一步法制备甲基丙烯酸甲酯疏水催化剂的研究
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摘要
甲基丙烯酸甲酯(MMA)是一种重要的有机化工原料,主要用于生产有机玻璃及树脂材料。世界上MMA主要采用丙酮氰醇法(ACH)生产,从绿色环保及经济效益方面考虑,开发新的工艺路线显得十分必要。甲基丙烯醛(MAL)一步法制MMA便是一种极有发展潜力的绿色工艺路线。
本文对甲基丙烯醛一步法制MMA的催化剂进行了研究,制备了新型疏水性钯催化剂,其催化性能较常规载体催化剂有较大改善。
首先采用等体积浸渍法制备了单钯疏水催化剂。选取比表面积、孔径均较大的SDB-4型苯乙烯-二乙烯基苯共聚物(SDB)作为催化剂载体,确定了活性金属Pd适宜的负载量为3%,适宜的H2还原温度为180～220℃,适宜的还原时间为8～12小时。在氢气流量30ml/min,200℃还原10小时的条件下制备了单钯催化剂Pd3%/SDB-4,该催化剂反应制备MMA产率为55.7%。
通过在钯中添加铋、铅等助催化剂制备了复合金属疏水催化剂,对各催化剂的催化活性进行了比较,并简要分析了各金属组分的助催化作用。以催化剂Pd3%Bi1.5%Pb0.6%/SDB-4为例考察了反应时间、反应温度、催化剂加入量、原料配比对MAL转化率和MMA选择性的影响。确定了最佳反应条件为醇醛摩尔比40:1,催化剂加入量4.5%,反应温度50℃,反应器氧气流速0.53m/h,反应时间6小时,在此条件下MAL转化率为86.9%,MMA选择性为90.3%。对催化剂寿命进行了考察,催化剂重复性较好,使用五次MMA产率仍然维持在75%以上。运用BET、XRD、ESEM等分析手段对催化剂进行了表征。
最后,对多相催化反应历程进行了探讨并对可能的催化反应机理进行了探索分析,对各反应现象作出了机理上的解释,并指出了提高催化剂性能的途径及方法。
Methyl methacrylate (MMA) is an important organic chemical material, mainly used for the production of PMMA and other resins.MMA was mainly produced by the old method of Acetone-Cyanohydrin(ACH) process in the world.It is very necessary to develop new production processes for the environmental and economic benefits. The process of one-step conversion of methacrolein(MAL) to MMA is a green process with great potential.
The catalysts used for one-step conversion of MAL to MMA were studied.A new series of hydrophobic palladium catalyst was prepared, its catalytic performance was greatly improved compared with the conventional catalysts.
Firstly,the hydrophobic sole-palladium catalysts were prepared by impregnation. The SDB-4 Styrene-Divinylbenzene copolymer(SDB) with great surface area and aperture was chosen as the carrier,the appropriate loading of Pd was 3%,reduction temperature is 180~220℃, reduction time is 8~12 hours.Pd3%/SDB-4 was prepared in the hydrogen with flow rate of 30ml/min under 200℃for 10 hours,MMA yield was 55.7%.
Secondly,hydrophobic multi-metal catalysts were prepared by the addition of bismuth, lead and other metals in the sole-palladium catalysts.Their catalytic activities were compared and the influence of each metal on the catalysts was briefly analyzed. The effects of reaction time, temperature, amounts of catalyst,mole ratio of reactants on MAL conversion rate and reaction selectivity were studied. The optimal reaction conditions were:mole ratio of methanol to MAL was 40/1,catalyst added 4.5%, reaction temperature was 50℃,flow rate of oxygen was 0.53m/h,reaction time was 6 hours.Under the above conditions, the MAL conversion rate reached 86.9%,the reaction selectivity was 90.3%. Life of the catalyst was also studied, MMA yield remains above 75% after the catalyst was used for five time.The catalysts were tested by BET,XRD and ESEM at last.
Finally, the heterogeneous catalytic reaction process was discussed as well as the possible catalytic mechanism.The appropriate explanation of reaction phenomenon and the way to improve catalytic properties were proposed.
本文对甲基丙烯醛一步法制MMA的催化剂进行了研究,制备了新型疏水性钯催化剂,其催化性能较常规载体催化剂有较大改善。
首先采用等体积浸渍法制备了单钯疏水催化剂。选取比表面积、孔径均较大的SDB-4型苯乙烯-二乙烯基苯共聚物(SDB)作为催化剂载体,确定了活性金属Pd适宜的负载量为3%,适宜的H2还原温度为180～220℃,适宜的还原时间为8～12小时。在氢气流量30ml/min,200℃还原10小时的条件下制备了单钯催化剂Pd3%/SDB-4,该催化剂反应制备MMA产率为55.7%。
通过在钯中添加铋、铅等助催化剂制备了复合金属疏水催化剂,对各催化剂的催化活性进行了比较,并简要分析了各金属组分的助催化作用。以催化剂Pd3%Bi1.5%Pb0.6%/SDB-4为例考察了反应时间、反应温度、催化剂加入量、原料配比对MAL转化率和MMA选择性的影响。确定了最佳反应条件为醇醛摩尔比40:1,催化剂加入量4.5%,反应温度50℃,反应器氧气流速0.53m/h,反应时间6小时,在此条件下MAL转化率为86.9%,MMA选择性为90.3%。对催化剂寿命进行了考察,催化剂重复性较好,使用五次MMA产率仍然维持在75%以上。运用BET、XRD、ESEM等分析手段对催化剂进行了表征。
最后,对多相催化反应历程进行了探讨并对可能的催化反应机理进行了探索分析,对各反应现象作出了机理上的解释,并指出了提高催化剂性能的途径及方法。
Methyl methacrylate (MMA) is an important organic chemical material, mainly used for the production of PMMA and other resins.MMA was mainly produced by the old method of Acetone-Cyanohydrin(ACH) process in the world.It is very necessary to develop new production processes for the environmental and economic benefits. The process of one-step conversion of methacrolein(MAL) to MMA is a green process with great potential.
The catalysts used for one-step conversion of MAL to MMA were studied.A new series of hydrophobic palladium catalyst was prepared, its catalytic performance was greatly improved compared with the conventional catalysts.
Firstly,the hydrophobic sole-palladium catalysts were prepared by impregnation. The SDB-4 Styrene-Divinylbenzene copolymer(SDB) with great surface area and aperture was chosen as the carrier,the appropriate loading of Pd was 3%,reduction temperature is 180~220℃, reduction time is 8~12 hours.Pd3%/SDB-4 was prepared in the hydrogen with flow rate of 30ml/min under 200℃for 10 hours,MMA yield was 55.7%.
Secondly,hydrophobic multi-metal catalysts were prepared by the addition of bismuth, lead and other metals in the sole-palladium catalysts.Their catalytic activities were compared and the influence of each metal on the catalysts was briefly analyzed. The effects of reaction time, temperature, amounts of catalyst,mole ratio of reactants on MAL conversion rate and reaction selectivity were studied. The optimal reaction conditions were:mole ratio of methanol to MAL was 40/1,catalyst added 4.5%, reaction temperature was 50℃,flow rate of oxygen was 0.53m/h,reaction time was 6 hours.Under the above conditions, the MAL conversion rate reached 86.9%,the reaction selectivity was 90.3%. Life of the catalyst was also studied, MMA yield remains above 75% after the catalyst was used for five time.The catalysts were tested by BET,XRD and ESEM at last.
Finally, the heterogeneous catalytic reaction process was discussed as well as the possible catalytic mechanism.The appropriate explanation of reaction phenomenon and the way to improve catalytic properties were proposed.
引文
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