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公开(公告)号：US5387719A
公开(公告)日：1995-02-07
申请号：US120427
申请日：1993-09-14
CPC分类号： B01J31/20 , B01J31/181 , B01J31/4046 , C07C45/50 , B01J2231/321 , B01J2531/822 , B01J2540/32 , B01J31/2234 , Y02P20/584
摘要： 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.
摘要翻译： 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。
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公开(公告)号：US6107524A
公开(公告)日：2000-08-22
申请号：US101692
申请日：1998-07-15
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。
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公开(公告)号：US5689010A
公开(公告)日：1997-11-18
申请号：US638592
申请日：1996-04-29
IPC分类号： B01J31/22 , C07B61/00 , C07C45/50 , C07C45/62 , C07C45/73 , C07C45/74 , C07C47/02 , C07C47/21 , C07C45/49
摘要： Aldehydes with a higher number of carbon atoms and high selection are prepared by reacting olefins, in particular from petrochemical refinery products, by a hydroformylation with aldol condensation using a mixed catalyst of rhodium-carbonyl-phosphines and Mannich catalyst.
摘要翻译： 通过使用铑 - 羰基膦和Mannich催化剂的混合催化剂通过使醛醇缩合的加氢甲酰化反应，使烯烃，特别是石油化学品炼油产物反应，制备具有较高碳原子数和高选择性的醛。
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4.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。
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公开(公告)号：US5919987A
公开(公告)日：1999-07-06
申请号：US716216
申请日：1996-09-13
申请人： Heinz-Josef Kneuper , Maik Aron , Frank-Michael Korgitzsch , Michael Nilles , Wolfgang Harder , Michael Roper , Rocco Paciello
发明人： Heinz-Josef Kneuper , Maik Aron , Frank-Michael Korgitzsch , Michael Nilles , Wolfgang Harder , Michael Roper , Rocco Paciello
IPC分类号： B01J23/46 , B01J31/40 , C07B61/00 , C07C27/22 , C07C29/141 , C07C29/16 , C07C31/02 , C07C45/50 , C07C45/80 , C07C47/02 , C07C51/235 , C07C209/00 , C07C45/00
CPC分类号： B01J31/20 , B01J31/4046 , C07C209/00 , C07C29/141 , C07C29/16 , C07C45/50 , C07C45/80 , C07C51/235 , B01J2231/321 , B01J23/464 , B01J2531/822 , B01J31/181 , B01J31/1815 , B01J31/1825 , B01J31/183 , Y02P20/584
摘要： An industrial preparation of aldehydes and/or alcohols from olefins of more than 3 carbon atoms by a catalytic hydroformylation of the olefin reactant at a pressure of from 50 to 1000 bar and a temperature of from 50 to 180.degree. C. in the presence of an uncomplexed rhodium catalyst homogeneously dissolved in the reaction medium. The catalytic activity of the rhodium is maintained, first by extracting it from the initially discharged reaction mixture by means of an aqueous solution of a nitrogen-containing complexing agent such as sulfonated or carboxylated pyridines, quinolines or the like. In a recycle of the complexed rhodium to be reused in the hydroformylation reaction, the aqueous rhodium-containing extract is fed to a precarbonylation stage where it subjected to a required precarbonylation in the presence of an essentially water-insoluble organic liquid and in the presence of carbon monoxide, synthesis gas or another gas mixture containing carbon monoxide at from 50 to 1000 bar and from 50 to 180.degree. C. The mixture discharged from this precarbonylation stage is then separated into an organic phase containing the main part of the rhodium and an aqueous phase containing the complexing agent. The resulting rhodium-containing organic phase with the regenerated catalyst is then fed into the hydroformylation stage to complete its recycle.
摘要翻译： PCT No.PCT / EP95 / 00825 Sec。 371日期1996年9月13日 102（e）日期1996年9月13日PCT 1995年3月6日PCT公布。 WO95 / 25080 PCT公开 日期1995年9月21日通过在50至1000巴的压力和50至180℃的温度下通过烯烃反应物的催化加氢甲酰化来工业制备大于3个碳原子的烯烃的醛和/或醇。 在均匀溶解在反应介质中的未络合的铑催化剂存在下进行。 保持铑的催化活性，首先通过含氮络合剂如磺化或羧化吡啶，喹啉等的水溶液从最初排出的反应混合物中提取铑的催化活性。 在加氢甲酰化反应中重复使用的复合铑的再循环中，含水铑萃取物进料到预羰化阶段，其中在基本上不溶于水的有机液体存在下进行所需的预羰基化， 一氧化碳，合成气或含有一氧化碳的另一种气体混合物，从50至1000巴和50至180℃。然后将从该预羰化阶段排出的混合物分离成含有主要部分铑的有机相， 相含有络合剂。 然后将所得到的含再生催化剂的含铑有机相进料到加氢甲酰化阶段以完成其再循环。
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公开(公告)号：US5717126A
公开(公告)日：1998-02-10
申请号：US505220
申请日：1995-08-07
IPC分类号： B01J31/28 , C07B61/00 , C07C45/50 , C07C47/02 , C07F9/6571 , C07F9/6574 , C07F15/00 , C07C45/49
CPC分类号： B01J31/066 , B01J31/1683 , B01J31/185 , B01J31/1865 , C07C45/50 , C07F15/008 , C07F9/6571 , C07F9/65719 , C07F9/65746 , B01J2531/821 , B01J2531/822
摘要： Phosphorus-containing calixarenes of the general formula I ##STR1## and a process for their preparation are described. Additionally, a process for the preparation of aldehydes by the hydroformylation of C.sub.3 -C.sub.20 -olefins by means of rhodium or ruthenium carbonyl complexes, in which the phosphorus-containing calixarenes of the formula I are used as ligands, is described.
摘要翻译： PCT No.PCT / EP94 / 01999 Sec。 371日期：1995年8月7日 102（e）日期1995年8月7日PCT提交1994年6月20日PCT公布。 第WO95 / 00525号公报 日期1995年1月5日描述了通式I的含磷的杯芳烃I及其制备方法。 另外，描述了通过使用式I的含磷杯芳烃用作配体的通过铑或钌羰基络合物通过C 3 -C 20烯烃的加氢甲酰化制备醛的方法。
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公开(公告)号：US5696297A
公开(公告)日：1997-12-09
申请号：US510540
申请日：1995-08-02
摘要： 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.
摘要翻译： 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。
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公开(公告)号：US5349097A
公开(公告)日：1994-09-20
申请号：US99236
申请日：1993-07-29
CPC分类号： C07C29/56
摘要： A process for the catalytic isomerization of secondary .alpha.-alkenols of formula I ##STR1## in which R.sup.1 is a C.sub.1 -C.sub.20 alkyl group or a C.sub.2 -C.sub.2 alkenyl group and in which R.sup.2 stands for hydrogen, a halogen atom, a C.sub.1 -C.sub.10 alkoxy group, a carbonyl group, or a C.sub.1 -C.sub.20 alkyl group and in which R.sup.1 and R.sup.2 can be joined together to complete a five-membered or six-membered carbocyclic ring, to primary .alpha.-alkenols of formula II ##STR2## or for the isomerization of primary .alpha.-alkenols of formula II to secondary .alpha.-alkenols of formula I, wherein the isomerization is carried out in the presence of organotrioxorhenium(VII) compounds of formula III ##STR3## in which R.sup.3 is a C.sub.1 -C.sub.10 alkyl group, a cyclopentadienyl group substituted by from one to five C.sub.1 -C.sub.4 alkyl groups, an unsubstituted cyclopentadienyl group, a C.sub.6 -C.sub.10 aryl group, or a C.sub.7 -C.sub.11 aralkyl group, or wherein the isomerization is carried out in the presence of organotrioxorhenium(VII) compounds of formula III attached to a polymeric support.
摘要翻译： 一种式Ⅰ的仲α-烯醇的催化异构化方法，其中R1是C1-C20烷基或C2-C2链烯基，其中R2代表氢，卤素原子， C 1 -C 10烷氧基，羰基或C 1 -C 20烷基，并且其中R 1和R 2可以连接在一起以完成五元或六元碳环，与式II的α-α-烯醇 （II）化合物或式II的仲α-烯醇的异构化转化为式I的仲α-烯醇，其中异构化在式III的有机三氧化铼（VII）化合物（III）的存在下进行，其中 其中R 3为C 1 -C 10烷基，被1至5个C 1 -C 4烷基取代的环戊二烯基，未取代的环戊二烯基，C 6 -C 10芳基或C 7 -C 11芳烷基，或其中异构化为 在连接到a的式III的有机三氧化钌（VII）化合物的存在下进行 聚合物支持。
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9.发明授权Process for preparing nitric acid with a concentration in the range from 50 to 77.8% by weight 有权制备浓度为50-77.8重量％浓度的硝酸的方法公开(公告)号：US08765009B2
公开(公告)日：2014-07-01
申请号：US12601534
申请日：2008-07-08
IPC分类号： C09K3/00
CPC分类号： C01B21/40 , C01B21/262
摘要： A process for preparing nitric acid by: catalytically oxidizing ammonia, to obtain a gas mixture containing NO and O2; cooling and condensing the gas mixture, thereby further oxidizing NO with O2, to obtain a gas stream containing NO2/N2O4 and an aqueous solution containing nitric acid; and countercurrently absorbing the NO2/N2O4 from the gas stream in an absorber with process water (H2O), to obtain nitric acid and an NOx-containing absorber offgas, wherein the water content of the nitric acid is regulated to a concentration in the range from 50 to 77.8% by weight and the NOx content of the absorber offgas to a concentration in the range from 20 to 500 ppm, by continuously measuring the water content of the process air supplied to the catalytic gas phase oxidation and, as a function of this, adjusting the amount of process water (Q-H2O) fed to the absorber.
摘要翻译： 一种通过以下方式制备硝酸的方法：催化氧化氨，得到含NO和O2的气体混合物; 冷却并冷凝气体混合物，从而进一步用O 2氧化NO，得到含有NO 2 / N 2 O 4的气流和含有硝酸的水溶液; 并用工艺用水（H 2 O）从吸收器中的气流中逆流吸收NO 2 / N 2 O 4，得到硝酸和含NO x的吸收剂废气，其中将硝酸的含水量调节至 50至77.8重量％，并且通过连续测量供应到催化气相氧化的工艺空气的水含量，吸收器的NOx含量废气至浓度在20至500ppm的范围内，并且作为其功能 ，调节供给到吸收器的工艺用水（Q-H 2 O）的量。
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公开(公告)号：US06770783B1
公开(公告)日：2004-08-03
申请号：US10070864
申请日：2002-03-12
申请人： Ralph Busch , Heinz-Josef Kneuper , Theodor Weber , Winfried Müller , Armin Stamm , Jochem Henkelmann
发明人： Ralph Busch , Heinz-Josef Kneuper , Theodor Weber , Winfried Müller , Armin Stamm , Jochem Henkelmann
IPC分类号： C07C5158
摘要： The invention relates to a method for producing acid chlorides by converting carboxylic acids with carbon oxychlorides or thionyl chloride in the presence of a catalyst adduct of an N,N-disubstituted formamide of general formula (I) and carbon oxychloride or thionyl chloride. In the formula, R1 and R2, independently from one another, mean C1- to C4-alkyl or R1 and R2 together mean a C4- or C5-alkylene chain. According to the inventive method, hydrogen chloride is added during and/or after the conversion.
摘要翻译： 本发明涉及在通式（I）的N，N-二取代甲酰胺与碳酰氯或亚硫酰氯的催化剂加合物存在下，用碳氧氯化物或亚硫酰氯转化羧酸制备酰氯的方法。 在该式中，R 1和R 2彼此独立地表示C 1至C 4 - 烷基或R 1和R 2一起表示C 4 - 或C 5-亚烷基链。 根据本发明的方法，在转化期间和/或之后加入氯化氢。
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