等级孔分子筛传质性能的表征策略研究进展

doi:10.3969/j.issn.1006-396X.2021.04.001

摘要/Abstract

摘要：

等级孔分子筛材料因其兼具高效传质与择形催化的优势而成为当前分子筛研究领域热点，然而其传质优化机制的不明确是制约等级孔分子筛材料设计思路与发展方向的主要因素。简要介绍了等级孔分子筛材料研究现状，并重点对等级孔分子筛材料传质机制研究进展，包括当前研究所面临的挑战和研究策略等方面进行了综述，探讨了传质机制研究在等级孔分子筛材料研发过程的重要意义，并对未来发展方向进行了展望。

关键词: 等级孔分子筛, 孔结构, 扩散传质, 频率响应技术, 单分子跟踪技术

Abstract:

The hierarchical zeolite has become a hotspot in the current molecular sieve research field due to its advantages of efficient mass transfer and shape selection catalysis.The unclear mass transfer optimization mechanism has become a bottleneck restricting the design and development of hierarchical zeolite.This paper briefly introduces recent research and development status of the hierarchical zeolite,reviewes with emphasis the research progress in mass transfer mechanism of Hierarchical zeolite,the current research challenges and the analysis of current research strategy etc,and discussed the significance of mass transfer mechanism in the research and development of graded porous molecular sieve materials and the prospect of future development.

Key words: Hierarchical zeolite, Pore structure, Mass transfer of diffusion, Frequency response technology, Single?molecule tracking technology

中图分类号:

TE624.9

张锦研, 王焕, 秦玉才, 宋丽娟. 等级孔分子筛传质性能的表征策略研究进展[J]. 石油化工高等学校学报, 2021, 34(4): 1-8.

Jinyan Zhang, Huan Wang, Yucai Qin, Lijuan Song. Progress in Characterization Strategies Mass Transfer Mechanism of Hierarchical Zeolite[J]. Journal of Petrochemical Universities, 2021, 34(4): 1-8.

图/表 8

图1 自然界中具有等级结构体系的示例

Fig.1 An example diagram of a hierarchical system in nature

图2 等级孔材料的属性特征和分类方法示意

Fig.2 Schematic diagram of attribute characteristics and classification method of graded hole materials

图3 不同形状催化剂Thiele模数与效率因子的关系

Fig.3 Relationship between Thiele modulus and efficiency factor of catalysts with different shapes

图4 等级孔分子筛材料的分类与孔结构成因示意

Fig.4 Classification of hierarchical zeolite and pore structure genesis diagram

图5 贯通的等级孔道及其中客体分子的运行轨迹示意

Fig.5 Schematic diagram of running trajectories of perforated hierarchical channels and guest molecules

图6 计算机模拟贯通孔和孤立孔结构的有效扩散系数与平衡压力的关系

Fig.6 The relationship between effective diffusion coefficient and equilibrium pressure for through?hole and isolate?hole structures simulated by computer

图7 等级孔材料内存在复杂的传质过程

Fig.7 Complex mass transfer processes exist in hierarchical materials

图8 单分子轨迹与TEM照片的合并与关联

Fig.8 Merges and association of Single?molecule trajectories with TEM images

参考文献 57

1	Pérez⁃Ramírez J，Christensen C H，Egeblad K，et al.Hierarchical zeolites：enhanced utilisation of microporous crystals in catalysis by advances in materials design［J］.Chemical Society Reviews，2008，37（11）：2530⁃2542.
2	郑健，秦玉才，宋丽娟，等.Y分子筛中硅铝桥羟基结构调变规律的理论研究［J］.石油化工高等学校学报，2019，32（1）：6⁃12.
	Zheng J，Qin Y C，Song L J，et al.Theoretical study on the regulation of hydroxyl structure of silica⁃alumina bridge in Y zeolite［J］.Journal of Petrochemical Universities，2019，32（1）：6⁃12.
3	Hartmann M，Schwieger W.Hierarchically⁃structured porous materials：From basic understanding to applications［J］.Chemical Society Reviews，2016，45（12）：3311⁃3312.
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	Schwieger W，Machoke A G，Weissenberger T，et al.Hierarchy concepts：Classification and preparation strategies for zeolite containing materials with hierarchical porosity［J］.Chemical Society Reviews，2016，45（12）：3353⁃3376.
6	Cychosz K A，Guillet⁃Nicolas R，García⁃Martínez J，et al.Recent advances in the textural characterization of hierarchically structured nanoporous materials［J］.Chemical Society Reviews，2017，46（2）：389⁃414.
7	Verboekend D，Nuttens N，Locus R，et al.Synthesis，characterisation，and catalytic evaluation of hierarchical faujasite zeolites：Milestones，challenges，and future directions［J］.Chemical Society Reviews，2016，45（12）：3331⁃3352.
8	Schneider D，Mehlhorn D，Zeigermann P，et al.Transport properties of hierarchical micro–mesoporous materials［J］.Chemical Society Reviews，2016，45（12）：3439⁃3467.
9	Yang X Y，Chen L H，Li Y，et al.Hierarchically porous materials：Synthesis strategies and structure design［J］.Chemical Society Reviews，2017，46（2）：481⁃558.
10	Serrano D P，Aguado J，Escola J M，et al.Hierarchical zeolites with enhanced textural and catalytic properties synthesized from organofunctionalized seeds［J］.Chemistry of Materials，2006，18（10）：2462⁃2464.
11	de Jong K P，Zečević J，Friedrich H，et al.Zeolite Y crystals with trimodal porosity as ideal hydrocracking catalysts［J］.Angewandte Chemie，2010，122（52）：10272⁃10276.
12	Na K，Jo C，Kim J，et al.Directing zeolite structures into hierarchically nanoporous architectures［J］.Science，2011，333（6040）：328⁃332.
13	Zhang X，Liu D，Xu D，et al.Synthesis of self⁃pillared zeolite nanosheets by repetitive branching［J］.Science，2012，336（6089）：1684⁃1687.
14	Chen L H，Li X Y，Rooke J C，et al.Hierarchically structured zeolites：Synthesis，mass transport properties and applications［J］.Journal of Materials Chemistry，2012，22（34）：17381⁃17403.
15	Verboekend D，Vilé G，Pérez‐Ramírez J.Hierarchical Y and USY zeolites designed by post‐synthetic strategies［J］.Advanced Functional Materials，2012，22（5）：916⁃928.
16	Yue Y，Liu H，Yuan P，et al.From natural aluminosilicate minerals to hierarchical ZSM⁃5 zeolites：A nanoscale depolymerization–reorganization approach［J］.Journal of Catalysis，2014，319：200⁃210.
17	Liu Z，Liu L，Song H，et al.Hierarchical SAPO⁃11 preparation in the presence of glucose［J］.Materials Letters，2015，154：116⁃119.
18	Wang Y，Ma J，Ren F，et al.Hierarchical architectures of ZSM⁃5 nanocrystalline aggregates with particular catalysis for lager molecule reaction［J］.Microporous and Mesoporous Materials，2017，240：22⁃30.
19	Mi S，Wei T，Sun J，et al.Catalytic function of boron to creating interconnected mesoporosity in microporous Y zeolites and its high performance in hydrocarbon cracking［J］.Journal of Catalysis，2017，347：116⁃126.
20	Jin D，Ye G，Zheng J，et al.Hierarchical silicoaluminophosphate catalysts with enhanced hydroisomerization selectivity by directing the orientated assembly of premanufactured building blocks［J］.ACS Catalysis，2017，7（9）：5887⁃5902.
21	Yue Y，Gu L，Zhou Y，et al.Template⁃free synthesis and catalytic applications of microporous and hierarchical ZSM⁃5 zeolites from natural aluminosilicate minerals［J］.Industrial & Engineering Chemistry Research，2017，56（36）：10069⁃10077.
22	Murray C D.The physiological principle of minimum work II.oxygen exchange in capillaries［J］.Proceedings of the National Academy of Sciences，1926，12（5）：299⁃304.
23	Zeigermann P，Kärger J，Valiullin R.Diffusion in microporous materials with embedded mesoporosities［J］.Microporous and Mesoporous Materials，2013，178：84⁃89.
24	Schmidt F，Paasch S，Brunner E，et al.Carbon templated SAPO⁃34 with improved adsorption kinetics and catalytic performance in the MTO⁃reaction［J］.Microporous and Mesoporous Materials，2012，164：214⁃221.
25	Bai P，Haldoupis E，Dauenhauer P J，et al.Understanding diffusion in hierarchical zeolites with house⁃of⁃cards nanosheets［J］.ACS nano，2016，10（8）：7612⁃7618.
26	Christensen C H，Johannsen K，Törnqvist E，et al.Mesoporous zeolite single crystal catalysts：Diffusion and catalysis in hierarchical zeolites［J］.Catalysis Today，2007，128（3⁃4）：117⁃122.
27	Zhao L，Shen B，Gao J，et al.Investigation on the mechanism of diffusion in mesopore structured ZSM⁃5 and improved heavy oil conversion［J］.Journal of Catalysis，2008，258（1）：228⁃234.
28	Meunier F C，Verboekend D，Gilson J P，et al.Influence of crystal size and probe molecule on diffusion in hierarchical ZSM⁃5 zeolites prepared by desilication［J］.Microporous and Mesoporous Materials，2012，148（1）：115⁃121.
29	Cho K，Cho H S，De Menorval L C，et al.Generation of mesoporosity in LTA zeolites by organosilane surfactant for rapid molecular transport in catalytic application［J］.Chemistry of Materials，2009，21（23）：5664⁃5673.
30	Vattipalli V，Qi X，Dauenhauer P J，et al.Long walks in hierarchical porous materials due to combined surface and configurational diffusion［J］.Chemistry of Materials，2016，28（21）：7852⁃7863.
31	Ruthven D M，Eic M.Intracrystalline diffusion in zeolites［J］.Guiding Journal of Traditional Chinese Medicine & Pharmacy，1988（368）：362–375.
32	Gueudré L，Milina M，Mitchell S，et al.Superior mass transfer properties of technical zeolite bodies with hierarchical porosity［J］.Advanced Functional Materials，2014，24（2）：209⁃219.
33	Mitra P P，Sen P N，Schwartz L M，et al.Diffusion propagator as a probe of the structure of porous media［J］.Physical Review Letters，1992，68（24）：3555.
34	Kärger J，Valiullin R.Mass transfer in mesoporous materials：The benefit of microscopic diffusion measurement［J］.Chemical Society Reviews，2013，42（9）：4172⁃4197.
35	Slade R C T.Quasielastic neutron scattering：Principles and applications in solid state chemistry，biology and materials science［M］.Adam Hilger：Bristol，1988：437.
36	Jobic H，Theodorou D N.Quasi⁃elastic neutron scattering and molecular dynamics simulation as complementary techniques for studying diffusion in zeolites［J］.Microporous and Mesoporous Materials，2007，102（1⁃3）：21⁃50.
37	Talmon Y，Shtirberg L，Harneit W，et al.Molecular diffusion in porous media by PGSE ESR［J］.Physical Chemistry Chemical Physics，2010，12（23）：5998⁃6007.
38	Wessig M，Spitzbarth M，Drescher M，et al.Multiple scale investigation of molecular diffusion inside functionalized porous hosts using a combination of magnetic resonance methods［J］.Physical Chemistry Chemical Physics，2015，17（24）：15976⁃15988.
39	Mahurin S M，Dai S，Barnes M D.Probing the diffusion of a dilute dye solution in mesoporous glass with fluorescence correlation spectroscopy［J］.The Journal of Physical Chemistry B，2003，107（48）：13336⁃13340.
40	Cherdhirankorn T，Retsch M，Jonas U，et al.Tracer diffusion in silica inverse opals［J］.Langmuir，2010，26（12）：10141⁃10146.
41	Teraoka I，Langley K H，Karasz F E.Diffusion of polystyrene in controlled pore glasses：Transition from the dilute to the semidilute regime［J］.Macromolecules，1993，26（2）：287⁃297.
42	Beschieru V，Rathke B，Will S.Particle diffusion in porous media investigated by dynamic light scattering［J］.Microporous and Mesoporous Materials，2009，125（1⁃2）：63⁃69.
43	Mehlhorn D，Inayat A，Schwieger W，et al.Probing mass transfer in mesoporous faujasite‐type zeolite nanosheet assemblies［J］.Chem.Phys.Chem.，2014，15（8）：1681⁃1686.
44	Yasuda Y.Determination of vapor diffusion coefficients in zeolite by the frequency response method［J］.The Journal of Physical Chemistry，1982，86（10）：1913⁃1917.
45	Ruthven D M.Diffusion in zeolites［J］.Studies in Surface Science & Catalysis，1995，97（6）：223⁃234.
46	Onyestyák G，Shen D，Rees L V C.Frequency⁃response study of micro⁃and macro⁃pore diffusion in manufactured zeolite pellets［J］.Journal of the Chemical Society，Faraday Transactions，1995，91（9）：1399⁃1405.
47	Song L，Rees L V C.Adsorption and diffusion of cyclic hydrocarbon in MFI⁃type zeolites studied by gravimetric and frequency⁃response techniques［J］.Microporous and Mesoporous Materials，2000，35：301⁃314.
48	Gobin O C，Reitmeier S J，Jentys A，et al.Comparison of the transport of aromatic compounds in small and large MFI particles［J］.The Journal of Physical Chemistry C，2009，113（47）：20435⁃20444.
49	Teixeira A R，Qi X，Chang C C，et al.On asymmetric surface barriers in MFI zeolites revealed by frequency response［J］.The Journal of Physical Chemistry C，2014，118（38）：22166⁃22180.
50	Qin Y C，Gao X H，Zhang H，et al.Measurements and distinguishment of mass transfer processes in fluid catalytic cracking catalyst particles by uptake and frequency response methods［J］.Catalysis Today，2015，245：147⁃154.
51	秦玉才，高雄厚，石利飞，等.原位晶化FCC催化剂传质性能的频率响应法辨析［J］.物理化学学报，2016，31（2）：527⁃535.
	Qin Y C，Gao X H，Shi L F，et al.Identification of mass transfer performance of in⁃situ crystalline FCC catalyst by frequency response method ［J］.Acta Physico⁃Chimica Sinica，2016，31（2）：527⁃535.
52	陈振涛，徐春明.重质油在孔道内扩散传质的研究进展［J］.化工学报，2015，67（1）：165⁃175.
	Chen Z T，Xu C M.Research progress on diffusion and mass transfer of heavy oil in pore channels［J］.Chemical Engineering Journal，2015，67（1）：165⁃175.
53	Zürner A，Kirstein J，Döblinger M，et al.Visualizing single⁃molecule diffusion in mesoporous materials［J］.Nature，2007，450（7170）：705⁃708.
54	Ristanović Z，Kubarev A V，Hofkens J，et al.Single molecule nanospectroscopy visualizes proton⁃transfer processes within a zeolite crystal［J］.Journal of the American Chemical Society，2016，138（41）：13586⁃13596.
55	Hendriks F C，Meirer F，Kubarev A V，et al.Single⁃molecule fluorescence microscopy reveals local diffusion coefficients in the pore network of an individual catalyst particle［J］.Journal of the American Chemical Society，2017，139（39）：13632⁃13635.
56	Hendriks F C，Mohammadian S，Ristanović Z，et al.Integrated transmission electron and single‐molecule fluorescence microscopy correlates reactivity with ultrastructure in a single catalyst particle［J］.Angewandte Chemie International Edition，2018，57（1）：257⁃261.
57	Li J，Gong Q，Jia W，et al.Insight into the alkylation⁃fficiency of methanol with toluene over HZSMZeolite II：Acidic properties also significantly affects reacting㏄athways［J］.Chemistry Select，2020，5（22）：6800⁃6808.

[1]	杨元涛,袁帅,刘宇键,马静红,李瑞丰. 正十二烷在改性Y型沸石内的ZLC扩散研究[J]. 石油化工高等学校学报, 2018, 31(6): 11-16.
[2]	杨玲,张乐,宋丽娟. 稀土离子浓度对Y型分子筛传质动力学的影响[J]. 石油化工高等学校学报, 2017, 30(6): 12-16.
[3]	王洪涛,韩静宇,张莉,李萍,金英杰. 共生沸石MFI/MOR和BEA/MOR合成与介孔改性[J]. 石油化工高等学校学报, 2017, 30(1): 8-13.
[4]	王焕,轩丽伟,张吉庆,王海彦. 含钛复合载体的制备与表征[J]. 石油化工高等学校学报, 2012, 25(5): 22-24.