EP2729438A1 - Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène - Google Patents

Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène

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Publication number
EP2729438A1
EP2729438A1 EP12730532.4A EP12730532A EP2729438A1 EP 2729438 A1 EP2729438 A1 EP 2729438A1 EP 12730532 A EP12730532 A EP 12730532A EP 2729438 A1 EP2729438 A1 EP 2729438A1
Authority
EP
European Patent Office
Prior art keywords
phase
formic acid
mixture
tertiary amine
catalyst
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP12730532.4A
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German (de)
English (en)
Inventor
Thomas Schaub
Donata Maria Fries
Rocco Paciello
Peter Bassler
Martin Schäfer
Stefan Rittinger
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BASF SE
Original Assignee
BASF SE
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Priority to EP12730532.4A priority Critical patent/EP2729438A1/fr
Publication of EP2729438A1 publication Critical patent/EP2729438A1/fr
Withdrawn legal-status Critical Current

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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
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • 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
    • 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
    • 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
    • B01J2531/96—Water
    • 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

Definitions

  • the invention relates to a process for the preparation of formic acid by reacting carbon dioxide with hydrogen in a hydrogenation reactor in the presence of a catalyst containing an element from the 8th, 9th or 10th group of the periodic table, a tertiary amine and a polar solvent, with formation of formic acid-amine adducts, which are then thermally cleaved to formic acid and tertiary amine.
  • Adducts of formic acid and tertiary amines can be thermally cleaved into free formic acid and tertiary amine and therefore serve as intermediates in the preparation of formic acid.
  • Formic acid is an important and versatile product. It is used, for example, for acidification in the production of animal feed, as a preservative, as a disinfectant, as an adjuvant in the textile and leather industry, as a mixture with their salts for de-icing of airplanes and runways and as a synthesis component in the chemical industry.
  • the said adducts of formic acid and tertiary amines can be prepared in various ways, for example (i) by direct reaction of the tertiary amine with formic acid, (ii) by hydrolysis of methyl formate to formic acid in the presence of the tertiary amine, (iii) by catalytic Hydration of carbon monoxide in the presence of the teriary amine or (iv) by hydrogenation of carbon dioxide to formic acid in the presence of the tertiary amine.
  • the latter method of catalytic hydrogenation of carbon dioxide has the particular advantage that carbon dioxide is available in large quantities and is flexible in its source.
  • EP 0 095 321 describes a process for the preparation of trialkylammonium formates, ie of an adduct of formic acid and a tertiary amine, by hydrogenation of carbon dioxide in the presence of a tertiary amine, a solvent and a transition metal catalyst of VIII.
  • Subgroup of the Periodic Table (Groups 8, 9, 10 according to IUPAC).
  • the catalyst used is preferably ruthenium trichloride.
  • tertiary amine and solvent triethylamine and a mixture of isopropanol and water are preferred.
  • the reaction takes place in an autoclave at 82 bar and 80 ° C.
  • the working up of the reaction mixture is carried out by distillation, whereby a first fraction containing isopropanol, water and triethylamine and a second fraction containing the adduct of formic acid and triethylamine are obtained.
  • the thermal decomposition of the adduct of formic acid and triethylamine to formic acid is not described in EP 0 095 321.
  • EP 0 151 510 also describes a process for the preparation of adducts of formic acid and triethylamine, wherein the catalyst used is a rhodium-containing complex catalyst.
  • the reaction is also carried out in an autoclave, the work-up of the resulting reaction mixture is carried out as in EP 0 095 321 by distillation.
  • EP 0 126 524 and EP 0 181 078 describe a process for the preparation of formic acid by thermal cleavage of adducts of formic acid and a teriary amine.
  • the process for producing formic acid comprises the following steps: i) reacting carbon dioxide and hydrogen in the presence of a volatile tertiary amine and a catalyst to obtain the adduct
  • Formic acid and the volatile tertiary amine ii) separation of the adduct of formic acid and volatile tertiary amine from the catalyst and the gaseous components in an evaporator, iii) separation of the unreacted volatile tertiary amine in a distillation column or in a phase separator of the adduct of formic acid and the volatile tertiary amine, iv) base exchange of the volatile tertiary amine in the adduct of formic acid and the volatile tertiary amine by a less volatile and weaker nitrogen base, such as 1-n-butylimidazole, v) thermal cleavage of the adduct of formic acid and the less volatile and weaker nitrogen base to give formic acid and the less volatile and weaker nitrogen base.
  • a less volatile and weaker nitrogen base such as 1-n-butylimidazole
  • EP 0 126 524 and EP 0 181 078 the volatile tertiary amine in the formic acid adduct must be exchanged by a less volatile and weaker nitrogen base, such as, for example, 1-n-butylimidazole, before the thermal cleavage.
  • a less volatile and weaker nitrogen base such as, for example, 1-n-butylimidazole
  • a further significant disadvantage of the processes according to EP 0 126 524 and EP 0 181 078 is the fact that the separation of the adduct of formic acid and volatile tertiary amine according to the above-described step ii) of EP 0 126 524 and EP 0 181 078 in one Evaporator is carried out in the presence of the catalyst.
  • the cleavage leads to a significant reduction in the yield of adduct of formic acid and volatile tertiary amine and thus to a reduction in the yield of the target product formic acid.
  • EP 0 329 337 proposes the addition of an inhibitor which reversibly inhibits the catalyst in order to solve this problem.
  • Preferred inhibitors include carboxylic acids, carbon monoxide and oxidizing agents.
  • the production of formic acid therefore comprises the steps i) to v) described above for EP 0 126 524 and EP 0 181 078, the addition of the inhibitor taking place after step i) and before or during step ii).
  • EP 0 329 337 A further disadvantage of EP 0 329 337 is that a large part of the catalyst in the process is inhibited. Therefore, in the process according to EP 0 329 337, the inhibited catalyst must be reactivated before reuse in the hydrogenation (step i)).
  • WO 2010/149507 describes a process for the preparation of formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine, a transition metal catalyst and a high boiling polar solvent with an electrostatic factor> 200 * 10 "30 cm, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol and glycerol to give a reaction mixture which contains the formic acid amine.
  • a tertiary amine such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1, 3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, dipropylene glycol, 1,5-pentanedi
  • Adduct Adduct, the tertiary amine, the high-boiling polar solvent and the catalyst
  • the reaction mixture is worked up according to WO 2010/149507 according to the following steps: 1) phase separation of the reaction mixture to obtain an upper phase containing the tertiary amine and the catalyst and a lower phase containing the formic acid-amine adduct, the high-boiling polar solvents and residues of the catalyst; Recycling of the upper phase for hydrogenation,
  • the process according to WO 2010/149507 has the advantage over the processes according to EP 0 095 321, EP 0 151 510, EP 0 126 524, EP 0 181 078 and EP 0 329 337 that it can be carried out without the complex base exchange step (step (iv)). ) and allows separation and recycling of the catalyst in its active form.
  • a disadvantage of the process of WO 2010/149507 is that the separation of the catalyst despite phase separation (step 1)) and extraction (step 2)) is not always completely successful, so that traces of catalyst contained in the raffinate in the thermal cracking in the distillation column in Step 3) can catalyze the cleavage of the formic acid-amine adduct to carbon dioxide and hydrogen and the tertiary amine. It is also disadvantageous that esterification of the formic acid formed with the high-boiling polar solvents (diols and polyols) occurs in the thermal cleavage of the formic acid-amine adduct in the distillation column. This leads to a reduction in the yield of the target product formic acid.
  • the object of the present invention was to provide a process for the preparation of formic acid by hydrogenation of carbon dioxide, which does not have the disadvantages of the prior art or only to a significantly reduced extent and which leads to concentrated formic acid in high yield and high purity , Furthermore, the method should allow a simpler process control, as described in the prior art, in particular a simpler process concept for working up the discharge from the hydrogenation reactor, simpler process steps, a smaller number of process stages or simpler Apparatuses. Furthermore, the method should also be able to be carried out with the lowest possible energy requirement.
  • At least one polar solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general formula ( A1)
  • R 1 , R 2 , R 3 independently of one another are unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic
  • X is in the range of 0.4 to 5 and
  • R 1 , R 2 , R 3 have the meanings given above,
  • step (b1) phase separation of the hydrogen mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase (U1) or
  • step (b2) Extraction of the at least one catalyst from the hydrogen mixture (H) obtained in step (a) in an extraction unit with an extractant containing at least one tertiary amine (A1) 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 catalyst or
  • step (b3) phase separation of the obtained in step (a) Hydnergemischs (H) in a first phase separation device in the upper phase (01) and the lower phase (U1) and extraction of the residues of the at least one catalyst from the lower phase (U1) in an extraction unit with a Extraction agent comprising the at least one tertiary amine (A1) 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 radicals of the at least one catalyst, (c) at least partially separating the at least one polar solvent from the lower phase (U 1), from the raffinate (R1) or from the raffinate (R2) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent, which is recycled to the hydrogenation reactor in step (a) and a biphasic bottoms mixture (S1)
  • step (A2) in a thermal cleavage unit to obtain the at least one tertiary amine (A1) which is recycled to the hydrogenation reactor in step (a) and formic acid discharged from the thermal cleavage unit, immediately before and / or during step (C) the lower phase (U 1), the raffinate (R1) or the raffinate (R2) is added at least one inhibitor selected from the group consisting of carboxylic acids other than formic acid, of carboxylic acid derivatives other than formic acid derivatives and oxidizing agents.
  • a reaction mixture (Rg) which comprises carbon dioxide, hydrogen, at least one catalyst containing at least one element selected from groups 8, 9 and 10 of the Periodic Table, at least one polar solvent selected from the Group consisting of methanol, ethanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general formula (A1).
  • the carbon dioxide used in process step (a) can be solid, liquid or gaseous. It is also possible to use gas mixtures containing large quantities of carbon dioxide, provided they are substantially free of carbon monoxide (volume fraction of ⁇ 1% CO).
  • the hydrogen used in the hydrogenation of carbon dioxide in process step (a) is generally gaseous.
  • Carbon dioxide and hydrogen may also contain inert gases, such as nitrogen or noble gases. However, their content is advantageously below 10 mol% based on the total amount of carbon dioxide and hydrogen in the hydrogenation reactor. Although quantities may also be tolerable, they generally require the use of a higher pressure in the reactor, requiring further compression energy.
  • Carbon dioxide and hydrogen can be fed to process stage (a) as separate streams. It is also possible to use a mixture containing carbon dioxide and hydrogen in process step (a).
  • tertiary amine (A1) is used in process step (a) in the hydrogenation of carbon dioxide.
  • tertiary amine (A1) is understood as meaning both one (1) tertiary amine (A1) and mixtures of two or more tertiary amines (A1).
  • the tertiary amine (A1) used in the process according to the invention is preferably selected in such a way or with the polar solvent that the hydrogenation mixture (H) obtained in process step (a), if appropriate after the addition of water, is at least biphasic.
  • the hydrogenation mixture (H) contains an upper phase (01) containing the at least one catalyst and the at least one tertiary amine (A1), and a lower phase (U 1) containing the at least one polar solvent, residues of the catalyst and at least one formic acid Amine adduct (A2).
  • the tertiary amine (A1) should be enriched in the upper phase (01), i. the upper phase (01) should contain the main part of the tertiary amine (A1).
  • enriched or "main part” with respect to the tertiary amine (A1) is a weight fraction of the free tertiary amine (A1) in the upper phase (01) of> 50% based on the total weight of the free tertiary Amine (A1) in the liquid phases, ie the upper phase (01) and the lower phase (U 1) in the hydrogenation mixture (H) to understand.
  • free tertiary amine (A1) is meant the tertiary amine (A1) which is not bound in the form of the formic acid-amine adduct (A2).
  • the weight fraction of the free tertiary amine (A1) in the upper phase (01) is preferably> 70%, in particular> 90%, in each case based on the total weight of the free tertiary amine (A1) in the upper phase (01) and the lower phase ( U 1) in the hydrogenation mixture (H).
  • the selection of the tertiary amine (A1) is generally carried out by a simple experiment in which the phase behavior and the solubility of the tertiary amine (A1) in the liquid phases (upper phase (01) and lower phase (U1)) under the process conditions in the process stage (a) be determined experimentally.
  • non-polar solvents such as aliphatic, aromatic or araliphatic solvents may be added to the tertiary amine (A1).
  • Preferred non-polar solvents are, for example, octane, toluene and / or xylenes (o-xylene, m-xylene, p-xylene).
  • the preferred tertiary amine to be used in the process according to the invention is an amine of the general formula
  • NR 1 R 2 R 3 in which the radicals R 1 , R 2 , R 3 are identical or different and independently of one another are an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical having in each case 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, wherein individual carbon atoms can be substituted independently of one another by a hetero group selected from the groups -O- and> N- and two or all three radicals with formation a chain comprising at least four atoms each can also be connected to each other.
  • a tertiary amine of the general formula (A1) is used, with the proviso that the total number of carbon atoms is at least 9.
  • Suitable tertiary amines of the formula (A1) are:
  • Di-methyl-decylamine dimethyldodecylamine, dimethyl-tetradecylamine, ethyl-di (2-propyl) amine, dioctyl-methylamine, dihexyl-methylamine.
  • triphenylamine methyldiphenylamine, ethyldiphenylamine, propyldiphenylamine, butyldiphenylamine, 2-ethylhexyldiphenylamine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, bis (2-ethylhexyl ) - phenylamine, tribenzylamine, methyl-dibenzylamine, ethyl-dibenzylamine and theirs by one or more methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl or 2-methyl-2- propyl groups substituted derivatives.
  • Nd-bis-C 1-4 -alkyl-piperidines N, N-di-d-bis-C 1-4 -alkyl-piperazines, N-crib-C 12 -alkyl-pyrrolidones, NC-bis-C 1-4 -alkyl-imidazoles and theirs one or more methyl.
  • DBU 1, 8-diazabicyclo [5.4.0] undsec-7-ene
  • DABCO 1, 4-diazabicyclo [2.2.2] octane
  • tropane N-methyl-8-azabicyclo [3.2 .1] octane
  • garnetane N-methyl-9-azabicyclo [3.3.1] nonane
  • 1-azabicyclo [2.2.2] octane quinuclidine
  • mixtures of two or more different tertiary amines (A1) can also be used.
  • the tertiary amine of the general formula (A1) is an amine in which the radicals R 1 , R 2 , R 3 are independent are selected from the group (to C 12 alkyl, C 5 - to C 8 cycloalkyl, benzyl and phenyl, a.
  • a saturated amine i. containing only single bonds of the general formula (A1).
  • An especially suitable amine in the process according to the invention is a tertiary amine of the general formula (A1) in which the radicals R 1 , R 2 , R 3 are independently selected from the group C 5 - to C 8 -alkyl, in particular tri -n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine,
  • Dimethylcyclohexylamine, methyldicyclohexylamine, dioctylmethylamine and dimethyldecylamine is used.
  • the tertiary amine used is an amine of the general formula (A1) in which the radicals R 1 , R 2 and R 3 are selected independently of one another from C 5 - and C 6 -alkyl.
  • tri-n-hexylamine is used as the tertiary amine of the general formula (A1).
  • the tertiary amine (A1) in the process according to the invention is preferably liquid in all process stages. However, this is not a mandatory requirement. It would also be sufficient if the tertiary amine (A1) were dissolved at least in suitable solvents.
  • Suitable solvents are in principle those which are chemically inert with respect to the hydrogenation of carbon dioxide, in which the tertiary amine (A1) and the catalyst dissolve well and in which, conversely, the polar solvent and the formic acid-amine adduct (A2) dissolve poorly ,
  • chemically inert, nonpolar solvents such as aliphatic, aromatic or araliphatic hydrocarbons, such as octane and higher alkanes, toluene, xylenes.
  • At least one polar solvent is selected in process step (a) in the hydrogenation of carbon dioxide from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1 - propanol and water used.
  • polar solvent is understood to mean both one (1) polar solvent and mixtures of two or more polar solvents.
  • the polar solvent used in the process according to the invention is preferably selected or matched with the tertiary amine (A1) so that it preferably meets the following criteria with regard to the phase behavior in the hydrogenation reactor in process step (a):
  • the polar solvent should preferably be selected such that the hydrogenation mixture (H) obtained in process step (a) is at least biphasic.
  • the polar solvent should be enriched in the lower phase (U 1), ie the lower phase (U 1) should contain the main part of the polar solvent.
  • enriched or “main part” with respect to the polar solvent is a weight fraction of the polar solvent in the lower phase (U 1) of> 50%, based on the total weight of the polar solvent in the liquid phases (upper phase ( 01) and lower phase (U 1)) in the hydrogenation reactor to understand.
  • the weight fraction of the polar solvent in the lower phase (U 1) is preferably> 70%, in particular> 90%, in each case based on the total weight of the polar solvent in the upper phase (01) and the lower phase (U 1).
  • the selection of the polar solvent satisfying the above criteria is generally accomplished by a simple experiment in which the phase behavior and the solubility of the polar solvent in the liquid phases (upper phase (01) and lower phase (U 1)) under the process conditions in Process step (a) are determined experimentally.
  • the polar solvent may be a pure polar solvent or a mixture of two or more polar solvents as long as the polar solvent or mixture of polar solvents meets the above-described phase behavior and solubility criteria in the upper phase (01) and the above Subphase (U 1) in the hydrogenation reactor in process step (a).
  • step (a) first of all a single-phase hydrogenation mixture is obtained, which is converted into the biphasic hydrogenation mixture (H) by the addition of water.
  • the biphasic hydrogenation mixture (H) is obtained directly in step (a).
  • the biphasic hydrogenation mixture (H) obtained in this embodiment can be directly fed to the work-up of step (b). It is also possible to additionally add Waser to the biphasic hydrogenation mixture (H) before further processing in step (b). This can lead to an increase of the distribution coefficient P K.
  • the ratio of alcohol to water is chosen so that together with the formic acid-amine adduct (A2) and the tertiary amine (A1) at least two-phase Hydrogenation mixture (H) containing the upper phase (01) and the lower phase (U 1) is formed.
  • a polar solvent a mixture of alcohol (selected from the group consisting of methanol, ethanol, 1 - propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl- 1 -propanol) and water is used, the ratio of alcohol to water is chosen so that, together with the formic acid-amine adduct (A2) and the tertiary amine (A1) first a single-phase hydrogenation mixture is formed, which is subsequently by addition of Water is transferred to the biphasic hydrogenation mixture (H).
  • the polar solvent used is water, methanol or a mixture of water and methanol.
  • diols and their formic acid esters, polyols and their formic acid esters, sulfones, sulfoxides and open-chain or cyclic amides as the polar solvent is not preferred. In a preferred embodiment, these polar solvents are not contained in the reaction mixture (Rg).
  • the molar ratio of the polar solvent or solvent mixture used in the process according to the invention in process step (a) to the tertiary amine (A1) used is generally 0.5 to 30 and preferably 1 to 20.
  • the catalyst used in the process according to the invention in process step (a) for the hydrogenation of carbon dioxide comprises at least one element selected from groups 8, 9 and 10 of the periodic table (nomenclature according to I UPAC).
  • Groups 8, 9 and 10 of the Periodic Table include Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt.
  • one (1) catalyst or a mixture of two or more catalysts can be used.
  • one (1) catalyst is used.
  • “catalyst” is understood to mean both one (1) catalyst and mixtures of two or more catalysts.
  • the catalyst contains at least one element selected from the group consisting of Ru, Rh, Pd, Os, Ir and Pt, more preferably at least one element selected from the group consisting of Ru, Rh and Pd. Most preferably, the catalyst contains Ru.
  • a complex-type compound (complex catalyst) of the above-mentioned elements is preferably used.
  • the reaction in process step (a) is preferably carried out homogeneously catalyzed.
  • homogeneously catalyzed means that the catalytically active part of the complex-like compound (of the complex catalyst) is present at least partially dissolved in the liquid reaction medium.
  • the complex catalyst used in process step (a) is dissolved in the liquid reaction medium, more preferably at least 95%, especially preferably more than 99%, most preferably the complex catalyst is completely dissolved in the liquid reaction medium (100%). ), in each case based on the total amount of complex catalyst present in the liquid reaction medium.
  • the amount of the metal components of the complex catalyst in process step (a) is generally from 0.1 to 5000 ppm by weight, preferably from 1 to 800 ppm by weight and more preferably from 5 to 800 ppm by weight, based in each case on the entire liquid reaction mixture (Rg) in the hydrogenation reactor.
  • the complex catalyst is selected so that it is enriched in the upper phase (01), ie the upper phase (01) contains the main part of the catalyst.
  • a distribution coefficient P K > 1.5 is preferred, and a distribution coefficient P K > 4 is particularly preferred.
  • the complex catalyst is generally selected by a simple experiment in which the phase behavior and the solubility of the complex catalyst in the liquid phases (upper phase (01) and lower phase (U 1)) under the process conditions in process step (a).
  • catalysts preferably homogeneous catalysts, in particular an organometallic complex compound containing an element from the 8th, 9th or 10th group of the periodic table and at least one phosphine group with at least one unbranched or branched, acyclic or cyclic, aliphatic radical having 1 to 12 carbon atoms, wherein individual carbon atoms may also be substituted by> P-.
  • organometallic complex compound containing an element from the 8th, 9th or 10th group of the periodic table and at least one phosphine group with at least one unbranched or branched, acyclic or cyclic, aliphatic radical having 1 to 12 carbon atoms, wherein individual carbon atoms may also be substituted by> P-.
  • radicals such as, for example, -CH 2 -C 6 HH are thus also included.
  • Suitable radicals are, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 1- (2-methyl) propyl, 2- (2-methyl) propyl, 1-pentyl, 1-hexyl, 1 - Heptyl, 1-octyl, 1 -nonyl, 1-decyl, 1-undecyl, 1-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, methylcyclopentyl, methylcyclohexyl, 1- (2-methyl) -pentyl, 1- (2-ethyl ) -hexyl, 1 (2-propyl) heptyl and norbornyl.
  • the number of carbon atoms is 3 to 12 and preferably at least 4 and preferably at most 8 carbon atoms.
  • Preferred radicals are ethyl, 1-butyl, sec-butyl, 1-octyl and cyclohexyl.
  • the phosphine group can contain one, two or three of the above-mentioned unbranched or branched, acyclic or cyclic, aliphatic radicals. These can be the same or different.
  • the phosphine group contains three of the above-mentioned unbranched or branched, acyclic or cyclic, aliphatic radicals, with particular preference, all three radicals are the same.
  • acyclic or cyclic, aliphatic radicals individual carbon atoms may also be substituted by> P-.
  • multidentate for example, bidentate or tridentate phosphine ligands are also included. These preferably contain the
  • the phosphine group contains radicals other than the abovementioned unbranched or branched, acyclic or cyclic, aliphatic radicals, these generally correspond to those which are customarily used in the case of phosphine ligands for organometallic complex catalysts.
  • acyclic or cyclic, aliphatic radicals these generally correspond to those which are customarily used in the case of phosphine ligands for organometallic complex catalysts.
  • phenyl, tolyl and xylyl examples of its called phenyl, tolyl and xylyl.
  • the organometallic complex compound may contain one or more, for example two, three or four, of the abovementioned phosphine groups having at least one unbranched or branched, acyclic or cyclic, aliphatic radical.
  • the remaining ligands of the organometallic complex may be of different nature. Examples which may be mentioned are hydride, fluoride, chloride, bromide, iodide, formate, acetate, propionate, carboxylate, acetylacetonate, carbonyl, DMSO, hydroxide, trialkylamine, alkoxide.
  • the homogeneous catalysts can be used both directly in their active form and starting from customary standard complexes such as [M (p-cymene) Cl 2 ] 2 , [M (benzene) Cl 2 ] n , [M (COD) (allyl)], [MCI 3 ⁇ H 2 O], [M (acetylacetonate) 3 ], [M (COD) Cl 2 ] 2 , [M (DMSO) 4 Cl 2 ] with M being the same element from the 8th, 9th or 10th Group of the periodic table with the addition of the corresponding or the corresponding phosphine ligands are produced only under reaction conditions.
  • preferred homogeneous catalysts are produced only under reaction conditions.
  • TOF values (turn-over-frequency) of greater than 1000 r.sup.- 1 can be achieved.
  • the hydrogenation of carbon dioxide in process step (a) is preferably carried out in the liquid phase at a temperature in the range of 20 to 200 ° C and a total pressure in the range of 0.2 to 30 MPa abs.
  • the temperature is at least 30 ° C and more preferably at least 40 ° C and preferably at most 150 ° C, more preferably at most 120 ° C and most preferably at most 80 ° C.
  • the total pressure is preferably at least 1 MPa abs and more preferably at least 5 MPa abs and preferably at most 15 MPa abs.
  • the hydrogenation is carried out in process step (a) at a temperature in the range of 40 to 80 ° C and a pressure in the range of 5 to 15 MPa abs.
  • the partial pressure of the carbon dioxide in process step (a) is generally at least 0.5 MPa and preferably at least 2 MPa and generally at most 8 MPa.
  • the hydrogenation in process step (a) is carried out at a partial pressure of the carbon dioxide in the range of 2 to 7.3 MPa.
  • the partial pressure of the hydrogen in process step (a) is generally at least 0.5 MPa and preferably at least 1 MPa and generally at most 25 MPa and preferably at most 10 MPa.
  • the hydrogenation is carried out in process step (a) at a partial pressure of hydrogen in the range of 1 to 10 MPa.
  • the molar ratio of hydrogen to carbon dioxide in the reaction mixture (Rg) in the hydrogenation reactor is preferably 0, 1 to 10 and more preferably 1 to 3.
  • the molar ratio of carbon dioxide to tertiary amine (A1) in the reaction mixture (Rg) in the hydrogenation reactor is preferably 0, 1 to 10 and more preferably 0.5 to 3.
  • the hydrogenation of carbon dioxide can be carried out batchwise or continuously in the process according to the invention.
  • the reactor is equipped with the desired liquid and optionally solid feedstocks and auxiliaries, and then carbon dioxide and the polar solvent are pressed to the desired pressure at the desired temperature.
  • the reactor is normally depressurized and the two liquid phases formed are separated from one another.
  • the feedstocks and auxiliaries, including carbon dioxide and hydrogen are added continuously. Accordingly, the liquid phases are continuously discharged from the reactor, so that the liquid level in the reactor remains the same on average. Preference is given to the continuous hydrogenation of carbon dioxide.
  • the average residence time of the components in the hydrogenation reactor contained in the reaction mixture (Rg) is generally from 5 minutes to 5 hours.
  • a hydrogenation mixture (H) is obtained in process step (a) which contains the catalyst, the polar solvent, the tertiary amine (A1) and the at least one formic acid-amine adduct (A2).
  • formic acid-amine adduct (A2) is understood as meaning both one (1) formic acid-amine adduct (A2) and mixtures of two or more formic acid-amine adducts (A2) or more formic acid-amine adducts (A2) are obtained in process step (a), if in the reaction mixture used (Rg) two or more tertiary amines (A1) are used.
  • a reaction mixture (Rg) is used in process step (a) which comprises a (1) tertiary amine (A1), a hydrogenation mixture (H) being obtained which comprises one (1) formic acid amine.
  • Adduct (A2) contains.
  • a reaction mixture (Rg) is used in process step (a) which comprises tri-n-hexylamine as the tertiary amine (A1) to give a hydrogenation mixture (H) which comprises the formic acid amine.
  • Adduct of tri-n-hexylamine and formic acid corresponds to the following formula (A3)
  • N (n-hexyl) 3 * Xj HCOOH (A3) N (n-hexyl) 3 * Xj HCOOH (A3).
  • the radicals R 1 , R 2 , R 3 have the meanings given above for the tertiary amine of the formula (A1), where the preferences mentioned there apply correspondingly.
  • x is in the range of 0.4 to 5.
  • the factor X indicates the average composition of the formic acid-amine adduct (A2) and (A3), ie, the ratio of bound tertiary amine (A1) to bound formic acid in the formic acid-amine adduct (A2) or (A3).
  • the factor x can be determined, for example, by determining the formic acid content by acid-base titration with an alcoholic KOH solution against phenolphthalein. In addition, a determination of the factor x, by determining the amine content by gas chromatography is possible.
  • the exact composition of the formic acid-amine adduct (A2) or (A3) depends on many parameters, such as the concentrations of formic acid and tertiary amine (A1), the pressure, the temperature and the presence and nature of other components, in particular of the polar solvent. Therefore, the composition of the formic acid amine adduct (A2) or (A3), ie the factor x ,, can also change over the individual process stages.
  • a formic acid-amine adduct (A2) or (A3) with a higher formic acid content generally forms, the excess bound tertiary amine (A1) being formed from the formic acid-amine adduct (A2 ) is split off and forms a second phase.
  • a formic acid-amine adduct (A2) or (A3) is generally obtained in which x is in the range from 0.4 to 5, preferably in the range from 0.7 to 1.6 ,
  • the formic acid-amine adduct (A2) is enriched in the lower phase (U 1), i. the lower phase (U 1) contains the major part of the formic acid-amine adduct.
  • the term "enriched" or "main part" with respect to the formic acid-amine adduct (A2) refers to a weight proportion of the formic acid-amine adduct (A2) in the lower phase (U 1) of> 50% to understand the total weight of the formic acid-amine adduct (A2) in the liquid phases (upper phase (01) and lower phase (U 1)) in the hydrogenation reactor.
  • the weight fraction of the formic acid-amine adduct (A2) in the lower phase (U 1) is preferably> 70%, in particular> 90%, in each case based on the total weight of the formic acid-amine adduct (A2) in the upper phase (01 ) and the lower phase (U 1).
  • the hydrogenation mixture (H) obtained in the hydrogenation of carbon dioxide in process step (a) preferably has two liquid phases and is further worked up in process step (b) according to one of the steps (b1), (b2) or (b3).
  • the hydrogenation mixture (H) is worked up further in step (b1).
  • the invention therefore also provides a process for the preparation of formic acid, comprising the steps
  • reaction mixture comprising carbon dioxide, hydrogen, at least one catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table, at least one polar solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general formula (A1)
  • R 1 , R 2 , R 3 independently represent an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical each having 1 to 16 carbon atoms, wherein individual carbon atoms independently of one another by a hetero group selected from the groups -O- and > N- may be substituted and two or all three radicals may also be linked together to form a chain comprising at least four atoms, in a hydrogenation reactor to obtain, optionally after addition of water, a biphasic hydrogenation mixture (H) containing an upper phase (01 ), which contains the at least one catalyst and the at least one tertiary amine (A1), and a lower phase (U1) containing the at least one polar solvent, residues of the at least one catalyst and at least one formic acid-amine adduct of the general formula (A2 contains)
  • H biphasic hydrogenation mixture
  • U1 lower phase
  • X is in the range of 0.4 to 5 and
  • R 1 , R 2 , R 3 have the meanings given above,
  • step (b1) phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase (U1),
  • Distillation device with preservation a distillate (D1) comprising the at least one polar solvent which is recycled to the hydrogenation reactor in step (a) and a biphasic bottom mixture (S1) containing an upper phase (O 2) containing the at least one tertiary amine (A 1) and a Subphase (U2) containing the at least one formic acid amine adduct (A2),
  • step (d) optionally working up of the first bottoms mixture (S1) obtained in step (c) by phase separation in a second phase separation device into the upper phase (02) and the lower phase (U2),
  • step (e) cleavage of the at least one formic acid-amine adduct (A2) contained in the bottom mixture (S1) or, if appropriate, in the bottom phase (U2) in a thermal splitting unit to give the at least one tertiary amine (A1) which is the hydrogenation reactor in step (a) is recycled, and formic acid derived from the thermal
  • Slitting unit is discharged, immediately before and / or during step (c) of the lower phase (U 1) at least one inhibitor selected from the group consisting of carboxylic acids other than formic acid, carboxylic acid derivatives different from formic acid derivatives and oxidizing agents is added.
  • the hydrogenation mixture (H) obtained in process step (a) is further worked-up in a first phase separation by phase separation to obtain a lower phase (U 1) comprising the at least one formic acid-amine adduct (A2) containing at least one polar solvent and radicals of the at least one catalyst and an upper phase (01) comprising the at least one catalyst and the at least one tertiary amine (A1).
  • the upper phase (01) is recycled to the hydrogenation reactor.
  • the lower phase (U 1) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
  • a further liquid phase comprising both liquid phases containing unreacted carbon dioxide and a gas phase containing unreacted carbon dioxide and / or unreacted hydrogen to the hydrogenation reactor.
  • a further liquid phase comprising both liquid phases containing unreacted carbon dioxide and a gas phase containing unreacted carbon dioxide and / or unreacted hydrogen to the hydrogenation reactor.
  • it is desirable for the discharge of unwanted by-products or impurities, a portion of the upper phase (01) and / or a portion of the carbon dioxide or carbon dioxide and Hydrogen-containing liquid or gaseous phases be desirable for the discharge of unwanted by-products or impurities, a portion of the upper phase (01) and / or a portion of the carbon dioxide or carbon dioxide and Hydrogen-containing liquid or gaseous phases.
  • phase separators are, for example, standard apparatuses and standard methods, which are described, for example, in E. Müller et al., "Liquid-liquid Extraction", in Ullman's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.b93_06, Chapter 3 Find "Apparatus”.
  • the liquid phase enriched with the formic acid-amine adducts (A2) and the polar solvent is heavier and forms the lower phase (U 1).
  • the phase separation may take place, for example, after relaxation to about or near atmospheric pressure and cooling of the liquid hydrogenation mixture, for example at about or near ambient temperature.
  • the polar solvent and the tertiary amine (A1) can be selected such that the separation of the lower phase (U 1) enriched with the formic acid-amine adducts (A2) and the polar solvent from the tertiary amine (A1 ) and catalyst-enriched upper phase (01) and the return of the upper phase (01) to the hydrogenation reactor can be carried out at a pressure of 1 to 30 MPa abs.
  • the pressure is preferably at most 15 MPa abs. It is thus possible, without prior relaxation, to separate both liquid phases (upper phase (01) and lower phase (U 1)) in the first phase separation device and to recirculate the upper phase (01) to the hydrogenation reactor without appreciable pressure increase.
  • the hydrogenation reactor functions simultaneously as the first phase separation device and the process steps (a) and (b1) are both carried out in the hydrogenation reactor.
  • the upper phase (01) remains in the hydrogenation reactor and the lower phase (U 1) is fed to the first distillation apparatus in process stage (c).
  • the process according to the invention is carried out in such a way that the pressure and the temperature in the hydrogenation reactor and in the first phase separation device are the same or approximately the same, under approx equal to a pressure difference of up to +/- 0.5 MPa or a temperature difference of up to +/- 10 ° C is understood.
  • the hydrogenation mixture (H) is worked up further in step (b3).
  • the invention therefore also provides a process for the preparation of formic acid, comprising the steps of homogeneously catalyzed reaction of a reaction mixture (Rg) containing carbon dioxide, hydrogen, at least one catalyst comprising at least one element selected from groups 8, 9 and
  • At least one polar solvent selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general Formula (A1)
  • R 1 , R 2 , R 3 independently represent an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical each having 1 to 16 carbon atoms, wherein individual carbon atoms independently of one another by a hetero group selected from the groups -O- and > N- may be substituted and two or all three radicals may also be linked together to form a chain comprising at least four atoms, in a hydrogenation reactor to obtain, optionally after addition of water, a biphasic hydrogenation mixture (H) containing an upper phase (01 ) containing the at least one 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 catalyst and at least one formic acid-amine adduct of the general formula (A2),
  • H biphasic hydrogenation mixture
  • U1 which contains the at least one polar solvent, residues of the at least one catalyst and at least one
  • R 2 , R 3 have the meanings given above,
  • step (b3) phase separation of the hydrogenation mixture (H) obtained in step (a) in a first phase separation device into the upper phase (01) and the lower phase
  • step (c) at least partially separating the at least one polar solvent from the raffinate (R2) in a first distillation apparatus to obtain a distillate (D1) containing the at least one polar solvent which is recycled to the hydrogenation reactor in step (a) and a biphasic mixture of bottoms (S1) comprising an upper phase (02) containing the at least one tertiary amine (A1), and a lower phase (U2) containing the at least one formic acid-amine adduct (A2), (d) optionally working up of the first bottoms mixture (S1) obtained in step (c) by phase separation in a second phase separation device into the upper phase (02) and the lower phase (U2), (e) cleavage in the bottoms mixture (S1) or optionally in the Subphase (U2) contained at least one formic acid-amine adduct (A2) in a thermal cleavage unit, to give the at least one tertiary amine (A1), which is recycled to the hydrogenation reactor in step
  • the hydrogenation mixture (H) obtained in process step (a) is separated into the lower phase (U 1) and the upper phase (01), which is recycled to the hydrogenation reactor, as described above for process step (b1) in the first phase separation device.
  • the statements and preferences made for process step (b1) apply correspondingly to process step (b3).
  • the hydrogenation reactor simultaneously acts as the first phase separation device. The upper phase (01) then remains in the hydrogenation reactor and the lower phase (U 1) is fed to the extraction unit.
  • the lower phase (U 1) obtained after phase separation is subsequently subjected in an extraction unit to extraction with at least one tertiary amine (A1) as extractant to remove the residues of the catalyst 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 catalyst.
  • the same tertiary amine (A1) used in process step (a) in the reaction mixture (Rg) is used as extractant, so that the statements and preferences with respect to the tertiary amine (A) for the process step (a) A1) apply correspondingly to process step (b3).
  • the extract (E2) obtained in process step (b3) is recycled in a preferred embodiment to the hydrogenation reactor in process step (a). This allows efficient recovery of the expensive catalyst.
  • the raffinate (R2) is fed in a preferred embodiment of the first distillation apparatus in process step (c).
  • the extractant used in process step (b3) is preferably the tertiary amine (A1) which is obtained in the thermal splitting unit in process step (e).
  • the thermal splitting unit in FIG. 1 In a preferred embodiment, in the thermal splitting unit in FIG. 1
  • Process step (e) obtained tertiary amine (A1) to the extraction unit in process step (b3) recycled.
  • the extraction is carried out in process step (b3) generally at temperatures in the range of 30 to 100 ° C and pressures in the range of 0, 1 to 8 MPa.
  • the extraction can also be carried out under hydrogen pressure.
  • the extraction of the catalyst may be carried out in any suitable apparatus known to those skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades and countercurrent extraction columns.
  • the hydrogenation mixture (H) is further worked up according to step (b2).
  • the invention therefore also provides a process for the preparation of formic acid, comprising the steps
  • reaction mixture comprising carbon dioxide, hydrogen, at least one catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table, at least one polar solvent selected from the group consisting of methanol, ethanol, 1 - propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and water and at least one tertiary amine of the general formula (A1) NR 1 R 2 R 3 (A1),
  • R 1 , R 2 , R 3 independently represent an unbranched or branched, acyclic or cyclic, aliphatic, araliphatic or aromatic radical each having 1 to 16 carbon atoms, wherein individual carbon atoms independently of one another by a hetero group selected from the groups -O- and > N- may be substituted and two or all three radicals may also be linked together to form a chain comprising at least four atoms, in a hydrogenation reactor to obtain, optionally after addition of water, a biphasic hydrogenation mixture (H) containing an upper phase (01 ), which contains the at least one catalyst and the at least one tertiary amine (A1), and a lower phase (U1) containing the at least one polar solvent, residues of the at least one catalyst and at least one formic acid-amine adduct of the general formula (A2 contains)
  • H biphasic hydrogenation mixture
  • U1 lower phase
  • R 1 , R 2 , R 3 have the meanings given above,
  • step (c) at least partially separating the at least one polar solvent from the raffinate (R1) in a first distillation apparatus to obtain a distillate (D1) comprising the at least one polar solvent which is recycled to the hydrogenation reactor in step (a) and a biphasic bottom mixture (S1) containing an upper phase (O 2) containing the at least one tertiary amine (A 1) and a Subphase (U2) containing the at least one formic acid amine
  • step (d) optionally working up of the first bottoms mixture (S1) obtained in step (c) by phase separation in a second phase separation device into the upper phase (02) and the lower phase (U2),
  • step (a) is recycled and from formic acid discharged from the thermal cleavage unit, wherein immediately before and / or during step (c) the raffinate (R1) at least one inhibitor selected from the group consisting of
  • Formic acid is added to various carboxylic acids, carboxylic acid derivatives other than formic acid derivatives and oxidizing agents.
  • the hydrogenation mixture (H) obtained in process step (a) is fed directly to the extraction unit without prior phase separation.
  • the statements and preferences made for process step (b3) apply accordingly.
  • the hydrogenation mixture (H) is in this case subjected in an extraction unit to extraction with at least one tertiary amine (A1) as extractant to remove the catalyst to obtain a raffinate (R1) containing the at least one formic acid-amine adduct (A2) and the at least a polar solvent and an extract (E1) containing the at least one tertiary amine (A1) and the residues of the catalyst.
  • the extraction medium used is the same tertiary amine (A1) which is present in process stage (a) in the reaction mixture (Rg), so that the statements made for process stage (a) and Preferences with respect to the tertiary amine (A1) for the process step (b2) apply accordingly.
  • the extract (E1) obtained in process step (b2) is recycled in a preferred embodiment to the hydrogenation reactor in process step (a). This allows efficient recovery of the expensive catalyst.
  • the raffinate (R1) is supplied in a preferred embodiment of the first distillation apparatus in process step (c).
  • the tertiary amine (A1) which is obtained in the thermal splitting unit in process step (e) is preferably used as extractant in process step (b2). In a preferred embodiment, the tertiary amine (A1) obtained in the thermal splitting unit in process step (e) is recycled to the extraction unit in process step (b2).
  • the extraction is carried out in process step (b2) generally at temperatures in the range of 30 to 100 ° C and pressures in the range of 0, 1 to 8 MPa.
  • the extraction can also be carried out under hydrogen pressure.
  • the extraction of the catalyst may be carried out in any suitable apparatus known to those skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades and countercurrent extraction columns. If appropriate, in addition to the catalyst, fractions of individual components of the polar solvent from the hydrogenation mixture (H) to be extracted in the extraction agent, the tertiary amine (A1), are also dissolved. This is not a disadvantage for the process, since the already extracted amount of polar solvent does not have to be supplied to the solvent removal and thus may save evaporation energy.
  • the lower phase (U 1) obtained according to process step (b1), the raffinate (R1) obtained according to process step (b2) or the raffinate (R2) obtained according to process step (b3) are at least one inhibitor added.
  • the lower phase (U 1) which is obtained according to process step (b1), contains residues of the catalyst in amounts of ⁇ 100 ppm, preferably ⁇ 80 ppm and in particular of ⁇ 60 ppm, in each case based on the total weight of the lower phase (U 1).
  • the raffinate (R1) obtained according to process step (b2) contains traces of the catalyst in amounts of ⁇ 5 ppm, preferably ⁇ 3 ppm and in particular of ⁇ 1 ppm, in each case based on the total weight of the raffinate (R1).
  • the raffinate (R2) obtained according to process step (b3) contains traces of the catalyst in amounts of ⁇ 5 ppm, preferably ⁇ 3 ppm and in particular ⁇ 1 ppm, in each case based on the total weight of the raffinate (R2).
  • the cleavage of free formic acid which is optionally contained in the lower phase (U 1), the raffinate (R 1) or the raffinate (R 2) or in the further work-up from the formic acid-amine adduct (A2) is formed by the radicals or catalyses traces of the catalyst.
  • the formic acid is split into carbon dioxide and hydrogen.
  • at least one inhibitor is added immediately before and / or during step (c) to the lower phase (U 1), the raffinate (R 1) or the raffinate (R 2).
  • the at least one inhibitor is added either immediately before or during step (c). In a further embodiment of the present invention, the at least one inhibitor is added immediately before and during step (c). In a further embodiment, the at least one inhibitor is added only immediately before step (c). In a further embodiment, the at least one inhibitor is added only during step (c).
  • step (c) is understood to mean addition of the inhibitor to the lower phase (U 1), the raffinate (R 1) or the raffinate (R 2) after removal from the first phase separation device or the extraction unit and before being fed to the first distillation apparatus in process step (c)
  • the addition of the inhibitor may be continuous or discontinuous.
  • inhibitor is understood as meaning both one (1) inhibitor and mixtures of two or more inhibitors. The inhibitor converts the catalyst into an inactive form, so that it can no longer catalyze the cleavage of the formic acid-amine adduct (A2) or of the free formic acid.
  • the inhibitor is selected from the group consisting of carboxylic acids other than formic acid, derivatives of carboxylic acids other than formic acid derivatives, and oxidizing agents.
  • the inhibitor used is a mixture of at least one carboxylic acid and at least one oxidizing agent.
  • the inhibitor is used in a molar ratio of 0.5 to 1000, preferably 1 to 30, based on the catalytically active metal component of the catalyst, which in the lower phase (U1), the raffinate (R1) or the raffinate (R2) is.
  • Preferred carboxylic acids are those having at least one carboxy group (-COOH) and another functional group, such as hydroxy groups (-OH), carboxy groups or thiol groups (-SH), since such carboxylic acids due to the chelate Effect effectively bind to the metal component of the catalyst, and convert the catalyst into an inactive form.
  • carboxylic acids are, for example, oxalic acid, lactic acid, maleic acid, phthalic acid, tartaric acid, citric acid, iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), nitriloacetic acid, methylglycinediacetic acid, diethylenetriaminepentaacetic acid (DTPA), dimercaptosuccinic acid.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • dimercaptosuccinic acid dimercaptosuccinic acid.
  • Carboxylic acid derivatives are understood in the context of the present invention to mean organic compounds whose functional group is formally derived from the
  • Suitable carboxylic acid derivatives are, for example, carboxylic acid esters, carboxylic acid amides, carboxylic acid halides (e.g.
  • Carboxylic acid chlorides include carboxylic acid salts (e.g., lithium, sodium, potassium,
  • carboxylic acid derivatives which can be prepared from the carboxylic acids described above, so that the above-described preferences for carboxylic acids apply correspondingly to the carboxylic acid derivatives.
  • Particularly suitable carboxylic acid derivatives are carboxylic acid salts and carboxylic anhydrides the above-mentioned carboxylic acids, wherein among the carboxylic acid salts, alkali metal salts and trialkylammonium salts are particularly preferred.
  • carboxylic acid derivatives examples include maleic anhydride, phthalic anhydride, the trisodium salt of methylglycinediacetic acid (available as Trilon M® ) and thioacetamide.
  • carboxylic acids can thus be added both in the form of the free acid, as well as in the form of their derivatives (carboxylic acid derivatives), wherein among the carboxylic acid derivatives Carbonklarealkalimetallsalze or
  • Carboxylic acid trialkylammonium salts are preferred.
  • the carboxylic acids and / or carboxylic acid derivatives can be added in bulk or in the form of a solution.
  • Suitable oxidizing agents are hydrogen peroxide, peroxycarboxylic acids, diacyl peroxides and trialkyl N-oxides.
  • Preferred oxidizing agents are hydrogen peroxide, peroxo formic acid and trihexyl N-oxide, since these oxidizing agents decompose under the process conditions in step (c) and / or the process conditions in step (e) to substances which are present anyway in the process according to the invention for the preparation of formic acid ,
  • the inhibitor is selected so that it is enriched in the phase which also contains the formic acid-amine adduct (A2).
  • thioacetamide is used as the inhibitor.
  • the inhibitor used is a mixture of hydrogen peroxide and EDTA.
  • a mixture of hydrogen peroxide and diethylenetriaminepentaacetic acid is used as the inhibitor.
  • EDTA is used as the inhibitor.
  • Trilon M is used as inhibitor.
  • meso-dimercaptosuccinic acid is used as inhibitor.
  • the inhibitor used is a mixture of hydrogen peroxide and meso-dimercaptosuccinic acid.
  • (c) at> 2, and more preferably at> 5.
  • enriched for the optional process step (d) is a distribution coefficient
  • Pi (d) [concentration inhibitor in the lower phase (U2)] / [concentration inhibitor in the upper phase (02)] of> 1 to understand.
  • (d ) at> 2 and more preferably at> 5.
  • ( e) [concentration of inhibitor in the lower phase (U3)] / [concentration of inhibitor in the upper phase (03)] is "enriched” for process step (e).
  • the polar solvent is at least partially separated from the lower phase (U1), from the raffinate (R1) or from the raffinate (R2) in a first distillation apparatus.
  • a distillate (D1) and a two-phase bottoms mixture (S1) are obtained.
  • the distillate (D1) contains the separated polar solvent and is added to the hydrogenation reactor in step (a) returned.
  • the bottoms mixture (S1) contains the upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2).
  • the polar solvent in the first distillation apparatus in process stage (c), the polar solvent is partly removed, so that the bottom mixture (S1) contains not yet separated polar solvent.
  • process step (c) for example, from 5 to 98% by weight of the polar solvent contained in the lower phase (U 1), in the raffinate (R 1) or in the raffinate (R 2), preferably 50 to 98% by weight, more preferably 80 to 98 wt .-% and particularly preferably 80 to 90 wt .-% are separated, in each case based on the total weight of the in the lower phase (U 1) in the raffinate (R1) or in the raffinate (R2) polar solvent.
  • the polar solvent is completely separated off in the first distillation apparatus in process stage (c).
  • “completely separated off” is a separation of more than 98% by weight of the polar solvent present in the lower phase (U 1), in the raffinate (R 1) or in the raffinate (R 2), preferably more than 98.5 wt .-%, particularly preferably more than 99 wt .-%, in particular more than 99.5 wt .-%, understood, in each case based on the total weight of the in the lower phase (U 1), in the raffinate (R1) or in the raffinate (R2) contained polar solvent.
  • the distillate (D1) separated in the first distillation apparatus is recycled in a preferred embodiment to the hydrogenation reactor in step (a).
  • a mixture of one or more alcohols and water is used as the polar solvent, it is also possible to remove from the first distillation apparatus a low-water distillate (D1 wa ) and a water-rich distillate (D1 wr ).
  • the water-rich distillate (D1 wr ) contains more than 50 wt .-% of the water contained in the distillate (D1), preferably more than 70 wt .-%, especially more than 80 wt .-%, in particular more than 90 wt .-%
  • the low-water distillate (D1 wa ) contains less than 50 wt .-% of the water contained in the distillate D1, preferably less than 30 wt .-%, more preferably less than 20 wt .-%, in particular less than 10 wt .-%.
  • the low-water distillate (D1 wa ) is recycled to the hydrogenation reactor in step (a).
  • the water-rich distillate (D 1 wr ) is fed to the upper phase (01).
  • the separation of the polar solvent from the lower phase (U 1), the raffinate (R 1) or the raffinate (R 2) can be carried out, for example, in an evaporator or in a distillation unit consisting of evaporator and column, the column containing packings, fillers and / or trays filled, done.
  • the at least partial removal of the polar solvent preferably takes place at a bottom temperature at which no free formic acid is formed from the formic acid-amine adduct (A2) at a given pressure.
  • the factor x, of the formic acid-amine adduct (A2) in the first distillation apparatus is generally in the range of 0.4 to 3, preferably in the range of 0.6 to 1, 8, particularly preferably in the range of 0.7 to 1, 7.
  • the bottom temperature in the first distillation apparatus is at least 20 ° C, preferably at least 50 ° C and more preferably at least 70 ° C, and generally at most 210 ° C, preferably at most 190 ° C.
  • the temperature in the first distillation apparatus is generally in the range of 20 ° C to 210 ° C, preferably in the range of 50 ° C to 190 ° C.
  • the pressure in the first distillation apparatus is generally at least 0.001 MPa abs, preferably at least 0.005 MPa abs and more preferably at least 0.01 MPa abs and generally at most 1 MPa abs and preferably at most 0, 1 MPa abs.
  • the pressure in the first distillation apparatus is generally in the range of 0.0001 MPa abs to 1 MPa abs, preferably in the range of 0.005 MPa abs to 0.1 MPa abs and more preferably in the range of 0.01 MPa abs to 0.1 MPa abs.
  • the formic acid-amine adduct (A2) and free tertiary amine (A1) can be obtained in the bottom of the first distillation apparatus, since the removal of the polar solvent gives formic acid-amine adducts with a lower amine content , This forms a bottom mixture (S1) which contains the formic acid-amine adduct (A2) and the free tertiary amine (A1).
  • the bottom mixture (S1) contains, depending on the separated amount of the polar solvent, the formic acid-amine adduct (A2) and optionally the free tertiary amine (A1) formed in the bottom of the first distillation apparatus. If appropriate, the bottoms mixture (S1) is further worked up in process step (d) for further work-up and then fed to process step (e). It is also possible to feed the bottoms mixture (S1) from process step (c) directly to process step (e).
  • the bottoms mixture (S1) obtained in step (c) can be separated in a second phase separation device into the upper phase (02) and the lower phase (U2).
  • the lower phase (U2) is then further worked up according to process step (e).
  • the upper phase (02) from the second phase separation device to the hydrogenation reactor in step (a) recycled.
  • the upper phase (02) is recycled from the second phase separation device to the extraction unit.
  • the method according to the invention thus comprises the steps (a), (b1), (c), (d) and (e).
  • the method according to the invention comprises the steps (a), (b2), (c), (d) and (e).
  • the method according to the invention comprises the steps (a), (b3), (c), (d) and (e).
  • the method according to the invention comprises the steps (a), (b1), (c) and (e).
  • the method according to the invention comprises the steps (a), (b2), (c) and (e).
  • the method according to the invention comprises the steps (a), (b3), (c) and (e).
  • the method according to the invention consists of the steps (a), (b1), (c), (d) and (e).
  • the process according to the invention consists of the steps (a), (b2), (c), (d) and (e).
  • the process according to the invention consists of the steps (a), (b3), (c), (d) and (e).
  • the process according to the invention consists of the steps (a), (b1), (c) and (e).
  • the process according to the invention consists of the steps (a), (b2), (c) and (e).
  • the process according to the invention consists of the steps (a), (b3), (c) and (e).
  • the bottom mixture (S1) obtained according to step (c) or the lower phase (U2) optionally obtained after the work-up according to step (d) is fed to a thermal splitting unit for further reaction.
  • the formic acid-amine adduct (A2) present in the bottom mixture (S1) or optionally in the bottom phase (U2) is cleaved in the thermal splitting unit to give formic acid and tertiary amine (A1).
  • the formic acid is discharged from the thermal splitting unit.
  • the tertiary amine (A1) is recycled to the hydrogenation reactor in step (a).
  • the tertiary amine (A1) from the thermal cleavage unit can be recycled directly to the hydrogenation reactor. It is also possible to first recycle the tertiary amine (A1) from the thermal splitting unit to the extraction unit in process stage (b2) or process stage (b3), and subsequently from the extraction unit to the hydrogenation reactor in step (a), this embodiment is preferred.
  • the thermal splitting unit comprises a second distillation apparatus and a third phase separation apparatus, wherein the cleavage of the formic acid-amine adduct (A2) is carried out in the second distillation apparatus to obtain a distillate (D2) discharged from the second distillation apparatus (taken ), and a biphasic bottoms mixture (S2) comprising an upper phase (03) containing the at least one tertiary amine (A1), and a lower phase (U3) containing the at least one formic acid-amine adduct (A2) and the at least contains an inhibitor.
  • D2 distillate
  • S2 biphasic bottoms mixture
  • the removal of the formic acid from the second distillation apparatus obtained in the second distillation apparatus can be carried out, for example, (i) overhead, (ii) overhead and via a side draw, or (iii) only a side draw. If the formic acid is removed overhead, formic acid with a purity of up to 99.99% by weight is obtained. When taken off via a side draw, aqueous formic acid is obtained, in which case a mixture with about 85% by weight of formic acid is particularly preferred. Depending on the water content of the sludge mixture (S1) or, if appropriate, the lower phase (U2) fed to the thermal splitting unit, the formic acid can be withdrawn increasingly as top product or reinforced via the side draw.
  • S1 sludge mixture
  • U2 the lower phase fed to the thermal splitting unit
  • thermal cleavage of the formic acid-amine adduct (A2) is generally carried out according to the process parameters known in the prior art with respect to pressure, temperature and apparatus design. These are described, for example, in EP 0 181 078 or WO 2006/021 41 1.
  • distillation columns are suitable, which generally contain packing, packings and / or trays.
  • the bottom temperature in the second distillation apparatus is at least 130 ° C, preferably at least 140 ° C and more preferably at least 150 ° C, and generally at most 210 ° C, preferably at most 190 ° C, particularly preferably at most 185 ° C.
  • the pressure in the second distillation apparatus is generally at least 1 hPa abs, preferably at least 50 hPa abs and more preferably at least 100 hPa abs, and generally at most 500 hPa, more preferably at most 300 hPa abs and more preferably at most 200 hPa abs.
  • the bottoms mixture (S2) obtained in the bottom of the second distillation apparatus is biphasic.
  • the bottoms mixture (S2) is fed to the third phase separation device of the thermal splitting unit and there in the upper phase (03) containing the tertiary amine (A1), and the lower phase (U3), the formic acid-amine adduct ( A2) and the inhibitor, separated.
  • the upper phase (03) is discharged from the third phase separator of the thermal splitting unit and recycled to the hydrogenation reactor in step (a).
  • the recycling can be carried out directly to the hydrogenation reactor in step (a) or the upper phase (03) is first supplied to the extraction unit in step (b2) or step (b3) and forwarded from there to the hydrogenation reactor in step (a).
  • the lower phase (U3) obtained in the third phase separation device is then supplied again to the second distillation device of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is then subjected to further cleavage in the second distillation apparatus, again giving formic acid and free tertiary amine (A1) and again in the bottom of the second distillation unit of the thermal splitting unit forming a two-phase bottoms mixture (S2), which is then fed again to the third phase separation device of the thermal splitting unit for further processing.
  • the inhibitor preferably remains in the phase in which the formic acid-amine adduct (A2) is also present, ie. in the lower phase (U3).
  • This has the advantage that the upper phase (03) containing the tertiary amine (A1) can be recycled to the hydrogenation reactor without significant amounts of inhibitor being recycled to the upper phase (03) in process stage (a), which hinder the hydrogenation reaction there could.
  • the feeding of the bottom mixture (S1) or optionally of the bottom phase (U2) to the thermal splitting unit in process step (e) can take place in the second distillation device and / or the third phase separation device.
  • the feed of the bottom mixture (S1) or optionally the lower phase (U2) in the second distillation device of the thermal separation unit takes place.
  • the feed of the bottom mixture (S1) or optionally the lower phase (U2) takes place both in the second distillation device of the thermal splitting unit, as well as in the third phase separation device of the thermal splitting unit.
  • the bottom mixture (S1) or optionally the Subphase (U2) divided into two partial streams, wherein a partial stream of the second distillation device and a partial stream of the third phase separator are fed to the thermal splitting unit.
  • FIG. 1 shows in detail: a block diagram of a preferred embodiment of the method according to the invention, a block diagram of a further preferred embodiment of the method according to the invention, a block diagram of a further preferred embodiment of the method according to the invention, a block diagram of a further preferred embodiment of the method according to the invention, a block diagram of a further preferred one Embodiment of the method according to the invention,
  • FIG. 6 shows a block diagram of a further preferred embodiment of the method according to the invention.
  • FIG. 1 A first figure.
  • Amine adduct (A2) (lower phase (U2)); Swamp mixture (S1) 7 stream containing formic acid-amine adduct (A2) and inhibitor; Lower phase (U3)
  • Stream Containing Extract E1
  • a stream 1 containing carbon dioxide and a stream 2 containing hydrogen are fed to a hydrogenation reactor 1-1. It is possible to supply the hydrogenation reactor 1-1 further streams (not shown) to compensate for any losses incurred by the tertiary amine (A1) or the catalyst.
  • a tertiary amine (A1) a polar solvent and a catalyst containing at least one element from Groups 8, 9 and 10 of the Periodic Table.
  • a two-phase hydrogenation mixture (H) is obtained which has an upper phase (01) comprising the catalyst and the tertiary amine (A1) and a lower phase (U 1) containing the polar solvent, residues of the catalyst and the formic acid-amine adduct (A2 ) contains.
  • the lower phase (U 1) is supplied as stream 3 to the distillation apparatus 11-1.
  • the upper phase (01) remains in the hydrogenation reactor 1-1.
  • the hydrogenation reactor 1-1 simultaneously acts as the first phase separation device.
  • the current 3 is added continuously or discontinuously, the inhibitor as stream 4.
  • the lower phase (U 1) is separated into a distillate (D1) containing the polar solvent, which is recycled as stream 5 to the hydrogenation reactor 1-1, and into a biphasic mixture (S1) containing an upper phase (02), containing the tertiary amine (A1) and the lower phase (U2) containing the formic acid-amine adduct (A2), inhibited residues of the catalyst and the inhibitor.
  • the bottoms mixture (S1) is fed as stream 6 to the third phase separation device 111-1 of the thermal splitting unit.
  • the sump mixture (S1) is separated to obtain an upper phase (03) containing the tertiary amine (A1) and a lower phase (U3) containing inhibited residues of the catalyst, the inhibitor and the formic acid-amine adduct (A2).
  • the upper phase (03) is recycled as stream 10 to the hydrogenation reactor 1-1.
  • the lower phase (U3) is supplied as stream 7 to the second distillation device IV-1 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-1 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a two-phase bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 9 from the distillation apparatus IV-1.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor is referred to as Stream 8 is returned to the third phase separation device 111-1 of the thermal splitter unit.
  • the sump mixture (S2) is separated into upper phase (03) and lower phase (U3).
  • Di upper phase (03) is recycled as stream 10 to the hydrogenation reactor 1-1.
  • the lower phase (U3) is recycled as stream 7 to the second distillation device IV-1.
  • a stream 11 containing carbon dioxide and a stream 12 containing hydrogen are fed to a hydrogenation reactor I-2. It is possible to supply the hydrogenation reactor I-2 with further streams (not shown) in order to compensate for any losses of the tertiary amine (A1) or of the catalyst which may occur.
  • the hydrogenation mixture (H) is fed as stream 13a to a first phase separator V-2.
  • the hydrogenation mixture (H) is separated into the upper phase (01) and the lower phase (U 1).
  • the upper phase (01) is recycled as stream 22 to the hydrogenation reactor I-2.
  • the lower phase (U 1) is supplied as stream 13b of the extraction unit VI-2.
  • the lower phase (U 1) is extracted with the tertiary amine (A1), which is recycled as stream 20 (upper phase (03)) from the third phase separation II I-2 to the extraction device VI-2.
  • a raffinate (R2) and an extract (E2) are obtained.
  • the raffinate (R2) contains the formic acid-amine adduct (A2) and the polar solvent and is supplied as stream 13c to the first distillation apparatus I I-2.
  • the extract (E2) contains the tertiary amine (A1) and the residues of the catalyst and is recycled as stream 21 to the hydrogenation reactor I-2.
  • the current 13c is continuously or discontinuously added to the inhibitor as stream 14.
  • the raffinate (R 2) is separated into a distillate (D 1) containing the polar solvent, which is recycled as stream 15 to the hydrogenation reactor I-2, and into a biphasic sump mixture (S 1).
  • the bottoms mixture (S1) contains an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor.
  • the bottoms mixture (S1) is fed as stream 16 to the second distillation device IV-2.
  • the formic acid-amine adduct present in the bottom mixture (S1) is cleaved in the second distillation device IV-2 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 19 from the second distillation device IV-2.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2), inhibited residues of the catalyst and the inhibitor is recycled as stream 18 to the third phase separation II I-2 of the thermal splitting unit.
  • the bottom mixture (S2) is separated to obtain an upper phase (03) comprising the tertiary amine (A1) and a lower phase (U3) containing inhibited residues of the catalyst, the inhibitor and the formic acid Amine adduct (A2).
  • the upper phase (03) is recycled from the third phase separator 111-2 as stream 20 to the extraction unit VI-2.
  • the lower phase (U3) is supplied as stream 17 to the second distillation device IV-2 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-2 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottom mixture (S2) are again obtained.
  • a stream 31 containing carbon dioxide and a stream 32 containing hydrogen are fed to a hydrogenation reactor 1-3. It is possible to supply the hydrogenation reactor 1-3 further streams (not shown) in order to compensate for any losses of the tertiary amine (A1) or of the catalyst.
  • carbon dioxide and hydrogen are reacted in the presence of a tertiary amine (A1), a polar solvent and a catalyst containing at least one element from Groups 8, 9 and 10 of the Periodic Table.
  • a two-phase hydrogenation mixture (H) which has an upper phase (01) comprising the catalyst and the tertiary amine (A1) and a lower phase (U 1) containing the polar solvent, residues of the catalyst and the formic acid-amine adduct (A2 ) contains.
  • the hydrogenation mixture (H) is supplied as stream 33a to a first phase separation device V-3.
  • the hydrogenation mixture (H) in the upper phase (01) and the lower phase (U 1) is separated.
  • the upper phase (01) is recycled as stream 42 to the hydrogenation reactor I-3.
  • the lower phase (U 1) is supplied as stream 33b to the extraction unit VI-3.
  • the lower phase (U 1) is extracted with the tertiary amine (A1), which is recycled as stream 40 (upper phase (03)) from the third phase separator II I-3 of the thermal splitting unit to the extraction unit VI-3.
  • a raffinate (R2) and an extract (E2) are obtained.
  • the raffinate (R2) contains the formic acid-amine adduct (A2) and the polar solvent and is supplied as stream 33c to the first distillation device 11-3.
  • the extract (E2) contains the tertiary amine (A1) and the residues of the catalyst and is recycled as stream 41 to the hydrogenation reactor I-2.
  • the flow 33c is added continuously or discontinuously to the inhibitor as stream 34.
  • the raffinate (R2) separated into a distillate (D1) containing the polar solvent, which is recycled as stream 35 to the hydrogenation reactor I-3, and into a two-phase bottoms mixture (S1).
  • the bottoms mixture (S1) contains an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2), inhibited residues of the catalyst and the inhibitor.
  • the sump mixture (S1) is supplied as stream 36 of the third phase separation device I I I-3 to the thermal splitting unit.
  • the bottom mixture (S1) is separated to obtain a top phase (03) comprising the tertiary amine (A1) and a lower phase (U3) containing inhibited residues of the catalyst, the inhibitor and the formic acid Amine adduct (A2).
  • the upper phase (03) is recycled as stream 40 to the extraction unit VI-3.
  • the lower phase (U3) is supplied as stream 37 to the second distillation device IV-3 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-3 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 39 from the distillation device IV-3.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor is referred to as Stream 38 to the third phase separation II I-3 of the thermal splitting unit recycled.
  • the third phase separation device I I I-3 the sump mixture (S2) is separated.
  • the upper phase (03) is recycled to the extraction unit VI-3.
  • the lower phase (U3) is recycled to the second distillation device IV-3.
  • a stream 51 containing carbon dioxide and a stream 52 containing hydrogen are fed to a hydrogenation reactor I-4. It is possible to supply the hydrogenation reactor I-4 with further streams (not shown) in order to compensate for any losses of the tertiary amine (A1) or of the catalyst which may occur.
  • carbon dioxide and hydrogen are reacted in the presence of a tertiary amine (A1), a polar solvent and a catalyst containing at least one element from Groups 8, 9 and 10 of the Periodic Table.
  • a two-phase hydrogenation mixture (H) which has an upper phase (01) comprising the catalyst and the tertiary amine (A1) and a lower phase (U 1) containing the polar solvent, residues of the catalyst and the formic acid-amine adduct (A2 ) contains.
  • the hydrogenation mixture (H) is fed as stream 53a to a first phase separator V-4.
  • the hydrogenation mixture (H) is separated into the upper phase (01) and the lower phase (U 1).
  • the upper phase (01) is recycled as stream 62 to the hydrogenation reactor I-4.
  • the lower phase (U 1) is supplied as stream 53b to the extraction unit VI-4. Therein, the lower phase (U 1) is extracted with the tertiary amine (A1), the current 60 (upper phase (03)) from the third phase separation II I-4 of the thermal splitting unit and the current 56c from the second phase separation VI 1-4 to the extraction unit VI-4 is recycled.
  • a raffinate (R2) and an extract (E2) are obtained.
  • the raffinate (R2) contains the formic acid-amine adduct (A2) and the polar solvent and is supplied as stream 53c to the first distillation apparatus 11-4.
  • the extract (E2) contains the tertiary amine (A1) and the residues of the catalyst and is recycled as stream 61 to the hydrogenation reactor I-4.
  • the current 53c is added continuously or discontinuously to the inhibitor as stream 54.
  • the raffinate (R 2) is separated into a distillate (D 1) containing the polar solvent, which is recycled as stream 55 to the hydrogenation reactor I-4, and into a biphasic sump mixture (S 1).
  • the bottoms mixture (S1) contains an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor.
  • the bottoms mixture (S1) is fed as stream 56a to the second phase separation VI I-4.
  • the second phase separation device VII-4 the bottom mixture (S1) is separated into the upper phase (02) and the lower phase (U2).
  • the upper phase (02) is recycled from the second phase separator VI I-4 as stream 56c to the extraction unit VI-4.
  • the lower phase (U2) is supplied as stream 56b to the second distillation device IV-4.
  • the formic acid-amine adduct (A2) present in the lower phase (U2) is cleaved in the second distillation apparatus IV-4 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 59 from the second distillation device IV-4.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor is referred to as Stream 58 to the third phase separation 111-4 of the thermal splitting unit recycled.
  • the bottom mixture (S2) is separated to obtain a top phase (03) comprising the tertiary amine (A1) and a lower phase (U3) containing inhibited residues of the catalyst, the inhibitor and the formic acid Amine adduct (A2).
  • the upper phase (03) is recycled from the third phase separation device I I I-4 as stream 60 to the extraction unit VI-4.
  • the lower phase (U3) is supplied as stream 57 to the second distillation device IV-4 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-4 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are again obtained.
  • a stream 71 containing carbon dioxide and a stream 72 containing hydrogen are fed to a hydrogenation reactor I-5. It is possible to supply the hydrogenation reactor I-5 further streams (not shown) to compensate for any losses of the tertiary amine (A1) or the catalyst occurring.
  • a tertiary amine (A1) a polar solvent and a catalyst containing at least one element from Groups 8, 9 and 10 of the Periodic Table.
  • a biphasic hydrogenation mixture (H) which has a top phase (01) containing the catalyst and the tertiary amine (A1) and a Subphase (U 1) containing the polar solvent, residues of the catalyst and the formic acid-amine adduct (A2).
  • the hydrogenation mixture (H) is supplied as stream 73a to a first phase separation device V-5.
  • the hydrogenation mixture (H) in the upper phase (01) and the lower phase (U 1) is separated.
  • the upper phase (01) is recycled as stream 82 to the hydrogenation reactor I-5.
  • the lower phase (U 1) is supplied as stream 73b of the extraction unit VI-5.
  • the lower phase (U 1) is extracted with the tertiary amine (A1), which is recycled as stream 80 (upper phase (03)) from the third phase separator of the thermal splitting unit to the extraction unit VI-5.
  • a raffinate (R2) and an extract (E2) are obtained.
  • the raffinate (R2) contains the formic acid-amine adduct (A2) and the polar solvent and is supplied as stream 73c to the first distillation device 11-5.
  • the extract (E2) contains the tertiary amine (A1) and the residues of the catalyst and is recycled as stream 81 to the hydrogenation reactor I-5.
  • the current 73c is added continuously or discontinuously to the inhibitor as stream 74.
  • the raffinate (R 2) is separated into a water-rich distillate (D 1 wr), a low-water distillate (D 1wa) and a biphasic bottom mixture (S1).
  • the water-rich distillate (D1 wr) is supplied as stream 83 to the stream 73a.
  • the low-water distillate (D1 wa) is recycled as stream 75 to the hydrogenation reactor I-5.
  • the embodiment according to FIG. 5 presupposes that the polar solvent used is a mixture of one or more alcohols with water.
  • the bottoms mixture (S1) contains an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2), inhibited residues of the catalyst and the inhibitor.
  • the sump mixture (S1) is fed as stream 76 to the third phase separator I I I-5 of the thermal splitting unit.
  • the bottom mixture (S1) is separated to obtain an upper phase (03) containing the tertiary amine (A1) and a lower phase (U3) containing inhibited residues of the catalyst, the inhibitor and the formic acid Amine adduct (A2).
  • the upper phase (03) is recycled as stream 80 to the extraction unit IV-5.
  • the lower phase (U3) is supplied as stream 77 to the second distillation device IV-5 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-5 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 79 from the distillation apparatus IV-5.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor is referred to as Stream 78 to the third phase separation II I-5 recycled thermal splitting unit.
  • the sump mixture (S2) is separated in the third phase separation device I I I-5.
  • the upper phase (03) is recycled as stream 80 to the extraction unit VI-5.
  • the lower phase (U3) is recycled as stream 77 to the second distillation device IV-5.
  • a stream 91 containing carbon dioxide and a stream 92 containing hydrogen are fed to a hydrogenation reactor I-6. It is possible to supply the hydrogenation reactor I-6 with further streams (not shown) in order to compensate for any losses of the tertiary amine (A1) or of the catalyst which may occur.
  • the hydrogenation mixture (H) is fed as stream 93a to the extraction unit VI-6.
  • the hydrogenation mixture (H) is extracted with the tertiary amine (A1), which is recycled as stream 100 (upper phase (03)) from the third phase separation device I II-6 of the thermal splitting unit to the extraction unit VI-6.
  • a raffinate (R1) and an extract (E1) are obtained.
  • the raffinate (R1) contains the formic acid-amine adduct (A2) and the polar solvent and is supplied as stream 93c to the first distillation apparatus I I-6.
  • the extract (E1) contains the tertiary amine (A1) and the catalyst and is recycled as stream 101 to the hydrogenation reactor I-6.
  • the current 93c is added continuously or discontinuously to the inhibitor as stream 94.
  • the raffinate (R1) is separated into a distillate (D1) containing the polar solvent, which is recycled as stream 95 to the hydrogenation reactor I-6, and into a biphasic mixture (S1).
  • the bottoms mixture (S1) contains an upper phase (02) containing the tertiary amine (A1) and a lower phase (U2) containing the formic acid-amine adduct (A2), inhibited residues of the catalyst and the inhibitor.
  • the sump mixture (S1) is supplied as stream 96 to the third phase separation device I I I-6 of the thermal splitting unit.
  • the bottom mixture (S1) is separated to obtain an upper phase (03) containing the tertiary amine (A1) and a lower phase (U3) containing inhibited residues of the catalyst, the inhibitor and the formic acid Amine adduct (A2).
  • the upper phase (03) is recycled as stream 100 to the extraction unit VI-6.
  • the lower phase (U3) is supplied as stream 97 to the second distillation device IV-6 of the thermal splitting unit.
  • the formic acid-amine adduct (A2) present in the lower phase (U3) is cleaved in the second distillation apparatus IV-6 into formic acid and free tertiary amine (A1).
  • a distillate (D2) and a bottoms mixture (S2) are obtained.
  • the distillate (D2) containing formic acid is discharged as stream 99 from the distillation device IV-6.
  • the biphasic bottoms mixture (S2) containing the upper phase (03) containing the tertiary amine (A1) and the lower phase (U3) containing the formic acid-amine adduct (A2) inhibited residues of the catalyst and the inhibitor is referred to as Stream 98 to the third phase separation II I-6 of the thermal cleavage unit recycled.
  • the bottom mixture (S2) is separated in the third phase separation device II-6.
  • the upper phase (03) is called current 100 to Extraction unit VI-6 recycled.
  • the lower phase (U3) is recycled as stream 97 to the second distillation device IV-6.
  • Hastelloy C autoclave equipped with a magnetic stir bar was charged under inert conditions with tertiary amine (A1), polar solvent and homogeneous catalyst. The autoclave was then closed and pressed at room temperature C0 2 . Subsequently, H 2 was pressed in and the reactor was heated with stirring (700 rpm). After the desired reaction time, the autoclave was cooled and the hydrogenation mixture (H) was depressurized.
  • the parameters and results of the individual experiments are given in Tables 1 .1 to 1 .5.
  • Examples A-1 to A-17 show that in the process according to the invention even with variation of the tertiary amine (A1), the polar solvent, the catalyst with respect to the ligands and the metal component, the amount of catalyst, and the amount of water added high to very high reaction rates of up to 0.98 mol kg -1 r 1 can be achieved.
  • All investigated systems formed two phases, the upper phase (01) in each case with the still free tertiary amine (A1) and the homogeneous catalyst, and the lower phase (U 1) in each case with the polar solvent and the formed formic acid-amine adduct (A2) was enriched.
  • Table 1.1 the upper phase (01) in each case with the still free tertiary amine (A1) and the homogeneous catalyst, and the lower phase (U 1) in each case with the polar solvent and the formed formic acid-amine adduct (A2) was enriched.
  • Hastelloy C autoclave equipped with a paddle or magnetic stirrer was charged under inert conditions with the tertiary amine (A1), polar solvent and catalyst. Subsequently, the autoclave was sealed and C0 2 were pressed at room temperature. Subsequently, H 2 was pressed in and the reactor was heated with stirring (700-1000 rpm). After the reaction time, the autoclave was cooled and the hydrogenation mixture (H) was depressurized. After the reaction, water was optionally added to the reaction and stirred for 10 minutes at room temperature.
  • a biphasic hydrogenation mixture (H) was obtained in which the upper phase (01) with the tertiary amine (A1) and the homogeneous catalyst, and the lower phase (U1) with the polar solvent and the formic acid-amine adduct formed (A2 ) was enriched.
  • the phases were then separated and the formic acid content of the lower phase (U1) was determined.
  • the total content of formic acid in the formic acid-amine adduct (A2) was determined by titration with 0.1 N KOH in MeOH potentiometrically using a "Mettler Toledo DL50" titrator. The parameters and results of the individual experiments are shown in Table 1.1
  • Examples A-18 to A-21 show that under comparable conditions using methanol-water mixtures as the polar solvent higher formic acid concentrations in the lower phase can be achieved compared to diols as the polar solvent.
  • Adduct (A2) was enriched.
  • the lower phase (U 1) was separated and added under inert conditions three times with the same amount (mass of amine corresponds to the mass of the lower phase (U 1)) fresh tertiary amine (A1) (10 minutes at room temperature and then separate phases) added to the catalyst extraction ,
  • the total content of formic acid in the formic acid-amine adduct (A2) was determined by titration with 0.1 N KOH in MeOH potentiometrically using a "Mettler Toledo DL50" titrator
  • the ruthenium content was determined by AAS The parameters and results of the individual Experiments are shown in Table 1 .6.
  • Examples B-1 to B-3 show that in the process according to the invention tertiary amine (A1) obtained in process step (e) can be used to extractively reduce the amount of ruthenium catalyst in the lower phase (U 1). By further extraction steps or a continuous countercurrent extraction, this value could be lowered further.
  • a biphasic hydrogenation mixture (H) was obtained, the upper phase (01) containing the free tertiary amine (A1) and the homogeneous catalyst, and the lower phase (U 1) containing the polar solvent and the formic acid amine formed.
  • Adduct (A2) was enriched.
  • the lower phase (U 1) was separated and stirred under inert conditions three times with the same amount (mass of amine corresponds to the mass of the lower phase) of fresh trialkylamine (stir for 10 minutes at room temperature and then separate phases).
  • the total content of formic acid in the formic acid / amine adduct was determined potentiometrically by titration with 0.1 N KOH in MeOH using a "Mettler Toledo DL50" titrator
  • the ruthenium content was determined by AAS
  • the parameters and results of the individual experiments are in Table 1 .13 reproduced.
  • Examples D-1 to D-4 show that by varying the catalyst and the amount of water added in the formation of formic acid, the ruthenium in the product phase can be depleted to levels below one ppm ruthenium.
  • the lower phase (U 1) was separated and under inert conditions three times with the same amount (mass of amine corresponds to the mass of the lower phase) fresh tertiary amine (A1) (10 minutes at room temperature stirring and then separate phases) for catalyst extraction added.
  • the total content of formic acid in the formic acid-amine adduct (A2) was determined by titration with 0.1 N KOH in MeOH potentiometrically using a "Mettler Toledo DL50" titrator
  • the ruthenium content was determined by AAS The parameters and results of the individual Experiments are shown in Tables 1 .14 to 1 .19.
  • Examples E-1 to E-9 show that by varying the catalyst, the amount of water added (both before and after the reaction) and the reaction conditions, the active catalyst can be used again for the C0 2 hydrogenation and the ruthenium in deplete the product phase down to 2 ppm with only one extraction.
  • Table 1.15 shows that by varying the catalyst, the amount of water added (both before and after the reaction) and the reaction conditions, the active catalyst can be used again for the C0 2 hydrogenation and the ruthenium in deplete the product phase down to 2 ppm with only one extraction.
  • Alcohol and water are distilled off from the product phase (containing the formic acid-amine adduct, lower phase (U1), raffinate (R1) or raffinate (R2)) under reduced pressure using a rotary evaporator.
  • the product phase containing the formic acid-amine adduct, lower phase (U1), raffinate (R1) or raffinate (R2)
  • a rotary evaporator In the bottom a biphasic mixture (trialkylamine and formic acid-amine adduct phase, bottom mixture (S1)), the two phases are separated and the formic acid content of the lower phase (U2) by potentiometric titration with 0.1 N KOH in MeOH with The amine and alcohol content are determined by gas chromatography and the parameters and results of the individual experiments are given in Table 1.20.
  • Examples F-1 to F-4 show that in the process according to the invention, various polar solvents can be separated under mild conditions from the product phase (lower phase (U1), raffinate (R1) or raffinate (R2)), a lower phase containing lower U2 (U2 ) and an upper phase (02), consisting predominantly of tertiary amine, is obtained.
  • product phase lower phase (U1), raffinate (R1) or raffinate (R2)
  • U2 lower phase containing lower U2
  • an upper phase (02) consisting predominantly of tertiary amine
  • Examples G1 and G2 (Thermal Separation of the Polar Solvent from the Trialkylamine Solvent-Formic Acid Mixtures and Cleavage of the Formic Acid-Amine Adduct) Alcohol and water are separated from the product phase (containing the formic acid amine subduct (U 1), raffinate ( R1) or raffinate (R2)) distilled off under reduced pressure by means of a rotary evaporator. A biphasic mixture is formed in the bottom (trialkylamine and formic acid-amine adduct phase, bottom mixture (S1)) and the two phases are separated.
  • the composition of the distillate (containing most of the methanol and water; distillate (D1)), the upper phase (containing the free trialkylamine, upper phase (02)) and the lower phase (containing the formic acid-amine adduct; lower phase (U2)) was determined by gas chromatography and by titration of the formic acid against 0.1 N KOH in MeOH potentiometrically with a "Mettler Toledo DL50" titrator
  • the formic acid is then removed from the lower phase (U2) from the first step in a vacuum distillation apparatus over a 10 cm Vigreux column
  • a single-phase bottom product (S2) consisting of the pure tertiary amine (A2) is obtained, which can be used for extraction of the catalyst and recycling into the hydrogenation
  • the composition of the sump (S2) and of the distillate was determined by Ga chromatography and by titration of the formic acid with against 0.1 N KOH in MeOH determined potentiometrically with a "Mettler Toledo
  • Examples G-1 and G-2 show that in the process according to the invention, various polar solvents can be separated from the product phase under mild conditions, with a lower (U3) formic acid and an upper phase (03) consisting predominantly of tertiary amine (A1).
  • U3 formic acid
  • U3 the formic acid-rich lower phase
  • the formic acid can then be cleaved off at higher temperatures from the tertiary amine (A1), the free tertiary amine (A1) being obtained.
  • the formic acid thus obtained still contains some water, which, however, can be separated off from the formic acid by a column having a greater separation efficiency.
  • the resulting in both the separation of the solvent and in the thermal cleavage tertiary amine (A1) can be used to extract the catalyst.
  • Examples H1 to H4 (preferred solubility of the inhibitors according to the invention in a biphasic mixture of formic acid-amine adduct (A2) and tertiary amine (A1))
  • Examples H-1 to H4 show that the inhibitors preferably accumulate in the formic acid-amine adduct (A3) phase in the process according to the invention and thus do not enter the hydrogenation stage.
  • Examples 11 and 12 Decomposition of formic acid in the hydrogenation mixture (H) from the C0 2 hydrogenation without addition of an inhibitor (reference values, Comparative Example 11) and with addition (Inventive Example AI2) in the solvent removal.
  • Inventive Example 12 A 250 mL Hastelloy C autoclave equipped with a magnetic stir bar was placed under inert conditions with trihexylamine (65.0 g), Metahnol (25.0 g), water (2.0 g), [Ru (PnOct 3 ) 4 (H) 2 ] (82 mg) and 1, 2-bis (dicyclohexylphosphino) ethane (20 mg). The autoclave was then closed and pressed at room temperature C0 2 (25.0 g). Subsequently, it was pressed onto 120 bar with H 2 and the reactor was heated to 70 ° C. with stirring (700 rpm). After 8 hours of reaction time, the autoclave was cooled and the hydrogenation mixture (H) relaxed.
  • the total content of formic acid in the formic acid-amine adduct (A3) in the lower phase (U 1) was determined potentiometrically by titration with 0.1 N KOH in MeOH using a "Mettler Toledo DL50" titrator
  • FIG. 7 shows the development of the percentage content of the lower phase (U 1) based on the total weight of the hydrogenation mixture (H).
  • FIG. 7 and Examples 11 and 12 show that the formic acid present in the formic acid-amine adduct (A3) in the lower phase (U 1) decomposes significantly more slowly at the temperatures of the methanol separation (80 ° C.) (removal of the polar solvent) when small amounts of an inhibitor such as H 2 0 2 are added (Example 12).
  • the decomposition rate is much faster than in the step of separation of the polar solvent and thus more relevant due to the higher bottom temperatures (> 130 ° C), so that further investigations for inhibitors Process step (e), ie the cleavage of the formic acid-amine adduct (A3) relate (Examples 13-125).
  • Comparative Examples 13-15 decomposition of formic acid in the cleavage of the formic acid-amine adduct (A3) without addition of an inhibitor; Simulation of process step (e) without addition of an inhibitor.
  • Comparative Examples 13-15 80.0 g of formic acid-amine adduct (A3), ie, adduct of formic acid and tri-n-hexylamine, (1: 1, 5, 20 wt .-% formic acid) and the ruthenium catalyst were in a glass flask weighed. The reaction mixture was refluxed to 130 ° C in the open system, forming an upper phase and a lower phase. The content of formic acid in the formic acid-amine adduct (A3) in the lower phase was determined by titration with 0.1 N KOH in MeOH potentiometrically hourly with a "Mettler Toledo DL50" - titrator, and also the ratio between upper and lower phase in Reaction mixture was determined.
  • A3 formic acid-amine adduct
  • Examples 13 and 15 show that the formic acid decomposes very rapidly in the lower phase at the temperatures of the cleavage (> 130 ° C.) (process step (e)), if ruthenium compounds (with or without phosphine ligand) are present and no inhibitor has been added
  • Inventive Examples 16-130 decomposition of formic acid in the cleavage of the formic acid-amine adduct (A3) with the addition of an inhibitor; Simulation of process step (e) with the addition of an inhibitor
  • Inventive Examples 16-130 80.0 g formic acid-amine adduct (A3), i. Adduct of formic acid and tri-n-hexylamine, (1: 1.5, 20 wt .-% formic acid) and the ruthenium catalyst and the inhibitor were weighed into a glass flask. The reaction mixture was refluxed to 130 ° C in the open system to form a lower phase and an upper phase. The content of formic acid in the formic acid-amine adduct (A3) in the lower phase was determined by titration with 0.1 N KOH in MeOH potentiometrically hourly with a "Mettler Toledo DL50" - titrator, and also the ratio between upper and lower phase in Reaction mixture was determined.
  • A3 formic acid-amine adduct
  • Examples 16 and 130 according to the invention show that the decomposition of formic acid in the cleavage (> 130 ° C.) (process stage (e)) can be markedly slowed down by the addition of inhibitors according to the invention and thus significantly lower formic acid losses occur during work-up.

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Abstract

L'invention concerne un procédé pour produire de l'acide formique par réaction de dioxyde de carbone avec de l'hydrogène dans un réacteur d'hydrogénation, en présence d'un catalyseur contenant un élément du 8ème, du 9ème ou du 10ème groupe de la classification périodique des éléments, d'une amine tertiaire et d'un solvant polaire, de manière à former des produits d'addition acide formique/amine qui sont ensuite soumis à une fission thermique pour donner lieu à de l'acide formique et à de l'amine tertiaire.
EP12730532.4A 2011-07-07 2012-06-27 Procédé de production d'acide formique par réaction de dioxyde de carbone avec de l'hydrogène Withdrawn EP2729438A1 (fr)

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US8946462B2 (en) 2011-11-10 2015-02-03 Basf Se Process for preparing formic acid by reaction of carbon dioxide with hydrogen
US9428438B2 (en) 2012-11-27 2016-08-30 Basf Se Process for preparing formic acid
CN111315716B (zh) * 2017-11-15 2023-04-14 索尔维公司 用于生产甲酸的方法
EP4089177A1 (fr) 2021-05-14 2022-11-16 Cebal - Centro De Biotecnologia Agrícola E Agro-Alimentar Do Alentejo Procédé de production d'acide formique utilisant des souches de e. coli
CN117138775B (zh) * 2023-07-24 2024-04-30 昆明贵金属研究所 一种无碱条件下催化二氧化碳加氢制甲酸的催化体系

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CA1220222A (fr) 1982-05-22 1987-04-07 David J. Drury Production des sels de formates
GB8307611D0 (en) 1983-03-18 1983-04-27 Bp Chem Int Ltd Formic acid
GB8401005D0 (en) 1984-01-14 1984-02-15 Bp Chem Int Ltd Formate salts
GB8424672D0 (en) * 1984-09-29 1984-11-07 Bp Chem Int Ltd Production of formic acid
NZ227890A (en) 1988-02-17 1992-02-25 Bp Chemical Ltd Production of formic acid from a nitrogenous base, carbon dioxide and hydrogen
EP0357243B1 (fr) * 1988-08-20 1995-02-01 BP Chemicals Limited Production de sels formiques de bases azotées
DE102004040789A1 (de) * 2004-08-23 2006-03-02 Basf Ag Verfahren zur Herstellung von Ameisensäure
KR20090123972A (ko) * 2007-03-23 2009-12-02 바스프 에스이 포름산의 제조 방법
WO2010149507A2 (fr) 2009-06-26 2010-12-29 Basf Se Procédé de préparation d'acide formique
UA104324C2 (ru) * 2009-06-26 2014-01-27 Басф Се Способ получения муравьиной кислоты

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KR20140044891A (ko) 2014-04-15
BR112013033528A2 (pt) 2017-02-07
RU2014104137A (ru) 2015-08-20
CA2838907A1 (fr) 2013-01-10

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