高水热稳定性介孔分子筛的低成本合成研究进展

doi:10.16085/j.issn.1000-6613.2022-1158

化工进展 ›› 2023, Vol. 42 ›› Issue (4): 1877-1884.DOI: 10.16085/j.issn.1000-6613.2022-1158

高水热稳定性介孔分子筛的低成本合成研究进展

李云闯¹(), 谢方明²(), 席亚男¹(), 万新月¹, 孙玉虎³, 赵永峰⁴, 李根¹^,⁴, 刘宏海², 高雄厚², 刘洪涛¹()

^1.北京化工大学化工资源有效利用国家重点实验室，北京 100029
^2.中国石油天然气股份有限公司石油化工研究院，北京 100195
^3.中国石油天然气股份有限公司华北石化分公司，河北任丘 062552
^4.中国石油技术开发有限公司，北京 100028

收稿日期:2022-06-21 修回日期:2022-09-15 出版日期:2023-04-25 发布日期:2023-05-08
通讯作者: 刘洪涛
作者简介:李云闯（1997—），男，硕士研究生，研究方向为分子筛的合成与表征。E-mail：liyunc1997@163.com
谢方明（1986—），男，硕士，高级工程师，研究方向为炼油技术。E-mail: xfm459@petrochina.com.cn
席亚男（1997—），女，硕士研究生，研究方向为分子筛的合成与表征。 E-mail: xiyanan1997@163.com。
基金资助:
中国石油天然气股份有限公司课题(DQZX-KY-21-008)

Low-cost synthesis of hydrothermally stable mesoporous aluminosilicates

LI Yunchuang¹(), XIE Fangming²(), XI Yanan¹(), WAN Xinyue¹, SUN Yuhu³, ZHAO Yongfeng⁴, LI Gen¹^,⁴, LIU Honghai², GAO Xionghou², LIU Hongtao¹()

^1.State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
^2.Petrochemical Research Institute, Petrochina Company Limited, Beijing 100195, China
^3.Petrochina North China Petrochemical Company, Renqiu 062552, Hebei, China
^4.China Petroleum Technology and Development Corporation, Beijing 100028, China.

Received:2022-06-21 Revised:2022-09-15 Online:2023-04-25 Published:2023-05-08
Contact: LIU Hongtao

摘要/Abstract

摘要：

将表面活性剂与微孔分子筛的纳米团簇进行组装的方法实现了介孔分子筛孔壁的部分晶化，可以大幅提高介孔分子筛的水热稳定性，但是较高的模板剂和水用量导致的较高合成成本限制了其进一步应用。本文结合低成本合成高稳定性介孔分子筛及其工业应用的研究历程，综述了在合成高稳定性介孔分子筛的同时降低有机模板剂和水的用量方面的研究进展，包括晶种协同作用法、母液循环法、亲水物质的引入法和复合模板剂法等，阐述了各种方法的合成机理和各自的优缺点，并指出在无有机模板剂条件下得到全结晶孔壁的介孔分子筛是未来的发展方向。

关键词: 介孔分子筛, 水热稳定性, 低模板剂, 低水量, 低成本合成

Abstract:

Hydrothermally stable mesoporous aluminosilicates (MAs) could be obtained via self-assembly of clusters of primary and secondary building units of microporous zeolites. However, high consumption of water and organic template hinder its industrial application. To solve this problem, hydrothermally stable MAs was proposed via the introduction of microporous precursor into the wall of mesophase. Based on the development process of microporous zeolite precursor assembly method, various strategies to decrease the consumption of organic template and water were summarized, including seed-assisted method, mother liquid recycling strategy, introduction of hydrophilic materials, and composite templates method. Based on the analysis of their advantages and disadvantages, future development directions are pointed out. Specifically, the MAs with fully crystallized walls of mesophase without organic template will be the research focus.

Key words: mesoporous aluminosilicate, hydrothermal stability, low template consumption, low water consumption, low-cost synthesis

中图分类号:

TQ426.95

李云闯, 谢方明, 席亚男, 万新月, 孙玉虎, 赵永峰, 李根, 刘宏海, 高雄厚, 刘洪涛. 高水热稳定性介孔分子筛的低成本合成研究进展[J]. 化工进展, 2023, 42(4): 1877-1884.

LI Yunchuang, XIE Fangming, XI Yanan, WAN Xinyue, SUN Yuhu, ZHAO Yongfeng, LI Gen, LIU Honghai, GAO Xionghou, LIU Hongtao. Low-cost synthesis of hydrothermally stable mesoporous aluminosilicates[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1877-1884.

图/表 7

参考文献 47

1	PEREGO Carlo, MILLINI Roberto. Porous materials in catalysis: Challenges for mesoporous materials[J]. Chemical Society Reviews, 2013, 42(9): 3956-3976.
2	HUSSAIN Murid, SONG Seon Ki, Son Ki IHM. Synthesis of hydrothermally stable MCM-41 by the seed crystallization and its application as a catalyst support for hydrodesulfurization[J]. Fuel, 2013, 106: 787-792.
3	LI Tianshu, DUAN Aijun, ZHAO Zhen, et al. Synthesis of ordered hierarchically porous L-SBA-15 material and its hydro-upgrading performance for FCC gasoline[J]. Fuel, 2014, 117: 974-980.
4	MOHAMMADI ZIARANI Ghodsi, LASHGARI Negar, BADIEI Alireza. Sulfonic acid-functionalized mesoporous silica (SBA-Pr-SO₃H) as solid acid catalyst in organic reactions[J]. Journal of Molecular Catalysis A: Chemical, 2015, 397: 166-191.
5	GLOTOV Aleksandr, LEVSHAKOV Nikolai, VUTOLKINA Anna, et al. Aluminosilicates supported La-containing sulfur reduction additives for FCC catalyst: Correlation between activity, support structure and acidity[J]. Catalysis Today, 2019, 329: 135-141.
6	ZHANG Zongtao, HAN Yu, ZHU Lei, et al. Strongly acidic and high-temperature hydrothermally stable mesoporous aluminosilicates with ordered hexagonal structure[J]. Angewandte Chemie International Edition, 2001, 40(7): 1258-1262.
7	HAN Yu, WU Shuo, SUN Yinyong, et al. Hydrothermally stable ordered hexagonal mesoporous aluminosilicates assembled from a triblock copolymer and preformed aluminosilicate precursors in strongly acidic media[J]. Chemistry of Materials, 2002, 14(3): 1144-1148.
8	DI Yan, YU Yi, SUN Yingyong, et al. Synthesis, characterization, and catalytic properties of stable mesoporous aluminosilicates assembled from preformed zeolite L precursors[J]. Microporous and Mesoporous Materials, 2003, 62(3): 221-228.
9	HAN Yu, LI Nan, ZHAO Lan, et al. Understanding of the high hydrothermal stability of the mesoporous materials prepared by the assembly of triblock copolymer with preformed zeolite precursors in acidic media[J]. The Journal of Physical Chemistry B, 2003, 107(31): 7551-7556.
10	刘子玉, 朱子彬, 王仁远, 等. 以MCM-22为原料合成高水热稳定性的介孔材料[J]. 催化学报, 2008, 29(9): 928-934.
	LIU Ziyu, ZHU Zibin, WANG Renyuan, et al. Synthesis of mesoporous materials with high hydrothermal stability from MCM-22[J]. Chinese Journal of Catalysis, 2008, 29(9): 928-934.
11	魏兵, 沈志虹, 张昌松, 等. 前驱体组装高水热稳定性介孔分子筛MSU-S[J]. 分子催化, 2009, 23(3): 233-236.
	WEI Bing, SHEN Zhihong, ZHANG Changsong, et al. Assembly of MSU-S with high hydrothermal stability from precursors[J]. Journal of Molecular Catalysis, 2009, 23(3): 233-236.
12	刘洪涛, 鲍晓军, 魏伟胜, 等. 提高中孔分子筛水热稳定性技术研究进展[J]. 化工进展, 2003, 22(6): 578-582.
	LIU Hongtao, BAO Xiaojun, WEI Weisheng, et al. Review on techniques to improve hydrothermal stability of mesoporous zeolites[J]. Chemical Industry and Engineering Progress, 2003, 22(6): 578-582.
13	ZHAO Dongyuan, HUO Qisheng, FENG Jianglin, et al. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures[J]. Journal of the American Chemical Society, 1998, 120(24): 6024-6036.
14	ZHAO Tiancong, ELZATAHRY Ahmed, LI Xiaomin, et al. Single-micelle-directed synthesis of mesoporous materials[J]. Nature Reviews Materials, 2019, 4(12): 775-791.
15	ZOU Yidong, ZHOU Xinran, MA Junhao, et al. Recent advances in amphiphilic block copolymer templated mesoporous metal-based materials: Assembly engineering and applications[J]. Chemical Society Reviews, 2020, 49(4): 1173-1208.
16	DUAN Linlin, WANG Changyao, ZHANG Wei, et al. Interfacial assembly and applications of functional mesoporous materials[J]. Chemical Reviews, 2021, 121(23): 14349-14429.
17	李艳荣, 宋明娟, 顾海芳, 等. 适合SBA-15介孔材料工业化生产的改良方法[J]. 催化学报, 2012, 33(8): 1360-1366.
	LI Yanrong, SONG Mingjuan, GU Haifang, et al. Improved synthesis of SBA-15 mesoporous silica fitting for industrial production[J]. Chinese Journal of Catalysis, 2012, 33(8): 1360-1366.
18	钱伯章. 中国石油介孔分子筛技术领跑世界[J]. 精细石油化工进展, 2019, 20(3): 58.
	QIAN Bozhang. Mesoporous zeolite technology of PetroChina leading the world[J]. Advances in Fine Petrochemicals, 2019, 20(3): 58.
19	KERR George T. Chemistry of crystalline aluminosilicates. Ⅰ. Factors affecting the formation of zeolite A[J]. The Journal of Physical Chemistry, 1966, 70(4): 1047-1050.
20	SUZUKI Kunio, HAYAKAWA Takashi. The effects of seeding in the synthesis of zeolite ZSM-48 in the presence of tetramethylammonium ion[J]. Microporous and Mesoporous Materials, 2005, 77(2/3): 131-137.
21	BOUIZI Younès, PAILLAUD Jean Louis, SIMON Laurent, et al. Seeded synthesis of very high silica zeolite A[J]. Chemistry of Materials, 2007, 19(4): 652-654.
22	MAJANO Gerardo, DARWICHE Ali, MINTOVA Svetlana, et al. Seed-induced crystallization of nanosized Na-ZSM-5 crystals[J]. Industrial & Engineering Chemistry Research, 2009, 48(15): 7084-7091.
23	WU Zhifeng, SONG Jiangwei, JI Yanyan, et al. Organic template-free synthesis of ZSM-34 zeolite from an assistance of zeolite L seeds solution[J]. Chemistry of Materials, 2008, 20(2): 357-359.
24	YANG Chengguang, REN Limin, ZHANG Haiyan, et al. Organotemplate-free and seed-directed synthesis of ZSM-34 zeolite with good performance in methanol-to-olefins[J]. Journal of Materials Chemistry, 2012, 22(24): 12238-12245.
25	MAJANO Gerardo, DELMOTTE Luc, VALTCHEV Valentin, et al. Al-rich zeolite beta by seeding in the absence of organic template[J]. Chemistry of Materials, 2009, 21(18): 4184-4191.
26	XIE Bin, ZHANG Haiyan, YANG Chengguang, et al. Seed-directed synthesis of zeolites with enhanced performance in the absence of organic templates[J]. Chemical Communications, 2011, 47(13): 3945-3947.
27	REN Nan, YANG Zhijian, Xinchun LYu, et al. A seed surface crystallization approach for rapid synthesis of submicron ZSM-5 zeolite with controllable crystal size and morphology[J]. Microporous and Mesoporous Materials, 2010, 131(1/2/3): 103-114.
28	YU Qingjun, ZHANG Qiang, LIU Jianwei, et al. Inductive effect of various seeds on the organic template-free synthesis of zeolite ZSM-5[J]. CrystEngComm, 2013, 15(38): 7680-7687.
29	ZHANG Haiyan, GUO Qiang, REN Limin, et al. Organotemplate-free synthesis of high-silica ferrierite zeolite induced by CDO-structure zeolite building units[J]. Journal of Materials Chemistry, 2011, 21(26): 9494-9497.
30	ZHANG Haiyan, YANG Chengguang, ZHU Longfeng, et al. Organotemplate-free and seed-directed synthesis of levyne zeolite[J]. Microporous and Mesoporous Materials, 2012, 155: 1-7.
31	IYOKI Kenta, ITABASHI Keiji, OKUBO Tatsuya. Progress in seed-assisted synthesis of zeolites without using organic structure-directing agents[J]. Microporous and Mesoporous Materials, 2014, 189: 22-30.
32	KAMIMURA Yoshihiro, TANAHASHI Shinya, ITABASHI Keiji, et al. Crystallization behavior of zeolite beta in OSDA-free, seed-assisted synthesis[J]. The Journal of Physical Chemistry C, 2011, 115(3): 744-750.
33	JIN Junsu, CAO Li, HU Qingxun, et al. An efficient synthesis of hydrothermally stable mesoporous aluminosilicates with significant decreased organic templates by a seed-assisted approach[J]. Journal of Materials Chemistry A, 2014, 2(21): 7853-7861.
34	CAO Li, ZHAO Xiaozheng, JIN Junsu, et al. Crystal-seeds-based strategy for the synthesis of hydrothermally stable mesoporous aluminosilicates with a largely decreased H₂O amount[J]. Industrial & Engineering Chemistry Research, 2014, 53(44): 17286-17293.
35	LIU Conghua, GAO Xionghou, MA Yanqing, et al. Study on the mechanism of zeolite Y formation in the process of liquor recycling[J]. Microporous and Mesoporous Materials, 1998, 25(1/2/3): 1-6.
36	PAN Huihua, PAN Qunxiong, ZHAO Yuansheng, et al. A green and efficient synthesis of ZSM-5 using NaY as seed with mother liquid recycling and in the absence of organic template[J]. Industrial & Engineering Chemistry Research, 2010, 49(16): 7294-7302.
37	ZUO Yi, WANG Xiangsheng, GUO Xinwen. Synthesis of titanium silicalite-1 with small crystal size by using mother liquid of titanium silicalite-1 as seed[J]. Industrial & Engineering Chemistry Research, 2011, 50(14): 8485-8491.
38	DUAN Fangzheng, LI Jiyang, CHEN Peng, et al. A low-cost route to the syntheses of microporous cobalt-substituted aluminophosphates by using the waste mother-liquor[J]. Microporous and Mesoporous Materials, 2009, 126(1/2): 26-31.
39	JIA Lixia, SONG Mingjuan, YE Xiuqun, et al. Recycling mother liquor to synthesize mesoporous SBA-15 silica[J]. Asian Journal of Chemistry, 2013, 25(17): 9627-9631.
40	CAO Li, HU Qingxun, JIN Junsu, et al. A multiple-assembly/one-pot-crystallization strategy for a relatively more eco-friendly synthesis of hydrothermally stable mesoporous aluminosilicates[J]. RSC Advances, 2014, 4(106): 61631-61633.
41	MI Xiaotong, LIU Honghai, WANG Baojie, et al. Urea as efficient additive toward decreasing water amount in synthesis of hydrothermally stable mesoporous aluminosilicates[J]. Industrial & Engineering Chemistry Research, 2017, 56(33): 9401-9407.
42	CHEN Han, ZHEN Fei, LIU Honghai, et al. Hydrophobic polypropylene glycol integration into the micelles: A general approach for high utilization efficiency of organic template[J]. Industrial & Engineering Chemistry Research, 2021, 60(26): 9482-9488.
43	ZHAO Xiaozheng, MI Xiaotong, CHEN Han, et al. Efficient synthesis of hydrothermally stable mesoporous aluminosilicates using trace amounts of an anionic surfactant as a co-template[J]. Industrial & Engineering Chemistry Research, 2019, 58(37): 17608-17614.
44	MI Xiaotong, WANG Jiujiang, LI Jiang, et al. A facile strategy to synthesize hydrothermally stable mesoporous aluminosilicates with significantly decreased organic templates and H₂O[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 558: 179-185.
45	LIU Hongtao, ZHANG Yi, LV Linyi, et al. Obtaining of mesoporous aluminosilicates with high hydrothermal stability by composite organic templates: Utility and mechanism[J]. Langmuir, 2021, 37(30): 9137-9143.
46	MI Xiaotong, YUAN Jiongliang, HAN Yueming, et al. Introduction of anionic surfactants to copolymer micelles: A key to improving utilization efficiency of P123 in synthesis of mesoporous aluminosilicates[J]. Industrial & Engineering Chemistry Research, 2017, 56(25): 7224-7228.
47	LIU Hongtao, XU Yajuan, WANG Jiujiang, et al. A triple template of P123/SDS/CS with simultaneously enhanced utilization efficiency of P123 and crystal seeds[J]. Journal of Alloys and Compounds, 2018, 765: 907-912.

序号	合成过程	模板剂耗量/g模板剂·(g产品)^-1	水耗量/g水·(g产品)^-1	水热前后比表面积^①/m²·g^-1	水热前后孔体积^①/cm³·g^-1
1	P123常规合成^[43]	1.92	75	651.0→218.0	0.84→0.34
2	F68常规合成^[44]	1.88	86	739.0→223.0	1.18→0.45
3	P123+晶种^[33-34]	0.79	34.3	704.5→231.4	0.79→0.39
4	P123,母液循环^[40]	0.97	22.75	635.7→95.5	1.01→0.20
5	P123/Urea^[41]	1.3	25	775.2→290.6	0.99→0.58
6	P123/PPG^[42]	0.85	—	803.0	0.97
7	P123/AES^[43]	0.88	17	666.0→235.0	0.91→0.48
8	F68/SDMBS^[44]	1.06	28.4	777.0→237.0	0.84→0.43
9	F68/PVA^[45]	0.82	17	775.4→251.2	0.88→0.49
10	P123/SDS^[46]	0.66	—	721.0	1.03
11	晶种/F68/SDS^[47]	0.77	19.8	625.5→230.6	0.77→0.43

序号	合成过程	模板剂耗量/g模板剂·(g产品)^-1	水耗量/g水·(g产品)^-1	水热前后比表面积^①/m²·g^-1	水热前后孔体积^①/cm³·g^-1
1	P123常规合成^[43]	1.92	75	651.0→218.0	0.84→0.34
2	F68常规合成^[44]	1.88	86	739.0→223.0	1.18→0.45
3	P123+晶种^[33-34]	0.79	34.3	704.5→231.4	0.79→0.39
4	P123,母液循环^[40]	0.97	22.75	635.7→95.5	1.01→0.20
5	P123/Urea^[41]	1.3	25	775.2→290.6	0.99→0.58
6	P123/PPG^[42]	0.85	—	803.0	0.97
7	P123/AES^[43]	0.88	17	666.0→235.0	0.91→0.48
8	F68/SDMBS^[44]	1.06	28.4	777.0→237.0	0.84→0.43
9	F68/PVA^[45]	0.82	17	775.4→251.2	0.88→0.49
10	P123/SDS^[46]	0.66	—	721.0	1.03
11	晶种/F68/SDS^[47]	0.77	19.8	625.5→230.6	0.77→0.43

[1]	张晨光, 封硕, 邢玉烨, 沈伯雄, 苏立超. 柴油车用NH₃-SCR铜基分子筛催化剂孤立态Cu²⁺研究进展[J]. 化工进展, 2023, 42(3): 1321-1331.
[2]	祝琳华, 吴植宇, 司甜. 介孔磷酸盐分子筛上钒物种的引入方式及其对丙烷氧化脱氢催化性能的影响[J]. 化工进展, 2019, 38(05): 2363-2371.
[3]	唐国旗1，张春富2，孙长山2，严斌2，杨国祥2，戴伟1，田保亮1. 活性氧化铝载体的研究进展 [J]. 化工进展, 2011, 30(8): 1756-.
[4]	柳杨1，2，衣怀峰3，陈宇1，2，吴玉龙2，陈曾1，杨明德2，童军茂1. SBA-15的改性及催化文冠果油制备生物柴油 [J]. 化工进展, 2011, 30(6): 1247-.
[5]	任艳群1，2，王冲1，莫家乐1，谭艳芝1，奚红霞1. 介孔分子筛载体在油品深度加氢脱硫中的应用研究进展 [J]. 化工进展, 2011, 30(4): 743-.
[6]	任文玲，陈绍云，张永春，李桂民. Zn/SBA-15介孔吸附剂的制备及脱附低浓度H2S性能[J]. 化工进展, 2011, 30(10): 2304-.
[7]	李建龙，张长远. 介孔分子筛集砷材料的制备与表征 [J]. 化工进展, 2010, 29(3): 579-.
[8]	黄勇，谌伟庆，石秋杰，孙戊晨. 介孔分子筛SBA-15在催化领域的应用进展 [J]. 化工进展, 2009, 28(12): 2140-.
[9]	陈汇勇，奚红霞，李忠，夏启斌. 分子筛构-效关系的分子模拟研究进展 [J]. 化工进展, 2007, 26(7): 914-.
[10]	张微，徐恒泳，毕亚东，李文钊. 介孔分子筛SBA–15的改性研究进展 [J]. 化工进展, 2007, 26(2): 152-.
[11]	奚立民，于红艳. MCM-48负载SO₄^2-/ZrO₂定位催化硝化合成3,4-二甲基硝基苯 [J]. 化工进展, 2006, 25(12): 1419-.
[12]	詹望成，卢冠忠，王艳芹. 介孔分子筛的功能化制备及催化性能研究进展 [J]. 化工进展, 2006, 25(1): 1-.

高水热稳定性介孔分子筛的低成本合成研究进展

Low-cost synthesis of hydrothermally stable mesoporous aluminosilicates

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 47

相关文章 12

编辑推荐

Metrics

本文评价