乙酸溶剂中空心钛硅分子筛催化甲苯氧化制甲基苯酚研究

石油炼制与化工 ›› 2019, Vol. 50 ›› Issue (6): 33-39.

乙酸溶剂中空心钛硅分子筛催化甲苯氧化制甲基苯酚研究

彭欣欣,林民,朱斌,夏长久,罗一斌,舒兴田

中国石化石油化工科学研究院

收稿日期:2018-10-19 出版日期:2019-06-12 发布日期:2019-07-01
通讯作者: 彭欣欣 E-mail:pengxx.ripp@sinopec.com
基金资助:
苯选择性氧化制苯酚和苯二酚

PREPARATION OF CRESOL FROM TOLUENE OXIDATION CATALYZED BY HTS ZEOLITE WITH ACETIC ACID AS SOLVENT

Peng Xinxin,Lin Min,Zhu Bin,Xia Changjiu,Luo Yibin,Shu Xingtian

Received:2018-10-19 Online:2019-06-12 Published:2019-07-01
Contact: Peng Xinxin E-mail:pengxx.ripp@sinopec.com
Supported by:

摘要/Abstract

摘要： 以钛硅分子筛（TS-1）经重排扩孔的空心钛硅分子筛（HTS）为催化剂、乙酸［36%（w），下同］为溶剂，考察了不同因素对甲苯与双氧水氧化反应制甲基苯酚（甲酚）的影响。结果表明：乙酸对该反应具有明显的促进作用；初期反应主要发生在分子筛的外表面；随着反应的进行，分子筛孔道中反应增加；在优化的反应条件下，甲苯转化率达15.1%，甲酚选择性超过95.0%，产物对邻比约为1.28。

关键词: 甲苯, 甲酚, 钛硅分子筛, 乙酸

Abstract: Cresol is an important chemical intermediate which is mainly produced through complicated and pollutant traditional methods. While titanium silicalite (TS-1) catalyzed toluene oxidation using hydrogen peroxide as oxidant is a clean route for cresol synthesis. This study investigated the effects of different factors on toluene and hydrogen peroxide reaction，using HTS as catalyst which is recrystalized from TS-1zeolite and acetic acid［36%（w）］as solvent. The results showed that acetic acid［36%（w）］ was effective for promoting the reaction. The oxidation occurred mainly at the outside of the zeolite in early reaction stage，while more reaction was taken place inside the channels of the zeolite as the reaction proceeds. Under optimized conditions，the toluene conversion rate，the selectivity of cresol and the molar ratio of para-cresol/ortho-cresol of cresol product reached to 15.1%，5.0% ，1.28，respectively.

Key words: toluene, cresol, titanium silicalite zeolite sieve, acetic acid

中图分类号:

彭欣欣林民朱斌夏长久罗一斌舒兴田. 乙酸溶剂中空心钛硅分子筛催化甲苯氧化制甲基苯酚研究[J]. 石油炼制与化工, 2019, 50(6): 33-39.

Peng Xinxin Lin Min Zhu Bin Xia Changjiu Luo Yibin Shu Xingtian. PREPARATION OF CRESOL FROM TOLUENE OXIDATION CATALYZED BY HTS ZEOLITE WITH ACETIC ACID AS SOLVENT[J]. Petroleum Processing and Petrochemicals, 2019, 50(6): 33-39.

参考文献

[1] 徐克勋.精细有机化工原料及中间体手册[M].北京:化学工业出版社, 1998. 3-107. [2] Weissermel K, Arpe H J.Industrial organic chemistry[M]. John Wiley & Sons, 2008. [3] Shinohara Y, Isaka T.Process for preparation of cresol and acetone from cymene hydroperoxide[P]. US 3720716. 1973. [4] Weber M, Weber M.Phenols[M]//Phenolic Resins: A Century of Progress. Springer, Berlin, Heidelberg, 2010: 9-23.. [5] Taramasso M, Perego G, Notari B.Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides[P]. US 4410501. 1983. [6] Esposito A, Taramasso M, Neri C.Hydroxylating aromatic hydrocarbons[P]. US 4396783. 1983. [7]Mukherjee P, Bhaumik A, Kumar R.Eco-friendly, selective hydroxylation of C-7 aromatic compounds catalyzed by TS-1/H2O2 system under solvent-free solid-liquid-liquid-type triphase conditions[J].Ind. Eng. Chem.Res., 2007, 46(25):8657-8664 [8]Sakullimcharoen S, Manit P, Mongkhonsi T.Catalytic activity of TS-1 on the hydroxylation of benzene and toluene with hydrogen peroxide in a bubble reactor[J].Chiang Mai Journal of Science, 2008, 35(1):163-170 [9]Boccuti M R, Rao K M, Zecchina A, et al.Spectroscopic Characterization of Silicalite and Titanium-silicalite[J].Studies in Surface Science and Catalysis, 1989, 48(1):133-144 [10] Bordiga S, Boscherini F, Coluccia S, et al.EXAFS Study of Ti-Silicalite: Structure of Framework Ti (IV) in Presence and in Absence of Reactive Molecules (H2O, NH3) [J].Catal Lett., 1994, 26(1-2):195-208 [11]Zecchina A, Bordiga S, Lamberti C, et al.Structural Characterization of Ti Centres in Ti-Silicalite and Reaction Mechanisms in Cyclohexanone Ammoximation[J].Catal Today, 1996, 32(1):97-106 [12]Clerici M G, Ingallina P.Epoxidation of lower olefins with hydrogen peroxide and titanium silicalite[J].Journal of Catalysis, 1993, 140(1):71-83 [13]Kumar R, Mukherjee P, Bhaumik A.Enhancement in the reaction rates in the hydroxylation of aromatics over TS-1H2O2 under solvent-free triphase conditions[J].Catalysis Today, 1999, 49(1-3):185-191

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