Abstract: Selective hydrogenation of butadiene in C4 mixture to produce 1-butene on Pd-Ag/Al2O3 catalyst was studied. The test results showed that selectivity of 1-butene produced from 1,3-butadiene hydrogenation was closely related to both inlet 1,3-butadiene concentration and H2/butadiene mole ratio. Under the conditions of inlet temperature 40 ℃，pressure 1.0 MPa，liquid space velocity 40h?1，when inlet butadiene concentration was more than 2.6%，selectivity of 1-butene maintained at more than 66%；when inlet butadiene concentration was less than 2.6%，selectivity of 1-butene began to decline as isomerization reaction was intensified. When inlet butadiene concentration was less than 1.0%，outlet 1,3-butadiene concentration could be reduced to less than 1.0×10-5. With the increase of H2/butadiene mole ratio，1-butene selectivity declined linearly when inlet butadiene concentration was between 0.50% and 0.85%，indicating that excess H2 with respect to butadiene was an important reason for isomerization and hydrogenation reactions of butene. H2-TPR and XPS results showed that Pd-Ag alloy was formed during catalyst reduction.

Key words: Pd-Ag catalyst, 1-butene, butadiene, selective hydrogenation, isomerization

摘要： 对Pd-Ag/Al2O3催化剂在裂解混合碳四选择加氢制丁烯反应中的性能进行了研究。实验结果表明，1,3-丁二烯加氢生成1-丁烯的选择性与反应器入口1,3-丁二烯浓度和氢/丁二烯比密切相关，在反应器入口温度40 ℃、反应压力1.0 MPa、液空速40 h?1的条件下，当入口丁二烯摩尔分数大于2.6%，1-丁烯选择性维持在66%以上；当入口丁二烯摩尔分数降至2.6%以下时， 1-丁烯选择性开始下降；当反应器入口1,3-丁二烯摩尔分数小于1.0%时，出口1,3-丁二烯摩尔分数可降至小于1.0×10-5。当反应器入口1,3-丁二烯摩尔分数为0.50%～0.85%时，1-丁烯选择性随着氢/丁二烯摩尔比的增加呈现线性下降趋势，表明过量的氢气是发生丁烯的异构化和加氢反应的重要原因。H2-TPR和XPS表征结果显示，Pd-Ag/Al2O3中的Pd和Ag还原过程中形成了Pd-Ag合金。

关键词: 钯银催化剂, 1-丁烯, 丁二烯, 选择加氢, 异构化