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1. 发明申请

US20090048425A1 PROCESS FOR PRODUCTION OF CYCLOOLEFIN 有权
标题翻译：生产环烯醇的方法
公开(公告)号：US20090048425A1
公开(公告)日：2009-02-19
申请号：US11912575
申请日：2006-08-18
申请人： Mitsuo Konishi , Teruhiko Inoue
发明人： Mitsuo Konishi , Teruhiko Inoue
IPC分类号： C08G61/10
CPC分类号： B01J23/46 , B01J23/60 , B01J23/96 , B01J27/053 , B01J38/64 , C07C5/11 , C07C2523/46 , C07C2527/053 , C07C2601/16 , Y02P20/584
摘要： According to the present invention, when cycloolefins are produced by partially hydrogenating a monocyclic aromatic hydrocarbon with hydrogen in the presence of a ruthenium catalyst, water, and a metal sulfate, the decrease in catalytic activity and cycloolefin selectivity is suppressed by reducing the concentration of chloride ions dissolved in the water in which the catalyst is present to 300 wt ppm or less and regenerating a part or all of the catalyst for reuse. Zinc sulfate is preferably used as the metal sulfate. Further, the raw materials and catalyst to be supplied to the reaction preferably have a reduced chloride ion content. This method can suppress the decrease in long-term catalytic activity and cycloolefin selectivity. Furthermore, the catalytic activity and cycloolefin selectivity after catalyst regeneration can be maintained at a high level. As a result, cycloolefins can be efficiently produced for a long period of time.
摘要翻译：根据本发明，当在钌催化剂，水和金属硫酸盐的存在下，通过氢气使单环芳族烃部分氢化制备环烯烃时，通过降低氯化物的浓度来抑制催化活性和环烯选择性的降低溶解在其中存在催化剂的水中的离子为300重量ppm以下，再生部分或全部催化剂用于再利用。硫酸锌优选用作金属硫酸盐。此外，供给反应的原料和催化剂优选具有减少的氯离子含量。该方法可以抑制长期催化活性和环烯烃选择性的降低。此外，催化剂再生后的催化活性和环烯选择性可以保持在高水平。因此，可以长时间有效地制造环烯烃。

2. 发明授权

US07947859B2 Process for production of cycloolefin 有权
标题翻译：环烯生产工艺
公开(公告)号：US07947859B2
公开(公告)日：2011-05-24
申请号：US11912575
申请日：2006-08-18
申请人： Mitsuo Konishi , Teruhiko Inoue
发明人： Mitsuo Konishi , Teruhiko Inoue
IPC分类号： C07C5/11 , C07C5/10
CPC分类号： B01J23/46 , B01J23/60 , B01J23/96 , B01J27/053 , B01J38/64 , C07C5/11 , C07C2523/46 , C07C2527/053 , C07C2601/16 , Y02P20/584
摘要： According to the present invention, when cycloolefins are produced by partially hydrogenating a monocyclic aromatic hydrocarbon with hydrogen in the presence of a ruthenium catalyst, water, and a metal sulfate, the decrease in catalytic activity and cycloolefin selectivity is suppressed by reducing the concentration of chloride ions dissolved in the water in which the catalyst is present to 300 wt ppm or less and regenerating a part or all of the catalyst for reuse. Zinc sulfate is preferably used as the metal sulfate. Further, the raw materials and catalyst to be supplied to the reaction preferably have a reduced chloride ion content. This method can suppress the decrease in long-term catalytic activity and cycloolefin selectivity. Furthermore, the catalytic activity and cycloolefin selectivity after catalyst regeneration can be maintained at a high level. As a result, cycloolefins can be efficiently produced for a long period of time.
摘要翻译：根据本发明，当在钌催化剂，水和金属硫酸盐的存在下，通过氢气使单环芳族烃部分氢化制备环烯烃时，通过降低氯化物的浓度来抑制催化活性和环烯选择性的降低溶解在其中存在催化剂的水中的离子为300重量ppm以下，再生部分或全部催化剂用于再利用。硫酸锌优选用作金属硫酸盐。此外，供给反应的原料和催化剂优选具有减少的氯离子含量。该方法可以抑制长期催化活性和环烯烃选择性的降低。此外，催化剂再生后的催化活性和环烯选择性可以保持在高水平。因此，可以长时间有效地制造环烯烃。

3. 发明申请

US20110257449A1 METHOD FOR PREPARING RUTHENIUM CATALYST FOR PRODUCING CYCLOOLEFIN AND METHOD AND APPARATUS FOR PRODUCING CYCLOOLEFIN 有权
标题翻译：制备环烯烃的钌催化剂的制备方法和制备环烯烃的方法和装置
公开(公告)号：US20110257449A1
公开(公告)日：2011-10-20
申请号：US13141146
申请日：2009-11-19
申请人： Mitsuo Konishi , Masakazu Sato
发明人： Mitsuo Konishi , Masakazu Sato
IPC分类号： C07C5/11 , B01J37/18 , B01J8/00
CPC分类号： B01J19/24 , B01J21/066 , B01J23/462 , B01J23/60 , B01J23/6522 , B01J23/8913 , B01J23/8953 , B01J35/006 , B01J37/031 , B01J37/14 , B01J37/18 , B01J2219/24 , C07C5/11 , C07C2523/46 , C07C2601/16 , C07C13/16 , C07C13/20
摘要： A method for preparing a ruthenium catalyst, including a step of reducing a ruthenium catalyst precursor by holding the ruthenium catalyst precursor in an aqueous solution containing a metal salt at a temperature within the range of more than 180° C. and 220° C. or less and a hydrogen partial pressure within the range of 0.6 MPa or more and 5 MPa or less. A method for producing a cycloolefin, including a step of preparing a ruthenium catalyst by the method including a step of reducing a ruthenium catalyst precursor in an aqueous solution containing a metal salt by holding the ruthenium catalyst precursor at a temperature within the range of more than 180° C. and 220° C. or less and a hydrogen partial pressure within the range of 0.6 MPa or more and 5 MPa or less, and a step of partially hydrogenating a monocyclic aromatic hydrocarbon by use of the ruthenium catalyst obtained.
摘要翻译：一种制备钌催化剂的方法，包括通过将钌催化剂前体在含有金属盐的水溶液中在大于180℃和220℃的温度范围内保持来还原钌催化剂前体的步骤，或 0.6MPa以上且5MPa以下的氢分压。一种制备环烯烃的方法，包括通过以下方法制备钌催化剂的步骤：将含有金属盐的水溶液中的钌催化剂前体还原，在钌催化剂前体的保持温度范围内， 180℃，220℃以下，氢分压在0.6MPa以上且5MPa以下的范围，以及通过使用得到的钌催化剂部分氢化单环芳烃的工序。

4. 发明授权

US09056309B2 Method for preparing ruthenium catalyst for producing cycloolefin and method and apparatus for producing cycloolefin 有权
标题翻译：制备环烯烃的钌催化剂的制备方法和制备环烯烃的方法和装置
公开(公告)号：US09056309B2
公开(公告)日：2015-06-16
申请号：US13141146
申请日：2009-11-19
申请人： Mitsuo Konishi , Masakazu Sato
发明人： Mitsuo Konishi , Masakazu Sato
IPC分类号： B01J37/16 , B01J37/18 , C07C5/11 , B01J23/60 , B01J23/46 , B01J23/652 , B01J23/89 , B01J35/00 , B01J37/03 , B01J37/14 , B01J21/06
CPC分类号： B01J19/24 , B01J21/066 , B01J23/462 , B01J23/60 , B01J23/6522 , B01J23/8913 , B01J23/8953 , B01J35/006 , B01J37/031 , B01J37/14 , B01J37/18 , B01J2219/24 , C07C5/11 , C07C2523/46 , C07C2601/16 , C07C13/16 , C07C13/20
摘要： A method for preparing a ruthenium catalyst, including a step of reducing a ruthenium catalyst precursor by holding the ruthenium catalyst precursor in an aqueous solution containing a metal salt at a temperature within the range of more than 180° C. and 220° C. or less and a hydrogen partial pressure within the range of 0.6 MPa or more and 5 MPa or less. A method for producing a cycloolefin, including a step of preparing a ruthenium catalyst by the method including a step of reducing a ruthenium catalyst precursor in an aqueous solution containing a metal salt by holding the ruthenium catalyst precursor at a temperature within the range of more than 180° C. and 220° C. or less and a hydrogen partial pressure within the range of 0.6 MPa or more and 5 MPa or less, and a step of partially hydrogenating a monocyclic aromatic hydrocarbon by use of the ruthenium catalyst obtained.
摘要翻译：一种制备钌催化剂的方法，包括通过将钌催化剂前体在含有金属盐的水溶液中在大于180℃和220℃的温度范围内保持来还原钌催化剂前体的步骤，或 0.6MPa以上且5MPa以下的氢分压。一种制备环烯烃的方法，包括通过以下方法制备钌催化剂的步骤：将含有金属盐的水溶液中的钌催化剂前体还原，在钌催化剂前体的保持温度范围内， 180℃，220℃以下，氢分压在0.6MPa以上且5MPa以下的范围，以及通过使用得到的钌催化剂部分氢化单环芳烃的工序。

5. 发明申请

US20110130600A1 METHOD FOR PRODUCING CYCLOOLEFIN AND PRODUCTION APPARATUS THEREOF 有权
标题翻译：生产环烯烃的方法及其生产装置
公开(公告)号：US20110130600A1
公开(公告)日：2011-06-02
申请号：US13055103
申请日：2009-06-12
申请人： Mitsuo Konishi
发明人： Mitsuo Konishi
IPC分类号： C07C5/11 , B01J8/00
CPC分类号： C07C5/11 , B01J23/462 , B01J23/96 , B01J38/70 , C07C2523/46 , Y02P20/584
摘要： There is provided a method for producing cycloolefin where the nickel which elutes in the liquid-contact portion of the reactor is removed from the reaction system of the partial hydrogenation reaction and cycloolefin can be stably produced from a monocyclic aromatic hydrocarbon over a long term. A method for producing a cycloolefin by a partial hydrogenation reaction of a monocyclic aromatic hydrocarbon in an aqueous phase, which contains a metal salt-containing acidic aqueous solution and a ruthenium catalyst in a reactor with a liquid-contact portion formed of a nickel-containing material, the method comprising a first step of bringing at least a part of the ruthenium catalyst contained in the aqueous phase into contact with oxygen, a second step of separating the aqueous phase containing the ruthenium catalyst that has been processed in the first step into a first phase containing the ruthenium catalyst at a high ratio and a second phase containing the ruthenium catalyst at a lower ratio than the first phase, and a third step of feeding the first phase to a reaction system of a partial hydrogenation reaction.
摘要翻译：提供一种生产环烯烃的方法，其中在反应器的液体接触部分中洗脱的镍从部分氢化反应的反应体系中除去和环烯烃可以从单环芳烃长期稳定地制备。通过在含有含金属盐的酸性水溶液和钌催化剂的水相中的单环芳烃的部分氢化反应制备环烯烃的方法，所述反应器中的液体接触部分由含镍的材料，所述方法包括使含有水相中的钌催化剂的至少一部分与氧接触的第一步骤，将在第一步骤中处理的含有钌催化剂的水相分离成第一步骤，第一阶段以高比例含有钌催化剂，第二相含有比第一相低的钌催化剂，第三步是将第一相进料到部分氢化反应的反应体系中。

6. 发明授权

US07005495B2 Polycarbonate diol having high proportion of primary terminal OH 有权
标题翻译：具有高比例的末端OH的聚碳酸酯二醇
公开(公告)号：US07005495B2
公开(公告)日：2006-02-28
申请号：US10275399
申请日：2001-05-24
申请人： Mitsuo Konishi , Tetsuo Masubuchi , Koshiro Yokota
发明人： Mitsuo Konishi , Tetsuo Masubuchi , Koshiro Yokota
IPC分类号： C08G18/44 , C08G64/00 , C08G64/02 , C07C69/96 , C07C69/003
CPC分类号： C08G64/0208 , C08G18/0895 , C08G18/10 , C08G18/44 , C08G64/42 , C08G18/3206
摘要： Disclosed is a polycarbonate diol having diol monomer units and carbonate monomer units, wherein the amount of at least one diol monomer unit selected from the group consisting of a 1,5-pentanediol unit and a 1,6-hexanediol unit is from 50 to 100% by mole, based on the total molar amount of the diol monomer units, and wherein the ratio of primary hydroxyl groups in all terminal groups of the polycarbonate diol is in a specific range. Also disclosed is a thermoplastic polyurethane obtained by copolymerizing the above-mentioned polycarbonate diol and a polyisocyanate.
摘要翻译：公开了具有二醇单体单元和碳酸酯单体单元的聚碳酸酯二醇，其中选自1,5-戊二醇单元和1,6-己二醇单元的至少一种二醇单体单元的量为50〜100 摩尔，基于二醇单体单元的总摩尔量，并且其中聚碳酸酯二醇的所有端基中的伯羟基的比例在特定范围内。还公开了通过使上述聚碳酸酯二醇和多异氰酸酯共聚得到的热塑性聚氨酯。

7. 发明授权

US06323300B1 Aromatic copolymer and composition containing the same 失效
标题翻译：芳族共聚物和含有它们的组合物
公开(公告)号：US06323300B1
公开(公告)日：2001-11-27
申请号：US09308589
申请日：1999-05-21
申请人： Kohei Kita , Tsuneaki Tanabe , Mitsuo Konishi
发明人： Kohei Kita , Tsuneaki Tanabe , Mitsuo Konishi
IPC分类号： C08G6514
CPC分类号： C08G65/44 , Y10T428/31551
摘要： Disclosed is an aromatic copolymer comprising a plurality of aromatic copolymer chains, each comprising (A) recurring 2,6-diphenylphenol units and (B) phenolic comonomer units, each comonomer unit being independently selected from the group consisting of (i) an oxyphenylene monomer unit which is monosubstituted with a monovalent aromatic group or a halogen atom, (ii) an &agr;-oxynaphthylene monomer unit, (iii) a &bgr;-oxynaphthylene monomer unit, and (iv) an oxyphenylene monomer unit which is substituted with at least one aliphatic group, wherein the amounts of (A) and (B) are from 50 to 98% by weight and from 2 to 50% by weight, based on the weight of the aromatic copolymer, provided that, when (iv) is present as the comonomer unit, the amount of (iv) is 20% by weight or less, based on the weight of (B), and wherein the aromatic copolymer has a weight average molecular weight of from 1,000 to 3,000,000. A method for producing the aromatic copolymer is also disclosed. The aromatic copolymer of the present invention has excellent electrical characteristics (such as a low dielectric constant), an excellent heat resistance, excellent film-forming properties, low water absorption properties and an excellent adhesion to other materials, and can be advantageously used as a material for various electronic parts.
摘要翻译：公开了包含多个芳族共聚物链的芳族共聚物，每个芳族共聚物链包含（A）重复的2,6-二苯基苯酚单元和（B）酚类共聚单体单元，每个共聚单体单元独立地选自（i）氧联苯单体被单价芳族基团或卤素原子单取代的单元，（ii）α-氧基萘基单体单元，（iii）β-氧基萘基单体单元，和（iv）被至少一个脂族基团取代的氧亚苯基单体单元基团，其中基于芳族共聚物的重量，（A）和（B）的量为50至98重量％和2至50重量％，条件是当（iv）作为共聚单体单元，基于（B）的重量，（iv）的量为20重量％以下，并且其中所述芳族共聚物的重均分子量为1,000〜3,000,000。还公开了制备芳族共聚物的方法。本发明的芳香族共聚物具有优异的电特性（例如低介电常数），优异的耐热性，优异的成膜性，低吸水性和与其它材料的优异粘附性，并且可以有利地用作各种电子零件的材料。

8. 发明授权

US4734536A Process for producing cycloolefins 失效
标题翻译：环烯烃的制备方法
公开(公告)号：US4734536A
公开(公告)日：1988-03-29
申请号：US914495
申请日：1986-10-02
申请人： Hajime Nagahara , Mitsuo Konishi
发明人： Hajime Nagahara , Mitsuo Konishi
IPC分类号： B01J23/60 , B01J23/62 , B01J23/64 , B01J23/89 , C07C5/11
CPC分类号： B01J23/8953 , B01J23/60 , B01J23/62 , B01J23/628 , B01J23/64 , C07C5/11 , B01J35/006 , C07C2101/16 , C07C2521/04 , C07C2521/06 , C07C2521/08 , C07C2523/08 , C07C2523/20 , C07C2523/26 , C07C2523/46 , C07C2523/745 , C07C2523/75
摘要： A process for producing a cycloolefin in high selectivity and yield by partial hydrogenation of a monocyclic armoatic hydrocarbon with hydrogen is disclosed. In this process, the hydrogenation reaction is carried out under a neutral or acidic condition in the presence of:(i) a particulate hydrogenating catalyst mainly comprising metallic ruthenium having an average crystallite size of 200 .ANG. or less,(ii) at least one zinc compound as a promoter,(iii) at least one additive selected from the group consisting of oxides, hydroxides and hydrates thereof Zr, Hf, Ti, Nb, Ta, Cr, Fe, Co, Al, Ga and Si, and(iv) water.
摘要翻译：公开了通过单氢环状烃与氢的部分氢化以高选择性和产率制备环烯烃的方法。在该方法中，氢化反应在中性或酸性条件下在以下存在下进行：（i）主要包含平均微晶尺寸为200或更小的金属钌的颗粒状氢化催化剂，（ii）至少一种锌化合物作为助催化剂，（iii）至少一种选自氧化物，氢氧化物和水合物的添加剂Zr，Hf，Ti，Nb，Ta，Cr，Fe，Co，Al，Ga和Si，和（iv）水。

9. 发明授权

US09174894B2 Method for producing cycloolefin and production apparatus thereof 有权
标题翻译：环烯烃的制造方法及其制造装置
公开(公告)号：US09174894B2
公开(公告)日：2015-11-03
申请号：US13055103
申请日：2009-06-12
申请人： Mitsuo Konishi
发明人： Mitsuo Konishi
IPC分类号： C07C5/11 , B01J8/00 , B01J23/96 , B01J38/70 , B01J23/46
CPC分类号： C07C5/11 , B01J23/462 , B01J23/96 , B01J38/70 , C07C2523/46 , Y02P20/584
摘要： There is provided a method for producing cycloolefin where the nickel which elutes in the liquid-contact portion of the reactor is removed from the reaction system of the partial hydrogenation reaction and cycloolefin can be stably produced from a monocyclic aromatic hydrocarbon over a long term. A method for producing a cycloolefin by a partial hydrogenation reaction of a monocyclic aromatic hydrocarbon in an aqueous phase, which contains a metal salt-containing acidic aqueous solution and a ruthenium catalyst in a reactor with a liquid-contact portion formed of a nickel-containing material, the method comprising a first step of bringing at least a part of the ruthenium catalyst contained in the aqueous phase into contact with oxygen, a second step of separating the aqueous phase containing the ruthenium catalyst that has been processed in the first step into a first phase containing the ruthenium catalyst at a high ratio and a second phase containing the ruthenium catalyst at a lower ratio than the first phase, and a third step of feeding the first phase to a reaction system of a partial hydrogenation reaction.
摘要翻译：提供一种生产环烯烃的方法，其中在反应器的液体接触部分中洗脱的镍从部分氢化反应的反应体系中除去和环烯烃可以从单环芳烃长期稳定地制备。通过在含有含金属盐的酸性水溶液和钌催化剂的水相中的单环芳烃的部分氢化反应制备环烯烃的方法，所述反应器中的液体接触部分由含镍的材料，所述方法包括使含有水相中的钌催化剂的至少一部分与氧接触的第一步骤，将在第一步骤中处理的含有钌催化剂的水相分离成第一步骤，第一阶段以高比例含有钌催化剂，第二相含有比第一相低的钌催化剂，第三步是将第一相进料到部分氢化反应的反应体系中。

10. 发明授权

US06706932B1 Process for the preparation of diol mixtures 失效
标题翻译：二醇混合物的制备方法
公开(公告)号：US06706932B1
公开(公告)日：2004-03-16
申请号：US10129143
申请日：2002-05-02
申请人： Mitsuo Konishi , Koshiro Yokota , Eizaburou Ueno
发明人： Mitsuo Konishi , Koshiro Yokota , Eizaburou Ueno
IPC分类号： C07C2700
CPC分类号： C07C29/149 , C07C51/42 , C07C31/207 , C07C31/20
摘要： Disclosed is a method for producing a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, which comprises: (A) providing a dicarboxylic acid mixture comprising succinic acid, glutaric acid and adipic acid and having a nitric acid content of 3% by weight or less, based on the total weight of the succinic, glutaric and adipic acids, wherein the dicarboxylic acid mixture is prepared by denitrating an aqueous by-product solution obtained in an adipic acid production process, and (B) subjecting the dicarboxylic acid mixture to hydrogenation in the presence of water, hydrogen gas and a hydrogenation catalyst containing an active metal species comprising ruthenium and tin, to thereby obtain a hydrogenation reaction mixture comprising a diol mixture comprising 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.
摘要翻译：公开了一种制备包含1,4-丁二醇，1,5-戊二醇和1,6-己二醇的二醇混合物的方法，其包括：（A）提供包含琥珀酸，戊二酸和己二酸的二羧酸混合物，并且具有基于琥珀酸，戊二酸和己二酸的总重量计，硝酸含量为3重量％以下，其中二羧酸混合物是通过对在己二酸生产过程中获得的副产物溶液进行脱硝制备的，（B）在水，氢气和含有钌和锡的活性金属物质的氢化催化剂的存在下使二羧酸混合物进行氢化，由此得到包含1,4-丁二醇的二醇混合物的氢化反应混合物， 1,5-戊二醇和1,6-己二醇。

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