公开(公告)号：US06458737B1

公开(公告)日：2002-10-01

申请号：US09709276

申请日：2000-11-13

申请人： Nobuji Kishimoto ,  Isao Nakamura ,  Yusei Nagamura ,  Akiyoshi Nakajima ,  Masashi Hashimoto ,  Kunika Takahashi

发明人： Nobuji Kishimoto ,  Isao Nakamura ,  Yusei Nagamura ,  Akiyoshi Nakajima ,  Masashi Hashimoto ,  Kunika Takahashi

IPC分类号： B01J3100

CPC分类号： C07C45/36 ,  B01J23/30 ,  B01J23/31 ,  B01J23/888 ,  C07C29/177 ,  C07C2601/14 ,  C07C47/544 ,  C07C31/276 ,  C07C33/26

摘要： The present invention has for its object to provide a novel catalyst by use of which methylbenzenes can be oxidized in gaseous phase in the presence of molecular oxygen to give the corresponding aromatic aldehydes in high yields, a process for producing an aromatic aldehyde from the corresponding methylbenzene in a high yield by use of said catalyst, and a process for producing cyclohexanedimethanol which comprises hydrogenating phthalaldehyde among the aromatic aldehydes which can be obtained as above. The present invention is directed to a catalyst for oxidation of methylbenzene which is used for the production of the corresponding aromatic aldehyde by the gas-phase oxidation of a methylbenzene in the presence of molecular oxygen, and has a composition of the following general formula (1): WaXbYcOx  (1)  wherein W represents a tungsten atom; X represents at least one kind of element selected from the group consisting of P, Sb, Bi and Si; Y represents at least one element selected from the group consisting of Fe, Co, Ni, Mn, Re, Cr, V, Nb, Ti, Zr, Zn, Cd, Y, La, Ce, B, Al, Tl, Sn, Mg, Ca, Sr, Ba, Li, Na, K, Rb and Cs; O represents an oxygen atom; a, b, c and x represent the numbers of atoms of W, X, Y and O, respectively; provided, however, the proportions of a, b and c are such that when a=12, b=0.5 to 10 and c=0 to 15; X represents a numerical value which is determined by the oxidized states of the elements other than oxygen.

摘要翻译： 本发明的目的是提供一种新的催化剂，其中使用甲基苯可以在分子氧存在下在气相中被氧化，以高产率得到相应的芳族醛，从相应的甲苯生产芳族醛的方法 通过使用所述催化剂以高产率，以及生产环己烷二甲醇的方法，其包括在如上所述可获得的芳族醛中氢化邻苯二甲醛。本发明涉及一种用于生产甲基苯的氧化的催化剂 相应的芳族醛通过甲基苯在分子氧存在下的气相氧化，并具有以下通式（1）的组成：其中W表示钨原子; X表示选自P，Sb，Bi和Si中的至少一种元素; Y表示选自Fe，Co，Ni，Mn，Re，Cr，V，Nb，Ti，Zr，Zn，Cd，Y，La，Ce，B，Al， Mg，Ca，Sr，Ba，Li，Na，K，Rb和Cs; O表示氧原子; a，b，c和x分别表示W，X，Y和O的原子数; 但是，a，b和c的比例使得当a = 12时，b = 0.5〜10，c = 0〜15; X表示由氧以外的元素的氧化态决定的数值。

公开(公告)号：US5206201A

公开(公告)日：1993-04-27

申请号：US704069

申请日：1991-05-22

申请人： Nobuji Kishimoto ,  Isao Nakamura ,  Taizou Matsueda ,  Yoshitaka Arita

发明人： Nobuji Kishimoto ,  Isao Nakamura ,  Taizou Matsueda ,  Yoshitaka Arita

IPC分类号： B01J23/28 ,  B01J27/199 ,  C07C45/36

CPC分类号： B01J23/002 ,  B01J23/28 ,  B01J27/199 ,  C07C45/36 ,  B01J2523/00

摘要： A catalyst for the production of a substituted benzaldehyde by catalytic vapor-phase oxidation of a substituted toluene, which catalyst has as a catalytically active substance being composed of an oxide represented by the general formula III:V.sub.a Mo.sub.b X.sub.c Y.sub.d O.sub.e (III)wherein V, Mo, and O are respectively for vanadium, molybdenum, and oxygen, X is at least one element selected from the group consisting of sodium, potassium, rubidium, cesium, and thallium, Y is at least one element selected from the group consisting of niobium, tantalum, phosphorus, antimony, bismuth, tellurium, tin, lead, boron, copper, and silver, and a, b, c, d, and e indicate the atomic ratios of relevant elements such that where a+b=1, then b=0.05 to 0.4, c=0.1 to 1, d=0 to 1, and e=the value determined by the state of oxidation of other elements.

公开(公告)号：US5844112A

公开(公告)日：1998-12-01

申请号：US666577

申请日：1996-07-01

申请人： Akira Kurusu ,  Nobuji Kishimoto ,  Isao Nakamura ,  Etsushige Matsunami

发明人： Akira Kurusu ,  Nobuji Kishimoto ,  Isao Nakamura ,  Etsushige Matsunami

IPC分类号： C07C253/24 ,  C07C253/26

CPC分类号： C07C253/24 ,  B01J23/00 ,  Y02P20/52

摘要： A method for the preparation of (meth)acrylonitriles following ammoxidation process comprising catalytically oxidizing at least one saturated hydrocarbon selected from the group consisting of propane and isobutane with a mixed gas containing mole-cular oxygen and ammonia in the presence of a catalyst, is provided, the method being characterized by the use of a catalyst composed of complex oxide which is expressed by the general formula (I) below: Cr.alpha.Sb.beta.W.gamma.Ox (I) (in which .alpha., .beta. and .gamma. denote the number of atoms of Cr, Sb and W, respectively, and when .alpha. is 1, .beta. is 0.5-5 and .gamma. is 0.2-2; and x is a value determined by valence of the existing elements). According to this method, the object nitriles can be prepared at high yields with industrial advantages.

摘要翻译： PCT No.PCT / JP96 / 00096 Sec。 371日期：1996年7月1日 102（e）日期1996年7月1日PCT 1996年1月22日PCT申请在氨氧化方法后制备（甲基）丙烯腈的方法包括用混合气体催化氧化至少一种选自丙烷和异丁烷的饱和烃 提供了在催化剂存在下含有摩尔氧和氨的方法，该方法的特征在于使用由以下通式（I）表示的复合氧化物组成的催化剂：CrαSbβWγOx （I）（其中α，β和γ分别表示Cr，Sb和W的原子数，当α为1时，β为0.5-5，γ为0.2-2; x为由 现有元素的价格）。 根据该方法，可以以高产率制备目标腈，具有工业优点。

公开(公告)号：US06756517B2

公开(公告)日：2004-06-29

申请号：US09895416

申请日：2001-07-02

申请人： Nobuji Kishimoto ,  Etsushige Matsunami

发明人： Nobuji Kishimoto ,  Etsushige Matsunami

IPC分类号： C07C5333

CPC分类号： C07C45/35 ,  B01J23/002 ,  B01J23/34 ,  B01J2523/00 ,  C07C5/48 ,  C07C45/33 ,  C07C45/34 ,  C07C51/252 ,  C07C2523/34 ,  Y02P20/52 ,  C07C11/02 ,  C07C47/22 ,  C07C57/04 ,  B01J2523/53 ,  B01J2523/72 ,  B01J2523/842 ,  B01J2523/51 ,  B01J2523/67 ,  B01J2523/56 ,  B01J2523/69 ,  B01J2523/17 ,  B01J2523/3712 ,  B01J2523/305 ,  B01J2523/12 ,  B01J2523/22 ,  B01J2523/62 ,  B01J2523/74 ,  B01J2523/55 ,  B01J2523/68 ,  B01J2523/13 ,  B01J2523/41 ,  B01J2523/54 ,  B01J2523/845

摘要： Lower alkenes of from 2 to 5 carbon atoms, such as propene, are produced by the vapor phase catalytic oxidative dehydrogenation of lower alkane, such as propane, using a mixed metal oxide catalyst of formula (1) as decribed, containing manganese and at least one additional metal as essential elements, e.g., Mn1Sb0.15Ox, Mn1P0.2Ox, Mn1S0.15W0.05Cr0.1Ox. The lower alkene may be further oxidatively dehydrogenated using a mixed metal oxide catalyst of formula (1), especially formula (2), as described, to produce a mixture of unsaturated aldehyde and unsaturated acid. The unsaturated aldehyde may be further oxidatively dehydrogenated in the vapor phase in the presence of mixed metal oxide catalyst of formula (1), especially formula (3).

摘要翻译： 通过低分子烷烃如丙烷的气相催化氧化脱氢，使用含有锰的至少一种式（1）的混合金属氧化物催化剂制备含2-5个碳原子的低级烯烃，如丙烯，至少 一种额外的金属作为必需元素，例如Mn1Sb0.15Ox，Mn1P0.2Ox，Mn1S0.15W0.05Cr0.1Ox。 可以使用如所述的式（1），特别是式（2）的混合金属氧化物催化剂进一步氧化降解烯烃，以产生不饱和醛和不饱和酸的混合物。 在式（1）的混合金属氧化物催化剂，特别是式（3）的存在下，不饱和醛可以在气相中进一步氧化脱氢。

公开(公告)号：US06635794B2

公开(公告)日：2003-10-21

申请号：US09983086

申请日：2001-10-23

申请人： Nobuji Kishimoto

发明人： Nobuji Kishimoto

IPC分类号： C07C5333

CPC分类号： C07C5/48 ,  B01J23/34 ,  B01J23/8892 ,  C07C2521/10 ,  C07C2523/02 ,  C07C2523/04 ,  C07C2523/06 ,  C07C2523/08 ,  C07C2523/10 ,  C07C2523/18 ,  C07C2523/20 ,  C07C2523/26 ,  C07C2523/30 ,  C07C2523/34 ,  C07C2523/36 ,  C07C2523/745 ,  C07C2523/75 ,  C07C2523/755

摘要： Novel oxidative dehydrogenation catalysts which are useful in vapor-phase oxidative dehydrogenation of lower alkanes with molecular oxygen to produce corresponding olefins at high yields are provided. The catalysts are characterized by containing Mn as the essential component and a crystal phase which is identified by the peaks appearing on their X-ray diffraction spectra (per Cu—K&agr; cathode) where the diffraction angle 2&thgr; (±0.3°) is at 32.9°, 55.2°, 23.1°, 38.2° and 65.8°. The use of those catalysts enables production of the olefins at high yields.

公开(公告)号：US5985788A

公开(公告)日：1999-11-16

申请号：US721994

申请日：1996-10-07

申请人： Nobuji Kishimoto ,  Taizou Matsueda

发明人： Nobuji Kishimoto ,  Taizou Matsueda

IPC分类号： B01J23/30 ,  B01J23/34 ,  B01J23/88 ,  C07B61/00 ,  C07C253/24 ,  C07C255/08 ,  B01J23/00 ,  C07C253/00

CPC分类号： B01J23/30 ,  C07C253/24 ,  B01J2523/00 ,  Y02P20/52

摘要： A process for the preparation of (meth)acrylonitriles following ammoxidation process comprising catalytically oxidizing at least one saturated hydrocarbon selected from the group consisting of propane and isobutane with a mixed gas containing molecular oxygen and ammonia in the presence of a catalyst, is provided, the process being characterized by the use of a catalyst composed of complex oxide which is expressed by the general formula (I) below:Mo.alpha.Sb.beta.W.gamma.Ox (I)(in which .alpha., .beta. and .gamma. denote the number of atoms of Mo, Sb and W, respectively, and when .alpha. is 1, .beta. is 0.5-10 and .gamma. is 0.5-10; and x is a value determined by valence of the existing elements)as supported on a refractory inorganic carrier.According to this process, the object nitrites can be prepared at high yields with industrial advantages.

摘要翻译： PCT No.PCT / JP96 / 00097 Sec。 371日期1996年10月7日第 102（e）日期1996年10月7日PCT 1996年1月22日PCT申请1.氨基氧化方法制备（甲基）丙烯腈的方法，包括用混合气体催化氧化至少一种选自丙烷和异丁烷的饱和烃 在催化剂存在下含有分子氧和氨，该方法的特征在于使用由以下通式（I）表示的复合氧化物组成的催化剂：MoαSbβWγOx（I ）（其中α，β和γ分别表示Mo，Sb和W的原子数，当α为1时，β为0.5-10，γ为0.5-10; x为通过 现有元素）作为负载在难熔无机载体上。 根据该方法，可以以高产率制备具有工业优点的对象亚硝酸盐。

公开(公告)号：US06479710B2

公开(公告)日：2002-11-12

申请号：US09267396

申请日：1999-03-15

申请人： Nobuji Kishimoto ,  Etsushige Matsunami

发明人： Nobuji Kishimoto ,  Etsushige Matsunami

IPC分类号： C07C4100

CPC分类号： C01G31/02 ,  B01J23/22 ,  B01J23/8472 ,  B01J37/0018 ,  B01J37/033 ,  C01P2002/02 ,  C01P2002/20 ,  C01P2002/72 ,  C01P2002/78 ,  C01P2006/82

摘要： A solid acid-base catalyst contains vanadium pentoxide hydrate. Moreover, it is preferable that the vanadium pentoxide hydrate in the solid acid-base catalyst has a composition which is represented by the following general equation (1): V2O5.nH2O  (1) (n: 0.1-3). Creation of the vanadium pentoxide hydrate was confirmed by measuring X-ray diffraction spectrum shown in FIG. 1. In accordance with the above arrangement, the solid acid-base catalyst can sufficiently display catalytic activity under mild conditions, and it can be suitably applied to various reactions, such as the syntheses of olefins or ethers through dehydration reactions of alcohols, the syntheses of aldehydes or ketones through dehydrogenation reactions of alcohols, hydrations and isomerization reactions of olefins, alkylations, esterifications, amidations, acetalizations, aminations, hydrogen shift reactions, aldol condensation reactions and polymerization reactions.

摘要翻译： 固体酸碱催化剂含有五氧化二钒水合物。 此外，固体酸 - 碱催化剂中的五氧化二钒水合物优选具有以下通式（1）表示的组成：（n：0.1-3）。五氧化二钒水合物的形成通过测定 图1所示的X射线衍射光谱。 根据上述配置，固体酸碱催化剂可以在温和条件下充分显示催化活性，可适用于各种反应，例如通过醇的脱水反应合成烯烃或醚，合成 通过醇的脱氢反应，烯烃的水合和异构化反应，烷基化，酯化，酰胺化，缩醛化，胺化，氢转移反应，醛醇缩合反应和聚合反应。

公开(公告)号：US06281378B1

公开(公告)日：2001-08-28

申请号：US09586777

申请日：2000-06-05

申请人： Nobuji Kishimoto ,  Etsushige Matsunami

发明人： Nobuji Kishimoto ,  Etsushige Matsunami

IPC分类号： C07C25500

CPC分类号： C07C5/48 ,  B01J23/22 ,  C07C45/36 ,  C07C67/40 ,  C07C253/24 ,  C07C253/28 ,  Y02P20/52 ,  C07C47/575 ,  C07C47/54 ,  C07C69/06 ,  C07C255/50 ,  C07C255/08

摘要： Vanadium-containing catalysts are obtained by using polyvanadic acid as a source of vanadium. Vanadium-containing catalysts are obtained by mixing catalyst components other than vanadium, or their precursors, with a polyvanadic acid sol which is formed by ion-exchanging a metavanadic acid aqueous solution with a proton-type cation-exchange resin and performing polycondensation, and by drying and/or calcining the mixture. Such vanadium-containing catalysts can fully exhibit their catalytic activity under mild reaction conditions, and can be suitably used for various reactions, such as synthesis of phthalic anhydride by the partial oxidation of o-xylene, synthesis of benzaldehyde by the partial oxidation of toluene, synthesis of benzoic acid by the partial oxidation of toluene, synthesis of anisaldehyde by the partial oxidation of p-methoxy toluene, synthesis of propylene by the oxidative dehydrogenation of propane, synthesis of isobutene by the oxidative dehydrogenation of isobutane, synthesis of methyl formate by the oxidative dehydrogenation of methanol, and synthesis of acrylonitrile by the ammoxidation of propane.

摘要翻译： 通过使用聚阴离子作为钒源，得到含钒催化剂。 含钒催化剂通过将除钒以外的催化剂组分或其前体与通过与质子型阳离子交换树脂离子交换偏钒酸水溶液并进行缩聚而形成的聚阴离子溶胶获得，并进行缩聚 干燥和/或煅烧该混合物。 这种含钒催化剂可以在温和的反应条件下充分发挥其催化活性，适用于各种反应，如通过邻二甲苯的部分氧化合成邻苯二甲酸酐，通过甲苯的部分氧化合成苯甲醛， 通过甲苯的部分氧化合成苯甲酸，通过对甲氧基甲苯的部分氧化合成茴香醛，通过丙烷的氧化脱氢合成丙烯，通过异丁烷的氧化脱氢合成异丁烯，通过甲酸甲酯合成甲酸甲酯 甲醇的氧化脱氢，丙烷的氨氧化合成丙烯腈。

公开(公告)号：US06239325B1

公开(公告)日：2001-05-29

申请号：US09313658

申请日：1999-05-18

申请人： Nobuji Kishimoto ,  Etsushige Matsunami

发明人： Nobuji Kishimoto ,  Etsushige Matsunami

IPC分类号： C07C532

CPC分类号： B01J23/8885 ,  B01J23/30 ,  B01J23/888 ,  C07C5/48 ,  C07C2523/12 ,  C07C2523/18 ,  C07C2523/30 ,  C07C2523/31 ,  C07C11/02

摘要： The invention provides process for oxidative dehydrogenation of lower alkanes, by vapor phase oxidative dehydrogenation of C2-C5 lower alkanes in the presence of a catalyst and molecular oxygen to produce the corresponding olefins, in which the catalyst has a composition expressed by a general formula (1) below: A&agr;Sb&bgr;W&ggr;D&dgr;Ox   (1) in which A is at least one metal selected from the group consisting of molybdenum and chromium; Sb is antimony; W is tungsten; O is oxygen; and D is at least one metal selected from the group consisting of V, Nb, Ta, Fe, Co, Ni, Cu, Ag, Zn, B, Tl, Sn, Pb, Te, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce and Sm; &agr;, &bgr;, &ggr;, &dgr; and x denote atomic numbers of A, Sb, W, D and O, respectively, where when &agr;=1, &bgr;=0.5-10, &ggr;=0.1-10 and &dgr;=0-3; and x is a numerical value determined by the state of oxidation of those elements other than oxygen. When these catalysts are used in reactions for oxidizing and dehydrogenating C2-C5 alkanes with molecular oxygen in vapor phase, corresponding olefins can be produced at high yield.

摘要翻译： 本发明提供了在催化剂和分子氧的存在下，通过C2-C5低级烷烃的气相氧化脱氢制备低级烷烃的方法，以产生相应的烯烃，其中催化剂具有由通式（ 1）：其中A是选自钼和铬中的至少一种金属; 锑是锑; W是钨; O是氧; 并且D是选自V，Nb，Ta，Fe，Co，Ni，Cu，Ag，Zn，B，Tl，Sn，Pb，Te，Li，Na，K，Rb，Cs中的至少一种金属 ，Mg，Ca，Sr，Ba，La，Ce和Sm; α，β，γ，δ和x分别表示A，Sb，W，D和O的原子序数，其中α= 1，β= 0.5-10，γ= 0.1-10和δ= 0-3; x是由氧以外的元素的氧化状态确定的数值。当这些催化剂用于在气相中用分子氧氧化和脱氢C2-C5烷烃的反应中时，可以高产率生产相应的烯烃。

公开(公告)号：US5877330A

公开(公告)日：1999-03-02

申请号：US776543

申请日：1997-01-29

申请人： Nobuji Kishimoto ,  Etsushige Matsunami

发明人： Nobuji Kishimoto ,  Etsushige Matsunami

IPC分类号： B01J23/22 ,  C07C5/48 ,  C07C45/36 ,  C07C67/40 ,  C07C253/24 ,  C07D307/77

CPC分类号： C07C253/24 ,  B01J23/22 ,  C07C45/36 ,  C07C5/48 ,  C07C67/40 ,  Y02P20/52

摘要： Vanadium-containing catalysts are obtained by using polyvanadic acid as a source of vanadium. Vanadium-containing catalysts are obtained by mixing catalyst components other than vanadium, or their precursors, with a polyvanadic acid sol which is formed by ion-exchanging a metavanadic acid aqueous solution with a proton-type cation-exchange resin and performing polycondensation, and by drying and/or calcining the mixture. Such vanadium-containing catalysts can fully exhibit their catalytic activity under mild reaction conditions, and can be suitably used for various reactions, such as synthesis of phthalic anhydride by the partial oxidation of o-xylene, synthesis of benzaldehyde by the partial oxidation of toluene, synthesis of benzoic acid by the partial oxidation of toluene, synthesis of anisaldehyde by the partial oxidation of p-methoxy toluene, synthesis of propylene by the oxidative dehydrogenation of propane, synthesis of isobutene by the oxidative dehydrogenation of isobutane, synthesis of methyl formate by the oxidative dehydrogenation of methanol, and synthesis of acrylonitrile by the ammoxidation of propane.

摘要翻译： PCT No.PCT / JP96 / 01547 Sec。 371日期1997年1月29日 102（e）1997年1月29日PCT PCT 1996年6月7日PCT公布。 公开号WO96 / 41678 日期：1996年12月27日使用聚钒酸作为钒源可得到含钒催化剂。 含钒催化剂通过将除钒以外的催化剂组分或其前体与通过与质子型阳离子交换树脂离子交换偏钒酸水溶液并进行缩聚而形成的聚阴离子溶胶获得，并进行缩聚 干燥和/或煅烧该混合物。 这种含钒催化剂可以在温和的反应条件下充分发挥其催化活性，适用于各种反应，如通过邻二甲苯的部分氧化合成邻苯二甲酸酐，通过甲苯的部分氧化合成苯甲醛， 通过甲苯的部分氧化合成苯甲酸，通过对甲氧基甲苯的部分氧化合成茴香醛，通过丙烷的氧化脱氢合成丙烯，通过异丁烷的氧化脱氢合成异丁烯，通过甲酸甲酯合成甲酸甲酯 甲醇的氧化脱氢，丙烷的氨氧化合成丙烯腈。