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1.发明授权
公开(公告)号：US4496768A
公开(公告)日：1985-01-29
申请号：US501859
申请日：1983-06-07
IPC分类号： B01J31/00 , B01J31/20 , B01J31/22 , C07B61/00 , C07C45/00 , C07C45/50 , C07C45/82 , C07C47/02 , C07C67/00 , C07F15/00
CPC分类号： B01J31/185 , B01J31/20 , C07C45/50 , C07C45/82 , C07F15/008 , B01J2231/321 , B01J2531/822
摘要： A continuous process for the production an aldehyde by hydroformylation of an optionally substituted alpha-olefin comprises:providing a hydroformylation zone containing a charge of a liquid reaction medium having dissolved therein a complex rhodium hydroformylation catalyst comprising rhodium in complex combination with carbon monoxide and with a cyclic phosphite having a bridgehead phosphorus atom linked to three oxygen atoms at least two of which form together with the bridgehead phosphorus atom part of a ring;supplying said alpha-olefin to the hydroformylation zone;maintaining temperature and pressure conditions in the hydroformylation zone conducive to hydroformylation of the alpha-olefin;supplying make-up hydrogen and carbon monoxide to the hydroformylation zone; andrecovering from the liquid hydroformylation medium a hydroformylation product comprising at least one aldehyde.
摘要翻译： 用于通过任选取代的α-烯烃的羰基化生产醛的连续方法包括：提供含有液体反应介质的加氢甲酰化区，该液体反应介质溶解有复合铑加氢甲酰化催化剂，其包含与一氧化碳复合组合的铑 环状亚磷酸酯，其具有连接至三个氧原子的桥头磷原子，其中至少两个与桥环磷原子部分一起形成; 将所述α-烯烃供应到加氢甲酰化区; 维持加氢甲酰化区中有利于α-烯烃加氢甲酰化的温度和压力条件; 向加氢甲酰化区提供补充氢和一氧化碳; 并从液体加氢甲酰化介质中回收含有至少一种醛的加氢甲酰化产物。
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公开(公告)号：US4482749A
公开(公告)日：1984-11-13
申请号：US501928
申请日：1983-06-07
IPC分类号： B01J31/00 , B01J31/20 , B01J31/22 , C07B61/00 , C07C45/00 , C07C45/50 , C07C45/82 , C07C47/02 , C07C67/00 , C07F15/00
CPC分类号： B01J31/185 , B01J31/20 , C07C45/50 , C07C45/82 , C07F15/008 , B01J2231/321 , B01J2531/822
摘要： A process for the production of a non-linear aldehyde by hydroformylation of an optionally substituted internal olefin comprises:providing a hydroformylation zone containing a charge of a liquid reaction medium having dissolved therein a complex rhodium hydroformylation catalyst comprising rhodium in complex combination with carbon monoxide and with a cyclic phosphite having a bridgehead phosphorus atom linked to three oxygen atoms at least two of which form together with the bridgehead phosphorus atom part of a ring;supplying said internal olefin to the hydroformylation zone;maintaining temperature and pressure conditions in the hydroformylation zone conducive to hydroformylation of the internal olefin;supplying make-up hydrogen and carbon monoxide to the hydroformylation zone; andrecovering from the liquid hydroformylation medium a hydroformylation product comprising at least one non-linear aldehyde.
摘要翻译： 通过任选取代的内烯烃的加氢甲酰化生产非线性醛的方法包括：提供含有其中溶解有液体反应介质的液体反应介质的加氢甲酰化区，该复合铑加氢甲酰化催化剂包含与一氧化碳复合组合的铑和 具有连接至三个氧原子的桥头磷原子的环状亚磷酸酯，其中至少两个与桥环磷原子部分形成环; 将所述内烯烃供应到加氢甲酰化区; 维持加氢甲酰化区中有利于内烯烃加氢甲酰化的温度和压力条件; 向加氢甲酰化区提供补充氢和一氧化碳; 并从液体加氢甲酰化介质中回收含有至少一种非直链醛的加氢甲酰化产物。
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公开(公告)号：US4496769A
公开(公告)日：1985-01-29
申请号：US501920
申请日：1983-06-07
IPC分类号： B01J31/00 , B01J31/20 , C07B61/00 , C07C45/00 , C07C45/50 , C07C45/82 , C07C67/00 , C07F15/00
CPC分类号： B01J31/185 , B01J31/20 , C07C45/50 , C07C45/82 , C07F15/008 , B01J2231/321 , B01J2531/822
摘要： A process for the production of an aldehyde by hydroformylation of an olefin comprises:providing a hydroformylation zone containing a charge of a liquid reaction medium having dissolved therein a complex rhodium hydroformylation catalyst comprising rhodium in complex combination with carbon monoxide and with an organic phosphite ligand of the general formula:(RO).sub.3 P (I) in which each R represents an optionally substituted hydrocarbyl radical;supplying said olefin to the hydroformylation zone;maintaining temperature and pressure conditions in the hydroformylation zone conducive to hydroformylation of the olefin;supplying make-up hydrogen and carbon monoxide to the hydroformylation zone;recovering from the liquid hydroformylation medium a hydroformylation product comprising at least one aldehyde; andsupplying make-up phosphite ligand to the hydroformylation zone at a rate sufficient to maintain a predetermined level of free phosphite ligand in the hydroformylation medium.
摘要翻译： 通过烯烃的加氢甲酰化生产醛的方法包括：提供含有液体反应介质装料的加氢甲酰化区，该液体反应介质溶解有复合铑加氢甲酰基化催化剂，其包含与一氧化碳复合组合的铑和与一氧化碳的有机亚磷酸酯配体 通式（RO）3P（I）其中每个R代表任选取代的烃基; 将所述烯烃供应到加氢甲酰化区; 维持加氢甲酰化区中有利于烯烃加氢甲酰化的温度和压力条件; 向加氢甲酰化区提供补充氢和一氧化碳; 从液体加氢甲酰化介质中回收含有至少一种醛的加氢甲酰化产物; 并以足以在加氢甲酰化介质中保持预定水平的游离亚磷酸酯配体的速率将补充亚磷酸酯配体供应到加氢甲酰化区。
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4.发明授权Continuous process for the production of aldehydes by hydroformylation of olefins 失效通过烯烃加氢甲酰化生产醛的连续方法
公开(公告)号：US4567306A
公开(公告)日：1986-01-28
申请号：US680834
申请日：1984-12-12
IPC分类号： B01J31/00 , B01J31/18 , C07B61/00 , C07C45/00 , C07C45/50 , C07C47/02 , C07C67/00 , C07F9/6574
CPC分类号： C07F9/65748 , C07C45/50
摘要： A continuous hydroformylation process for the production of an aldehyde by hydroformylation of an olefin comprises:providing a hydroformylation zone containing a charge of a liquid reaction medium having dissolved therein (a) a complex rhodium hydroformylation catalyst comprising rhodium in complex combination with carbon monoxide and with a cyclic phosphite having a phosphorus atom linked to three oxygen atoms at least two of which form together with the phosphorus atom part of a ring and (b) a ligand stabilizing amount of a tertiary amine;supplying said olefin to the hydroformylation zone;maintaining temperature and pressure conditions in the hydroformylation zone conducive to hydroformylation of the olefin;supplying make-up hydrogen and carbon monoxide to the hydroformylation zone; andrecovering from the liquid hydroformylation medium a hydroformylation product comprising at least one aldehyde.
摘要翻译： 用于通过烯烃的加氢甲酰化生产醛的连续加氢甲酰化方法包括：提供含有溶解在其中的液体反应介质的加料的加氢甲酰化区（a）复合铑加氢甲酰化催化剂，其包含与一氧化碳复合组合的铑， 具有与三个氧原子连接的磷原子的环状亚磷酸酯，其中至少两个与环的磷原子部分一起形成，（b）配体稳定量的叔胺; 将所述烯烃供应到加氢甲酰化区; 维持加氢甲酰化区中有利于烯烃加氢甲酰化的温度和压力条件; 向加氢甲酰化区提供补充氢和一氧化碳; 并从液体加氢甲酰化介质中回收含有至少一种醛的加氢甲酰化产物。
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公开(公告)号：US5434313A
公开(公告)日：1995-07-18
申请号：US313298
申请日：1994-10-06
IPC分类号： B01J23/04 , B01J27/232 , C07B61/00 , C07C45/66 , C07C45/72 , C07C45/74 , C07C45/81 , C07C45/82 , C07C47/19 , C07C47/21 , C07C47/22
摘要： An aldolisation-dehydration process is disclosed for converting an aldehyde, e.g. n-valeraldehyde, to a substituted acrolein, e.g. propyl butyl acrolein (2-propylhept-2-enal). Aldolisation and dehydration are effected in a stirred tank reactor (16; 111) using an alkali catalyst, such as sodium hydroxide. A reaction product stream (23; 113) containing both organic and aqueous phases is distilled (in column 25; 123) to yield a heterogeneous azeotrope containing water and aldehyde. On condensation and phase separation the lower water layer (34; 150) can be discharged from the plant without the need for neutralisation. From the bottom of the distillation zone a mixture (36;157) of substituted acrolein and alkali catalyst solution is obtained. The substituted acrolein is recovered as product (45;173), while the catalyst solution (47;175) is recycled to the aldolisation reactor. Part (49; 181) of the catalyst solution is purged to control the level of Cannizzaro reaction products.
摘要翻译： PCT No.PCT / GB93 / 00729 Sec。 371日期：1994年10月6日 102（e）日期1994年10月6日PCT提交1993年4月7日PCT公布。 公开号WO93 / 20034 日期为1993年10月14日。公开了醛脱水脱水方法，用于转化醛，例如 正戊醛，取代的丙烯醛，例如 丙基丁基丙烯醛（2-丙基庚-2-烯醛）。 使用碱催化剂如氢氧化钠在搅拌釜反应器（16; 111）中进行醛化和脱水。 蒸馏含有有机相和水相的反应产物流（23; 113）（在第25列;第123列），得到含有水和醛的非均相共沸物。 在冷凝和相分离时，下水层（34; 150）可以从设备中排出而不需要中和。 从蒸馏区的底部获得取代的丙烯醛和碱催化剂溶液的混合物（36; 157）。 将取代的丙烯醛作为产物（45; 173）回收，同时催化剂溶液（47; 175）再循环到醛醇化反应器中。 将催化剂溶液的部分（49; 181）吹扫以控制Cannizzaro反应产物的水平。
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公开(公告)号：US5426207A
公开(公告)日：1995-06-20
申请号：US142125
申请日：1993-10-28
CPC分类号： C07C68/06 , Y02P20/582
摘要： A diaryl carbonate is produced by transesterification of a dialkyl carbonate, such as dimethyl carbonate, with an aromatic hydroxy compound, such as phenol, in three successive reaction zones. A transesterification catalyst, such as a titanate ester or ester mixture is used in each zone. Conditions are selected to maximize formation of alkyl aryl carbonate in the first and second reaction zones, while conversion to diaryl carbonate is favored in the third reaction zone. The vaporous mixture from the first two reaction zones is a mixture containing alkyl alcohol, dialkyl carbonate, alkyl aryl carbonate and aromatic hydroxy compound. This mixture is separated in an alkyl alcohol recovery zone by distillation in the distillation columns to produce useful recycle streams. The second of these distillation columns can be operated at a lower pressure than the first, thus enabling the heat of vaporization of this mixture to be used as the source of heat for the reboiler of the second distillation column of the alkyl alcohol recovery zone.
摘要翻译： 碳酸二芳基酯通过碳酸二烷基酯如碳酸二甲酯与芳族羟基化合物如苯酚在三个连续的反应区中进行酯交换来制备。 在每个区域中使用酯交换催化剂，例如钛酸酯或酯混合物。 选择条件以最大限度地在第一和第二反应区中形成碳酸烷基芳基酯，同时在第三反应区中转化为碳酸二芳基酯是有利的。 来自前两个反应区的气态混合物是含有烷基醇，碳酸二烷基酯，碳酸烷基芳基酯和芳族羟基化合物的混合物。 在蒸馏塔中通过蒸馏在烷基醇回收区中分离该混合物以产生有用的再循环流。 这些蒸馏塔中的第二个可以在比第一蒸馏塔低的压力下操作，从而使得该混合物的蒸发热能用作烷基醇回收区的第二蒸馏塔的再沸器的热源。
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公开(公告)号：US5252198A
公开(公告)日：1993-10-12
申请号：US781172
申请日：1991-12-11
CPC分类号： C10G45/16 , B01J8/22 , C10G65/04 , C10G2400/14
摘要： A hydrodesulfurization process is provided for continuously effecting hydrodesulfurization of a liquid sulfur-containing hydrocarbon feedstock which comprises: (a) providing a hydrodesulfurization zone maintained under hydrodesulfurization conditions and comprising a column reactor having a plurality of reaction trays therein mounted one above another, each tray defining a respective reaction stage adapted to hold a predetermined liquid volume and a charge of a sulfided solid hydrodesulfurization catalyst therein, liquid downcomer means associated with each reaction tray adapted to allow liquid to pass down the column reactor from that tray but to retain solid catalyst thereon, and gas upcomer means associated with each reaction tray adapted to allow gas to enter that tray from below and to agitate the mixture of liquid and catalyst on that tray; (b) supplying liquid sulfur-containing hydrocarbon feedstock to the uppermost one of said plurality of reaction trays; (c) supplying hydrogen-containing gas below the lowermost one of said plurality of reaction trays; (d) allowing liquid to pass downward through the column reactor from tray to tray; (e) allowing hydrogen-containing gas to pass upward through the column reactor from tray to tray; (f) recovering from the uppermost one of said plurality of reaction trays and off-gas containing hydrogen sulfide produced by hydrodesulfurization; and (g) recovering from the lowermost one of said plurality of reaction trays a liquid hydrocarbon product of reduced sulfur content.
摘要翻译： PCT No.PCT / GB90 / 00717 Sec。 371日期1991年12月11日 102（e）日期1991年12月11日PCT提交1990年5月9日PCT公布。 出版物WO90 / 13612 PCT 日本1990年11月15日提供加氢脱硫方法，用于连续地进行含液硫烃原料的加氢脱硫，该方法包括：（a）提供在加氢脱硫条件下保持的加氢脱硫区，并且包括在其中具有多个反应塔的塔式反应器 每个托盘限定适于保持预定液体体积的相应反应阶段和其中的硫化固体加氢脱硫催化剂的电荷的每个托盘，与每个反应塔板相关联的液体降液装置，其适于允许液体从塔式反应器中通过 托盘，但是在其上保持固体催化剂，以及与每个反应塔相关联的气体升降装置，其适于允许气体从下方进入该塔盘并搅动该托盘上的液体和催化剂的混合物; （b）将液体含硫烃原料供应到所述多个反应塔盘中的最上面的一个; （c）在所述多个反应塔板中的最下面的一个反应塔板之下提供含氢气体; （d）允许液体从塔盘向下通过塔式反应器; （e）允许含氢气体通过塔式反应器从塔盘向托盘通过; （f）从所述多个反应塔板中的最上面一个回收和含有由加氢脱硫产生的硫化氢的废气; 和（g）从所述多个反应塔中的最下面的一个反应塔中回收具有降低的硫含量的液体烃产物。
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公开(公告)号：US4287127A
公开(公告)日：1981-09-01
申请号：US139568
申请日：1980-04-11
IPC分类号： C07C43/15 , C07C43/162 , C07C45/49 , C07D307/08
CPC分类号： C07D307/08 , C07C43/15 , C07C43/162 , C07C45/49
摘要： Tetrahydrofuran is produced by converting allyl alcohol to an allyl t-alkyl or -cycloalkyl ether of the general formula: ##STR1## wherein R.sub.1 and R.sub.2 each, independently of the other, represent a C.sub.1 to C.sub.4 alkyl radical, and R.sub.3 and R.sub.4 each, independently of the other, represent a hydrogen atom or a C.sub.1 to C.sub.3 alkyl radical, or wherein R.sub.1 represents a C.sub.1 to C.sub.4 alkyl radical, R.sub.2 and R.sub.3 together with the carbon atoms to which they are attached form a 5-membered or 6-membered cycloaliphatic ring, and R.sub.4 represents a hydrogen atom or a C.sub.1 to C.sub.3 alkyl radical, followed by reacting resulting compound of formula (III) under hydroformylation conditions with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst to form a corresponding aldehyde-ether of the general formula: ##STR2## reducing resulting aldehyde-ether of the general formula (I) a corresponding hydroxy-ether of the general formula: ##STR3## and cleaving resulting hydroxy-ether of the general formula (II) under dehydrating conditions to produce tetrahydrofuran. Typically R.sub.1 and R.sub.2 each represent a methyl group while R.sub.3 and R.sub.4 each represent a hydrogen atom. The alkene of the general formula: ##STR4## released upon cleavage of the hydroxy-ether of formula (II) can be recycled for reaction with further allyl alcohol to form a further quantity of the ether of the general formula (III).
摘要翻译： 四氢呋喃是通过将烯丙醇转化为通式为（III）的烯丙基t-烷基或 - 环烷基醚制备的：其中R 1和R 2各自独立地表示C 1至C 4烷基，R 3和 R 4各自独立地表示氢原子或C 1至C 3烷基，或其中R 1表示C 1至C 4烷基，R 2和R 3与它们所连接的碳原子一起形成5元或 6元环脂族环，R4代表氢原子或C1-C3烷基，然后在加氢甲酰化催化剂存在下，在加氢甲酰化条件下使所得式（III）化合物与一氧化碳和氢气反应形成相应的醛 （I）将通式（I）的所得醛 - 醚还原成相应的通式为：（II）的羟基醚，并将所得羟基醚除去，得到通式 式（II） 在脱水条件下生产四氢呋喃。 通常R 1和R 2各自表示甲基，而R 3和R 4各自表示氢原子。 可以将通式（II）的羟基醚裂解后释放的通式为：（IV）的烯烃再循环进一步与另外的烯丙醇反应以形成另外的通式（III）的醚， 。
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公开(公告)号：US5292428A
公开(公告)日：1994-03-08
申请号：US781173
申请日：1991-12-11
CPC分类号： C10G45/72 , C10G49/007 , C10G65/04 , C10G2400/14
摘要： Liquid sulphur-containing hydrocarbon feedstock is passed through two or more hydrodesulfurization zones and connected in a series each containing a packed bed of solid sulfurized catalyst. The liquid is passed from the first zone to the next until the final zone. Make up hydrogen is supplied to a hydrodesulfurization zone (i) other than the first hydrodesulfurization zone; hydrogen-containing gas is recovered from each hydrodesulfurization zone. The first hydrodesulfurization zone is supplied with hydrogen-containing gas recovered from a subsequent hydrodesulfurization zone. Hydrogen-containing gas recovered from the first hydrodesulfurization zone is purged. Liquid material recovered from the first hydrodesulfurization zone is recycled to the inlet of the hydrosulfurization zone so as to provide diluent for admixture with liquid feedstock. Any other hydrodesulfurization zone other than the first hydrodesulfurization zone and other than the hydrodesulfurization zone of step (i) is supplied with hydrogen-containing gas recovered from another hydrodesulfurization zone. The sulfur content of the hydrogen-containing gas and of the liquid hydrocarbon feedstock supplied to the first hydrodesulfurization zone is monitored and, if necessary, sulfur-containing material selected from hydrogen sulfide and active sulfur-containing materials is supplied to the first hydrodesulfurization zone so as to maintain the catalyst charge thereof in sulfided form.
摘要翻译： PCT No.PCT / GB90 / 00718 Sec。 371日期1991年12月11日 102（e）日期1991年12月11日PCT提交1990年5月9日PCT公布。 出版物WO90 / 13617 日期为1990年11月15日。液体含硫烃原料通过两个或更多个加氢脱硫区并连续地连续地包含固体硫化催化剂的填充床。 液体从第一区域传递到下一个区域直到最终区域。 补充氢气供应到除第一加氢脱硫区之外的加氢脱硫区（i）; 从每个加氢脱硫区回收含氢气体。 向第一加氢脱硫区供应从后续加氢脱硫区回收的含氢气体。 从第一加氢脱硫区回收的含氢气体被清除。 从第一加氢脱硫区回收的液体材料再循环到加氢硫化区的入口，以提供用于与液体原料混合的稀释剂。 除了第一加氢脱硫区以外，除了步骤（i）的加氢脱硫区之外的任何其他加氢脱硫区都被供给从另一个加氢脱硫区回收的含氢气体。 监测供应给第一加氢脱硫区的含氢气体和液态烃原料的硫含量，如果需要，选择硫化氢和含活性硫的材料的含硫材料供应到第一加氢脱硫区， 以使其催化剂装料保持硫化形式。
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公开(公告)号：US5093535A
公开(公告)日：1992-03-03
申请号：US476453
申请日：1990-06-04
申请人： George E. Harrison , Alan J. Dennis
发明人： George E. Harrison , Alan J. Dennis
IPC分类号： B01J8/02 , C07B31/00 , C07B61/00 , C07C5/10 , C07C13/18 , C07C29/14 , C07C29/141 , C07C31/125
CPC分类号： B01J8/02 , C07C29/141 , B01J2208/00061 , B01J2208/00141 , B01J2208/00212 , B01J2208/00256 , B01J2208/00495 , B01J2208/0053 , B01J2208/00539 , B01J2208/00548 , B01J2208/0061
摘要： A liquid phase catalytic hydrogenation process is described in which an organic feedstock, such as an aldehyde containing from 2 to about 20 carbon atoms, is contracted with hydrogen in the presence of a solid hydrogenation catalyst under hydrogenation conditions to produce a hydrogenation product, such as the corresponding alcohol containing from 2 to about 20 carbon atoms, which process comprises passing a feed solution of the organic feedstock in an inert diluent therefor downwardly in co-current with a hydrogen-containing gas through a hydrogenation zone containing a bed of a particulate hydrogenation catalyst whose particles substantially all lie in the range of from about 1.5 mm to about 5 mm, maintaining the bed of catalyst particles under temperature and pressure conditions conducive to hydrogenation, recovering from a bottom part of the bed a liquid phase containing the hydrogenation product, controlling the rate of supply of the feed solution to the bed so as to maintain a superficial liquid velocity of the liquid down the bed in the range of from about 1.5 cm/sec to about 5 cm/sec, and controlling the rate of supply of the hydrogen-containing gas to the bed so as to maintain at the top surface of the bed of catalyst particles a flow of hydrogen-containing gas containing from 1.00 to about 1.15 times the stoichiometric quantity of hydrogen theoretically necessary to convert the organic feedstock completely to the hydrogenation product.
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