公开(公告)号：US06545178B1

公开(公告)日：2003-04-08

申请号：US09314719

申请日：1999-05-18

申请人： Michio Tanimoto ,  Daisuke Nakamura ,  Tatsuya Kawajiri

发明人： Michio Tanimoto ,  Daisuke Nakamura ,  Tatsuya Kawajiri

IPC分类号： C07C5116

CPC分类号： C07C45/35 ,  B01J23/002 ,  B01J23/8876 ,  B01J2523/00 ,  C07C51/252 ,  C07C47/22 ,  C07C57/04 ,  B01J2523/13 ,  B01J2523/41 ,  B01J2523/54 ,  B01J2523/68 ,  B01J2523/69 ,  B01J2523/842 ,  B01J2523/845 ,  B01J2523/3712 ,  B01J2523/56

摘要： In the production of acrolein and acrylic acid by the catalytic gas phase oxidation of propylene with a molecular oxygen-containing gas, a method is provided which enables acrolein and acrylic acid to be stably produced with a high yield for a long time from propylene by effectively repressing such secondary reactions as are responsible for the formation of organic acids, high boiling compounds, and tarry compounds, the deposition of carbonized materials, and the deterioration of the quality of products. The content of unsaturated hydrocarbons (excluding propylene) of 2-5 carbon atoms in the raw material for propylene is kept below 500 ppm (by weight). Particularly, it is proper to use a raw material for propylene which has a content of unsaturated hydrocarbons (excluding propylene) of 2-5 carbon atoms of not more than 200 ppm (by weight) and a total content of diene and acetylenic compounds of 2-5 carbon atoms of not more than 200 ppm (by weight). The reaction scheme is shown below:

摘要翻译： 通过丙烯与含分子氧气体的催化气相氧化制备丙烯醛和丙烯酸，提供了一种使丙烯醛和丙烯酸长时间从丙烯中高效率稳定生产的方法， 抑制负责形成有机酸，高沸点化合物和焦油化合物的这种二次反应，碳化材料的沉积以及产品质量的劣化。 丙烯原料中2-5个碳原子的不饱和烃（不包括丙烯）的含量保持在500ppm以下（重量）。 特别地，使用具有2-5个碳原子的不饱和烃（不包括丙烯）的含量不超过200ppm（重量），二烯和炔属化合物的总含量为2的丙烯的原料是适当的 -5个碳原子不超过200ppm（重量）。 反应方案如下：

公开(公告)号：US06429332B1

公开(公告)日：2002-08-06

申请号：US08456085

申请日：1995-05-31

申请人： Michio Tanimoto ,  Tatsuya Kawajiri ,  Hiromi Yunoki ,  Yukio Aoki

发明人： Michio Tanimoto ,  Tatsuya Kawajiri ,  Hiromi Yunoki ,  Yukio Aoki

IPC分类号： C07C5116

CPC分类号： B01J35/0006 ,  B01J23/8877 ,  B01J23/8885 ,  B01J27/053 ,  B01J27/188

摘要： A catalyst for the production of acrylic acid by the vapor-phase catalytic oxidation of acrolein or acrolein-containing gas and a method for the production of acrylic acid by the use of this catalyst are provided. The catalyst of this invention comprises (A) a catalyst having Mo and V as essential components and used for the production of acrylic acid by vapor-phase catalytic oxidation of acrolein and (B) a solid acid having acid strength (Ho) of not more than −11.93. Since this catalyst excels in catalytic activity and service life, it allows acrylic acid to be produced stably at a high yield for a long time.

摘要翻译： 提供了通过气相催化氧化丙烯醛或含丙烯醛的气体生产丙烯酸的催化剂和通过使用该催化剂生产丙烯酸的方法。 本发明的催化剂包括（A）具有Mo和V作为必要成分的催化剂，用于通过丙烯醛的气相催化氧化制备丙烯酸和（B）酸强度（Ho）不大于的固体酸 比-11.93。 由于该催化剂在催化活性和使用寿命方面优异，因此能够以高产率长时间稳定地制备丙烯酸。

公开(公告)号：US06170670B2

公开(公告)日：2001-01-09

申请号：US09142179

申请日：1998-09-23

申请人： Yasuhiro Kato ,  Daisuke Nakamura ,  Tatsuya Kawajiri

发明人： Yasuhiro Kato ,  Daisuke Nakamura ,  Tatsuya Kawajiri

IPC分类号： B07B134

CPC分类号： B01J8/003 ,  B01J8/002 ,  B01J8/06 ,  B01J8/16 ,  B01J2208/00752

摘要： An apparatus for feeding a granular catalyst to a destination such as a reactor at a constant feeding rate uniformly charges the catalyst material into the device. The granular catalyst is loaded into individual compartments of a hopper and is ejected at a discharge rate controlled by a gate. When a vibrator is activated, a trough is caused to vibrate in its obliquely upward direction and the granular material in the trough is smoothly conveyed toward outlets of granular material passages formed in the trough, and is introduced to reaction tubes of the reactor via sieves. Powdery waste of the granular catalyst produced by the vibration of the trough is removed by letting it fall the sieves made in the granular material passages.

摘要翻译： 将粒状催化剂以恒定进料速度送入诸如反应器的目的地的装置将催化剂材料均匀地装入装置中。 颗粒状催化剂被装载到料斗的各个隔室中，并以由浇口控制的排出速率喷射。 当振动器被激活时，使槽在其向上倾斜的方向上振动，并且槽中的颗粒材料平滑地被输送到形成在槽中的颗粒材料通道的出口，并通过筛引入反应器的反应管。 通过将谷物的振动产生的颗粒状催化剂的粉末状废弃物通过使其落在粒状材料通道中制成的筛子而被除去。

公开(公告)号：US5981804A

公开(公告)日：1999-11-09

申请号：US995642

申请日：1997-12-22

申请人： Ikuo Kurimoto ,  Tatsuya Kawajiri ,  Hideo Onodera ,  Michio Tanimoto ,  Yukio Aoki

发明人： Ikuo Kurimoto ,  Tatsuya Kawajiri ,  Hideo Onodera ,  Michio Tanimoto ,  Yukio Aoki

IPC分类号： B01J23/887 ,  B01J27/053 ,  B01J35/00 ,  C07C45/32 ,  C07C45/35 ,  C07C45/37 ,  C07C51/23 ,  C07C51/25 ,  C07C45/34 ,  B01J23/84

CPC分类号： C07C51/23 ,  B01J23/002 ,  B01J23/8876 ,  B01J27/053 ,  B01J35/0006 ,  C07C45/32 ,  C07C45/35 ,  C07C45/37 ,  C07C51/252 ,  B01J2523/00 ,  B01J35/002

摘要： A catalyst for the production of unsaturated aldehyde and unsaturated carboxylic acid by the vapor-phase catalytic oxidation of at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether and a method for the production of unsaturated aldehyde and unsaturated carboxylic acid by the use of this catalyst are provided. The catalyst of this invention comprises (A) a catalyst having Mo, Bi and Fe as essential components and used for the production of unsaturated aldehyde and unsaturated carboxylic acid by vapor-phase catalytic oxidation of propylene, isobutylene, t-butanol and/or methyl-t-butyl ether and (B) a solid acid having acid strength (Ho) of not more than -11.93. Since this catalyst excels in catalytic activity and service life, it allows unsaturated aldehyde and unsaturated carboxylic acid to be produced stably at a high yield for a long time.

摘要翻译： 用于通过气相催化氧化至少一种选自丙烯，异丁烯，叔丁醇和甲基叔丁基醚的化合物来生产不饱和醛和不饱和羧酸的催化剂及其制备方法 的不饱和醛和不饱和羧酸。 本发明的催化剂包含（A）具有Mo，Bi和Fe作为必需组分的催化剂，用于通过丙烯，异丁烯，叔丁醇和/或甲基的气相催化氧化生产不饱和醛和不饱和羧酸 叔丁基醚和（B）酸强度（Ho）不大于-11.93的固体酸。 由于该催化剂在催化活性和使用寿命方面优异，因此可以长时间以高产率稳定地制备不饱和醛和不饱和羧酸。

公开(公告)号：US5442108A

公开(公告)日：1995-08-15

申请号：US208667

申请日：1994-03-11

申请人： Tatsuya Kawajiri ,  Hideyuki Hironaka ,  Kazuyuki Uekawa ,  Michio Tanimoto ,  Hiromi Yunoki ,  Tsuyoshi Kudoh

发明人： Tatsuya Kawajiri ,  Hideyuki Hironaka ,  Kazuyuki Uekawa ,  Michio Tanimoto ,  Hiromi Yunoki ,  Tsuyoshi Kudoh

IPC分类号： B01J23/88 ,  B01J23/92 ,  B01J23/94 ,  B01J38/06 ,  B01J38/12 ,  C07B61/00 ,  C07C51/21 ,  C07C51/487 ,  C07C57/05 ,  C07C57/055 ,  C07C57/07 ,  C07C51/16

CPC分类号： C07C51/487 ,  B01J23/94 ,  B01J38/06 ,  B01J38/12 ,  Y02P20/584

摘要： A process for removal of solid organic matters formed and deposited in the reaction system when an unsaturated aldehyde or an unsaturated aidehyde-containing gas is subjected to catalytic gaseous oxidation in the presence of an oxidizing catalyst to prepare an unsaturated carboxylic acid corresponding thereto, which process comprises contacting the solid organic matters with a mixed gas containing at least 3 volume % of molecular oxygen and at least 0.1 volume % of steam at a temperature of 260.degree. to 450.degree. C.

摘要翻译： 当在氧化催化剂存在下使不饱和醛或不饱和含酐气体进行催化气体氧化以制备与其相对应的不饱和羧酸时，去除在反应体系中形成和沉积的固体有机物质的方法， 包括在260-450℃的温度下使固体有机物质与含有至少3体积％分子氧和至少0.1体积％蒸汽的混合气体接触。

公开(公告)号：US5177260A

公开(公告)日：1993-01-05

申请号：US608832

申请日：1990-11-05

申请人： Tatsuya Kawajiri ,  Shinichi Uchida ,  Hideyuki Hironaka

发明人： Tatsuya Kawajiri ,  Shinichi Uchida ,  Hideyuki Hironaka

IPC分类号： B01J23/885 ,  B01J23/887 ,  B01J23/888 ,  C07C51/25 ,  C07C57/04 ,  C07C57/055

CPC分类号： B01J23/8885 ,  B01J23/002 ,  B01J23/885 ,  B01J23/8877 ,  C07C51/252 ,  B01J2523/00

摘要： A method for the production of acrylic acid by the vapor-phase oxidation of acrolein with a molecular oxygen-containing gas in the presence of a catalyst formed of an oxide or a composite oxide of a metal element composition represented by the following formula I:Mo.sub.a V.sub.b W.sub.c Cu.sub.d X.sub.e Y.sub.f (I)wherein X is at least one element selected from the group consisting of Zr, Ti and Ce, Y is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and the subscripts a, b, c, d, e, and f are such that b=1 to 14, 0

公开(公告)号：US6069271A

公开(公告)日：2000-05-30

申请号：US178737

申请日：1998-10-27

申请人： Michio Tanimoto ,  Kazuyuki Uekawa ,  Tatsuya Kawajiri

发明人： Michio Tanimoto ,  Kazuyuki Uekawa ,  Tatsuya Kawajiri

IPC分类号： B01J23/88 ,  B01J8/06 ,  B01J23/00 ,  B01J23/888 ,  C07B61/00 ,  C07C51/235 ,  C07C51/25 ,  C07C57/055 ,  C07C51/16

CPC分类号： B01J23/002 ,  B01J8/067 ,  C07C51/252 ,  B01J2208/00212 ,  B01J2208/00513 ,  B01J2208/025 ,  B01J23/8885 ,  B01J2523/00

摘要： A method for producing acrylic acid from propylene at high efficiency by two-stage catalytic oxidation using a single fixed bed shell-and-tube heat exchanger type reactor is provided. The method comprises dividing the shell space of said reactor into an upper space and lower space with a partition plate, allowing a heating medium to circulate in each of the spaces substantially independently of each other, and carrying out the vapor phase oxidation under specific conditions. Said specific conditions including providing a first stage catalyst layer at lower portion of each of the reaction tubes, a second stage catalyst layer at upper portion thereof and an inert substance layer therebetween, and making void ratio of the inert substance layer 40-99.5%.

摘要翻译： 提供了通过使用单个固定床管壳式热交换器型反应器通过两阶段催化氧化从丙烯生产丙烯酸的方法。 该方法包括用分隔板将所述反应器的壳体空间分成上部空间和下部空间，允许加热介质基本上彼此独立地在每个空间中循环，并在特定条件下进行气相氧化。 所述具体条件包括在每个反应管的下部提供第一级催化剂层，在其上部设置第二级催化剂层，并且在其间具有惰性物质层，并使惰性物质层的空隙率为40-99.5％。

公开(公告)号：US5198581A

公开(公告)日：1993-03-30

申请号：US679319

申请日：1991-04-02

申请人： Tatsuya Kawajiri ,  Hideyuki Hironaka ,  Shinichi Uchida ,  Yukio Aoki

发明人： Tatsuya Kawajiri ,  Hideyuki Hironaka ,  Shinichi Uchida ,  Yukio Aoki

IPC分类号： B01J23/88 ,  B01J23/887 ,  B01J27/18 ,  B01J27/192 ,  C07B61/00 ,  C07C27/00 ,  C07C27/14 ,  C07C45/32 ,  C07C45/35 ,  C07C45/37 ,  C07C47/20 ,  C07C47/22 ,  C07C51/21 ,  C07C51/23 ,  C07C51/235 ,  C07C51/25 ,  C07C57/02 ,  C07C57/05

CPC分类号： C07C45/37 ,  B01J23/002 ,  B01J23/88 ,  B01J23/8876 ,  B01J23/8885 ,  B01J27/192 ,  C07C45/32 ,  C07C45/35 ,  C07C51/23 ,  C07C51/235 ,  C07C51/252 ,  B01J2523/00

摘要： A process for producing an unsaturated aldehyde or an unsaturated acid comprises catalytically oxidizing propylene or at least one compound selected from isobutylene, tert.-butyl alcohol and methyl-tert.-butyl ether in a gaseous phase with molecular oxygen or a molecular oxygen-containing gas using a fixed bed multipipe reactor, wherein(a) a plurality of composite oxides, different in occupied volume, are used as catalyst,(b) a plurality of reaction zones are provided along an axial direction in each reaction pipe of the fixed bed multipipe reactor, and(c) the plurality of the catalysts different in occupied volume are filled in the plurality of the reaction zones such that the occupied volumes become lower from the starting gas inlet side to the outlet side.

公开(公告)号：US4892856A

公开(公告)日：1990-01-09

申请号：US201026

申请日：1988-06-01

申请人： Tatsuya Kawajiri ,  Shinichi Uchida ,  Masahiro Wada

发明人： Tatsuya Kawajiri ,  Shinichi Uchida ,  Masahiro Wada

IPC分类号： B01J23/28 ,  B01J23/30 ,  B01J23/31 ,  B01J23/88 ,  B01J23/887 ,  B01J23/888 ,  B01J35/10 ,  B01J37/02 ,  C07B61/00 ,  C07C51/00 ,  C07C51/25 ,  C07C57/055 ,  C07C67/00

CPC分类号： B01J23/8878 ,  B01J23/002 ,  B01J23/28 ,  B01J23/30 ,  B01J23/8877 ,  B01J23/8885 ,  B01J35/023 ,  B01J35/1009 ,  B01J35/1014 ,  B01J35/1038 ,  B01J35/1042 ,  B01J35/108 ,  B01J37/0221 ,  C07C51/252 ,  B01J2523/00

摘要： A catalyst for use in the production of acrylic acid by catalytic gas phase oxidation of acrolein, comprising active substances represented by general formulaMo.sub.(a) V.sub.(b) A.sub.(c) B.sub.(d) C.sub.(e) D.sub.(f) O.sub.(x)wherein Mo represents molybdenum, V represents vanadium, A represents at least one element selected from the group consisting of tungsten and niobium, B represents at least one element selected from the group consisting of iron, copper, bismuth, chromium, antimony, and thallium, C represents at least one element selected from the group consisting of alkali metals and alkaline earth metals, D represents at least one element selected from the group consisting of silicon, aluminum and titanium, and O represents oxygen; and further, a, b, c, d, e, f and x represent atomic ratios of Mo, V, A, B, C, D, and O respectively, and when a=12, then b=2 to 14, c=0 to 12, d=0 to 6, e=0 to 6 and f=0 to 30 and x is a numerical value determined depending upon the oxidation states of the other elements, and characterized by having a specific surface area of 0.50 to 15.0 m.sup.2 /g, a pore volume of 0.10 to 0.90 cc/g and a pore diameter distribution in which the pore diameters are distributed concentratedly in the ranges of from 0.1 to less than 1.0 .mu.m, from 1.0 to less than 10.0 .mu.m and from 10.0 to 100 .mu.m. The catalyst can be prepared, with good reproducibility, by charging an unfired catalyst material powder composition into a centrifugal flow coating apparatus to form particles having an average diameter of 2 to 10 mm, and then firing the particles.

公开(公告)号：US4873217A

公开(公告)日：1989-10-10

申请号：US156669

申请日：1988-02-17

申请人： Tatsuya Kawajiri ,  Hideo Onodera ,  Shinichi Uchida ,  Yukio Aoki ,  Masahiro Wada

发明人： Tatsuya Kawajiri ,  Hideo Onodera ,  Shinichi Uchida ,  Yukio Aoki ,  Masahiro Wada

IPC分类号： B01J23/88 ,  B01J23/881 ,  B01J23/882 ,  B01J23/887 ,  C07C45/34 ,  C07C45/35 ,  C07C45/37 ,  C07C51/23 ,  C07C51/25

CPC分类号： B01J35/1038 ,  B01J23/002 ,  B01J23/88 ,  B01J23/881 ,  B01J23/8876 ,  B01J35/1009 ,  B01J35/108 ,  B01J37/0221 ,  C07C45/34 ,  C07C45/35 ,  C07C45/37 ,  C07C51/23 ,  C07C51/252 ,  B01J2523/00

摘要： A catalyst used for producing, by catalytic gas phase oxidation of a C.sub.3 -C.sub.5 oelfin or tertiary alcohol, the corresponding unsaturated aldehyde and unsaturated carboxylic acid, said catalyst characterized by comprising molybdenum, iron and bismuth and having a specific surface area in the range from 1 to 20 m.sup.2 /gr, a pore volume in the range from 0.1 to 1.0 cc/gr and a pore diameter distribution in which the pore diameters are collectively distributed in the range of each of from 1 to 10 microns and from 0.1 to less than 1 micron; and a process for preparing said catalyst by charging an unfired material power into a centrifugal flow coating device to form particles having the average particle diameter of 2 to 10 mm and then firing the particles.