模板剂用量对片状ZSM-5合成及其催化裂解丁烯性能的影响

石油炼制与化工 ›› 2026, Vol. 57 ›› Issue (11): 91-98.

模板剂用量对片状ZSM-5合成及其催化裂解丁烯性能的影响

张臻浩¹,梁晋嘉¹,赵晨阳¹,韩蕾²,范彬彬¹,李文林¹,于峰¹

1. 太原理工大学化学与化工学院
2. 中石化石油化工科学研究院有限公司

收稿日期:2026-05-07 修回日期:2026-07-13 出版日期:2026-11-12 发布日期:2026-10-19
通讯作者: 张臻浩 E-mail:2627692608@qq.com
基金资助:
炼油工艺与催化剂国家工程研究中心课题;山西省科技成果转化引导专项;国家自然科学基金重点项目

EFFECTOFTEMPLATE CONTENT ON THE SYNTHESIS OFSHEET-LIKE ZSM-5 AND ITS CATALYTIC CRACKING PERFORMANCE OF 1-BUTENE

Received:2026-05-07 Revised:2026-07-13 Online:2026-11-12 Published:2026-10-19

摘要/Abstract

摘要： 系统考察了模板剂四丙基氢氧化铵（TPAOH）用量对合成片状ZSM-5分子筛孔结构、酸性质及其催化裂解丁烯性能的影响。结果表明：在所采用的合成体系中，当TPAOH/Si摩尔比为0.5~2.0时，所制备的一系列HZ5-xT分子筛均为高结晶度的片状ZSM-5分子筛；随着模板剂TPAOH含量的增加，合成样品的晶体在a轴和c轴方向上的尺寸明显增大，介孔孔体积及外比表面积也相应提高，同时样品的硅铝比也有所上升。在1-丁烯催化裂解反应中，HZ5-xT样品的酸性质对产物分布的影响更为显著。产物中C₁~C₄烷烃及芳烃的含量随样品中强酸酸量的增加而升高，而丙烯及C₅+非芳烃组分的含量则随强酸酸量的增加而降低。

关键词: 模板剂, 四丙基氢氧化铵, 片状ZSM-5, 1-丁烯, 裂解, 酸量, 晶体尺寸

Abstract: This study systematically investigated the effects of TPAOH content during the synthesis process on the pore properties, acidity, and catalytic butene cracking performance of the obtained sheet-like ZSM-5 zeolites. The results show that within the adopted synthesis system, when the TPAOH/Si molar ratio is in the range of 0.5—2.0, all the prepared HZ5-xT zeolites are sheet-like ZSM-5 with high crystallinity. As TPAOH content in the synthesis system increases, the crystal sizes of the synthesized sheet-like ZSM-5 samples along the a-axis and c-axis increase significantly, and the mesopore volume and external surface area are also enhanced, while the Si/Al ratio of the synthesized HZ5-xT samples increases. In the catalytic cracking reaction of 1-butene, the acidic properties of the HZ5-xT samples have a more significant effect on the product distribution. The contents of C₁—C₄ alkanes and aromatics in the products increase with increasing strong acid amount of the HZ5-xT samples, whereas the contents of propene and C₅+ components decrease with increasing strong acid amount.

Key words: template, TPAOH, sheet-like ZSM-5, 1-butene, cracking, acidity, crystal dimension

张臻浩梁晋嘉赵晨阳韩蕾范彬彬李文林于峰. 模板剂用量对片状ZSM-5合成及其催化裂解丁烯性能的影响[J]. 石油炼制与化工, 2026, 57(11): 91-98.

参考文献

[1] Vafi L, Karimzadeh R. A novel method for enhancing the stability of ZSM-5 zeolites used for catalytic cracking of LPG: catalyst modification by dealumination and subsequent silicon loading [J]. Chinese Journal of Catalysis, 2016, 37(4): 628–635. [2] Zuo C, Su Q. Research progress on propylene preparation by propane dehydrogenation [J]. Molecules, 2023, 28(8): 3594. [3] Yang M, Fan D, Wei Y X, et al. Recent progress in methanol‐to‐olefins (MTO) Catalysts [J]. Advanced Materials, 2019, 31(50): 1902181. [4] Liu S S, Li D, Yang S Y, et al. Local heat exchanger network optimization of industrial coal-to-olefin process based on hot direct feed/discharge strategy [J]. Applied Thermal Engineering, 2022, 207: 118161. [5] 王瑞霖, 许友好, 阳文杰等. 1-戊烯和正戊烷在不同硅/铝比ZSM-5分子筛上的高温裂解性能[J]. 石油学报（石油加工）, 2025, 41(4): 960-968. [6] Gholami Z, Gholami F, Ti?ler Z, et al. A review on production of light olefins via fluid catalytic cracking [J]. Energies, 2021, 14(4): 1089. [7] 段绘州，刘鑫辉，吴一鹏等. 铝源种类对ZSM-5分子筛铝原子分布及丁烯裂解反应性能的影响[J]. 石油炼制与化工, 2026, 57(2): 158-165. [8] Wu T, Chen S L, Yuan G M, et al. Enhanced catalytic performance in butylene cracking by hierarchical surface silicon-rich ZSM-5 [J]. Fuel Processing Technology, 2017, 167: 162–170. [9] Ma X, Yang J B, Zhou J, et al. Synthesis of small crystal ZSM-5 zeolite by solvent-free method and catalytic cracking performance of butene [J]. Journal of Fuel Chemistry and Technology, 2025, 53(1): 163–173. [10] Wu T, Li S J, Yuan G M, et al. Enhanced selectivity of propylene in butylene catalytic cracking over W-ZSM-5 [J]. Fuel Processing Technology, 2018, 173: 143–152. [11] Zhang H T, Xi Z X, Wang H Y, et al. High stability catalyst for butene cracking with ultrathin ZSM-5 nanoplates [J]. Industrial & Engineering Chemistry Research, 2024, 63(36): 15637–15645. [12] Auepattana-aumrung C, Suriye K, Jongsomjit B, et al. Inhibition effect of Na+ form in ZSM-5 zeolite on hydrogen transfer reaction via 1-butene cracking [J]. Catalysis Today, 2020, 358: 237–245. [13] Zhang R R, Wang Z B. Catalytic cracking of 1-butene to propylene by Ag modified HZSM-5 [J]. Chinese Journal of Chemical Engineering, 2015, 23(7): 1131–1137. [14] Shi J, Zhao G L, Teng J W, et al. Morphology control of ZSM-5 zeolites and their application in cracking reaction of C4 olefin [J]. Inorganic Chemistry Frontiers, 2018, 5(11): 2734–2738. [15] Chen Y H, Zhang Q, Han D M, et al. Fluoride-and OSDA-free synthesis of ZSM-5 with controllable b-axis orientation: Insights into the role of medium alkalinity and seed induction [J]. Advanced Powder Technology, 2024, 35(11). [16] Zhu P, Liu C, Yu Y R, et al. Low-cost and fluoride-free synthesis of MFI zeolite nanosheets with enhanced stability for benzene alkylation with ethanol [J]. Journal of Energy Chemistry, 2025, 100: 458–468. [17] Ren S, Tian C, Yue Y H, et al. Selective alkylation of benzene with methanol to toluene and xylene over sheet-like ZSM-5 with controllable b-oriented length [J]. Catalysis Letters, 2023, 154(3): 858–867. [18] Dai W J, Zhang L N, Liu R Z, et al. Plate-like ZSM-5 zeolites as robust catalysts for the cracking of hydrocarbons [J]. ACS Applied Materials & Interfaces, 2022, 14(9): 11415–11424. [19] Dai W J, Kouvatas C, Tai W, et al. Platelike MFI crystals with controlled crystal faces aspect ratio [J]. Journal of the American Chemical Society, 2021, 143(4): 1993–2004. [20] Zhang J X, Zhou A, Gawande K, et al. B-axis-Oriented ZSM-5 nanosheets for efficient alkylation of benzene with methanol: synergy of acid sites and diffusion [J]. ACS Catalysis, 2023, 13(6): 3794–3805. [21] Liu J J, Shen X H, Ling L X, et al. Impact of the Al sites of ZSM-5 zeolite on product distribution in methanol to aromatics reaction [J]. Journal of Porous Materials, 2025, 32(3): 1135–1147. [22] Yue Q D, Wu J W, Liu H H, et al. Seeded growth of urea-promoted ZSM-5 nanoplates with short-axis thickness for enhanced methanol-to-olefin reactions [J]. Inorganic Chemistry Frontiers, 2026, 13(7): 2925–2935. [23] Pashkova V, Sklenak S, Klein P, et al. Location of framework Al atoms in the channels of ZSM-5: effect of the (hydrothermal) synthesis [J]. Chemistry-a European Journal, 2016, 22(12): 3937–3941. [24] Rzepka P, Huthwelker T, Dedecek J, et al. Aluminum distribution and active site locations in the structures of zeolite ZSM-5 catalysts [J]. Science, 2025, 388(6745): 423–428. [25] Lin L, Qiu C, Zhuo Z, et al. Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5 [J]. Journal of Catalysis, 2014, 309: 136–145.