乙炔法合成氯乙烯用无汞催化剂的制备与优化
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摘要
采用浸渍法制备了四氯化锡为主要活性组分的无汞催化剂,在固定床反应器上评价了该催化剂活性。结果表明,以四氯化锡为主要活性组分的催化剂中加入助剂可明显提高稳定性,催化剂中加入稀土元素稳定性最高,多组分复合催化剂活性和稳定性明显高于单一和双组分催化剂。筛选制备了SnCl_4-CuCl_2-BiCl_3-CeCl_3/C催化剂,在反应温度为120℃,空速为90 h~(-1),V(HCl)/V(C_2H_2)=1.1的条件下进行正交优化,结果表明,22%Sn Cl_4/6%CuCl_2/10%BiCl_3/2%CeCl_3/C催化剂初始转化率可达95.1%,选择性为99.5%。
The mercury-free catalyst with tin tetrachloride as the main active component is prepared by impregnation method,and its activity is evaluated on a fixed bed reactor. The results show that the addition of auxiliary can help to improve the stability of the catalyst with tin tetrachloride as the main active component.The catalyst added with rare earth elements has the highest stability.The activity and stability of the multi-component composite catalyst are obviously higher than that of the single component and the two components catalysts.The SnCl_4-CuCl_2-BiCl_3-CeCl_3/C catalyst is prepared through screening.Orthogonal optimization is carried out under the conditions that reaction temperature is 120℃,space velocity is 90 h~(-1),and V_(HCl)/V_(C2 H2)= 1. 1,and the result indicates that the initial conversion of 22%Sn Cl_4/_6%CuCl_2/10% BiCl_3/_2%CeCl_3/C catalyst can reach 95. 1% and the selectivity is 99. 5%.
The mercury-free catalyst with tin tetrachloride as the main active component is prepared by impregnation method,and its activity is evaluated on a fixed bed reactor. The results show that the addition of auxiliary can help to improve the stability of the catalyst with tin tetrachloride as the main active component.The catalyst added with rare earth elements has the highest stability.The activity and stability of the multi-component composite catalyst are obviously higher than that of the single component and the two components catalysts.The SnCl_4-CuCl_2-BiCl_3-CeCl_3/C catalyst is prepared through screening.Orthogonal optimization is carried out under the conditions that reaction temperature is 120℃,space velocity is 90 h~(-1),and V_(HCl)/V_(C2 H2)= 1. 1,and the result indicates that the initial conversion of 22%Sn Cl_4/_6%CuCl_2/10% BiCl_3/_2%CeCl_3/C catalyst can reach 95. 1% and the selectivity is 99. 5%.
引文
[1]陈万银,郑伟玲.乙炔氢氯化无汞催化剂研发进展及前景分析[J].中国氯碱,2015,(8):20-23,26.
[2]王鹏程,杨雪超,李瑛.多元配方乙炔氢氯化反应催化剂研究进展[J].聚氯乙烯,2015,(4):1-8,17.
[3]Zhou K,Jia J,Li X,et al.Continuous vinyl chloride monomer production by acetylene hydroc hlorination on Hg-free bismuth catalyst:From lab-scale catalyst characterization,catalytic evaluation to a pilot-scale trial by circulating regeneration in coupled fluidized beds[J].Fuel Processing Technology,2013,108(4):12-18.
[4]贾金超,李小港,罗国华,等.乙炔氢氯化制氯乙烯反应中水蒸汽对铜铋催化剂活性组分的稳定作用[J].过程工程学报,2012,(3):510-515.
[5]郭燕燕.乙炔氢氯化非贵金属无汞催化剂的研究[D].呼和浩特:内蒙古大学,2014.
[6]Calvillo L,Celorrio V,Moliner R,et al.Influence of the support on the physicochemical properties of Pt electrocatalysts:Comparison of catalysts supported on different carbon materials[J].Mater Chem Phys,2011,127(1-2):335-341.
[7]Zhang C L,Kang L H,Zhu M Y,et al.Nitrogen-doped active carbon as a metal-free catalyst for acetylene hydrochlorination[J].RSC Adv,2015,5(10):7461-7468.
[8]Conte M,Davies T,Carley A F,et al.Selective formation of chloroethane by the hydrochlorination of ethane using zinc catalysts[J].J Catal,2007,252(1):23-29.
[9]郭燕燕,刘鹰,胡瑞生,等.Sn Cl2-Zn Cl2/C无汞乙炔氢氯化催化剂的制备与优化[J].应用化学,2014,(5):624-626.
[10]王声洁,沈本贤,肖卫国,等.Au-K/C催化剂用于乙炔氢氯化反应制氯乙烯的催化性能[J].华东理工大学学报(自然科学版),2010,(1):20-24.
[11]Conte M,Carley A F,Attard G,et al.Hydrochlorination of acetylene using supported bimetallic Au-based catalysts[J].Journal of Catalysis,2008,257(1):190-198.
[12]张会平,肖新颜,杨立春.K2CO3活化法制备椰壳活性炭[J].华南理工大学学报(自然科学版),2006,(3):63-66.
[13]Chen Chen,Lin Xingyi,Yu Zhengxi,et al.Effect of HNO3treated activated carbon on its catalytic activity for vinyl acetate synthesis[J].Petrochemical Technolo-gy,2004,33(11):1024-1027.
[2]王鹏程,杨雪超,李瑛.多元配方乙炔氢氯化反应催化剂研究进展[J].聚氯乙烯,2015,(4):1-8,17.
[3]Zhou K,Jia J,Li X,et al.Continuous vinyl chloride monomer production by acetylene hydroc hlorination on Hg-free bismuth catalyst:From lab-scale catalyst characterization,catalytic evaluation to a pilot-scale trial by circulating regeneration in coupled fluidized beds[J].Fuel Processing Technology,2013,108(4):12-18.
[4]贾金超,李小港,罗国华,等.乙炔氢氯化制氯乙烯反应中水蒸汽对铜铋催化剂活性组分的稳定作用[J].过程工程学报,2012,(3):510-515.
[5]郭燕燕.乙炔氢氯化非贵金属无汞催化剂的研究[D].呼和浩特:内蒙古大学,2014.
[6]Calvillo L,Celorrio V,Moliner R,et al.Influence of the support on the physicochemical properties of Pt electrocatalysts:Comparison of catalysts supported on different carbon materials[J].Mater Chem Phys,2011,127(1-2):335-341.
[7]Zhang C L,Kang L H,Zhu M Y,et al.Nitrogen-doped active carbon as a metal-free catalyst for acetylene hydrochlorination[J].RSC Adv,2015,5(10):7461-7468.
[8]Conte M,Davies T,Carley A F,et al.Selective formation of chloroethane by the hydrochlorination of ethane using zinc catalysts[J].J Catal,2007,252(1):23-29.
[9]郭燕燕,刘鹰,胡瑞生,等.Sn Cl2-Zn Cl2/C无汞乙炔氢氯化催化剂的制备与优化[J].应用化学,2014,(5):624-626.
[10]王声洁,沈本贤,肖卫国,等.Au-K/C催化剂用于乙炔氢氯化反应制氯乙烯的催化性能[J].华东理工大学学报(自然科学版),2010,(1):20-24.
[11]Conte M,Carley A F,Attard G,et al.Hydrochlorination of acetylene using supported bimetallic Au-based catalysts[J].Journal of Catalysis,2008,257(1):190-198.
[12]张会平,肖新颜,杨立春.K2CO3活化法制备椰壳活性炭[J].华南理工大学学报(自然科学版),2006,(3):63-66.
[13]Chen Chen,Lin Xingyi,Yu Zhengxi,et al.Effect of HNO3treated activated carbon on its catalytic activity for vinyl acetate synthesis[J].Petrochemical Technolo-gy,2004,33(11):1024-1027.