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负载型Cu-Co尖晶石复合氧化物催化剂的制备及其性能研究
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摘要
正丁醛可用作树脂、塑料增塑剂、硫化促进剂等的中间体。丁醛的生产多采用丙烯羰基合成法,本文以过渡金属复合氧化物代替铑膦配合物,采用浸渍法制备催化剂,并研究其催化氧化性能。以氧化铝、氧化锆、二氧化硅以及氧化铝和二氧化硅的复合物为载体,以硝酸钴、硝酸铜为金属源,经浸渍、烘干,并于马弗炉中500℃焙烧制得Co系催化剂。经XRD、FT-IR表征,结果表明Cu-Co氧化物形成了尖晶石结构。采用固定床反应装置,以CuCo_2O_4尖晶石型复合氧化物为催化剂,考察了载体、反应温度等因素对正丁醇催化氧化生成正丁醛性能的影响。在反应温度为380℃,反应的空速为1h~(-1),氧醇比为0.5时,以氧化铝为载体的催化剂,正丁醇的转化率为75.5%,正丁醛的选择性为79.6%;以二氧化硅为载体,转化率为68.1%,选择性为78%;以氧化锆为载体的效果不明显。
The n-butylaldehyde can be used as resin,plastic plasticizer,vulcanization accelerator.The method of propylene carbonyl synthesis can be used to product butyraldehyde.In this paper,the catalyst was prepared by impregnation using transition metal oxide instead of rhodium-phosphine.Co catalysts were get after impregnation;filtration;drying;and 500℃ in muffle furnace with Al_2O_3,ZrO_2,SiO_2 and the compound of Al_2O_3 and SiO_2 as carrier,Cu(NO_3)_2,Co(NO_3)_2 as metal source.The results showed that Cu-Co oxides form spinel structure that characterized by XRD and FT-IR.Inspected the different temperatures,carriers with CuCo_O_4 as catalyst,using fixed-bed reactor.The conversion rate was 75.5%,,selectivity was 79.6%using Al_2O_3 as carrier when the reaction temperature was 380℃,speed was 1h~(-1),and the ratio between oxygen and butanol was 0.5 while the conversion was 68.1%,selectivity was 78%with SiO_2 as carrier.The effect was not obvious based on ZrO_2.
引文
[1]Kohjio,Tankshit,Seijik.Activ Site of Substituted Cobalt Spine Oxide for Selective Oxidation of CO/H2 Part[J].Applied Catalysis A:General,1996,146(2):255-267.
    [2]包天舒.羰基合成从丁醛到戊醛的工艺分析[J].化工进展,2013,32(增刊):42-47.

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