Enhancement of the Stability of Au-Cu/AC Acetylene Hydrochlorination Bimetallic Catalyst with Melamine Treated Support

Document Type : Research Article


1 State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, P.R. CHINA + \ Tianjin Dagu Chemical Co., Ltd. Tianjin, 300455, P.R. CHINA

2 State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, P.R. CHINA

3 Tianjin Dagu Chemical Co., Ltd. Tianjin, 300455, P.R. CHINA


This paper highlights the experimental and theoretical studies on the Melamine treated Active Carbon (MAC) support for an Au-Cu bimetallic catalyst in acetylene hydrochlorination reaction. Compared to the original Active Carbon (AC) loaded with the same amount of 0.1wt% Au and 1.0wt% Cu,  MAC supported catalyst(MACH), wherein Carbon/C6H6N6 mass ratio was 5:3, exhibited excellent catalytic activity. The initial conversion of acetylene increased from 77.5% to 82.7% at 150 and atmospheric pressure. The gas hourly space velocity (GHSV) was 120h-1 under a feed volume ratio VHCl/VC2H2 of 1.05. As polymerization of acetylene on the catalyst was the main cause of deactivation, accelerated deactivation test was carried out. The result indicated MACH performed good anti-coking capacity. Based on the characterization by using BET, XRD, SEM, TGA, TPD and XPS techniques, the variation of O1s XPS spectra of the synthesized catalysts was observed that was in line with DFT results. It is postulated that the better stability and the better dispersion of gold actions were ascribed to the additional metal and the modified substrateThe electron transmission from the auxiliary and the elevated groups on the catalyst surface partially inhibited the reduction of the Au3+ active species. Meanwhile, the stronger adsorption energy of HCl was also beneficial to catalytic activity and stability. 


Main Subjects

[1] Zhang J., Liu N., Li W., Progress on Cleaner Production of Vinyl Chloride Monomers over Non-Mercury Catalysts, Front Chem. Sci. Eng., 5: 514-520 (2011).
[2] Adams M.D., The Mechanisms of Adsorption of Hg(CN)2 and HgCl2 on to Activated Carbon, Hydrometallurgy., 26: 201-210 (1991).
[3] Nkos, B., Coville N.J., Hutchings G.J., Vapour Phase Hydrochlorination of Acetylene with Group VIII and IB Metal Chloride Catalysts, Appl. Catal., 43: 33-39 (1988).
[4] Nkosi B., Coville N.J., Hutchings G.J., Hydrochlorination of Acetylene Using Gold Catalysts: A Study of Catalyst Deactivation, J. Catal., 128: 366-377 (1991).
[5] Conte M., Carley A.F., Hutchings G.J., Reactivation of a Carbon-Supported Gold Catalyst for the Hydrochlorination of Acetylene,Catal. Lett., 124: 165-167 (2008).
[6] Mitchenko S.A., Khomutov E.V., Shubin A.A., Mechanochemical Activation of K2PtCl6: Heterogeneous Catalyst for Gas-Phase Hydrochlorination of Acetylene, Theor. Exp. Chem., 39: 255-258 (2003).
[8] Conte M., Carley A.F., Heirene C., Hydrochlorination of Acetylene Using a Supported Gold Catalyst:
A Study of the Reaction Mechanism
, J. Catal., 250: 231-239 (2007).
[9] Wei X., Shi H., Qian W., Gas-Phase Catalytic Hydrochlorination of Acetylene in a Two-Stage Fluidized-Bed Reactor, Ind. Eng. Chem. Res., 48: 128-133 (2009).
[10] Hutching G.J., Haruta M., A Golden Age of Catalysis: A Perspective. Appl. Catal. A., 291: 2-5 (2005).
[11] Jia J., Haraki K., Kondo J.N., Domen K., Tamaru K., Selective Hydrogenation of Acetylene over Au/Al2O3 Catalyst, J. Phys. Chem., 104: 11153-11156 (2000).
[12] Zhang G., Zhang J., Zhang M., Wang X., Polycondensation of Thiourea into Carbon Nitride Semiconductors as Visible Light Photocatalysts, J. Mater. Chem., 22: 8083-8091 (2012).
[13] Wang L., Shen B., Zhao J., Bi X., Trimetallic Au-Cu-K for Acetylene Hydrochlorination, Can. J. Chem. Eng., 95(6): 1069-1075 (2017).
[14] Conte M., Carley A.F., Attard G., Herzing A.A., Kiely C.J., Hutchings G.J., Hydrochlorination of Acetylene Using Supported Bimetallic Au-Based Catalysts, J.Catal., 257: 190-198 (2008).
[15] Wang S., Shen B., Song Q., Kinetics of Acetylene Hydrochlorination over Bimetallic Au–Cu/C Catalyst, Catal. Lett., 134: 102-109 (2010).
[16] Zhang H., Dai B., Wang X., Li W., Han Y., Gu J., Zhang J., Non-mercury Ctalytic Acetylene Hydrochlorination over Bimetallic Au-Co(III)/SAC Catalysts for Vinyl Chloride Monomer Production, Green. Chem., 15: 829-836 (2013).
[17] Li X., Zhu M., Dai B., AuCl3 on Polypyrrole-Modified Carbon Nanotubes as Acetylene Hydrochlorination Catalysts, Appl. Catal. B., 142: 234-240 (2013).
[18] Wang X., Dai B., Wang Y., Yu F., Nitrogen-Doped Pitch-Based Spherical Active Carbon as a Nonmetal Catalyst for Acetylene Hydro -chlorination, Chem. Cat. Chem., 6: 2339-2344 (2014).
[19] Li X., Wang Y., Kang L., A Novel, Non-Metallic Graphitic Carbon Nitride Catalyst for Acetylene Hydrochlorination, J. Catal., 311: 288-294 (2014).
[20] Song Q.L., Wang S.J., Shen B.X., Palladium-Based Catalysts for the Hydrochlorination of Acetylene: Reasons for Deactivation and Its Regeneration, Petrol.Sci.Technol., 28: 1825-1833 (2010).
[21] Zhao J., Cheng X., Wang L., Ren R., Zeng J., Yang H., Shen B. Free-Mercury Catalytic Acetylene Hydrochlorination Over Bimetallic Au-Bi/γ-Al2O3: A Low Gold Content Catalyst. Catal. Lett., 144: 2191-2197 (2014).
[22] Zhang H., Dai B., Wang X., Xu L., Zhu M., Hydrochlorination of Acetylene to Vinyl Chloride Monomer over Bimetallic Au-La/SAC Catalysts,J. Ind. and Eng. Chem., 18: 49-54 (2012).
[23] Bulushev D.A., Yuranov I., Suvorova E.I., Buffat P.A., Kiwi-Minsker L., Highly Dispersed Gold on Activated Carbon Fibers for Low-Temperature CO Oxidation, J. Catal.,224: 8-17 (2004).
[24] Lakshminarayanan P.V., Toghiani H., Pittman C.U., Nitric Acid Oxidation of Vapor Grown Carbon Nanofibers, Carbon., 42: 2433-2442 (2004).
[25] Zielke U., Hüttinger K.J., Hoffman W.P., Surface-Oxidized Carbon Fibers: I. Surface Structure and Chemistry, Carbon., 34: 983-998 (1996).
[26] Conte M., Davies C.J., Morgan D.J., Carley A.F., Johnston P., Hutchings G.J., Characterization of Au3+ Species in Au/C Catalysts for the Hydrochlorination Reaction of Acetylene, Catal. Lett., 144: 1-8 (2014).
[27] Zhang J., He Z., Li W., Han Y., Deactivation Mechanism of AuCl3 Catalyst in Acetylene Hydrochlorination Reaction: a DFT Study, Rsc.Adv., 2: 4814-4821 (2012).
[28] Aboul-Gheit A.K., Awadallah A.E., Aboul-Gheit N.A., Solyman E.S.A., Abdel-Aaty M.A., Effect of Hydrochlorination and Hydrofluorination of Pt/H-ZSM-5 and Pt–Ir/H-ZSM-5 Catalysts for n-Hexane Hydroconversion, Appl. Catal. A-gen., 334: 304-310 (2008).
[29] Xu J., Zhao J., Xu J., Zhang T., Li X., Di X., Ni J., Wang J., Cen J. Influence of Surface Chemistry of Activated Carbon on the Activity of Gold/Activated Carbon Catalyst in Acetylene Hydrochlorination. Ind. Eng.Chem. Res., 53: 14272-1304281 (2014).