›› 2017, Vol. 25 ›› Issue (9): 1217-1221.DOI: 10.1016/j.cjche.2016.12.003
• Catalysis, kinetics and reaction engineering • 上一篇 下一篇
Xiaolong Xu, Haihua He, Jia Zhao, Bailin Wang, Shanchuan Gu, Xiaonian Li
Xiaolong Xu, Haihua He, Jia Zhao, Bailin Wang, Shanchuan Gu, Xiaonian Li
摘要： Mercuric chloride supported on activated carbon (HgCl2/AC) is used as an industrial catalyst for the hydrochlorination of acetylene. Loss of HgCl2 by sublimating from the surface of activated carbon causes the irreversible deactivation of mercury catalyst and environmental pollution. In this work, a ligand coordination approach based on the Principle of Hard and Soft Acids and Bases (HSAB) was employed to design more stable lowmercury catalyst. The low-mercury catalysts (4% HgCl2 loading) were prepared by using HgCl2 and potassium halides (KX, X=Cl, I) as precursors. The HgCl2-4KI/AC catalyst showed best catalytic stability than HgCl2/AC and HgCl2-4KCl/AC in the hydrochloriantion of acetylene. HgCl2 could form more stable complex with KI, K2HgI4 as the main active component of the HgCl2-4KI/AC catalyst. The characterizations of XRD and EDX analysis illustrated that the active component of HgCl2-4KI/AC was highly dispersed on the surface of activated carbon. The sublimation rates of HgCl2 from the catalysts verified that the active component with larger stability constant had better thermal stability. Using Hg(Ⅱ) complexes with high stability constant as the active component may be the research direction of developing highly stable low-mercury catalyst for the hydrochlorination of acetylene.
|  T. Yang, Production, application and prospect of PVC resin in China, China Plast. 22(2) (2008) 1-8(in Chinese).
 Q.S. Han, F. Sun, Contrast analysis on PVC produced by ethylene method and acetylene method, Polyvinyl Chloride 37(9) (2009) 5-7(in Chinese).
 F.Z. Xin, Contrast of vinyl chloride production processes, Yunnan Chem. Technol. 37(1) (2010) 65-67(in Chinese).
 X.B. Wei, H.B. Shi, W.Z. Qian, G.H. Luo, Y. Jin, F. Wei, Gas-phase catalytic hydrochlorination of acetylene in a two-stage fluidized-bed reactor, Ind. Eng. Chem. Res. 48(1) (2009) 128-133.
 J.L. Bing, C.Z. Li, Review on development of China's PVC industry in the past 10 years and analysis on the trends in the year 2010, Polyvinyl Chloride 39(5) (2001) 1-8(in Chinese).
 J.L. Zhang, N. Liu, W. Li, B. Dai, Progress on cleaner production of vinyl chloride monomers over non-mercury catalysts, Front. Chem. Sci. Eng. 5(4) (2011) 514-520.
 G.J. Hutchings, D.T. Grady, Effect of drying conditions on carbon supported mercuric chloride catalysts, Appl. Catal. 16(1985) 411-415.
 G.J. Hutchings, Vapor phase hydrochlorination of acetylene:Correlation of catalytic activity of supported metal chloride catalysts, J. Catal. 96(1985) 292-295.
 K. Zhou, W. Wang, Z. Zhao, G.H. Luo, J.T. Miller, M.S. Wong, F. Wei, Synergistic GoldBismuth catalysis for non-mercury hydrochlorination of acetylene to vinyl chloride monomer, ACS Catal. 4(2014) 3112-3116.
 K. Zhou, J.C. Jia, C.H. Li, H. Xu, J. Zhou, G.H. Luo, F. Wei, A low content Au-based catalyst for hydrochlorination of C2H2 and its industrial scale-up for future PVC processes, Green Chem. 17(2015) 356-364.
 J. Zhao, J.T. Xu, J.H. Xu, J. Ni, T.T. Zhang, X.L. Xu, X.N. Li, Activated-carbon-supported gold-cesium(I) as highly effective catalysts for hydrochlorination of acetylene to vinyl chloride, ChemPlusChem 80(2015) 196-201.
 J. Zhao, J.T. Xu, J.H. Xu, T.T. Zhang, X.X. Di, J. Ni, X.N. Li, Enhancement of Au/AC acetylene hydrochlorination catalyst activity and stability via nitrogen-modified activated carbon support, Chem. Eng. J. 262(2015) 1152-1160.
 J. Zhao, S.C. Gu, X.L. Xu, T.T. Zhang, Y. Yu, X.X. Di, J. Ni, Z.Y. Pan, X.N. Li, Supported ionic-liquid-phase-stabilized Au(Ⅲ) catalyst for acetylene hydrochlorination, Catal. Sci. Technol. 6(2016) 3263-3270.
 S.A. Mitchenko, T.V. Krasnyakova, I.V. Zhikharev, Catalytic hydrochloriantion of acetylene on mechanochemically-activated K2PdCl4, Theor. Exp. Chem. 44(5) (2008) 316-319.
 L. Wang, F. Wang, J.D. Wang, X.L. Tang, Y.L. Zhao, D. Yang, F.M. Jia, T. Hao, Hydrochlorination of acetylene to vinyl chloride over Pd supported on zeolite Y, React. Kinet. Mech. Catal. 110(2013) 187-194.
 L. Wang, F. Wang, J.D. Wang, Non-mercury catalytic acetylene hydrochlorination over a NH4F-urea-modified Pd/HY catalyst for vinyl chloride monomer production, New J. Chem. 40(2016) 3019-3023.
 Y.F. Pu, J.L. Zhang, L. Yu, Y.H. Jin, W. Li, Active ruthenium species in acetylene hydrochlorination, Appl. Catal. A Gen. 488(2014) 28-36.
 G.B. Li, W. Li, H.Y. Zhang, Y.F. Pu, M.X. Sun, J.L. Zhang, Non-mercury catalytic acetylene hydrochlorination over Ru catalysts enhanced by carbon nanotubes, RSC Adv. 5(2015) 9002-9008.
 S.A. Mitchenko, T.V. Krasnyakova, R.S. Mitchenko, A.N. Korduban, Acetylene catalytic hydrochlorination over powder catalyst prepared by pre-milling of K2PtCl4 salt, J. Mol. Catal. A Chem. 275(2007) 101-108.
 S.A.Mitchenko,E.V.Khomutov,A.A.Shubin, Y.M. Shul'ga,Catalytichydrochlorination of acetyleneby gaseous HCl on the surfaceof mechanically pre-activated K2PtCl6 salt, J. Mol. Catal. A Chem. 212(2004) 345-352.
 X. Huang, F. Yu, M.Y. Zhu, F.H. Ouyang, B. Dai, J.M. Dan, Hydrochlorination of acetylene using expanded multilayered vermiculite (EML-VMT)-supported catalysts, Chin. Chem. Lett. 26(2015) 1101-1104.
 J. Zhang, T.Y. Liu, R. Chen, X.H. Liu, Vermiculite as a natural silicate crystal for hydrogen generation from photocatalytic splitting of water under visible light, RSC Adv. 4(2014) 406-408.
 L.L. Xu, X.G. Wang, H.Y. Zhang, B. Dai, Z.Y. Liu, Q.F. Zhang, Application of a novel carbon carrier in acetylene hydrochlorination, Chem. Ind. Eng. Prog. 30(2011) 536-541(in Chinese).
 M.H. Chen, K. Xu, J.X. Liao, X.H. Chen, Effects of Cd cocatalytic mechanism in multielement catalytic system on performance of low-level mercury catalyst, Polyvinyl Chloride 42(5) (2014) 26-29(in Chinese).
 X.L. Xu, J. Zhao, C.S. Lu, T.T. Zhang, X.X. Di, S.C. Gu, X.N. Li, Improvement of the stability of Hg/AC catalysts by CsCl for the high-temperature hydrochlorination of acetylene, Chin. Chem. Lett. 27(2016) 822-826.
 Y. Zhou, Q. Yang, Q. Luo, W.W. Jiang, Preparation and optimization of a new-type low-mercury catalyst for hydrochlorination of acetylene, Appl. Chem. Ind. 40(12) (2011) 2147-2150(in Chinese).
 Z.Q. Chen, X.Y. Ma, Application of environmental low-mercury catalyst, China ChlorAlkali 6(2009) 9-11(in Chinese).
 P. Johnston, N. Carthey, G.J. Hutchings, Discovery, development, and commercialization of gold catalysts for acetylene hydrochlorination, J. Am. Chem. Soc. 137(2015) 14548-14557.
 X.J. Liu, Y.F. Zhu, F. Gao, Inorganic Element Chemistry, Science Press, Beijing, 2010(in Chinese).
 China Chlor-Alkali Industry Association, HG/T 4192-2011, Low-Level Mercury Catalyst for Chloroethylene Synthesis, Chemical Industry Press, Beijing, 2011(in Chinese).
 Y.C. Xie, N.F. Yang, Y.J. Liu, Y.Q. Tang, Spontaneous dispersion of some active components onto the surfaces of carriers, Sci. Sinica 26(1983) 337-350.
 R.G. Pearson, Hard and soft acids and bases, HSAB, part I fundamental principles, J. Chem. Educ. 45(9) (1965) 581-587.
 R.G. Pearson, Hard and soft acids and bases, HSAB, part Ⅱ underlying theories, J. Chem. Educ. 45(10) (1968) 643-648.
|||Lutai Song, Li Liu, Mingyuan Zhu, Bin Dai. Process monitoring of the Au-S bond conversion in acetylene hydrochlorination[J]. 中国化学工程学报, 2022, 45(5): 32-40.|
|||Fangjie Lu, Dong Xu, Yusheng Lu, Bin Dai, Mingyuan Zhu. High nitrogen carbon material with rich defects as a highly efficient metal-free catalyst for excellent catalytic performance of acetylene hydrochlorination[J]. 中国化学工程学报, 2021, 29(1): 196-203.|
|||Chao Liu, Chenhui Liu, Jinhui Peng, Libo Zhang, Shixing Wang, Aiyuan Ma. Surface chemical characterization of deactivated low-level mercury catalysts for acetylene hydrochlorination[J]. Chinese Journal of Chemical Engineering, 2018, 26(2): 364-372.|
|||Dongfang Zhao, Guanghui Liu, Jian Sun, Lisheng Wang. Enthalpy of phase transition of isonicotinic acid[J]. , 2017, 25(7): 971-975.|
|||Tongtong Zhang, Jia Zhao, Jiangtao Xu, Jinhui Xu, Xiaoxia Di, Xiaonian Li. Oxygen and nitrogen-doped metal-free carbon catalysts for hydrochlorination of acetylene[J]. Chinese Journal of Chemical Engineering, 2016, 24(4): 484-490.|
|||WeiWang, DapengHu, Yanqiu Pan, Guohua Chen. Numerical investigation on freeze-drying of aqueous material frozen with pre-built pores[J]. Chinese Journal of Chemical Engineering, 2016, 24(1): 116-125.|
|||王维, 陈墨, 陈国华. Issues in Freeze Drying of Aqueous Solutions[J]. , 2012, 20(3): 551-559.|