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    • 85. 发明授权
    • Method of preparing aldehydes by hydroformylation with a rhodium catalyst and recovery of the rhodium catalyst by extraction
    • 通过用铑催化剂加氢甲酰化制备醛的方法,并通过萃取回收铑催化剂
    • US06225507B1
    • 2001-05-01
    • US09117662
    • 1998-08-04
    • Bernhard GiesslerHeinz-Josef KneuperMichael RöperRocco PacielloKnut OppenländerWolfgang Günther
    • Bernhard GiesslerHeinz-Josef KneuperMichael RöperRocco PacielloKnut OppenländerWolfgang Günther
    • C07C4550
    • B01J31/20B01J31/1658B01J31/4046B01J2231/321B01J2531/822C07C45/50C07F9/3817C08G73/0206Y02P20/584C07C47/02
    • A process for the preparation of aldehydes or aldehydes and alcohols by hydroformylation of olefins containing more than 3 carbon atoms, comprising a hydroformylation stage, in which the olefin is hydroformylated under a pressure of form 50 to 1000 bar and at a temperature of from 50° to 180° C. by means of a rhodium catalyst dissolved in a homogenous reaction medium and a catalyst recovery stage comprising extraction of the rhodium catalyst with an aqueous solution of chelating agent, isolation of alcohols and/or aldehyde from the extracted hydroformylation product steam, precarbonylation of the aqueous rhodium-containing extract in the presence of carbon monoxide, synthesis gas as, or a gas mixture containing carbon monoxide under a pressure of from 50 to 1000 bar and at a temperature of from 50° to 180° C., separation of the effluent of the precarbonylation stage into an organic phase containing the major portion of the rhodium and an aqueous phase containing the chelating agent and recycling of the organic phase to the hydroformylation stage, where the rhodium catalyst is extracted from the effluent of the hydroformylation stage using an aqueous solution of a sulfonic acid group-free, water-soluble polymer capable of chelating rhodium.
    • 一种通过加氢甲酰化含有多于3个碳原子的烯烃制备醛或醛和醇的方法,包括加氢甲酰化阶段,其中烯烃在50至1000巴的压力和50℃的温度下加氢甲酰化 通过溶解在均匀的反应介质中的铑催化剂和催化剂回收阶段,包括用螯合剂的水溶液萃取铑催化剂,从提取的加氢甲酰化产物蒸汽中分离出醇和/或醛, 在50至1000巴的压力和50至180℃的温度下,在一氧化碳,合成气或含有一氧化碳的气体混合物存在下,含铑水溶液提取物的预羰基化,分离 的预羰化阶段的流出物进入含有主要部分铑的有机相和含有螯合剂的水相 并将有机相再循环到加氢甲酰化阶段,其中使用不含磺酸基团的能够螯合铑的水溶性聚合物的水溶液从加氢甲酰化阶段的流出物中提取铑催化剂。
    • 87. 发明授权
    • Process for preparing a rhodium complex solution and process for
producing an aldehyde
    • 制备铑配合物溶液的方法和制备醛的方法
    • US5936130A
    • 1999-08-10
    • US926481
    • 1997-09-10
    • Tomoyuki MoriMasaki TakaiTomohiko InoueKazuyuki Yokoyama
    • Tomoyuki MoriMasaki TakaiTomohiko InoueKazuyuki Yokoyama
    • C01G55/00B01J31/24B01J31/40C07C45/50C07C47/055
    • B01J31/1845B01J31/2404B01J31/4046B01J31/4053C07C45/50B01J2231/321B01J2531/822B01J31/0235B01J31/04B01J31/26Y02P20/584
    • A process for producing a rhodium complex solution, which comprises contacting an aqueous solution of a water-soluble rhodium compound and an organic solvent solution of a water-insoluble tertiary organic phosphorus compound, preferably in the presence of a C.sub.2-8 carboxylic acid, in a gas atmosphere containing carbon monoxide, followed by two phase separation, and recovering an organic solvent phase containing a rhodium-tertiary organic phosphorus compound complex. As the above aqueous solution of a rhodium compound, an aqueous solution having rhodium extracted into an aqueous phase from a waste catalyst liquid separated from a hydroformylation reaction step by oxidation treatment in the presence of a recovery accelerator such as a carboxylic acid, an amine, ammonia or an inorganic acid, is used, whereby recycling of rhodium represented by hydroformylation reaction/recovery of the catalyst/regeneration of the catalyst, is made possible, and a cumbersome step of preparing a complex catalyst from an inorganic salt or the like, or a step of preparing a soluble salt from a metal or oxide by combustion in water of the recovered catalyst, can be omitted.
    • 一种制备铑络合物溶液的方法,其包括使水溶性铑化合物的水溶液与水不溶性叔有机磷化合物的有机溶剂溶液,优选在C2-8羧酸存在下,在 含有一氧化碳的气体气氛,然后进行两相分离,并回收含有铑 - 叔有机磷化合物络合物的有机溶剂相。 作为上述铑化合物的水溶液,通过在回收促进剂如羧酸,胺等存在下,通过氧化处理,从加氢甲酰化反应步骤中分离出的废催化剂液体将含有铑的水溶液萃取到水相中, 氨或无机酸,从而可以通过加氢甲酰化反应/催化剂的回收/催化剂的再生来代替的铑的回收成为可能,并且从无机盐等制备复合催化剂的繁琐步骤,或 可以省略通过在回收的催化剂的水中燃烧而从金属或氧化物制备可溶性盐的步骤。
    • 90. 发明授权
    • Hydroformylation process
    • 加氢甲酰化过程
    • US5773666A
    • 1998-06-30
    • US836880
    • 1997-05-27
    • Toshihiro OmatsuJin TokuyasuMasahiro MuranakaTakashi Onishi
    • Toshihiro OmatsuJin TokuyasuMasahiro MuranakaTakashi Onishi
    • B01J31/24C07C45/49C07C45/50C07C45/80C07C45/82
    • B01J31/0247B01J31/0202B01J31/0204B01J31/0225B01J31/0267B01J31/0271B01J31/24B01J31/2404B01J31/4046B01J31/4053C07C45/49C07C45/50C07C45/80C07C45/82B01J2231/321B01J2531/822B01J2531/96B01J2540/32Y02P20/584
    • Described is a process for hydroformylation of an olefinic compound, which comprises, carrying out the reaction in the presence of: a) a rhodium compound, b) a tertiary organic phosphorus compound represented by the following formula (1): P(X.sub.1)(X.sub.2)(X.sub.3 --SO.sub.3 M) (1) wherein X.sub.1 and X.sub.2 each independently represents a monovalent hydrocarbon group having 1-15 carbon atoms and X.sub.3 represents a divalent hydrocarbon group having 1-15 carbon atoms and M represents an alkali metal, and c) a polar organic compound; separating the rhodium compound, the tertiary organic phosphorus compound represented by the formula (1) and the polar organic compound from the resulting reaction mixture by extraction with water; subjecting the extracted water layer to removal of water and addition of at least one acidic substance selected from sulfonic acids to prepare a concentrate containing the rhodium compound, the tertiary organic phosphorus compound represented by the formula (1) and the polar organic compound; and recycling the resulting concentrate to a reactor for reuse.
    • PCT No.PCT / JP96 / 02771 Sec。 371日期:1997年5月27日 102(e)日期1997年5月27日PCT提交1996年9月26日PCT公布。 公开号WO97 / 11931 日期1997年4月3日描述了烯烃化合物的加氢甲酰基化方法,其包括在以下存在下进行反应:a)铑化合物,b)由下式(1)表示的叔有机磷化合物: P(X1)(X2)(X3-SO3M)(1)其中X1和X2各自独立地表示具有1-15个碳原子的一价烃基,X3表示具有1-15个碳原子的二价烃基,M表示碱 金属,和c)极性有机化合物; 通过用水萃取从得到的反应混合物中分离铑化合物,由式(1)表示的叔有机磷化合物和极性有机化合物; 对提取出的水层进行脱水,加入至少一种选自磺酸的酸性物质,制备含有铑化合物的浓缩物,式(1)表示的叔有机磷化合物和极性有机化合物; 并将所得浓缩物再循环到反应器中以便再利用。