PtSn-Mg(Zn)AlO催化剂应用于乙烷脱氢反应研究

吴小平; 王晨光; 张琦; 刘琪英; 张兴华; 马隆龙

doi:10.11949/j.issn.0438-1157.20190569

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PtSn-Mg(Zn)AlO催化剂应用于乙烷脱氢反应研究

催化、动力学与反应器 | 更新时间：2020-06-24

- PtSn-Mg(Zn)AlO催化剂应用于乙烷脱氢反应研究
- Study on ethane dehydrogenation over PtSn-Mg(Zn)AlO catalyst
- 化工学报 2019年70卷第11期页码：4268-4277
- 作者机构：
  
  中国科学院广州能源研究所，中国科学院可再生能源与天然气水合物重点实验室，广东广州 510640
- 作者简介：
  
  吴小平（1990—），男，博士，研究助理，wuxp@ms.giec.ac.cn
  王晨光（1982—），男，博士，研究员，wangcg@ms.giec.ac.cn
- 基金信息：
  
  国家自然科学基金面上基金项目(51776206)
- DOI：10.11949/j.issn.0438-1157.20190569
  中图分类号： TQ 028.8
- 收稿：2019-05-27，
  
  修回：2019-08-09，
  
  纸质出版：2019-11-05
- 稿件说明：
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吴小平, 王晨光, 张琦, 刘琪英, 张兴华, 马隆龙. PtSn-Mg(Zn)AlO催化剂应用于乙烷脱氢反应研究[J]. 化工学报, 2019, 70(11): 4268-4277

WU Xiaoping, WANG Chenguang, ZHANG Qi, LIU Qiying, ZHANG Xinghua, MA Longlong. Study on ethane dehydrogenation over PtSn-Mg(Zn)AlO catalyst[J]. CIESC Journal, 2019, 70(11): 4268-4277
吴小平, 王晨光, 张琦, 刘琪英, 张兴华, 马隆龙. PtSn-Mg(Zn)AlO催化剂应用于乙烷脱氢反应研究[J]. 化工学报, 2019, 70(11): 4268-4277 DOI： 10.11949/j.issn.0438-1157.20190569.

WU Xiaoping, WANG Chenguang, ZHANG Qi, LIU Qiying, ZHANG Xinghua, MA Longlong. Study on ethane dehydrogenation over PtSn-Mg(Zn)AlO catalyst[J]. CIESC Journal, 2019, 70(11): 4268-4277 DOI： 10.11949/j.issn.0438-1157.20190569.

摘要

采用阴离子交换法合成了一系列不同Zn和Pt含量的PtSn-Mg(Zn)AlO催化剂用于乙烷脱氢反应。实验结果表明，在水滑石载体中掺杂少量的Zn对乙烷脱氢反应有明显影响。当Zn含量为2%（质量）时Pt基催化剂活性性能最优，在550℃时乙烷初始转化率达到27.1%，2 h平均转化率为21.6%。BET和SEM结果表明PtSn-Mg(Zn)AlO催化剂比PtSn-MgAlO催化剂比表面积更大，TEM结果显示，PtSn-Mg(Zn)AlO催化剂和PtSn-MgAlO催化剂的金属颗粒的平均直径分别为（1.49±0.31）nm 和（2.0±0.23）nm，说明Zn的掺杂在一定程度上改变了催化剂的结构，能减小Pt颗粒的尺寸，更好地分散Pt颗粒，从而改善乙烷催化脱氢反应性能。此外，考察温度对乙烷脱氢反应性能影响，发现温度越高乙烷初始转化率越高，但催化剂越易失活；考察Pt负载量对乙烷脱氢反应性能的影响，发现增加Pt含量并不能使乙烷转化率得到相应倍数的增加，即增加Pt含量反而使Pt的利用率降低了，因此适量降低PtSn-Mg(2-Zn)AlO催化剂中Pt含量对研究乙烷脱氢反应有深远意义。

Abstract

A series of PtSn-Mg(Zn)AlO catalysts with different Zn and Pt contents were synthesized by anion exchange method for ethane dehydrogenation. The experimental results show that the doping of a small amount of Zn in the hydrotalcite precursor has a significant effect on the performance of ethane dehydrogenation. When the Zn content is 2% (mass)

the Pt-based catalyst exhibits the best performance with an initial ethane conversion of 27.1% and an average ethane conversion of 21.6% for a period of 2 h at 550℃. To study the effect of Zn doping on the performance of ethane dehydrogenation and the structure of catalyst

the prepared catalysts were characterized by XRD

BET

SEM and TEM. The BET and SEM results show that the PtSn-Mg(Zn)AlO catalyst has larger specific surface area than the PtSn-MgAlO catalyst. The TEM results show that the average diameter of the PtSn-Mg(Zn)AlO catalyst and the PtSn-MgAlO catalyst are (1.49 ± 0.31) nm and (2.0 ± 0.23) nm

respectively

which shows that the doping of Zn changes the structure of the catalyst to some extent

and better disperse Pt particles

thereby improving the catalyst reaction performance. Furthermore

the effect of temperature and Pt loading on the performance of ethane dehydrogenation were investigated. It was found that the ethane initial conversion was higher at higher temperatures

but the catalyst was more susceptible to deactivation. The effect of Pt loading on the dehydrogenation performance of ethane was investigated. It was found that increasing the Pt content did not increase the ethane conversion rate by a corresponding multiple

that is

increasing the Pt content reduced the utilization rate of Pt. Therefore

proper reduction of Pt content in Pt-based catalyst has far-reaching significance for studying the ethane dehydrogenation reaction.

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references

Sattler J J H B , Ruiz-Martinez J , Santillan-Jimenez E , et al . Catalytic dehydrogenation of light alkanes on metals and metal oxides [J]. Chemical Reviews , 2014 , 114 ( 20 ): 10613 - 10653 .

张海娟 , 高杰 , 张浩楠 , 等 . 低碳烷烃深加工制烯烃技术的研究进展 [J]. 石油化工 , 2016 , 45 ( 12 ): 1411 - 1419 .

Zhang H J , Gao J , Zhang H N , et al . Progresses in processes and catalysts for dehydrogenation of light paraffins to olefins [J]. Petrochemical Technology , 2016 , 45 ( 12 ): 1411 - 1419 .

Long L L , Lang W Z , Liu X , et al . Improved catalytic stability of PtSnIn/ x Ca-Al catalysts for propane dehydrogenation to propylene [J]. Chemical Engineering Journal , 2014 , 257 : 209 - 217 .

郭秋双 , 蔡奇 , 孙彦民 , 等 . 低碳烷烃脱氢催化剂的研究进展 [J]. 无机盐工业 , 2016 , 48 ( 8 ): 11 - 15 .

Guo Q S , Cai Q , Sun Y M , et al . Research progress of low carbon alkane dehydrogenation catalyst [J]. Inorganic Chemical Industry , 2016 , 48 ( 8 ): 11 - 15 .

Wu J , Sharada S M , Ho C , et al . Ethane and propane dehydrogenation over PtIr/Mg(Al)O [J]. Applied Catalysis A-General , 2015 , 506 : 25 - 32 .

Cavani F , Ballarini N , Cericola A . Oxidative dehydrogenation of ethane and propane: how far from commercial implementation? [J]. Catalysis Today , 2007 , 127 : 113 - 131 .

Dong A H , Wang K , Zhu S Z , et al . Facile preparation of PtSn-La/Al 2 O 3 catalyst with large pore size and its improved catalytic performance for isobutane dehydrogenation [J]. Fuel Processing Technology , 2017 , 158 : 218 - 225 .

Deng L D , Miura H , Shishido T , et al . Elucidating strong metal-support interactions in Pt-Sn/SiO 2 catalyst and its consequences for dehydrogenation of lower alkanes [J]. Journal of Catalysis , 2018 , 365 : 277 - 291 .

Cheng M , Zhao H H , Yang J , et al . Synthesis and catalytic performance of a dual-sites Fe-Zn catalyst based on ordered mesoporous Al 2 O 3 for isobutane dehydrogenation [J]. Catalysis Letters , 2019 , 149 ( 5 ): 1326 - 1336 .

Jang E J , Lee J , Jeong H Y , et al . Controlling the acid-base properties of alumina for stable PtSn-based propane dehydrogenation catalysts [J]. Applied Catalysis A-General , 2019 , 572 : 1 - 8 .

Pham H N , Sattler J J H B , Weckhuysen B M , et al . Role of Sn in the regeneration of Pt/gamma-Al 2 O 3 light alkane dehydrogenation catalysts [J]. ACS Catalysis , 2016 , 6 ( 4 ): 2257 - 2264 .

Dixit M , Kostetskyy P , Mpourmpakis G . Structure-activity relationships in alkane dehydrogenation on gamma-Al 2 O 3 : site-dependent reactions [J]. ACS Catalysis , 2018 , 8 ( 12 ): 11570 - 11578 .

Baronetti G T , Demiguel S R , Scelza O A , et al . State of metallic phase in Pt-Sn/Al 2 O 3 catalysts prepared by different deposition techniques [J]. Applied Catalysis , 1986 , 24 : 109 - 116 .

Liu G , Zeng L , Zhao Z J , et al . Platinum-modified ZnO/Al 2 O 3 for propane dehydrogenation: minimized platinum usage and improved catalytic stability [J]. ACS Catalysis , 2016 , 6 ( 4 ): 2158 - 2162 .

Szeto K C , Jones Z R , Merle N , et al . A strong support effect in selective propane dehydrogenation catalyzed by Ga(i-Bu)(3) grafted onto gamma-alumina and silica [J]. ACS Catalysis , 2018 , 8 ( 8 ): 7566 - 7577 .

Yang K , Yin Y B , Lai S S , et al . Aromatization of n -butane and i -butane over PtSnK/ZSM-5 catalysts: influence of SiO 2 /Al 2 O 3 ratio [J]. Catalysis Letters , 2018 , 148 ( 11 ): 3570 - 3582 .

Liu X , Lang W Z , Long L L , et al . Improved catalytic performance in propane dehydrogenation of PtSn/gamma-Al 2 O 3 catalysts by doping indium [J]. Chemical Engineering Journal , 2014 , 247 : 183 - 192 .

Xia K , Lang W Z , Li P P , et al . The properties and catalytic performance of PtIn/Mg(Al)O catalysts for the propane dehydrogenation reaction: effects of pH value in preparing Mg(Al)O supports by the co-precipitation method [J]. Journal of Catalysis , 2016 , 338 : 104 - 114 .

Shen L L , Xia K , Lang W Z , et al . The effects of calcination temperature of support on PtIn/Mg(Al)O catalysts for propane dehydrogenation reaction [J]. Chemical Engineering Journal , 2017 , 324 : 336 - 346 .

王延臻 , 王鹏成 , 段红玲 , 等 . 铂锡催化剂用于混合低碳烷烃脱氢生产异丁烯化 [J]. 化工学报 , 2011 , 62 ( 11 ): 3143 - 3148 .

Wang Y Z , Wang P C , Duan H L , et al . Platinum-tin catalysts for dehydrogenation of mixed low hydrocarb ons into isobutene [J]. CIESC Journal , 2011 , 62 ( 11 ): 3143 - 3148 .

Xiong H F , Lin S , Goetze J , et al . Thermally stable and regenerable platinum-tin clusters for propane dehydrogenation prepared by atom trapping on ceria [J]. Angewandte Chemie-International Edition , 2017 , 56 ( 31 ): 8986 - 8991 .

Saeedizad M , Sahebdelfar S , Mansourpour Z . Deactivation kinetics of platinum-based catalysts in dehydrogenation of higher alkanes [J]. Chemical Engineering Journal , 2009 , 154 : 76 - 81 .

Sun P P , Siddiqi G , Vining W C , et al . Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation [J]. Journal of Catalysis , 2011 , 282 ( 1 ): 165 - 174 .

Fang S Q , Zhang K T , Wang C G , et al . The properties and catalytic performance of PtSn/Mg( x -Ga)AlO catalysts for ethane dehydrogenation [J]. RSC Advances , 2017 , 7 ( 37 ): 22836 - 22844 .

Zhang Q , Zhang K T , Zhang S H , et al . Ga 3+ -stabilized Pt in PtSn-Mg(Ga)(Al)O catalyst for promoting ethane dehydrogenation [J]. Journal of Catalysis , 2018 , 368 : 79 - 88 .

Zhang Y W , Zhou Y M , Tang M H , et al . Effect of La calcination temperature on catalytic performance of PtSnNaLa/ZSM-5 catalyst for propane dehydrogenation [J]. Chemical Engineering Journal , 2012 , 181 : 530 - 537 .

Wu J , Peng Z M , Bell A T . Effects of composition and metal particle size on ethane dehydrogenation over Pt x Sn100- x /Mg(Al)O (70 < = x < = 100) [J]. Journal of Catalysis , 2014 , 311 : 161 - 168 .

Galvita V , Siddiqi G , Sun P P , et al . Ethane dehydrogenation on Pt/Mg(Al)O and PtSn/Mg(Al)O catalysts [J]. Journal of Catalysis , 2010 , 271 : 209 - 219 .

陈领鹏 , 田志鹏 , 吕微 , 等 . 离子交换法制备Pt-Sn E / Mg(Al)O催化剂及其烷烃催化脱氢性能 [J]. 燃料化学学报 , 2016 , 44 ( 5 ): 597 - 606 .

Chen L P , Tian Z P , Lyu W , et al . Preparation of Pt-Sn E /Mg(Al)O catalyst by anion exchange method and its performance in alkane dehydrogenation [J]. Journal of Fuel Chemistry and Technology , 2016 , 44 ( 5 ): 597 - 606 .

Belskaya O B , Stepanova L N , Gulyaeva T I , et al . Zinc influence on the formation and properties of Pt/Mg(Zn)AlO x catalysts synthesized from layered hydroxides [J]. Journal of Catalysis , 2016 , 341 : 13 - 23 .

Wang Y J , Wang Y M , Wang S R , et al . Propane dehydrogenation over PtSn catalysts supported on ZnO-modified MgAl 2 O 4 [J]. Catalysis Letters , 2009 , 132 : 472 - 479 .

Lupan O , Emelchenko G A , Ursaki V V , et al . Synthesis and characterization of ZnO nanowires for nanosensor applications [J]. Materials Research Bulletin , 2010 , 45 : 1026 - 1032 .

郭秋双 , 杨玉旺 , 李晓云 , 等 . 丙烷脱氢制丙烯 Cr 2 O 3 /Al 2 O 3 催化剂的失活研究 [J]. 无机盐工业 , 2019 , 51 ( 4 ): 86 - 89 .

Guo Q S , Yang Y W , Li X Y , et al . Deactivation of propane dehydrogenation to produce propylene Cr 2 O 3 /Al 2 O 3 catalysts [J]. Inorganic Chemical Industry , 2019 , 51 ( 4 ): 86 - 89 .

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