WO2013050367A3 - Method for producing formic acid by reacting carbon dioxide with hydrogen - Google Patents

Method for producing formic acid by reacting carbon dioxide with hydrogen Download PDF

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Publication number
WO2013050367A3
WO2013050367A3 PCT/EP2012/069458 EP2012069458W WO2013050367A3 WO 2013050367 A3 WO2013050367 A3 WO 2013050367A3 EP 2012069458 W EP2012069458 W EP 2012069458W WO 2013050367 A3 WO2013050367 A3 WO 2013050367A3
Authority
WO
WIPO (PCT)
Prior art keywords
phase
formic acid
tertiary amine
mixture
raffinate
Prior art date
Application number
PCT/EP2012/069458
Other languages
German (de)
French (fr)
Other versions
WO2013050367A2 (en
Inventor
Thomas Schaub
Oliver Bey
Anton Meier
Donata Maria Fries
Randolf Hugo
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Priority to CA2851175A priority Critical patent/CA2851175A1/en
Priority to RU2014118032/04A priority patent/RU2014118032A/en
Priority to BR112014008338A priority patent/BR112014008338A2/en
Priority to CN201280059095.3A priority patent/CN103974927A/en
Priority to IN3122DEN2014 priority patent/IN2014DN03122A/en
Priority to EP12766684.0A priority patent/EP2763950A2/en
Priority to SG11201400997TA priority patent/SG11201400997TA/en
Priority to KR1020147011873A priority patent/KR20140074373A/en
Publication of WO2013050367A2 publication Critical patent/WO2013050367A2/en
Publication of WO2013050367A3 publication Critical patent/WO2013050367A3/en

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Classifications

    • 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
    • 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
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • 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
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
    • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases

Landscapes

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

Abstract

The invention relates to a method for producing formic acid, comprising the following steps: (a) reacting, in a homogeneously catalyzed manner, a reaction mixture (Rg) containing carbon dioxide, hydrogen, at least one polar solvent and at least one tertiary amine in the presence of at least one coordination catalyst in a hydrogenation reactor in order to obtain a two-phase hydrogenation mixture (H) containing an upper phase (O1), which contains the at least one coordination catalyst and the at least one tertiary amine (A1), and a lower phase (U1), which contains the at least one polar solvent, residues of the at least one coordination catalyst, and at least one formic acid/amine adduct; (b) processing the hydrogenation mixture (H) obtained in step (a) according to one of the following steps: (b1) phase-separating the hydrogenation mixture (H) obtained in step (a) in a first phase-separating device into the upper phase (O1) and the lower phase (U1), or (b2) extracting the at least one coordination catalyst from the hydrogenation mixture (H) obtained in step (a) in an extraction unit with an extracting agent containing the at least one tertiary amine (A1) in order to obtain a raffinate (R1) containing the at least one formic acid/amine adduct (A2) and the at least one polar solvent and an extract (E1) containing the at least one tertiary amine (A1) and the at least one coordination catalyst, or (b3) phase-separating the hydrogenation mixture (H) obtained in step (a) in a first phase-separating device into the upper phase (O1) and the lower phase (U1) and extracting the residues of the at least one coordination catalyst from the lower phase (U1) in an extraction unit by means of an extracting agent containing the at least one tertiary amine (A1) in order to obtain a raffinate (R2) containing the at least one formic acid/amine adduct (A2) and the at least one polar solvent and an extract (E2) containing the at least one tertiary amine (A1) and the residues of the at least one coordination catalyst; (c) separating the at least one polar solvent from the lower phase (U1), from the raffinate (R1), or from the raffinate (R2) in a first distillation device in order to obtain a distillate (D1) containing the at least one polar solvent, which is fed back into the hydrogenation reactor in step (a), and a two-phase bottom mixture (S1) containing an upper phase (O2), which contains the at least one tertiary amine (A1), and a lower phase (U2), which contains the at least one formic acid/amine adduct (A2); (e) cleaving the at least one formic acid/amine adduct (A2) contained in the bottom mixture (S1) or optionally in the lower phase (U2) in a thermal cleaving unit in order to obtain the at least one tertiary amine (A1), which is fed back to the hydrogenation reactor in step (a), and formic acid, which is discharged from the thermal cleaving unit, wherein carbon monoxide is added to the lower phase (U1), the raffinate (R1), or the raffinate (R2) directly before and/or during step (c) and/or carbon monoxide is added to the bottom mixture (S1) or optionally the bottom phase (U2) directly before and/or during step (e).
PCT/EP2012/069458 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen WO2013050367A2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA2851175A CA2851175A1 (en) 2011-10-07 2012-10-02 Process for preparing formic acid by reacting carbon dioxide with hydrogen
RU2014118032/04A RU2014118032A (en) 2011-10-07 2012-10-02 METHOD FOR PRODUCING FORMIC ACID BY TRANSFORMING CARBON DIOXIDE WITH HYDROGEN
BR112014008338A BR112014008338A2 (en) 2011-10-07 2012-10-02 process for preparing formic acid
CN201280059095.3A CN103974927A (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen
IN3122DEN2014 IN2014DN03122A (en) 2011-10-07 2012-10-02
EP12766684.0A EP2763950A2 (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen
SG11201400997TA SG11201400997TA (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen
KR1020147011873A KR20140074373A (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11184297.7 2011-10-07
EP11184297 2011-10-07

Publications (2)

Publication Number Publication Date
WO2013050367A2 WO2013050367A2 (en) 2013-04-11
WO2013050367A3 true WO2013050367A3 (en) 2013-10-03

Family

ID=46963751

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/069458 WO2013050367A2 (en) 2011-10-07 2012-10-02 Method for producing formic acid by reacting carbon dioxide with hydrogen

Country Status (10)

Country Link
EP (1) EP2763950A2 (en)
JP (1) JP2014530216A (en)
KR (1) KR20140074373A (en)
CN (1) CN103974927A (en)
BR (1) BR112014008338A2 (en)
CA (1) CA2851175A1 (en)
IN (1) IN2014DN03122A (en)
RU (1) RU2014118032A (en)
SG (1) SG11201400997TA (en)
WO (1) WO2013050367A2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201112231D0 (en) * 2011-07-15 2011-08-31 Verdant Bioproducts Ltd Micro-organism
US8596013B2 (en) 2012-04-04 2013-12-03 Valinge Innovation Ab Building panel with a mechanical locking system
US9428438B2 (en) 2012-11-27 2016-08-30 Basf Se Process for preparing formic acid
WO2016024293A1 (en) 2014-08-12 2016-02-18 Council Of Scientific & Industrial Research Metal catalyzed process for reduction of co2 to sodium formate and formic acid

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095321A2 (en) * 1982-05-22 1983-11-30 BP Chemicals Limited Production of formate salts
EP0181078A1 (en) * 1984-09-29 1986-05-14 BP Chemicals Limited Process for the preparation of formic acid
EP0329337A2 (en) * 1988-02-17 1989-08-23 BP Chemicals Limited The production of formic acid from a nitrogenous base, carbon dioxide and hydrogen
WO2008116799A1 (en) * 2007-03-23 2008-10-02 Basf Se Method for producing formic acid
WO2010149507A2 (en) * 2009-06-26 2010-12-29 Basf Se Method for producing formic acid

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004040789A1 (en) 2004-08-23 2006-03-02 Basf Ag Process for the preparation of formic acid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095321A2 (en) * 1982-05-22 1983-11-30 BP Chemicals Limited Production of formate salts
EP0181078A1 (en) * 1984-09-29 1986-05-14 BP Chemicals Limited Process for the preparation of formic acid
EP0329337A2 (en) * 1988-02-17 1989-08-23 BP Chemicals Limited The production of formic acid from a nitrogenous base, carbon dioxide and hydrogen
WO2008116799A1 (en) * 2007-03-23 2008-10-02 Basf Se Method for producing formic acid
WO2010149507A2 (en) * 2009-06-26 2010-12-29 Basf Se Method for producing formic acid

Also Published As

Publication number Publication date
WO2013050367A2 (en) 2013-04-11
CA2851175A1 (en) 2013-04-11
JP2014530216A (en) 2014-11-17
CN103974927A (en) 2014-08-06
SG11201400997TA (en) 2014-09-26
KR20140074373A (en) 2014-06-17
IN2014DN03122A (en) 2015-05-22
BR112014008338A2 (en) 2017-04-18
RU2014118032A (en) 2015-11-20
EP2763950A2 (en) 2014-08-13

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