甲醇气相氧化羰基化合成碳酸二甲酯的研究 Ⅱ助剂对催化性能的影响

• 作 者: 姜瑞霞 王延吉 赵新强 王淑芳
• 机 构: 河北工业大学化工学院!天津 300130,河北工业大学化工学院!天津 300130,河北工业大学化工学院!天津 300130,河北工业大学化工学院!天津 300130
• 出 处: 燃料化学学报
• 发表日期: 1999年04期
• 关键词: 羰基化 碳酸二甲酯 催化剂合成 甲醇气相 固相催化剂 反应性能 单程转化率 催化活性位 原子比 催化剂制备

考察了碱金属助剂对ＰｄＣｌ２－ＣｕＣｌ２ＡＣ催化剂上甲醇气相氧化羰基化直接合成碳酸二甲酯反应性能的影响及助剂的作用。结果表明：采用不同碱金属助剂时的碳酸二甲酯收率顺序为Ｋ＞Ｎａ＞Ｌｉ；ＫＯＡｃ助剂的主要作用是与ＰｄＣｌ２、ＣｕＣｌ２发生化学反应，促进催化活性位的形成；ＫＯＡｃ为助剂母体的效果明显好于ＫＣｌ母体；Ｋ助剂的最佳含量为２～３ｗ％；在反应温度Ｔ＝１５２℃，进料气体空速和液体空速分别为１４８３ｈ－１和４ｈ－１，进料ＣＯＯ２比为２８３时，对于Ｐｄ＝０６１ｗ％，原子比为ＰｄＣｕＫ＝１１４１４的ＰｄＣｌ２－ＣｕＣｌ２－ＫＯＡｃＡＣ催化剂，在６ｈ的运转时间内碳酸二甲酯的时空收率可达到３１７～３６１ｇＬ－ｃａｔｈ，甲醇的单程转化率为１４８～１６９％

The effects of alkali promoters on the catalytic performance of direct synthesis of dimethyl carbonate by vapor-phase oxidative carbonylation of methanol on PdCl2-CuCl2AC catalyst were investigated. The results showed that the order of yield of dimethyl carbonate was K> Na> Li with different alkali promoters. The main effect of KOAc additive was to react with PdCl2 and CuCl2 to promote the formation of catalytically active sites. KOAc was The results showed that the effect of the agent was obviously better than that of KCl; the optimal content of K promoter was 2 ~ 3w%; at the reaction temperature T = 152 ℃, the space velocity and liquid space velocity of the feed gas were 1483h-1 and 4h-1, When the feed COO2 ratio is 283, PdCl2-CuCl2-KOAc AC catalyst with Pd 0 Cu  K = 1  1414 for Pd = 061w% Space-time yield of dimethyl carbonate can reach 317 ~ 361g  L-cat  h, one-way methanol conversion rate of 14  8 ~ 16  9%