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    • 24. 发明申请
    • PROCESS FOR THE CO-PRODUCTION OF BUTANE-1,4-DIOL AND GAMMA-BUTYROLACTONE
    • 合成1,4-丁二醇和γ-丁内酯的方法
    • WO1988000937A1
    • 1988-02-11
    • PCT/GB1987000547
    • 1987-07-31
    • DAVY McKEE (LONDON) LIMITEDTURNER, KeithSHARIF, MohammadRATHMELL, ColinKIPPAX, John, WilsonCARTER, Anthony, BenjaminSCARLETT, JohnREASON, Arthur, JamesHARRIS, NormanHARRISON, George, EdwinWOOD, Michael, Anthony
    • DAVY McKEE (LONDON) LIMITED
    • C07C29/136
    • C07D315/00C07C29/177C07C31/207
    • A process for the co-production of butane-1,4-diol and gamma-butyrolactone which comprises: (a) esterifying maleic anhydride by reaction with an alkyl alcohol to form the corresponding dialkyl maleate; (b) hydrogenating resulting dialkyl maleate to yield a reaction product mixture comprising said alkyl alcohol, butane-1,4-diol and gamma-butyrolactone; (c) recovering alkyl alcohol from said reaction product mixture; (d) recycling recovered alkyl alcohol to step (a); and (e) recovering butane-1,4-diol and gamma-butyrolactone from the reaction product mixture of step (c); wherein said process comprises: (i) continuously supplying maleic anhydride and a molar excess of an alkyl alcohol to a monoesterification zone maintained at an elevated temperature thereby to form the corresponding mono-alkyl maleate; (ii) continuously supplying resulting mono-alkyl maleate in admixture with a molar excess of said alkyl alcohol to a primary catalytic esterification zone containing a charge of a solid esterification catalyst and maintained under esterification conditions thereby to form an intermediate ester-containing mixture containing a major amount of the corresponding dialkyl maleate and a minor amount of said mono-alkyl maleate; (iii) continuously supplying a first liquid feed comprising said monoalkyl maleate to a secondary esterification zone containing a charge of a solid esterification catalyst; (iv) continuously supplying a second feed stream comprising said alkyl alcohol to said secondary esterification zone; (v) maintaining said secondary esterification zone at an elevated temperature sufficient to form or maintain therein a vaporous stream containing said alkyl alcohol; (vi) intimately contacting said first liquid feed in said secondary esterification zone in the presence of said catalyst with said vaporous stream; (vii) recovering from said secondary esterification zone a vaporous effluent stream containing, in addition to alkyl alcohol vapour, also water in vapour form, said water being produced in said secondary esterification zone by esterification of said monoalkyl maleate with said alkyl alcohol; (viii) recovering from said secondary esterification zone a liquid product containing said dialkyl maleate; (ix) vaporising dialkyl maleate produced in said secondary esterification zone in a stream of a hydrogen-containing gas; (x) passing resulting vaporous dialkyl maleate containing stream through a plurality of hydrogenation zones connected in series, each containing a charge of a solid esterification catalyst and each maintained under ester hydrogenation conditions; (xi) controlling the reaction conditions in each of the plurality of hydrogenation zones so as to produce a predetermined butane-1,4-diol:gamma-butyrolactone molar ration in the reaction product mixture; and (xii) recovering from the reaction product mixture (1) an alkyl alcohol fraction, (2) a butane-1,4-diol fraction, and (3) a gamma-butyrolactone fraction.
    • 共同生产丁烷-1,4-二醇和γ-丁内酯的方法,其包括:(a)通过与烷基醇反应酯化马来酸酐以形成相应的马来酸二烷基酯; (b)将得到的马来酸二烷基酯氢化,得到包含所述烷基醇,丁烷-1,4-二醇和γ-丁内酯的反应产物混合物; (c)从所述反应产物混合物中回收烷基醇; (d)将回收的烷基醇再循环到步骤(a)中; 和(e)从步骤(c)的反应产物混合物中回收丁烷-1,4-二醇和γ-丁内酯; 其中所述方法包括:(i)将马来酸酐和摩尔过量的烷基醇连续供应到保持在升高的温度下的单酯化区,从而形成相应的马来酸单烷基酯; (ii)将所得马来酸单烷基酯与摩尔过量的所述烷基醇连续供应到含有固体酯化催化剂装料的初级催化酯化区,并保持在酯化条件下,从而形成含中间体含酯混合物, 主要量的相应的马来酸二烷基酯和少量的所述马来酸单烷基酯; (iii)将包含所述马来酸单烷基酯的第一液体进料连续供给到含有固体酯化催化剂的二次酯化区; (iv)将包含所述烷基醇的第二进料流连续供应到所述仲酯化区; (v)将所述仲酯化区保持在足以在其中形成或保持含有所述烷基醇的蒸气流的高温下; (vi)在所述催化剂存在下使所述第二液体进料与所述蒸气流紧密接触; (vii)从所述次级酯化区回收除了烷基醇蒸气以外还含有蒸气形式的水的蒸气流出物流,所述水在所述仲酯化区中通过所述马来酸单烷基酯与所述烷基醇的酯化反应产生; (viii)从所述仲酯化区回收含有所述马来酸二烷基酯的液体产物; (ix)在含氢气体的气流中在所述二级酯化区中产生的马来酸二烷基酯蒸发; (x)将所得的含马来酸二烷基酯的物流通过串联连接的多个氢化区,每个含有固体酯化催化剂的电荷,并分别保持在酯氢化条件下; (xi)控制多个氢化区中的每一个中的反应条件,以便在反应产物混合物中产生预定的丁烷-1,4-二醇:γ-丁内酯摩尔比; 和(xii)从反应产物混合物(1)中回收烷基醇馏分,(2)丁烷-1,4-二醇馏分和(3)γ-丁内酯馏分。