工业氟硅酸合成钛硅介孔分子筛催化环己烯环氧化

doi:10.11949/j.issn.0438-1157.20160187

化工学报 ›› 2016, Vol. 67 ›› Issue (10): 4176-4186.DOI: 10.11949/j.issn.0438-1157.20160187

• 催化、动力学与反应器 • 上一篇下一篇

工业氟硅酸合成钛硅介孔分子筛催化环己烯环氧化

金放, 刘铁良, 王先桥, 吴元欣

武汉工程大学化工与制药学院, 绿色化工过程教育部重点实验室, 湖北省新型反应器与绿色化学工艺重点实验室, 湖北武汉 430073

收稿日期:2016-02-22 修回日期:2016-05-11 出版日期:2016-10-05 发布日期:2016-10-05
通讯作者: 吴元欣
基金资助:
国家自然科学基金项目（21306143，E041102）；湖北省中低品位磷矿资源开发利用协同创新中心开放基金项目；湖北省教育厅自然科学研究项目（D20161503）。

Synthesis of mesoporous titanosilicates from industrial by-product hexafluosilicic acid and application for catalytic cyclohexene epoxidation

JIN Fang, LIU Tieliang, WANG Xianqiao, WU Yuanxin

Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology, Key Laboratory for Green Chemical Process of Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073, Hubei, China

Received:2016-02-22 Revised:2016-05-11 Online:2016-10-05 Published:2016-10-05
Supported by:
supported by the National Natural Science Foundation of China(21306143, E041102).

摘要/Abstract

摘要：

利用磷肥工业副产的氟硅酸为原料，在十六烷基三甲基溴化铵（CTAB）溶液中与氨水和钛酸四丁酯（TBOT）反应，水热陈化制取钛硅介孔分子筛，通过改变水热时间、CTAB的加入量、硅钛比和模板剂的脱除方法研究实验条件对钛硅介孔分子筛的结构和性能的影响，采用氮气吸脱附、扫描电镜、透射电镜和固体紫外漫反射对样品进行表征。结果表明，SiO₂:CTAB:TBOT:NH₃:H₂O的摩尔比为1:1.50:0.03:10:150，水浴时间为5 h时，所得样品的比表面积可达1116 m²·g^-1，介孔体积为0.79 cm³·g^-1。合成的钛硅介孔分子筛作为催化剂应用于环己烯环氧化反应，环己烯的转化率可达68.10%，环氧环己烷产物选择性为96.60%，Ti活性位的转化频率达到99.5 h^-1。该方法可以提高磷肥副产低浓度氟硅酸的附加值，降低钛硅介孔分子筛催化剂的生产成本。

关键词: 氟硅酸, 介孔, 分子筛, 水热, 催化

Abstract:

The hexafluosilicic acid, a by-product in phosphate fertilizer industry, was used as the raw material for hydrothermal synthesis of mesoporous titanosilicates with cetyltrimethylammonium bromide (CTAB) as the cationic surfactant and ammonia as neutralization agent. The influence of synthesis conditions including hydrothermal time, the ratio of CTAB to silica, Si/Ti ratio, and surfactant removal methods on the structures and properties of mesoporous titanosilicates were investigated by characterization of the resulting product with techniques of X-ray diffraction (XRD), nitrogen adsorption/desorption, scanning electron microscopy (SEM), solid UV light scattering. At the optimized synthesis condition of the ratio of SiO₂:CTAB:Ti(OC₄H₉)4:NH₃:H₂O=1:1.50:0.03:10:150 and the hydrothermal time of 5 h, mesoporous titanosilicate had specific surface area of 1116 m²·g^-1 and porosity of 0.79 cm³·g^-1. When used as catalyst for cyclohexene epoxidation. this mesoporous titanosilicate showed good catalytic activities with cyclohexene conversion of 68.10%, cyclohexene epoxide selectivity of 96.60%, and turnover frequencies of Ti active sites of 99.5 h^-1. This new synthesis technique will greatly improve profit of phosphate fertilizer industry by utilizing the by-product hexafluosilicic acid for the production of value-added mesoporous titanosilicate.

Key words: hexafluosilicic acid, mesoporous, molecular sieves, hydrothermal, catalysis

中图分类号:

TQ028.8

金放, 刘铁良, 王先桥, 吴元欣. 工业氟硅酸合成钛硅介孔分子筛催化环己烯环氧化[J]. 化工学报, 2016, 67(10): 4176-4186.

JIN Fang, LIU Tieliang, WANG Xianqiao, WU Yuanxin. Synthesis of mesoporous titanosilicates from industrial by-product hexafluosilicic acid and application for catalytic cyclohexene epoxidation[J]. CIESC Journal, 2016, 67(10): 4176-4186.

参考文献 35

[1]	KRESGE C T, BECK J S, VARTULI J C, et al. A new family of mesoporous molecular sieves prepared with liquid crystal templates[J]. J. Am. Chem. Soc., 1992, 114:10834-10843.
[2]	BECK J S, VARTULI J C, KENNEDY G J, et al. Molecular or supramolecular templating:defining the role of surfactant chemistry in the formation of microporous and mesoporous molecular sieves[J]. Chem. Mater., 1994, 6:1816-1821.
[3]	ELAM J W, LIBERA J A, HUYHN T H, et al. Atomic layer deposition of aluminum oxide in mesoporous silica gel[J]. J. Phys. Chem. C, 2010, 114(41):17286-17292.
[4]	SHAH M, DAI J, GUO Q, et al. Products and production routes for the catalytic conversion of seed oil into fuel and chemicals:a comprehensive review[J]. Sci. China. Ser. B, 2015, 58(7):1110-1121.
[5]	蔡超. 功能化MCM-41介孔材料的合成与催化性能的研究[D]. 天津:天津大学, 2011. CAI C. Functionalization of MCM-41 mesoporous materials synthesis and catalytic properties of research[D]. Tianjin:Tianjin University, 2011.
[6]	BASTAS F S, LIMA O A, FERMANDES C R F A. Mesoporous molecular sieve MCM-41 synthesis from fluoride media[J]. J. Chem. Eng., 2011, 28(4):649-658.
[7]	MARIN N, MARTINEZ J J, BORDA G, et al. Control of the chemoselectivity in the oxidation of geraniol over lanthanum, titanium and niobium catalysts supported on mesoporous silica MCM-41[J]. Top. Catal., 2012, 55(7-10):620-624.
[8]	邹函君. 改性MCM-41介孔分子筛的制备、表征及其性能研究[D]. 重庆:重庆大学, 2013. ZOU H J. Modified MCM-41 mesoporous molecular sieves the preparation, characterization and its performance study[D]. Chongqing:Chongqing University, 2013.
[9]	XIE Y, ZHANG Y, OUYANG J, et al. Mesoporous material Al-MCM-41 from natural halloysite[J]. Phys. Chem. Miner., 2014, 41(7):497-503.
[10]	LIN K, PESCARMONA P P, HOUTHOOFD K, et al. Direct room-temperature synthesis of methyl-functionalized Ti-MCM-41 nanoparticles and their catalytic performance in epoxidation[J]. J. Catal., 2009, 263(1):75-82.
[11]	TANEV P T, CHIBWE M, PINNAVAIA T J. Titanium-containing mesoporous molecular sieves for catalytic oxidation of aromatic compounds[J]. Nature, 1992, 368(6469):321-323.
[12]	EIMAR G, CASUSCELLI S, GHIONE G, et al. Synthesis, characterization and selective oxidation properties of Ti-containing mesoporous catalysts[J]. Appl. Catal. A, 2006, 298:232-242.
[13]	周志刚. 钛硅分子筛催化环己烯环氧化[D]. 湘潭:湘潭大学, 2009. ZHOU Z G. Titanium silicon molecular sieve catalytic cyclohexene epoxidation[D]. Xiangtan:Xiangtan University, 2009.
[14]	何远东. 双介孔Ti-MCM-41的制备及其催化性能研究[D]. 哈尔滨:哈尔滨工业大学, 2014. HE Y D. Double the preparation of mesoporous Ti-MCM-41 and its catalytic performance[D]. Harbin:Harbin Institute of Technology, 2014.
[15]	杜记民, 陈慧娟, 桑然然, 等. 钛硅分子筛的水热合成及其催化环己烯环氧化反应[J]. 河北师范大学学报(自然科学版), 2014, 38(1):68-72. DU J M, CHEN H J, SANG R R, et al. Titanium silicon molecular sieve of hydrothermal synthesis and catalytic cyclohexene epoxidation reaction[J]. Journal of Hebei Normal University (Natural Science Edition), 2014, 38(1):68-72.
[16]	史春风, 朱斌, 林民. 空心钛硅分子筛在环己烷温和氧化反应中的催化性能[J]. 石油学报(石油加工), 2014, 30(5):792-797. SHI C F, ZHU B, LIN M. The hollow titanium silicon molecular sieve catalytic properties in moderate cyclohexane oxidation reaction[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2014, 30(5):792-797.
[17]	陈文静, 李文, 汤建新. 杂化介孔二氧化硅溶胶的制备及表征[J]. 湖南工业大学学报, 2011, 25(4):23-26. CHEN W J, LI W, TANG J X. Preparation and characterization of hybrid mesoporous silica sol[J]. Journal of Hunan University of Technology, 2011, 25(4):23-26.
[18]	冯伟, 邢伟, 禚淑萍. 水热法调节二氧化硅孔结构的探讨[J]. 山东理工大学学报(自然科学版), 2012, 26(2):21-24. FENG W, XIN W, ZHUO S P. Hydrothermal method to adjust the pore structure of silicon dioxide[J]. Journal of Shandong University of Science and Technology(Natural Science), 2012, 26(2):21-24.
[19]	VARTULI J C, ROTH W J, BECK J S, et al. The synthesis and properties of M41S and related mesoporous materials[J]. Mol. Sieves, 1998, 1:97-119
[20]	张爱菊, 沈毅, 李子成. 硅基介孔材料的合成机理及其应用[J]. 河北理工学院学报, 2006, 28(1):75-79. ZHANG A J, SHEN Y, LI Z C. Silicon-based synthetic mechanism of mesoporous materials and their applications[J]. Journal of Hebei Institute of Technology, 2006, 28(1):75-79.
[21]	许俊强, 储伟, 陈慕华, 等. 介孔分子筛V-MCM-41的水热法制备与合成机理[J]. 催化学报, 2006, 27(8):671-677. XU J Q, CHU W, CHEN M H, et al. Mesoporous molecular sieve V-MCM-41 of the hydrothermal method and synthesis mechanism[J]. Chin. J. Catal., 2006, 27(8):671-677.
[22]	谢永贤, 陈文, 徐庆. 有序介孔材料的合成及机理[J]. 材料导报, 2002, 16(1):51-53. XIE Y X, CHEN W, XU Q. The synthesis of ordered mesoporous materials and its mechanism[J]. Material Review, 2002, 16(1):51-53.
[23]	JIN F, CHEN S Y, LEE Z F, et al. New Ti-incorporated MCM-36 as an efficient epoxidation catalyst prepared by pillaring MCM-22 layers with titanosilicate[J]. J. Catal., 2014, 319:247-257.
[24]	HE Y J, NIVARTHY G S, EDER F, et al. Synthesis, characterization and catalytic activity of the pillared molecular sieve MCM-36[J]. Microp. Mesop. Mat., 1998, 25:207-224.
[25]	JIN F, CHANG C, YANG C, et al. New mesoporous titanosilicate MCM-36 material synthesized by pillaring layered ERB-1 precursor[J]. J. Mate. Chem. A, 2015, 3:8715-8724.
[26]	唐嘉伟. 新型介孔材料的设计合成及其功能研究[D]. 上海:复旦大学, 2008. TANG J W. The design of new mesoporous materials synthesis and function research[D]. Shanghai:Fudan University,2008.
[27]	THOMMES M, SMARSLY B, GROENEWOLT M, et al. Adsorption hysteresis of nitrogen and argon in pore networks and characterization of novel micro-and mesoporous silicas[J]. Langmuir, 2006, 22(2):756-764.
[28]	MIHAI G D, MEYNEN V, BEYERS E, et al. Synthesis, structural characterization and photocatalytic activity of Ti-MCM-41 mesoporous molecular sieves[J]. J. Porous Mater., 2009, 1(16):109-118.
[29]	THOMMES M. Physical adsorption characterization of nanoporous materials[J]. Chemie Ingenieur Technik, 2010, 82(7):1059-1073.
[30]	牛奎. 以特种阴离子表面活性剂为模板的介孔材料的合成、表征与应用[D]. 无锡:江南大学, 2011. NIU K. With special anionic surfactant as template synthesis, characterization and applications of the mesoporous materials[D]. Wuxi:Jiangnan University, 2011.
[31]	KUO F, CHEN S, LIN T, et al. Effect of combination sequence of precursors on the structural and catalytic properties of Ti-SBA-15[J]. RSC Advances, 2013, 3(31):12604-12610.
[32]	LIN T, CHEN C, JANG L, et al. Preparation and catalytic properties of mesoporous titanosilicate of cubic Pm3n structure[J]. Microp. Mesop. Mat., 2014, 198:194-202.
[33]	BU Y, WANG Y, ZHANG Y, et al. Epoxidation of cyclohexene on modified Ti-containing mesoporous MCM-41[J]. React. Kinet. Catal. Lett., 2007, 90(1):77-84.
[34]	CHEN L Y, CHUAH G K, JAENICKE S. Ti-containing MCM-41 catalysts for liquid phase oxidation of cyclohexene with aqueous H2O2 and tert-butyl hydroperoxide[J]. Catal. Lett., 1998, 50:107-114.
[35]	LIN K F, PESCARMONA P P, HOUTHOOFD, et al. Direct room-temperature synthesis of methyl-functionalized Ti-MCM-41 nanoparticles and their catalytic performance in epoxidation[J]. J. Catal., 2009, 263(1):75-82.

工业氟硅酸合成钛硅介孔分子筛催化环己烯环氧化

Synthesis of mesoporous titanosilicates from industrial by-product hexafluosilicic acid and application for catalytic cyclohexene epoxidation

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