CO气相偶联合成草酸二甲酯催化剂的研制
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摘要
考察助剂、制备方法和还原介质对CO气相偶联合成草酸二甲酯催化剂性能的影响。结果表明,以贵金属Pd为活性组分,非贵金属C为助剂,以α-Al_2O_3为载体,采用分步等体积浸渍法制备的催化剂,在水合肼还原后,具有良好的反应活性和稳定性。在反应温度130℃,空速3 000 h~(-1)时,产物中草酸二甲酯含量90%以上,时空收率平均可达813 g·(L·h)~(-1)。催化剂PC-3反应500 h后,物理性能和反应活性变化不大。
The effects of promoters,preparation methods,and reductants on catalysts for CO gaseous phase coupling reaction to dimethyl oxalate were investigated.The results showed that the catalyst with Pd as active component,non-precious C as promoter and α-Al_2O_3 as support prepared by step-by-step equal volume impregnation showed good reactivity and stability after reduced by hydrazine hydrate.When reaction temperature was 130 ℃ and space velocity was 3 000 h~(-1),content of dimethyl oxalate in product was more than 90% and average yield of dimethyl oxalate reached to 813 g·(L·h)~(-1).After 500 h of reaction,physicochemical properties and acticity of catalyst PC-3 changed little.
The effects of promoters,preparation methods,and reductants on catalysts for CO gaseous phase coupling reaction to dimethyl oxalate were investigated.The results showed that the catalyst with Pd as active component,non-precious C as promoter and α-Al_2O_3 as support prepared by step-by-step equal volume impregnation showed good reactivity and stability after reduced by hydrazine hydrate.When reaction temperature was 130 ℃ and space velocity was 3 000 h~(-1),content of dimethyl oxalate in product was more than 90% and average yield of dimethyl oxalate reached to 813 g·(L·h)~(-1).After 500 h of reaction,physicochemical properties and acticity of catalyst PC-3 changed little.
引文
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[10]尹东学,李振花,项铁丽,等. CO气相偶联合成草酸二乙酯Pd-Fe/α-Al2O3催化剂研究[J].天然气化工,2004,29(2):20-23.Yin Dongxue,Li Zhenhua,Xiang Tieli,et al. Study of PdFe/α-Al2O3catalyst for CO coupling to diethyl oxalate[J]. Natural Gas Chemical Industry,2004,29(2):20-23.
[2]张旭. CO气相偶联制草酸酯研究进展[J].工业催化,2013,21(8):12-17.Zhang Xu. Advance in synthesis of oxalic ester by gas phase CO coupling[J]. Industrial Catalysis,2013,21(8):12-17.
[3]Uchiumi S,Ataka K,Matsuzaki T. Oxidative reactions by a palladium-klkyl nitrite system[J]. Journal of Organic Chemistry,1999,18(2):3-5.
[4]马中义,孟翔宇,王宏伟,等. CO气相催化偶联合成草酸酯的研究进展[J].石油化工,2009,38(4):456-462.Ma Zhongyi,Meng Xiangyu,Wang Hongwei,et al. Progress in research of oxalate synthesis by gas phase catalytic coupling of CO[J]. Petrochemical Technology,2009,38(4):456-462.
[5]马中义,王宏伟,周玮,等.一种合成草酸酯的催化剂及其制备方法:中国,CN101596455A[P]. 2009-12-9.
[6]刘艳侠,李伍成,梁旭,等.一种草酸酯合成反应的催化剂及其制备方法:中国,CN102407111A[P]. 2012-04-11.
[7]王宏伟,逄彬,王天来,等.载体和助剂对CO气相合成草酸二甲酯的影响[J].化工科技,2010,18(5):24-26.Wang Hongwei,Pang Bin,Wang Tianlai,et al. Effects of supports and promoter on gaseous catalyzing synthesis of dimethyl oxalate[J]. Science&Technology in Chemical Industry,2010,18(5):24-26.
[8]赵秀阁,吕兴龙,赵红钢,等.气相法CO与亚硝酸甲酯偶联合成草酸二甲酯用Pd/α-Al2O3催化剂的研究[J].催化学报,2004,25(2):125-128.Zhao Xiuge,Lv Xinglong,Zhao Honggang,et al. Study on Pd/α-Al2O3catalyst for vapor-phase coupling reaction of CO with CH3ONO to(CH3OOC)2[J]. Chinese Journal of Catalysis,2004,25(2):125-128.
[9]赵红钢,肖文德,朱毓群.气相合成草酸酯的催化剂及其制备方法:中国,CN1381310A[P]. 2002-11-27.
[10]尹东学,李振花,项铁丽,等. CO气相偶联合成草酸二乙酯Pd-Fe/α-Al2O3催化剂研究[J].天然气化工,2004,29(2):20-23.Yin Dongxue,Li Zhenhua,Xiang Tieli,et al. Study of PdFe/α-Al2O3catalyst for CO coupling to diethyl oxalate[J]. Natural Gas Chemical Industry,2004,29(2):20-23.