WO2020101413A1 - Procédé de préparation et dispositif de préparation d'acide formique par réaction d'hydrogénation de dioxyde de carbone - Google Patents

Procédé de préparation et dispositif de préparation d'acide formique par réaction d'hydrogénation de dioxyde de carbone Download PDF

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WO2020101413A1
WO2020101413A1 PCT/KR2019/015595 KR2019015595W WO2020101413A1 WO 2020101413 A1 WO2020101413 A1 WO 2020101413A1 KR 2019015595 W KR2019015595 W KR 2019015595W WO 2020101413 A1 WO2020101413 A1 WO 2020101413A1
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formic acid
amine
reactor
carbon dioxide
catalyst
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Korean (ko)
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정광덕
윤성호
김성훈
아흐산자릴
임상엽
박종민
하리야나담 구나세카구니야
박광호
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한국과학기술연구원
국민대학교산학협력단
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Priority claimed from KR1020190145730A external-priority patent/KR102285717B1/ko
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Publication of WO2020101413A1 publication Critical patent/WO2020101413A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid
    • C07C53/06—Salts thereof

Definitions

  • the present invention relates to a formic acid production method and a manufacturing apparatus, and more particularly, to a formic acid production apparatus capable of recycling a product, including a fixed hydrogenation reactor, and a method for efficiently producing formic acid using the same .
  • Formic acid is a compound that can be used for multiple purposes. For example, it may be used as a raw material for fuel cells, an auxiliary for acidification in the manufacture of animal feed, an antiseptic, an auxiliary in the textile or leather industry, or a reactant for ice-making in aircraft or runways.
  • the technical problem of the present invention is to provide a formic acid production apparatus and a manufacturing method capable of solving a problem in which a catalyst is dissolved in a product to decompose formic acid and the yield of formic acid is significantly reduced while using a hydrogenation reaction process of carbon dioxide.
  • the present invention is a method for producing formic acid by a hydrogenation reaction of carbon dioxide, a carbonation step of producing ammonium bicarbonate by reacting carbon dioxide, amine and water; A hydrogenation step of reacting the ammonium bicarbonate with hydrogen in the presence of a catalyst to form a formic acid-amine adduct; And a base exchange step of replacing the amine of the formic acid-amine addition compound with another auxiliary base to form a formic acid-auxiliary base addition compound, and a separation step of distilling the formic acid-auxiliary base addition compound to obtain formic acid.
  • a method for producing formic acid is provided.
  • the present invention is a device for producing formic acid by hydrogenation of carbon dioxide, a carbonation reactor for producing ammonium bicarbonate by reacting carbon dioxide, amine and water; A hydrogenation reactor for reacting the ammonium bicarbonate and hydrogen in the presence of a catalyst to form a formic acid-amine adduct; A base exchange reactor for reacting the formic acid-amine addition compound and an auxiliary base to form a formic acid-auxiliary base addition compound in which the amine of the formic acid-amine addition compound is substituted with the auxiliary base; And a distiller for distilling the formic acid-auxiliary base addition compound to obtain formic acid.
  • the formic acid production method and apparatus according to the present invention uses a trickle bed reactor in which a heterogeneous catalyst is fixed, the product obtained after the reaction does not contain a catalyst component, and thus, a catalyst recovery system is not required separately, and catalyst particles Can be prevented from being crushed.
  • a uniform aqueous solution is formed through a liquid-to-liquid reaction, and since the aqueous solution does not cause phase separation, reaction efficiency may be increased.
  • the present invention does not need to use only purified carbon dioxide as a reactant, it is possible to simplify the process of capturing, purifying, and pressing carbon dioxide, thereby increasing economic efficiency.
  • FIG. 1 is a flowchart illustrating a formic acid production process according to a hydrogenation reaction of carbon dioxide according to an embodiment of the present invention.
  • Figure 2 shows the configuration of a formic acid production apparatus according to an embodiment of the present invention.
  • Figure 3 shows the configuration of a formic acid production apparatus according to another embodiment of the present invention.
  • Figure 4 shows the configuration of a formic acid production apparatus according to another embodiment of the present invention.
  • Figure 5 shows the configuration of a formic acid production apparatus according to another embodiment of the present invention.
  • the present invention relates to a method and apparatus for producing formic acid by hydrogenation of carbon dioxide.
  • the present invention will be described in detail with reference to the drawings and examples.
  • the method for producing formic acid by hydrogenation of carbon dioxide includes 1) a carbonation step of preparing ammonium bicarbonate by reacting carbon dioxide, amine and water; 2) a hydrogenation step of reacting the ammonium bicarbonate with hydrogen in the presence of a catalyst to form a formic acid-amine adduct; 3) a base exchange step of exchanging the amine of the formic acid-amine addition compound with another auxiliary base to form a formic acid-auxiliary base addition compound, and 4) a separation step of distilling the formic acid-auxiliary base addition compound to obtain formic acid. It is characteristic. Referring to FIG. 1, it is possible to understand the manufacturing process of the present invention, which basically leads to a carbonation step, a hydrogenation step, a base exchange step, and a separation step.
  • the carbonation step may be represented by Chemical Formula 1 below, and ammonium bicarbonate is formed by the reaction of carbon dioxide, water, and amine. (S100).
  • NR 1 R 2 R 3 is a tertiary amine
  • R 1 , R 2 to R 3 are each independently an alkyl group having 1 to 6 carbon atoms, wherein R 1 , R 2 to R 3 are in It is preferable that the total number of carbons contained is 12 or less.
  • R 1 , R 2 to R 3 may be, independently of each other, an alkyl group having 2 or 3 carbon atoms, and the alkyl group may be linear, branched or cyclic, and saturated or unsaturated hydrocarbon.
  • two alkyl groups among the alkyl groups may be combined to form a saturated or unsaturated ring with N.
  • the tertiary amine usable in the present invention is triethylamine, tripropylamine, tributylamine, N, N-dimethylbutylamine, N-methylpiperidine, 1-ethylpiperidine, NN -Dimethylpiperazine, dimethylcyclohexylamine, dimethylhexylamine, N-methylpyrrolidine, N-ethylpyrrolidine, dimethylphenethylamine, dimethyloctylamine, and the like, but is not particularly limited thereto.
  • the process of preparing formic acid by hydrogenation reaction of carbon dioxide is a non-spontaneous reaction, and ⁇ G (gibbs free energy change) has a positive value.
  • ⁇ G gibbs free energy change
  • the ⁇ G change in Gibbs free energy of the hydrogenation reaction of carbon dioxide has a negative value, so that You can overcome the thermodynamic limitations.
  • a tertiary amine that satisfies a pk a (ionization constant) of 6.5 to 14, and preferably has a pk a of 9.0 to 12.0.
  • pk a ionization constant
  • (HNR 1 R 2 R 3 ) + (HCO 3 ) ⁇ may be an ammonium salt such as ammonium bicarbonate, and may exist in the form of an aqueous solution. Since tertiary amines may have low solubility in water, tertiary amines and water may cause phase separation between liquids, and when phase separation occurs between liquids, the reaction efficiency in the subsequent hydrogenation process is lowered. This can happen. However, since the ammonium salt of ammonium bicarbonate produced in the carbonation step may exist as an aqueous solution together with water, in the present invention, phase separation between liquids of reactants in the hydrogenation process can be minimized by introducing such a carbonation process before the hydrogenation process. have.
  • the carbon dioxide is contained and supplied in the exhaust gas, and the amine is reacted through a process of selectively absorbing the carbon dioxide in the exhaust gas.
  • the hydrogenation step is a process for synthesizing the formic acid precursor, and may be represented by the following Chemical Formula 2. That is, a formic acid-amine addition compound is formed according to the hydrogenation reaction of ammonium bicarbonate produced in the carbonation step (S200).
  • R 1 , R 2 to R 3 are as defined in Chemical Formula 1.
  • NR 1 R 2 R 3 : HCO 2 H is a formic acid-amine adduct compound, and may be an ammonium salt such as (HNR 1 R 2 R 3 ) + (HCO 2 ) - (ammonium formate).
  • the formic acid-amine addition compound may additionally include a free amine or a mixture of free formic acid.
  • the formic acid production process through the hydrogenation reaction of carbon dioxide efficiently performs a hydrogenation reaction using a catalyst, and proposes a commercially available formic acid production method.
  • the catalyst uses a fixed hydrogenation reactor, that is, a trickle bed reactor in which a heterogeneous catalyst is fixed, the product obtained after the reaction does not contain a catalyst component, and accordingly, a catalyst recovery system is not required. It is possible to prevent the catalyst particles from being crushed.
  • the catalyst usable in the present invention may be a catalyst in which an active metal or an active metal salt contains nitrogen or is supported in a porous carrier doped with nitrogen.
  • the active metal or the active metal salt is immobilized on a carrier containing nitrogen, since the active metal and the active metal salt are not eluted in the solvent, the active component of the catalyst is not eluted into the product, so that the decomposition reaction of formic acid is suppressed and the yield of formic acid is reduced. Is not reduced.
  • the active metal usable in the present invention may be selected from iridium (Ir), ruthenium (Ru), or mixtures thereof, and examples of the active metal salt include chloride, acetate, and acetylacetonate salts of the active metal. (acetylacetonate), nitrate (nitrate), hydroxide (hydroxide), sulfate (sulfate) or sulfide (sulfide), and the like, but is not particularly limited thereto.
  • the porous carrier usable in the present invention specifically includes, for example, a nitrogen-doped porous carbon body, a COF (covalent organic framework) having a nitrogen-containing frame ligand, a nitrogen-doped metal oxide, or a metal nitride.
  • a nitrogen-doped porous carbon body a COF (covalent organic framework) having a nitrogen-containing frame ligand, a nitrogen-doped metal oxide, or a metal nitride.
  • COF covalent organic framework
  • porous carbon body doped with nitrogen examples include graphene, activated carbon, graphite, and carbon nanotubes, and COF (covalent organic framework) may be used.
  • COF is a three-dimensional organic structure that forms a complex with an active metal, has a structure including a linker and a frame ligand forming a cavity with the linker, and an active metal salt in which two or more anionic ligands are introduced into the coordination zone of the active metal complex
  • the linker may be triazine or heptazine, and it is preferable to include a triazine linker.
  • the triazine linker is synthesized by triple polymerization of cyano groups (-CN) through ion-thermal synthesis, and the manufacturing method is simple, and unlike metal-ligand coordination, it is composed of covalent bonds, which has good thermal and chemical durability.
  • the frame ligand forms a cavity together with the linker, and may be a heterocyclic aromatic functional group containing nitrogen.
  • the heterocyclic aromatic functional group one or more of pyrene, pyridine, pyrrole, triphenylamine, porphyrin, bipyridine, bipyrrole, phenylpyridine, bipyrimidine, biimidazole or derivatives thereof may be selected.
  • a frame ligand as bipyridine makes it easy to prepare triazine-coupled COF, and has excellent catalytic activity.
  • the anionic ligands in the COF is an oxygen anion ligand selected from the acetoacetic carboxylates, oxalates, carbonates, acetyl carbonate (oxyanionic ligand) or Cl -, Br -, I - , SO 4 -, CF 3 SO 3 -, NO 3 - , PF 6 -It may be an anionic ligand selected from.
  • acetylacetonate is bound to the metal in a two-coordinate, which may be transformed into one coordination after promoting disproportionation of hydrogen molecules by receiving hydrogen cations when hydrogen molecules are separated in a hydrogenation reaction. . Accordingly, since the hydrogen cation does not interfere with the active metal-ligand bond portion (NN coordination bond), the stability and efficiency of the catalyst can be increased.
  • Ru as the active metal coordinated with COF.
  • Ru forms a Ru-H by combining with hydride generated in the disproportionation of hydrogen, and this form can be more stabilized than other metals, so the reaction rate can be increased.
  • another porous carrier usable in the present invention may be a metal nitride containing nitrogen.
  • the metal of the metal nitride may include aluminum (Al), silicon (Si), titanium (Ti), zirconium (Zr), or magnesium (Mg).
  • the supported catalyst according to the present invention is not limited to the active metal or the active metal salt containing nitrogen or being supported in a nitrogen-doped porous carrier, and the active metal or active metal salt also does not contain nitrogen. It is possible.
  • the base exchange step is a process of forming a formic acid-auxiliary base adduct through a base exchange reaction in which the tertiary amine in the formic acid-amine adduct is exchanged with another auxiliary base (S300). At this time, it is preferable to use a base having a lower pk a and a higher boiling point than the tertiary amine.
  • the base exchange reaction may be to exchange the amine of the formic acid-amine addition compound with an imidazole-based base.
  • R 1 , R 2 to R 3 are the same as defined in Chemical Formula 1, and IM is a hydrophobic base and can be called an auxiliary amine or auxiliary base.
  • the auxiliary base can also form formic acid-auxiliary base adducts in the form of IM: HCO 2 H.
  • the auxiliary base usable in the present invention may be N-alkylimidazole, N-alkylpyrrolidone, N-formyl acetamide, N-alkylacetamide, N-formylmorpholine or derivatives thereof.
  • the midazole, N-alkylpyrrolidone, and N-alkylacetamide derivatives may have one to four carbon atoms of the alkyl group.
  • pk a of the auxiliary base IM is 6.5 to 9, lower than pk a of the tertiary amine NR 1 R 2 R 3 in Formula 1, and the boiling point of IM is higher than that of NR 1 R 2 R 3 It is preferred.
  • the next step is distillation of the formic acid-base addition compound to obtain pure formic acid (S400).
  • the separated formic acid-auxiliary base addition compound can be finally obtained by pure formic acid by separating the auxiliary base through distillation.
  • the method for producing formic acid according to the present invention has an advantage that formic acid can be efficiently produced through recycling of products, for example, unreacted carbon dioxide discharged after the hydrogenation step, the carbonate reaction, base exchange reaction, and After the distillation step, all of the amine or base discharged can be recycled and used again in the reaction.
  • the apparatus for producing formic acid by hydrogenation of carbon dioxide includes a carbonation reactor for producing ammonium bicarbonate by reacting carbon dioxide, amine and water; A hydrogenation reactor for reacting the ammonium bicarbonate and hydrogen in the presence of a catalyst to produce a formic acid-amine adduct; A base exchange reactor for preparing a formic acid-auxiliary base adduct compound in which the amine of the formic acid-amine adduct is substituted by the auxiliary base by reacting the formic acid-amine adduct and the auxiliary base; And a distiller for distilling the formic acid-auxiliary base addition compound to obtain formic acid.
  • the hydrogenation reactor is preferably a trickle bed reactor in which a heterogeneous catalyst is fixed.
  • the formic acid production apparatus may further include an amine storage container to form an aqueous amine solution by mixing water and an amine at the front end of the carbonation reactor.
  • the carbonation reactor may be an absorption tower in which flue gas containing carbon dioxide is supplied from the bottom, and an amine aqueous solution containing water and amine is supplied from the top, or homogenization to form an ammonium bicarbonate by reacting a high purity carbon dioxide with an amine aqueous solution. Can be.
  • the formic acid production apparatus further comprises a separator for separating the amine discharged from the carbonated reactor and recycling it to the carbonated reactor between the carbonated reactor and the hydrogenated reactor, or the hydrogenation reactor and the base between the exchange reactors, a separator for separating unreacted carbon dioxide and hydrogen discharged from the hydrogenation reactor and recycling the hydrogenation reactor may be further included. Meanwhile, the amine separated at the top of the distiller moves to the amine storage container, and the base separated at the bottom of the distiller can be recycled to the base exchange reactor again.
  • water 14 and amine 15 are injected into an amine storage container V3, and accordingly, an amine aqueous solution or an aqueous dispersion 13 in which amine is homogeneously dispersed in water may be formed.
  • the amine aqueous solution 13 is introduced into an absorber or an absorption tower (AC1).
  • the absorber (AC1) is a carbonated reactor, and a carbonated step in which ammonium bicarbonate is prepared as shown in Chemical Formula 1 is performed.
  • the amine aqueous solution 13 may be supplied at the upper portion of the absorber, and the exhaust gas 1 containing carbon dioxide may be supplied at the lower portion.
  • the amine aqueous solution 13 may absorb or collect carbon dioxide in the flue gas 1 to generate ammonium bicarbonate 3.
  • carbon dioxide contained in the exhaust gas 1 is collected and the remaining residual gas 2 may be discharged from the upper portion of the absorber to the outside.
  • the carbon dioxide gas in the flue gas 1 is captured by an amine, so that an aqueous solution of ammonium bicarbonate 3 is formed, and the aqueous solution of ammonium bicarbonate can be transferred to the hydrogenation reactor R1 through a liquid pump.
  • the concentration of the amine aqueous solution 13 supplied to the absorber AC1 is preferably in the range of 0.02 to 7.0M, preferably in the range of 0.1 to 7.0M, and more preferably 1.0 to 6.5M. Within this concentration range, amine is not phase-separated from the aqueous amine solution, and it is possible to prevent excessively high energy consumption in the separation process described later by containing appropriate water.
  • the molar ratio of carbon dioxide to amine may be 0.1 to 3.0, preferably 0.2 to 2.0. This is because it is possible to represent an appropriate conversion rate of carbon dioxide and a production rate of formic acid in the molar ratio range.
  • the absorber AC1 may use a conventional absorption tower used to capture carbon dioxide, and may fill the packing material to increase absorption efficiency.
  • the absorber AC1 may perform the reaction at a pressure of 1 to 50 atmospheres and a temperature of 5 to 150 ° C, and a pressure range of 1 to 20 atmospheres and a temperature range of 5 to 80 ° C is more preferable.
  • the ammonium bicarbonate 3 and hydrogen 4 formed in the absorber AC1 may be introduced into the homogenizer H1.
  • the homogenizer may also be a bicarbonate reaction of Chemical Formula 1 as a carbonization reactor.
  • the homogenizer (H1) can simultaneously act as a preheater, the temperature of the homogenizer has a range of 20 to 200 ° C, and a range of 50 to 150 ° C is preferred. In this temperature range, the carbonation reaction of Formula 1 may be sufficiently performed, and the amine may not be deteriorated.
  • the pressure of the homogenizer H1 is in the range of 20 to 300 atmospheres, and the range of 40 to 200 atmospheres is efficient.
  • the pressure of the homogenizer H1 can be maintained at the same pressure as that of the hydrogenation reactor R1, and within this range, it can represent the reaction rate of the appropriate hydrogenation process.
  • the ammonium bicarbonate, a mixture of hydrogen to unreacted carbon dioxide (16-1) is supplied to the hydrogenation reactor (R1), the hydrogenation reactor (R1) can be carried out the formic acid precursor synthesis process represented by the formula (2) . That is, in the formic acid precursor synthesis process, a hydrogenation reaction is performed by reacting ammonium bicarbonate 3 and hydrogen 4 on a fixed heterogeneous catalyst, and formic acid-amine addition compound 6 can be formed by hydrogenation. .
  • the hydrogenation reactor (R1) is a reactor suitable for gas-liquid reaction by a heterogeneous catalyst according to reaction conditions, and a catalyst-immobilized gas-liquid mixed reactor may be used.
  • a catalyst-immobilized gas-liquid mixed reactor may be used.
  • a trickle bed reactor (TBR; trickle) bed reactor to increase the efficiency of the process.
  • the trickle bed reactor is a simple type reactor used in a catalytic reaction, in which liquid and gaseous fluids flow in a bed filled with catalyst particles.
  • the liquid phase may flow downward, and the gas phase may also be co-current depending on the flow downward.
  • the present invention is not limited to this, and the gas phase may be countercurrent with the upward flow in the opposite direction to the liquid phase.
  • the contact area between the catalyst and the reactant can be widened to improve reactivity.
  • the trickle bed reactor does not require a catalyst recovery device. Therefore, in order to recover the catalyst, an additional process such as separation by additionally adding a separate device or solvent may not be required.
  • the product does not contain a catalyst component, and thus the problem that the yield of formic acid is lowered may not occur, which is useful.
  • ammonium bicarbonate, hydrogen and carbon dioxide obtained from the absorber (AC1) are introduced into the hydrogenation reactor (R1), so that the ternary reaction of liquid (ammonium bicarbonate) -gas (hydrogen and carbon dioxide) -solid (catalyst) is performed. do.
  • the amine, water, hydrogen, and carbon dioxide as reactants are simultaneously introduced into the hydrogenation reactor (R1) without proceeding to the bicarbonate reaction represented by Chemical Formula 1 in the absorber (AC1), the amine does not dissolve in water. It may also be a four-component reaction of (water) -liquid (aqueous tertiary amine solution) -gas (hydrogen and carbon dioxide) -solid (catalyst).
  • the present invention can be controlled to prevent phase separation between liquids of the reactants through the carbonation process according to Chemical Formula 1 above. As such, by further including a carbonation process prior to the hydrogenation process, the reaction rate can be increased, and the reaction efficiency can be increased.
  • phase separation between solutions of the reactants may occur depending on the concentration conditions of the amine shown in Chemical Formula 1. Therefore, in order not to cause phase separation, the concentration of the tertiary amine aqueous solution 13 can be adjusted as described above.
  • the molar ratio of hydrogen to carbon dioxide is suitably in the range of 0.4 to 10, preferably 0.5 to 3, and more preferably 0.8 to 2.0. It is economical to match the molar ratio to this range, and may be advantageous in terms of energy consumption due to the conversion rate of carbon dioxide.
  • the temperature of the hydrogenation reactor (R1) is preferably in the range of 40 to 200 ° C, in this range the reaction can be carried out at an appropriate reaction rate, the tertiary amine may not be degraded.
  • the pressure of the hydrogenation reactor (R1) is 20 to 300 atm, the reaction in this range can be carried out at an appropriate reaction rate, it is economical.
  • the mixture of formic acid-amine adduct and non-reacted gas (16-2) is introduced into a gas-liquid separator (V1), and after separating the liquid product and unreacted gas, the unreacted gas is carbon dioxide to hydrogen (5 ) Can be recycled from the separator (V1) through the homogenizer (H1) to the hydrogenation reactor (R1).
  • the pressure of the separator is 20 to 300 atm, which can be maintained at the same pressure as that of the hydrogenation reactor.
  • the temperature of the separator is 40 to 200 ° C, which is more than the boiling point of carbon dioxide, carbon dioxide can be separated from the formic acid-amine addition compound (6), and the separated carbon dioxide gas can be recycled.
  • the formic acid-amine addition compound (6) separated from the separator (V1) is introduced into the distiller (D1).
  • the formic acid-amine adduct compound 6 introduced into the distiller is distilled, and the formic acid-amine adduct compound 7 in which formic acid is concentrated under the distiller may be formed.
  • the amine 8 may be separated from the top of the distiller, which may be recycled to the absorber AC1 in the form of an aqueous solution via an amine storage container V3.
  • the molar ratio of formic acid to amine in the formic acid-amine adduct (6) ranges from 0.1 to 2.0. Further, in the case of formic acid-amine adduct (7) in which formic acid is concentrated, formed by distillation of formic acid-amine adduct (6), the molar ratio of formic acid to amine is in the range of 1.0 to 3.0.
  • distillation may be performed at a pressure of 10 to 760 mmHg.
  • reboilers By adding reboilers to the upper and lower portions of the distiller D1, materials obtained at upper and lower portions of the distiller can be refluxed respectively, and the temperature of the reboiler is preferably not higher than 200 ° C.
  • formic acid-amine adduct compound (7) enriched in formic acid is mixed with formic acid-amine adduct compound and auxiliary amine base in a storage vessel (V2) and supplied to a reaction distiller (D2). It can be separated into adducts and amines.
  • the auxiliary amine base is separated from the bottom product of the distiller (D3) and supplied to the storage container (V2).
  • a mixture (9) of formic acid-auxiliary base addition compound and amine is formed in the reaction distiller (D2), and at the same time, the base can be separated from the formic acid-auxiliary base flaw detection section at the bottom of the column. .
  • the separated amine 11 may be recycled to the absorber AC1 via the amine storage container V3.
  • distillation may be performed at a pressure of 10 to 750 mmHg.
  • reboilers to the top and bottom of the reaction distiller (D2), it is possible to reflux the materials obtained at the top or bottom of the distiller, respectively, and it is preferable that the temperature of the reboiler does not exceed 200 ° C.
  • the formic acid-auxiliary base addition compound 10 which is the lower phase obtained under the reaction distiller D2, is introduced into another distiller D3 to separate the auxiliary base 12, whereby pure formic acid can be formed.
  • the separated auxiliary base 12 may be recycled to the storage container V2.
  • the distiller (D3) capable of obtaining pure formic acid is distilled at a pressure of 10 to 750 mmHg, and the temperature of the reboiler is preferably not higher than 200 ° C.
  • the temperature of the reboiler is preferably not higher than 200 ° C.
  • Figure 3 shows the configuration of a formic acid production apparatus according to another embodiment of the present invention.
  • the amine is added in excess to the absorber (AC1), the reactant amine and water may be phase-separated, so that a phase separator (V4) may be further included between the absorber (AC1) and the hydrogenation reactor (R1).
  • phase separator (V4) Since the phase separator (V4) is connected to the absorber (AC1), it is possible to receive the ammonium bicarbonate (3) produced in the absorber. At this time, when the amine is excessively supplied to the absorber, ammonium bicarbonate 3 may not exist as a single phase of the amine aqueous solution and water, as the concentration of free amine is high, and may exist as a phase separation between liquids. . Thus, by adding a phase separator (V4), the liquids with separated phases can be separated, and the ammonium bicarbonate (3-1) obtained at the bottom of the separator (V4) can be supplied to the hydrogenation reactor (R1), The amine 3-2 obtained at the top of (V4) can be recycled to the absorber AC1 via the amine storage container V3. Other processes can be performed in the same manner as described above.
  • FIG. 4 shows the configuration of a formic acid production apparatus according to another embodiment of the present invention.
  • high-purity purified carbon dioxide may be stored in a carbon dioxide storage container V5.
  • high-purity carbon dioxide (1 ') may be used as the reactant.
  • carbon dioxide, which is a reactant of the present reaction is not necessarily required to have high purity.
  • High-purity carbon dioxide (1 ') may be subjected to a homogenizer (H1) before being introduced into the hydrogenation reactor (R1). Therefore, in the homogenizer, the amine aqueous solution 13 and carbon dioxide 1 'can form ammonium bicarbonate 3 through the carbonation reaction according to Chemical Formula 1.
  • H1 homogenizer
  • the reaction rate can be increased, and the reaction efficiency can be increased.
  • Other processes can be performed in the same manner as described above.
  • FIG. 5 shows the configuration of a formic acid production apparatus according to another embodiment of the present invention.
  • the high-purity carbon dioxide is stored as a reactant in the carbon dioxide storage container V5, as in FIG. 4, the high-purity carbon dioxide 1 'may go through the homogenizer H1 before being introduced into the hydrogenation reactor.
  • the amine and water may be phase separated. Therefore, the phase-separated amine can be separated from the separator (V1), and the amine (5-1) obtained from the top of the separator (V1) can be recycled to the absorber (AC1) via the amine storage container (V3), Other processes can be performed in the same manner as described above.
  • Ru (OH) X -Al 2 O 3 was prepared in the same manner as in Catalyst Preparation Example 1-1, except that 2 g of Al 2 O 3 (aluminium oxide) was used instead of 2 g of TiO 2 .
  • Ir (OH) X -TiO 2 was prepared in the same manner as in Catalyst Preparation Example 1-1, except that 182.8 mg of IrCl 3 was used instead of 127 mg of RuCl 3 .
  • Ir (OH) X in the same manner as in catalyst preparation example 1-1, except that 182.8 mg of IrCl 3 was used instead of 127 mg of RuCl 3 and 2 g of Al 2 O 3 was used instead of 2 g of TiO 2. -Al 2 O 3 was prepared.
  • Table 1 below shows the catalyst activity in the formic acid production process of the catalyst synthesized according to the catalyst preparation example.
  • catalysts using a nitrogen-containing porous carbon carrier synthesized according to catalyst preparation examples 3-1 to 3-3 are not doped with nitrogen synthesized according to catalyst preparation examples 1-1 to 1-4. Compared to catalysts using a metal oxide as a carrier, it can be seen that formic acid was produced at a high concentration despite the use of a very small amount of catalyst.
  • catalysts using a nitrogen-containing porous carbon carrier synthesized according to catalyst preparation examples 3-1 to 3-3, nitrogen-doped metal oxide or metal nitride synthesized according to catalyst preparation examples 2-1 to 2-4 Even when compared with catalysts used as carriers, it can be seen that formic acid was prepared at a high concentration.
  • a CO 2 absorption tower having a height of 2 m and an inner diameter of 10 cm was filled with a packing material (Mellapak 2X, Sulzer). 10% of CO 2 -N 2 gas was supplied at 5 Nm 3 / h at the bottom of the absorption tower, and 1.9 M triethylamine aqueous solution was supplied at 2 L / h at the top of the absorption tower. The temperature of the absorption tower was maintained at 20 ° C. As a result, about 2M of triethylammonium bicarbonate aqueous solution was obtained at the bottom of the absorption column.
  • a 2 M triethylammonium bicarbonate aqueous solution and H 2 were introduced into a trickle bed reactor (TBR) filled with 8 g of a 3.2 RuCl 3 -COF supported catalyst prepared previously.
  • TBR trickle bed reactor
  • the TBR has an inner diameter of 7 mm and a length of 42 cm.
  • the flow rate of the triethylammonium bicarbonate aqueous solution of was 1153.0 g / h, and the flow rate of H 2 was 54 L / h
  • the reaction pressure was maintained at 120 atm and the reaction temperature at 120 ° C.
  • the concentrated formic acid-trimethylamine adduct and n-butyl imidazole were placed in a stirrer such that the weight ratio was 2.1: 2.1, stirred at room temperature for about 20 minutes, and then distilled using a 20-stage distillation column.
  • the distillation column used a column made of silver coated glass.
  • the feed solution which is a mixture of formic acid-trimethylamine adduct and n-butyl imidazole, was supplied in 10 stages, the flow rate of the feed solution was 220 g / h, and the reflux ratio was controlled within the range of 1.5 to 2.0.
  • the distillation column was maintained at a pressure of 55 mbar, and the temperature of the reboiler was maintained at 105 ° C. Pure triethylamine was obtained at the top of the distillation column, and formic acid- (n-butylimidazole) adduct at a molar ratio of 1: 1 was obtained at the bottom of the distillation column.
  • Formic acid was separated from the formic acid- (n-butylimidazole) adduct using a 30-stage distillation column.
  • the flow rate of the feed liquid was 200 g / h, and the reflux ratio was controlled within the range of 2.0 to 2.5.
  • the distillation column was maintained at a pressure of 50 mbar, and the temperature of the reboiler was maintained at 150 ° C. Accordingly, a formic acid- (n-butylimidazole) azeotrope having a formic acid of 13 to 15 mol% was obtained at the bottom of the distillation column, and more than 99% formic acid was obtained at the top of the distillation column.
  • the bicarbonate process was performed using a homogenizer, and a triethylammonium bicarbonate aqueous solution was obtained by supplying pure carbon dioxide and a triethylamine aqueous solution to the homogenizer.
  • the 3.2 RuCl 3 -COF supported catalyst 4g was introduced into the filled TBR to obtain a mixture of formic acid-triethylamine adduct and unreacted gas.
  • the homogenizer was a tubular reactor with an inner diameter of 7 mm and a length of 40 cm, and was filled with silica beads.
  • the TBR has an inner diameter of 7 mm and a length of 42 cm, and the reaction pressure is maintained at 120 atm and the reaction temperature at 120 ° C.
  • the hydrogenation reaction results were measured by varying the concentration of the aqueous solution of triethylamine, the ratio of carbon dioxide to triethylamine, and the ratio of hydrogen to carbon dioxide.
  • Table 2 shows the conversion rate of CO 2 and formic acid productivity obtained according to various reaction conditions in a formic acid production process by hydrogenation of carbon dioxide.
  • phase separation was not observed until the concentration of triethylamine was 3.5 mol%, but when it was 4 mol% or more, phase separation of the reactants was observed.
  • formic acid was hardly observed in the upper amine, and formic acid was observed only in the lower formic acid-triethylamine adduct.
  • the concentration of formic acid in the formic acid-triethylamine addition compound was independent of the concentration of the reactant triethylamine.
  • it can be seen that the conversion rate of CO 2 and the productivity of formic acid are reduced under conditions that cause phase separation compared to conditions where no phase separation occurs.
  • Table 3 uses the manufacturing apparatus used in Formic Acid Preparation Example 2, and the TBR 3.2 Filled with 4 g of RuCl 3 -COF catalyst, the experimental results according to the reaction temperature change in the formic acid synthesis process are shown. According to the results of Table 3, it can be seen that as the temperature of the aqueous solution increases, the conversion rate of CO 2 and the productivity of formic acid increase, respectively.
  • Table 4 shows the experimental results according to the reaction pressure change in the process of manufacturing formic acid by using the manufacturing apparatus used in Preparation Example 2, and TBR is filled with 3.2 g of a 3.2 RuCl 3 -COF catalyst. According to the results of Table 4, it can be seen that the shorter the contact time, the lower the conversion rate of CO 2 and the productivity of formic acid decreases.
  • V2, V3 Amine storage container
  • V5 CO2 storage container

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Abstract

La présente invention concerne un procédé de préparation et un dispositif de préparation d'acide formique et, plus spécifiquement, un dispositif de préparation d'acide formique et un procédé de préparation d'acide formique de manière efficace à l'aide de celui-ci, le dispositif comprenant un réacteur d'hydrogénation auquel est fixé un catalyseur, et permettant le recyclage d'un produit.
PCT/KR2019/015595 2018-11-16 2019-11-15 Procédé de préparation et dispositif de préparation d'acide formique par réaction d'hydrogénation de dioxyde de carbone WO2020101413A1 (fr)

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Cited By (2)

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WO2022101287A1 (fr) * 2020-11-10 2022-05-19 Shell Internationale Research Maatschappij B.V. Systèmes et procédés de génération d'un acide carboxylique à partir d'un flux de gaz co2
WO2022105300A1 (fr) * 2020-11-20 2022-05-27 南京延长反应技术研究院有限公司 Système de réaction à micro-interface amélioré et procédé de préparation d'acide formique par hydrogénation de dioxyde de carbone

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EP0597151A1 (fr) * 1992-11-10 1994-05-18 Universiteit Twente Procédé de préparation de l'acide formique
US20160137573A1 (en) * 2014-11-14 2016-05-19 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Methods and catalyst systems for carbon dioxide conversion
KR20160097062A (ko) * 2015-02-06 2016-08-17 국민대학교산학협력단 수소화 반응 촉매 및 그의 제조방법

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US4855496A (en) * 1984-09-29 1989-08-08 Bp Chemicals Limited Process for the preparation of formic acid
EP0597151A1 (fr) * 1992-11-10 1994-05-18 Universiteit Twente Procédé de préparation de l'acide formique
US20160137573A1 (en) * 2014-11-14 2016-05-19 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Methods and catalyst systems for carbon dioxide conversion
KR20160097062A (ko) * 2015-02-06 2016-08-17 국민대학교산학협력단 수소화 반응 촉매 및 그의 제조방법

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022101287A1 (fr) * 2020-11-10 2022-05-19 Shell Internationale Research Maatschappij B.V. Systèmes et procédés de génération d'un acide carboxylique à partir d'un flux de gaz co2
WO2022105300A1 (fr) * 2020-11-20 2022-05-27 南京延长反应技术研究院有限公司 Système de réaction à micro-interface amélioré et procédé de préparation d'acide formique par hydrogénation de dioxyde de carbone

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