WO2007073240A1 - Catalyst, a method for the production thereof and a dihydroxyalkane production method - Google Patents
Catalyst, a method for the production thereof and a dihydroxyalkane production method Download PDFInfo
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- WO2007073240A1 WO2007073240A1 PCT/RU2006/000602 RU2006000602W WO2007073240A1 WO 2007073240 A1 WO2007073240 A1 WO 2007073240A1 RU 2006000602 W RU2006000602 W RU 2006000602W WO 2007073240 A1 WO2007073240 A1 WO 2007073240A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the catalyst method for its preparation and method for producing dihydroxyalkanes
- the invention relates to the field of production of dihydroxyalkanes by catalytic hydrogenation, in particular by catalytic hydrogenation of carboxylic groups of hydroxycarboxylic acids.
- Dihydroxyalkanes such as ethylene glycol and propylene glycol
- ethylene glycol and propylene glycol are used in the manufacture of polyester resins, as part of anti-icing solutions, and in the manufacture of food, cosmetic and medicinal products.
- Propylene glycol in contrast to ethylene glycol, is less toxic.
- propylene glycol is based on organic compounds contained in oil.
- Propylene glycol is obtained by hydration of propylene oxide, the hydrolysis stage of which requires high pressure and high temperature.
- the production of propylene oxide is a complex multi-stage process, characterized by the formation of a large number of by-products and low yield of the target product, which leads to environmental problems.
- a known catalyst for the process of direct reduction of hydroxycarboxylic acids to dihydroxyalkanes consisting of copper deposited in an amount of from 9 to 22 wt.% On silicon dioxide, the surface hydroxyl groups of which can be closed by silanol and / or alkyl groups.
- the catalyst is prepared by the method of impregnation in terms of moisture capacity as follows: silica gel (Sab-O-Sil® BH-5, Sabot® Corroratiop) is dried at a temperature of 12 0 0 C, impregnated with an ethanol solution of copper nitrate hydrate, then the catalyst is restored in a stream of hydrogen at a temperature of 300 ° C for 8 hours
- Hydrogenation of the carboxyl group of the hydroxycarboxylic acid is carried out in the vapor phase at a hydrogen pressure of from less than 0.9 atm to 27.5 atm and a temperature of from 112.5 to 275 ° C.
- a hydrogen pressure of 1 atm under optimal conditions the conversion of lactic acid reaches 7.3% with a selectivity of 75% [US 6455742, C07C29 / 141, 09.24.2002].
- a disadvantage of the known catalyst is the low productivity of the target product.
- the invention solves the problem of increasing the productivity of the process.
- EFFECT increased activity and selectivity of the catalyst
- the problem is solved by the composition of the catalyst for the production of dihydroxyalkanes by catalytic hydrogenation of the carboxyl groups of hydroxycarboxylic acids based on copper and silicon oxide, which contains 22.5-53.1 wt.% Copper.
- the problem is also solved by the method of preparation of the catalyst, which is prepared by reductive thermal decomposition of copper silicate, and a catalyst is obtained which contains 22.5-53.0 wt.% Copper.
- the catalyst is prepared by reductive thermal decomposition in a stream of hydrogen at a temperature of 380-450 0 C for a period of at least 2 hours.
- Natural and synthetic silicates with a given copper content can be used as copper silicate.
- the problem is also solved by the method of producing dihydroxyalkanes by catalytic hydrogenation of the carboxyl groups of hydroxycarboxylic acids at a temperature of 180-200 0 C in the presence of a copper-silicon catalyst, where the catalyst described above is used as a catalyst.
- Example 1 The invention is illustrated by the following examples.
- Example 1 The invention is illustrated by the following examples.
- a catalyst containing 22.5 wt.% Copper is prepared by thermal decomposition of copper silicate in a stream of hydrogen at a temperature of 400 0 C for 2 hours
- the catalyst is used in the hydrogenation reaction of lactic acid.
- a glass / quartz tubular U-shaped thermostatically controlled reactor 0.5 g of a 0.25-0.5 mm fraction catalyst mixed with 0.63 to 1.6 mm fraction quartz glass is placed.
- Set the operating temperature to 200 ° C in the reactor, the flow of hydrogen 10 l / h and meter the aqueous solution of lactic acid (16 wt.%) At a speed of 0.3 ml / h.
- liquid products are collected in a trap and analyzed by gas chromatography.
- the composition of the reaction products 36.8% - propionic acid, 43.7% - propylene glycol, 16.3% - lactic acid.
- composition of the reaction products 29.1% - propionic acid, 66.3% - propylene glycol, 3.4% - lactic acid.
- composition of the reaction products 2.1% - acetic acid, 46.2% - ethylene glycol,
- the use of the proposed catalyst in the process of catalytic hydrogenation of the carboxyl groups of hydroxycarboxylic acids allows to increase the productivity of the target product by increasing the activity and selectivity of the catalyst.
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The intention relates to producing dihydroxialkanes by catalytic hydration, in particular by catalytically hydrating carboxylic groups of hydroxy carboxylic acids. A copper- and silicon oxide-based catalyst whose copper content ranges from 22.5 to 53.0 mass % is also disclosed. The inventive catalyst is produced by a copper silicate reducing thermal decomposition and is used for producing dihydroxialkanes. Said invention makes it possible to increase the catalyst activity and selectivity.
Description
Катализатор, способ его приготовления и способ получения дигидроксиалканов The catalyst, method for its preparation and method for producing dihydroxyalkanes
Изобретение относится к области получения дигидроксиалканов каталитическим гидрированием, в частности каталитическим гидрированием карбоксильных групп гидроксикарбоновых кислот. Дигидроксиалканы, такие как этиленгликоль и пропиленгликоль, находят применение в производстве полиэфирных смол, в составе антиобледеняющих растворов, в производстве пищевых, косметических и лекарственных продуктов. Пропиленгликоль в отличие от этиленгликоля менее токсичен.The invention relates to the field of production of dihydroxyalkanes by catalytic hydrogenation, in particular by catalytic hydrogenation of carboxylic groups of hydroxycarboxylic acids. Dihydroxyalkanes, such as ethylene glycol and propylene glycol, are used in the manufacture of polyester resins, as part of anti-icing solutions, and in the manufacture of food, cosmetic and medicinal products. Propylene glycol, in contrast to ethylene glycol, is less toxic.
Традиционно производство пропиленгликоля базируется на органических соединениях, содержащихся в нефти. Пропиленгликоль получают путем гидратации пропиленоксида, стадия гидролиза которого требует высокого давления и высокой температуры. Производство пропиленоксида представляет собой сложный многостадийный процесс, отличающийся образованием большого количества побочных продуктов и низким выходом целевого продукта, что приводит к возникновению экологических проблем. [ShmапtTraditionally, the production of propylene glycol is based on organic compounds contained in oil. Propylene glycol is obtained by hydration of propylene oxide, the hydrolysis stage of which requires high pressure and high temperature. The production of propylene oxide is a complex multi-stage process, characterized by the formation of a large number of by-products and low yield of the target product, which leads to environmental problems. [Shmapt
Н.Н. Оrgапiс Вuildiпg Вlосs оf thе Сhеmiсаl iпdustrу, Wilеу, Nеw Yоrk, Nеw Yоrk pp.281-283 (1989)].N.N. Orgapis Вuildiпg Вlосs оf thе Chemisal Industrial, Wеlе, New York, New York pp. 281-283 (1989)].
В связи с необходимостью разработки более дешевого и экологически безопасного способа получения пропиленгликоля особый интерес представляет его производство из возобновляемых источников сырья, таких как растения. Хорошо известно, что растения в процессе переработки атмосферного диоксида углерода производят глюкозу, ферментация которой приводит к образованию молочной кислоты.Due to the need to develop a cheaper and environmentally friendly method for producing propylene glycol, of particular interest is its production from renewable sources of raw materials, such as plants. It is well known that plants in the process of processing atmospheric carbon dioxide produce glucose, the fermentation of which leads to the formation of lactic acid.
Количество природных ресурсов далеко не безгранично, цена продуктов переработки природных ресурсов несомненно будет возрастать. С другой стороны, очевиден прогресс в технологиях ферментации и сепарации, поэтому цена продуктов ферментации будет снижаться. Более того, тогда как
производство глюкозы и молочной кислоты будет увеличиваться, цена молочной кислоты должна упасть из-за растущей конкуренции и снижения средних затрат по мере увеличения объема выпуска.The amount of natural resources is far from unlimited, the price of natural resources processing products will undoubtedly increase. On the other hand, progress in fermentation and separation technologies is obvious, so the price of fermentation products will decrease. Moreover, whereas glucose and lactic acid production will increase, the price of lactic acid should fall due to increasing competition and lower average costs as output increases.
Конверсия карбоксильной группы молочной кислоты в гидроксильную группу приводит к 1,2-пpoпaндиoлy. Таким образом, если найти экономически оправданный метод восстановления карбоксильной группы гидроксикарбоновой кислоты до гидроксильной группы, был бы найден путь производства 1 ,2-пpoпaндиoлa из возобновляемого ресурса.The conversion of the carboxyl group of lactic acid to the hydroxyl group leads to 1,2-propanediol. Thus, if an economically viable method of reducing the carboxyl group of a hydroxycarboxylic acid to a hydroxyl group is found, a way to produce 1, 2-propanediol from a renewable resource would be found.
Хорошо известно, что каталитическое гидрирование карбоновых кислот - это трудноосуществимый процесс, поэтому на практике его осуществляют в две стадии, когда карбоновую кислоту сначала превращают в производное, например эфир или ангидрид. Методы прямого восстановления карбоновых кислот также описаны в литературе [US 4613707, C07C29/136, 23.09.76], но требуют высокого давления водорода и обычно ведутся в жидкой фазе. Процесс прямого восстановления гидроксикарбоновых кислот до дигидроксиалканов, в частности процесс, проходящий при низких давлениях водорода мог бы снизить затраты, связанные с превращением карбоксильной группы в ее производное и затраты на закупку и использование дорогостоящего оборудования для создания и поддержания высокого давления. Известен катализатор для процесса прямого восстановления гидроксикарбоновых кислот до дигидроксиалканов, состоящий из меди, нанесенной в количестве от 9 до 22 мac.% на диоксид кремния, поверхностные гидроксильные группы которого могут быть закрыты силанольными и/или алкильными группами. Катализатор готовят методом пропитки по влагоемкости следующим образом: силикагель (Саb-О-Sil® BH-5, Саbоt® Соrроrаtiоп) высушивают при температуре 12O0C, пропитывают этанольным раствором гидрата нитрата меди, затем проводят восстановление катализатора в токе водорода при температуре 300°C в течение 8 ч.It is well known that the catalytic hydrogenation of carboxylic acids is a difficult process, therefore, in practice it is carried out in two stages, when the carboxylic acid is first converted to a derivative, for example, ether or anhydride. Direct reduction methods for carboxylic acids are also described in the literature [US 4613707, C07C29 / 136, 09.23.76], but require high hydrogen pressure and are usually carried out in the liquid phase. The process of direct reduction of hydroxycarboxylic acids to dihydroxyalkanes, in particular, the process taking place at low hydrogen pressures, could reduce the costs associated with the conversion of the carboxyl group to its derivative and the purchase and use of expensive equipment to create and maintain high pressure. A known catalyst for the process of direct reduction of hydroxycarboxylic acids to dihydroxyalkanes, consisting of copper deposited in an amount of from 9 to 22 wt.% On silicon dioxide, the surface hydroxyl groups of which can be closed by silanol and / or alkyl groups. The catalyst is prepared by the method of impregnation in terms of moisture capacity as follows: silica gel (Sab-O-Sil® BH-5, Sabot® Corroratiop) is dried at a temperature of 12 0 0 C, impregnated with an ethanol solution of copper nitrate hydrate, then the catalyst is restored in a stream of hydrogen at a temperature of 300 ° C for 8 hours
Гидрирование карбоксильной группы гидроксикарбоновой кислоты проводят в паровой фазе при давлении водорода от менее чем 0,9 атм до 27,5 атм и температуре от 112,5 до 275°C. При давлении водорода 1 атм в оптимальных условиях конверсия молочной кислоты достигает 7,3% с селективностью 75% [US 6455742, C07C29/141, 24.09.2002].
Недостатком известного катализатора является невысокая производительность по целевому продукту.Hydrogenation of the carboxyl group of the hydroxycarboxylic acid is carried out in the vapor phase at a hydrogen pressure of from less than 0.9 atm to 27.5 atm and a temperature of from 112.5 to 275 ° C. At a hydrogen pressure of 1 atm under optimal conditions, the conversion of lactic acid reaches 7.3% with a selectivity of 75% [US 6455742, C07C29 / 141, 09.24.2002]. A disadvantage of the known catalyst is the low productivity of the target product.
Изобретение решает задачу увеличения производительности процесса. Технический результат - повышение активности и селективности катализатораThe invention solves the problem of increasing the productivity of the process. EFFECT: increased activity and selectivity of the catalyst
Задача решается составом катализатора получения дигидроксиалканов каталитическим гидрированием карбоксильных групп гидроксикарбоновых кислот на основе меди и оксида кремния, который содержит 22.5-53.1 мac.% меди. Задача решается также способом приготовления катализатора, который готовят восстановительным терморазложением силиката меди, при этом получают катализатор, который содержит 22.5-53.0 мac.% меди.The problem is solved by the composition of the catalyst for the production of dihydroxyalkanes by catalytic hydrogenation of the carboxyl groups of hydroxycarboxylic acids based on copper and silicon oxide, which contains 22.5-53.1 wt.% Copper. The problem is also solved by the method of preparation of the catalyst, which is prepared by reductive thermal decomposition of copper silicate, and a catalyst is obtained which contains 22.5-53.0 wt.% Copper.
Катализатор готовят восстановительным терморазложением в токе водорода при температуре 380-4500C в течение времени не менее 2 ч. В качестве силиката меди можно использовать природные и синтетические силикаты с заданным содержанием меди.The catalyst is prepared by reductive thermal decomposition in a stream of hydrogen at a temperature of 380-450 0 C for a period of at least 2 hours. Natural and synthetic silicates with a given copper content can be used as copper silicate.
Задача решается также способом получения дигидроксиалканов каталитическим гидрированием карбоксильных групп гидроксикарбоновых кислот при температуре 180-2000C в присутствие медно-кремниевого катализатора, где в качестве катализатора используют катализатор, описанный выше.The problem is also solved by the method of producing dihydroxyalkanes by catalytic hydrogenation of the carboxyl groups of hydroxycarboxylic acids at a temperature of 180-200 0 C in the presence of a copper-silicon catalyst, where the catalyst described above is used as a catalyst.
Сущность изобретения иллюстрируется следующими примерами. Пример 1.The invention is illustrated by the following examples. Example 1
Катализатор, содержащий 22,5 мac.% меди, готовят методом терморазложения силиката меди в токе водорода при температуре 4000C в течение 2 ч.A catalyst containing 22.5 wt.% Copper is prepared by thermal decomposition of copper silicate in a stream of hydrogen at a temperature of 400 0 C for 2 hours
Катализатор применяют в реакции гидрирования молочной кислоты. В стеклянный/кварцевый трубчатый U-образный термостатируемый реактор помещают 0,5 г катализатора фракции 0.25-0.5 мм, смешанного с кварцевым стеклом фракции от 0,63 до 1,6 мм. Устанавливают рабочую температуру 200°C в реакторе, поток водорода 10 л/ч и дозируют водный раствор молочной кислоты (16 мac.%) со скоростью 0,3 мл/ч. На выходе из реактора жидкие продукты собирают в ловушку и анализируют газохроматографически.
Состав продуктов реакции: 36,8% - пропионовая кислота, 43,7% - пропиленгликоль, 16,3% - молочная кислота.The catalyst is used in the hydrogenation reaction of lactic acid. In a glass / quartz tubular U-shaped thermostatically controlled reactor, 0.5 g of a 0.25-0.5 mm fraction catalyst mixed with 0.63 to 1.6 mm fraction quartz glass is placed. Set the operating temperature to 200 ° C in the reactor, the flow of hydrogen 10 l / h and meter the aqueous solution of lactic acid (16 wt.%) At a speed of 0.3 ml / h. At the outlet of the reactor, liquid products are collected in a trap and analyzed by gas chromatography. The composition of the reaction products: 36.8% - propionic acid, 43.7% - propylene glycol, 16.3% - lactic acid.
Пример 2.Example 2
Аналогичен примеру 1, с тем отличием, что используют катализаторы с содержанием меди 45,5 мac.%.Similar to example 1, with the difference that they use catalysts with a copper content of 45.5 wt.%.
Состав продуктов реакции: 29,1% - пропионовая кислота, 66,3% - пропиленгликоль, 3,4% - молочная кислота.The composition of the reaction products: 29.1% - propionic acid, 66.3% - propylene glycol, 3.4% - lactic acid.
Пример 3.Example 3
Аналогичен примеру 1, с тем отличием, что используют катализатор с содержанием меди 53,1 мac.% процесс ведут при температуре 180°C, скоростью подачи раствора молочной кислоты 0,3 мл/ч с концентрацией 16% мае.Similar to example 1, with the difference that they use a catalyst with a copper content of 53.1 wt.% The process is carried out at a temperature of 180 ° C, the feed rate of a solution of lactic acid 0.3 ml / h with a concentration of 16% in May.
Состав продуктов реакции: 23,8% - пропанол, 54,2% - пропионовая кислота, 2,4% - пропиленгликоль, 0,8% - молочная кислота. Пример 4.The composition of the reaction products: 23.8% - propanol, 54.2% - propionic acid, 2.4% - propylene glycol, 0.8% - lactic acid. Example 4
Аналогичен примеру 2, с тем отличием, что процесс ведут при температуре 1800C со скоростью подачи раствора молочной кислоты 0,2 мл/ч.Similar to example 2, with the difference that the process is carried out at a temperature of 180 0 C with a feed rate of a lactic acid solution of 0.2 ml / h.
Состав продуктов реакции: 17,1% - пропионовая кислота, 71,6% - пропиленгликоль, 12,3% - молочная кислота. Пример 5.The composition of the reaction products: 17.1% - propionic acid, 71.6% - propylene glycol, 12.3% - lactic acid. Example 5
Аналогичен примеру 4, с тем отличием, что процесс ведут со скоростью подачи раствора молочной кислоты 0,3 мл/ч.Similar to example 4, with the difference that the process is conducted with a feed rate of a solution of lactic acid of 0.3 ml / h
Состав продуктов реакции: 13,5% пропионовая кислота, 36,4% пропиленгликоль, 51,1% молочная кислота. Пример 6.The composition of the reaction products: 13.5% propionic acid, 36.4% propylene glycol, 51.1% lactic acid. Example 6
Аналогичен примеру 4, с тем отличием, что процесс ведут со скоростью подачи раствора молочной кислоты 0,4 мл/ч.Similar to example 4, with the difference that the process is conducted with a feed rate of a lactic acid solution of 0.4 ml / h.
Состав продуктов реакции: 9,4% - пропионовая кислота, 32,2% пропиленгликоль, 59,4% молочная кислота. Пример 7.The composition of the reaction products: 9.4% - propionic acid, 32.2% propylene glycol, 59.4% lactic acid. Example 7
Аналогичен примеру 4, с тем отличием, что процесс ведут со скоростью подачи раствора молочной кислоты 0,9 мл/ч.
Состав продуктов реакции: 5,1% пропионовая кислота, 11,3% пропиленгликоль, 84,6% - молочная кислота.Similar to example 4, with the difference that the process is conducted with a feed rate of a lactic acid solution of 0.9 ml / h. The composition of the reaction products: 5.1% propionic acid, 11.3% propylene glycol, 84.6% - lactic acid.
Результаты тестирования катализаторов обобщены в таблице.The test results of the catalysts are summarized in the table.
ТаблицаTable
Пример 8.Example 8
Аналогичен примеру 1, с тем отличием, что используют катализатор с содержанием меди 45,5 мac.%, и процесс ведут при температуре 200°C, в качестве субстрата используют гликолевую кислоту с концентрацией 19 мac.%.Similar to example 1, with the difference that they use a catalyst with a copper content of 45.5 wt.%, And the process is carried out at a temperature of 200 ° C, glycolic acid with a concentration of 19 wt.% Is used as a substrate.
Состав продуктов реакции: 2,1% - уксусная кислота, 46,2% - этиленгликоль,The composition of the reaction products: 2.1% - acetic acid, 46.2% - ethylene glycol,
6,4% - 2-мeтил-l,3-диoкcaлaн, 45,2% - гликолевая кислота.6.4% - 2-methyl-l, 3-dioxalane, 45.2% - glycolic acid.
Как видно из приведенных примеров и таблицы использование предлагаемого катализатора в процессе каталитического гидрирования карбоксильных групп гидроксикарбоновых кислот позволяет увеличить производительность по целевому продукту за счет повышения активности и селективности катализатора.
As can be seen from the above examples and the table, the use of the proposed catalyst in the process of catalytic hydrogenation of the carboxyl groups of hydroxycarboxylic acids allows to increase the productivity of the target product by increasing the activity and selectivity of the catalyst.
Claims
1. Катализатор получения дигидроксиалканов каталитическим гидрированием карбоксильных групп гидроксикарбоновых кислот на1. The catalyst for the production of dihydroxyalkanes by catalytic hydrogenation of carboxylic groups of hydroxycarboxylic acids on
5 основе меди и оксида кремния, отличающийся тем, что катализатор содержит 22.5-53.0 мае. % меди.5 based on copper and silicon oxide, characterized in that the catalyst contains May 22.5-53.0. % copper.
2. Способ приготовления катализатора получения дигидроксиалканов каталитическим гидрированием карбоксильных групп гидроксикарбоновых кислот на основе меди и оксида кремния, отличающийся тем, что его2. A method of preparing a catalyst for the production of dihydroxyalkanes by catalytic hydrogenation of carboxyl groups of hydroxycarboxylic acids based on copper and silicon oxide, characterized in that it
Ю готовят восстановительным терморазложением силиката меди, при этом получают катализатор, содержащий 22.5-53.0 мае. % меди.Yu is prepared by reductive thermal decomposition of copper silicate, and a catalyst is obtained containing May 22.5–53.0. % copper.
3. Способ получения дигидроксиалканов каталитическим гидрированием карбоксильных групп гидроксикарбоновых кислот в присутствие медно-кремниевого катализатора температуре 180-2000C,3. The method of producing dihydroxyalkanes by catalytic hydrogenation of carboxyl groups of hydroxycarboxylic acids in the presence of a copper-silicon catalyst at a temperature of 180-200 0 C,
15 отличающийся тем, что в качестве катализатора используют катализатор по п. 1 или катализатор, полученный по способу по п. 2. 15 characterized in that the catalyst according to claim 1 or the catalyst obtained by the method according to claim 2 is used as a catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2005141791 | 2005-12-21 | ||
| RU2005141791/04A RU2290994C1 (en) | 2005-12-21 | 2005-12-21 | Catalyst, method for preparation thereof, and dihydroxyalkane production process |
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| WO2007073240A1 true WO2007073240A1 (en) | 2007-06-28 |
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| PCT/RU2006/000602 WO2007073240A1 (en) | 2005-12-21 | 2006-11-15 | Catalyst, a method for the production thereof and a dihydroxyalkane production method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011036189A3 (en) * | 2009-09-22 | 2012-02-23 | Springhill S.A. | The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols |
| CN110713433A (en) * | 2018-07-12 | 2020-01-21 | 长春石油化学股份有限公司 | Process for the hydrogenation of acids to alcohols |
| CN114345339A (en) * | 2021-12-30 | 2022-04-15 | 厦门大学 | Supported binary metal catalyst, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU442822A1 (en) * | 1973-01-26 | 1974-09-15 | Казанский химический комбинат им.Вахитова | The method of preparation of the catalyst for the hydrogenation of liquid acids |
| US4780448A (en) * | 1985-02-02 | 1988-10-25 | Basf Aktiengesellschaft | Preparation of a catalyst containing copper and silica |
| US20020087035A1 (en) * | 1999-09-02 | 2002-07-04 | Wisconsin Alumni Research Foundation. | Method for catalyticallly reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids |
-
2005
- 2005-12-21 RU RU2005141791/04A patent/RU2290994C1/en not_active IP Right Cessation
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2006
- 2006-11-15 WO PCT/RU2006/000602 patent/WO2007073240A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU442822A1 (en) * | 1973-01-26 | 1974-09-15 | Казанский химический комбинат им.Вахитова | The method of preparation of the catalyst for the hydrogenation of liquid acids |
| US4780448A (en) * | 1985-02-02 | 1988-10-25 | Basf Aktiengesellschaft | Preparation of a catalyst containing copper and silica |
| US20020087035A1 (en) * | 1999-09-02 | 2002-07-04 | Wisconsin Alumni Research Foundation. | Method for catalyticallly reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011036189A3 (en) * | 2009-09-22 | 2012-02-23 | Springhill S.A. | The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols |
| EA021350B1 (en) * | 2009-09-22 | 2015-05-29 | Спрингхилл С.А. | Method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols |
| CN110713433A (en) * | 2018-07-12 | 2020-01-21 | 长春石油化学股份有限公司 | Process for the hydrogenation of acids to alcohols |
| CN110713433B (en) * | 2018-07-12 | 2023-06-23 | 长春石油化学股份有限公司 | Process for the preparation of alcohols by hydrogenation of acids |
| CN114345339A (en) * | 2021-12-30 | 2022-04-15 | 厦门大学 | Supported binary metal catalyst, preparation method and application thereof |
| CN114345339B (en) * | 2021-12-30 | 2023-02-21 | 厦门大学 | Supported binary metal catalyst, preparation method and application thereof |
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| RU2290994C1 (en) | 2007-01-10 |
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