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    • 2. 发明授权
    • Process for producing aldehydes by hydroformylation of olefins
    • 通过烯烃加氢甲酰化生产醛的方法
    • US6107524A
    • 2000-08-22
    • US101692
    • 1998-07-15
    • Rocco PacielloHeinz-Josef KneuperBernhard GeisslerMichael Roper
    • Rocco PacielloHeinz-Josef KneuperBernhard GeisslerMichael Roper
    • B01J31/22B01J31/16B01J31/18B01J31/40C07B61/00C07C27/22C07C29/16C07C31/125C07C45/50C07C45/80C07C47/02
    • C07C45/80B01J31/1815B01J31/4046C07C29/16C07C45/50B01J2231/321B01J2531/822B01J31/1658Y02P20/584
    • 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 from 50 to 1000 bar and at a temperature of from 50.degree. to 180.degree. C. using a rhodium catalyst that is dissolved in a homogeneous reaction medium and by extraction of the rhodium catalyst, in whicha) the hydroformylation is carried out in the presence of a rhodium complex, which exhibits, as ligand, a polydentate, organic nitrogen compound that is free from phosphorus and capable of forming complexes with Group VIII metals, which additionally contains at least one tertiary nitrogen radical that is capable of being protonized by a weak acid,b) the effluent of the hydroformylation stage is subjected to extraction with an aqueous solution of a distillable acid optionally following separation or partial separation of aldehydes and alcohols,(c) the aqueous acid extract is subjected to thermal treatment in the presence of an organic solvent or solvent mixture, which is inert under the hydroformylation conditions, with distillation of the aqueous acid, by means of which treatment the complex is deprotonized and transferred to the organic phase, and(d) the organic phase containing the catalyst complex is recycled to the hydroformylation stage.
    • PCT No.PCT / EP97 / 00372 Sec。 371日期:1998年7月15日 102(e)1998年7月15日PCT PCT 1997年1月28日PCT公布。 公开号WO97 / 28113 日期:1997年8月7日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,该方法包括加氢甲酰化阶段,其中烯烃在50至1000巴的压力和温度下加氢甲酰化 使用溶解在均匀的反应介质中并通过萃取铑催化剂的铑催化剂,其中a)在铑配合物的存在下进行加氢甲酰化,其表现出作为 配体,多齿,有机氮化合物,其不含磷并能够与VIII族金属形成络合物,其另外含有至少一个能够被弱酸质子化的叔氮基团,b)加氢甲酰化的流出物 任选在醛和醇的分离或部分分离后,用可蒸馏的酸的水溶液萃取阶段,(c )酸性水提取物在有机溶剂或溶剂混合物存在下进行热处理,所述有机溶剂或溶剂混合物在加氢甲酰化条件下是惰性的,同时蒸馏酸水溶液,通过该处理将络合物去质子化并转移到有机溶剂 相,和(d)含有催化剂络合物的有机相再循环到加氢甲酰化阶段。
    • 5. 发明授权
    • Preparation of aldehydes
    • 醛的制备
    • US5696297A
    • 1997-12-09
    • US510540
    • 1995-08-02
    • Heinz-Josef KneuperRocco PacielloMichael Roper
    • Heinz-Josef KneuperRocco PacielloMichael Roper
    • C07C45/50C07C45/80
    • C07C45/50C07C45/80
    • Aldehydes or aldehydes and alcohols are prepared by hydroformylation of olefins of more than 3 carbon atoms by a process comprising the stage of hydroformylation by means of a rhodium catalyst homogeneously dissolved in the reaction medium, the separation of the rhodium catalyst from the discharge from the hydroformylation reaction and the recycling of the rhodium separated from the hydroformylation discharge to the hydroformylation stage, wherein the rhodium catalyst is extracted from the hydroformylation discharge into the aqueous phase by means of an aqueous solution of a water-soluble, phosphorus-containing complexing agent selected from the group consisting of the mono- or polysulfonated mono- and oligophosphines and/or from the group consisting of the mono- or polycarboxylated mono- or oligophosphines or the mono- or polysulfonated oligophosphites and the aldehyde or the aldehyde and the alcohol are isolated from the extracted hydroformylation discharge, the aqueous rhodium-containing extract is fed to a precarbonylation stage and is subjected to a precarbonylation in the precarbonylation stage in the presence of an essentially water-insoluble, organic liquid and in the presence of carbon monoxide or of a carbon monoxide-containing gas mixture.
    • 醛或醛和醇通过包括通过均匀溶解在反应介质中的铑催化剂的加氢甲酰化阶段的方法加氢甲酰化大于3个碳原子的烯烃来制备,铑催化剂与加氢甲酰化的分离 反应和从加氢甲酰化放电分离出的铑的再循环到加氢甲酰化阶段,其中通过水溶性含磷络合剂的水溶液将铑催化剂从加氢甲酰化排放物中提取到水相中,所述水溶性含磷络合剂选自 由单或多羧基单 - 和寡膦组成的组和/或由单羧酸或多羧基单 - 或寡膦或单磺酸或多磺酸的低聚亚磷酸酯和醛或醛和醇组成的组分离自 提取加氢甲酰化放电,含水铑 将入料提取物进料至预羰化阶段,并在基本上不溶于水的有机液体和一氧化碳或含一氧化碳的气体混合物存在下,在预羰化阶段进行预羰基化。
    • 6. 发明授权
    • Preparation of aldehydes
    • 醛的制备
    • US5387719A
    • 1995-02-07
    • US120427
    • 1993-09-14
    • Heinz-Josef KneuperMichael RoeperRocco Paciello
    • Heinz-Josef KneuperMichael RoeperRocco Paciello
    • C07B61/00C07C45/50C07C47/02C07C45/00C07C45/78
    • B01J31/20B01J31/181B01J31/4046C07C45/50B01J2231/321B01J2531/822B01J2540/32B01J31/2234Y02P20/584
    • A process for the preparation of aldehydes by hydroformylation of olefins having more than 7 carbon atoms, comprising hydroformylation by means of a rhodium catalyst dissolved homogeneously in the reaction medium, removal of the rhodium catalyst from the hydroformylation reaction product, and recycling of the rhodium separated off from the hydroformylation product into the hydroformylation step, in which the rhodium catalyst is extracted from the hydroformylation product into the aqueous phase by means of an aqueous solution of a nitrogen-containing complexing agent from the group comprising of sulfonated pyridines, sulfonated quinolines, substituted or unsubstituted, sulfonated or sulfonated substituent-carrying 2,2'-bipyridines, 1,10-phenanthrolines, 2,2'-biquinolines, 2,2',6',2"-terpyridines and porphines, and/or from the group comprising of carboxylated pyridines, carboxylated quinolines, substituted or unsubstituted, carboxylated or carboxylated substituent-carrying 2,2'-bipyridines, 1,10-phenanthrolines, 2,2'-biquinolines, 2,2',6',2"-terpyridines and porphines, and the aqueous, rhodium-containing extract is recycled into the hydroformylation step.
    • 一种通过使具有多于7个碳原子的烯烃的加氢甲酰化制备醛的方法,包括通过均匀地溶解在反应介质中的铑催化剂进行加氢甲酰化,从加氢甲酰化反应产物中除去铑催化剂,以及回收分离的铑 从加氢甲酰化产物进入加氢甲酰化步骤,其中通过含有磺化吡啶,磺化喹啉,取代的含氮络合剂的水溶液将铑催化剂从加氢甲酰化产物中提取到水相中 或未取代的磺化或磺化取代基的2,2'-联吡啶,1,10-菲咯啉,2,2'-二喹啉,2,2',6',2“ - 三联吡啶和卟吩,和/或 羧基化吡啶类,羧基化喹啉,取代或未取代的羧基化或羧基取代基的2,2'-二吡啶基 nes,1,10-菲咯啉,2,2'-二喹啉,2,2',6',2“ - 三联吡啶和卟吩,并将含水铑的提取物再循环到加氢甲酰化步骤中。
    • 7. 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。