公开(公告)号：US06452040B2

公开(公告)日：2002-09-17

申请号：US09779205

申请日：2001-02-08

申请人： Yasuhiro Shingai ,  Sei Nakahara ,  Yukihiro Yoneda ,  Masakazu Asami ,  Masatoshi Ueoka

发明人： Yasuhiro Shingai ,  Sei Nakahara ,  Yukihiro Yoneda ,  Masakazu Asami ,  Masatoshi Ueoka

IPC分类号： C07C6726

CPC分类号： C07C67/26 ,  C07C69/54

摘要： The present invention provides a production process for a hydroxyalkyl (meth)acrylate which process enables to maintain the oxygen concentration of a gas phase portion of a reactor within a specific low concentration range in any stage of before adding raw materials, during the reaction, and after the reaction. The production process comprises the step of carrying out a reaction between (meth)acrylic acid and an alkylene oxide in the presence of a catalyst in order to produce the hydroxyalkyl (meth)acrylate, wherein an inert gas and/or a mixed gas of oxygen and an inert gas with a beforehand adjusted oxygen concentration of 0.1 to 14 vol % is used to maintain the oxygen concentration of a gas phase portion of a reactor in the range of 0.1 to 14 vol % (1) before adding the alkylene oxide or (2) during the above reaction or (3) between the completion of the above reaction and the charge for the next reaction. In addition, another production process comprises the step of carrying out a reaction between (meth)acrylic acid and an alkylene oxide in the presence of a catalyst in order to produce the hydroxyalkyl (meth)acrylate, wherein the oxygen concentration of a gas phase portion of a reactor is maintained in the range of 0.1 to 14 vol % throughout the production steps.

摘要翻译： 本发明提供一种（甲基）丙烯酸羟烷基酯的制备方法，该方法能够在反应期间在添加原料之前的任何阶段将反应器的气相部分的氧浓度保持在特定的低浓度范围内，以及 反应后。 该制备方法包括在催化剂存在下进行（甲基）丙烯酸和烯化氧之间的反应以制备（甲基）丙烯酸羟烷基酯的步骤，其中惰性气体和/或氧气的混合气体 使用事先调节氧浓度为0.1〜14体积％的惰性气体，在加入环氧烷之前将反应器的气相部分的氧浓度维持在0.1〜14体积％（1）的范围内，或（ 2）在上述反应期间或（3）完成上述反应和下一反应的电荷之间。 此外，另一种制备方法包括在催化剂存在下进行（甲基）丙烯酸和烯化氧之间的反应以制备（甲基）丙烯酸羟烷基酯的步骤，其中气相部分的氧浓度 的反应器在整个生产步骤中保持在0.1至14体积％的范围内。

公开(公告)号：US06660881B2

公开(公告)日：2003-12-09

申请号：US09928574

申请日：2001-08-12

申请人： Hajime Matsumoto ,  Tetsuya Kajihara ,  Yasuhiro Shingai ,  Masatoshi Ueoka ,  Yukihiro Yoneda ,  Masahiro Uemura ,  Sei Nakahara ,  Fumio Munechika

发明人： Hajime Matsumoto ,  Tetsuya Kajihara ,  Yasuhiro Shingai ,  Masatoshi Ueoka ,  Yukihiro Yoneda ,  Masahiro Uemura ,  Sei Nakahara ,  Fumio Munechika

IPC分类号： C07C6954

CPC分类号： C07C67/08 ,  C07C67/26 ,  C07C69/54

摘要： The present invention provides a process for producing a (meth)acrylic ester which enables to obtain a (meth)acrylic ester in an excellent reaction yield. The process for producing a (meth)acrylic ester uses an alcohol and an acid as raw materials and an ion-exchange resin as a catalyst, and the process is characterized by comprising a dehydration step and an esterification step, wherein the esterification reaction step follows the dehydration step in which water impregnated in the ion-exchange resin is removed by using as a dehydrating solvent at least one member selected from the group consisting of the alcohol, the acid, and the resulting ester.

公开(公告)号：US06787001B2

公开(公告)日：2004-09-07

申请号：US10086931

申请日：2002-03-01

申请人： Kazuhiko Sakamoto ,  Sei Nakahara ,  Yukihiro Matsumoto ,  Kenji Sanada ,  Masatoshi Ueoka

发明人： Kazuhiko Sakamoto ,  Sei Nakahara ,  Yukihiro Matsumoto ,  Kenji Sanada ,  Masatoshi Ueoka

IPC分类号： B01D336

CPC分类号： B01D3/36 ,  C07C51/44 ,  Y10S203/09 ,  Y10S203/22 ,  C07C57/04

摘要： A method for distilling a raw material liquid containing (meth)acrylic acid substantially free from azeotropic solvents, collected with a collection agent from a mixed gas obtained by gas phase catalytic oxidation reactions which includes feeding to a distillation column the raw material liquid which temperature is substantially equal to that of the entrance place in the column.

摘要翻译： 一种蒸馏含有基本上不含共沸溶剂的（甲基）丙烯酸的原料液体的方法，该方法包括将由气相催化氧化反应获得的混合气体用收集剂收集，该方法包括向蒸馏塔中加入温度为 基本上等于列中入口处的位置。

公开(公告)号：US06664418B1

公开(公告)日：2003-12-16

申请号：US09361183

申请日：1999-07-27

申请人： Kazuhiko Sakamoto ,  Kazuo Ohkouchi ,  Masahiro Uemura ,  Sei Nakahara ,  Masatoshi Ueoka

发明人： Kazuhiko Sakamoto ,  Kazuo Ohkouchi ,  Masahiro Uemura ,  Sei Nakahara ,  Masatoshi Ueoka

IPC分类号： C07C5718

CPC分类号： C07B63/04 ,  C07C51/50 ,  C07C57/04

摘要： A method for inhibiting polymerization during transportation, storage and/or production of (meth)acrylic acid or an ester thereof includes adding an N-oxyl compound and water to a vinyl compound; or dissolving an N-oxyl compound in water and adding the solution to a vinyl compound in a process of recovering, purifying, and/or synthesizing of the vinyl compound. The method can effectively inhibit polymerization of the vinyl compound.

摘要翻译： 在（甲基）丙烯酸或其酯的运输，储存和/或生产过程中抑制聚合的方法包括向乙烯基化合物中加入N-氧基化合物和水; 或将N-氧基化合物溶解在水中，并在回收，纯化和/或合成乙烯基化合物的过程中将溶液加入到乙烯基化合物中。 该方法可有效抑制乙烯基化合物的聚合。

公开(公告)号：US6084127A

公开(公告)日：2000-07-04

申请号：US31068

申请日：1998-02-26

申请人： Kazuhiko Sakamoto ,  Fumio Shibusawa ,  Sei Nakahara ,  Takahiro Takeda ,  Masatoshi Ueoka

发明人： Kazuhiko Sakamoto ,  Fumio Shibusawa ,  Sei Nakahara ,  Takahiro Takeda ,  Masatoshi Ueoka

IPC分类号： C07C51/48 ,  C07C51/42

CPC分类号： C07C51/48

摘要： An improved method which enables stable and effective recovery of acrylic acid over a prolonged period is provided, said method comprising contacting an acrylic acid-containing gas obtained upon gas-phase catalytic oxidation of propylene and/or acrolein, with water, whereby collecting the acrylic acid in form of an aqueous solution, introducing said aqueous solution into an azeotropic separation column and distilling it in the presence of an azeotropic solvent to isolate and recover the acrylic acid, in which polymerization of the acrylic acid in the azeotropic separation column is prevented. Said method is characterized by using as the azeotropic solvent either a mixed solvent composed of solvent A (eg., ethyl acrylate, methyl methacrylate, etc.) and solvent B (eg., toluene, heptane, etc.) (first embodiment) or the solvent A alone (second embodiment).

摘要翻译： 提供了能够在长时间内稳定且有效地回收丙烯酸的改进方法，所述方法包括使丙烯和/或丙烯醛气相催化氧化获得的含丙烯酸的气体与水接触，由此收集丙烯酸 酸的水溶液形式，将所述水溶液引入共沸分离塔并在共沸溶剂存在下蒸馏，以分离和回收丙烯酸，其中防止共沸分离塔中丙烯酸的聚合。 所述方法的特征在于使用由溶剂A（例如丙烯酸乙酯，甲基丙烯酸甲酯等）和溶剂B（例如甲苯，庚烷等）组成的混合溶剂作为共沸溶剂（第一实施方案）或 溶剂A单独（第二实施方式）。

公开(公告)号：US07048834B2

公开(公告)日：2006-05-23

申请号：US09745896

申请日：2000-12-21

申请人： Yoshitake Ishii ,  Kouji Ueno ,  Kazuhiko Sakamoto ,  Sei Nakahara ,  Masatoshi Ueoka ,  Tetsuji Mitsumoto ,  Takeshi Nishimura ,  Mamoru Takamura ,  Hisao Nakama

发明人： Yoshitake Ishii ,  Kouji Ueno ,  Kazuhiko Sakamoto ,  Sei Nakahara ,  Masatoshi Ueoka ,  Tetsuji Mitsumoto ,  Takeshi Nishimura ,  Mamoru Takamura ,  Hisao Nakama

IPC分类号： B01D3/34 ,  B01D3/42 ,  C07C51/44 ,  C07C51/487 ,  C07C57/07

CPC分类号： C07C51/44 ,  C07C51/487 ,  C07C57/04

摘要： The present invention provides an industrially easy and economical method for purification of acrylic acid which enables to efficiently eliminate impurities from a crude acrylic acid containing aldehydes as the impurities while the formation of acrylic acid polymer is inhibited. The method for purification of acrylic acid includes the step of distilling a crude acrylic acid which is charged with an aldehyde treatment chemical, wherein the concentration ratio of furfural to acrolein by weight in the crude acrylic acid is adjusted so as to satisfy the following equation: (furfural concentration by weight)/(acrolein concentration by weight)≦100.

摘要翻译： 本发明提供了一种工业上容易和经济的丙烯酸纯化方法，其能够在抑制丙烯酸聚合物形成的同时，有效地除去含粗醛的丙烯酸作为杂质的杂质。 纯化丙烯酸的方法包括蒸馏装入醛处理化学品的粗丙烯酸的步骤，其中调整粗丙烯酸中的糠醛与丙烯醛的重量比，以满足下列等式： （糠醛浓度按重量计）/（丙烯醛浓度重量）<= 100。<？in-line-formula description =“In-line formula”end =“lead” “公式”end =“tail”？>

公开(公告)号：US06348135B1

公开(公告)日：2002-02-19

申请号：US09521434

申请日：2000-03-08

申请人： Sei Nakahara ,  Yukihiro Matsumoto ,  Masatoshi Ueoka

发明人： Sei Nakahara ,  Yukihiro Matsumoto ,  Masatoshi Ueoka

IPC分类号： B01D334

CPC分类号： C07C51/44 ,  C07C67/54 ,  Y10S203/22 ,  Y10S203/90 ,  C07C57/04 ,  C07C69/54

摘要： In a process for the purification of (meth)acrylic acid and/or its ester using a distillation unit containing a distillation column, a multitubular reboiler and a pipe connecting these elements, an oxygen containing gas is supplied from a least one point in regions between the distillation column and an inlet of the multitubular reboiler and/or in regions between the inlet and an inlet side tube sheet of the multitubular reboiler. This process can effectively prevent the formation of polymerization products and can stably purify (meth)acrylic acid and/or its ester over a long time.

摘要翻译： 在使用含有蒸馏塔，多管再沸器和连接这些元素的管道的蒸馏装置来纯化（甲基）丙烯酸和/或其酯的方法中，含氧气体从至少一个点在 蒸馏塔和多管再沸器的入口和/或在多管再沸器的入口和入口侧管板之间的区域中。 该方法可以有效地防止聚合产物的形成，并且可以长时间稳定地纯化（甲基）丙烯酸和/或其酯。

公开(公告)号：US06649787B1

公开(公告)日：2003-11-18

申请号：US09684396

申请日：2000-10-10

申请人： Sei Nakahara ,  Masatoshi Ueoka

发明人： Sei Nakahara ,  Masatoshi Ueoka

IPC分类号： C07C6952

CPC分类号： C07C67/08 ,  C07C67/54 ,  C07C69/54

摘要： An improvement is provided in a method for preparing an (meth)acrylic acid ester comprising an esterification step for forming the (meth)acrylic acid ester by esterification reaction between (meth)acrylic acid and the corresponding aliphatic alcohol having 1 to 4 carbon atoms in the presence of an acidic catalyst, and a separation-purification step comprising an acid-separating column, a low boiling matter-separating column and a rectification column for separating and purifying the (meth)acrylic acid ester from the (meth)acrylic acid ester-containing mixture obtained in the esterification step. This improvement lies in that by circulating the bottom residue of the rectification column into the esterification step and/or the separation-purification step, the remaining polymerization inhibitor in the bottom residue is effectively reused and the remaining (meth)acrylic acid ester in the bottom residue is efficiently recovered.

摘要翻译： 在（甲基）丙烯酸酯的制备方法中提供了改进，所述方法包括通过（甲基）丙烯酸和相应的具有1至4个碳原子的脂族醇之间的酯化反应形成（甲基）丙烯酸酯的酯化步骤 酸性催化剂的存在和分离纯化步骤，其包括酸分离塔，低沸点物分离塔和精馏塔，用于从（甲基）丙烯酸酯分离和纯化（甲基）丙烯酸酯 在酯化步骤中获得的混合物。 这种改进在于，通过使精馏塔的底部残留物循环到酯化步骤和/或分离纯化步骤中，底部残留物中的剩余聚合抑制剂被有效地再利用，并且底部的剩余的（甲基）丙烯酸酯 残留物有效回收。

公开(公告)号：US06482981B2

公开(公告)日：2002-11-19

申请号：US09753810

申请日：2001-01-03

申请人： Kouji Ueno ,  Masatoshi Ueoka ,  Sei Nakahara

发明人： Kouji Ueno ,  Masatoshi Ueoka ,  Sei Nakahara

IPC分类号： C07C5142

CPC分类号： C07C51/43 ,  C07C51/252 ,  C07C51/46 ,  C07C57/04

摘要： A method of producing highly purified acrylic acid in a high yield is provided. A method of producing acrylic acid including the steps of an oxidation step, an absorption step, a distillation step, a crystallization step, and a dimer decomposition step.

摘要翻译： 提供了以高产率生产高纯度丙烯酸的方法。 一种生产丙烯酸的方法，包括以下步骤：氧化步骤，吸收步骤，蒸馏步骤，结晶步骤和二聚体分解步骤。

公开(公告)号：US06966973B2

公开(公告)日：2005-11-22

申请号：US10186569

申请日：2002-07-01

申请人： Sei Nakahara ,  Kazuhiko Sakamoto ,  Yukihiro Matsumoto ,  Kenji Sanada ,  Masatoshi Ueoka

发明人： Sei Nakahara ,  Kazuhiko Sakamoto ,  Yukihiro Matsumoto ,  Kenji Sanada ,  Masatoshi Ueoka

IPC分类号： B01D3/00 ,  B01D3/32 ,  B01J19/02 ,  C07B61/00 ,  C07C51/235 ,  C07C51/25 ,  C07C51/44 ,  C07C57/05 ,  C22C38/00 ,  B01V19/00

CPC分类号： C07C51/252 ,  B01D3/225 ,  B01D3/322 ,  B01J19/02 ,  B01J2219/00101 ,  B01J2219/0277 ,  C07C51/44 ,  Y10S159/15 ,  C07C57/04

摘要： The present invention provides an apparatus for producing (meth)acrylic acid and a process for producing (meth)acrylic acid with this apparatus wherein the apparatus enables the production of (meth)acrylic acid stably for a long period of time by effectively inhibiting the polymerization of (meth)acrylic acid in its production process (for example, in a reboiler). At least a part of the apparatus is made of a nickel-chromium-iron alloy with a molybdenum content of 3 to 20 mass %, but not including 3 mass %, or with a molybdenum content of 1 to 4 mass % and a copper content of 0.5 to 7 mass %.

摘要翻译： 本发明提供一种用于生产（甲基）丙烯酸的装置和用于生产（甲基）丙烯酸的方法，该装置能够通过有效地抑制聚合来长时间稳定地生产（甲基）丙烯酸 的（甲基）丙烯酸在其制备方法中（例如，在再沸器中）。 该装置的至少一部分由钼含量为3〜20质量％，但不包括3质量％，或者含有1〜4质量％的钼含量和铜含量的镍 - 铬 - 铁合金 为0.5〜7质量％。