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    • 2. 发明授权
    • Production of mainly linear aldehydes
    • 生产主要是线性醛
    • US3929898A
    • 1975-12-30
    • US27693672
    • 1972-08-01
    • BASF AG
    • NIENBURG HANS-JUERGENKUMMER RUDOLFHOHENSCHUTZ HEINZSTROHMEYER MAXTAVS PETER
    • C07C67/333B01J23/00C07B61/00C07C45/00C07C45/50C07C67/00C07C45/08
    • C07C45/50C07C47/02
    • A process for the production of mainly linear aldehydes by hydroformylation of an olefinically unsaturated compound of from two to twenty carbon atoms with carbon monoxide and hydrogen at elevated temperature and superatmospheric pressure in the presence of a cobalt carbonyl complex prepared prior to the hydroformylation from an aqueous solution of a cobalt salt, wherein in a first stage an aqueous solution of a cobalt salt is treated with carbon monoxide and hydrogen at a temperature of from 50* to 200*C and at a pressure of from 100 to 400 atmospheres in the presence of activated carbon, a zeolite or a basic ion exchanger which has been loaded with cobalt carbonyl, the aqueous solution containing cobalt salt and cobalt carbonyl hydride thus obtained and the mixture of carbon monoxide and hydrogen, without releasing the pressure, are extracted at a temperature of 20* to 100*C and at a pressure of 100 to 400 atmospheres in a second stage with a saturated hydrocarbon or the olefinically unsaturated compound used for the hydroformylation (provided they are insoluble in water and liquid under the conditions used), water-insoluble oxo reaction product or hydrogenated oxo reaction product, the aqueous phase is separated and the organic phase containing the carbonyl complex thus obtained and the mixture of carbon monoxide and hydrogen are transferred to a third stage and, after supplying olefinically unsaturated compound (if this has not been used or has only partly been used for extraction in the abovementioned stage) hydroformylation is carried out at a temperature of from 70* to 170*C and a pressure of from 100 to 400 atmospheres. The products of the process are suitable for the production of detergent alcohols and plasticizers and for the production of carboxylic acids and amines.
    • 通过在二氧化碳和氢气的烯属不饱和化合物与一氧化碳和氢气在升高的温度和超大气压下,在羰基化羰基络合物存在下,在氢化甲酰化之前,从水溶液中加氢甲酰化制备主要线性醛的方法 钴盐溶液,其中在第一阶段中钴盐的水溶液用一氧化碳和氢气在50至200℃的温度和100至400大气压的压力下在有 活性炭,已经负载有羰基钴的沸石或碱性离子交换剂,由此获得的含有钴盐和羰基氢化钴的水溶液和一氧化碳和氢气的混合物而不释放压力,在 20〜100℃,在100〜400个大气压的压力下,在第二阶段用饱和烃或硫酸 用于加氢甲酰化的烯属不饱和化合物(只要它们在所用条件下不溶于水和液体),水不溶性氧代反应产物或氢化羰基反应产物,分离水相,并将含有羰基络合物的有机相如此得到 将一氧化碳和氢气的混合物转移到第三阶段,在提供烯属不饱和化合物(如果没有使用或仅在上述阶段中仅部分用于萃取)之后,加氢甲酰化在 70〜170℃,压力为100〜400个大气压。
    • 10. 发明专利
    • PREPARATION OF BUTANEDICARBOXYLIC ACID ESTERS
    • CA1126753A
    • 1982-06-29
    • CA332104
    • 1979-07-19
    • BASF AG
    • PLATZ ROLFKUMMER RUDOLFSCHNEIDER HEINZ-WALTER
    • B01J31/00C07B61/00C07C67/38C07C69/44C07C69/533
    • O.Z. 0050/033363 In a process for the preparation of butanedicarboxylic acid esters, whereina) an aqueous cobalt salt solution is treated, at from 50 to 200.degree.C and under a pressure of from 50 to 500 bar, with excess carbon monoxide and hydrogen in the presence of active charcoal laden with cobalt carbonyl,b) the resulting aqueous solution of cobalt carbonyl hydride is extracted with butadiene, or with a hydrocarbon mixture containing butadiene, and the aqueous phase is separated off,c) the butadiene, or the butadiene/hydrocarbon mixture, containing cobalt carbonyl hydride, cobalt carbonyl and butenyl-cobalt tricarbonyl, is reacted with carbon monoxide and a C1-C4-alkanol in excess in the presence of from 0.5 to 2 moles, per mole of butadiene, of a tertiary nitrogen base having a pKa of from 3 to 11, at from 80 to 150.degree.C and under a pressure of from 300 to 2,000 bar,d) the tertiary nitrogen base contained in the resulting reaction mixture is removed until its content reaches 0.1-0.3 mole per mole of pentenoic acid ester, excess hydrocarbons are also removed, the pentenoic acid ester remaining in the reaction mixture is reacted with carbon monoxide and a C1-C4-alkanol in excess at from 140 to 200.degree.C and under a pressure of from 100 to 400 bar in the presence of the amounts of cobalt carbonyl and tertiary nitrogen base present in the reaction mixture, and excess alkanol and free nitrogen base are then distilled off, ande) the reaction mixture which is left and which con O.Z. 0050/033363 tains a cobalt catalyst, butanedicarboxylic acid ester and by-products is treated with oxidizing agents in the presence of the aqueous acid solution which has been removed in stage b), and the mixture is separated into an organic phase, from which butanedicarboxylic acid ester is isolated by distillation, and an aqueous phase, containing cobalt salts, which is recycled to stage a), the improvement that the aqueous phase separated off in stage b) is heated at from 250 to 350.degree.C under superatmospheric pressure, before being used in stage e).