WO2013014160A1 - Procédé permettant de fabriquer des foramides et des esters d'acide formique - Google Patents

Procédé permettant de fabriquer des foramides et des esters d'acide formique Download PDF

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Publication number
WO2013014160A1
WO2013014160A1 PCT/EP2012/064508 EP2012064508W WO2013014160A1 WO 2013014160 A1 WO2013014160 A1 WO 2013014160A1 EP 2012064508 W EP2012064508 W EP 2012064508W WO 2013014160 A1 WO2013014160 A1 WO 2013014160A1
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alkyl
group
catalyst
amine
reaction
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PCT/EP2012/064508
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German (de)
English (en)
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Thomas Schaub
Rocco Paciello
Marek Pazicky
Giuseppe Fachinetti
Debora Preti
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Basf Se
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Priority to KR1020147001728A priority Critical patent/KR20140044871A/ko
Priority to EP12737838.8A priority patent/EP2736872A1/fr
Priority to RU2014107102/04A priority patent/RU2014107102A/ru
Priority to JP2014522065A priority patent/JP2014523448A/ja
Priority to CA2837793A priority patent/CA2837793A1/fr
Priority to CN201280036780.4A priority patent/CN103702968A/zh
Priority to BR112014001571A priority patent/BR112014001571A2/pt
Publication of WO2013014160A1 publication Critical patent/WO2013014160A1/fr
Priority to ZA2014/01358A priority patent/ZA201401358B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—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
    • B01J31/02—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
    • B01J31/0238—Amines with a primary amino group
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g

Definitions

  • the present invention relates to a process for the preparation of formamides and formic acid esters, ie of formamide and its / V-substituted derivatives, as well as esters of formic acid and alcohols starting from carbon dioxide and hydrogen.
  • Formamide and its N-substituted derivatives are important selective solvents and extractants because of their polarity. They are z. B. for the extraction of butadiene from C 4 cuts, acetylene from C 2 cracker fractions and aromatics used from aliphatic.
  • Formic acid esters such as methyl formate or ethyl formate are used as foaming agents or fragrances.
  • Formamide, / V-alkylformamide and / V, / V-dialkylformamide are prepared by reacting methyl formate, which is accessible by the reaction of carbon monoxide with methanol, with ammonia, / V-alkylamines or / V, / V-dialkylamines.
  • the liberated methanol can be recycled to the Methylformiatsynthese from carbon monoxide and methanol.
  • Other formic acid esters are obtained by the reaction of formic acid with the corresponding alcohol with dehydration.
  • ammonia or the abovementioned amines are reacted at 20 to 100 ° C. and 2 to 10 MPa directly with carbon monoxide instead of methyl formate.
  • Work is carried out in methanol as a solvent with alkoxides as catalysts (Hans-Jürgen Arpe, Industrial Organic Chemistry, 6th edition, 2007, pages 48 to 49).
  • Carbon monoxide is a comparatively expensive Cr building block.
  • a disadvantage of carbon monoxide is beyond its toxicity, which makes working under high safety precautions necessary.
  • the relatively high pressures in the production of formamides from carbon monoxide are costly.
  • the object of the present invention is to provide a process for the preparation of carboxylic acid derivatives, in particular formamide and N-substituted formamide derivatives and formic acid esters, based on the starting materials carbon dioxide, hydrogen and an amine or an alcohol. The process should preferably be able to be operated continuously.
  • the preparation of the carboxylic acid derivatives, in particular of formamide and N- substituted formamide derivatives and formic acid esters, should preferably take place in one reaction step (integrated process).
  • the target products, ie formamide, the N-substituted formamide derivatives or the formic esters are to be made accessible with high yields and selectivities.
  • the work-up of the reaction product from the hydrogenation reactor and the catalyst separation should be technically simple, require little energy, and preferably exclusively with substances already present in the process, without additional auxiliaries.
  • R is selected from the group consisting of OR 1 and NR 2 R 3, wherein unsubstituted or at least monosubstituted CRCI 5 alkyl, C5-C 1 0-cycloalkyl, C 5 -C 10 heterocyclyl, C 5 -C 10 aryl, or C 5 -C 10 heteroaryl, wherein the substituents are selected from the group consisting of C 1 -C 5 -alkyl, C -C 6 -alkoxy, C 5 -C 10 -cycloalkyl and C 5 -C 10 -aryl;
  • R 2 and R 3 are independently hydrogen, unsubstituted or at least mono-substituted Ci-C 5 alkyl, C 5 -C 10 cycloalkyl, C 5 -C 10 - heterocyclyl, C 5 -C 10 aryl or C 5 -C 10 - Heteroaryl are, wherein the substituents are selected from the group consisting of CrCi 5 alkyl, C 5 -C 10 cycloalkyl and C 5 -C 10 aryl or
  • R 2 and R 3 together with the nitrogen atom form a five- or six-membered ring, which optionally additionally contains one or more heteroatoms selected from O, S and N, which carries the substituent R 4 , wherein
  • R 4 is hydrogen or CC 6 alkyl; by reaction of a reaction mixture (Rg) comprising carbon dioxide, hydrogen and an alcohol of the general formula (Ib) R 1 -OH (Ib)
  • the inventive method allows the use of inexpensive carbon dioxide instead of the relatively expensive carbon monoxide as a Ci building block.
  • inventive method allows easy separation of the catalyst, good product yield and simple workup of the product mixture.
  • a reaction mixture (Rg) is reacted which contains carbon dioxide, hydrogen, an alcohol (Ib) or an amine (Ic).
  • a reaction mixture (Rg) containing an alcohol (Ia) forms as the carboxylic acid derivative (Ia) formic acid ester (Ia1) according to the general reaction equation (II), wherein for the formic acid ester (Ia1) the abovementioned definitions apply to R 1 accordingly.
  • reaction mixture (Rg) containing an amine (Ia) forms as carboxylic acid derivative (Ia) a formamide compound (Ia2) according to the general reaction equation (I II), wherein for the formamide compound (Ia2), the above Definitions for R 2 and R 3 apply accordingly.
  • R 1 is unsubstituted or at least monosubstituted C 1 -C 8 -alkyl, wherein the substituents are selected from the group consisting of CC 6 alkyl and CC 6 alkoxy.
  • R 1 is unsubstituted or at least monosubstituted C 1 -C 8 -alkyl, the substituents being selected from the group consisting of CC 6 -alkyl and CC 6 -alkoxy.
  • branched, unbranched, saturated and unsaturated groups are understood by C 1 -C 15 -alkyl.
  • Preferred are saturated alkyl groups having 1 to 6 carbon atoms (C 1 -C 6 -alkyl). More preferred are saturated alkyl groups having 1 to 4 carbon atoms (C 1 -C 4 alkyl).
  • saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
  • unsaturated alkyl groups alkenyl, alkynyl
  • the C -C alkyl group may be unsubstituted or substituted with one or more substituents selected from the group Ci-C 5 alkyl, d-Ce-alkoxy, C 5 -C 10 - cycloalkyl, C 5 -C 10 aryl.
  • C 5 -C 10 -cycloalkyl is understood here to mean saturated, unsaturated monocyclic and polycyclic groups.
  • Examples of C 5 -C 0 cycloalkyl are cyclopentyl, cyclohexyl or cycloheptyl.
  • the cycloalkyl groups may be unsubstituted or substituted with one or more substituents as above to the group C-
  • C 5 -C 10 -aryl means an aromatic ring system having 5 to 10 carbons.
  • the aromatic ring system may be monocyclic or bicyclic.
  • aryl groups are phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl.
  • the aryl group may be unsubstituted or substituted with one or more substituents as defined above for C 1 -C 15 alkyl.
  • C 5 -C 10 heteroaryl is understood as meaning a heteroaromatic system which contains at least one heteroatom selected from the group consisting of N, O and S.
  • the heteroaryl groups may be monocyclic or bicyclic.
  • the present invention also includes N-oxides of the nitrogen-containing heteroaryls.
  • heteroaryls are thienyl, benzothienyl, 1-naphthothienyl, thianthrenyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, isoindolyl, indazolyl, purinyl, isoquinolinyl, quinolinyl, acridinyl, naphthyridinyl, quinoxalinyl, Quinazolinyl, cinnolinyl, piperidinyl, carbolinyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl.
  • the heteroaryl groups may be unsubstit
  • C 5 -C 10 -heterocyclyl is understood as meaning five- to ten-membered ring systems which contain at least one heteroatom from the group consisting of N, O and S.
  • the ring systems can be monocyclic or bicyclic.
  • heterocyclic ring systems examples include piperidinyl, pyrrolidinyl, pyrrolinyl, pyrazolinyl, pyrazolidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, piperazinyl, indolinyl, dihydrofuranyl, tetrahydrofuranyl, dihydrothiophenyl, tetrahydrothiophenyl, dihydropyranyl and tetrahydropyranyl.
  • C 1 -C 6 -alkoxy (C 1 -C 6 -alkyl-O-) radicals are understood.
  • alkyl moiety of the alkoxy group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
  • Particularly preferred as alcohol (Ib) is an alcohol selected from the group consisting of methanol, ethanol, 2-methoxyethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1 - Pentanol, 1 -hexanol, 1-heptanol and 1 - used octanol.
  • the corresponding formic acid esters (Ia1) are selected from the group consisting of methyl formate, ethyl formate, 2-methoxyethyl formate, 1-propyl formate, 2-propyl formate, 1-butyl formate, 2-butyl formate, 2-methyl-1-propyl formate, 1-pentyl formate, 1-Hexylformiat, 1-Heptylformiat, 1-Octylformiat accessible.
  • methanol is used as the alcohol (Ib) and methyl formate is obtained as the formic acid ester (Ia1).
  • amine (Ic) an amine selected from the group consisting of ammonia, methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, isobutylamine, diisobutylamine
  • the corresponding formamide compounds (Ia2) are selected from the group consisting of formamide, methylformamide, dimethylformamide, ethylformamide, diethylformamide, n-propylformamide, di-n-propylformamide, isopropylformamide, diisopropylformamide, diisopropylformamide, diisopropylformamide, diisopropy
  • an amine selected from the group consisting of ammonia, methylamine and dimethylamine is used as the amine (Ic).
  • the corresponding formamide compounds (Ia2) selected from the group consisting of formamide, methylformamide, dimethylformamide accessible.
  • ammonia is used as the amine (Ic) and formamide is obtained as the formamide compound (Ia2).
  • morpholine is used as amine (Ic) and formylmorpholine is obtained as formamide compound (Ia2).
  • hydrogenation reactors it is possible in principle to use all reactors which are fundamentally suitable for heterogeneously catalyzed gas / liquid reactions under the given temperature and given pressure. Suitable standard reactors for gas-liquid reaction systems are described, for example, in KD Henkel, "Reactor Types and Their Industrial Applications” and in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, DOI: 10.1002 / 14356007.b04_087. Examples which may be mentioned stirred tank reactors, tubular reactors, tube bundle reactors or fixed bed reactors.
  • the amines (Ic) or alcohols (Ib) used in the process according to the invention are fed to the hydrogenation reactor in liquid or gaseous form.
  • the molar ratio of the alcohol (Ib) or amine (Ic) used in the process according to the invention to the carbon dioxide used is generally from 0.01 to 30 and preferably from 0.2 to 5.
  • the carbon dioxide used in the reaction of carbon dioxide with hydrogen in the hydrogenation reactor can be used solid, liquid or gaseous. It is also possible to use commercially available carbon dioxide-containing gas mixtures.
  • the hydrogen and carbon dioxide may also contain other inert gases such as nitrogen or noble gases.
  • the gold catalysts used in the process according to the invention are also tolerant of carbon monoxide, which often leads to poisoning of hydrogenation catalysts.
  • the hydrogen used in the reaction in the hydrogenation reactor and the carbon dioxide may therefore also contain carbon monoxide as an impurity.
  • the carbon monoxide content in the gas streams fed to the hydrogenation reactor is below 20 mol% based on the total amount of carbon dioxide and hydrogen in the hydrogenation reactor. While larger amounts may also be tolerable, they generally require the use of a higher pressure in the reactor, requiring further compression energy.
  • the hydrogenation of carbon dioxide takes place in the liquid phase preferably at a temperature of 20 to 200 ° C and a total pressure of 0.2 to 30 MPa abs.
  • the total pressure preferably at least 1 MPa abs. and more preferably at least 5 MPa abs and preferably at most 15 MPa abs. is.
  • the temperature is at least 30 ° C and more preferably at least 100 ° C and preferably at most 180 ° C, more preferably at most 170 ° C and most preferably at most 160 ° C.
  • the partial pressure of the carbon dioxide is generally at least 0.5 MPa and preferably at least 2 MPa and generally at most 8 MPa.
  • the partial pressure of hydrogen is generally at least 0.5 MPa and preferably at least 1 MPa and generally at most 25 MPa and preferably at most 15 MPa.
  • the molar ratio of hydrogen to carbon dioxide in the feed of the hydrogenation reactor is preferably 0.1 to 10 and more preferably 1 to 3.
  • the molar ratio of carbon dioxide to the amine (Ic) or alcohol (Ib) in the feed of the hydrogenation reactor is generally from 0.01 to 30 and preferably from 0.2 to 5.
  • the catalyst used in the process according to the invention contains a catalytically active metal component which contains gold.
  • a heterogeneous catalyst is used.
  • gold is present in metallic form, ie oxidation state (0).
  • the metal component of the catalyst may contain, in addition to gold, one or more other metals, such as noble metals selected from the group consisting of Pd, Pt, Ag and Cu in the form of alloys.
  • the metal component may also contain metal promoters. Preference is given to using pure metal as the metal component, ie a metal component which contains at least 50% by weight, preferably at least 70% by weight and in particular 90% by weight of gold, based in each case on the total weight of the metal component.
  • the metal component of the catalyst is preferably used in the form of nanoparticles.
  • the average particle diameter (D 50 ) is usually in the range of 0.1 to 50 nm.
  • the metal component of the catalyst can be used as such.
  • the metal component itself forms the actual catalyst, i. the metal component of the catalyst is used in unsupported form.
  • gold itself is suitable, d. H. in pure form, or gold, on a support material (supported gold).
  • gold black i.e., colloidally precipitated elemental gold.
  • a catalyst containing the metal component and a support material (supported catalyst).
  • the metal component is then fixed on the surface of the carrier material.
  • Supported gold nanoparticles can also be used.
  • catalysts gold alloys such as Au-M on supports, wherein M may be a noble metal such as Pd or Pt as well as other metals such as Ag or Cu.
  • Different metal promoters can also be located in one and the same catalyst.
  • Preferably supported gold catalysts are used in the process according to the invention.
  • carriers a wide variety of materials may be used, such as inorganic oxides, graphite, polymers or metal.
  • inorganic oxides silica, magnesia, zirconia and / or titania are preferred.
  • magnesium oxide aluminum oxide, silicon oxide, gallium oxide, zirconium oxide, cerium oxide and / or titanium oxide as support material.
  • the heterogeneous catalyst can be used in a wide variety of geometric shapes and sizes, such as pellets, cylinders, hollow cylinders, spheres, rods or extrudates. The average particle diameter is usually between 1 and 10 mm.
  • nets, woven mesh wires or knits are also applicable.
  • the heterogeneous catalyst In the case of a supported catalyst, the heterogeneous catalyst generally contains between 0.01 and 50% by weight, preferably between 0.1 and 20% by weight and more preferably 0.1 to 5% by weight of gold based on the total mass of the catalyst used supported catalyst. In the case of an unsupported catalyst, the gold content is generally between 0.01 and 100 wt.% With respect to the total amount of catalyst used.
  • Suitable gold catalysts are commercially available or can be obtained by treating a support material with the solution of a gold compound or by coprecipitation followed by drying, heat treatment and / or calcination by known methods.
  • the gold catalyst generally contains gold particles with a diameter of 0.1 to 50 nm, measured by means of X-ray diffraction. In addition, particles with a diameter of less than 0.1 nm or even particles larger than 50 nm may be included.
  • the heterogeneous catalyst has a BET surface area in the range of 1 m 2 / g to 1000 m 2 / g (determination of the BET surface according to DIN ISO 9277).
  • the BET surface area of the heterogeneous catalyst is in the range of 10 m 2 / g to 500 m 2 / g.
  • the volume of the heterogeneous catalyst in the hydrogenation reactor is generally between 0.1 and 95% of the reaction volume of the hydrogenation reactor, the catalyst volume being calculated from the catalyst mass divided by the bulk density of the catalyst.
  • the reaction mixture (Rg) may additionally contain a polar solvent.
  • a polar solvent This is particularly advantageous when an amine (Ic) is reacted with carbon dioxide and hydrogen to formamide compound (Ia2) according to the general reaction equation (III).
  • Amines (Ic) such as ammonia, can form salts with carbon dioxide.
  • a polar solvent By using a polar solvent, the solubility of these salts in the reaction mixture (Rg) can be improved.
  • the reaction mixture (Rg) may contain a polar solvent or mixtures of two or more polar solvents.
  • Suitable classes of substances which are suitable as polar solvents are preferably alcohols and diols and also their formic acid esters, formamides such as formamide, methylformamide or dimethylformamide, or water.
  • suitable alcohols are methanol, ethanol, 2-methoxyethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-1-propanol.
  • Suitable classes of compounds which are suitable as polar solvents are preferably diols and also their formic acid esters, polyols and also their formic acid esters, sulfones, sulfoxides, open-chain or cyclic amides and mixtures of the mentioned classes of substances.
  • Suitable diols and polyols are, for example, 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.
  • a suitable sulfone is tetramethylene sulfone (sulfolane).
  • Suitable sulfoxides are, for example, dialkyl sulfoxides, preferably C to C 6 - dialkyl sulfoxides, in particular dimethyl sulfoxide.
  • Suitable open-chain or cyclic amides are formamide, methylformamide, dimethylformamide, / V-methylpyrrolidone, acetamide and / V-methylcaprolactam.
  • the molar ratio of the polar solvent or solvent mixture to be used in the process according to the invention to the amine (Ic) used is generally 0.5 to 30 and preferably 1 to 20.
  • 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 hydrogen are pressed to the desired pressure at the desired temperature.
  • the reactor is usually depressurized and the liquid reaction mixture is separated from the heterogeneous catalyst.
  • the feeds and auxiliaries, including the carbon dioxide and hydrogen are continuously fed to the hydrogenation reactor.
  • the catalyst can be used as a fixed bed (fixed bed reactor).
  • the heterogeneous catalyst is fixed in the hydrogenation reactor. It is also possible to suspend the catalyst in the reaction mixture (Rg).
  • a liquid phase is continuously removed from the hydrogenation 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 reaction mixture (Rg) in the hydrogenation reactor is generally 10 minutes to 5 hours.
  • a hydrogenation mixture (H) obtained which contains the carboxylic acid derivative (Ia), water of reaction and optionally unreacted alcohol (Ib) or unreacted amine (Ic).
  • the hydrogenation mixture (H) may additionally contain the polar solvent or solvent mixture. In the event that a suspended heterogeneous catalyst is used, this is also contained in the hydrogenation mixture (H).
  • the catalyst In the case of a fixed bed catalyst, the catalyst usually remains by its fixation in the hydrogenation reactor and the hydrogenation mixture contains no catalyst, i. less than 5 ppm of the gold catalyst based on the total weight of the reaction mixture (Rg). In the case of unfixed, suspended heterogeneous catalysts, these are usually retained by known measures, such as fabric or filter, in the reactor outlet in the hydrogenation reactor. However, the catalyst can also be separated off after the reaction by simple measures such as filtration, decantation or centrifugation in a subsequent step of the hydrogenation mixture (H) and recycled to the hydrogenation reactor. After separation of the catalyst, the hydrogenation mixture (H) is virtually free of gold (hydrogenated hydrogenation mixture (Ha)), i.
  • the gold content of the worked-up hydrogenation mixture (Ha) is below 5 ppm by weight, based on the worked-up hydrogenation mixture (Ha).
  • the reclaimed hydrogenation mixture (Ha) is worked up by distillation to give first stream containing the carboxylic acid derivative (Ia), a second stream containing unreacted alcohol (Ib) or unreacted amine (Ic), and a third stream containing the water of reaction.
  • reaction is carried out in the presence of a polar solvent
  • this can be separated via a fourth stream.
  • the work-up by distillation can be one, two or more stages depending on the separation problem.
  • the distillation can be carried out on removal of low-boiling polar solvents such as the monohydric alcohols methanol, ethanol, propanols and butanols under atmospheric pressure or in vacuo.
  • the polar solvents are recycled to the hydrogenation reactor.
  • distillation units for the work-up by distillation of the worked-up hydrogenation mixture (Ha).
  • evaporators such as falling film evaporator can be used.
  • the distillation unit to be used generally comprises a distillation column containing packing, packing and / or trays.
  • the distillation unit When using an additional polar solvent, the distillation unit consists of at least one, preferably two to three, distillation columns. These columns contain, depending on the separation problems z. B. packing, packages and / or floors.
  • the carboxylic acid derivatives (Ia) (target products) are discharged from the process and, if necessary, fed to a preferably distillative fine purification.
  • FIG. 1 shows a block diagram of a plant for a preferred embodiment of the process according to the invention for the preparation of formamide compounds (Ia2) starting from carbon dioxide, hydrogen and an amine (Ic)
  • FIG. 2 shows a block diagram of a plant for a preferred embodiment of the process according to the invention for the preparation of formic acid esters (Ia1) starting from carbon dioxide, hydrogen and an alcohol (Ib).
  • FIG. 3 shows a block diagram of a plant for a preferred embodiment of the process according to the invention for the preparation of formamide compounds (Ia2) starting from carbon dioxide, hydrogen and an amine (Ic) with the addition of a polar solvent
  • carbon dioxide, stream 1, hydrogen, stream 2, and the amine (Ic), stream 3 are fed into the hydrogenation reactor 1-1. In this they are reacted in the presence of the heterogeneous gold catalyst to the formamide compound (Ia2) and water of reaction. From the liquid hydrogenation mixture (H) containing the formamide compound (Ia2), water of reaction, the heterogeneous catalyst and unreacted amine (Ic), the heterogeneous catalyst is separated. The reclaimed hydrogenation mixture (Ha) thus obtained is supplied as stream 4 to the distillation unit 11-1.
  • the worked-up hydrogenation mixture (Ha) is separated by distillation to give the formamide compound (Ia2), stream 5, reaction water effluent, stream 6, and unreacted amine (Ic), stream 7, which is recycled to the hydrogenation reactor 11-1.
  • the worked-up hydrogenation mixture (Ha) is separated by distillation to give the formic acid ester (Ia1), stream 15, elution of water of reaction, stream 6, and unreacted alcohol (Ib), stream 17, which is recycled to the hydrogenation reactor II-2.
  • carbon dioxide, stream 21, hydrogen, stream 22, and the amine (Ic) stream 23 are fed to the hydrogenation reactor I-3, which also contains a polar solvent. In this they are reacted in the presence of the heterogeneous gold catalyst to a formamide compound (Ia2) and water of reaction.
  • the heterogeneous catalyst is separated.
  • the reclaimed hydrogenation mixture (Ha) thus obtained is supplied as stream 44 to the distillation unit 11-3.
  • the reclaimed hydrogenation mixture (Ha) is separated by distillation to give the formamide compound (Ia2), stream 25, elution of water of reaction, stream 26, and unreacted amine (Ic), stream 27, which is recycled to the hydrogenation 11-3 and of the polar solvent, which as stream 28 is also recycled to the hydrogenation reactor 11-3.
  • Examples A-1 to A-1 show that formamides and formic acid esters are easily obtained by using the gold catalysts by CO 2 hydrogenation.
  • reaction solution worked up hydrogenation mixture (Ha)
  • Ha worked up hydrogenation mixture
  • Comparative Examples A12 and A13 show that with the use of standard hydrogenation catalysts such as Raney nickel or palladium on carbon under otherwise identical conditions as in the gold catalysts no formamide (Raney nickel) or only in much poorer yields (factor 15 lower at Pd). This shows the advantage of using the catalysts of the invention for this reaction.

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

Abstract

La présente invention concerne un procédé de fabrication de dérivés d'acide carboxylique de la formule générale (la) suivante : H-(C=0)-R (la), où R est choisi dans le groupe constitué de OR1 et NR2R3, où R1 est un alkyle en C1-C15, un cyclo-alkyle en C5-C10, un hétéro-cyclyle en C5-C10, un aryle en C5-C10 ou hétéro-aryle en C5-C10 non substitué ou au moins monosubstitué, les substituants étant choisis dans le groupe constitué d'alkyle en C1-C15, d'alkoxy en C1-C6, de cyclo-alkyle en C5-C10 et d'aryle en C5-C10 ; R2 et R3 indépendants l'un de l'autre sont un atome d'hydrogène, un groupe non substitué ou au moins monosubstitué d'alkyle en C1-C15, de cyclo-alkyle en C5-C10, d'hétéro-cyclyle en C5-C10, d'aryle en C5-C10 ou d'hétéro-aryle en C5-C10 ; les substituants étant choisis dans le groupe constitué d'alkyle en C1-C15, de cyclo-alkyle en C5-C10 et d'aryle en C5-C10 ou bien R2 et R3 ensemble avec l'atome d'azote forment un anneau à cinq ou six membres qui contient éventuellement en plus un ou plusieurs hétéroatomes choisis parmi O, S et N qui porte le substituant R4 qui est soit de l'hydrogène, soit de l'alkyle en C1-C6 ; ce procédé s'effectue en transformant un mélange réactif (Rg) comprenant du dioxyde de carbone, de l'hydrogène et un alcool de la formule générale (Ib) R1-OH (Ib) où R1 présente les interprétations ci-avant ou est une amine de la formule générale (Ic) NHR2R3 (Ic), dans laquelle R2 et R3 indépendants l'un de l'autre présentent les interprétations ci-avant, dans un réacteur d'hydrogénation en présence d'un catalyseur comprenant de l'or à une pression située entre 0,2 et 30 MPa et à une température située entre 20 et 200 °C.
PCT/EP2012/064508 2011-07-27 2012-07-24 Procédé permettant de fabriquer des foramides et des esters d'acide formique WO2013014160A1 (fr)

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EP12737838.8A EP2736872A1 (fr) 2011-07-27 2012-07-24 Procédé permettant de fabriquer des foramides et des esters d'acide formique
RU2014107102/04A RU2014107102A (ru) 2011-07-27 2012-07-24 Способ получения формамидов и сложных эфиров муравьиной кислоты
JP2014522065A JP2014523448A (ja) 2011-07-27 2012-07-24 ホルムアミドおよびギ酸エステルの製造方法
CA2837793A CA2837793A1 (fr) 2011-07-27 2012-07-24 Procede permettant de fabriquer des foramides et des esters d'acide formique
CN201280036780.4A CN103702968A (zh) 2011-07-27 2012-07-24 制备甲酰胺和甲酸酯的方法
BR112014001571A BR112014001571A2 (pt) 2011-07-27 2012-07-24 processo para preparar derivados de ácido carboxílico
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WO2015121357A1 (fr) * 2014-02-17 2015-08-20 Bayer Technology Services Gmbh Procédé d'hydrogénation du dioxyde de carbone en formamides
US10290219B2 (en) * 2014-08-01 2019-05-14 Shenzhen Cimc-Tianda Airport Support Ltd. Machine vision-based method and system for aircraft docking guidance and aircraft type identification
DE102019111058A1 (de) * 2019-04-29 2020-10-29 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Verfahren zur katalytischen Herstellung von Harnstoff

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WO2015192282A1 (fr) * 2014-06-16 2015-12-23 Rhodia Operations Processus de formylation pour la préparation de formamides aromatiques
CN105985254B (zh) * 2015-02-17 2018-03-16 上海中科绿碳化工科技有限公司 一种制备甲酰胺类化合物的方法
US10435349B2 (en) * 2017-08-02 2019-10-08 Eastman Chemical Company Iron-catalyzed cross-coupling of methanol with secondary or tertiary alcohols to produce formate esters
CN107915653B (zh) * 2017-12-04 2020-02-14 苏州大学 催化酯和胺进行反应制备酰胺的方法
CN108623493B (zh) * 2018-06-20 2021-01-19 大连理工大学 一种温和条件下以co2为碳源的n-甲酰化合成方法
CN113979882A (zh) * 2021-11-29 2022-01-28 宿迁新亚科技有限公司 一种制备二丁基甲酰胺的生产工艺

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Publication number Priority date Publication date Assignee Title
WO2015121357A1 (fr) * 2014-02-17 2015-08-20 Bayer Technology Services Gmbh Procédé d'hydrogénation du dioxyde de carbone en formamides
US10290219B2 (en) * 2014-08-01 2019-05-14 Shenzhen Cimc-Tianda Airport Support Ltd. Machine vision-based method and system for aircraft docking guidance and aircraft type identification
DE102019111058A1 (de) * 2019-04-29 2020-10-29 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Verfahren zur katalytischen Herstellung von Harnstoff
WO2020221690A1 (fr) 2019-04-29 2020-11-05 Thyssenkrupp Industrial Solutions Ag Procédé de production catalytique d'urée

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