公开(公告)号：US20110201848A1

公开(公告)日：2011-08-18

申请号：US13124973

申请日：2009-10-19

申请人： Hirofumi Ii ,  Tomoyuki Itou ,  Yoshiki Kawamura ,  Toshiyuki Matsushita

发明人： Hirofumi Ii ,  Tomoyuki Itou ,  Yoshiki Kawamura ,  Toshiyuki Matsushita

IPC分类号： C07C29/136 ,  C07C35/14

CPC分类号： C07C29/149 ,  C07C29/80 ,  C07C31/20

摘要： There is provided a process for preparing 1,6-hexanediol by esterifying a carboxylic acid mixture resulted from oxidation of cyclohexane with oxygen, and then hydrogenating the esters, which substantially does not contain a compound leading to a high ester value.A process for preparing 1,6-hexanediol from a carboxylic acid mixture containing adipic acid and 6-hydroxycaproic acid, the carboxylic acid mixture is obtained as a by-product in oxidization of cyclohexane to cyclohexanone/cyclohexanol using oxygen or an oxygen-containing gas, the process comprises esterifying the acids with an alcohol, followed by hydrogenation, and the process is characterized by comprising the following steps of: a) separating a component having a boiling point lower than that of water and the alcohol used in the esterification from a mixture obtained by the hydrogenation in a first distillation step; b) separating an EV component having a boiling point higher than that of 1,6-hexanediol further in a second distillation step; c) separating an EV component having a boiling point lower than that of 1,6-hexanediol further in a third distillation step; and then d) obtaining 1,6-hexanediol in a fourth distillation step, in this order.

摘要翻译： 提供了通过用氧气将环己烷氧化产生的羧酸混合物酯化制备1,6-己二醇然后氢化基本上不含导致高酯值的化合物的酯的方法。 从含有己二酸和6-羟基己酸的羧酸混合物制备1,6-己二醇的方法，羧酸混合物是使用氧或含氧气体将环己烷氧化成环己酮/环己醇的副产物 ，该方法包括用醇将酸酯化，然后氢化，该方法的特征在于包括以下步骤：a）将沸点低于水的组分和用于酯化的醇从 在第一蒸馏步骤中通过氢化获得的混合物; b）在第二蒸馏步骤中进一步分离沸点高于1,6-己二醇的EV组分; c）在第三蒸馏步骤中进一步分离沸点低于1,6-己二醇的EV组分; 然后d）在第四蒸馏步骤中依次得到1,6-己二醇。

公开(公告)号：US20100137625A1

公开(公告)日：2010-06-03

申请号：US12598700

申请日：2008-05-15

申请人： Hirofumi II

发明人： Hirofumi II

IPC分类号： C07F1/08 ,  C07C27/04

CPC分类号： B01J23/80 ,  B01J23/72 ,  B01J35/006 ,  B01J37/18 ,  C07C29/149 ,  C07C67/08 ,  C07C31/20 ,  C07C69/44 ,  C07C69/42 ,  C07C69/675

摘要： An objective is to provide a process for preparing 1,5-pentanediol and/or 1,6-hexanediol comprising esterifying, with an alcohol such as methanol, ethanol, butanol or 1,6-hexanediol, a mixture of carboxylic acids such as glutaric acid, adipic acid and 6-hydroxycaproic acid which are a by-product in preparation of cyclohexanone by oxidation of cyclohexane with oxygen or an oxygen-containing gas; and hydrogenating the resulting esterified product in the presence of a copper-containing catalyst, which process is an industrially suitable process for preparing 1,5-pentanediol and/or 1,6-hexanediol in a high yield while controlling deterioration of the catalyst. The above objective is achieved by hydrogenating the esterified product with a catalyst obtained by prereducing a copper-containing catalyst in an alcohol having an acid value (AV) of 0.5 mg KOH/g or less or an ester having an acid value (AV) of 0.5 mg KOH/g or less.

摘要翻译： 目的是提供一种制备1,5-戊二醇和/或1,6-己二醇的方法，其包括用醇如甲醇，乙醇，丁醇或1,6-己二醇酯化，羧酸如戊二酸的混合物 酸，己二酸和6-羟基己酸，它们是通过用氧或含氧气体氧化环己烷而制备环己酮的副产物; 并在含铜催化剂的存在下氢化所得酯化产物，该方法是工业上合适的方法，以高产率制备1,5-戊二醇和/或1,6-己二醇，同时控制催化剂的劣化。 上述目的是通过将酸性值（AV）为0.5mgKOH / g以下的醇中还原含铜催化剂或酸值（AV）为0.5以下的酯来获得的催化剂氢化酯化物， 0.5mg KOH / g以下。

公开(公告)号：US20050038282A1

公开(公告)日：2005-02-17

申请号：US10946475

申请日：2004-09-21

申请人： Ryoji Sugise ,  Shuji Tanaka ,  Hirofumi Ii ,  Kazuaki Mii

发明人： Ryoji Sugise ,  Shuji Tanaka ,  Hirofumi Ii ,  Kazuaki Mii

IPC分类号： C07C201/04 ,  C07C203/00 ,  C07C23/02

CPC分类号： C07C201/04 ,  C07C203/00

摘要： An alkyl nitrite is produced with high efficiency by bringing a nitrogen monoxide gas into contact with an aqueous solution of an alkyl alcohol and nitric acid in a reactor 2, which aqueous solution may be a liquid fraction generated in an alkyl nitrite-production process in which an alkyl alcohol is reacted with nitrogen monoxide and oxygen in a reaction column 1.

摘要翻译： 通过在反应器2中使一氧化氮气体与烷基醇和硝酸的水溶液接触，可以高效率地生产亚硝酸烷基酯，该水溶液可以是在亚硝酸烷基酯制备方法中产生的液体馏分，其中 在反应塔1中使烷基醇与一氧化氮和氧气反应。

公开(公告)号：US09174918B2

公开(公告)日：2015-11-03

申请号：US13522979

申请日：2011-01-20

申请人： Shuji Tanaka ,  Hirofumi Ii

发明人： Shuji Tanaka ,  Hirofumi Ii

IPC分类号： C07C67/02 ,  C07C67/03 ,  C07C68/00 ,  C08G64/30

CPC分类号： C07C67/03 ,  C07C68/00 ,  C08G64/307 ,  C07C69/36 ,  C07C69/96

摘要： Disclosed is a process for preparing a diaryl oxalate which comprises the step of transesterifying a dialkyl oxalate or/and an alkylaryl oxalate with an aryl alcohol in the presence of a tetra(aryloxy)titanium as a catalyst, wherein the tetra(aryloxy)titanium is fed into a reaction system of the transesterification as an aryl alcohol solution of the tetra(aryloxy)titanium which is prepared by reacting a tetraalkoxy titanium and an excess amount of the aryl alcohol and removing a by-producing alkyl alcohol.

摘要翻译： 公开了一种制备草酸二芳基酯的方法，其包括在四（芳氧基）钛作为催化剂存在下，使草酸二烷基酯和/或草酸烷基芳基酯与芳基醇酯交换的步骤，其中四（芳氧基）钛为 加入作为四（芳氧基）钛的芳基醇溶液的酯交换反应体系，其通过使四烷氧基钛和过量的芳基醇反应并除去副产物烷基醇制备。

公开(公告)号：US08304585B2

公开(公告)日：2012-11-06

申请号：US12087422

申请日：2007-01-12

申请人： Hirofumi Ii ,  Tomoyuki Ito ,  Yoshiki Kawamura ,  Toshiyuki Matsushita

发明人： Hirofumi Ii ,  Tomoyuki Ito ,  Yoshiki Kawamura ,  Toshiyuki Matsushita

IPC分类号： C07C27/04 ,  C07C27/00 ,  C07C27/26 ,  C07C69/74

CPC分类号： C07C29/149 ,  C07C29/80 ,  C07C67/03 ,  C07C67/08 ,  C07C69/675 ,  C07C69/44 ,  C07C31/20

摘要： A method is provided for producing highly pure 1,6-hexanediol in which the contents of impurities such as 1,4-cyclohexanediol, 1,5-hexanediol, 1,2-cyclohexanediol, 1,7-pentanediol, 1,5-pentanediol and high boiling point components are significantly reduced. The process contains the steps of (1) treating an aqueous extraction concentrate of a reaction mixture obtained by oxidation of cyclohexane with a lower alcohol to esterify monocarboxylic acids and dicarboxylic acids contained in the extract, and simultaneously removing and separating by distillation water, excess lower alcohols and carboxylic acid esters; (2) converting oligomer esters contained in the bottom liquid to carboxylic acid esters by depolymerizing the oligomer esters at a high temperature and high pressure in the presence of a lower alcohol and a catalyst; and (3) hydrogenating the carboxylic acid esters distilled off in step (1) and the carboxylic acid esters obtained in step (2) either respectively or collectively to convert to 1,6-hexanediol.

摘要翻译： 提供了一种制备高纯度1,6-己二醇的方法，其中杂质含量如1,4-环己二醇，1,5-己二醇，1,2-环己二醇，1,7-戊二醇，1,5-戊二醇 高沸点成分显着降低。 该方法包括以下步骤：（1）通过用低级醇将环己烷氧化得到的反应混合物的水提取浓缩物处理以酯化提取物中所含的一元羧酸和二羧酸，同时通过蒸馏水除去和分离，过量的 醇和羧酸酯; （2）通过在低级醇和催化剂的存在下在高温高压下使低聚物酯解聚，将底部液体中所含的低聚物酯转化为羧酸酯; 和（3）分别或共同地氢化步骤（1）中馏出的羧酸酯和步骤（2）中获得的羧酸酯以转化为1,6-己二醇。

公开(公告)号：US20090048471A1

公开(公告)日：2009-02-19

申请号：US12087422

申请日：2007-01-12

申请人： Hirofumi Ii ,  Tomoyuki Ito ,  Yoshiki Kawamura ,  Toshiyuki Matsushita

发明人： Hirofumi Ii ,  Tomoyuki Ito ,  Yoshiki Kawamura ,  Toshiyuki Matsushita

IPC分类号： C07C29/48

CPC分类号： C07C29/149 ,  C07C29/80 ,  C07C67/03 ,  C07C67/08 ,  C07C69/675 ,  C07C69/44 ,  C07C31/20

摘要： A method is provided for obtaining highly pure 1,6-hexanediol in which the contents of impurities such as 1,4-cyclohexanediol, 1,5-hexanediol, 1,2-cyclohexanediol, 1,7-pentanediol, 1,5-pentanediol and high boiling point components are significantly reduced.This process for producing 1,6-hexanediol from cyclohexane comprises the steps of: (1) treating an aqueous extraction concentrate of a reaction mixture obtained by oxidation of cyclohexane with a lower alcohol to esterify monocarboxylic acids and dicarboxylic acids contained in the extract, and simultaneously remove and separate by distillation water, excess lower alcohols and carboxylic acid esters; (2) converting oligomer esters contained in the bottom liquid to carboxylic acid esters by depolymerizing the oligomer esters at a high temperature and high pressure in the presence of a lower alcohol and a catalyst; and (3) hydrogenating the carboxylic acid esters distilled off in the step (1) and the carboxylic acid esters obtained in the step (2) either respectively or collectively to convert to 1,6-hexanediol.

摘要翻译： 提供了一种获得高纯度1,6-己二醇的方法，其中杂质含量如1,4-环己二醇，1,5-己二醇，1,2-环己二醇，1,7-戊二醇，1,5-戊二醇 高沸点成分显着降低。 用于从环己烷生产1,6-己二醇的方法包括以下步骤：（1）通过用低级醇氧化环己烷得到的反应混合物的水提取浓缩物，以酯化提取物中所含的一元羧酸和二羧酸， 同时通过蒸馏水，过量的低级醇和羧酸酯去除和分离; （2）通过在低级醇和催化剂的存在下在高温高压下使低聚物酯解聚，将底部液体中所含的低聚物酯转化为羧酸酯; 和（3）分别或共同地氢化步骤（1）中蒸馏的羧酸酯和步骤（2）中获得的羧酸酯以转化为1,6-己二醇。

公开(公告)号：US5731453A

公开(公告)日：1998-03-24

申请号：US814089

申请日：1997-03-10

申请人： Keigo Nishihira ,  Shuji Tanaka ,  Yuki Nishida ,  Hirofumi Ii ,  Satoru Fujitsu ,  Katsumasa Harada ,  Ryoji Sugise ,  Koichi Kashiwagi ,  Takashi Doi

发明人： Keigo Nishihira ,  Shuji Tanaka ,  Yuki Nishida ,  Hirofumi Ii ,  Satoru Fujitsu ,  Katsumasa Harada ,  Ryoji Sugise ,  Koichi Kashiwagi ,  Takashi Doi

IPC分类号： C07C67/02 ,  C07C67/03 ,  C07C68/00 ,  C07C69/36 ,  C07C69/96

CPC分类号： C07C67/03 ,  C07C68/00 ,  Y02P20/127

摘要： A diaryl carbonate with a high degree of purity is produced at a high yield by (A) subjecting (a) a diaryl oxalate and a phenol compound or (b) an alkylaryl oxalate to transesterification reaction in one or two stages in the presence of a catalyst to prepare a diaryl oxalate, while removing a by-product from the reaction system; (B) collecting the diaryl oxalate from the resultant reaction product mixture of the step (A); (C) subjecting the diaryl oxalate to a decarbonylation reaction, preferably in the presence of a phosphorous compound-containing catalyst, to convert the diaryl oxalate to a corresponding diaryl carbonate, while removing a reaction by-product comprising carbon monoxide from the reaction system; and (D) collecting the diaryl carbonate from the reaction product mixture of the step (C).

摘要翻译： 通过（A）在（a）草酸二芳基酯和酚化合物或（b）草酸烷基芳基酯在一个或两个阶段中存在下进行酯交换反应，以高产率生产具有高纯度的碳酸二芳基酯 催化剂，以制备草酸二芳基酯，同时从反应体系中除去副产物; （B）从所得步骤（A）的反应产物混合物中收集草酸二芳基酯; （C）优选在含磷化合物的催化剂存在下使草酸二芳基酯进行脱羰反应，将草酸二芳基酯转化为相应的碳酸二芳基酯，同时从反应体系中除去包含一氧化碳的反应副产物; 和（D）从步骤（C）的反应产物混合物中收集碳酸二芳基酯。

公开(公告)号：US5705677A

公开(公告)日：1998-01-06

申请号：US757070

申请日：1996-11-26

申请人： Keigo Nishihira ,  Shuji Tanaka ,  Yuki Nishida ,  Hirofumi Ii ,  Satoru Fujitsu

发明人： Keigo Nishihira ,  Shuji Tanaka ,  Yuki Nishida ,  Hirofumi Ii ,  Satoru Fujitsu

IPC分类号： C07C69/017 ,  C07C69/36

CPC分类号： C07C69/017 ,  C07C69/36

摘要： A novel crystalline adduct of diphenyl oxalate and phenol in a molar ratio of 1:2 and having a high purity is produced by melting a mixture containing diphenyl oxalate and phenol at a temperature of 100.degree. C. or more; cooling the melt to a temperature of less than 100.degree. C. to allow a resultant adduct of diphenyl oxalate and phenol in a molar ratio of 1:2 to crystallize and deposit from the melt; and collecting the crystalline adduct. Diphenyl oxalate with a high purity is produced by melting the crystalline adduct to dissociate it into diphenyl oxalate and phenol, and evaporating away the dissociated phenol from the melt to collect the dissociated diphenyl oxalate.

摘要翻译： 通过在100℃或更高的温度下熔化含有草酸二苯酯和苯酚的混合物，产生摩尔比为1:2且具有高纯度的草酸二苯酯和苯酚的新型结晶加合物; 将熔体冷却至低于100℃的温度，使所得到的草酸二苯酯和苯酚的摩尔比为1:2的加合物从熔体中结晶和沉积; 并收集结晶加合物。 通过熔化结晶加合物将其分解成草酸二苯酯和苯酚，并将离解的苯酚从熔体中蒸发掉以收集离解的草酸二苯酯，从而产生高纯度的二苯基草酸盐。

公开(公告)号：US06472498B2

公开(公告)日：2002-10-29

申请号：US09923466

申请日：2001-08-06

申请人： Ryoji Sugise ,  Shuji Tanaka ,  Kohichi Kashiwagi ,  Takashi Doi ,  Hirofumi Ii ,  Masayuki Nishio ,  Shinichi Yoshida ,  Yutaka Asada ,  Kazuo Miyamoto

发明人： Ryoji Sugise ,  Shuji Tanaka ,  Kohichi Kashiwagi ,  Takashi Doi ,  Hirofumi Ii ,  Masayuki Nishio ,  Shinichi Yoshida ,  Yutaka Asada ,  Kazuo Miyamoto

IPC分类号： C08G6400

CPC分类号： C07C68/08 ,  C07C69/96 ,  C08G64/307

摘要： A composition consisting essentially of a diaryl carbonate and contains a furan ring-containing compound in an amount of not more than 1 ppm is favorably employable for producing less colored polycarbonate.

摘要翻译： 基本上由碳酸二芳酯组成并且含有不超过1ppm的含呋喃环的化合物的组合物有利地用于制备较少着色的聚碳酸酯。

公开(公告)号：US5892089A

公开(公告)日：1999-04-06

申请号：US944231

申请日：1997-10-06

申请人： Katsumasa Harada ,  Ryoji Sugise ,  Koichi Kashiwagi ,  Yoichi Imbe ,  Takashi Doi ,  Keigo Nishihira ,  Shuji Tanaka ,  Hirofumi Ii

发明人： Katsumasa Harada ,  Ryoji Sugise ,  Koichi Kashiwagi ,  Yoichi Imbe ,  Takashi Doi ,  Keigo Nishihira ,  Shuji Tanaka ,  Hirofumi Ii

IPC分类号： C07C68/00

CPC分类号： C07C68/00

摘要： A process for preparing a diaryl carbonate from a diaryl oxalate in a liquid phase by decarbonylation is conducted by the steps of:1) performing a decarbonylation reaction of a diaryl oxalate in the presence of an organic phosphorus compound catalyst to give a reaction mixture of a diaryl carbonate and the organic phosphorus compound catalyst;2) recovering the diaryl carbonate from the reaction mixture; and3) performing a decarbonylation reaction of a diaryl oxalate in the presence of the reaction mixture from which the diaryl carbonate has been recovered and to which a halogen atom-containing compound is added, to give a reaction mixture of a diaryl carbonate and the organic phosphorus compound catalyst.

摘要翻译： 通过脱羰由草酸二芳基酯在液相中制备碳酸二芳基酯的方法是通过以下步骤进行的：1）在有机磷化合物催化剂存在下进行草酸二芳基酯的脱羰基化反应，得到 碳酸二芳酯和有机磷化合物催化剂; 2）从反应混合物中回收碳酸二芳基酯; 和3）在已经回收了碳酸二芳基酯并且含有含卤原子的化合物的反应混合物存在下进行草酸二芳酯的脱羰基反应，得到碳酸二芳基酯和有机物的反应混合物 磷化合物催化剂。