Citation: DONG Zhaoxia, SONG Tongyang, LU Jiqing, XIE Guanqun, LUO Mengfei. Gas Phase Dehydrochlorination of 1, 1, 2-Trichloroethane over Cr₂O₃ Catalysts[J]. Chinese Journal of Applied Chemistry, ;2019, 36(5): 515-523. doi: 10.11944/j.issn.1000-0518.2019.05.180245 shu

Gas Phase Dehydrochlorination of 1, 1, 2-Trichloroethane over Cr₂O₃ Catalysts

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, China

Corresponding author: XIE Guanqun, gqxie@zjnu.cn LUO Mengfei, mengfeiluo@zjnu.cn
Received Date: 17 July 2018
Revised Date: 12 October 2018
Accepted Date: 27 November 2018

Fund Project: the Natural Science Foundation of Zhejiang Province, China LY16B070001Supported by the Natural Science Foundation of Zhejiang Province, China(No.LY16B070001)

Figures(6)

A series of Cr₂O₃ catalysts was prepared by a precipitation method and tested for the gas phase dehydrochlorination of 1, 1, 2-trichloroethane(TCE) to synthesize cis-1, 2-dichloroethylene(cis-DCE). X-ray diffraction(XRD), hydrogen temperature-programmed reduction(H₂-TPR), ammonia temperature-programmed desorption(NH₃-TPD) and X-ray photoelectron spectroscopy(XPS) were used to study the dehydrochlorination of TCE on Cr₂O₃ catalyst and its reaction mechanism. It is found that the conversion ratio of TCE on the catalysts decreases with the increase of the calcination temperature, while the selectivity to cis-DCE first increases and then decreases. The best performance is obtained on the catalyst calcined at 400℃, with a TCE conversion ratio of 70.8% and a cis-DCE selectivity of 90.0%. In addition, the areal specific reaction rate also first increases and then decreases with the increase of the calcination temperature, with the highest value being obtained on the catalysts calcined at 400℃(0.801×10^-2 μmol/(s·m²). The catalytic behaviors of the catalysts are well related to their surface Cr₂O₃ species. Turnover frequencies(TOFs) calculated based on the surface acidity and the highest value being obtained on the catalysts calcined at 400℃(2.82×10^-5 s^-1) show that the oxidation states of the surface Cr species are important for the reaction and the Cr species with an average valence of 3.2 are appropriate for the reaction.
- Cr₂O₃ catalysts,
- 1, 1, 2-trichloroethane,
- dehydrochlorination,
- cis-1, 2-dichloroethylene,
- surface Cr₂O₃ species
1. [1]
  JIN Lirui, ZHANG Xiaojun, LI Hui. Diversity of 1, 1, 1-Trichloroethane Degrading Dehalobacter spp. in Contaminated Groundwater[J]. Microbiol China, 2013,40(8):1522-1530.
2. [2]
  Mukhopadhyay S, Tung H S, Nair H. Method for Producing Fluorinated Organic Compounds.WO2007056149Al[P]. 2007-05-18
3. [3]
  Wang H, Tung H S. Dehydrochlorination of Hydrochlorofluorocarbons Using Pre-treated Activated Carbon Catalysts: WO, 2009021154A2[P]. 2009-02-12
4. [4]
  Li X G, Li T, Zhang T. Nano-TiO₂-Catalyzed Dehydrochlorination of 1, 1, 2, 2-Tetrachloroethane:Roles of Crystalline Phase and Exposed Facets[J]. Environ Sci Technol, 2018,52(7):4031-4039. doi: 10.1021/acs.est.7b05479
5. [5]
  Dofling J, Janssen D B. Estimates of Gibbs Free Energies of Formation of Chlorinated Aliphatic Compounds[J]. Biodegradation, 1994,5(1):21-28.
6. [6]
  Kokubo K, Kitasaka K, Oshima T. Effects of the Cation Binding Mode on E-Z Isomerization of 1, 2-Dichloroethylene[J]. Org Lett, 2006,8(8):1597-1600.
7. [7]
  Turton D A, Martin D F, Wynne K. Optical Kerr-Effect Study of Trans- and Cis-1, 2-Dichloroethene:Liquid Liquid Transition or Super-Arrhenius Relaxation[J]. Phys Chem Chem Phys, 2010,12(16):4191-4200. doi: 10.1039/b918196b
8. [8]
  Van der Heijden A W A M, Mens A J M, Bogerd R. Dehydrochlorination of Intermediates in the Production of Vinyl Chloride over Lanthanum Oxide-based Catalysts[J]. Catal Lett, 2008,122(3/4):238-246.
9. [9]
  Tang C, Jin Y, Lu J. Highly Efficient Mg(OH)Cl/SiO₂ Catalysts for Selective Dehydrochlorination of 1, 1, 2-Trichloroethane[J]. Appl Catal A, 2015,508:10-15.
10. [10]
  JIN Yanxia, TANG Cen, MENG Xiuqing. Highly Stable CsNO₃/SiO₂ Catalysts for the Synthesis of Vinylidene Chloride Using a Gaseous Phase Method[J]. Acta Phys-Chim Sin, 2016,32(2):510-518.
11. [11]
  HU Yihao, SONG Tongyang, WANG Yuejuan. Gas Phase Dehydrochlorination of 1, 1, 2-Trichloroethane over Zn/SiO₂ Catalysts:Acidity and Deactivation[J]. Acta Phys-Chim Sin, 2017,33(5):1017-1026.
12. [12]
  Song T Y, Dong Z X, Song J D. Dehydrochlorination of 1, 1, 2-Trichloroethane over SiO₂-Supported Alkali and Transition Metal Catalysts:Tunable Selectivity Controlled by the Acid-base Properties of the Catalysts[J]. Appl Catal B, 2018,236:368-376. doi: 10.1016/j.apcatb.2018.04.018
13. [13]
  WANG Yun, LIANG Yan, HE Jun. Catalytic Behaviors of Cr₂O₃ and CrO₃/Cr₂O₃ Catalysts for Gas Phase Fluorination of 2-Chloro-1, 1, 1-trifluoroethane:Active Spedes and Catalyst Deactivation[J]. Chinese J Inorg Chem, 2017,33(1):123-133.
14. [14]
  Han W, Li X, Tang H. Preparation of fluorinated Cr₂O₃ Hexagonal Prism and Catalytic Performance for the Dehydrofluorination of 1, 1-Difluoroethane to Vinyl Fluoride[J]. J Nanopart Res, 2015,17(9):1-12.
15. [15]
  Lim S, Kim M S, Choi J W. Catalytic Dehydrofluorination of 1, 1, 1, 2, 3-Pentafluoropropane(HFC-245eb) to 2, 3, 3, 3-Tetrafluoropropene(HFO-1234yf) Using in-situ Fluorinated Chromium Oxyfluoride Catalyst[J]. Catal Today, 2017,293:42-48.
16. [16]
  Luo J W, Song J D, Jia W Z. Catalytic Dehydrofluorination of 1, 1, 1, 3, 3-Pentafluoropropane to 1, 3, 3, 3-Tetrafluoropropene over Fluorinated NiO/Cr₂O₃ Catalysts[J]. Appl Surf Sci, 2018,433:904-913.
17. [17]
  Wang F, Fan J L, Zhao Y. Effects of Yttrium-doping on the Performance of Cr₂O₃, Catalysts for Vapor Phase Fluorination of 1, 1, 2, 3-Tetrachloropropene[J]. J Fluorine Chem, 2014,166:78-83. doi: 10.1016/j.jfluchem.2014.07.030
18. [18]
  Cheng Y X, Fan J L, Xie Z Y. Effects of M-promoter(M = Y, Co, La, Zn) on Cr₂O₃ Catalysts for Fluorination of Perchloroethylene[J]. J Fluorine Chem, 2013,156:66-72. doi: 10.1016/j.jfluchem.2013.08.016
19. [19]
  Zhang W X, Liang Y, Luo J W. Morphological Effects of Ordered Cr₂O₃, Nanorods and Cr₂O₃, Nanoparticles on Fluorination of 2-Chloro-1, 1, 1-trifluoroethane[J]. J Mater Sci, 2016,51(13):6488-6496.
20. [20]
  Grzybowska B, Sloczyn'ski J, Grabowski R. Chromium Oxide/Alumina Catalysts in Oxidative Dehydrogenation of Isobutane[J]. J Catal, 1998,178(2):687-700.
21. [21]
  Niedersen K U, Schreier E, Kemnitz E. Isomerization Reaction of 1, 1, 2, 2-Tetrafluoroethane on Chromia—A Study of the Active Sites on the Surface[J]. J Catal, 1997,167(1):210-214.
22. [22]
  Wang X, Xie Y C, Wang X. Total Oxidation of CH₄ on Sn-Cr Composite Oxide Catalysts[J]. Appl Catal B, 2001,35(2):85-94.
23. [23]
  FAN Jinglian. Vapor-Phase Fluorination of 1, 1, 2, 3-Tetrachloropropene to Synthesis Tetrafluoropropene[D]. Zhejiang Normal University, 2014(in Chinese).
24. [24]
  Bobet J L, Desmoulins-Krawiec S, Grigorova E. Addition of Nanosized Cr₂O₃ to Magnesium for Improvement of the Hydrogen Sorption Properties[J]. J Alloys Compd, 2003,351(1):217-221.
25. [25]
  Lin Y, Cai W, Tian X. Polyacrylonitrile/Ferrous Chloride Composite Porous Nanofibers and Their Strong Cr-Removal Performance[J]. J Mater Chem, 2011,21(4):991-997. doi: 10.1039/C0JM02334E
26. [26]
  Liu B, Terano M, Liu B. Investigation of the Physico-Chemical State and Aggregation Mechanism of Surface Cr Species on a Phillips CrO_x/SiO₂ Catalyst by XPS and EPMA[J]. J Mol Catal A, 2001,172(1/2):227-240.
27. [27]
  Gaspar A B, Perea C A C, Dieguez L C. Characterization of Cr/SiO₂ Catalysts and Ethylene Polymerization by XPS[J]. Appl Surf Sci, 2005,252(4):939-949. doi: 10.1016/j.apsusc.2005.01.031
28. [28]
  Gao S, Dong C, Luo H. Scanning Electrochemical Microscopy Study on the Electrochemical Behavior of CrN Film Formed on 304 Stainless Steel by Magnetron Sputtering[J]. Electrochim Acta, 2013,114:233-241. doi: 10.1016/j.electacta.2013.10.009
29. [29]
  Fu X Z, Luo X X, Luo J L. Ethane Dehydrogenation over Nano-Cr₂O₃ Anode Catalyst in Proton Ceramic Fuel Cell Reactors to Co-produce Ethylene and Electricity[J]. J Power Sources, 2011,196(3):1036-1041. doi: 10.1016/j.jpowsour.2010.08.043
30. [30]
  Berteau P, Delmon B, Berteau P. Modified Aluminas: Relationship Between Activity in 1-Butanol Dehydration and Acidity Measured by NH₃ TPD[J]. Catal Today, 1989,5(2):121-137. doi: 10.1016/0920-5861(89)80020-3
1. [1]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
2. [2]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-0. doi: 10.3866/PKU.WHXB202309020
3. [3]
  Liyang ZHANG , Dongdong YANG , Ning LI , Yuanyu YANG , Qi MA . Crystal structures, luminescent properties and Hirshfeld surface analyses of three cadmium(Ⅱ) complexes based on 2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)benzoate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1943-1952. doi: 10.11862/CJIC.20240079
4. [4]
  Yajin Li , Huimin Liu , Lan Ma , Jiaxiong Liu , Dehua He . Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst. Acta Physico-Chimica Sinica, 2024, 40(9): 2308005-0. doi: 10.3866/PKU.WHXB202308005
5. [5]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . Simultaneously Improving Inter-Plane Crystallization and Incorporating K Atoms in g-C₃N₄ Photocatalyst for Highly-Efficient H₂O₂ Photosynthesis. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-0. doi: 10.3866/PKU.WHXB202406005
6. [6]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
7. [7]
  Ting-Ting Huang , Jin-Fa Chen , Juan Liu , Tai-Bao Wei , Hong Yao , Bingbing Shi , Qi Lin . A novel fused bi-macrocyclic host for sensitive detection of Cr₂O₇²⁻ based on enrichment effect. Chinese Chemical Letters, 2024, 35(7): 109281-. doi: 10.1016/j.cclet.2023.109281
8. [8]
  Yuanyuan Ping , Wangqing Kong . 光催化碳氢键官能团化合成1-苯基-1,2-乙二醇. University Chemistry, 2025, 40(6): 238-247. doi: 10.12461/PKU.DXHX202408092
9. [9]
  Xiaofang Li , Zhigang Wang . 调节金助催化剂的d_z²占据轨道增强光催化合成H₂O₂. Acta Physico-Chimica Sinica, 2025, 41(7): 100080-0. doi: 10.1016/j.actphy.2025.100080
10. [10]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
11. [11]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
12. [12]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
13. [13]
  Linlin Wu , Yonghua Zhou , Zhongbei Li , Liu Deng , Younian Liu , Limiao Chen , Jianhan Huang . Digital Education Promoting Applied Chemistry Comprehensive Experiments: A Case Study of Catalytic Oxidation of Hydrogen Chloride and Reaction Kinetics. University Chemistry, 2025, 40(9): 273-278. doi: 10.12461/PKU.DXHX202411018
14. [14]
  Ya-Nan Yang , Zi-Sheng Li , Sourav Mondal , Lei Qiao , Cui-Cui Wang , Wen-Juan Tian , Zhong-Ming Sun , John E. McGrady . Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–. Chinese Chemical Letters, 2024, 35(8): 109048-. doi: 10.1016/j.cclet.2023.109048
15. [15]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
16. [16]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . Remarkable Photocatalytic H₂O₂ Production Efficiency over Ultrathin g-C₃N₄ Nanosheet with Large Surface Area and Enhanced Crystallinity by Two-Step Calcination. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-0. doi: 10.3866/PKU.WHXB202406019
17. [17]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂. Acta Physico-Chimica Sinica, 2025, 41(1): 100001-0. doi: 10.3866/PKU.WHXB202308032
18. [18]
  Xuewei BA , Cheng CHENG , Huaikang ZHANG , Deqing ZHANG , Shuhua LI . Preparation and luminescent performance of Sr_1-xZrSi₂O₇∶xDy³⁺ phosphor with high thermal stability. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 357-364. doi: 10.11862/CJIC.20240096
19. [19]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . 具有富电子Pt^δ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-0. doi: 10.1016/j.actphy.2025.100081
20. [20]
  Yi Yang , Xin Zhou , Miaoli Gu , Bei Cheng , Zhen Wu , Jianjun Zhang . Femtosecond transient absorption spectroscopy investigation on ultrafast electron transfer in S-scheme ZnO/CdIn₂S₄ photocatalyst for H₂O₂ production and benzylamine oxidation. Acta Physico-Chimica Sinica, 2025, 41(6): 100064-0. doi: 10.1016/j.actphy.2025.100064

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(711)
HTML views(87)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Gas Phase Dehydrochlorination of 1, 1, 2-Trichloroethane over Cr2O3 Catalysts

Metrics

通讯作者: 陈斌, bchen63@163.com

Gas Phase Dehydrochlorination of 1, 1, 2-Trichloroethane over Cr₂O₃ Catalysts