RU2013158468A - METHOD FOR PRODUCING FORMIC ACID - Google Patents

METHOD FOR PRODUCING FORMIC ACID Download PDF

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RU2013158468A
RU2013158468A RU2013158468/04A RU2013158468A RU2013158468A RU 2013158468 A RU2013158468 A RU 2013158468A RU 2013158468/04 A RU2013158468/04 A RU 2013158468/04A RU 2013158468 A RU2013158468 A RU 2013158468A RU 2013158468 A RU2013158468 A RU 2013158468A
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tertiary amine
formic acid
catalyst
mixture
heterogeneous
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RU2013158468/04A
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Russian (ru)
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Джузеппе ФАКИНЕТТИ
Дебора ПРЕТИ
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Басф Се
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J35/31—
    • B01J35/613—
    • 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
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/06—Washing
    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
    • B01J35/50—

Abstract

1. Способ получения муравьиной кислоты путем гидрирования диоксида углерода в присутствии третичного амина(I) и катализатора при давлении, равном от 0,2 до 30 МПа абс., и при температуре, равной от 0 до 200°C, в котором катализатором является гетерогенный катализатор, содержащий золото.2. Способ по п.1, в котором гетерогенным катализатором, содержащим золото, является катализатор на подложке.3. Способ по п.2, в котором гетерогенный катализатор на подложке содержит диоксид кремния, оксид алюминия, оксид циркония, оксид магния и/или оксид титана в качестве подложки.4. Способ по п.2, в котором гетерогенный катализатор на подложке содержит от 0,1 до 20 мас.% золота в пересчете на полную массу катализатора на подложке.5. Способ по п.1, в котором третичный амин(I) содержит не более чем 9 атомов углерода.6. Способ по п.1, в котором третичным амином(I) является триметиламин, триэтиламин и/или трипропиламин.7. Способ по любому из пп.1-6, в котором смесь продуктов, полученную гидрированием, содержащую муравьиную кислоту и третичный амин(I), вводят в реакцию с третичным амином(II), который содержит от 12 до 48 атомов углерода, высвободившийся третичный амин(I) отделяют, получая таким образом смесь продуктов, содержащую муравьиную кислоту и третичный амин(II), и муравьиную кислоту удаляют из указанной смеси продуктов путем отгонки.8. Способ по п.7, в котором третичным амином(II) является трипентиламин, тригексиламин, тригептиламин, триоктиламин, метилдициклогексиламин, диоктилметиламин и/или диметилдециламин.9. Способ по п.7, в котором реакцию смеси продуктов, содержащей муравьиную кислоту и третичный амин(I), с третичным амином(II) проводят при температуре, равн1. A method for producing formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine(I) and a catalyst at a pressure of 0.2 to 30 MPa abs. and at a temperature of 0 to 200°C, in which the catalyst is a heterogeneous catalyst containing gold.2. The method according to claim 1, wherein the heterogeneous gold-containing catalyst is a supported catalyst. The method according to claim 2, wherein the heterogeneous supported catalyst contains silica, alumina, zirconium oxide, magnesium oxide and/or titanium oxide as the support. The method according to claim 2, wherein the heterogeneous supported catalyst contains from 0.1 to 20 wt.% gold, based on the total weight of the supported catalyst. The method according to claim 1, wherein the tertiary amine(I) contains no more than 9 carbon atoms.6. Method according to claim 1, wherein the tertiary amine(I) is trimethylamine, triethylamine and/or tripropylamine.7. Method according to any one of claims 1 to 6, wherein the mixture of products obtained by hydrogenation containing formic acid and a tertiary amine(I) is reacted with a tertiary amine(II) which contains from 12 to 48 carbon atoms, releasing the tertiary amine (I) is separated, thereby obtaining a product mixture containing formic acid and tertiary amine (II), and formic acid is removed from said product mixture by distillation.8. The method according to claim 7, wherein the tertiary amine(II) is tripentylamine, trihexylamine, triheptylamine, trioctylamine, methyldicyclohexylamine, dioctylmethylamine and/or dimethyldecylamine.9. The method according to claim 7, in which the reaction of a mixture of products containing formic acid and a tertiary amine(I) with a tertiary amine(II) is carried out at a temperature equal to

Claims (12)

1. Способ получения муравьиной кислоты путем гидрирования диоксида углерода в присутствии третичного амина(I) и катализатора при давлении, равном от 0,2 до 30 МПа абс., и при температуре, равной от 0 до 200°C, в котором катализатором является гетерогенный катализатор, содержащий золото.1. A method of producing formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine (I) and a catalyst at a pressure of 0.2 to 30 MPa abs. And at a temperature of 0 to 200 ° C, in which the catalyst is heterogeneous a catalyst containing gold. 2. Способ по п.1, в котором гетерогенным катализатором, содержащим золото, является катализатор на подложке.2. The method according to claim 1, in which the heterogeneous catalyst containing gold is a supported catalyst. 3. Способ по п.2, в котором гетерогенный катализатор на подложке содержит диоксид кремния, оксид алюминия, оксид циркония, оксид магния и/или оксид титана в качестве подложки.3. The method according to claim 2, in which the heterogeneous catalyst on the substrate contains silicon dioxide, alumina, zirconia, magnesium oxide and / or titanium oxide as a substrate. 4. Способ по п.2, в котором гетерогенный катализатор на подложке содержит от 0,1 до 20 мас.% золота в пересчете на полную массу катализатора на подложке.4. The method according to claim 2, in which the heterogeneous catalyst on the substrate contains from 0.1 to 20 wt.% Gold in terms of the total weight of the catalyst on the substrate. 5. Способ по п.1, в котором третичный амин(I) содержит не более чем 9 атомов углерода.5. The method according to claim 1, in which the tertiary amine (I) contains no more than 9 carbon atoms. 6. Способ по п.1, в котором третичным амином(I) является триметиламин, триэтиламин и/или трипропиламин.6. The method according to claim 1, in which the tertiary amine (I) is trimethylamine, triethylamine and / or tripropylamine. 7. Способ по любому из пп.1-6, в котором смесь продуктов, полученную гидрированием, содержащую муравьиную кислоту и третичный амин(I), вводят в реакцию с третичным амином(II), который содержит от 12 до 48 атомов углерода, высвободившийся третичный амин(I) отделяют, получая таким образом смесь продуктов, содержащую муравьиную кислоту и третичный амин(II), и муравьиную кислоту удаляют из указанной смеси продуктов путем отгонки.7. The method according to any one of claims 1 to 6, in which a mixture of products obtained by hydrogenation containing formic acid and a tertiary amine (I) is reacted with a tertiary amine (II), which contains from 12 to 48 carbon atoms released the tertiary amine (I) is separated, thereby obtaining a product mixture containing formic acid and tertiary amine (II), and formic acid are removed from the mixture of products by distillation. 8. Способ по п.7, в котором третичным амином(II) является трипентиламин, тригексиламин, тригептиламин, триоктиламин, метилдициклогексиламин, диоктилметиламин и/или диметилдециламин.8. The method according to claim 7, in which the tertiary amine (II) is tryptylamine, trihexylamine, triheptylamine, trioctylamine, methyldicyclohexylamine, dioctylmethylamine and / or dimethyldecylamine. 9. Способ по п.7, в котором реакцию смеси продуктов, содержащей муравьиную кислоту и третичный амин(I), с третичным амином(II) проводят при температуре, равной от 20 до 200°C, и давлении, равном от 0,01 до 20 МПа абс.9. The method according to claim 7, in which the reaction of a mixture of products containing formic acid and a tertiary amine (I) with a tertiary amine (II) is carried out at a temperature of from 20 to 200 ° C and a pressure of from 0.01 up to 20 MPa abs. 10. Способ по п.7, в котором третичный амин(I), который высвобождается по реакции смеси продуктов, содержащей муравьиную кислоту и третичный амин(I), с третичным амином(II) и отделяется, рециркулируют на стадию гидрирования диоксида углерода.10. The method according to claim 7, in which the tertiary amine (I), which is released by the reaction of a mixture of products containing formic acid and tertiary amine (I) with a tertiary amine (II) and is separated, is recycled to the stage of hydrogenation of carbon dioxide. 11. Способ по п.7, в котором перегонку смеси продуктов, содержащей муравьиную кислоту и третичный амин(II), проводят в аппарате для перегонки при температуре в нижней части, равной от 100 до 300°C, и давлении, равном от 30 до 3000 гПа абс.11. The method according to claim 7, in which the distillation of a mixture of products containing formic acid and tertiary amine (II) is carried out in a distillation apparatus at a temperature in the lower part equal to from 100 to 300 ° C and a pressure equal to from 30 to 3000 hPa abs. 12. Способ по любому из пп.7-11, в котором на стадии удаления муравьиной кислоты путем отгонки получают кубовый продукт, содержащий третичный амин(II), и его рециркулируют на стадию реакции смеси продуктов, содержащей муравьиную кислоту и третичный амин(I), с третичным амином(II). 12. The method according to any one of claims 7 to 11, wherein in the step of removing formic acid by distillation, a bottoms product containing tertiary amine (II) is obtained, and it is recycled to the reaction step of a mixture of products containing formic acid and tertiary amine (I) , with tertiary amine (II).
RU2013158468/04A 2011-06-09 2012-06-08 METHOD FOR PRODUCING FORMIC ACID RU2013158468A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11169224 2011-06-09
EP11169224.0 2011-06-09
PCT/EP2012/060845 WO2012168396A1 (en) 2011-06-09 2012-06-08 Process for preparing formic acid

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EP (1) EP2718256A1 (en)
JP (1) JP2014520107A (en)
KR (1) KR20140033491A (en)
CN (1) CN103619798A (en)
BR (1) BR112013031120A2 (en)
CA (1) CA2837764A1 (en)
RU (1) RU2013158468A (en)
WO (1) WO2012168396A1 (en)

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JP6289310B2 (en) * 2014-08-27 2018-03-07 一般財団法人電力中央研究所 Catalyst or precursor thereof, method for hydrogenating carbon dioxide using these, and method for producing formate
KR101684766B1 (en) 2015-02-06 2016-12-08 국민대학교산학협력단 Catalyst for hydrogenation reaction and Method for synthesizing thereof
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CN106622224B (en) * 2015-11-04 2019-07-26 中国科学院大连化学物理研究所 Application of the nanometer Au-based catalyst in formic acid or formates synthesis
CN110121490B (en) * 2017-01-18 2022-04-08 株式会社大赛璐 Process for producing acetic acid
US10207977B2 (en) 2017-01-18 2019-02-19 Daicel Corporation Method for producing acetic acid
KR102026538B1 (en) 2017-11-21 2019-09-27 국민대학교산학협력단 Hydrogenation catalyst and hydrogenation of carbon dioxide using the catalyst
KR102285717B1 (en) 2018-11-16 2021-08-04 한국과학기술연구원 Apparatus and method of preparing formic acid by hydrogenation of carbon dioxide
KR102245163B1 (en) 2019-09-18 2021-04-26 한국화학연구원 Heterogeneous Catalyst Complex for Carbon Dioxide Conversion
US11607674B2 (en) 2019-11-19 2023-03-21 Korea Research Institute Of Chemical Technology Heterogeneous catalyst complex for carbon dioxide conversion
KR102422368B1 (en) * 2020-09-29 2022-07-18 한국화학연구원 An Esterification Method of Metal Organic Acid Salt and Carbon dioxide Conversion System Using the Same
KR102570842B1 (en) 2019-11-19 2023-08-28 한국화학연구원 Heterogeneous Catalyst Complex for Carbon dioxide Conversion

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WO2012168396A1 (en) 2012-12-13
CN103619798A (en) 2014-03-05
EP2718256A1 (en) 2014-04-16
JP2014520107A (en) 2014-08-21
KR20140033491A (en) 2014-03-18
CA2837764A1 (en) 2012-12-13
BR112013031120A2 (en) 2016-12-06

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