铜基催化剂上甘油脱水制备羟基丙酮  

Dehydration of Glycerol to Acetol over Copper-Based Catalysts

作　　者：牛莎莎[1,2] 朱玉雷[1,3] 郑洪岩 张维[1,2] 李永旺[1,3] 

机构地区：[1]中国科学院山西煤炭化学研究所,山西太原030001 [2]中国科学院研究生院,北京100049 [3]中科合成油技术有限公司,山西太原030032

出　　处：《催化学报》2011年第2期345-351,共7页

基　　金：国家自然科学基金(20976185)

摘　　要：采用共沉淀法制备了一系列铜基催化剂,在N2中于高压釜中,考察了其催化甘油脱水制备羟基丙酮的反应性能.结果表明,Cu/SiO2催化剂具有较高的催化甘油脱水活性,但目的产物羟基丙酮易与反应产生的H2生成1,2-丙二醇,使得羟基丙酮选择性不高.因此,在固定床反应器上详细考察了在优选的Cu/SiO2催化剂上反应气氛、温度和空速对甘油脱水性能的影响.与纯H2或N2相比,在5%H2-95%N2混合气气氛下反应,Cu/SiO2催化剂表现出较高的活性和羟基丙酮选择性.采用H2-N2混合气作为反应气氛,在一定程度上抑制了N2气氛下催化剂的失活和H2气氛下羟基丙酮的过度加氢.在220oC,常压,5%H2-95%N2混合气气氛和WHSV=0.08h-1条件下,甘油转化率和羟基丙酮选择性分别高达98.8%和84.6%.A series of Cu-based catalysts were prepared by the co-precipitation method,and their catalytic properties for the dehydration of glycerol to acetol were tested under N2 atmosphere in a stainless steel autoclave. The results showed that the Cu/SiO2 catalyst had higher catalytic activity than other catalysts. However,acetol can easily react with hydrogen that originated from the reaction process to 1,2-propanediol,leading to the low selectivity for acetol. Therefore,a fixed-bed reactor was selected to further investigate the effects of reaction atmosphere,reaction temperature,and WHSV on dehydration of glycerol over the Cu/SiO2 catalyst. In comparison with pure H2 or pure N2 atmosphere,the Cu/SiO2 catalyst exhibited significantly higher activity and selectivity for acetol under the mixed atmosphere of 5% H2-95% N2. Under the mixed atmosphere,Cu/SiO2 showed a slower deactivation rate compared with N2 atmosphere and a more proper hydrogenation than that under H2 atmosphere. Under the optimal reaction conditions of 220 oC,WHSV of 0.08 h-1,and ambient 5%H2/N2 pressure,glycerol conversion and selectivity for acetol can be as high as 98.8% and 84.6%,respectively.

关 键 词：甘油 羟基丙酮 脱水 铜基催化剂 

分 类 号：TQ224.2[化学工程—有机化工]