晶种溶液辅助合成ZSM-5沸石及偏三甲苯异构化催化性能研究

摘要/Abstract

摘要： 以四丙基氢氧化铵为模板剂,商业硅溶胶为硅源,在100 ℃下合成了晶种溶液。同时,在无模板剂体系下,以晶种溶液辅助成功合成了结晶度良好的ZSM-5沸石,并探究了其合成条件。采用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、N₂吸附-脱附、傅里叶变换红外光谱(FT-IR)、X射线荧光光谱(XRF)和氨气程序升温脱附(NH₃-TPD)测试方法对合成的沸石样品进行表征。结果表明:在无模板剂存在下,仅添加0.5%(质量分数)晶种溶液即可合成ZSM-5沸石;同时,在最佳合成条件下,170 ℃晶化8 h可合成亚微米级ZSM-5沸石团聚体,粒径为500 nm左右。此外,在偏三甲苯异构化反应中,硅铝比为30的样品具有更好的催化性能,其偏三甲苯质量转化率、均三甲苯质量收率及均三甲苯选择性分别为32.81%、20.81%和63.42%。

关键词: ZSM-5沸石, 晶种溶液, 绿色合成, 无模板剂, 团聚体, 异构化

Abstract: The seed solution was synthesized at 100 ℃ using tetrapropylammonium hydroxide as template and commercial silica sol as silicon source. Meanwhile, ZSM-5 zeolites with well crystallinity were successfully synthesized by adding seed solution in the template-free system, and the synthetic conditions of ZSM-5 zeolites were explored. The synthesized zeolites samples were characterized by X-ray powder diffraction (XRD), scanning-electron microscopy (SEM), N₂ adsorption-desorption, fourier transform infrared (FT-IR), X-ray fluorescence spectroscopy (XRF) and ammonium temperature-programmed desorption (NH₃-TPD). The results show that ZSM-5 zeolites are synthesized by adding only 0.5% (mass fraction) seed solution in the template-free system. Meanwhile, submicron-scale ZSM-5 zeolite aggregates with the size of ~500 nm are synthesized at 170 ℃ for 8 h under optimal synthesis conditions. Furthermore, in the isomerization of trimethylbenzene, the sample with n(SiO₂)/n(Al₂O₃) ratio of 30 has better catalytic performance. Mass conversion of 1, 2, 4-trimethylbenzene, mass yield of 1, 3, 5-trimethylbenzene and selectivity of 1, 3, 5-trimethylbenzene are 32.81%, 20.81% and 63.42%, respectively.

Key words: ZSM-5 zeolite, seed solution, green synthesis, template-free, aggregate, isomerization

中图分类号:

TQ426.6

张红智, 张燕挺, 宋金锐, 刘景怡, 高玉芳, 李宁, 李晓峰. 晶种溶液辅助合成ZSM-5沸石及偏三甲苯异构化催化性能研究[J]. 硅酸盐通报, 2023, 42(7): 2563-2578.

ZHANG Hongzhi, ZHANG Yanting, SONG Jinrui, LIU Jingyi, GAO Yufang, LI Ning, LI Xiaofeng. Seed Solution-Assisted Synthesis of ZSM-5 Zeolite and Its Catalytic Performance of Trimethylbenzene Isomerization[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(7): 2563-2578.

参考文献

[1] ALFARO S, VALENZUELA M A, BOSCH P. Synthesis of silicalite-1 by dry-gel conversion method: factors affecting its crystal size and morphology[J]. Journal of Porous Materials, 2009, 16(3): 337-342.
[2] LI Y, LI L, YU J H. Applications of zeolites in sustainable chemistry[J]. Chem, 2017, 3(6): 928-949.
[3] SHI J, WANG Y D, YANG W M, et al. Recent advances of pore system construction in zeolite-catalyzed chemical industry processes[J]. Chemical Society Reviews, 2015, 44(24): 8877-8903.
[4] HARTMANN M, MACHOKE A G, SCHWIEGER W. Catalytic test reactions for the evaluation of hierarchical zeolites[J]. Chemical Society Reviews, 2016, 45(12): 3313-3330.
[5] SHAMZHY M, OPANASENKO M, CONCEPCIÓN P, et al. New trends in tailoring active sites in zeolite-based catalysts[J]. Chemical Society Reviews, 2019, 48(4): 1095-1149.
[6] TIAN H F, YANG X, TIAN H Z, et al. Realization of rapid synthesis of H-ZSM-5 zeolite by seed-assisted method for aromatization reactions of methanol or methane[J]. Canadian Journal of Chemistry, 2021, 99(11): 874-880.
[7] WANG S, WANG P F, QIN Z F, et al. Relation of catalytic performance to the aluminum siting of acidic zeolites in the conversion of methanol to olefins, viewed via a comparison between ZSM-5 and ZSM-11[J]. ACS Catalysis, 2018, 8(6): 5485-5505.
[8] LIANG T Y, CHEN J L, QIN Z F, et al. Conversion of methanol to olefins over H-ZSM-5 zeolite: reaction pathway is related to the framework aluminum siting[J]. ACS Catalysis, 2016, 6(11): 7311-7325.
[9] USLAMIN E A, SAITO H, KOSINOV N, et al. Aromatization of ethylene over zeolite-based catalysts[J]. Catalysis Science & Technology, 2020, 10(9): 2774-2785.
[10] JIN T, XIA D H, XIANG Y Z, et al. The effect of metal introduced over ZSM-5 zeolite for C9 heavy aromatics hydrodealkylation[J]. Petroleum Science and Technology, 2009, 27(16): 1821-1835.
[11] KIM T, KIM G P, JANG J, et al. An investigation on the selective hydrodealkylation of C₉⁺ aromatics over alkali-treated Pt/H-ZSM-5 zeolites[J]. Catalysis Science & Technology, 2016, 6(14): 5599-5607.
[12] VERMEIREN W, GILSON J. Impact of zeolites on the petroleum and petrochemical industry[J]. Topics in Catalysis, 2009, 52(9): 1131-1161.
[13] ARGAUER R J, LANDOLT G R. Crystalline zeolite ZSM-5 and method of preparing the same: U.S. Patent 3, 702, 886[P]. 1972-11-14.
[14] LOK B M, CANNAN T R, MESSINA C A. The role of organic molecules in molecular sieve synthesis[J]. Zeolites, 1983, 3(4): 282-291.
[15] SANG S Y, CHANG F X, LIU Z M, et al. Difference of ZSM-5 zeolites synthesized with various templates[J]. Catalysis Today, 2004, 93/94/95: 729-734.
[16] MENG L Q, MEZARI B, GOESTEN M G, et al. One-step synthesis of hierarchical ZSM-5 using cetyltrimethylammonium as mesoporogen and structure-directing agent[J]. Chemistry of Materials: a Publication of the American Chemical Society, 2017, 29(9): 4091-4096.
[17] XUE T, LI S S, WU H H, et al. Eco-friendly and cost-effective synthesis of ZSM-5 aggregates with hierarchical porosity[J]. Industrial & Engineering Chemistry Research, 2017, 56(46): 13535-13542.
[18] MAJANO G, DARWICHE A, MINTOVA S, et al. Seed-induced crystallization of nanosized Na-ZSM-5 crystals[J]. Industrial & Engineering Chemistry Research, 2009, 48(15): 7084-7091.
[19] MENG X J, XIAO F S. Green routes for synthesis of zeolites[J]. Chemical Reviews, 2014, 114(2): 1521-1543.
[20] LI Q A, CONG W W, XU C Y, et al. New insight into the inductive effect of various seeds on the template-free synthesis of ZSM-5 zeolite[J]. CrystEngComm, 2021, 23(48): 8641-8649.
[21] ZENG S J, WANG R W, LI A, et al. Solvent-free synthesis of nanosized hierarchical sodalite zeolite with a multi-hollow polycrystalline structure[J]. CrystEngComm, 2016, 18(36): 6779-6783.
[22] MA Q A, FU T J, REN K, et al. Controllable orientation growth of ZSM-5 for methanol to hydrocarbon conversion: cooperative effects of seed induction and medium pH control[J]. Inorganic Chemistry, 2022, 61(35): 13802-13816.
[23] NIU X J, BAI Y, DU Y E, et al. Size controllable synthesis of ZSM-5 zeolite and its catalytic performance in the reaction of methanol conversion to aromatics[J]. Royal Society Open Science, 2022, 9(3): 211284.
[24] GAO X, ZHANG L, TAO Z C, et al. New insight into seeding process leading to improved zeolitic acidity and surface properties for its catalytic application in propane aromatization[J]. Catalysis Today, 2021, 368: 232-242.
[25] PETUSHKOV A. Synthesis and characterization of nanocrystalline and mesoporous zeolites[D]. Iowa City, IA, USA: The University of Iowa, 2011.
[26] 王燕, 王明, 张旭斌, 等. Ni-Mo/HM上偏三甲苯异构化性能研究[J]. 化学工业与工程, 2016, 33(1): 35-39.
WANG Y, WANG M, ZHANG X B, et al. Research on the isomerization of 1, 2, 4-trimethylbenzene over Ni-Mo/HM[J]. Chemical Industry and Engineering, 2016, 33(1): 35-39 (in Chinese).
[27] YU Q J, ZHANG Q, LIU J W, et al. Inductive effect of various seeds on the organic template-free synthesis of zeolite ZSM-5[J]. CrystEngComm, 2013, 15(38): 7680-7687.
[28] RAZAVIAN M, FATEMI S, KOMASI M. Seed-assisted OSDA-free synthesis of ZSM-5 zeolite and its application in dehydrogenation of propane[J]. Materials Research Bulletin, 2015, 65: 253-259.
[29] XUE T, DONG L L, ZHANG Y, et al. Green and cost-effective preparation of small-sized ZSM-5[J]. Acta Physico-Chimica Sinica, 2018, 34(8): 920-926.
[30] NADA M H, LARSEN S C. Insight into seed-assisted template free synthesis of ZSM-5 zeolites[J]. Microporous and Mesoporous Materials, 2017, 239: 444-452.
[31] JACOBSEN C J H, MADSEN C, JANSSENS T V W, et al. Zeolites by confined space synthesis-characterization of the acid sites in nanosized ZSM-5 by ammonia desorption and ²⁷Al/²⁹Si-MAS NMR spectroscopy[J]. Microporous and Mesoporous Materials, 2000, 39(1/2): 393-401.
[32] SHESTAKOVA D O, SASHKINA K A, PARKHOMCHUK E V. Template-free synthesis of hierarchical zeolite ZSM-5[J]. Petroleum Chemistry, 2019, 59(8): 838-844.
[33] PAN H H, PAN Q X, ZHAO Y S, 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.
[34] UGUINA M A, DE LUCAS A, RUIZ F, et al. Synthesis of ZSM-5 from ethanol-containing systems. Influence of the gel composition[J]. Industrial & Engineering Chemistry Research, 1995, 34(2): 451-456.
[35] RAZAVIAN M, FATEMI S. Synthesis and evaluation of seed-directed hierarchical ZSM-5 catalytic supports: inductive influence of various seeds and aluminosilicate gels on the physicochemical properties and catalytic dehydrogenative behavior[J]. Materials Chemistry and Physics, 2015, 165: 55-65.
[36] XU F, DONG M, GOU W Y, et al. Rapid tuning of ZSM-5 crystal size by using polyethylene glycol or colloidal silicalite-1 seed[J]. Microporous and Mesoporous Materials, 2012, 163: 192-200.
[37] HAMIDZADEH M, GHASSEMZADEH M, TARLANI A, et al. The effect of hydrothermal impregnation of Ni, Co, and Cu on HZSM-5 in the nitrogen oxide removal[J]. International Journal of Environmental Science and Technology, 2018, 15(1): 93-104.
[38] KANG N Y, SONG B S, LEE C W, et al. The effect of Na₂SO₄ salt on the synthesis of ZSM-5 by template free crystallization method[J]. Microporous and Mesoporous Materials, 2009, 118(1/2/3): 361-372.
[39] CUNDY C S, COX P A. The hydrothermal synthesis of zeolites: history and development from the earliest days to the present time[J]. ChemInform, 2003, 103(3): 663-702.
[40] 马广伟, 姜向东. ZSM-5/MOR共生分子筛的合成机理Ⅰ: 合成工艺对共生物相的影响[J]. 硅酸盐学报, 2009, 37(11): 1847-1852+1858.
MA G W, JIANG X D. Synthesis mechanism of ZSM-5/mordenite intergrowth molecular sieves-effect of synthesis conditions on intergrowth phase[J]. Journal of the Chinese Ceramic Society, 2009, 37(11): 1847-1852+1858 (in Chinese).
[41] SHAYIB R M, GEORGE N C, SESHADRI R, et al. Structure-directing roles and interactions of fluoride and organocations with siliceous zeolite frameworks[J]. Journal of the American Chemical Society, 2011, 133(46): 18728-18741.
[42] HAN S Y, LIU Y, YIN C R, et al. Fast synthesis of submicron ZSM-5 zeolite from leached illite clay using a seed-assisted method[J]. Microporous and Mesoporous Materials, 2019, 275: 223-228.