PROGRESS IN SIDE-CHAIN ALKYLATION OF TOLUENE WITH METHANOL TO STYRENE

Abstract

Abstract: The process of toluene-methanol side-chain alkylation to styrene is simple, and the raw materials are widely available and cheap. It is a significant way for industrial production of styrene. The mechanism and thermodynamics of side chain alkylation of toluene with methanol were introduced, the influence of catalyst properties on the reaction process was analyzed, and the research progress of zeolite and non-zeolite catalysts for the reaction in recent years was reviewed. The analysis shows that the research of side-chain alkylation catalyst for toluene mainly focuses on two aspects: one is the modification of X zeolite catalyst which controls the reaction process of reactants by adjusting the surface acid and base properties of X zeolite;the other is that developing new efficient side chain alkylation catalyst with matching acid-base properties and suitable pore structure is also the main research direction.

Key words: toluene, methanol, side-chain alkylation, styrene, acid-base catalysis

References

[1]谭捷. 国内外苯乙烯的供需现状及发展前景分析[J]. 乙醛醋酸化工, 2019(8):8-15.
[2]刘春玲. 苯乙烯生产现状及工艺技术进展[J]. 中国石油和化工标准与质量, 2012, 32(5):19-19.
[3]佚名. 美开发出甲苯甲醇制苯乙烯新工艺[J]. 天然气化工(C1化学与化工), 2010(4):69-69.
[4]许峰, 秦丽红, 刘亚录, 等. 甲苯-甲醇侧链烷基化制苯乙烯的研究进展[J]. 石油学报(石油加工), 2014, 30(2):311-319.
[5]王文月, 朱卫. 甲苯与甲醇侧链烷基化X型沸石催化剂的吸附量热研究[J]. 催化学报, 1998, 019(4):334-338.
[6]王文月, 沈俭一. X型沸石催化剂的甲苯甲醇侧链烷基化反应和吸附量热研究[J]. 无机化学学报, 1998, 014(3):322-326.
[7]Vasanthy B K, Palanichamy M, Krishnasamy V. Side chain alkylation of toluene with isopropanol and methanol over alkali exchanged zeolites[J]. Applied Catalysis. A: General, 1996, 148(1):51-61.
[8]Borgna A, Seplveda J, Magni S I, et al. Active sites in the alkylation of toluene with methanol：a study by selective acid-base poisoning[J]. Applied Catalysis A: General, 2004, 276(1-2):207-215．
[9]Giordano N, Pino L, Cavallaro S, et al. Alkylation of toluene with methanol on zeolites: The role of electronegativity on the chain or ring alkylation[J]. Zeolites, 1987, 7:131-134.
[10]Ko?ová G, Kotrla J, Ernst S, et al. Characterization of basic sites in zeolites for toluene side-chain alkylation with methanol[J]. Studies in surface science and catalysis, 2005, 158:1629-1636.
[11]Itoh H, Miyamoto A, Murakami Y. Mechanism of the side-chain alkylation of toluene with methanol[J]. Journal of Catalysis, 1980, 64(2):284-294.
[12]Wieland W S, Davis R J, Garces J M. Side-Chain Alkylation of Toluene with Methanol over Alkali-Exchanged Zeolites X, Y, L and β[J]. Journal of Catalysis, 1998, 173(2):490-500.
[13]Unland, Mark L. Infrared study of methanol decomposition on alkali metal X-type zeolites[J]. The Journal of Physical Chemistry, 1978, 82(5):580-583.
[14]Yashima T, Sato K, Hayasaka T, et al. Alkylation on synthetic zeolites III. Alkylation of toluene with methanol and formaldehyde on alkali cation exchanged zeolites[J]. Journal of Catalysis, 1972, 26(3):303-312.
[15]Palomares A E, Eder-Mirth G, Lercher J A. Selective alkylation of toluene over basic zeolites: an in situ infrared spectroscopic investigation[J]. Journal of Catalysis, 1997, 168(2):442-449.
[16]Rep M, Palomares A E, Eder-Mirth G , et al. Interaction of Methanol with Alkali Metal Exchanged Molecular Sieves. 1. IR Spectroscopic Study[J]. Journal of Physical Chemistry B, 2000, 104(35):8624-8630.
[17]Chen H, Li X, Zhao G, et al. Free radical mechanism investigation of the side-chain alkylation of toluene with methanol on basic zeolites X[J]. Chinese Journal of Catalysis, 2015, 36(10):1726-1732.
[18]Hunger M, Schenk U, Weitkamp J. Mechanistic studies of the side-chain alkylation of toluene with methanol on basic zeolites Y by multi-nuclear NMR spectroscopy[J]. Molecular Catalysis, 1998, 134(s1-3):97-109.
[19]Hattori H, Alabi W O, Jermy B R, et al. Pathway to Ethylbenzene Formation in Side-Chain Alkylation of Toluene with Methanol Over Cesium Ion-Exchanged Zeolite X[J]. Catalysis Letters, 2013, 143(10):1025-1029.
[20]Alabi W O, Tope B B, Jermy R B, et al. Modification of Cs-X for styrene production by side-chain alkylation of toluene with methanol[J]. Catalysis Today, 2014, 226(22):117-123.
[21]Garces J M, Vrieland G E, Bates S I, et al. Basic Molecular Sieve Catalysts Side-Chain Alkylation of Toluene By Methanol[J]. Studies in surface science and catalysis, 1985, 20:67-74.
[22]Li P, Han Q, Zhang X, et al. A new insight into the reaction behaviors of side-chain alkylation of toluene with methanol over CsX[J]. Catalysis science & technology, 2018, 8:3346-3356.
[23]Borgna A, Magni S, Sepúlveda J, et al. Side-chain alkylation of toluene with methanol on Cs-exchanged NaY zeolites: effect of Cs loading[J]. Catalysis Letters, 2005, 102(1-2):15-21.
[24]Han H, Liu M, Ding F, et al. Effects of Cesium Ions and Cesium Oxide in Side-Chain Alkylation of Toluene with Methanol over Cesium-Modified Zeolite X[J]. Industrial & Engineering Chemistry Research, 2016, 55(7):1849-1858
[25]Hattori H, Amusa A A, Jermy R B, et al. Zinc oxide as efficient additive to cesium ion-exchanged zeolite X catalyst for side-chain alkylation of toluene with methanol[J]. Journal of Molecular Catalysis A Chemical, 2016, 424:98-105.
[26]王宇红, 张志新, 周敬来. 甲苯/甲醇在碱性沸石上侧链烷基化反应的研究Ⅲ.X型沸石添加稀土元素La,Ce改性[J]. 天然气化工, 1998, 23(4):7-11.
[27]Han H, Liu M, Nie X, et al. The promoting effects of alkali metal oxide in side-chain alkylation of toluene with methanol over basic zeolite X[J]. Microporous & Mesoporous Materials, 2016, 234:61-72.
[28]Wieland W S, Davis R J, Garces J M. Solid base catalysts for side-chain alkylation of toluene with methanol[J]. Catalysis Today, 1996, 28(4):443-450.
[29]Li P, Han Q, Yuan Y, et al. The Role of Boron Sites in Side-chain Alkylation of Toluene with Methanol and a High Performance Composite Catalyst[J]. Catalysis Science & Technology, 2020,10:4321-4331.
[30]Wang H, Wang B, Wen Y, et al. High-Yielded Side-Chain Alkylation from Toluene and Methanol Over K3PO4/CsX[J]. Catalysis Letters, 2016, 147(1):1-6.
[31]林丹, 赵会民, 张小月, 等. 甲苯甲醇侧链烷基化反应中甲酸盐的形成及其作用[J]. 催化学报, 2012, 33(6):1041-1047.
[32]King S T, Garces J M. In situ infrared study of alkylation of toluene with methanol on alkali cation-exchanged zeolites[J]. Journal of Catalysis, 1987, 104(1):59-70.
[33]Philippou A, Anderson M W. Solid-State NMR Investigation of the Alkylation of Toluene with Methanol over Basic Zeolite X[J]. 1994, 116(13):5774-5783.
[34]Hunger M, Schenk U, Seiler M, et al. In situ MAS NMR spectroscopy of surface compounds formed from methanol and from a toluene/methanol mixture on basic zeolite X[J]. Journal of Molecular Catalysis A Chemical, 2000, 156(1):153-161.
[35]Tope B B, Alabi W O, Aitani A M, et al. Side-chain alkylation of toluene with methanol to styrene over cesium ion-exchanged zeolite X modified with metal borates[J]. Applied Catalysis A: General, 2012, 443(7):214-220.
[36]李永光, 畅晋英, 王建平. 甲苯甲醇侧链烷基化反应中沸石催化剂酸碱中心的作用Ⅱ.改性的X型和双组分改性的X/ZSM-5双沸石催化剂[J]. 燃料化学学报, 1993, 23(1):18-22.
[37]Wang X, Wang G, Shen D, et al. Side-chain alkylation of toluene with methanol on KX/KZSM-5 binary zeolite catalysts[J]. Zeolites, 1991, 11(3):254-257.
[38]惠海涛, 高俊华, 刘平, 等. 负载型KX/KZSM-5双沸石催化甲苯甲醇侧链烷基化反应的研究[J]. 天然气化工, 2013, 26(6):7-11.
[39]Han Q, Li P, Zhang Y, et al. Conversion of MeOH and Toluene into Styrene and Ethylbenzene Using Composite Catalysts Containing MeOH Dehydrogenation Components[J]. ChemCatChem, 2019, 11(6):1610-1614.
[40]Tanabe K, Takahashi O, Hattori H. Anomalous effect of nitrogen on side-chain alkylation of toluene with methanol over solid bases[J]. Reaction Kinetics & Catalysis Letters, 1977, 7(3):347-352.
[41]于爱敏, 吕宝成, 章福祥, 等. 氮化改性的AlPO_4-5催化甲苯甲醇侧链烷基化反应[C]. 全国青年催化学术会议. 2007:158-159.
[42]Jiang N, Jin H, Jeong E Y, et al. MgO Encapsulated Mesoporous Zeolite for the Side Chain Alkylation of Toluene with Methanol[J]. Journal of Nanoscience and Nanotechnology, 2010, 10(1):227-232.
[43]Aziz M A H, Jalil A A, Rahman A F A, et al. Toluene side chain alkylation with methanol over silica catalyst[J]. IOP Conference Series Materials Science and Engineering, 2020, 808:012004.
[44]Wang B, Wen Y, Huang W. Synthesis and application of novel solid acid-base catalysts for side chain alkylation of toluene with methanol[J]. Russian Journal of Applied Chemistry, 2014, 87(12):1943-1947.
[45]Hao C, Wen Y, Wang B, et al. Synthesis of HTLcs modified by K3PO4 for side chain alkylation of toluene with methanol[J]. Green Energy & Environment, DOI: 10.1016/j.gee.2020.06.007.
[46]Manivannan R, Pandurangan A. Formation of ethyl benzene and styrene by side chain methylation of toluene over calcined LDHs[J]. Applied Clay Science, 2009, 44(1-2):137-143.
[47]宋兰兰, 李振荣, 赵亮富, 等. 甲苯与甲醇侧链烷基化合成苯乙烯KX催化剂失活现象的研究[J]. 天然气化工(C1化学与化工), 2013, 38(2):46-50.
[48]Seo D W, Rahma S T, Reddy B M, et al. Carbon dioxide assisted toluene side-chain alkylation with methanol over Cs-X zeolite catalyst[J]. Journal of CO2 Utilization, 2018, 26:254-261.
[49]Zheng R, Liu Z, Wang Y, et al. Industrial catalysis: Strategies to enhance selectivity[J]. Chinese Journal of Catalysis, 2020, 41(7):1032-1038.