甲基丙烯醛氧化酯化制备甲基丙烯酸甲酯催化剂的制备与表征
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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合成工艺路线。
本文对甲基丙烯醛一步氧化法制备MMA的催化剂进行了研究,选取比表面积、孔径均较大的疏水的苯乙烯-二乙烯基苯共聚物(SDB)作为催化剂载体,采用等体积浸渍法将PdCl2等活性组分负载到载体上,然后经过干燥、还原得到催化剂。考察了不同的干燥方式对催化剂活性的影响, XRD表明采用常压干燥比减压干燥催化剂活性组分的分散度更好,评价结果进一步说明催化剂的活性较高。
考察了主催化活性组分Pd含量及助催化组分种类及含量对催化活性的的影响规律。添加铋(Bi)、铅(Pb)等助组分能够明显提高单钯疏水催化剂的催化性能。在单Pd催化剂的存在条件下甲基丙烯醛的选择性为33.50%,转化率为42.50%,添加Bi金属后,在催化剂Pd5Bi/SDB的存在条件下,甲基丙烯醛的转化率为51.63%,选择性为69.36%;添加Pb金属后,在催化剂Pd5Pb/SDB的存在条件下,甲基丙烯醛的转化率为71.65%,选择性为78.15%,均能显著提高甲基丙烯醛的选择性和转化率。对于双组分催化剂,相同的添加量下,Pd-Pb/SDB要比Pd-Bi/SDB的催化活性强。
制备新型催化剂,并以此催化剂为例考察了反应时间、反应温度、催化剂加入量、原料配比、PH值对MAL转化率和MMA选择性的影响。确定了适宜的反应条件为醇醛摩尔比40:1,催化剂加入量为总反应物质量的3.6%,反应温度50℃,氧气流量为6ml/min,反应时间4小时,PH值为10.5左右,在此条件下甲基丙烯醛的转化率为MMA的选择性为91.20%,MAL的转化率为87.68%。
Methyl methacrylate (MMA) is an important organic chemical material, mainly used for the produce 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 produce processes for the environmental and economic benefits. The process of one-step conversion of methacrolein(MAL) to MMA is a green synthetic process with great potential.
The catalysts used a hydrophobic catalyst material styrene - divinylbenzene copolymer (SDB) as carrier for one-step oxidative-esterification of MAL to MMA were studied.The active component such as PdCl2 was impregnented on SDB by the incipenent wetness method,and reduced it to prepare a hydrophobic catalyst . The different drying ways were studied for the catalytic activity.XRD shows that dring at normal pressure with a better dispersion than drying at vacuum,catalytic test further illustrates the catalysts with a higher activity.
The effect of the content of Pd and promoting component for the catalytic activity was studied.The palladium(Pd) catalyst’s catalytic property could be improved drastically with bismium(Bi) or lead(Pb).The MAL conversion was 33.50% and the MMA selectivity was 42.50% with the existence of Pd5/SDB;The MAL conversion was 51.63% and the MMA selectivity was 69.36% with the existence of Pd5Bi/SDB;The MAL conversion was 71.65% and the MMA selectivity was 78.15% with the existence of Pd5Pb/SDB.The catalytic activity of Pd-Pb/SDB is better than that of Pd5Bi/SDB under the same component addition .
Technological conditions were optimized by using a new catalyst.Under the reaction conditions:mole ratio of methanol to MAL 40:1,catalyst additive 3.6% (all raws), reaction temperature 50℃,flow rate of oxygen 6ml/min,reaction time 4 hours and PH value 10.5, the MAL conversion and MMA selectivity were 87.68% and 91.20% respectly.
本文对甲基丙烯醛一步氧化法制备MMA的催化剂进行了研究,选取比表面积、孔径均较大的疏水的苯乙烯-二乙烯基苯共聚物(SDB)作为催化剂载体,采用等体积浸渍法将PdCl2等活性组分负载到载体上,然后经过干燥、还原得到催化剂。考察了不同的干燥方式对催化剂活性的影响, XRD表明采用常压干燥比减压干燥催化剂活性组分的分散度更好,评价结果进一步说明催化剂的活性较高。
考察了主催化活性组分Pd含量及助催化组分种类及含量对催化活性的的影响规律。添加铋(Bi)、铅(Pb)等助组分能够明显提高单钯疏水催化剂的催化性能。在单Pd催化剂的存在条件下甲基丙烯醛的选择性为33.50%,转化率为42.50%,添加Bi金属后,在催化剂Pd5Bi/SDB的存在条件下,甲基丙烯醛的转化率为51.63%,选择性为69.36%;添加Pb金属后,在催化剂Pd5Pb/SDB的存在条件下,甲基丙烯醛的转化率为71.65%,选择性为78.15%,均能显著提高甲基丙烯醛的选择性和转化率。对于双组分催化剂,相同的添加量下,Pd-Pb/SDB要比Pd-Bi/SDB的催化活性强。
制备新型催化剂,并以此催化剂为例考察了反应时间、反应温度、催化剂加入量、原料配比、PH值对MAL转化率和MMA选择性的影响。确定了适宜的反应条件为醇醛摩尔比40:1,催化剂加入量为总反应物质量的3.6%,反应温度50℃,氧气流量为6ml/min,反应时间4小时,PH值为10.5左右,在此条件下甲基丙烯醛的转化率为MMA的选择性为91.20%,MAL的转化率为87.68%。
Methyl methacrylate (MMA) is an important organic chemical material, mainly used for the produce 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 produce processes for the environmental and economic benefits. The process of one-step conversion of methacrolein(MAL) to MMA is a green synthetic process with great potential.
The catalysts used a hydrophobic catalyst material styrene - divinylbenzene copolymer (SDB) as carrier for one-step oxidative-esterification of MAL to MMA were studied.The active component such as PdCl2 was impregnented on SDB by the incipenent wetness method,and reduced it to prepare a hydrophobic catalyst . The different drying ways were studied for the catalytic activity.XRD shows that dring at normal pressure with a better dispersion than drying at vacuum,catalytic test further illustrates the catalysts with a higher activity.
The effect of the content of Pd and promoting component for the catalytic activity was studied.The palladium(Pd) catalyst’s catalytic property could be improved drastically with bismium(Bi) or lead(Pb).The MAL conversion was 33.50% and the MMA selectivity was 42.50% with the existence of Pd5/SDB;The MAL conversion was 51.63% and the MMA selectivity was 69.36% with the existence of Pd5Bi/SDB;The MAL conversion was 71.65% and the MMA selectivity was 78.15% with the existence of Pd5Pb/SDB.The catalytic activity of Pd-Pb/SDB is better than that of Pd5Bi/SDB under the same component addition .
Technological conditions were optimized by using a new catalyst.Under the reaction conditions:mole ratio of methanol to MAL 40:1,catalyst additive 3.6% (all raws), reaction temperature 50℃,flow rate of oxygen 6ml/min,reaction time 4 hours and PH value 10.5, the MAL conversion and MMA selectivity were 87.68% and 91.20% respectly.
引文
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[12]钱伯章,甲基丙烯酸甲酯的生产技术及市场[J],精细石油化工进展,2002,3(1O):9～13
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[16]王玉荣,胡志香,甲基丙烯酸甲酯生产现状及发展建议[J],化工技术经济,2005,23(2):14～19
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[18]王喜正,赵双霞等,MMA工艺技术及催化剂新进展[J],齐鲁石油化工,2005,33(4):292～297
[19]胡玉才,甲基丙烯酸甲酯的绿色催化合成进展[J],精细化工中间体,2005,35(5):15～17
[20]迟洪盘,崔英华,张献军等,异丁醛一步氧化制甲基丙烯酸甲酯的研究[J],沈阳化工,1992(2):1～4
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[22]Robert Karil,Grassellt,Dev,Dhanaraj Suresh,Preparation of esters from unsatured aldehydes and alcohols[P],US,3819685,1974-7-25
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