双有机结构导向剂合成高硅MCM-22分子筛及其催化性能

石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (11): 60-66.

双有机结构导向剂合成高硅MCM-22分子筛及其催化性能

刘闯,王振东,杨为民

中石化（上海）石油化工研究院有限公司，绿色化工与工业催化国家重点实验室

收稿日期:2023-04-13 修回日期:2023-07-20 出版日期:2023-11-12 发布日期:2023-10-29
通讯作者: 王振东 E-mail:wangzd.sshy@sinopec.com
基金资助:
国家自然科学基金

SYNTHESIS OF HIGH SILICA MCM-22 ZEOLITE WITH DUAL ORGANIC STRUCTURE-DIRECTING AGENTS AND ITS CATALYTIC PERFORMANCE

Received:2023-04-13 Revised:2023-07-20 Online:2023-11-12 Published:2023-10-29
Contact: Zhen-dong WANG E-mail:wangzd.sshy@sinopec.com
Supported by:
National Natural Science Foundation of China

摘要/Abstract

摘要： 采用六亚甲基亚胺（HMI）和N,N,N-三甲基-1-金刚烷基氢氧化铵（TMAdaOH）为双有机结构导向剂（OSDA），通过对晶化时间、OSDA用量和投料硅铝比等参数的考察，优化了高硅铝比、高结晶度MCM-22分子筛的合成条件。采用X射线衍射（XRD）、扫描电镜（SEM）、氮气物理吸附-脱附、氨程序升温脱附（NH₃-TPD）、热重分析（TGA）等手段表征其物化性质，同时考察其催化三异丙苯（TiPB）裂解的性能。结果表明：在双有机结构导向剂的作用下，以宽投料硅铝比合成的MCM-22分子筛具有晶相纯、固体收率高、酸性质可调的优点；投料n(SiO₂)/n(Al₂O₃)为60~100的高硅MCM-22分子筛催化三异丙苯裂解的性能比投料n(SiO₂)/n(Al₂O₃)=30的常规MCM-22分子筛更好。

关键词: MCM-22分子筛, 高硅, 双有机结构导向剂, 三异丙苯, 裂解

Abstract: MCM-22 zeolite with high crystallinities was synthesized under optimized the crystallization time, amount of TMAdaOH and SiO2/Al2O3 molar ratio conditions by using hexamethyleneimine (HMI) and N,N,N-trimethyl-1-ammonium adamantine (TMAdaOH) as dual organic structure-directing agents. The zeolite was characterized by X-ray diffraction, scanning electron microscopy, N₂ adsorption-desorption, NH₃-TPD and TG analysis. The catalytic performance of H-type MCM-22 zeolite for the pyrolysis of triisopropylbenzene (TiPB) was investigated. The results showed that with the addition of a small amount of TMAdaOH, MCM-22 zeolite could be synthesized under a wide range of n(SiO₂)/n(Al₂O₃), and MCM-22 zeolite had the advantages of crystal purity, high solid yield and adjustable acidity. The high silica MCM-22 with n(SiO₂)/n(Al₂O₃) of 60-100 displayed better cracking performance for TiPB than that of conventional MCM-22 with n(SiO₂)/n(Al₂O₃) of 30.

Key words: MCM-22 zeolite, high silica, dual organic structure-directing agent, TiPB, cracking

刘闯王振东杨为民. 双有机结构导向剂合成高硅MCM-22分子筛及其催化性能[J]. 石油炼制与化工, 2023, 54(11): 60-66.

参考文献

[1] Leonowicz Michael E., Lawton Jeffrey A., Lawton Stephen L., et al. MCM-22: A molecular sieve with two independent multidimensional channel systems[J]. Science, 1994, 264(5167): 1910-1913.
[2] http://europe.iza-structure.org/IZA-SC/framework.php?STC=MWW, [2007- 07- 01].
[3] Yang Weimin, Wang Zhendong, Sun Hongmin, et al. Advances in development and industrial applications of ethylbenzene processes[J]. Chinese Journal of Catalysis, 2016, 37(1): 16-26.
[4] 赵松, 谢伟, 刘月明, 等. Ti-MWW催化丁酮氨肟化连续淤浆床工艺[J]. 催化学报, 2011, 32(1): 179-183.
[5] Li Xiangcheng, Yuan Xiaohong, Xia Guopeng, et al. Catalytic production of γ-valerolactone from xylose over delaminated Zr-Al-SCM-1 zeolite via a cascade process[J]. Journal of Catalysis, 2020, 392: 175-185.
[6] Li Guanna, Pidko Evgeny A., and Hensen Emiel J. M. Synergy between lewis acid sites and hydroxyl groups for the isomerization of glucose to fructose over Sn-containing zeolites: A theoretical perspective[J]. Catalysis Science & Technology, 2014, 4: 2241-2250.
[7] Graaff William N. P. van der, Tempelman Christiaan H. L., Pidko Evgeny A., et al. Influence of pore topology on synthesis and reactivity of Sn-modified zeolite catalysts for carbohydrate conversions[J]. Catalysis Science & Technology, 2017, 7: 3511-3162.
[8] Guo Qiang, Fan Fengtao, Evgeny A, et al. Highly active and recyclable Sn-MWW zeolite catalyst for sugar conversion to methyl lactate and lactic acid[J]. ChemSusChem, 2013, 6(8): 1352-1356.
[9] Roth Wieslaw J., Cejka Jiri, Millini Roberto, et al. Swelling and interlayer chemistry of layered MWW zeolites MCM-22 and MCM-56 with high Al content[J]. Chemistry of Materials, 2015, 27(13): 4620-4629.
[10] Wang Zhendong, Cichocka Magdalena O., Luo Yi, et al. Controllable direct-syntheses of delaminated MWW-type zeolites[J]. Chinese Journal of Catalysis, 2020, 41(7): 1062-1066.
[11] 张云贤, 王振东, 张斌, 等. 无硼体系MCM-22分子筛的合成[J]. 化学反应工程与工艺, 2014, 30(6): 557-560.
[12] Yan Menghui, Jin Fang, Ding Yigang, et al. Synthesis of titanium incorporated MWW zeolite by sequential deboronation and atom-planting treatment of ERB-1 as epoxidation catalyst[J]. Industrial & Engineering Chemistry Research, 2019, 58, 12, 4764-4773.
[13] 王振东, 张云贤, 张斌, 等. 以高哌嗪为有机结构导向剂合成MCM-22分子筛[J]. 石油化工, 2014, 增刊: 144-146.
[14] Xu Le, Ji Xinyi, Li Shenhui, et al. Self-assembly of cetyltrimethylammonium bromide and lamellar zeolite precursor for the preparation of hierarchical MWW zeolite[J]. Chemistry of Materials, 2016, 28: 4512-4521.
[15] Chu Weifeng, Li Xiujie, Liu Shenglin, et al. Direct synthesis of three-dimensional MWW Zeolite with cyclohexylamine as an organic structure-directing agent[J]. Journal of Materials Chemistry A, 2018, 6(26): 12244-12249.
[16] Camblor Miguel A., Corma Avelino and Diaz-Cabanas Maria-Jose. Synthesis and structural characterization of MWW type zeolite ITQ-1, the pure silica analog of MCM-22 and SSZ-25[J]. The Journal of Physical Chemistry B, 1998, 102: 44-51.
[17] Camblor Miguel A., Corell Cati, Corma Avelino, et al. A new microporous polymorph of silica isomorphous to zeolite MCM-22[J]. Chemistry of Materials, 1996, 8(10): 2415-2417.
[18] Xu Guoliang, Zhu Xiangxue, Niu Xionglei, et al. One-pot synthesis of high silica MCM-22 zeolites and their performances in catalytic cracking of 1-butene to propene[J]. Microporous and Mesoporous Materials, 2009, 118: 44-51.
[19] Al-Khattaf S., Atias J. A., Jarosch K., et al. Diffusion and catalytic cracking of 1,3,5 tri-iso-propyl-benzene in FCC catalysts[J]. Chemical engineering science, 2002, 57(22): 4909-4920.
[20] Li Yuekun, Ma Duozheng, Fu Wenhua, et al. Direct synthesis of ultrathin FER zeolite nanosheets via a dual-template approach[J]. RSC Advances, 2022, 12(22), 14183-14189.
[21] Wang Quanhua, Zhang Lichen, Yao Zhenjiang, et al. Synthesis of loosely aggregating polycrystalline ZSM-5 with luxuriant mesopore structure and its hierarchically cracking for bulky reactants[J]. Materials Chemistry and Physics, 2020, 243: 122610.