尿素改性β-分子筛催化苯与煤制油烷基化制重烷基苯

doi:10.11944/j.issn.1000-0518.2019.03.180189

摘要/Abstract

摘要：

对β-分子筛(n(Si)：n(Al)=15：1)分别进行酸洗、碱洗改性,制备出孔结构、酸性等性质不同的分子筛催化剂。通过扫描电子显微镜(SEM)、X射线衍射(XRD)、N₂吸附-脱附、NH₃-TPD和Py-FTIR等表征手段对分子筛催化剂的结构、性能及其在苯的烷基化反应中的应用进行了研究。结果表明,盐酸浸洗对β-分子筛的孔径、比表面积及孔容均有扩大作用,但在酸性上有所减弱;NaOH溶液浸洗造成了分子筛骨架的崩塌,对其酸性与孔结构均造成了破坏;尿素改性不仅改善了分子筛的孔结构性质,而且对分子筛酸性影响较小,是一种温和、有效的改性方式。尿素改性β-分子筛催化剂催化苯与煤基冷阱油的烷基化反应活性最好,烯烃转化率达91.2%,且重烷基苯2位异构体(2-HAB)和3位异构体(3-HAB)在产物中含量最高,选择性分别为50.1%和33.5%,占整个烷基化产物的84%。

关键词: β-分子筛;, 煤基冷阱油, 烷基化反应, 尿素

Abstract:

Molecular sieve catalysts with different pore structures and acidity were prepared by acid pickling and alkali washing modification of β-molecular sieve with n(Si)：n(Al)=15：1. The structure, properties, and the application of β-molecular sieve catalysts in alkylation of benzene were investigated by scanning electron microscopy(SEM), X-ray diffraction(XRD), N₂ adsorption-desorption, NH₃-TPD(temperature programmed desorption) and Py-FTIR(Fourier transform infrared spectroscopy). The results show that hydrochloric acid leaching can enlarge the pore size, specific surface area and pore volume of β-molecular sieve, but weaken the acidity, while the sodium hydroxide solution leaching results in the collapse of molecular sieve skeleton, leading to the destruction of the acidity and the pore structure. Modification by urea not only improves the pore structure of molecular sieve, but also has little effect on the acidity of molecular sieve. It is a mild and effective way to modify the molecular sieve. β-molecular sieve catalyst modified with urea has the best activity in alkylation of benzene with coal-based cold trap oil:the conversion of olefin is 91.2%, and the selectivities of 2-HAB(heavy alkylbenzene) and 3-HAB isomers are 50.1% and 33.55%, respectively, accounting for 84% of the total alkylation product.

Key words: β-molecular sieve;, coal-based cold trap oil, alkylation reaction, urea

石文路, 乔庆东, 李琪, 任铁强, 于廷云. 尿素改性β-分子筛催化苯与煤制油烷基化制重烷基苯[J]. 应用化学, 2019, 36(3): 291-299.

SHI Wenlu, QIAO Qingdong, LI Qi, REN Tieqiang, YU Tingyun. Alkylation of Benzene with Coal Oil to Heavy Alkylbenzene Catalyzed by Urea Modified β-Molecular Sieve[J]. Chinese Journal of Applied Chemistry, 2019, 36(3): 291-299.

参考文献

[1]	LIU Liangqun,ZHANG Yiting,ZHOU Hongliang,et al. A Surfactant for Oil Displacement-Heavy Alkylbenzene[J]. Daily Chem Sci,2015,38(9):40-41,45(in Chinese). 刘良群,张轶婷,周洪亮,等. 一种驱油用表面活性剂原料——重烷基苯[J]. 日用化学品科学,2015,38(9):40-41,45.
[2]	CAO Fengying,BAI Ziwu,GUO Qi,et al. Synthesis of Alkylbenzene for Oil Displacement[J]. Daily Chem Sci,2015,38(2):28-30,38(in Chinese). 曹凤英,白子武,郭奇,等. 驱油用烷基苯合成技术研究[J]. 日用化学品科学,2015,38(2):28-30,38.
[3]	CUI Zhenggang,ZOU Wenhua,ZHANG Tianlin,et al. Synthesis of Heavy Alkylbenzene Sulfonate and Its Application in Improving Oil Recovery[J]. J East China Univ Technol,1999,(4):19-26(in Chinese). 崔正刚,邹文华,张天林,等. 重烷基苯磺酸盐的合成及其在提高石油采收率中的应用[J]. 华东理工大学学报,1999,(4):19-26.
[4]	LI Lingyun.Study on a Synthetic Process of Multi-component Heavy Alkylbenzene Sulfonate for Tertiary Oil Recovery[J]. Inner Mongolia Petrochem Ind,2015,41(1):5-8(in Chinese). 李凌云. 一种三次采油用多组份重烷基苯磺酸盐合成工艺研究[J]. 内蒙古石油化工,2015,41(1):5-8.
[5]	LI Peijun,XU Fan,MENG Xian'ge. Comprehensive Development and Utilization of Heavy Alkylbenzene[J]. China Wash Prod Ind,2011,(2):56-60(in Chinese). 李佩均,徐凡,孟宪革. 合成重烷基苯的综合开发和利用[J]. 中国洗涤用品工业,2011,(2):56-60.
[6]	Jian W Y S. Research Progress of Catalysts for Alkylation of Benzene with Long-Chain Alkenes[J]. Guang Zhou Chem Ind Tech,2004,2:001.
[7]	Aitani A,Wang J S B,Wang I,et al. Environmental Benign Catalysis for Linear Alkylbenzene Synthesis:A Review[J]. Catal Surv Asia,2014,18(1):1-12.
[8]	Olivier-Bourbigou H,Magna L,Morvan D.Ionic Liquids and Catalysis:Recent Progress from Knowledge to Applications[J]. Appl Catal A:Genl,2010,373(1/2):1-56.
[9]	Zhang Q,Zhang S,Deng Y.Recent Advances in Ionic Liquid Catalysis[J]. Green Chem,2011,13(10):2619-2637.
[10]	He Y,Wan C,Zhang Q,et al. Durability Enhanced Ionic Liquid Catalyst for Friedel Crafts Reaction Between Benzene and 1-Dodecene:Insight into Catalyst Deactivation[J]. RSC Adv,2015,5(76):62241-62247.
[11]	Bellussi G,Pazzuconi G,Perego C,et al. Liquid-Phase Alkylation of Benzene with Light Olefins Catalyzed by β-Zeolites[J]. J Catal,1995,157(1):227-234.
[12]	Corma A,Martinez-Soria V,Schnoeveld E.Alkylation of Benzene with Short-Chain Olefins over MCM-22 Zeolite:Catalytic Behaviour and Kinetic Mechanism[J]. J Catal,2000,192(1):163-173.
[13]	Azizi N,Torkiyan L,Saidi M R.Highly Efficient One-Pot Three-Component Mannich Reaction in Water Catalyzed by Heteropoly Acids[J]. Org Lett,2006,8(10):2079-2082.
[14]	WANG Guoliang,LI Shuben,LIU Jinlong.Advances in Heteropoly Acids and Their Supported Catalysts[J]. Refining Technol Eng,2002,32(9):46-51(in Chinese). 王国良,李树本,刘金龙. 杂多酸及其负载型催化剂的研究进展[J]. 炼油技术与工程,2002,32(9):46-51.
[15]	HAN Bingbing,HAN Shejiao,JIN Yong.Alkylation of Benzene with Long Chain Olefin Catalyzed by Molecular Sieve[J]. Chem React Eng Process,1997,(2):190-193(in Chinese). 韩宾兵,韩社教,金涌. 分子筛催化下苯与长直链烯烃的烷基化反应研究[J]. 化学反应工程与工艺,1997,(2):190-193.
[16]	TONG Huijuan,LI Gong.Effects of Structure and Acidity of Different Molecular Sieves on Alkylation of Benzene with 1-Dodecene[J]. J Liaoning Univ Pet Chem Technol,2003,23(4):7-10(in Chinese). 佟惠娟,李工. 不同分子筛的结构和酸性对苯与1-十二烯烷基化反应的影响[J]. 辽宁石油化工大学学报,2003,23(4):7-10.
[17]	WU Yihui. Pore Modification, Characterization and Acid Catalytic Properties of Beta Molecular Sieve[D]. Dalian:Dalian University of Technology,2012(in Chinese). 吴义辉. Beta分子筛孔道调变、表征及酸催化性能研究[D]. 大连:大连理工大学,2012.
[18]	ZHOU Zhifeng.Progress in Catalysts for Alkylation of Benzene with Long Chain Olefins[J]. Liaoning Chem Ind,2015,44(5):569-571(in Chinese). 周治峰. 苯与长链烯烃的烷基化反应催化剂的研究进展[J]. 辽宁化工,2015,44(5):569-571.