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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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公开(公告)号：US4503275A
公开(公告)日：1985-03-05
申请号：US532821
申请日：1983-09-16
IPC分类号： B01J31/10 , C07B61/00 , C07C27/00 , C07C29/10 , C07C31/20 , C07C43/15 , C07C43/162 , C07C45/49 , C07C67/00 , C07C29/00
CPC分类号： C07C43/162 , C07C29/10 , C07C43/15 , C07C45/49
摘要： Butane-1,4-diol 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 (II) to form a corresponding hydroxy-ether of the general formula: ##STR3## and cleaving resulting hydroxy-ether of the general formula (II) to give butane-1,4-diol. 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： 丁烯-1,4-二醇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元脂环族环，R4代表氢原子或C1至C3烷基，然后在加氢甲酰化存在下，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 催化剂形成相应的通式为醛的醚：（I）还原所得通式（II）的醛 - 醚，形成相应的通式为（II）的羟基醚和 切割得到的羟基醚一般为 （II），得到丁烷-1,4-二醇。 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：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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公开(公告)号：US4383125A
公开(公告)日：1983-05-10
申请号：US139591
申请日：1980-04-11
IPC分类号： B01J31/00 , B01J31/24 , C07B61/00 , C07C43/15 , C07C43/188 , C07C45/00 , C07C45/49 , C07C45/50 , C07C47/198 , C07C67/00
CPC分类号： C07C47/198 , C07C43/15 , C07C43/188 , C07C45/49
摘要： Aldehyde ethers 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, and wherein Y represents --CH.sub.2 --CH.sub.2 --C.sub.2 or --CH.sub.2 --CH (CH.sub.3)--, are prepared by hydroformylation of a corresponding compound of formula: ##STR2## by reaction with hydrogen and carbon monoxide in the presence of a hydroformylation catalyst, e.g. a rhodium complex catalyst. Preferred compounds include 4-t-butoxybutyraldehyde and 3-t-butoxy-2-methylpropionaldehyde. The compounds are useful chemical intermediates in the production of, for example, butane-1,4-diol, butyrolactone and tetrahydrofuran.
摘要翻译： 通式为（I）的醛醚其中R 1和R 2各自独立地表示C 1〜C 4烷基，R 3和R 4各自独立地表示氢原子或C 1〜 C3烷基，或其中R1表示C1至C4烷基，R2和R3与它们所连接的碳原子一起形成5元或6元环脂环，R4表示氢原子或C1至 C 3烷基，其中Y代表-CH 2 -CH 2 -C 2或-CH 2 -CH（CH 3） - 是通过相应的式（IV）化合物的羰基化来制备的：通过与氢和一氧化碳在 存在加氢甲酰化催化剂，例如 铑配合物催化剂。 优选的化合物包括4-叔丁氧基丁醛和3-叔丁氧基-2-甲基丙醛。 该化合物是生产例如丁烷-1,4-二醇，丁内酯和四氢呋喃的有用的化学中间体。
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公开(公告)号：US5053551A
公开(公告)日：1991-10-01
申请号：US278437
申请日：1988-11-21
申请人： George E. Harrison , Alan J. Dennis
发明人： George E. Harrison , Alan J. Dennis
IPC分类号： B01J31/24 , C07B61/00 , C07C20060101 , C07C45/00 , C07C45/49 , C07C45/50 , C07C45/82 , C07C47/02 , C07C67/00
摘要： Continuous process for hydroformylation of olefins containing, typically, from 6 to 20 carbon atoms to produce the corresponding aldehydes. The rate of formation of high boiling aldehyde condensation products is minimized by use of a high boiling inert solvent whose boiling point, at the pressure prevailing in the product recovery zone, lies intermediate between that of the highest boiling aldehyde product produced in the hydroformylation reaction and that of the ligand, as well as by maintaining the concentration of product aldehyde at or below a predetermined minor amount. In this way the length of a production run can be significantly extended before it becomes necessary to shut down the plant due to accumulation of high boiling aldehyde condensation products.
摘要翻译： PCT No.PCT / GB87 / 00408 Sec。 371日期：1988年11月21日 102（e）日期1988年11月21日PCT Filted 1987年6月12日PCT Pub。 出版物WO88 / 00179 日期1988年1月14日。含有通常含有6至20个碳原子的烯烃加氢甲酰化的连续方法以产生相应的醛。 通过使用高沸点惰性溶剂使得高沸点醛缩合产物的形成速率最小化，其沸点在产物回收区中的压力处于加氢甲酰化反应中产生的最高沸点醛产物的沸点和 配体的浓度，以及通过将产品醛的浓度保持在或低于预定的微量。 以这种方式，生产运行的长度可以在由于高沸点醛缩合产物的积聚而需要关闭工厂之前显着延长。
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7.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：US4560226A
公开(公告)日：1985-12-24
申请号：US465866
申请日：1983-02-07
申请人： Alan J. Dennis
发明人： Alan J. Dennis
CPC分类号： H01R12/675 , H01R31/06 , H01R4/242
摘要： A subminiature multi-pin/socket connector member (10) comprising an elongate housing and at least two rows of contactor units (11) mounted in the housing, each contactor unit including a contactor portion (12) extending from a front face of the housing and a termination (13) extending from a rear face of the housing, the contactor units and terminations being, each collectively, arranged in staggered formation, wherein the pitch of the terminations differs from the pitch of the contactor units.Also a contactor unit (11) e.g. for a subminiature multi-pin/socket connector, the unit being formed of e.g. metal strip material and comprising a contactor portion (2) e.g. of pin or socket form, a termination (13) and a torsionally flexible bridge portion (15) interconnecting the contacting portion and the termination.
摘要翻译： PCT No.PCT / GB82 / 00191第 371日期1983年2月7日 一种超小型多针/插座连接器构件（10），包括细长壳体和安装在壳体中的东部两排接触器单元（11），其特征在于， 每个接触器单元包括从壳体的前表面延伸的接触器部分（12）和从壳体的后表面延伸的接头（13），接触器单元和端接件各自以交错的形式布置，其中 端子的间距与接触器单元的间距不同。 接触器单元（11） 对于超小型多针/插座连接器，该单元由例如， 金属条材料，并且包括接触器部分（2） 销或插座形式，端接件（13）和互连接触部分和端接件的扭转柔性桥接部分（15）。
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公开(公告)号：US4414420A
公开(公告)日：1983-11-08
申请号：US366166
申请日：1982-04-07
IPC分类号： B01J31/00 , B01J31/24 , C07B61/00 , C07C43/15 , C07C43/188 , C07C45/00 , C07C45/49 , C07C45/50 , C07C47/198 , C07C67/00
CPC分类号： C07C47/198 , C07C43/15 , C07C43/188 , C07C45/49
摘要： Aldehyde ethers 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, and wherein Y represents --CH.sub.2 --CH.sub.2 --CH.sub.2 or --CH.sub.2 --CH (CH.sub.3)--, are prepared by hydroformylation of a corresponding compound of formula. ##STR2## by reaction with hydrogen and carbon monoxide in the presence of a hydroformylation catalyst, e.g. a rhodium complex catalyst. Preferred compounds include 4-t-butoxybutyraldehyde and 3-t-butoxy-2-methylpropionaldehyde. The compounds are useful chemical intermediates in the production of, for example, butane-1,4-diol, butyrolactone and tetrahydrofuran.
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公开(公告)号：US4287370A
公开(公告)日：1981-09-01
申请号：US132292
申请日：1980-03-20
申请人： Norman Harris , Alan J. Dennis , Thomas F. Shevels
发明人： Norman Harris , Alan J. Dennis , Thomas F. Shevels
CPC分类号： C07C45/50
摘要： n-Valeraldehyde is produced by hydroformylation of butene-1 in the presence of one or more of cis- and trans-butene-2 and iso-butylene using a rhodium complex catalyst such as HRh(CO)PPh.sub.3).sub.3. Reaction conditions include use of at least about 100 moles of free triorganophosphine per gram atom of rhodium, a temperature of about 80.degree. C. to about 130.degree. C., a total pressure of not more than about 50 kg/cm.sup.2 absolute, a partial pressure of carbon monoxide of not more than about 1.5 kg/cm.sup.2 absolute, and a partial pressure of hydrogen of from about 1.0 to about 7.5 kg/cm.sup.2 absolute. An n-/iso-ratio of 20:1 and a conversion efficiency of butene-1 to n-valeraldehyde of over 85% are possible under these conditions with essentially no resin formation despite the presence of iso-butylene. The n-/iso-valeraldehyde mixture can be aldolized and reduced without intermediate purification to give a commercially acceptable C.sub.10 -plasticizer alcohol.
摘要翻译： 在使用铑络合物催化剂如HRh（CO）PPh 3）3的一种或多种顺式 - 和反式 - 丁烯-2和异丁烯的存在下，丁烯-1的加氢甲酰化产生正戊醛。 反应条件包括使用至少约100摩尔游离三有机膦/克原子铑，温度约80℃至约130℃，总压力不超过约50千克/厘米2绝对值，部分 一氧化碳压力绝对不超过约1.5kg / cm2，绝对压力为约1.0至约7.5kg / cm2的氢分压。 在这些条件下，即使存在异丁烯也基本上没有树脂形成，可以使20:1的n- /等比率和丁烯-1与正戊醛的转化效率在85％以上。 正 - 异戊醛混合物可以醛化和还原而不进行中间纯化，得到商业上可接受的C10增塑剂酒精。
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