公开(公告)号：WO2004078696A1

公开(公告)日：2004-09-16

申请号：PCT/JP2004/002214

申请日：2004-02-25

申请人： SHOWA DENKO K.K. ,  SAIHATA, Meiko ,  UCHIDA, Hiroshi

发明人： SAIHATA, Meiko ,  UCHIDA, Hiroshi

IPC分类号： C07C67/055

CPC分类号： C07C67/055 ,  C07C29/095 ,  C12C11/02 ,  C07C33/03 ,  C07C69/007 ,  C07C69/01 ,  C07C33/025 ,  C07C69/15 ,  C07C69/155

摘要： A process for producing a lower aliphatic carboxylic acid alkenyl, comprising reacting a lower olefin, a lower aliphatic carboxylic acid and oxygen in a gas phase in the presence of a catalyst comprising a support having supported thereon a catalyst component containing a compound containing alkali metal and/or alkaline earth metal, an element belonging to Group 11 of the Periodic Table or a compound containing at least one of these elements, and palladium, wherein the outflow ratio of the compound containing alkali metal and/or alkaline earth metal is from 1.0(10-5 to 0.01%/h.

摘要翻译： 一种制备低级脂族羧酸烯基的方法，包括在催化剂存在下使气相中的低级烯烃，低级脂族羧酸和氧反应，所述催化剂包括其上负载有载体的载体，所述催化剂组分含有含有碱金属的化合物和 /或碱土金属，属于元素周期表第11族的元素或含有这些元素中的至少一种的化合物和钯，其中含碱金属和/或碱土金属的化合物的流出比为1.0（ 10-5〜0.01％/ h。

公开(公告)号：WO2003048097A1

公开(公告)日：2003-06-12

申请号：PCT/GB2002/005415

申请日：2002-11-29

申请人： BP CHEMICALS LIMITED ,  FIORENTINO, Michele ,  NEWTON, David ,  SALEM, George, Frederick ,  WILLIAMS, Bruce, Leo

发明人： FIORENTINO, Michele ,  NEWTON, David ,  SALEM, George, Frederick ,  WILLIAMS, Bruce, Leo

IPC分类号： C07C51/215

CPC分类号： C07C51/25 ,  C07C51/215 ,  C07C67/055 ,  C07C253/24 ,  Y02P20/52 ,  Y02P20/582 ,  C07C53/08 ,  C07C69/01 ,  C07C69/15 ,  C07C255/08

摘要： A process for reacting in a fluid bed reactor at least one oxidisable reactant with molecular oxygen in the presence of a catalytically active fluidised bed of solid particles. In the process a molecular oxygen-containing gas having an oxygen concentration greater than that of air is introduced into the fluidised bed whilst the fluidised bed is maintained in a turbulent regime. The process is suitable for oxidation, ammoxidation and carboxylation processes, including the production of maleic anhydride, acrylonitrile, ethylene, acetic acid and vinyl acetate.

摘要翻译： 在流化床反应器中在固体颗粒的催化活性流化床存在下使至少一种可氧化反应物与分子氧反应的方法。 在该过程中，将氧浓度大于空气的分子含氧气体引入流化床中，同时流化床保持在湍流状态。 该方法适用于氧化，氨氧化和羧化过程，包括马来酸酐，丙烯腈，乙烯，乙酸和乙酸乙烯酯的生产。

公开(公告)号：WO02004392A1

公开(公告)日：2002-01-17

申请号：PCT/US2001/021184

申请日：2001-07-05

IPC分类号： B01J23/66 ,  B01J21/08 ,  B01J23/52 ,  B01J23/58 ,  B01J31/04 ,  B01J31/30 ,  B01J37/02 ,  B01J37/03 ,  B01J37/06 ,  B01J37/16 ,  B01J37/18 ,  C07B61/00 ,  C07C67/055 ,  C07C69/15 ,  C07C27/10 ,  B01J23/44 ,  B01J23/48 ,  B01J23/56 ,  C07C51/02 ,  C07C51/16 ,  C07C67/00 ,  C07C67/05

CPC分类号： B01J31/30 ,  B01J21/08 ,  B01J23/52 ,  B01J23/58 ,  B01J31/04 ,  B01J37/0203 ,  B01J37/031 ,  B01J37/06 ,  B01J37/16 ,  B01J37/18 ,  C07C67/055 ,  C07C69/01 ,  C07C69/15

摘要： A shell impregnated catalyst of Pd-Au produced on a silica support to have a Pd loading of 1.8 g/L of catalyst to about 7.2 g/L and a Au to Pd weight ratio of 0.3 to 2.0 by impregnating the support with aqueous solutions of palladium and gold salts or acids and thereafter precipitating water insoluble compounds of Pd and Au on the with alkali metal silicate or hydroxide solutions, then dried, and the surface precipitated compounds of Pd and Au are then reduced by reaction with ethylene or hydrogen at a temperature of greater than 150 DEG C up to 310 DEG C or with hydrogen up to 299 DEG C until substantially all of the Pd and Au contents are reduced to a free metal state, after which the support is impregnated with potassium acetate to an extent of 6 to 7 weight percent of the weight of the total catalyst. For production of vinyl acetate (VA) such catalyst has a space-time yield (STY) and specific activity (SA) about 20-30 % greater than an otherwise identical catalyst composition that is formed from impregnated support reduced at 150 DEG C, and in a temperature range of 140 DEG C to 160 DEG C at a gas hourly space velocity of 4500/hr will at 120 psig exhibit a VA selectivity of 90 % or greater when operated under reaction conditions that result in a STY of at least 600.

摘要翻译： 在二氧化硅载体上生产的Pd-Au的壳体浸渍催化剂，其Pd载量为1.8g / L的催化剂至约7.2g / L，Au与Pd的重量比为0.3至2.0，通过用水溶液浸渍载体 钯和金盐或酸，然后用碱金属硅酸盐或氢氧化物溶液沉淀出Pd和Au的水不溶性化合物，然后干燥，然后通过与乙烯或氢气在一定温度下反应而使Pd和Au的表面沉淀化合物还原 大于150℃至310℃或氢气至299℃，直到基本上所有的Pd和Au含量都被还原成自由金属状态，然后将载体用乙酸钾浸渍至6 至总催化剂重量的7重量％。 对于乙酸乙烯酯（VA）的生产，这种催化剂的时空产率（STY）和比活度（SA）比由在150℃下还原的浸渍载体形成的另外相同的催化剂组合物大20-30％，以及 在140℃至160℃的温度范围内，在120psig下的气时空速为4500psig，当在至少600℃的STY的反应条件下操作时，VA选择性为90％以上。

公开(公告)号：WO01036091A1

公开(公告)日：2001-05-25

申请号：PCT/US2000/028723

申请日：2000-10-17

IPC分类号： B01J31/28 ,  B01J23/52 ,  B01J23/89 ,  B01J37/02 ,  B01J37/03 ,  B01J37/16 ,  B01J37/34 ,  C07B61/00 ,  C07C67/055 ,  C07C69/15 ,  B01J23/44 ,  C07C69/01

CPC分类号： B01J37/343 ,  B01J23/52 ,  B01J23/8926 ,  C07C67/055 ,  C07C69/01 ,  C07C69/15

摘要： A catalyst effective for the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid, comprising a porous support on the porous surfaces of which is deposited catalytically effective amounts of metallic palladium and gold, and optionally, one or more additional catalytically active metals such as copper, prepared by steps comprising impregnating the support with one or more aqueous solutions, of water-soluble compounds of the metals, fixing the metals on the support as water-insoluble compounds in one or more fixing steps by reaction with an appropriate alkaline compound, at least one of said fixing steps being carried out in a solution of the alkaline compound in which the impregnated support is immersed, while sonicating, i.e., applying ultrasound waves to, such solution, and reducing the water-insoluble compounds of the catalytically active metals to their free metallic form.

摘要翻译： 通过乙烯，氧气和乙酸的反应生产乙酸乙烯酯有效的催化剂，其包含多孔表面上的多孔载体是沉积有催化有效量的金属钯和金，以及任选的一种或多种另外的催化活性金属 例如铜，通过包括用一种或多种水溶液浸渍载体的步骤制备的水溶性金属化合物，通过与适当的碱反应在一个或多个固定步骤中将金属固定在载体上作为水不溶性化合物 化合物，所述固定步骤中的至少一个在浸渍了浸渍载体的碱性化合物的溶液中进行，同时超声处理，即对这种溶液施加超声波，并还原催化的水不溶性化合物 活性金属以其游离金属形式。

公开(公告)号：WO00003965A1

公开(公告)日：2000-01-27

申请号：PCT/EP1998/004382

申请日：1998-07-14

IPC分类号： C07B63/04 ,  C07C51/50 ,  C07C57/075 ,  C07C67/62 ,  C07C69/54 ,  C07C231/22 ,  C07C233/09 ,  C07C253/32 ,  C07C255/08 ,  C07D211/94 ,  C07C57/04 ,  C07C69/15

CPC分类号： C07C231/22 ,  C07B63/04 ,  C07C51/50 ,  C07C67/62 ,  C07C253/32 ,  C07C303/42 ,  C07D211/94 ,  C07C57/04 ,  C07C69/54 ,  C07C69/01 ,  C07C309/24 ,  C07C255/08 ,  C07C233/09 ,  C07C69/15

摘要： Selected derivatives of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and 1-oxyl-2,2,6,6-tetramethyl-4-aminopiperidine are surprisingly effective as inhibitors to prevent the premature polymerization of acrylic and methacrylic acids, their esters, their amides, vinyl acetate and acrylonitrile in the presence of water. Some of these derivatives are new compounds.

摘要翻译： 1-氧基-2,2,6,6-四甲基-4-羟基哌啶和1-氧基-2,2,6,6-四甲基-4-氨基哌啶的选择性衍生物出人意料地有效地用作防止丙烯酸过早聚合的抑制剂 甲基丙烯酸，它们的酯，它们的酰胺，乙酸乙烯酯和丙烯腈。 这些衍生物中的一些是新化合物。

公开(公告)号：WO99067022A1

公开(公告)日：1999-12-29

申请号：PCT/EP1999/004031

申请日：1999-06-11

IPC分类号： B01J23/52 ,  B01J23/58 ,  B01J37/02 ,  C07B61/00 ,  C07C67/05 ,  C07C67/055 ,  C07C69/15 ,  B01J23/44

CPC分类号： B01J37/0221 ,  B01J23/52 ,  B01J23/58 ,  B01J35/008 ,  B01J37/0238 ,  C07C67/055 ,  C07C69/01 ,  C07C69/15

摘要： The invention relates to a method for preparing supported catalysts containing Pd/Au by a CVD (chemical vapour deposition) process using evaporable Pd/au precursors. According to said method, appropriate noble-metal precursors are deposited in the vapour phase on porous supports, then chemically or thermally reduced to metal and hence fixed on the support. The invention relates especially to producing Pd/Au shell catalysts on porous supports according to said method. Catalysts so produced can be used for a variety of heterogeneous catalysis reactions such as hydrogenation and oxidation. Pd/Au shell catalysts produced according to said method can be used for the synthesis of vinyl acetate.

摘要翻译： 本发明涉及一种方法，用于生产的Pd / Au的含有汽化的Pd / Au的前体的CVD（化学气相沉积）的负载型催化剂。 适合于通过上多孔载体的模制品气相为此贵金属前体可以被沉积，然后热或化学还原成金属，并由此固定在载体上。 特别地，本发明涉及的Pd / Au壳催化剂对多孔载体的制备此方法。 如此制备的载体上的催化剂可用于各种非均相催化反应，例如氢化和氧化的。 根据该方法制备，根据本发明的Pd / Au壳催化剂可以在乙酸乙烯酯的合成中使用。

公开(公告)号：WO99023057A1

公开(公告)日：1999-05-14

申请号：PCT/US1998/021241

申请日：1998-10-08

IPC分类号： C07C67/04 ,  C07C67/00 ,  C07C69/01

CPC分类号： C07C67/04 ,  C07C69/01 ,  C07C69/24

摘要： A process is disclosed for forming a vinyl ester from a carboxylic acid and acetylene in the presence of a zinc carboxylate catalyst, wherein a mixture of carboxylic acid and zinc carboxylate catalyst is formed and the water content of the mixture is reduced to between about 0.02 wt.% and about 0.3 wt.%, prior to introduction of the acetylene into the reactor. Optionally, water is introduced into the reactor during the reaction to hydrate any anhydride by-product of the reaction present in the reactor to carboxylic acid reactant. Water is added during the reaction in an amount that is sufficient to convert the anhydride by-product to carboxylic acid reactant, but does not raise the amount of water in the reaction mixture to a level that will reduce the reactivity of the catalyst or reduce the rate of the vinylation reaction.

摘要翻译： 公开了一种在羧酸锌催化剂存在下从羧酸和乙炔形成乙烯基酯的方法，其中形成羧酸和羧酸锌催化剂的混合物，并且混合物的水含量降低至约0.02重量％ 在将乙炔引入反应器之前，将其重量％和约0.3重量％。 任选地，在反应期间将水引入反应器中以将存在于反应器中的反应物的任何酸酐副产物水合成羧酸反应物。 在反应过程中加入水的量足以将酸酐副产物转化为羧酸反应物，但不会将反应混合物中的水量提高到将降低催化剂反应性或降低催化剂反应性的水平 乙烯反应速率。

公开(公告)号：WO1998018553A1

公开(公告)日：1998-05-07

申请号：PCT/US1997019996

申请日：1997-10-29

申请人： MILLENNIUM PETROCHEMICALS INC.

发明人： MILLENNIUM PETROCHEMICALS INC. ,  AUGUSTINE, Steven, M. ,  SMITH, David, W. ,  HANES, Ronnie, M. ,  EVANS, Michael, D.

IPC分类号： B01J23/52

CPC分类号： B01J23/52 ,  C07C67/055 ,  C07C69/01 ,  C07C69/15

摘要： An improved process for producing high activity and high selectivity supported palladium-gold catalysts is provided. The process involves calcining the support impregnated with a palladium salt and gold salt in a non-reducing atmosphere and at a temperature ranging from 100 DEG C to 600 DEG C prior to reducing the metals. Catalysts of the invention are useful for the production of vinyl acetate in the vapor phase by reaction of ethylene, acetic acid and oxygen.

摘要翻译： 提供了一种用于生产高活性和高选择性的钯 - 金催化剂的改进方法。 该方法包括在还原金属之前，在非还原气氛中和在100℃至600℃的温度下煅烧浸有钯盐和金盐的载体。 本发明的催化剂可用于通过乙烯，乙酸和氧的反应在气相中生产乙酸乙烯酯。

公开(公告)号：WO1994021374A1

公开(公告)日：1994-09-29

申请号：PCT/US1993002648

申请日：1993-03-15

申请人： QUANTUM CHEMICAL CORPORATION

发明人： QUANTUM CHEMICAL CORPORATION ,  SMITH, David, W. ,  HANES, Ronnie, M. ,  SCHEBEN, John, A. ,  AUGUSTINE, Steve, M.

IPC分类号： B01J23/52

CPC分类号： B01J37/12 ,  B01J23/52 ,  C07C67/055 ,  C07C69/01 ,  C07C69/15

摘要： A method for pretreatment of a palladium-gold catalyst useful in the synthesis of vinyl acetate. A virgin catalyst, following reduction to the metallic palladium and gold, is first heated at elevated temperatures in the presence of an oxidizing agent such as air. The oxidizing agent is withdrawn and an inert gas such as nitrogen is introduced. The catalyst is heated again at a temperature up to 500 DEG C in the presence of a reducing agent such as hydrogen or ethylene. Improvements in selectivity and yield are obtained.

摘要翻译： 一种用于合成乙酸乙烯酯的钯 - 金催化剂的预处理方法。 首先在氧化剂如空气存在下，在升高的温度下加热金属钯和金之后的原始催化剂。 取出氧化剂，引入惰性气体如氮气。 在还原剂如氢气或乙烯的存在下，在高达500℃的温度下再次加热催化剂。 获得了选择性和产率的改善。

公开(公告)号：WO1992009554A1

公开(公告)日：1992-06-11

申请号：PCT/US1991008757

申请日：1991-11-27

申请人： UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY ...

发明人： UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY ... ,  MOKHTARZADETH, Morteza ,  MURRAY, Rex, Eugene

IPC分类号： C07C67/10

CPC分类号： C07C67/10 ,  C07C67/54 ,  C07C69/01 ,  C07C69/24 ,  C07C69/78 ,  C07C69/56 ,  C07C69/54

摘要： A process for the preparation of an alkenyl derivative of a Bronsted acid by the transvinylation reaction of an alkenyl derivative of a first Bronsted acid with a second Bronsted acid includes azeotropic distillation of the transvinylation reaction mixture for the separation and recovery as a product the alkenyl derivative of the second Bronsted acid.

摘要翻译： 通过第一布朗斯台德酸的链烯基衍生物与第二布朗斯台德酸的反缩合反应制备布朗斯台德酸的链烯基衍生物的方法包括共价蒸馏作为产物的分离和回收的转乙烯化反应混合物，链烯基衍生物 的第二个布朗斯台德酸。