三元孔道结构纳米ZSM-5分子筛团聚体的合成

doi:10.11962/1006-4990.2020-0235

摘要/Abstract

摘要：

采用正丁胺和ZSM-5晶种双模板体系水热合成了一系列ZSM-5分子筛,考察了晶种、正丁胺添加量和晶化条件对分子筛物理化学性能、孔道结构和形貌的影响。对所得分子筛分别进行X射线衍射（XRD）、氮气吸-脱附、扫描电子显微镜（SEM）表征分析。结果表明：分子筛为三元孔道结构的纳米ZSM-5分子筛团聚体,正丁胺和晶种在合成过程中具有协同作用。在正丁胺与二氧化硅物质的量比为0.26、晶种添加量为3%（质量分数）、在120 ℃晶化24 h后再在170 ℃晶化48 h条件下合成的分子筛总比表面积和外比表面积分别为364 m²/g和59 m²/g。

关键词: 纳米ZSM-5分子筛团聚体, 正丁胺, 晶种, 协同作用

Abstract:

A series of ZSM-5 zeolite were hydrothermally synthesized by using the double template system of n-butylamine and ZSM-5 crystal seed.The influence of content of seed and n-butylamine,and crystallication process on the physicochemical properties,pore structure and morphology of obtained zeolites were investigated.The obtained zeolites were subjected to X-ray diffraction（XRD）,N₂ adsorption-desorption and scanning electron microscopy（SEM） characterization analysis.The analysis results showed that the obtained material was aggregated nano-sized ZSM-5 zeolite with ternary pore structure,and n-butylamine and seed crystals had a synergistic effect in the synthesis process.Under the synthesis conditions of n（n-butyla-mine）/n（SiO₂）=0.26,seed addition amount of 3%（mass fraction） and crystallization at 120 ℃ for 24 h and then at 170 ℃ for 48 h,the specific surface area and external surface area were 364 m²/g and 59 m²/g,respectively.

Key words: aggregated nano-sized ZSM-5 zeolites, n-butylamine, seed, synergistic effect

中图分类号:

TQ127.2

李孝国,米晓彤,侯章贵. 三元孔道结构纳米ZSM-5分子筛团聚体的合成[J]. 无机盐工业, 2020, 52(12): 104-108.

Li Xiaoguo,Mi Xiaotong,Hou Zhanggui. Synthesis of aggregated nano-sized ZSM-5 zeolite with ternary pore structure[J]. Inorganic Chemicals Industry, 2020, 52(12): 104-108.

图/表 10

表1

图1

图2

图3

表2

图4

图5

图6

图7

图8

参考文献 11

[1]	Wen C, Wang C, Chen L, et al. Effect of hierarchical ZSM-5 zeolite support on direct transformation from syngas to aromatics over the iron-based catalyst[J]. Fuel, 2019,244:492-498. doi: 10.1016/j.fuel.2019.02.041
[2]	Chen H. Aggregates of superfine ZSM-5 crystals:The effect of NaOH on the catalytic performance of methanol to propylene reaction[J]. Microporous and Mesoporous Materials, 2017,244:301-309. doi: 10.1016/j.micromeso.2017.02.014
[3]	Pan F. A fast route for synthesizing nano-sized ZSM-5 aggregates[J]. Journal of Materials and Chemistry, 2014,2(48):20667-20675.
[4]	Hamidzadeh M, Komeili S, Saeidi M. Seed-induced synjournal of ZSM-5 aggregates using the Silicate-1 as a seed:characterization and effect of the Silicate-1 composition[J]. Microporous and Mesoporous Materials, 2018,268:153-161. doi: 10.1016/j.micromeso.2018.04.016
[5]	Lestari A, Ginting S B, Saputra H. Effect of seed amounts on the synjournal of zeolite ZSM-5 using coal bottom ash and rice husk as sources of silica and alumina by using seeding method[J]. Materials Science Forum, 2019,948:9-13. doi: 10.4028/www.scientific.net/MSF.948
[6]	Majid H N, Sarah C L. Insight into seed-assisted template free synjournal of ZSM-5 zeolites[J]. Microporous and Mesoporous Materials, 2018,239:444-452. doi: 10.1016/j.micromeso.2016.10.040
[7]	Gao Y, Zheng B, Wu G, et al. Effect of the Si/Al ratio on the performance of hierarchical ZSM-5 zeolites for methanol aromatization[J]. RSC Advances, 2016,6(87):83581-83588. doi: 10.1039/C6RA17084F
[8]	Wu Z. Synjournal and consequence of aggregated nanosized ZSM-5 zeolite crystals for methanol to propylene reaction[J]. Industrial &Engineering Chemistry Research, 2019,58:10737-10749.
[9]	Zhang L. F-assisted synjournal of a hierarchical ZSM-5 zeolite for methanol to propylene reaction:a b-oriented thinner dimensional morphology[J]. RSC Advances, 2015,5(75):61354-61363.
[10]	Xue T, Li S, Wu H H, et al. Eco-friendly and cost-effective synjournal of ZSM-5 aggregates with hierarchical porosity[J]. Industrial & Engineering Chemistry Research, 2017,56:13535-13542.
[11]	Shen K, Wangz N, Chen X, et al. Seed-induced and additive-free synjournal of oriented nanorod-assembled meso/macroporous zeolites:Toward efficient and cost-effective catalysts for the MTA reaction[J]. Catalysis Science & Technology, 2017,7(21):5143-5153.

样品	n（NBA）/ n（SiO₂）	晶种添加量/%	相对结晶度/%	样品	n（NBA）/ n（SiO₂）	晶种添加量/%	相对结晶度/%
Z-0-0.26	0.26	0	—	Z-3-0.15	0.15	3	122
Z-1-0.26	0.26	1	99	Z-3-0.50	0.50	3	95
Z-3-0.26	0.26	3	100	Z-1	0.26	3	93
Z-5-0.26	0.26	5	98	Z-2	0.26	3	93

样品	S_BET/ （m²·g^-1）	S_micro/ （m²·g^-1）	S_ext/ （m²·g^-1）	V_BET/ （cm³·g^-1）	V_micro/ （cm³·g^-1）	V_ext/ （cm³·g^-1）
Z-0-0.26	290	257	33	0.12	0.10	0.02
Z-1-0.26	306	264	42	0.14	0.10	0.04
Z-3-0.26	319	269	50	0.15	0.10	0.05
Z-5-0.26	324	279	45	0.16	0.11	0.05
Z-1	336	280	56	0.16	0.11	0.05
Z-2	364	304	59	0.17	0.12	0.05

[1]	常洋,李孝国,侯章贵,米晓彤,尉琳琳. 低硅铝比纳米团聚体ZSM-5的合成工艺研究[J]. 无机盐工业, 2020, 52(6): 92-95.
[2]	王子楠,陈葵,朱家文,张玉荣,林发蓉,周晓葵. 晶种和盐处理剂对煅烧过程中二氧化钛晶型转变的影响[J]. 无机盐工业, 2020, 52(3): 45-50.
[3]	邓魁,裴广斌,王茜. 一种低晶种比率生产超细氢氧化铝的工艺方法研究[J]. 无机盐工业, 2020, 52(10): 121-124.
[4]	李志强,杨立斌,沙作良,王彦飞,朱亮,赵晓昱. 氯化钾间歇冷却结晶生长规律及粒度控制实验研究[J]. 无机盐工业, 2019, 51(8): 33-36.
[5]	姜科,周康根. 结晶法从含氟废水中合成粗颗粒冰晶石[J]. 无机盐工业, 2019, 51(6): 53-56.
[6]	吴风风, 孔凡滔, 吴秋芳. 晶种法制备亚微米纺锤形碳酸钙[J]. 无机盐工业, 2016, 48(9): 40-.
[7]	马松亮, 董广峰, 胡莉. 不纯净钾盐镁矾转化粒度研究[J]. 无机盐工业, 2016, 48(8): 57-.
[8]	周靖辉, 胡毅, 于海斌, 孙彦民, 刘峰, 季超. 高纯硅溶胶制备及在加氢精制催化剂中的应用[J]. 无机盐工业, 2016, 48(12): 89-.
[9]	吴健春, 王斌. 钛液水解工艺对偏钛酸性能的影响[J]. 无机盐工业, 2013, 45(8): 33-.
[10]	王勇, 焦其帅, 崔琳, 赵风云, 刘润静, 胡永其. 纳米硫酸钡晶种法制备亚微米硫酸钡的工艺研究[J]. 无机盐工业, 2013, 45(7): 15-.
[11]	杨丽萍, 石文建, 秦军, 谢占金. 工业废渣磷石膏水热合成硫酸钙晶须的研究[J]. 无机盐工业, 2013, 45(4): 49-.
[12]	葛启龙, 汪晓军, 何耀忠, 黎兆中. 利用氧化铁红厂废水制备氧化铁红晶种的研究[J]. 无机盐工业, 2012, 44(12): 48-.
[13]	周国娥. 关于钛白水解的几点见解[J]. 无机盐工业, 2011, 43(7): 42-.
[14]	赵瑞祥;安永峰. 添加晶种对氟硅酸钠结晶的影响[J]. 无机盐工业, 2009, 0(12): 0-0.
[15]	周振君;郭艳杰;吴学倩;肖素岗. 晶种水热法制备α-氧化铝微粉的生长动力学研究[J]. 无机盐工业, 2008, 0(12): 0-0.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会