Silicalite-1分子筛的低成本合成及其MTP催化性能

doi:10.16085/j.issn.1000-6613.2024-0345

摘要/Abstract

摘要：

分子筛的高效、环保和合成廉价在学术及工业应用领域都具有重要的意义。传统水热合成法中非有机胺体系因其弱导向性和杂晶相的竞争生长导致纯硅MFI分子筛（Silicalite-1）的合成极具挑战性。本文在甲醇体系中成功合成出Silicalite-1分子筛，并重点考察了水热合成过程中甲醇的作用和晶化条件（水硅比、醇硅比等）对分子筛合成的影响。使用蒙特卡罗模拟、X射线衍射（XRD）、扫描电子显微镜（SEM）、热重（TG）、N₂-吸附脱附和NH₃-程序升温脱附（NH₃-TPD）等方法进行了计算与表征。结果表明：引入晶种可以明显改善甲醇体系在晶化初期成核困难的问题，当晶种投入量为3%（质量分数）、醇硅比为3.3时可以直接合成出高结晶度的纯相Silicalite-1分子筛，该分子筛表现出优异的甲醇制丙烯（MTP）反应催化活性。最后，本文提出的Silicalite-1分子筛低成本合成策略具有显著的科研价值和工业化应用前景。

关键词: 分子筛, 合成, 蒙特卡罗模拟, 催化剂, 稳定性

Abstract:

The efficient, environmentally friendly, and cost-effective synthesis of zeolites holds significant importance in both academic and industrial applications. Traditionally, the synthesis of pure silicon MFI zeolite (Silicalite-1) through hydrothermal methods employing non-organic amine systems posed substantial challenges due to weak directing abilities and competitive growth of impure phases. In this study, Silicalite-1 zeolite was successfully synthesized in a methanol system, and particular attention was paid to the role of methanol and the crystallization conditions (water-to-silica ratio, alcohol-to-silica ratio, etc.) during the hydrothermal synthesis process. Computational and characterization techniques such as Monte Carlo simulations, XRD, SEM, TG, N₂ adsorption-desorption, and NH₃-TPD were employed. The results indicated that the introduction of seed crystals significantly improved the initial nucleation difficulties in the methanol system; a pure phase of Silicalite-1 with high crystallinity was directly synthesized when the seed crystal input was 3% and the alcohol-to-silica ratio was 3.3, showing excellent catalytic activity in the MTP reaction. Lastly, the low-cost synthesis strategy for Silicalite-1 proposed in this paper has notable research value and industrial application prospects.

Key words: molecular sieves, synthesis, Monte Carlo simulation, catalyst, stability

中图分类号:

TQ221.2

陶金泉, 贾亦静, 白天瑜, 姚荣鹏, 黄文斌, 崔岩, 周亚松, 魏强. Silicalite-1分子筛的低成本合成及其MTP催化性能[J]. 化工进展, 2025, 44(3): 1550-1558.

TAO Jinquan, JIA Yijing, BAI Tianyu, YAO Rongpeng, HUANG Wenbin, CUI Yan, ZHOU Yasong, WEI Qiang. Synthesis and catalytic MTP performance of Silicalite-1 zeolite with low cost[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1550-1558.

图/表 18

图1 Silicalite-1晶种XRD图谱和SEM图片

图2 不同醇硅比合成的Silicalite-1分子筛XRD谱图

图3 不同醇硅比合成的Silicalite-1分子筛SEM图

图4 不同水硅比合成的Silicalite-1分子筛XRD谱图

图5 客体分子吸附在MFI晶胞中的结构示意图

表1 不同水热体系客体分子负载量与相互作用能

体系	客体分子/cell	相互作用能/kJ·mol^-1
S1	42H₂O	-908.9
S2	42H₂O，2MeOH	-889.3
S3	41H₂O，4MeOH	-1085.2
S4	7H₂O，3TPA	-980.9

图6 不同晶种加入量下合成的Silicalite-1分子筛XRD谱图

图7 晶种辅助甲醇体系与单一甲醇体系合成的Silicalite-1分子筛相对结晶度

图8 晶种法与甲醇体系合成的Silicalite-1分子筛TG图

图9 晶种辅助甲醇体系合成的Silicalite-1分子筛的N2吸附脱附曲线

图10 晶化35h时不同晶种添加量下合成的Silicalite-1分子筛XRD谱图

图11 不同晶化时间下合成的Silicalite-1分子筛的相对结晶度

图12 1000mL釜合成的Silicalite-1分子筛的XRD谱图

图13 1000mL釜合成的Silicalite-1分子筛的SEM图

表2 分子筛的孔结构和酸性质

样品	比表面积/m²・g^-1			酸量/μmol・g^-1
样品	S_BET	S_Micro	S_Ext	总酸量	强酸	弱酸
MS-1	347	234	113	137	44	57
TPA-S-1	321	266	55	75	41	22
NKS-1	315	277	38	43	14	19
85HZSM-5	301	237	64	1197	92	357

图14 MS-1、TPA-S-1、NKS-1和85HZSM-5的甲醇转化率和反应时间的关系

图15 MS-1、TPA-S-1、NKS-1和85HZSM-5的丙烯收率和反应时间的关系

表3 反应10h不同催化剂MTP反应甲醇转化率和主要产物收率对比

样品	主要产物收率/%								丙烯收率/乙烯收率
样品	CH₄	C₂H₆	C₂H₄	C₃H₈	C₃H₆	C₄H₁₀	C₄H₈	C₅₊	丙烯收率/乙烯收率
MS-1	0.8	0.4	4.6	1.9	32.1	3.6	14.2	36.3	7.0
TPA-S-1	0.7	0.2	4.9	1.7	29.1	1.7	15.3	44.3	5.9
NKS-1	0.7	0.2	4.4	1.5	27.6	4.1	15.1	45.5	6.2
85HZSM-5	1.0	0.3	6.2	1.1	27.5	5.4	20.2	45.4	4.4

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