CIESC Journal ›› 2016, Vol. 67 ›› Issue (4): 1340-1347.doi: 10.11949/j.issn.0438-1157.20150424

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Reaction mechanism of electrochemical reduction of acetylene to ethylene

SONG Xiuli1,2, JIA Ruilong1, XIE Xuejia1, LIANG Zhenhai1, ZHU Zhenping3   

  1. 1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China;
    2. Department of Chemistry, Taiyuan Normal University, Taiyuan 030031, Shanxi, China;
    3. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
  • Received:2015-04-07 Revised:2015-11-24 Online:2016-04-05 Published:2015-11-26
  • Supported by:

    supported by the National Natural Science Foundation of China and Shenhua Group Corp.(U1261103) and the Open Fund of State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences (J12-13-913).

Abstract:

Electrochemical synthesis of ethylene from acetylene was put forward and the synthesized ethylene was characterized by gas chromatography (GC). First-principle calculations were carried out to examine the adsorption of acetylene over the Pd (111) surface. The electrochemical reduction behavior of acetylene has been investigated on a Pd electrode by cyclic voltammetry (CV) and stable polarization curves in sulfuric acid. The formation mechanism of ethylene in the sulfuric acid was proposed and the transfer coefficients of the reaction were calculated. The results showed that the acetylene molecule tended to be adsorbed through the threefold parallel-bridge configuration that was computed to be the most stable because of its lowest adsorption energy. The rate-determining step in the electrolysis process has been obtained. The rate of this step obtained from the assumed process agreed well with the experiment results.

Key words: acetylene, ethylene, absorption, reduction, electrochemistry mechanism, first-principles, rate-determining step

CLC Number: 

  • O643

[1] XIE K C, LI W Y, ZHAO W. Coal chemical industry and its sustainable development in China[J]. Energy, 2010, 35: 4349-4355.
[2] 迟洪泉. 国内外乙烯工业现状与展望[J]. 化工技术经济, 2006, 24(4): 6-9, 15. CHI H Q. Current situation and future development of ethylene industry[J]. Chemical Techno-Economics, 2006, 24(4): 6-9, 15.
[3] YAN B H, XU P C, CLIFF Y G, et al. Experimental study on coal pyrolysis to acetylene in thermal plasma reactors[J]. Chemical Engineering Journal, 2012, 207/208: 109-116.
[4] WU C N, CHEN J Q, CHENG Y. Thermodynamic analysis of coal pyrolysis to acetylene in hydrogen plasma reactor[J]. Fuel Processing Technology, 2010, 91: 823-830.
[5] BAO S, SCHINDLER K M, HOFMANN P, et al. The local adsorption structure of acetylene on Cu (111)[J]. Surface Science, 1993, 291(3): 295-308.
[6] KYRIAKOU G, KIM J, TIKHOV M S, et al. Acetylene coupling on Cu (111): formation of butadiene, benzene, and cyclooctatraene[J]. Journal of Physical Chemistry B, 2005, 109(21): 10952-10956.
[7] IBACH H, LEHWALD S. Identification of surface radicals by vibration spectroscopy: reactions of C2H2, C2H4, and H2 on Pt (111)[J]. The Journal of Physical Chemistry B, 1978, 15(2): 407-415.
[8] ORMEROD R M, LAMBERT R M, BENNETT D W, et al. Temperature programmed desorption of co-adsorbed hydrogen and acetylene on Pd (111)[J]. Surface Science, 1995, 330(1): 1-10.
[9] SONG X L, DU H Y, LIANG Z H, et al. Paired electrochemical synthesis of ethylene and oxalic acid from acetylene[J]. International Journal of Electrochemical Science, 2013, 8(5): 6566-6573.
[10] HUANG B B, DURANT C, ISSE A A, et al. Highly selective electrochemical hydrogenation of acetylene to ethylene at Ag and Cu cathodes[J]. Electrochemistry Communications, 2013, 34: 90-93.
[11] 梁镇海, 宋秀丽, 段东红, 等. 一种乙炔双极电化学合成乙烯和草酸的方法: ZL201110226331.3[P]. 2012-02-22. LIANG Z H SONG X L, DUAN D H, et al. Method for double-electrode electrochemical synthesis of ethene and oxalic acid from acetylene:ZL201110226331.3[P]. 2012-02-22.
[12] XIE X J, SONG X L, DONG W Y, et al. Adsorption mechanism of acetylene hydrogenation on the Pd (111) surface[J]. Chinese Journal of Chemistry, 2014, 32: 631-636.
[13] SHETH P A, NEUROCK M, SMITH C M. A first-principles analysis of acetylene hydrogenation over Pd (111)[J]. Journal of Physical Chemistry B, 2003, 107(9): 2009-2017.
[14] KANG J H, SHIN E W, KIM W J, et al. Selective hydrogenation of acetylene on TiO2-added Pd catalysts[J]. Journal of Catalysis, 2002, 208(2): 310-320.
[15] ZHANG Q W, LI J, LIU X X, et al. Synergetic effect of Pd and Ag dispersed on Al2O3 in the selective hydrogenation of acetylene[J]. Applied Catalysis A: General, 2002, 197(2): 221-223.
[16] 王功华. 乙炔加氢动力学研究及反应器模拟计算[D]. 北京: 北京化工大学, 2003. WANG G H. Dynamics study on acetylene hydrogenation and simulating calculation of reactor[D]. Beijing: Beijing University of Chemical Technology, 2003
[17] BOND G C, WELLS P B. The hydrogenation of acetylene(Ⅱ): The reaction of acetylene with hydrogen catalyzed by alumina-supported palladium[J]. Journal of Catalysis, 1966, 5(1): 65-73.
[18] BOND G C, WELLS P B. The hydrogenation of acetylene(Ⅲ): The reaction of acetylene with hydrogen catalyzed by alumina-supported rhodium and iridium[J]. Journal of Catalysis, 1966, 5(3): 419-427.
[19] SHETH P A, NEUROCK M, SMITH C M. A first-principles analysis of acetylene hydrogenation over Pd(111)[J]. The Journal of Physical Chemistry B, 2003, 107: 2009-2017.
[20] 高鹏, 朱永明. 电化学基础教程[M]. 北京: 化学工业出版社, 2013: 108-109. GAO P, ZHU Y M. A Course Book of Electrochemistry[M]. Beijing: Chemical Industry Press, 2013: 108-109.
[21] YU J G, CAI X J, ZHANG H B, et al. Electrooxidation of hydroxypivalaldehyde in an undivided cell[J]. Chemical Research in Chinese Universities, 2006, 22(5): 626-630.

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