WO2019096190A1 - Procédé de production d'acide formique - Google Patents

Procédé de production d'acide formique Download PDF

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Publication number
WO2019096190A1
WO2019096190A1 PCT/CN2018/115552 CN2018115552W WO2019096190A1 WO 2019096190 A1 WO2019096190 A1 WO 2019096190A1 CN 2018115552 W CN2018115552 W CN 2018115552W WO 2019096190 A1 WO2019096190 A1 WO 2019096190A1
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WO
WIPO (PCT)
Prior art keywords
substituted
compound
catalyst
process according
diol
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Application number
PCT/CN2018/115552
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English (en)
Inventor
Vitaly ORDOMSKY
Stéphane STREIFF
Willinton Yesid HERNANDEZ ENCISO
Renate Schwiedernoch
Original Assignee
Solvay Sa
Le Centre National De La Recherche Scientifique
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Sa, Le Centre National De La Recherche Scientifique filed Critical Solvay Sa
Priority to CN201880070887.8A priority Critical patent/CN111315716B/zh
Priority to EP18877890.6A priority patent/EP3710420A4/fr
Publication of WO2019096190A1 publication Critical patent/WO2019096190A1/fr

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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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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

Definitions

  • the present invention relates to a process for producing formic acid by the reaction of carbon dioxide with hydrogen in the presence of a solvent, a substituted or non-substituted quinone compound and/or a substituted or non-substituted hydroquinone compound, and a metal catalyst.
  • Formic acid is an important and versatile product. It is used, for example, for acidification in the production of animal feeds, as preservative, as disinfectant, as auxiliary in the textile and leather industry, as a mixture with its salts for deicing aircraft and runways and also as synthetic building block in the chemical industry.
  • the present invention relates to a process for producing formic acid, comprising reacting carbon dioxide with hydrogen in the presence of a solvent, a substituted or non-substituted quinone compound and/or a substituted or non-substituted hydroquinone compound, and a catalyst comprising a metal chosen from the group consisting of Pd, Pt, Ru, Rh, Au, Ag, Ir, Ni and Co.
  • the present invention also relates to a composition
  • a composition comprising:
  • a catalyst comprising a metal chosen from the group consisting of Pd, Pt, Ru, Rh, Au, Ag, Ir, Ni and Co.
  • any particular upper concentration can be associated with any particular lower concentration.
  • hydrocarbon group refers to a group which contains carbon and hydrogen bonds.
  • a hydrocarbon group may be linear, branched, or cyclic, and may contain a heteroatom such as oxygen, nitrogen, sulfur, halogen, etc.
  • alkyl means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.
  • alkenyl as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched.
  • the group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z.
  • Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl.
  • the group may be a terminal group or a bridging group.
  • aryl refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. Examples of aryl groups include phenyl, naphthyl and the like.
  • arylalkyl or the term “aralkyl” refers to alkyl substituted with an aryl.
  • arylalkoxy refers to an alkoxy substituted with aryl.
  • cyclic group means a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group.
  • alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
  • cycloalkyl as used herein means cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.
  • Heterocyclic may also mean a heterocyclic group fused with a benzene-ring wherein the fused rings contain carbon atoms together with 1 or 2 heteroatom’s which are selected from N, O and S.
  • the present invention relates to a process for producing formic acid, comprising reacting carbon dioxide with hydrogen in the presence of a solvent, a substituted or non-substituted quinone compound and/or a substituted or non-substituted hydroquinone compound, and a catalyst comprising a metal chosen from the group consisting of Pd, Pt, Ru, Rh, Au, Ag, Ir, Ni and Co.
  • the reaction can be performed under wild reaction conditions. No high gas pressure and high reaction temperature is needed when the substituted or non-substituted quinone compound and/or the substituted or non-substituted hydroquinone compound is added into the reaction medium.
  • the class includes some heterocyclic compounds.
  • the class includes some heterocyclic compounds.
  • the substituted or non-substituted quinone compound, or the substituted or non-substituted hydroquinone compound may have 5 to 20 carbon atoms.
  • the substituted or non-substituted quinone compound, or the substituted or non-substituted hydroquinone compound may comprise at least one cyclic ring. More preferably, the substituted or non-substituted quinone compound, or the substituted or non-substituted hydroquinone compound comprises one, two or three cyclic rings, which can be bridged ring and/or fused ring systems.
  • the substituted or non-substituted quinone compound, or the substituted or non-substituted hydroquinone compound comprises at least one five-membered or six-membered ring.
  • the substituted or non-substituted quinone compound, or the substituted or non-substituted hydroquinone compound comprises cyclic ring which contains carbon atoms together with 1 or 2 heteroatoms which are selected from N, O and S.
  • non-substituted quinone compound examples include 1, 2-benzoquinone, 1, 4-benzoquinone, 1, 4-naphthoquinone, 9, 10-phenanthraquinone and 9, 10-anthraquinone.
  • non-substituted hydroquinone compound examples include benzene-1, 4-diol, benzene-1, 2-diol, naphthalene-1, 4-diol, phenanthrene-9, 10-diol and anthracene-9, 10-diol.
  • the substituted quinone compound or substituted hydroquinone compound can bear one or more substituents.
  • Said substituent may be hydroxyl, halo, amino, C 1 -C 12 hydrocarbon group, such as alkyl, alkenyl, aryl, cycloalkyl, C 1 -C 12 hydroxyalkyl or C 1 -C 12 haloalkyl.
  • Preferred substituent may be C 1 -C 5 straight aliphatic hydrocarbon group.
  • substituted quinone compound may have a general formula (I) :
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is C 1 -C 12 alkyl.
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is C 1 -C 5 alkyl.
  • the substituted quinone compound is 1-methyl-9, 10-anthraquinone, 2-methyl-9, 10-anthraquinone, 1-ethyl-9, 10-anthraquinone, 2-ethyl-9, 10-anthraquinone, 1-amyl-9, 10-anthraquinone or 2-amyl-9, 10-anthraquinone. More preferably, the substituted quinone compound is 2-ethyl-9, 10-anthraquinone.
  • substituted hydroquinone compound may have a general formula (II):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is C 1 -C 12 alkyl.
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is C 1 -C 5 alkyl.
  • the substituted hydroquinone compound is 1-methylanthracene-9, 10-diol, 2-methylanthracene-9, 10-diol, 1-ethylanthracene-9, 10-diol, 2-ethylanthracene-9, 10-diol, 1-amylanthracene-9, 10-diol or 2-amylanthracene-9, 10-diol. More preferably, the substituted hydroquinone compound is 2-ethylanthracene-9, 10-diol.
  • a mixture of the substituted or non-substituted quinone compound and the substituted or non-substituted hydroquinone compound can be added into the reaction medium.
  • the substituted or non-substituted quinone compound and the substituted or non-substituted hydroquinone compound can be mixed before being introduced to the reaction medium. Alternatively, only the substituted or non- substituted quinone compound is added into the reaction medium and then the mixture forms when partial substituted or non-substituted quinone compound is hydrogenated to the substituted or non-substituted hydroquinone compound during the reaction of carbon dioxide with hydrogen.
  • the catalyst comprises a metal chosen from the group consisting of Pd, Pt, Ru, Rh, Au, Ag, Ir, Co and Ni.
  • the catalyst can be a supported or non-supported metal catalyst.
  • the catalyst is a supported metal catalyst.
  • the support is not particularly limited. Typical examples of support are carbon, alumina, titania and silica.
  • the loading of metal on the support may be from 1 wt. %to 50 wt. %.
  • the supported metal catalyst can comprise only one metal element.
  • the supported metal catalyst can comprise at least two metal elements.
  • the catalyst comprises two metal elements.
  • the supported metal catalyst may comprise at least one noble metal element chosen from the group consisting of Pd, Pt, Ru and Au. More preferably, the supported metal catalyst comprises Pd.
  • Preferred supported metal catalyst may be Pd/Al 2 O 3 , Pd/C and Pd-Au/C.
  • the catalyst of present invention can even be Raney-type catalysts such as Raney nickel, Raney cobalt.
  • the catalyst is Raney nickel.
  • Raney nickel is an alloy containing catalytically active nickel and a catalytically inactive component, such as aluminum or silicon.
  • the Raney nickel alloy always has a very high surface area and also contains hydrogen gas (H 2 ) adsorbed on the nickel surface.
  • the Raney nickel mentioned above may notably be Ni-Al, Ni-Si, Ni-Sn, Ni-Co-Si alloys. Among these, Ni-Al alloy is more preferable.
  • the weight ratio of the substituted or non-substituted quinone compound and/or the substituted or non-substituted hydroquinone compound to the catalyst according to the invention may be in the range of 0.01 to 100 and preferably 0.01 to 10.
  • the weight ratio of the substituted or non-substituted quinone compound and/or the substituted or non-substituted hydroquinone compound to the supported metal catalyst is in the range of 0.1 to 2 and preferably 0.5 to 1.5.
  • the reaction according to the invention may be performed in the absence or in the presence of a solvent.
  • the solvent may be protic, aprotic or a combination of protic and aprotic solvents.
  • suitable solvent include water, toluene, octanol, xylene, benzene, n-butanol, and acetonitrile.
  • the reaction medium can be a two-liquid-phase system, such as a mixture of water and an organic solvent that is immiscible with water.
  • the reaction medium can be a single-liquid-phase system.
  • the reaction medium can optionally comprise a basic compound.
  • the basic compound is an amine.
  • the basic compound can notably be lithium hydroxide (LiOH) , sodium hydroxide (NaOH) , potassium hydroxide (KOH) , rubidium hydroxide (RbOH) , caesium hydroxide (CsOH) , sodium carbonate (Na 2 CO 3 ) , sodium bicarbonate (NaHCO 3 ) , potassium carbonate (K 2 CO 3 ) , potassium bicarbonate (KHCO 3 ) , trimethylamine (N (CH 3 ) 3 ) or triethylamine (N (CH 2 CH 3 ) 3 ) .
  • Preferred basic compounds are trimethylamine (N (CH 3 ) 3 ) , triethylamine (N (CH 2 CH 3 ) 3 ) , sodium hydroxide (NaOH) and potassium hydroxide (KOH) .
  • the basic compound can help to increase the yield of formic acid.
  • the basic compound can easily be separated from formic acid by well-known ways. For instance, when trimethylamine (N (CH 3 ) 3 ) or triethylamine (N (CH 2 CH 3 ) 3 ) is added to the reaction medium, it can be removed by evaporation.
  • Carbon dioxide (CO 2 ) according to the present invention is in the gas form.
  • the gas pressure of CO 2 may be from 2 bar to 40 bar and preferably from 25 bar to 35 bar.
  • the gas pressure of H 2 may be from 2 bar to 40 bar and preferably from 25 bar to 35 bar.
  • the reaction temperature according to the present invention may be from 25°C to 80°C.
  • the reaction time according to the present invention may be from 1 hour to 20 hours and preferably from 2 hour to 6 hours.
  • the process according to the present invention may be a one-step process.
  • the catalyst comprising a metal chosen from the group consisting of Pd, Pt, Ru, Rh, Au, Ag, Ir, Ni and Co, and optionally the basic compound together, formic acid is then produced under reaction condition as mentioned above.
  • the metal catalyst is first modified by the deposition of the substituted or non-substituted quinone compound and/or the substituted or non-substituted hydroquinone compound. Afterwards, by mixing carbon dioxide, hydrogen, the solvent, modified metal catalyst and optionally the basic compound together, formic acid is then produced under reaction condition above mentioned.
  • the process involves the following steps:
  • step (iii) reacting carbon dioxide with hydrogen in the presence of a solvent, the solid composite obtained at step (ii) , and optionally a basic compound.
  • the catalyst in step (i) can be preferably supported metal catalyst comprising at least one noble metal element chosen from the group consisting of Pd, Pt, Ru and Au.
  • the solvent in step (i) or step (iii) is not particularly limited.
  • the solvent in step (i) can preferably be some organic solvents, such as toluene, octanol, xylene, benzene, n-butanol, and acetonitrile.
  • the solvent in step (iii) can preferably be water.
  • the concentration of formic acid produced by above mentioned multi-step process may be in the range of 0.60 to 0.80 mol/L.
  • the reaction results in the obtention of a solid comprising the catalyst and a reaction product.
  • the process then comprises the additional steps of:
  • step (iv) exposing the solution obtained at step (iii) to a basic compound and then heating the solution.
  • the catalyst in this embodiment can be preferably a supported metal catalyst comprising at least one noble metal element chosen from the group consisting of Pd, Pt, Ru and Au.
  • the weight ratio of the substituted or non-substituted quinone compound and/or the substituted or non-substituted hydroquinone compound to the supported metal catalyst in this embodiment is in the range of 10 to 80 and preferably 15 to 50.
  • the non-polar solvent can be toluene, xylene or benzene.
  • the polar solvent in step (ii) can be methanol, ethanol or water.
  • step (iv) as the same meaning as above mentioned.
  • the heating in step (iv) is performed under an inert or CO 2 atmosphere.
  • the heating temperature is from 25°C to 80°C.
  • the concentration of formic acid produced by above mentioned multi-step process may be in the range of 0.60 to 1.00 mol/L.
  • the present invention also relates to a composition
  • a composition comprising:
  • a catalyst comprising a metal chosen from the group consisting of Pd, Pt, Ru, Rh, Au, Ag, Ir, Ni and Co.
  • the composition may further comprise a basic compound.
  • the catalyst was prepared by addition of 50 mg of 14 wt. %Pd-26 wt. %Au/C in the solution of 50 mg 2-ethyl-9, 10-anthraquinone (EQ) dissolved in 1 ml of xylene. Solvent was removed afterwards in the rotovap and the catalyst was dried at 80°C in vacuum.
  • the catalyst was added in 50 ml stainless steel reactor together with 0.6 g of trimethylamine in 4 g of water as formic acid extracting solution.
  • the reactor was sealed and pressurized with 30 bar of H 2 and 30 bar of CO 2 .
  • the reaction was heated to 60°C for 17 h under continuous stirring. After reaction the products were analyzed by NMR and Ionic conductivity method.
  • the amount of produced formic acid was 115 mg with concentration 0.65 M in aqueous solution. No other products of CO 2 hydrogenation was observed in the products.
  • the catalyst was prepared by addition of 50 mg of 40 wt. %Pd/C in the solution of 50 mg 2-ethyl-9, 10-anthraquinone (EQ) dissolved in 1 ml of xylene. Solvent was removed afterwards in the rotovap and the catalyst was dried at 80°C in vacuum.
  • the catalyst was added in 50 ml stainless steel reactor together with 0.9 g of trimethylamine in 6 g of water as formic acid extracting solution.
  • the reactor was sealed and pressurized with 30 bar of H 2 and 30 bar of CO 2 .
  • the reaction was heated to 60°C for 5 h under continuous stirring. After reaction the products were analyzed by NMR and Ionic conductivity method.
  • the amount of produced formic acid was 154 mg with concentration 0.55 M in aqueous solution. No other products of CO 2 hydrogenation was observed in the products.
  • the catalyst was prepared by addition of 50 mg of 40 wt. %Pd/C in the solution of 100 mg 2-ethyl-9, 10-anthraquinone (EQ) dissolved in 1 ml of xylene. Solvent was removed afterwards in the rotovap and the catalyst was dried at 80°C in vacuum.
  • EQ 2-ethyl-9, 10-anthraquinone
  • the catalyst was added in 50 ml stainless steel reactor together with 0.9 g of trimethylamine in 6 g of water as formic acid extracting solution.
  • the reactor was sealed and pressurized with 30 bar of H 2 and 30 bar of CO 2 .
  • the reaction was heated to 60°C for 5 h under continuous stirring. After reaction the products were analyzed by NMR and Ionic conductivity method.
  • the amount of produced formic acid was 2234 mg with concentration 0.81 M in aqueous solution. No other products of CO 2 hydrogenation was observed in the products.
  • the test like in the example 13 has been repeated 3 times by recycling and reusing the metal catalyst.
  • the amount of produced formic acid was 157, 149 and 152 mg. It indicates on high reproducibility of the results and high efficiency of the process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'acide formique par réaction du dioxyde de carbone avec de l'hydrogène en présence d'un catalyseur hétérogène.
PCT/CN2018/115552 2017-11-15 2018-11-15 Procédé de production d'acide formique WO2019096190A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880070887.8A CN111315716B (zh) 2017-11-15 2018-11-15 用于生产甲酸的方法
EP18877890.6A EP3710420A4 (fr) 2017-11-15 2018-11-15 Procédé de production d'acide formique

Applications Claiming Priority (2)

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CN2017110998 2017-11-15
CNPCT/CN2017/110998 2017-11-15

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WO2019096190A1 true WO2019096190A1 (fr) 2019-05-23

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103649036A (zh) * 2011-07-07 2014-03-19 巴斯夫欧洲公司 通过使二氧化碳与氢气反应制备甲酸的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4822253B2 (ja) * 2005-08-23 2011-11-24 独立行政法人産業技術総合研究所 二酸化炭素と水素からギ酸塩の製造方法
GB2464710B (en) * 2008-10-23 2011-01-05 Schlumberger Holdings Production of formic acid and catalyst therefor
RU2013103599A (ru) * 2010-06-29 2014-08-10 Басф Се Способ получения муравьиной кислоты в результате взаимодействия диоксида углерода с водородом
US20130331607A1 (en) * 2012-06-11 2013-12-12 Basf Se Process for preparing formic acid
EP2767530A1 (fr) * 2013-02-15 2014-08-20 EOS Holding SA Hydrogénation de dioxyde de carbone directe en acide formique dans des milieux acides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103649036A (zh) * 2011-07-07 2014-03-19 巴斯夫欧洲公司 通过使二氧化碳与氢气反应制备甲酸的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NGUYEN, LAN THI MAI ET AL.: "Catalytic C02 hydrogenation to formic acid over carbon nanotube-graphene supported PdNi alloy catalysts", RSC ADV., vol. 5, 3 December 2015 (2015-12-03), pages 105560 - 105566, XP055610017 *
ROHMANN, KAI ET AL.: "Hydrogenation of C02 to Formic Acid with a Highly Active Ruthenium Acriphos Complex in DMSO and DMSO/Water", ANGEW. CHEM. INT. ED., vol. 55, 30 June 2016 (2016-06-30), pages 8966 - 8969, XP055610019 *
See also references of EP3710420A4 *

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EP3710420A4 (fr) 2021-08-04
CN111315716A (zh) 2020-06-19
EP3710420A1 (fr) 2020-09-23
CN111315716B (zh) 2023-04-14

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