: synthesis of DEET. Catal Lett 98:69–73

    Article  CAS  Google Scholar 

  27. Zhang Y, Li X, Yu G, Cheng Y (2006) Kinetics of liquid phase catalytic oxidation of m-xylene to isophthalic acid (Chinese). Chem React Eng Technol 22:97–102

    CAS  Google Scholar 

  28. Parshall GW (1980) Homogeneous catalysis. Wiley, New York

    Google Scholar 

  29. Wang Q, Zhang Y, Cheng Y, Li X (2008) Reaction mechanism and kinetics for the liquid-phase catalytic oxidation of meta-xylene to meta-phthalic acid. AIChE J 54:2674–2688

    Article  CAS  Google Scholar 

  30. Qin Z-Z, Su T-M, Jiang Y-X, Ji H-B, Qin W-G (2014) Preparation of W-modified FeAMo catalyst and its applications in the selective oxidization ofp-xylene to terephthalaldehyde. Chem Eng J 242:414–421

    Article  CAS  Google Scholar 

  31. Sun W, Sun J, Xu Z, Zhao L (2015) Experimental study and modeling of homogenous catalytic oxidation of m-xylene to isophthalic acid. Ind Eng Chem Res 54:3293–3298

    Article  CAS  Google Scholar 

  32. Lv H-F, Wu S-Q, Liu N, Long X-L, Yuan W-K (2011) A study on the m-xylene oxidation to isophthalic acid under the catalysis of bromine-free homogeneous catalytic system. Chem Eng J 172:1045–1053

    Article  CAS  Google Scholar 

  33. Song Y (2002) Development of catalytic processes for aromatic amides and carboxylic acids, M.S. Thesis, Chemical Engineering, Louisiana State University, Baton Rouge, LA

  34. Tsuji Y, Ohsumi T, Kondo T, Watanabe Y (1986) Dodecacarbonyltriruthenium catalysed carbonylation of amines and hydroamidation of olefins. J Organomet Chem 309:333–344

    Article  CAS  Google Scholar 

  35. Carra S, Morbidelli M (1987) Gas-liquid reactors. Chemical Industries (Dekker) 545–666

  36. Yan WS, Liu QH, Wang C, Yang XY, Yao T, He JF, Sun ZH, Pan ZY, Hu FC, Wu ZY, Xie Z, Wei SQ (2014) Realizing ferromagnetic coupling in diluted magnetic semiconductor quantum dots. J Am Chem Soc 136:1150–1155

    Article  CAS  Google Scholar 

  37. Brill WF (1960) Terephthalic acid by single-stage oxidation. Ind Eng Chem 52:837–840

    Article  CAS  Google Scholar 

  38. Lide DR (2006) CRC handbook of chemistry and physics, 87th edn. CRC Press, Boca Raton

    Google Scholar 

  39. Damyanova S, Perez CA, Schmal M, Bueno JMC (2002) Characterization of ceria-coated alumina carrier. Appl Catal A 234:271–278

    Article  CAS  Google Scholar 

  40. He L, Yu Y, Zhang C, He H (2011) Complete catalytic oxidation of o-xylene over CeO2 nanocubes. J Environ Sci 23:160–165

    Article  CAS  Google Scholar 

  41. Hronec M, Ilavsky J (1984) Liquid phase oxidation of toluene to benzaldehyde by air. Ind Eng Chem Prod Res Dev 23:455–458

    Article  Google Scholar 

Download references

Acknowledgments

The authors thank MGK Co., EagleView Technologies, the Fundamental Research F unds for the Central Universities (FRF-BR-15-027A, FRF-BR-14-001B) and NSFC (Grant No. 51371018) for financial support. The authors thank Dana Doucet for experimental assistance.

Author information

Authors and Affiliations

  1. Center for Modern Physics Technology and Department of Applied Physics, School of Mathematics and Physics, University of Science and Technology Beijing, Beijing, 100083, China

    Yujun Song

  2. Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA, 70803, USA

    Yujun Song, Kathy T. Hart & Kerry M. Dooley

Authors
  1. Yujun Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kathy T. Hart
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kerry M. Dooley
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yujun Song.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Song, Y., Hart, K.T. & Dooley, K.M. Waste-Reducing Catalytic Oxidation of m-Xylene to m-Toluic Acid. Catal Lett 146, 1213–1220 (2016). https://doi.org/10.1007/s10562-016-1746-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-016-1746-1

Keywords

Search

Navigation