封装型丙烷脱氢催化剂的研究进展

doi:10.19964/j.issn.1006-4990.2024-0190

摘要/Abstract

摘要：

丙烷脱氢制丙烯（PDH）是增产重要化学品丙烯的一条重要技术路线。PDH反应作为结构不敏感型反应，C—H活化仅需单个金属或金属-氧位点即可发生；而其C—C活化的竞争反应则需要在聚集态的金属或氧化物位点上才能发生，因此PDH催化剂的开发策略大多是通过限域效应或金属载体强相互作用等构筑亚纳米尺度的脱氢活性中心以提高催化性能。近年来，利用分子筛孔道的限域效应构筑稳定的亚纳米尺寸活性位成为了近年来PDH领域的研究热点。首先对分子筛封装金属物种材料进行归纳分类，介绍了合成策略，并讨论了金属物种进入分子筛微孔内部的定性和定量的表征方法；然后总结了分子筛封装型金属催化剂包括贵金属催化剂及非贵金属催化剂应用于PDH反应的最新合成研究进展，同时介绍了其催化机理和结构-性能构效关系；最后提出了目前分子筛封装金属催化剂在丙烷脱氢工艺中的局限性和未来发展方向，以期为丙烷脱氢催化剂的制备提供新的思路。

关键词: 丙烷脱氢, 分子筛, 封装, 限域效应, 贵金属, 非贵金属

Abstract:

Propane dehydrogenation（PDH） to propylene is an important technological pathway for increasing the production of the vital chemical propylene.The PDH reaction，being a structure-insensitive process，requires only a single metal or metal-oxygen site for C—H activation to occur.However，the competing C—C activation reaction requires aggregation state metal or oxide sites to take place.Therefore，the development strategy of PDH catalysts often involves constructing sub-nanometer dehydrogenation active centers through confinement effects or strong metal-support interactions.In recent years，utilizing the confinement effect of zeolite channels to construct stable sub-nanometer-sized active sites has become a research hotspot in PDH field.The metal species encapsulated in zeolites were firstly systematically classified，synthesis strategies were introduced，and qualitative and quantitative methods for characterizing the entry of metal species into the micropores of zeolites were discussed.Then，the latest synthetic research progress of zeolite-encapsulated metal catalysts was summarized，including precious and non-precious metal catalysts for propane dehydrogenation reaction.Meanwhile，catalytic mechanisms and structure-function relationships were also discussed.Finally，the limitations and future development directions of zeolite-encapsulated metal catalysts in the propane dehydrogenation process were proposed to provide new insights for the preparation of metal-loaded zeolite propane dehydrogenation catalysts.

Key words: propane dehydrogenation, zeolite, encapsulation, confinement effect, noble metal, non-noble metal

中图分类号:

TQ426.6

王延苏, 冯晴, 刘国柱, 于海斌, 孙彦民, 南军. 封装型丙烷脱氢催化剂的研究进展[J]. 无机盐工业, 2024, 56(11): 95-104.

WANG Yansu, FENG Qing, LIU Guozhu, YU Haibin, SUN Yanmin, NAN Jun. Advances in encapsulated catalysts for propane dehydrogenation[J]. Inorganic Chemicals Industry, 2024, 56(11): 95-104.

图/表 10

图1

图2

图3

图4

图5

图6

表1

图7

图8

图9

参考文献 41

1	CHEN Sai， CHANG Xin， SUN Guodong，et al.Propane dehydrogenation：Catalyst development，new chemistry，and emerging technologies［J］.Chemical Society Reviews，2021，50（5）：3315-3354.
2	XU Zhikang， XU Rui， YUE Yuanyuan，et al.Bimetallic Pt-Sn nanocluster from the hydrogenolysis of a well-defined surface compound consisting of ［（AlO）Pt（COD）Me］ and ［（AlO）SnPh₃］ fragments for propane dehydrogenation［J］.Journal of Catalysis，2019，374：391-400.
3	SHI Lei， DENG Gaoming， LI Wencui，et al.Al₂O₃ nanosheets rich in pentacoordinate Al（3+） ions stabilize Pt-Sn clusters for propane dehydrogenation［J］.Angewandte Chemie，2015，54（47）：13994-13998.
4	SUN Qiming， WANG Ning， FAN Qiyuan，et al.Frontispiece：Subnanometer bimetallic platinum-zinc clusters in zeolites for propane dehydrogenation［J］.Angewandte Chemie International Edition，2020，59（44）：e202084461.
5	DENG Lidan， SHISHIDO T， TERAMURA K，et al.Effect of reduction method on the activity of Pt-Sn/SiO₂ for dehydrogenation of propane［J］.Catalysis Today，2014，232：33-39.
6	QU Ziqiang， SUN Qiming.Advances in zeolite-supported metal cat-alysts for propane dehydrogenation［J］.Inorganic Chemistry Frontiers，2022，9（13）：3095-3115.
7	ZHANG Bofeng， SONG Mingxia， XU Mingrui，et al.Recent advances in metal-zeolite catalysts for direct propane dehydrogenation［J］.Energy & Fuels，2023，37（24）：19419-19432.
8	SUN Qiming， WANG Ning， YU Jihong.Advances in catalytic applications of zeolite-supported metal catalysts［J］.Advanced Materials，2021，33（51）：e2104442.
9	WANG Yansu， HU Zhongpan， LV Xianwei，et al.Ultrasmall PtZn bimetallic nanoclusters encapsulated in silicalite-1 zeolite with superior performance for propane dehydrogenation［J］.Journal of Catalysis，2020，385：61-69.
10	解则安，吕聪敏，初晓，等.微孔分子筛限域Pt基丙烷脱氢催化剂制备的研究进展［J］.沈阳师范大学学报（自然科学版），2022，40（2）：115-120.
	XIE Zean， Congmin LÜ， CHU Xiao，et al.Synthesis research progress of microporous molecular zeolites confined Pt-based catalysts for direct dehydrogenation of propane［J］.Journal of Shenyang Normal University（Natural Science Edition），2022， 40（2）：115-120.
11	LIU Meng， MIAO Caixia， WU Zhijie.Recent advances in the synthesis，characterization，and catalytic consequence of metal species confined within zeolite for hydrogen-related reactions［J］.Industrial Chemistry & Materials，2024，2（1）：57-84.
12	ZHANG Qiang， GAO Shiqin， YU Jihong.Metal sites in zeolites：Synthesis，characterization，and catalysis［J］.Chemical Reviews，2023，123（9）：6039-6106.
13	ZHANG Wei， WANG Haizhi， JIANG Jiawei，et al.Size dependence of Pt catalysts for propane dehydrogenation：From atomically dispersed to nanoparticles［J］.ACS Catalysis，2020，10（21）：12932-12942.
14	王延苏，刘国柱，于海斌.非贵金属催化剂用于丙烷脱氢的研究进展［J］.无机盐工业，2023，55（12）：1-11.
	WANG Yansu， LIU Guozhu， YU Haibin.Research progress of non-precious metal catalysts for propane dehydrogenation［J］.Inorganic Chemicals Industry，2023，55（12）：1-11.
15	ZHU Jun， YANG Minglei， YU Yingda，et al.Size-dependent reaction mechanism and kinetics for propane dehydrogenation over Pt catalysts［J］.ACS Catalysis，2015，5（11）：6310-6319.
16	WANG Ning， SUN Qiming， BAI Risheng，et al. In situ confinement of ultrasmall Pd clusters within nanosized silicalite-1 zeolite for highly efficient catalysis of hydrogen generation［J］.Journal of the American Chemical Society，2016，138（24）：7484-7487.
17	MOLINER M， GABAY J E， KLIEWER C E，et al.Reversible transformation of Pt nanoparticles into single atoms inside high-silica chabazite zeolite［J］.Journal of the American Chemical Society，2016，138（48）：15743-15750.
18	ZHANG Jian， WANG Liang， SHAO Yi，et al.A Pd@Zeolite catalyst for nitroarene hydrogenation with high product selectivity by sterically controlled adsorption in the zeolite micropores［J］.Angewandte Chemie，2017，56（33）：9747-9751.
19	LI Shiwen， BUREL L， AQUINO C，et al.Ultimate size control of encapsulated gold nanoparticles［J］.Chemical Communications，2013，49（76）：8507-8509.
20	LIU Lichen， DÍAZ U， ARENAL R，et al.Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D［J］.Nature Materials，2017，16（1）：132-138.
21	WANG Yansu， SUO Yujun， LV Xianwei，et al.Enhanced performances of bimetallic Ga-Pt nanoclusters confined within silicalite-1 zeolite in propane dehydrogenation［J］.Journal of Colloid and Interface Science，2021，593：304-314.
22	WEI Xueer， CHENG Jiawei， LI Yubing，et al.Bimetallic clusters confined inside silicalite-1 for stable propane dehydrogenati- on［J］.Nano Research，2023，16（8）：10881-10889.
23	ZHU Jie， OSUGA R， ISHIKAWA R，et al.Ultrafast encapsulation of metal nanoclusters into MFI zeolite in the course of its crystallization：Catalytic application for propane dehydrogenation［J］.Angewandte Chemie，2020，59（44）：19669-19674.
24	RYOO R， KIM J，JO C，et al.Rare-earth-platinum alloy nanoparticles in mesoporous zeolite for catalysis［J］.Nature，2020， 585（7824）：221-224.
25	LIU Lichen， LOPEZ-HARO M， LOPES C W，et al.Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis［J］.Nature Materials，2019，18（8）：866-873.
26	QI Liang， BABUCCI M， ZHANG Yanfei，et al.Propane dehydrogenation catalyzed by isolated Pt atoms in ≡SiOZn-OH nests in dealuminated zeolite beta［J］.Journal of the American Chemical Society，2021，143（50）：21364-21378.
27	MA Yue， SONG Shaojia， LIU Changcheng，et al.Germanium-enriched double-four-membered-ring units inducing zeolite-confined subnanometric Pt clusters for efficient propane dehydrogenation［J］.Nature Catalysis，2023，6：506-518.
28	ZENG Lei， CHENG Kang， SUN Fanfei，et al.Stable anchoring of single rhodium atoms by indium in zeolite alkane dehydrogenation catalysts［J］.Science，2024，383（6686）：998-1004.
29	HU Zhongpan， QIN Gangqiang， HAN Jingfeng，et al.Atomic insight into the local structure and microenvironment of isolated co-motifs in MFI zeolite frameworks for propane dehydrogenation［J］.Journal of the American Chemical Society，2022，144（27）：12127-12137.
30	QU Ziqiang， HE Guangyuan， ZHANG Tianjun，et al.Tricoordinated single-atom cobalt in zeolite boosting propane dehydrogenation［J］.Journal of the American Chemical Society，2024， 146（13）：8939-8948.
31	XIE Linjun， WANG Rui， CHAI Yuchao，et al.Propane dehydrogenation catalyzed by in situ partially reduced zinc cations confined in zeolites［J］.Journal of Energy Chemistry，2021，63：262-269.
32	SONG Shaojia， YANG Kun， ZHANG Peng，et al.Silicalite-1 stabilizes Zn-hydride species for efficient propane dehydrogenati- on［J］.ACS Catalysis，2022，12（10）：5997-6006.
33	CHAI Yicong， CHEN Shunhua， CHEN Yang，et al.Dual-atom catalyst with N-colligated Zn₁Co₁ species as dominant active sites for propane dehydrogenation［J］.Journal of the American Chemical Society，2024，146（1）：263-273.
34	YUE Yuanyuan， FU Jing， WANG Chuanming，et al.Propane dehydrogenation catalyzed by single Lewis acid site in Sn-Beta zeolite［J］.Journal of Catalysis，2021，395：155-167.
35	HU Bo， SCHWEITZER N M， ZHANG Guanghui，et al.Isolated Fe^II on silica as a selective propane dehydrogenation catalyst［J］.ACS Catalysis，2015，5（6）：3494-3503.
36	YUN J H， LOBO R F.Catalytic dehydrogenation of propane over iron-silicate zeolites［J］.Journal of Catalysis，2014，312：263- 270.
37	XU Guangyue， ZHANG Xiang， DONG Zhuoya，et al.Ferric single-site catalyst confined in a zeolite framework for propane dehydrogenation［J］.Angewandte Chemie，2023，62（44）：e202305915.
38	SEARLES K， SIDDIQI G， SAFONOVA O V，et al.Silica-supported isolated gallium sites as highly active，selective and stable propane dehydrogenation catalysts［J］.Chemical Science，2017，8（4）：2661-2666.
39	PHADKE N M， MANSOOR E， BONDIL M，et al.Mechanism and kinetics of propane dehydrogenation and cracking over Ga/H-MFI prepared via vapor-phase exchange of H-MFI with GaCl₃ ［J］.Journal of the American Chemical Society，2019，141（4）：1614-1627.
40	NI Lingli， KHARE R， BERMEJO-DEVAL R，et al.Highly active and selective sites for propane dehydrogenation in zeolite Ga-BEA［J］.Journal of the American Chemical Society，2022，144（27）：12347-12356.
41	YUAN Yong， LEE J S， LOBO R F.Ga⁺-chabazite zeolite：A highly selective catalyst for nonoxidative propane dehydrogenati-on［J］.Journal of the American Chemical Society，2022，144（33）：15079-15092.

催化剂	反应温度/℃	反应空速/h^-1	丙烷初始转化率/%	丙烯选择性/%	失活速率K_d/h^-1
0.36%Pt0.68% Sn/Al₂O₃-sheet^［3］	590	9.4	48.7~44.6	98.7	0.007
0.3Pt0.5Zn@S-1^［9］	550	6.5	45~42	99.0~99.9	0.002
0.3Pt0.5Zn@S-1^［9］	525	1	62~61	99.0~99.9	0.001 5
0.3Pt0.5Zn@S-1^［9］	550	1	69~66	98.0~99.9	0.007
1.5Ga0.1Pt@S-1^［21］	600	0.65	45.9~41.5	92~95	0.006 8
1.5Ga@S-1^［21］	600	0.65	16~9	79~83	0.027
PtSn@S-1^［22］	550	3.6	45	99
0.04Pt-0.36Zn-DeAlBEA^［26］	550	7 390	32	99
Pt₄-Ge₂-d₄r@UTL^［27］	500	0.75	54	99

[1]	刘新龙, 杨振宇, 郝赫, 刘姝昕, 武晨阳, 王兴利, 马清清. 粉煤灰提铝残渣制备体型化4A分子筛的研究[J]. 无机盐工业, 2025, 57(3): 78-85.
[2]	郭颖君, 吴松松, 丁春艳, 赵世凯, 宋涛, 温广武. 锶长石微晶玻璃转晶制备SSZ-13分子筛膜[J]. 无机盐工业, 2025, 57(2): 76-82.
[3]	范景新, 李滨, 洪鲁伟, 洪美花, 龚鑫. 芳烃重整油脱烯烃剂研究现状及展望[J]. 无机盐工业, 2025, 57(2): 14-25.
[4]	柳黄飞, 张莉, 刘涛. 分子筛快速合成技术研究进展[J]. 无机盐工业, 2025, 57(2): 36-43.
[5]	孙庆昊, 李克艳, 郭新闻. Pd/ZnIn₂S₄纳米片光催化苯甲醇氧化耦合产氢的研究[J]. 无机盐工业, 2025, 57(1): 113-119.
[6]	王健捷, 束小龙, 肖霞, 王鹏, 范晓强, 孔莲, 解则安, 赵震. 多级孔花状ZSM-5分子筛的合成及其正辛烷催化裂解反应性能研究[J]. 无机盐工业, 2024, 56(8): 139-146.
[7]	祝增虎, 王敏, 彭正军, 贾国凤, 李燕. 氯化锂溶液中钾离子的吸附分离研究[J]. 无机盐工业, 2024, 56(6): 61-66.
[8]	李永恒, 米晓彤, 张培培. 全结晶纳米ZSM-5分子筛团聚体的合成及在甲苯甲基化中的应用[J]. 无机盐工业, 2024, 56(5): 135-140.
[9]	狄璐, 王卫国, 陈珏先, 吴传淑. 过渡金属负载Silicalite-1分子筛的制备及其催化糠醛加氢性能研究[J]. 无机盐工业, 2024, 56(4): 125-132.
[10]	周旋, 李梦锐, 陈一尘, 樊辉强, 王宾, 袁刚. 镍基磷化物复合材料在催化电解水析氢性能提升方面的研究进展[J]. 无机盐工业, 2024, 56(4): 8-15.
[11]	赵闯, 陈自浩, 张博宇, 李犇, 靳凤英, 李滨, 孙振海, 郭春垒. 分子筛吸附剂对不同类型柴油吸附分离性能的研究[J]. 无机盐工业, 2024, 56(3): 80-85.
[12]	陈星亮, 范文娟, 常会, 黄海平, 蒋志强. Fe³⁺协同Ni基金属-有机框架提升电催化析氧反应活性的研究[J]. 无机盐工业, 2024, 56(2): 152-158.
[13]	赖慧龙, 于飞, 杨冬霞, 马江丽, 殷雪梅, 常仕英. 基于不同Cu-CHA催化剂方案的NH₃-SCR性能及氨存储特性研究[J]. 无机盐工业, 2024, 56(12): 159-166.
[14]	冯晴, 王延苏, 周微, 刘洋, 孙彦民, 南军. 接力催化CO₂制备高附加值化学品中催化剂的研究进展[J]. 无机盐工业, 2024, 56(11): 81-94.
[15]	赵世永, 肖雨辰, 马清清, 杨珍妮, 王纪镇, 樊晓萍. 粉煤灰提铝残渣制备4A分子筛及Cu（Ⅱ）吸附研究[J]. 无机盐工业, 2024, 56(10): 127-134.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会