乙炔氢氯化反应用催化剂的制备及优化

Preparation and optimization of catalysts for acetylene hydrochlorination

在固定床反应器上评价不同种类助剂制备的催化剂活性来筛选较适宜的活性组分组合,通过正交设计优选出无汞催化剂的基础配方,考察了添加0.6%的三氯化钌、氯化钯、氯化银等贵金属活性成分及氯化汞后催化剂的活性情况,并进一步优化三氯化钌、氯化汞质量分数来提高催化剂活性。结果表明:助剂氯化钡较氯化钠、氯化铈更能与氯化亚铜/氯化铋间相互协同催化;活性炭上负载12%Cu Cl、16%Bi Cl3、4%Ba Cl2时制备的催化剂活性最佳,转化率可高达66.4%,继续添加氯化银能提高稳定性,但并不能改善催化剂的活性,添加氯化钯仅能改善反应初期催化剂活性,随着反应进行活性不断降低,而添加三氯化钌及氯化汞后催化剂活性明显提升,质量分数为1%时,平均转化率在72.2%以上,特别是氯化汞的转化率可增加至92%,较未加前增加了27%。

The activity of catalyst prepared from different kinds of additives in a fixed bed reactor is evaluated to determine the optimum catalyst composition. Based on the orthogonal experiment,the optimum formulation of mercury-free catalyst is optimized. The effects of adding 0. 6 % of ruthenium trichloride,palladium chloride,silver chloride and other noble metal active ingredients,or 0. 6 % of mercuric chloride on the catalytic activity are studied. Further optimization of the amount of ruthenium chloride and mercuric chloride is performed to increase the catalyst activity. The results show that barium chloride is more suitable for mutual cooperative catalysis with cupric chloride/bismuth chloride than sodium chloride and cerium chloride. The best catalytic activity could be achieved when the catalysts is prepared by loading 12%Cu Cl,16% BiCl3 and 4% BaCl2 on activated carbon. The conversion rate of acetylene can be up to 66. 38%. Further addition of silver chloride could improve the stability,but does not improve the activity of the catalyst. Incorporation of palladium chloride can only improve the initial activity,but the activity is gradually decreased as the reaction proceeds.However,the introduction of mercuric chloride and ruthenium chloride can improve catalytic activity significantly. When the amounts of mercuric chloride and ruthenium chloride are up to 1 wt%,the average conversion will be over 72. 15%.Especially for mercuric chloride,the conversion of acetylene can be up to 92%,which is increased by 27% compared with the catalyst without mercuric chloride.