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    • 6. 发明授权
    • Method for producing hexanediol
    • 己二醇的制备方法
    • US06727395B1
    • 2004-04-27
    • US10018338
    • 2001-12-19
    • Frank SteinThomas KrugThomas NöbelHarald Rust
    • Frank SteinThomas KrugThomas NöbelHarald Rust
    • C07C2700
    • C07C29/149C07C31/20
    • A process for preparing 1,6-hexanediol from a carboxylic acid mixture comprising adipic acid, 6-hydroxycaproic acid and small amounts of 1,4-cyclohexanediols which is obtained as by-product in the oxidation of cyclohexane to cyclohexanone/cyclohexanol after water extraction of the reaction mixture followed by extraction with aqueous sodium hydroxide solution, by esterification of the acids and hydrogenation comprises a) liberating the carboxylic acids from the alkaline extract by addition of a mineral acid, b) fractionating the organic phase comprising carboxylic acids to give a distillate comprising the low molecular weight monocarboxylic acids and a residue comprising adipic acid and 6-hydroxycaproic acid, c) reacting the monocarboxylic an dicarboxylic acids present in the aqueous dicarboxylic acid mixture with a low molecular weight alcohol to give the corresponding carboxylic esters, d) freeing the esterification mixture obtained of excess alcohol and low boilers in a first distillation step, e) fractionating the bottom product in a second distillation step to give an ester fraction essentially free of 1,4-cyclohexanediols and a fraction comprising at least the major part of the 1,4-cyclohexanediols, f) catalytically hydrogenating the ester fraction which is essentially free of 1,4-cyclohexanediols and g) isolating 1,6-hexanediol from the hydrogenation product in a manner known per se in a final distillation step.
    • 从包含己二酸,6-羟基己酸和少量1,4-环己二醇的羧酸混合物制备1,6-己二醇的方法,其在水提取后在环己烷氧化成环己酮/环己醇时作为副产物获得 的反应混合物,然后用氢氧化钠水溶液萃取,通过酸的酯化和氢化反应,包括a)通过加入无机酸从碱性提取物中释放出羧酸,b)将包含羧酸的有机相分馏得到馏出物 包括低分子量单羧酸和包含己二酸和6-羟基己酸的残基,c)使一元羧酸与二羧酸混合物中存在的二羧酸与低分子量醇反应,得到相应的羧酸酯,d)释放 在第一馏出物中获得过量酒精和低锅炉的酯化混合物 e步骤,e)在第二蒸馏步骤中分馏底部产物,得到基本上不含1,4-环己烷二醇的酯馏分和至少包含大部分1,4-环己烷二醇的馏分,f)催化氢化酯 基本上不含1,4-环己烷二醇的馏分,和g)在最终蒸馏步骤中以本身已知的方式从氢化产物中分离出1,6-己二醇。
    • 9. 发明授权
    • Purification of esters of tetrahydro-pyran-4-carboxylic acid
    • 四氢 - 吡喃-4-羧酸酯的纯化
    • US5414097A
    • 1995-05-09
    • US185179
    • 1994-01-24
    • Rolf FischerNorbert GoetzThomas KuekenhoehnerHarald RustWerner Schnurr
    • Rolf FischerNorbert GoetzThomas KuekenhoehnerHarald RustWerner Schnurr
    • C07D309/08
    • C07D309/08
    • A process for purifying esters of tetrahydropyran-4-carboxylic acid of the formula I ##STR1## where R.sup.1 to R.sup.3 are each C.sub.1 -C.sub.4 -alkyl, and R.sup.2 and R.sup.3 are each additionally hydrogen, from mixtures produced in the reaction of butyrolactones of the formula II ##STR2## where R.sup.2 and R.sup.3 have the abovementioned meanings, and R.sup.4 is hydrogen, alkyl of 1-6 carbons or acyl of the formula --CO--R.sup.2, with alcohols of the formula R.sup.1 OH in the presence of oxide catalysts, by distillation, which entailsa) removing overhead, in a first column with 5-25 theoretical plates with a distillate pressure of 700-1100 mbar and a distillate temperature of 50.degree.-80.degree. C., an alcohol and up to 10% of the water,b) transferring the bottom product from the first column into a second column with 18-40 theoretical plates, into which a water entrainer is metered between plates 15 and 30, and is circulated, and which operates with a distillate pressure of 35-350 mbar and a distillate temperature of 18.degree.-70.degree. C., with the esters of tetrahydropyran-4-carboxylic acid being removed between plates 8 and 18 at 90.degree.-150.degree. C., and, where appropriate,c) feeding the bottom product from the second column into a third column with 5-25 theoretical plates, and returning the overhead products at a distillate pressure of 1-100 mbar and a distillate temperature of 90.degree.-140.degree. C. to the synthesis of the esters of tetrahydropyran-4-carboxylic acid.
    • 用于纯化式I的四氢吡喃-4-羧酸的酯的方法,其中R 1至R 3各自为C 1 -C 4 - 烷基,R 2和R 3各自为氢, 其中R 2和R 3具有上述含义,R 4是氢,1-6个碳的烷基或式-CO-R 2的酰基,其中式R 1 OH的醇在存在下 氧化物催化剂,通过蒸馏,其需要a)在具有5-25理论塔板的第一塔中,馏出物压力为700-1100毫巴,馏出物温度为50-80℃,醇和升高 至10%的水,b)将底部产物从第一塔转移到具有18-40理论塔板的第二塔中,其中在15和30之间计量水夹带剂,并循环,并且其以 馏出液压力为35-350毫巴,馏出物温度为18-70℃, 其中四氢吡喃-4-羧酸的酯在90℃-150℃下在板8和18之间除去,并且在适当的情况下,c)将底部产物从第二塔进料到具有5-25理论值的第三塔 将塔顶馏出物返回到馏出物压力为1-100毫巴,馏出液温度为90-140℃,以合成四氢吡喃-4-羧酸酯。