Reaction mechanism of electrochemical reduction of acetylene to ethylene

doi:10.11949/j.issn.0438-1157.20150424

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

Previous Articles Next Articles

Reaction mechanism of electrochemical reduction of acetylene to ethylene

SONG Xiuli^1,2, JIA Ruilong¹, XIE Xuejia¹, LIANG Zhenhai¹, ZHU Zhenping³

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:2016-04-05
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).

乙炔电还原制备乙烯的反应机理

宋秀丽^1,2, 贾瑞龙¹, 解学佳¹, 梁镇海¹, 朱珍平³

1. 太原理工大学化学化工学院, 山西太原 030024;
2. 太原师范学院化学系, 山西太原 030031;
3. 中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001

通讯作者: 梁镇海
基金资助:
国家自然科学基金委员会与神华集团有限责任公司联合资助项目(U1261103);中国科学院山西煤炭化学研究所煤转化国家重点实验室开放基金项目(J12-13-913)。

Abstract

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

摘要：

选择钯电还原乙炔制备乙烯并通过气相色谱法对产品进行表征,利用第一性原理计算方法探讨乙炔在催化剂Pd (111)表面的吸附情况,采用循环伏安法研究钯电极在硫酸溶液中还原乙炔的电极过程,测定电极的稳态极化曲线并根据极化曲线推算Tafel斜率,重点结合表观传递系数及反应级数对拟定的乙炔电还原制备乙烯的反应机理进行验证。实验结果表明:乙炔分子在Pd (111)面上呈平行桥键构型时最稳定;钯电极在硫酸溶液中可将乙炔电还原为乙烯;得出了反应最可能的速率控制步骤。

关键词: 乙炔, 乙烯, 吸附, 还原, 电化学机理, 第一性原理, 速率控制步骤

CLC Number:

O643
O646

SONG Xiuli, JIA Ruilong, XIE Xuejia, LIANG Zhenhai, ZHU Zhenping. Reaction mechanism of electrochemical reduction of acetylene to ethylene[J]. CIESC Journal, 2016, 67(4): 1340-1347.

宋秀丽, 贾瑞龙, 解学佳, 梁镇海, 朱珍平. 乙炔电还原制备乙烯的反应机理[J]. 化工学报, 2016, 67(4): 1340-1347.

References 21

[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.

Reaction mechanism of electrochemical reduction of acetylene to ethylene

乙炔电还原制备乙烯的反应机理

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 21

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Congqi HUANG, Yimei WU, Jianye CHEN, Shuangquan SHAO. Simulation study of thermal management system of alkaline water electrolysis device for hydrogen production [J]. CIESC Journal, 2023, 74(S1): 320-328.
[2]	Zhenghao JIN, Lijie FENG, Shuhong LI. Energy and exergy analysis of a solution cross-type absorption-resorption heat pump using NH₃/H₂O as working fluid [J]. CIESC Journal, 2023, 74(S1): 53-63.
[3]	Runmiao GAO, Mengjie SONG, Enyuan GAO, Long ZHANG, Xuan ZHANG, Keke SHAO, Zekang ZHEN, Zhengyong JIANG. Review on greenhouse gas reduction related to refrigerants in cold chain [J]. CIESC Journal, 2023, 74(S1): 1-7.
[4]	Xiaoxiong FAN, Lifang HAO, Chuigang FAN, Songgeng LI. Study on the catalytic denitrification performance of low-temperature NH₃-SCR over LaMnO₃/biochar catalyst [J]. CIESC Journal, 2023, 74(9): 3821-3830.
[5]	Hao WANG, Zhenlei WANG. Model simplification strategy of cracking furnace coking based on adaptive spectroscopy method [J]. CIESC Journal, 2023, 74(9): 3855-3864.
[6]	Zehao MI, Er HUA. DFT and COSMO-RS theoretical analysis of SO₂ absorption by polyamines type ionic liquids [J]. CIESC Journal, 2023, 74(9): 3681-3696.
[7]	Yuanchao LIU, Bin GUAN, Jianbin ZHONG, Yifan XU, Xuhao JIANG, Duan LI. Investigation of thermoelectric transport properties of single-layer XSe₂(X=Zr/Hf) [J]. CIESC Journal, 2023, 74(9): 3968-3978.
[8]	Song HE, Qiaomai LIU, Guangshuo XIE, Simin WANG, Juan XIAO. Two-phase flow simulation and surrogate-assisted optimization of gas film drag reduction in high-concentration coal-water slurry pipeline [J]. CIESC Journal, 2023, 74(9): 3766-3774.
[9]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[10]	Xingzhi HU, Haoyan ZHANG, Jingkun ZHUANG, Yuqing FAN, Kaiyin ZHANG, Jun XIANG. Preparation and microwave absorption properties of carbon nanofibers embedded with ultra-small CeO₂ nanoparticles [J]. CIESC Journal, 2023, 74(8): 3584-3596.
[11]	Lingding MENG, Ruqing CHONG, Feixue SUN, Zihui MENG, Wenfang LIU. Immobilization of carbonic anhydrase on modified polyethylene membrane and silica [J]. CIESC Journal, 2023, 74(8): 3472-3484.
[12]	Chengying ZHU, Zhenlei WANG. Operation optimization of ethylene cracking furnace based on improved deep reinforcement learning algorithm [J]. CIESC Journal, 2023, 74(8): 3429-3437.
[13]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[14]	Yuying GUO, Jiaqiang JING, Wanni HUANG, Ping ZHANG, Jie SUN, Yu ZHU, Junxuan FENG, Hongjiang LU. Water-lubricated drag reduction and pressure drop model modification for heavy oil pipeline [J]. CIESC Journal, 2023, 74(7): 2898-2907.
[15]	Qiyu ZHANG, Lijun GAO, Yuhang SU, Xiaobo MA, Yicheng WANG, Yating ZHANG, Chao HU. Recent advances in carbon-based catalysts for electrochemical reduction of carbon dioxide [J]. CIESC Journal, 2023, 74(7): 2753-2772.