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    Method for the production of aldehydes
    1.
    发明授权
    Method for the production of aldehydes 失效
    醛的生产方法

    公开(公告)号：US06310261B1

    公开(公告)日：2001-10-30

    申请号：US09582780

    申请日：2000-07-03

    申请人： Bernhard Geissler ,  Michael Röper ,  Edgar Zeller ,  Rocco Paciello ,  Jürgen Decker ,  Hartwig Voss ,  Norbert Mahr

    发明人： Bernhard Geissler ,  Michael Röper ,  Edgar Zeller ,  Rocco Paciello ,  Jürgen Decker ,  Hartwig Voss ,  Norbert Mahr

    IPC分类号： C07C4550

    CPC分类号： C08G73/0206 ,  B01J31/1658 ,  B01J31/1805 ,  B01J2231/321 ,  B01J2531/80 ,  B01J2531/822 ,  C07C45/50 ,  Y02P20/584 ,  C07C47/02

    摘要： The invention relates to a method for the production of aldehydes or aldehydes and alcohols by hydroformylation of olefins in the presence of a complexing catalyst homogeneously dissolved in a reaction mixture, containing a metal of Group VIIIa of the periodic table of the elements and a phosphorus-free, polydentate nitrogen compound suitable for complex formation as ligand at temperatures ranging from 50 to 100° C. and pressures from 20 to 1,000 bar and recirculating the catalyst complex in the hydroformylation reaction, wherein a) derivatized polyamines are used that are substantially non-water soluble and suitable for complex formation and have a mean molecular weight of more than 1,000 Dalton and at least 10 nitrogen atoms; b) the catalyst complex remaining in the bottom of the distillation column and the excess ligands obtained from the reaction mixture are recirculated totally or partially in the hydroformylation once the hydroformylation reaction and the separation or partial separation by distillation of the aldehydes and the alcohols has been completed; c) continues or at least batchwise evacuation of at least part of the high boiler from the bottom of the distillation of the reaction mixture is then carried out.

    摘要翻译： 本发明涉及通过在均匀溶解在含有元素周期表第Ⅷa族金属的反应混合物的络合催化剂存在下烯烃的加氢甲酰化生产醛或醛和醇的方法， 在50至100℃的温度和20至1,000巴的压力下适合于络合物形成配位体的多余的多齿氮化合物，并且在加氢甲酰基化反应中再循环催化剂配合物，其中a）使用基本上不相容的衍生的多胺， 水溶性且适合于络合物形成，并且具有大于1,000道尔顿和至少10个氮原子的平均分子量; b）一旦加氢甲酰化反应和通过蒸馏醛和醇的分离或部分分离已经被残留在蒸馏塔底部的催化剂络合物和从反应混合物中得到的过量配体在加氢甲酰化反应中被全部或部分再循环 完成 c）然后执行从反应混合物的蒸馏底部继续或至少间歇抽出高锅炉的至少一部分。

    Method for producing phosphabenzene compounds
    3.
    发明授权
    Method for producing phosphabenzene compounds 失效
    膦酸化合物的制备方法

    公开(公告)号：US06255532B1

    公开(公告)日：2001-07-03

    申请号：US09509672

    申请日：2000-03-30

    申请人： Rocco Paciello ,  Edgar Zeller ,  Bernhard Breit ,  Michael Röper

    发明人： Rocco Paciello ,  Edgar Zeller ,  Bernhard Breit ,  Michael Röper

    IPC分类号： C07F950

    CPC分类号： C07F9/6568 ,  B01J31/2419 ,  B01J31/2461 ,  B01J2231/321 ,  B01J2531/822 ,  B01J2531/845

    摘要： A process for the preparation of phosphabenzene compounds of the formulae I and II where R1 to R6, independently of one another, are hydrogen, COOM SO3M, NR3X, NR2, OR, COOR or SR, where M is hydrogen, NH4 or an alkali metal, X is an anion, R is hydrogen, C1-6-alkyl, or C1-12-alkyl, C6-12-aryl, C7-12-aralkyl or C3-6-heterocycloalkyl having 1 to 3 heteroatoms which may be substituted by the above radicals or linked to form fused rings, and —W— is a bridge comprising a covalent bond, an oxo group, a sulfur group, an amino group, a di-C1-6-alkylsilicon group or a C1-16-radial, which may be part of one or more linked cyclic or aromatic rings and may be interrupted by 1 to 3 heteroatoms, where the phosphabenzene ring o- or m-position not bonded to the bridge may carry one of the radicals R1 to R6, with the exception of bis-3,3′-(2,4,6-triphenyl-3-phosphabenzene)-1,1-biphenyl, by reacting corresponding pyrilium salts with PH3 in the presence of a catalytic amount of acid and in the presence or absence of a solvent or diluent, where the pyrilium salts are mixed with PH3 at above 0° C. and reacted at from 0° C. to 200° C. and at a pressure greater than 1 bar.

    摘要翻译： 制备式I和II的膦酸化合物的方法，其中R 1至R 6彼此独立地为氢，COOM SO 3 M，NR 3 X，NR 2，OR，COOR或SR，其中M为氢，NH 4或碱金属， X是阴离子，R是氢，C 1-6 - 烷基或C 1-12 - 烷基，C 6-12 - 芳基，C 7-12 - 芳烷基或具有1至3个杂原子的C 3-6 - 杂环烷基，其可以被 并且-W-是包含共价键，氧代基团，硫基团，氨基基团，二-C1-6烷基硅基团或C1-16-放射状核团的桥， 其可以是一个或多个连接的环状或芳香环的一部分，并且可以被1至3个杂原子中断，其中未键合到桥的膦酰基环或 - 位置可以携带基团R1至R6中的一个，其中 通过使相应的吡啶鎓盐与PH 3在催化量的酸的存在下反应，并在存在或不存在下，将双-3'' - （2,4,6-三苯基-3-苯基苯基） 没有溶剂或稀释剂，其中吡啶鎓盐在0℃下与PH3混合，并在0℃至200℃和大于1巴的压力下反应。

    Process for producing aldehydes by hydroformylation of olefins
    4.
    发明授权
    Process for producing aldehydes by hydroformylation of olefins 失效
    通过烯烃加氢甲酰化生产醛的方法

    公开(公告)号：US6107524A

    公开(公告)日：2000-08-22

    申请号：US101692

    申请日：1998-07-15

    申请人： Rocco Paciello ,  Heinz-Josef Kneuper ,  Bernhard Geissler ,  Michael Roper

    发明人： Rocco Paciello ,  Heinz-Josef Kneuper ,  Bernhard Geissler ,  Michael Roper

    IPC分类号： B01J31/22 ,  B01J31/16 ,  B01J31/18 ,  B01J31/40 ,  C07B61/00 ,  C07C27/22 ,  C07C29/16 ,  C07C31/125 ,  C07C45/50 ,  C07C45/80 ,  C07C47/02

    CPC分类号： C07C45/80 ,  B01J31/1815 ,  B01J31/4046 ,  C07C29/16 ,  C07C45/50 ,  B01J2231/321 ,  B01J2531/822 ,  B01J31/1658 ,  Y02P20/584

    摘要： 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.

    摘要翻译： 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。

    Phosphabenzene compounds and their use in hydroformylation
    9.
    发明授权
    Phosphabenzene compounds and their use in hydroformylation 失效
    膦酸化合物及其在加氢甲酰化中的应用

    公开(公告)号：US06509505B1

    公开(公告)日：2003-01-21

    申请号：US09936346

    申请日：2001-09-11

    申请人： Rocco Paciello ,  Thomas Mackewitz ,  Michael Röper ,  Bernhard Breit

    发明人： Rocco Paciello ,  Thomas Mackewitz ,  Michael Röper ,  Bernhard Breit

    IPC分类号： C07F950

    CPC分类号： B01J31/2419 ,  B01J31/2466 ,  B01J2531/80 ,  B01J2531/822 ,  C07C45/50 ,  C07D309/34 ,  C07F9/6568 ,  C07F15/008 ,  C07C47/02

    摘要： Phosphabenzene compounds of the formula (I) where the radicals R1 to R13 are, independently of one another, hydrogen, COOM, SO3M, NR3X, NR2, OR, COOR or SR (where M=hydrogen, NH4 or alkali metal, X=anion, R=hydrogen or C1-C6-alkyl), or C1-C12-alkyl, C6-C12-aryl, C7-C12-aralkyl, C7-C12-alkaryl or C3-C6-heteroaromatics, where the alkyl, aryl, alkaryl and aralkyl radicals may bear the abovementioned radicals as substituents and two or more of the radicals may be joined to form aliphatic or fused-on rings, where at least one of the radicals R4 and R8 and at least one of the radicals R9 and R13 is not hydrogen, can be used for preparing hydroformylation catalysts.

    摘要翻译： 其中基团R 1至R 13彼此独立地为氢，COOM，SO 3 M，NR 3 X，NR 2，OR，COOR或SR（其中M =氢，NH 4或碱金属，X =阴离子）的式（I） 或C 1 -C 12 - 烷基，C 6 -C 12 - 芳基，C 7 -C 12 - 芳烷基，C 7 -C 12烷芳基或C 3 -C 6 - 杂芳族化合物，其中烷基，芳基，烷芳基 并且芳烷基可以带有上述基团作为取代基，并且两个或更多个基团可以连接形成脂族或稠合环，其中基团R 4和R 8中的至少一个以及基团R 9和R 13中的至少一个是 不是氢，可用于制备加氢甲酰化催化剂。

    Method of preparing aldehydes by hydroformylation with a rhodium catalyst and recovery of the rhodium catalyst by extraction
    10.
    发明授权
    Method of preparing aldehydes by hydroformylation with a rhodium catalyst and recovery of the rhodium catalyst by extraction 失效
    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

    公开(公告)号：US06225507B1

    公开(公告)日：2001-05-01

    申请号：US09117662

    申请日：1998-08-04

    申请人： Bernhard Giessler ,  Heinz-Josef Kneuper ,  Michael Röper ,  Rocco Paciello ,  Knut Oppenländer ,  Wolfgang Günther

    发明人： Bernhard Giessler ,  Heinz-Josef Kneuper ,  Michael Röper ,  Rocco Paciello ,  Knut Oppenländer ,  Wolfgang Günther

    IPC分类号： C07C4550

    CPC分类号： B01J31/20 ,  B01J31/1658 ,  B01J31/4046 ,  B01J2231/321 ,  B01J2531/822 ,  C07C45/50 ,  C07F9/3817 ,  C08G73/0206 ,  Y02P20/584 ,  C07C47/02

    摘要： 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.

    摘要翻译： 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。