梯级孔丝光沸石负载的钒基催化剂上异丁烷脱氢性能

doi:10.16085/j.issn.1000-6613.2019-0191

化工进展 ›› 2019, Vol. 38 ›› Issue (11): 4965-4970.DOI: 10.16085/j.issn.1000-6613.2019-0191

梯级孔丝光沸石负载的钒基催化剂上异丁烷脱氢性能

李芹^1,²()

1. 中国石油大学(北京)新能源与材料学院，北京 102249
2. 北京中石大新能源研究院有限公司，北京 102249

收稿日期:2019-01-29 出版日期:2019-11-05 发布日期:2019-11-05
通讯作者: 李芹
作者简介:李芹（1985—），硕士，工程师，研究方向为低碳烃类净化及脱氢等。E-mail: qinli_85@163.com。

Synthesis of hierarchical mordenite supported vanadium based catalysts and their application in the iso-butane dehydrogenation reaction

Qin LI^1,²()

1. College of New Energy and Materials, China University of Petroleum (Beijing), Beijing 102249, China
2. China University of Petroleum-Beijing Institute of New Energy Co. , Ltd. , Beijing 102249, China

Received:2019-01-29 Online:2019-11-05 Published:2019-11-05
Contact: Qin LI

摘要/Abstract

摘要：

以十二烷基二甲基苄基溴化铵为介孔模板剂合成了具有梯级孔结构的丝光沸石分子筛，并以之为载体通过浸渍负载制备了钒基催化剂。通过X射线衍射（XRD）、N₂吸附-脱附、扫描电镜（SEM）、程序升温脱附法（NH₃-TPD）等技术对制备的催化剂进行了表征。由表征结果可知，制备的钒基催化剂上出现了孔径为2～3nm的介孔，比表面积及总孔容等都有不同程度增加，弱酸中心数量升高，中强酸及强酸数量下降，催化剂的相对结晶度随模板剂用量的增多也逐渐下降。催化剂上异丁烷脱氢反应评价结果表明，梯级孔结构的引入能够明显改善催化剂的异丁烷脱氢性能，催化剂上异丁烷转化率略微降低、异丁烯选择性明显升高、裂解等副反应受到抑制、积炭的聚合度有所下降。合成时模板剂的添加量存在最优值，V-MOR-2样品表现出最优的催化活性。

关键词: 分子筛, 梯级孔, 催化剂, 烷烃, 脱氢

Abstract:

Hierarchical mordenites were synthesized by using dodecyl dimethyl benzyl ammonium bromide as templates and used as support for the vanadium based catalysts for iso-butane dehydrogenation reaction. The structural and acid properties were investigated by XRD, N₂ adsorption, SEM and NH₃-TPD. According to the characterization results, the specific surface areas and total pore volumes of the vanadium based increased due to the introduction of mesopores which were in the range of 2—3nm. Besides, the weak acid sites increased on the hierarchical mordenites supported vanadium based catalysts while the medium-strong and strong acid sites decreased as well as the crystallinity. The catalytic tests results of iso-butane dehydrogenation showed that the iso-butene selectivity largely increased due to the improved mass transfer efficiency and decreased strong acid sites although the iso-butane conversion slightly decreased. The side reactions were also prohibited and the condensation degree of the coke formed during the dehydrogenation process decreased. The optimized addition catalytic performance was obtained over the V-MOR-2 sample.

Key words: zeolite, hierarchical, catalyst, alkane, dehydrogenation

中图分类号:

TQ426

李芹. 梯级孔丝光沸石负载的钒基催化剂上异丁烷脱氢性能[J]. 化工进展, 2019, 38(11): 4965-4970.

Qin LI. Synthesis of hierarchical mordenite supported vanadium based catalysts and their application in the iso-butane dehydrogenation reaction[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4965-4970.

图/表 7

图1 催化剂XRD谱图

表1 V-MOR催化剂的物化性质

样品	硅铝比 ^①	DDBAB/Al₂O₃^②	V₂O₅质量分数/%	比表面积/m²·g^-1	孔容/cm³·g^-1	总孔容/ cm³·g^-1
V-MOR-0	27.8	0	3.90	417.5	0.015	0.192
V-MOR-1	27.5	0.2	3.86	436.1	0.054	0.226
V-MOR-2	26.7	0.4	3.89	451.3	0.061	0.235
V-MOR-3	28.9	0.6	3.93	423.8	0.047	0.214

图2 催化剂的N2吸附-脱附等温线及孔径分布图

图3 催化剂SEM图

图4 V-MOR催化剂的NH3-TPD谱图

图5 V-MOR催化剂异丁烷脱氢反应评价结果（评价条件：580℃、常压、GHSV=200h-1）

图6 反应后催化剂TPO谱图

参考文献 15

1	JAMESO, MANDALS, ALELEN. Lower alkanes dehydrogenation: strategies and reaction routes to corresponding alkenes[J]. Fuel Processing Technology, 2016, 149: 239-255.
2	CARRERPA, SCHLOEGLR, WACHSE. Critical literature review of the kinetics for the oxidative dehydrogenation of propane over well-defined supported vanadium oxide catalysts[J]. ACS Catalysis, 2014, 4(10): 3357-3380.
3	TIANY, BAIP, LIUS. VO_x-K₂O/γ-Al₂O₃ catalyst for nonoxidative dehydrogenation of isobutane[J]. Fuel Processing Technology, 2016, 151: 31-39.
4	BAIP, MAZ, LIT. Relationship between surface chemistry and catalytic performance of mesoporous γ-Al₂O₃ supported VO_x catalyst in catalytic dehydrogenation of propane[J]. ACS Applied Materials & Interfaces, 2016, 8(39): 25979-25990.
5	RODEMERCKU, SOKOLOVS, STTOYANOVAM. Influence of support and kind of VO_x species on isobutene selectivity and coke deposition in non-oxidative dehydrogenation of isobutane[J]. Journal of Catalysis, 2016, 338: 174-183.
6	WANGX, LIR, YUC. Enhancing the dimethyl ether carbonylation performance over mordenite catalysts by simple alkaline treatment[J]. Fuel, 2019, 239: 794-803.
7	LIX, PRINSR, BOKHOVENA. Synthesis and characterization of mesoporous mordenite[J]. Journal of Catalysis, 2009, 262(2): 257-265.
8	BOVERIM, MARQUEZ-ÁLVAREZC, ÁLABLODE. Steam and acid dealumination of mordenite: characterization and influence on the catalytic performance in linear alkylbenzene synthesis[J]. Catalysis Today, 2006, 114(2): 217-225.
9	LUB, YAKUSHIY, OUMIY. Control of crystal size of high-silica mordenite by quenching in the course of crystallization process[J]. Microporous and Mesoporous Materials, 2006, 95(1): 141-145.
10	CAREROA, KETURAKISJ, ORREGOA. Anomalous reactivity of supported V₂O₅ nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor[J]. Dalton Trans., 2013, 42(35): 12644-12653.
11	JACKSONS, RUGMINIS, STAIRP. A comparison of catalyst deactivation of vanadia catalysts used for alkane dehydrogenation[J]. Chemical Engineering Journal, 2006, 120(1/2): 127-132.
12	LAAKC, SAGALAL, ZECEVICJ. Mesoporous mordenites obtained by sequential acid and alkaline treatments-atalysts for cumene production with enhanced accessibility[J]. Journal of Catalysis, 2010, 276(1): 170-180.
13	LÓNYIF, VALYONJ. On the interpretation of the NH₃-TPD patterns of H-ZSM-5 and H-mordenite[J]. Microporous and Mesoporous Materials, 2001, 47(2): 293-301.
14	SATTLERB, RUIZ-MARTINEZJ, SANTILLAN-JIMENEZE. Catalytic dehydrogenation of light alkanes on metals and metal oxides[J]. Chemical Reviews, 2014, 114(20): 10613-10653.
15	CHAOUATIN, SOUALAHA, CHATERM. Mechanisms of coke growth on mordenite zeolite[J]. Journal of Catalysis, 2016, 344: 354-364.

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梯级孔丝光沸石负载的钒基催化剂上异丁烷脱氢性能

Synthesis of hierarchical mordenite supported vanadium based catalysts and their application in the iso-butane dehydrogenation reaction

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