蒽醌法双氧水钯催化剂的制备及工业应用  

Preparation and application of palladium-based catalyst for producing hydrogen peroxide through anthraquinone route

作　　者：沈冲 杨盟飞 冯彬 张哲 白立光 赵晓东 SHEN Chong;YANG Mengfei;FENG Bin;ZHANG Zhe;BAI Liguang;ZHAO Xiaodong(Liming Research and Design Institute of Chemical Industry Co.,Ltd.,Luoyang 471000,Henan,China)

机构地区：[1]黎明化工研究设计院有限责任公司,河南洛阳471000

出　　处：《精细化工》2022年第4期746-751,760,共7页Fine Chemicals

基　　金：河南省重大科技专项(创新示范专项,79819);洛阳市科技重大专项(1901027A)。

摘　　要：以铝溶胶、丙烯酸-丙烯酰胺共聚物(AA/AM)、六亚甲基四胺为原料,采用油柱成型法制备氧化铝球形颗粒,并使用浸渍法得到Pd/Al_(2)O_(3)催化剂。将Pd/Al_(2)O_(3)用于2-乙基蒽醌催化加氢反应。使用N_(2)吸附-脱附、XRD、TEM、CO脉冲滴定对催化剂结构进行了表征,考察了AA/AM对催化剂结构的影响。结果表明,AA/AM的加入没有改变催化剂的晶体结构,但会增加催化剂比表面积和孔径,同时使催化剂表面Pd粒子的尺寸减小,Pd的分散度增大。与未改性的催化剂APC-Q-1S相比,添加AA/AM的改性催化剂LDHA-1在实验室反应器中的活性由12.5 g/L增加至14.5 g/L,在过氧化氢产能(以100%H_(2)O_(2)计,下同)为10 kg/d的模型实验装置和2000t/a的工业生产装置中的时空产率分别提升77.0%和70.0%;在过氧化氢产能为55000 t/a的工业生产装置中,时空产率可达8.55 kg H_(2)O_(2)/(kg cat·d),显著高于现有工业用催化剂[≤6.14 kg H_(2)O_(2)/(kg cat·d)]。Alumina spherical granules were synthesized via oil-drop method using alumina sol,acrylic acid-acrylamide copolymer(AA/AM)and hexamethylenetetramine as raw materials.Then Pd/Al_(2)O_(3)catalyst was prepared by wet impregnation for the catalytic hydrogenation of 2-ethylanthraquinone.The catalyst was characterized by N_(2)adsorption-desorption,XRD,TEM and CO pulse titration.The effect of AA/AM on the structure of the catalyst was studied.The result showed that the addition of AA/AM did not change the crystal structure of the catalyst,but increased specific surface area and pore size.Meanwhile,the addition of AA/AM decreased the size of Pd particles on the catalyst surface and increased the dispersion of Pd.Compared with those of unmodified APC-Q-1S,the catalytic activity of LDHA-1 catalyst modified by AA/AM in a laboratory reactor increased from 12.5 to 14.5 g/L,and the space-time yields of LDHA-1 in a model plant with hydrogen peroxide capacity(on the basis of 100%H_(2)O_(2),the same below)of 10 kg/d and in an industrial plant with hydrogen peroxide capacity of 2000 t/a increased by 77.0%and 70.0%,respectively.The space-time yield in the industrial plant with hydrogen peroxide capacity of 55000 t/a was up to 8.55 kg H_(2)O_(2)/(kg cat·d),significantly higher than those of commercial catalysts[≤6.14 kg H_(2)O_(2)/(kg cat·d)].

关 键 词：Pd/Al_(2)O_(3)催化剂 比表面积 孔径 2-乙基蒽醌加氢 过氧化氢 工业应用 催化技术 

分 类 号：TQ123.6[化学工程—无机化工] TQ426