表面活性剂对SAPO-34晶体形貌的调控研究

doi:10.13218/j.cnki.csdc.2018.07.004

日用化学工业 ›› 2018, Vol. 48 ›› Issue (7): 382-387.doi: 10.13218/j.cnki.csdc.2018.07.004

表面活性剂对SAPO-34晶体形貌的调控研究

何祖光¹,李晓峰¹,狄春雨¹,李志宏¹,郭云鸦¹,窦涛²

1.太原理工大学精细化工研究所,山西太原 030024;
2.中国石油大学 CNPC催化重点实验室,北京 102249

出版日期:2018-07-22 发布日期:2019-03-22
通讯作者: 李晓峰,教授,电话:(0351)6014915,E-mail:lixiaofeng6008@163.com。
作者简介:何祖光(1991-),男,河南周口人,硕士研究生;电话:15034046671,E-mail:799765935@qq.com。
基金资助:
国家科技型中小企业技术创新项目(14C26211400552)

Study on the control of SAPO-34 crystal morphology by the surfactant

HE Zu-guang¹,LI Xiao-feng¹,DI Chun-yu¹,LI Zhi-hong¹,GUO Yun-ya¹,DOU Tao²

1.Institute of Special Chemicals,Taiyuan University of Technology,Taiyuan,Shanxi 030024,China;
2.CNPC Key Laboratory of Catalysis,China University of Petroleum,Beijing 102249,China

Online:2018-07-22 Published:2019-03-22

摘要/Abstract

摘要： 分别以拟薄水铝石为铝源,磷酸为磷源,硅溶胶为硅源,三乙胺和四乙基氢氧化铵为模板剂,在反应体系中添加十八烷基三甲基溴化铵(STAB)合成板层状小晶粒SAPO-34分子筛。通过XRD、SEM、FT-IR、NH₃-TPD和N₂吸附-脱附等手段对样品进行表征。并且考察了样品在甲醇制烯烃(MTO)反应中的催化性能。结果表明,由于STAB长链分子的存在,在反应中形成了特定的有机序列,可以使分子筛样品的粒径变小,厚度变薄,强酸量略微增加,对比与传统方法做出的分子筛样品,具有更高的催化寿命和双烯(乙烯+丙烯)选择性。

关键词: 十八烷基三甲基溴化铵, SAPO-34, 板层状, 小晶粒, 甲醇制烯烃

Abstract: The layered and small crystals of SAPO-34 molecular sieve were synthesized by adding a certain amount of octadecyltrimethylammonium bromide (STAB) and using pseudoboehmite as aluminum source,phosphoric acid as phosphorus source,silica sol as silicon source,and triethylamine and tetraethylammonium hydroxide as templates.The samples were characterized by XRD,SEM,FT-IR,NH₃-TPD and BET.The catalytic performances of these samples for converting methanol to olefins (MTO) were also evaluated.Results show that,due to the presence of STAB,a specific organic sequence is formed in the reaction and therefore the particle size becomes smaller and thinner and the content of strong acid increases slightly.In contrast with the molecular sieve samples prepared by traditional methods,it has higher catalytic lifetime and selectivity to ethylene and propylene.

Key words: octadecyltrimethylammonium bromide, SAPO-34 molecular sieve, layered, small crystal, conversion of methanol to olefins

中图分类号:

TQ423.12

何祖光,李晓峰,狄春雨,李志宏,郭云鸦,窦涛. 表面活性剂对SAPO-34晶体形貌的调控研究[J]. 日用化学工业, 2018, 48(7): 382-387.

HE Zu-guang,LI Xiao-feng,DI Chun-yu,LI Zhi-hong,GUO Yun-ya,DOU Tao. Study on the control of SAPO-34 crystal morphology by the surfactant[J]. China Surfactant Detergent & Cosmetics, 2018, 48(7): 382-387.

参考文献

[1] Wang H S,He X O.Ethylene process technology [M].Beijing:China Petrochemical Press,2000:1。
[2] Zhu J,Cui Y,Chen Y J,et al.Recent research on process from methanol to olefins [J].Ciesc Journal,2010,61(7):1674-1684.
[3] Di C Y.Synthesis and characterization of sapo-34 molecular sieve with lamellar morphology and its catalytic performance in MTO reaction [D].Taiyuan:Taiyuan university of technology,2012.
[4] Wilson S,Barger P.The characteristics of SAPO-34 which influence the conversion of methanol to light olefins [J].Microporous & Mesoporous Materials,1999,29(1/2):117-126.
[5] Flanigen E M.Zeolites and molecular sieves:an historical perspective [J].Studies in Surface Science & Catalysis,2001,58:13-34.
[6] Song W,Haw J F.Improved methanol-to-olefin catalyst with nanocages functionalized through ship-in-a-bottle synthesis from PH₃ [J].Angewandte Chemie,2003,42(8):892.
[7] Chen D,Moljord K,Fuglerud T,et al.The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction [J].Microporous & Mesoporous Materials,1999,29(1/2):191-203.
[8] Yang M,Tian P,Wang C,et al.A top-down approach to prepare silicoaluminophosphate molecular sieve nanocrystals with improved catalytic activity [J].Chemical Communications,2014,50(15):1845-1847.
[9] Yang D X,Wang P F,Xu H S,et al.Two-step crystallization synthesis and catalytic performance of nano-scaled SAPO-34 molecular sieve [J].Chemical Journal of Chinese Universities,2011(4):939-945.
[10] Zhu W P,Li F,Xue Y P,et al.Research advances in small crystal SAPO-34 molecular sieves[J].Natural Gas Chemical Industry,2014(1):72-76,81.
[11] Nishiyama N,Kawaguchi M,Hirota Y,et al.Size control of SAPO-34 crystals and their catalyst lifetime in the methanol-to-olefin reaction [J].Applied Catalysis A:General,2009,362(1/2):193-199.
[12] Hirota Y,Murata K,Tanaka S,et al.Dry gel conversion synthesis of SAPO-34 nanocrystals [J].Materials Chemistry & Physics,2010,123(2/3):507-509.
[13] Li X F,Wang P,Di C Y,et al.The preparation of layered SAPO-34 molecular sieve with double ammonium template and its catalytic performance for MTO reaction [J].Acta Petrolei Sinica (Petroleum Processing Section),2016(6):1099-1105.
[14] Xie S J,Niu X L,Xu L Y,et al.Synthesis of small crystal MCM-22 zeolite [J].Petrochemical Technology,2004,33(S1):39-41.
[15] Xu J,Wu Y,Wang C,et al.Dispersion polymerization of acrylamide with 2-acrylamide-2-methyl-1-propane sulfonate in aqueous solution of sodium sulfate [J].Journal of Polymer Research,2009,16(5):569-575.
[16] Han L,Cui X,Liu X M.Particle size control for SAPO-11 molecular sieves [J].Chinese Journal of Inorganic Chemistry,2013,29(3):565-570.
[17] Li L G,Tang Y,Zhang Y M,et al.Application of surfactants in controlling of size and shape of nano materials [J].Modern Chemical Industry,2005(S1):286-289.
[18] Yang G,Wei Y,Xu S,et al.Nanosize-enhanced lifetime of SAPO-34 catalysts in methanol-to-olefin reactions [J].Journal of Physical Chemistry C,2013,117(16):8214-8222.
[19] Serrano D P,Grieken R V,Sánchez P,et al.Crystallization mechanism of all-silica zeolite beta in fluoride medium [J].Microporous & Mesoporous Materials,2001,46(1):35-46.
[20] Cundy C S,Cox P A.The hydrothermal synthesis of zeolites:Precursors,intermediates and reaction mechanism [J].ChemInform,2005,82(1/2):1-78.

表面活性剂对SAPO-34晶体形貌的调控研究

Study on the control of SAPO-34 crystal morphology by the surfactant

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 1

Metrics

本文评价

推荐阅读 10