Synthesis of Acetic Acid by Catalytic Oxidation of Butenes (Part 1)

T. Yamashita, S. Ninagawa, Tetsuya Kato
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引用次数: 7

Abstract

The probability of acetic acid synthesis from n-butenes and isobutene was studied with V2O5-binary catalysts. As a second component, following atoms were added to V2O5 in the form of oxide or metal; Rh, B, Cr, Nb, Zn, Pd, Ta, Zr, Si, Ni, Ge, Fe, Ca, Pt, W, Li, Cd, As, Co, Te, Mg, Mn, Mo, Cu, Ag, P, Ba, Ti, Sn, Al, and Sb.In the presence of water, n-butenes and isobutene were oxidized to acetic acid with more than 40% selectivity based on the carbon atom at about 100% conversion of each butene with air containing 3% of butene over V-Cr(3/7), V-Rh(8/2), V-B(5/5) and V-Nb(5/5) catalysts at 270∼310°C.Acetaldehyde, acetone, formaldehyde, maleic acid, formic acid, propionic acid, acrylic acid and citoraconic acid were obtained in low yields from n-butenes.On the other hand, from isobutene methacrylic acid and isobutylic acid were formed in addition to above by-products in low yields.As to the reaction path, acetic acid was considered to be formed via hydration of butenes to form an alcoholic intermediate1)), followed by oxydehydrogenation on the catalyst which had some different active sites to induce other reactions at the same time.
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丁烯催化氧化合成乙酸(一)
用v2o5 -二元催化剂研究了正丁烯和异丁烯合成乙酸的可能性。作为第二组分,下列原子以氧化物或金属的形式加入到V2O5中;Rh、B、Cr、Nb、Zn、Pd、Ta、Zr、Si、Ni、Ge、Fe、Ca、Pt、W、Li、Cd、As、Co、Te、Mg、Mn、Mo、Cu、Ag、P、Ba、Ti、Sn、Al和sb .在水的存在下,正丁烯和异丁烯在含有3%丁烯的空气中,在270 ~ 310°C的条件下,每种丁烯的转化率约为100%,选择性超过40%。正丁烯以低收率制得乙醛、丙酮、甲醛、马来酸、甲酸、丙酸、丙烯酸和柠檬酸。另一方面,除上述副产物外,异丁烯还生成了甲基丙烯酸和异丁酸,产率较低。在反应途径上,认为乙酸是由丁烯水化生成醇中间体1)),然后在具有不同活性位点的催化剂上氧化脱氢,同时引发其他反应。
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