干胶转化法合成整体式SSZ-13分子筛

doi:10.11949/j.issn.0438-1157.20161381

摘要/Abstract

摘要：

采用干胶转化法合成了整体式SSZ-13分子筛，先成型后晶化，系统地考察了物料配比及晶化条件对合成结果的影响，通过X射线衍射（XRD）、X射线荧光（XRF）、热重-差热分析仪（TG-DTA）、扫描电子显微镜（SEM）、氨气的程序升温吸附-脱附（NH₃-TPD）、傅里叶红外光谱仪（FI-IR）、液体核磁共振谱（NMR）对产物进行表征分析，并讨论了混合模板剂N，N，N-三甲基-1-金刚烷氢氧化铵和氯化胆碱在晶化过程中起的作用。结果表明，合成的整体式SSZ-13分子筛具有典型的介孔堆积孔、较大的比表面积，在空气中热稳定性良好。氯化胆碱加速了分子筛晶化，缩短了晶化时间，提高产物的结晶度，明显降低了N，N，N-三甲基-1-金刚烷氢氧化铵的使用量，起到了辅助结构导向的作用，且混合模板剂均填充产物孔道。

关键词: 干胶转化, 整体式, SSZ-13, 分子筛, 结晶, 氯化胆碱, 结构导向, 成核

Abstract:

In this work, monolithic SSZ-13 zeolite was synthesized using dry-gel conversion method. The influences of the gel composition and crystallization conditions on the crystallization of SSZ-13 zeolite were investigated. The as-synthesized product was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF),thermo gravimetric-differential thermal analysis (TG-DTA, scanning electron microscope(SEM), NH₃ temperature-programmed desorption(NH₃-TPD, Nuclear Magnetic Resonance (NMR). The roles of N,N,N-trimethyl-1-adamantanammonium (TMADa⁺) and choline chloridein crystallization reaction were discussed. According to the result, the monolithic SSZ-13 zeolite has typical accumulated mesopores, larger surface area and better thermal stability in air. The results in FT-IR and NMR spectra show that choline chloride could act as a secondary structure-directing agent and fill in the pores of zeolite, which significantly reduced the amount of TMADa⁺. It was confirmed that Choline Chloride favors accelerating zeolite nucleation, shortening the crystallization time, and improving crystallinity of the as-synthesized product.

Key words: dry-gel conversion, monolithic, SSZ-13, zeolite, crystallization, choline chloride, structural-directing, nucleation

中图分类号:

TQ426.94

冯晴, 裴仁彦, 刘红光, 于海斌, 张丽娟, 张耀日. 干胶转化法合成整体式SSZ-13分子筛[J]. 化工学报, 2017, 68(3): 1231-1238.

FENG Qing, PEI Renyan, LIU Hongguang, YU Haibin, ZHANG Lijuan, ZHANG Yaori. Synthesis of monolithic SSZ-13 zeolite by dry-gel conversion method[J]. CIESC Journal, 2017, 68(3): 1231-1238.

参考文献 33

[1]	ZONES S I. Zeolite SSZ-13 and its method of preparation:US4544538[P]. 1985-10-01.
[2]	杨博, 郭翠梨, 程景耀. SSZ-13分子筛的合成及应用进展[J]. 化工进展, 2014, 33(2):368-373. YANG B, GUO C L, CHENG J Y. Progress in synthesis and application of SSZ-13 zeolite[J]. Chem. Ind. & Eng. Pro., 2014, 33(2):368-373.
[3]	WU L L, EMIELL J M, HENSEN. Comparison of mesoporous SSZ-13 and SAPO-34 zeolite catalysts for the methanol-to-olefins reaction[J]. Catal. Today, 2014, 235:160-168.
[4]	李鹏, 张维萍, 包信和, 等. SSZ-13和RUB-50分子筛上甲醇制烯烃的对比研究[J]. 催化学报, 2011, 32(2):293-298. LI P, ZHANG W P, BAO X H, et al. A comparative study of methanol to olefins over SSZ-13 and RUB-50 zeolites[J]. Chin. J. Catal., 2011, 32(2):293-298.
[5]	王文婷. SSZ-13分子筛在MTO反应中的应用[D]. 天津:天津工业大学, 2005. WANG W T. Application of SSZ-13 zeolite in MTO reaction[D]. Tianjin:Tianjin Polytechnic University, 2005.
[6]	DAI W L, SUN X M, TANG B, et al. Verifying the mechanism of the ethene-to-propene conversion on zeolite H-SSZ-13[J]. J. Catal., 2014, 324:10-20.
[7]	郑艺鸿, 布娜, 袁晓蕾, 等. SSZ-13分子筛膜在CO2/N2体系中的分离性能研究[J]. 江西师范大学学报, 2015, (4):411-414. ZHENG Y H, BU N, YUAN X L, et al. The studies on CO2/N2 separation performance of SSZ-13 membranes[J]. Journal of Jiangxi Normal University, 2015, (4):411-414.
[8]	ZHENG Y H, HU N, WANG H M, et al. Preparation of steam-stable high-silica CHA(SSZ-13) membranes for CO2/CH4 and C2H4/C2H6 separation[J]. J. Membr. Sci., 2015, 475:303-310.
[9]	任丽敏, 张一波, 肖丰收, 等. 由新型铜胺络合物模板剂设计合成活性优异的Cu-SSZ-13分子筛[J]. 催化学报, 2012, 33(1):92-100. REN L M, ZHANG Y B, XIAO F S, et al. Design and synthesis of a catalytically active Cu-SSZ-13 zeolite from a copper-amine complex template[J]. Chin. J. Catal., 2012, 33(1):92-100.
[10]	REN L, ZHU L, YANG C, et al. Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH3[J]. Chem. Commun. 2011, 47(35):9789-9791.
[11]	ZHENG Y, MICHAEL P. HAROLD, DAN L. Effects of CO, H2 and C3H6 on Cu-SSZ-13 catalyzed NH3-SCR[J]. Catal. Today, 2016, 264:44-54.
[12]	KIM Y J, LEE J K, MIN K M, et al. Hydrothermal stability of Cu-SSZ13 for reducing NOx by NH3[J]. J. Catal., 2014, 331:447-457.
[13]	KWAK J H, TONKYN R G, KIM D H, et al. Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3[J]. J Catal, 2010, 275(22):187-190.
[14]	俞华锋, 张国佩, 韩丽娜, 等. 微波辐射法制备Cu-SSZ-13催化剂及其对柴油车尾气NOx的脱除[J]. 物理化学学报, 2015, 31(11):2065-2173. YU H F, ZHANG G P, HAN L N, et al. Cu-SSZ-13 catalyst synthesized under microwave irradiation and its performance in catalytic removal of NOx from vehicle exhaust[J]. Acta. Phys. Chim. Sin., 2015, 31(11):2165-2173.
[15]	ZONES S I. Preparation of zeolite SSZ-13:US8007763B2[P]. 2011-08-30.
[16]	WU L L, DEGIRMENCI V, MAGUSIN PCCM, et al. Dual template synthesis of highly mesoporous SSZ-13 zeolite with improved stability in the methanol-to-olefins reaction[J]. Catal. Commun., 2012, 48:9492-9494.
[17]	WU L L, DEGIRMENCI V, MAGUSIN PCCM, et al. Mesoporous SSZ-13 zeolite prepared by a dual-template method with improved performance in the methanol-to-olefins reaction[J]. J. Catal., 2013, 289:27-40.
[18]	韩玉, 刘红光, 裴仁彦, 等. 混合模板法低成本合成SSZ-13分子筛的研究[J]. 无机盐工业, 2016, 48(9):36-39. HAN Y, LIU H G, PEI R Y, et al. Cheap and rapid synthesis of SSZ-13 zeolite with dual templates[J]. Ino. Chem. Ind., 2016, 48(9):36-39.
[19]	MENG X J, XIAO F S. Green routes for synthesis[J]. Chem. Rev., 2014, 114(2):1521-1543.
[20]	XU W, DONG J, LI J, et al. A novel method torthe prepatation of zeolite ZSM-5[J]. Chem. Commun, 1990:755-756.
[21]	杨娜, 岳明波, 王一萌.干胶法合成分子筛[J]. 化学进展, 2012, 24(2/3):253-261. YANG N, YUE M B, WANG Y M. Synthesis of zeolites by dry gel conversion[J]. Chem. Pro., 2012, 24(2/3) 253-261.
[22]	林淑勤, 陈立宇, 张璐璐, 等. 干胶液相转化法合成SAPO-34分子筛的晶化过程研究[J].天然气化工, 2011, 36(2):23-27. LIN S Q, CHEN L Y, ZHANG L L, et al. The research of crystallinity in synthesis of SAPO-34 zeolite by dry gel conversion[J]. Nat. Gas. Ind., 2011, 36(2):23-27.
[23]	孟祥举, 吴勤明, 肖丰收, 等. 一种通过固相研磨合成SSZ-13分子筛的方法:CN10409917A[P]. 2015-06-17. MENG X J, WU M B, XIAO F S, et al. A method for synthesizing SSZ-13 zeolite bysolidphare grinding:CN 104709917A[P]. 2015-06-17.
[24]	JIN Y Y, SUN Q Q, GUO D, et al. Solvent-free synthesis of silicoaluminophosphate zeolites[J]. Angew Chem. & Int. Ed., 2013, 52(35):9172-9175.
[25]	MENG X J, XIAO F S. Green routes for synthesis[J]. Chem. Rev., 2014, 114(2):1521-1543.
[26]	蒋丽蓉, 郎春燕, 陈小平. 氯化胆碱合成工艺及催化剂研究进展[J]. 化工进展, 2013, 32, 187-191. JIANG L R, LANG C Y, CHEN X P. Research progress of process and catalyst in synthesis of choline chloride[J].Chem. Ind. & Eng. Pro., 2013, 32:187-191.
[27]	邢淑建, 程志林, 于海斌, 等. 纳米丝光沸石的合成及表征[J]. 分子催化, 2008, 22(2):111-116. XING S J, CHENG Z L, YU H B, et al. Synthesis and characterization of mordenite nanocrystal[J]. J. Mol. Catal., 2008, 22(2):111-116.
[28]	徐如人, 庞文琴, 于吉红, 等. 分子筛与多孔材料化学[M]. 北京:科学出版社, 2004:145-147. XU R R, PANG W Q, YU J H, et al. Chemistry Zeolite and Porous Materials[M]. Beijing:Science Press, 2004:145-147.
[29]	NIKOLAY K, CLEMENT A, GERARD J, et al. Influence of the Si/Al ratio on the separation properties of SSZ-13 zeolite membranes[J]. J. Membr. Sci., 2015, 484:140-145.
[30]	LINN S, DAVIDE M, STIAN S. Mesopore formation in zeolite H-SSZ-13 by desilication with NaOH[J]. Microporous Mesoporous Mater., 2010, 132:384-394.
[31]	RUBIN M K, ROSINSKI E J, PLANK C J. Crystaline zeolite ZSM-34 and method of preparing the same:US4086186[P]. 1978-04-25.
[32]	孙莉, 张强, 李春义, 等. 不同晶化条件对ZSM-34分子筛性质的影响[J]. 石油炼制与化工, 2015, 12(46):5-9. SUN L, ZHANG Q, LI C Y, et al. The influence on the properties of ZSM-34 zeolite under different crystallization conditions[J]. Pet. Process. Petroche., 2015, 12(46):5-9.
[33]	裴仁彦, 田志坚, 于海斌, 等. 季铵盐-季戊四醇低共熔混合物中合成磷酸铝分子筛[J]. 工业催化, 2013, 6(21):37-40. PEI R Y, TIAN Z J, YU H B, et al. Synthesis of aluminophosphate zeolites in quaternary ammonium salts and pentaerythritol eutectic mixture[J]. Chin. J. Catal., 2013, 6(21):37-40.