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11.发明授权Preparation of amines from olefins over crystalline oxides based on aluminum phosphates and having faujasite structure 失效基于磷酸铝制成结晶氧化物并具有八面沸石结构的烯烃中的胺
公开(公告)号：US5786510A
公开(公告)日：1998-07-28
申请号：US784772
申请日：1997-01-16
申请人： Karsten Eller , Rudolf Kummer , Peter Stops
发明人： Karsten Eller , Rudolf Kummer , Peter Stops
IPC分类号： B01J29/83 , C07B61/00 , C07C209/60 , C07C211/07 , C07C211/30 , C07C209/02
CPC分类号： C07C209/60 , Y02P20/582
摘要： A process for the preparation of amines of the general formula I ##STR1## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 denote hydrogen, C.sub.1 -C.sub.20 alkyl, C.sub.2 -C.sub.20 alkynyl, C.sub.3 -C.sub.20 cycloalkyl, C.sub.4 -C.sub.20 alkylcycloalkyl, C.sub.4 -C.sub.20 cycloalkylalkyl, aryl, C.sub.7 -C.sub.20 alkylaryl or C.sub.7 -C.sub.20 aralkyl, R.sup.1 and R.sup.2 together denote a saturated or unsaturated C.sub.3 -C.sub.9 alkylene dichain and R.sup.3 or R.sup.5 denotes C.sub.21 -C.sub.200 alkyl, C.sub.21 -C.sub.200 alkenyl or they together form a C.sub.2 -C.sub.12 alkylene dichain, by the reaction of olefins of the general formula II ##STR2## in which R.sup.3, R.sup.4, R.sup.5 and R.sup.6 have the aforementioned meanings, with ammonia or primary or secondary amines of the general formula III ##STR3## in which R.sup.1 and R.sup.2 have the aforementioned meanings, at temperatures ranging from 200.degree. to 350.degree. C. and pressures of from 100 to 300 bar in the presence of a heterogeneous catalyst, wherein the heterogeneous catalysts used are crystalline oxides based on aluminum phosphates and having faujasite structure.
摘要翻译： 制备通式I的胺的方法（Ⅰ）其中R1，R2，R3，R4，R5和R6表示氢，C1-C20烷基，C2-C20炔基，C3-C20环烷基， C 4 -C 20烷基环烷基，C 4 -C 20环烷基烷基，芳基，C 7 -C 20烷基芳基或C 7 -C 20芳烷基，R 1和R 2一起表示饱和或不饱和的C 3 -C 9亚烷基二酮，R 3或R 5表示C 21 -C 200烷基，C 21 -C 20烯基 或者它们一起形成C 2 -C 12亚烷基二酮，通过其中R3，R4，R5和R6具有上述含义的通式II（II）的烯烃与一般的氨或伯或仲胺反应， 式III（III）其中R1和R2具有上述含义，在200〜350℃的温度和100〜300巴的压力下，在多相催化剂存在下使用，其中使用的多相催化剂 是基于磷酸铝并具有八面沸石结构的结晶氧化物。
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公开(公告)号：US5773660A
公开(公告)日：1998-06-30
申请号：US784548
申请日：1997-01-21
申请人： Karsten Eller , Rudolf Kummer , Eugen Gehrer
发明人： Karsten Eller , Rudolf Kummer , Eugen Gehrer
IPC分类号： B01J29/08 , C07B43/04 , C07B61/00 , C07C209/60 , C07C211/03 , C07C211/07 , C07C209/02
CPC分类号： C07C209/60
摘要： A process for preparing amines of the formula I ##STR1## where R.sup.1,R.sup.2,R.sup.3,R.sup.4,R.sup.5 and R.sup.6 are each hydrogen, C.sub.1 -C.sub.20 -alkyl, C.sub.2 -C.sub.20 -alkenyl, C.sub.2 -C.sub.20 -alkynyl, C.sub.3 -C.sub.20 -cycloalkyl, C.sub.4 -C.sub.20 -alkylcycloalkyl, C.sub.4 -C.sub.20 -cycloalkylalkyl, aryl, C.sub.7 -C.sub.20 -alkylaryl or C.sub.7 -C.sub.20 -aralkyl, R.sup.1 and R.sup.2 are together a saturated or unsaturated C.sub.3 -C.sub.9 -alkylene dichain, and R.sup.3 or R.sup.5 is C.sub.21 -C.sub.200 -alkyl or C.sub.21 -C.sub.200 -alkenyl or together they are a C.sub.2 -C.sub.12 -alkylene dichain, by reacting olefins of the formula II ##STR2## where R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are each as defined above, with ammonia or primary or secondary amines of the formula III ##STR3## where R.sup.1 and R.sup.2 are each as defined above, at temperatures from 200.degree. to 350.degree. C. and pressures from 100 to 300 bar in the presence of a heterogeneous catalyst using a heterogeneous catalyst comprising hexagonal faujasite.
摘要翻译： 制备式I的胺的方法其中R 1，R 2，R 3，R 4，R 5和R 6各自为氢，C 1 -C 20 - 烷基，C 2 -C 20 - 烯基，C 2 -C 20 - 炔基，C 3 -C 20 - 环烷基，C 4 -C 20 - 烷基环烷基，C 4 -C 20 - 环烷基烷基，芳基，C 7 -C 20 - 烷基芳基或C 7 -C 20 - 芳烷基，R 1和R 2一起是饱和或不饱和的C 3 -C 9 - 亚烷基二烯基，R3或 R5是C21-C200-烷基或C21-C200-烯基，或者它们一起是C2-C12-亚烷基二烯，通过使式II的烯烃（II）反应，其中R3，R4，R5和R6各自定义 与式III（III）的氨或伯胺或仲胺，其中R 1和R 2各自如上定义，在200-350℃的温度和100-300巴的压力下，在存在 使用包含六边形八面沸石的多相催化剂的多相催化剂。
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13.发明授权
公开(公告)号：US4454358A
公开(公告)日：1984-06-12
申请号：US337683
申请日：1982-01-07
IPC分类号： C07C29/132 , B01J31/00 , B01J31/20 , C07B61/00 , C07C27/00 , C07C27/04 , C07C29/149 , C07C29/80 , C07C29/92 , C07C31/08 , C07C67/00 , B01D3/00
CPC分类号： C07C29/80 , C07C29/149 , C07C67/08 , C07C67/36 , C07C67/54 , Y02P20/52 , Y10S203/06 , Y10S203/20
摘要： Ethanol is produced continuously via the carbonylation of methanol, by(a) carbonylating methanol, in a reactor R, in the presence of a carbonyl complex of a metal of group VIII of the periodic table and of a halogen compound,(b) separating, in a distillation column D1, the reactor discharge, into a top fraction comprising methyl acetate, methanol, dimethyl ether and an organohalogen compound, and into a bottom fraction comprising water, small quantities of acetic acid and the catalyst, if the latter is not in a fixed bed, the residence time being so adjusted that the greater part of the acetic acid reacts with the methanol present to give methyl acetate,(c) separating the top fraction from D1, in a distillation column D2, into a top fraction comprising small quantities of methyl acetate, methanol, dimethyl ether and the organo-halogen compound, and a bottom fraction comprising methyl acetate and methanol, and recycling the top fraction to reactor R,(d) distilling off, via the top of distillation column D3, the greater part of the water from the bottom fraction from D1and removing this water from circulation, and recycling to reactor R the bottom fraction consisting of small quantities of water, acetic acid and the catalyst,(e) using hydrogen to hydrogenate, in the hydrogenation reactor H, the bottom fraction from D2, in a conventional manner, to give a mixture of methanol and ethanol, and(f) separating the mixture into ethanol and methanol in a distillation column D4, and recycling the methanol to reactor R.
摘要翻译： 通过（a）在反应器R中羰基化甲醇，在周期表第VIII族金属的羰基络合物和卤素化合物的存在下，连续生产乙醇，（b）分离， 在蒸馏塔D1中，反应器排出成为包含乙酸甲酯，甲醇，二甲醚和有机卤素化合物的顶级馏分，并进入包含水，少量乙酸和催化剂的底部馏分，如果后者不在 固定床，停留时间如此调节，使得大部分乙酸与存在的甲醇反应得到乙酸甲酯，（c）将蒸馏塔D2中的顶馏分与D1分离成包含小分子的顶馏分 数量的乙酸甲酯，甲醇，二甲醚和有机卤素化合物，以及包含乙酸甲酯和甲醇的底部馏分，并将顶部馏分再循环到反应器R中，（d）通过顶部o蒸馏 f蒸馏塔D3，来自D1的底部馏分的大部分水从循环中除去，并且将反应器R再循环到由少量水，乙酸和催化剂组成的底部馏分，（e）使用氢气 以常规方式在氢化反应器H中将来自D2的塔底馏分氢化，得到甲醇和乙醇的混合物，和（f）将混合物在蒸馏塔D4中分离成乙醇和甲醇，并将甲醇再循环至 反应器
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14.发明授权
公开(公告)号：US4350572A
公开(公告)日：1982-09-21
申请号：US204637
申请日：1980-11-06
CPC分类号： C07C67/60
摘要： A process for purifying carboxylic acid esters which have been obtained by reacting olefinically unsaturated compounds with carbon monoxide and alkanols and which contain aldehydes or acetals, wherein the said esters are treated with a strongly acidic agent, with or without addition of water.
摘要翻译： 通过使烯属不饱和化合物与一氧化碳和链烷醇反应并且含有醛或缩醛而获得的羧酸酯的方法，其中所述酯用强酸性剂处理，或不加入水。
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公开(公告)号：US4305888A
公开(公告)日：1981-12-15
申请号：US813971
申请日：1977-07-08
IPC分类号： C07C55/02 , C07C51/00 , C07C55/10 , C07C55/12 , C07C55/14 , C07C55/16 , C07C55/18 , C07C55/20 , C07C55/21 , C07C67/00 , C07C209/00 , C07C211/09 , C07C87/14
摘要： A process for the manufacture of salts of alkanedicarboxylic acids of 4 to 12 carbon atoms and alkanediamines of 3 to 14 carbon atoms, comprising reacting esters of alkanols of 1 to 4 carbon atoms and alkanedicarboxylic acids of 4 to 12 carbon atoms with alkanediamines of 3 to 14 carbon atoms in stoichiometric amounts in the presence of water at an elevated temperature, with continuous removal of the alkanols formed, in which process the reaction is carried out, from the start, in the presence of the particular salt of alkanedicarboxylic acid and alkanediamine which is to be manufactured.
摘要翻译： 一种制备4至12个碳原子的链烷二羧酸盐和3至14个碳原子的烷二胺的方法，包括使1至4个碳原子的链烷醇与4至12个碳原子的烷基二羧酸酯与3个烷二胺反应 在高温存在下，在水存在下，化学计算量为14个碳原子，连续除去所形成的链烷醇，在该过程中进行反应，从一开始就在特定的烷基二羧酸和烷二胺盐存在下 将被制造。
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公开(公告)号：US4259520A
公开(公告)日：1981-03-31
申请号：US2329
申请日：1979-01-10
IPC分类号： C07C67/38
CPC分类号： C07C67/38
摘要： In a process for the preparation of butanedicarboxylic acid esters by(a) reacting butadiene or hydrocarbon mixtures containing butadiene with carbon monoxide and a C.sub.1 -C.sub.4 -alkanol in the presence of a tertiary nitrogen base and a cobalt carbonyl catalyst at from 80.degree. to 150.degree. C. under superatmospheric pressure,(b) removing the greater part of the tertiary nitrogen base together with any excess hydrocarbon and(c) reacting the resulting pentenoic acid ester, in the presence of the catalyst remaining in the reaction mixture, and in the presence of the remaining amount of tertiary nitrogen base, with carbon monoxide and a C.sub.1 - to C.sub.4 -alkanol at from 140.degree. to 200.degree. C. under superatmospheric pressure, to give the butanedicarboxylic acid ester, the improvement wherein the reaction mixture in stage c) is substantially free from dissolved butadiene or butadiene bonded to the catalyst.Butanedicarboxylic acid esters may be used for the preparation of polymers.
摘要翻译： 在（a）将叔丁基或含有丁二烯的烃混合物与一氧化碳和C 1 -C 4烷醇在叔氮碱和羰基钴催化剂存在下反应制备丁烷二羧酸酯的方法中， （b）将大部分叔氮碱与任何过量的烃一起除去，和（c）使所得戊烯酸酯在残留在反应混合物中的催化剂存在下反应，并在 在超大气压下，在140℃至200℃下存在剩余量的叔氮碱，一氧化碳和一种C 1 -C 4烷醇，得到丁烷二羧酸酯，其中阶段c中的反应混合物 ）基本上不含结合到催化剂上的溶解的丁二烯或丁二烯。 丁二羧酸酯可用于制备聚合物。
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公开(公告)号：US4258203A
公开(公告)日：1981-03-24
申请号：US58944
申请日：1979-07-19
CPC分类号： C07C67/38
摘要： Multistep process for the preparation of butanedicarboxylic acid by the hydrogenation of carbon monoxide under pressure in the presence of a cobalt carbonyl catalyst, the improvement of heating at a temperature of 250.degree. to 350.degree. C. under superatmospheric pressure the resulting aqueous solution of cobalt carbonyl hydride that has been extracted with butadiene or with mixtures thereof before using in a subsequent step of the multistep process.
摘要翻译： 通过在羰基钴催化剂存在下加压一氧化碳制备丁烷二羧酸的多步法，在超大气压下在250℃至350℃的温度下加热，得到羰基钴水溶液 氢化物，在多步骤的后续步骤中使用之前已用丁二烯或其混合物萃取。
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公开(公告)号：US4256909A
公开(公告)日：1981-03-17
申请号：US66552
申请日：1979-08-15
摘要： In a process for the preparation of dimethyl butanedicarboxylates, wherein(a) butadiene or a hydrocarbon mixture containing butadiene is reacted with carbon monoxide and methanol in the presence of a tertiary nitrogen base and a cobalt carbonyl catalyst at from 80.degree. to 150.degree. C. under superatmospheric pressure,(b) the greater part of the tertiary nitrogen base and any excess hydrocarbons are removed and(c) the methyl pentenoate thus obtained is reacted with carbon monoxide and methanol, in the presence of a cobalt carbonyl catalyst and the residual amount of tertiary nitrogen base, at from 140.degree. to 200.degree. C. under superatmospheric pressure, to give the dimethyl butanedicarboxylate, the improvement that the reaction mixture obtained in stage (a) after reaction of the butadiene is cooled until it separates into two phases, and a part-stream of from 20 to 80% by volume of the lower phase is recycled to stage (a).
摘要翻译： 在制备丁二酸二甲酯的方法中，其中（a）丁二烯或含有丁二烯的烃混合物在叔氮碱和羰基钴催化剂存在下在80-150℃下与一氧化碳和甲醇反应。 在超大气压下，（b）除去大部分叔氮碱和任何过量的烃，并且（c）由此获得的戊烯酸甲酯在羰基钴催化剂存在下与一氧化碳和甲醇反应，剩余量 的叔氮碱，在超大气压下，在140〜200℃下，得到丁二酸二甲酯，改善在丁二烯反应后阶段（a）中得到的反应混合物冷却至分离为两相， 并且将下层相的20〜80体积％的一部分流循环至（a）阶段。
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公开(公告)号：US4171451A
公开(公告)日：1979-10-16
申请号：US883216
申请日：1978-03-03
摘要： A process for the manufacture of butanedicarboxylic acid esters, wherein(a) an aqueous cobalt salt solution is treated, at from 50.degree. to 200.degree. C. and under a pressure of from 50 to 500 bars, 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 butadiene-hydrocarbon mixture, containing cobalt carbonyl hydride, cobalt carbonyl and butenyl-cobalt tricarbonyl is reacted with carbon monoxide and an excess of an alkanol of 1 to 4 carbon atoms in the presence of from 0.5 to 2 moles, per mole of butadiene, of a tertiary nitrogen base having a pK.sub.a of from 3 to 11, at from 80.degree. to 150.degree. C. under a pressure of from 300 to 2,000 bars, and(d) the resulting reaction mixture is freed from the tertiary nitrogen base contained therein, except for from 0.1 to 0.3 mole per mole of pentenoic acid ester, and from excess hydrocarbons, the pentenoic acid ester remaining in the reaction mixture is reacted with carbon monoxide and an excess of an alkanol of 1 to 4 carbon atoms at from 140.degree. to 200.degree. C. and under pressures of from 100 to 400 bars in the presence of the amounts of cobalt carbonyl and tertiary nitrogen base contained in the reaction mixture, and excess alkanol and free nitrogen base are then distilled off, and(e) the reaction mixture which remains, and which contains cobalt catalyst, the butanedicarboxylic acid ester and by-products is treated with an oxidizing agent in an aqueous acid medium and the mixture is separated into an organic phase, from which the butanedicarboxylic acid ester is isolated by distillation, and into an aqueous phase containing cobalt salts.Butanedicarboxylic acid esters may be used for the manufacture of adipic acid and of nylons.
摘要翻译： 一种制备丁烷二羧酸酯的方法，其中（A）在50至200℃和50至500巴的压力下处理苛性钴盐溶液，其中过量的一氧化碳和氢气在 （B）碳酸氢盐的结晶水溶液是用丁二烯或含有二丁烯和水相的烃混合物分离的，（C）丁二烯或二苯乙烯混合物 ，含有碳酸氢二乙酯，碳酸氢钾和二苯乙酮三溴化硼与一氧化碳反应，另有1至4个碳原子的碱金属在0.5至2摩尔浓度范围内反应，每次可以达到丁二烯，碱性氮 在300至2,000巴的压力下具有3至11，80至150℃的PKa，以及（D）结合反应混合物来自含有其的碱性氮碱，除F 或从0.1至0.3毫升的硝酸酯和超级碳氢化合物，反应混合物中的硝酸酯反应在一氧化碳和超过1至4个碳原子的碱性物质在140°至200°的条件下反应 在反应混合物中所含的羰基钴和叔氮碱的量存在下，在100-400巴的压力下，然后蒸出过量的链烷醇和游离氮碱，和（E）反应混合物 剩余的，其中含有钴催化剂，溴化苹果酸酯和副产物与氧化剂在酸性介质中进行处理，并且混合物分离成有机相，其中通过蒸馏分离所述溴化乙酸酯，和 进入含有钴酸盐的水相。
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公开(公告)号：US4071563A
公开(公告)日：1978-01-31
申请号：US669844
申请日：1976-03-24
申请人： Rudolf Kummer , Kurt Schwirten , Hans-Dieter Schindler, deceased , by Ute Lang nee Schindler, heir-at-law , by Rainer Schindler, heir-at-law
发明人： Rudolf Kummer , Kurt Schwirten , Hans-Dieter Schindler, deceased , by Ute Lang nee Schindler, heir-at-law , by Rainer Schindler, heir-at-law
CPC分类号： C07C45/512 , C07C45/49 , C07C45/515
摘要： Pent-4-en-1-al is manufactured by passing an acetaldehyde-acetal of the general formula ##STR1## where R is allyl or alkyl of 1 to 3 carbon atoms, in the gas phase and at from 350.degree. to 450.degree. C, over an active-surface catalyst.
摘要翻译： Pent-4-en-1-al是通过在气相和350至450℃下通过通式为“IMAGE”的乙醛缩醛，其中R为烯丙基或1至3个碳原子的烷基 ，在活性表面催化剂上。
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