WO2021091182A1 - Procédé de fabrication d'acide formique et appareil de fabrication utilisant un gaz synthétique - Google Patents

Procédé de fabrication d'acide formique et appareil de fabrication utilisant un gaz synthétique Download PDF

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WO2021091182A1
WO2021091182A1 PCT/KR2020/015152 KR2020015152W WO2021091182A1 WO 2021091182 A1 WO2021091182 A1 WO 2021091182A1 KR 2020015152 W KR2020015152 W KR 2020015152W WO 2021091182 A1 WO2021091182 A1 WO 2021091182A1
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formic acid
carbon dioxide
formate
group
amine
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PCT/KR2020/015152
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Korean (ko)
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정광덕
김홍곤
박종민
김성훈
윤성호
박광호
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한국과학기술연구원
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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
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • 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
    • 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
    • B01J23/462—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
    • 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
    • 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
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0248—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid

Definitions

  • the present invention relates to a process and apparatus for producing formic acid using a mixture of hydrogen and carbon dioxide produced by a water gas conversion reaction of syngas.
  • Formic acid is a compound that can be used for many purposes.
  • it can be used as an auxiliary agent for acidification, disinfectant or textile in the manufacture of animal feed, as an auxiliary agent in the leather industry, as a reactant for deicing of aircraft or runways, and the like.
  • one of the processes for commercially preparing formic acid was to carbonylate synthesized methanol to prepare methyl formate, and then hydrate it.
  • this process in order to prepare formic acid using methanol, a total of three steps of a synthesis process of methanol, a carbonylation process of methanol, and a hydration process of methyl formate are required.
  • Noyori and Jessop et al implemented a process of producing formic acid by carrying out a hydrogenation reaction on a homogeneous catalyst under supercritical carbon dioxide conditions. Since then, a number of Ru-based and Ir-based homogeneous catalysts have been developed, and as a result, catalysts having high activity up to a level of hundreds of thousands of TON (turnover numbers) have been developed. Nevertheless, the hydrogenation reaction of carbon dioxide has not been commercialized due to the problem of development of a reaction system and process for recovering a homogeneous catalyst.
  • US 20120157711A1 uses an amine having 6 or more carbons per molecule as a catalyst to recover the catalyst through phase separation into a solvent layer in which a homogeneous catalyst is well dissolved and a solvent layer in which formic acid is mainly dissolved. , It has been disclosed that an alcohol solvent is separately added.
  • a mixture of hydrogen and carbon dioxide is prepared by a water gas reaction of synthesis gas, introduced into a formate generating reactor without a separate separation process, and additionally required carbon dioxide is collected using an amine, which is a reaction medium, and is directly carbon dioxide.
  • the present invention provides a process for converting carbon monoxide contained in the synthesis gas into carbon dioxide and hydrogen by supplying syngas to a water gas conversion unit together with a required amount of water; A step of supplying a mixed gas containing carbon dioxide and hydrogen converted by the water gas conversion unit to a formate generation unit equipped with a formic acid production catalyst to generate formate; And a step of separating formic acid by supplying the formic acid salt to a formic acid separation unit, wherein the synthesis gas is at least one selected from the group consisting of hydrocarbons having 1 to 5 carbon atoms, coal, biomass, biogas, and steel mill by-product gas. It provides a manufacturing process of formic acid that is derived from.
  • a water gas conversion unit for converting carbon monoxide contained in the synthesis gas into carbon dioxide and hydrogen by the water gas reaction of the synthesis gas
  • a formate generating unit for generating formate by reacting the mixed gas containing hydrogen and carbon dioxide with an amine-based compound in the presence of a catalyst
  • a formic acid separation unit for separating formic acid from the formic acid salt, wherein the synthesis gas is derived from at least one selected from the group consisting of hydrocarbons having 1 to 5 carbon atoms, coal, biomass, biogas, and steelworks by-product gas. It provides an apparatus for producing formic acid.
  • synthesis gas is used as a reaction raw material, it is not necessary to use purified carbon dioxide and hydrogen as a reaction raw material for the hydrogenation of carbon dioxide, and thus economical efficiency can be improved compared to a conventional manufacturing process of formic acid by hydrogenation of carbon dioxide. have.
  • the formate generation unit filled with a heterogeneous catalyst since the formate generation unit filled with a heterogeneous catalyst is used, the product does not contain a catalyst component, a separate catalyst recovery system is not required, and catalyst particles are prevented from being crushed.
  • FIG. 1 is a flowchart illustrating a manufacturing process and a manufacturing apparatus for formic acid according to the present invention.
  • Example 2 is a reference diagram for explaining the analysis result of the catalyst prepared in Example 1 of the present invention.
  • Example 3 is a flow chart showing the manufacturing process of the catalyst in Example 2 of the present invention.
  • Example 4 is a reference diagram for explaining the analysis result of the catalyst prepared in Example 4 of the present invention.
  • Example 5 is a reference diagram for explaining the analysis result of the catalyst prepared in Example 6 of the present invention.
  • FIG. 6 is a schematic diagram showing a fixed bed reactor used in the manufacturing process of formic acid according to the present invention.
  • Example 7 is a reference diagram for explaining the productivity results of formate in Example 15 of the present invention.
  • FIG. 8 is a schematic diagram showing a fluidized bed reactor used in the manufacturing process of formic acid according to the present invention.
  • Example 9 is a flowchart illustrating a manufacturing process of formic acid according to Example 17 of the present invention.
  • the present invention converts carbon monoxide contained in the synthesis gas into carbon dioxide and hydrogen by a water gas reaction of the synthesis gas and supplies it to a reactor (for example, a formate generation reactor) without a separate separation process, and is also included in the combustion flue gas.
  • the present invention relates to a process and apparatus for producing formic acid through a process of collecting carbon dioxide as an amine compound as a reaction medium and supplying it to a reactor, and then hydrogenating carbon dioxide in a reactor containing a heterogeneous catalyst, separating and purifying it. .
  • the manufacturing process of formic acid according to the present invention includes a process of converting carbon monoxide contained in synthesis gas into carbon dioxide and hydrogen (hereinafter referred to as'A-1 process'); The process of producing formate (hereinafter referred to as'A-2 process'); And a process of separating formic acid (hereinafter referred to as'A-3 process').
  • the manufacturing process of formic acid according to the present invention may further include a process of generating a carbonic acid-amine adduct compound (hereinafter referred to as'A-4 process'), if necessary.
  • the manufacturing process of formic acid according to the present invention may further include a process of gas-liquid separating a product containing formic acid salt (hereinafter referred to as'A-5 process'), if necessary.
  • the apparatus for producing formic acid according to the present invention may include a water gas conversion unit 100, a formate generation unit 200, and a formic acid separation unit 300.
  • the apparatus for producing formic acid according to the present invention may further include a carbon dioxide collecting unit 400 as necessary.
  • the apparatus for producing formic acid according to the present invention may further include a gas-liquid separation unit 500.
  • the A-1 process is a process of generating carbon dioxide and hydrogen from carbon monoxide and water contained in the synthesis gas as a reaction raw material, and supplying the synthesis gas to the water gas conversion unit 100 to convert carbon monoxide contained in the synthesis gas into hydrogen and carbon dioxide. It can be converted into a process of generating carbon dioxide and hydrogen.
  • the A-1 process may include a water gas reaction as shown in Reaction Formula 1 below.
  • the water gas reaction thermodynamically may proceed to a completion reaction as the temperature decreases, and the conversion rate of carbon monoxide may decrease as the temperature increases.
  • This water gas reaction may be carried out in one step, but it may be carried out in two steps to increase the reaction efficiency.
  • the water gas reaction may be carried out through a high-temperature water gas reaction in which the reaction is performed at a high temperature of 300 degrees or higher and a low-temperature water gas reaction in which the reaction is performed at a temperature of 300 degrees or less.
  • the high-temperature water gas reaction may be performed under conditions of a molar ratio of water to CO of 10:1 to 1:1, a reaction temperature of 300 to 500 degrees, and a reaction pressure of 1 to 50 atmospheres.
  • a mixed oxide-based catalyst such as Fe, Cr, and Zn may be used for the high-temperature water gas reaction.
  • the low-temperature water gas reaction may be performed under conditions of a molar ratio of water to CO of 10:1 to 1:1, a reaction temperature of 100 to 300 degrees and a reaction pressure of 1 to 50 atmospheres.
  • a catalyst such as Cu, ZnO, Al 2 O 3 may be used for the low-temperature water gas reaction.
  • Zr and/or Ga oxide may be added to the catalyst.
  • Syngas which is the stream (1) supplied to the water gas conversion unit 100 in the A-1 process, is at least one selected from the group consisting of hydrocarbons having 1 to 5 carbon atoms, coal, biomass, biogas, and steel mill by-product gas. It may be derived from.
  • the synthesis gas may include a reactant obtained by reforming a hydrocarbon having 1 to 5 carbon atoms such as methane, ethane, propane, butane or pentane.
  • the synthesis gas may include a reactant obtained by reforming or gasifying coal or biomass.
  • the synthesis gas may include a reactant obtained by reforming biogas or by-product gas from a steel mill. The reforming reaction and gasification reaction may be performed by a conventionally known method.
  • the mixed gas generated through the A-1 process may be supplied to the A-2 process as a stream 2 containing carbon dioxide and hydrogen.
  • the mixed gas obtained through the A-1 process is directly supplied to the formate generation unit 200 to be described later without a separate separation process, the hydrogen production process and carbon dioxide that were performed to produce hydrogen and carbon dioxide, which are raw materials for producing formic acid.
  • the collection and purification process of is omitted, so that the efficiency (economy) of the manufacturing process of formic acid can be improved compared to the conventional one.
  • the A-4 process is a process of generating a carbonic acid-amine addition compound, and may include a process of generating a carbonic acid-amine addition compound by supplying combustion exhaust gas and an amine-based compound to the carbon dioxide collecting unit 400.
  • This A-4 process may be selectively performed as needed. That is, in the A-4 process, the molar ratio (b/a) of carbon dioxide (a) and hydrogen (b) contained in the mixed gas supplied to the formate generation unit 200 is lower than 2.0, so that carbon dioxide is generated in the formate generation reaction. It is performed when insufficient, and may include a reaction of absorption of carbon dioxide by an amine-based compound as shown in Scheme 2 below. At this time, carbon dioxide may be physically absorbed by some solvents.
  • the combustion exhaust gas (stream 8) and the amine compound are supplied to the carbon dioxide collecting unit 400, and the carbon dioxide contained in the combustion exhaust gas is absorbed by the amine compound, which is a reaction medium, and NR 1 R 2 Carbonic acid-amine adducts such as R 3 H + :HCO 3 -and the like may be produced.
  • the carbonate-amine adduct is specifically ammonium bicarbonate ((HNR 1 R 2 R 3 ) + (HCO 3 ) - ), or ammonium carbonate (HNR 1 R 2 R 3 ) 2 2+ (CO 3 ) 2- ) It may contain an ammonium salt such as.
  • the carbonate-amine addition compound may take the form of an aqueous solution.
  • trialkylamine when used as the amine compound, the solubility in water is low, so that the trialkylamine and water may undergo phase separation between liquids in the hydrogenation reaction of carbon dioxide. When the phase separation occurs in this way, the reaction efficiency in the hydrogenation process of carbon dioxide may be lowered.
  • the carbonic-amine adduct is an ammonium salt such as ammonium bicarbonate, (HNR 1 R 2 R 3 ) + (HCO 3 ) - ) as the main component, the solubility in water is high, so that water in the hydrogenation reaction of carbon dioxide Over-phase separation can be minimized, and thus, the present invention can increase the reaction efficiency in the hydrogenation process of carbon dioxide.
  • the molar ratio (c/b) of HCO 3 - to NR 1 R 2 R 3 H + in the carbonate-amine adduct may be 0.1 to 1.0.
  • the amine-based compound reacting with the combustion exhaust gas may be a compound represented by the following formula (1).
  • R 1 to R 3 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms or bonded to each other (e.g., R 1 and R 2 Bond, a bond of R 2 and R 3 , or a bond of R 2 and R 3 ) to form an aliphatic ring or an aromatic ring, and the alkyl group and cycloalkyl group of R 1 to R 3 are each independently an alkyl group having 1 to 10 carbon atoms And it may be unsubstituted or substituted with one or more substituents selected from the group consisting of an aryl group having 6 to 10 carbon atoms.
  • R 1 to R 3 may be 12 or less, and specifically, R 1 , R 2 and R 3 may each independently be an alkyl group having 2 or 3 carbon atoms.
  • the alkyl group may be linear or branched, and specifically, may be a methyl group, an ethyl group, a propyl group, a butyl group, or the like.
  • the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and the like.
  • the aromatic ring may be an aromatic ring containing or not including a hetero atom such as N, O, or S.
  • the aryl group may be a phenyl group, a naphthyl group, or the like.
  • the amine-based compound represented by Formula 1 is trimethylamine, triethylamine, tripentylamine, tripropylamine, tributylamine, trihexylamine ( trihexylamine), N,N-dimethylbutylamine, dimethylcyclohexylamine, dimethylphenethylamine, and isoamylamine have.
  • the amine-based compound reacting with the combustion exhaust gas may be a dialkyl piperazine (N,N-dialkyl piperazine) such as dimethyl piperazine (N,N-dimethyl piperazine) and diethyl piperazine (N,N-diethyl piperazine); Morpholine; N-alkyl morpholine such as N-methyl morpholine, N-ethyl morpholine, N-propyl morpholine, N-butyl morpholine, etc.
  • dialkyl piperazine such as dimethyl piperazine (N,N-dimethyl piperazine) and diethyl piperazine (N,N-diethyl piperazine); Morpholine; N-alkyl morpholine such as N-methyl morpholine, N-ethyl morpholine, N-propyl morpholine, N-butyl morpholine, etc.
  • Alkylpiperidine such as methylpiperidine, ethylpiperidine, propylpiperidine, and butylpipeirdine
  • alkylpyrrolidines such as methylpyrrolidine, ethylpyrrolidine, propylpyrrolidine, butylpyrrolidine, etc. I can.
  • the amine-based compound may be dialkylpiperazine, alkylpiperidine, alkylpyrrolidine, or alkylmorpholine, which does not require a separate phase separation process due to its high solubility in water.
  • the absorption reaction of carbon dioxide may be carried out at a reaction temperature of 10 to 100 degrees (specifically, 20 to 80 degrees) and a reaction pressure of 1 to 50 atm (specifically, 1 to 20 atm).
  • the product including the carbonic acid-amine adduct produced through the A-4 process may be discharged from the carbon dioxide collecting unit 400 as a stream 7 and supplied to the formate generating unit 200.
  • the stream 7 may contain a carbonic acid-amine adduct, an amine-based compound, and carbon dioxide.
  • stream (7) may contain free amines or mixtures of free carbonic acids with carbonic-amine adducts.
  • the carbon dioxide collecting unit 400 may include a carbon dioxide absorption tower in which a carbon dioxide absorption reaction occurs from combustion exhaust gas.
  • the A-2 process is a process of generating formate, which is a formic acid precursor, and a mixed gas containing carbon dioxide and hydrogen generated by the water gas conversion unit 100 is transferred to the formate generating unit 200 provided with a catalyst. It can be made in the process of producing formate by supplying. Specifically, in the A-2 process, formate (amine-formic acid adduct) is generated through the reaction of carbon dioxide, an amine compound, and hydrogen, and may include a hydrogenation reaction of carbon dioxide as shown in Scheme 3 below.
  • water H 2 O
  • auxiliary amines e.g., n-methylpyrrolidone and n-butylimidazole
  • water may be supplied as auxiliary solvents, or a mixture of auxiliary amines and water may be supplied as auxiliary solvents.
  • the auxiliary amine is an aproctic amine, N-methylpyrrolidone, N-formyl morpholine, N-methylacetamide , N,N-dimethylacetamide, NN-diethylacetamide, N-ethylacetamide, N-butylimidazole , N-methylimidazole and N-ethylimidazole may be one or more selected from the group consisting of (N-ethylimidazole).
  • carbon dioxide (CO 2 ) may be dissolved in a solution.
  • carbon dioxide (CO 2 ) is carbon dioxide (CO 2) converted in the water gas conversion unit 100, or a separate carbon dioxide (CO 2 ) with the mixed gas supplied to the formate generation unit 200 (stream (2))) 2 ) may have been additionally supplied.
  • the separate carbon dioxide (CO 2 ) may be supplied from the carbon dioxide collecting unit 400 or through a carbon dioxide supply line (not shown) separately provided in the formate generating unit 200.
  • acid-amine addition compound (d NR 1 R 2 R 3 H +: xHCO 3 -) is herein to mean that the supply in the above-described carbon dioxide absorption portion 400, a carbon dioxide-amine instead of the amine addition compound based
  • the compound may directly participate in the reaction.
  • the amine-based compound may be supplied from the carbon dioxide collecting unit 400 or may be supplied to the formate generating unit 200 through a separate supply line.
  • the amine-based compound is the same component as the amine-based compound described in step A-4, a description thereof will be omitted.
  • This amine-based compound may be separated and discharged from the formic acid separation unit 300 as a stream 6 after the formate generation reaction, and may be supplied (circulated) to the carbon dioxide collection unit 400.
  • the molar ratio (e/d) of HCO 2 - to NR 1 R 2 R 3 H + in the formate (amine-formic acid adducted compound) generated through Scheme 3 may be 0.1 to 2.5.
  • the production reaction of formic acid by hydrogenation of carbon dioxide is a nonspontaneous reaction, and ⁇ G (Gibs-free energy change) may have a positive value.
  • ⁇ G Gabs-free energy change
  • ⁇ G Gabs-free energy change
  • NR 1 R 2 R 3 in Chemical Formula 1 an amine-based compound
  • ⁇ G (Gibs-free energy change) of the hydrogenation reaction of carbon dioxide may have a negative value, and thus conventional carbon dioxide It can overcome the thermodynamic limitation of hydrogenation reaction.
  • the molar ratio of hydrogen to carbon dioxide contained in the feed (stream (2) + (7) + (4) in Fig. 1) introduced into the formate generation unit 200 as an unreacted circulating gas may be 0.1 to 10.0.
  • the molar ratio of hydrogen to carbon dioxide may be 0.5 to 3.0, more specifically 0.5 to 1.5. More specifically, the molar ratio of hydrogen to carbon dioxide may be 0.8 to 1.2.
  • the molar ratio of hydrogen to carbon dioxide is less than 0.1, the conversion rate of carbon dioxide is very low, so that the yield of formic acid to carbon dioxide can be reduced. Is increased, the size of the reactor increases, the conversion production rate of carbon dioxide decreases, and the catalyst is reduced and can be easily deactivated.
  • the molar ratio of hydrogen to carbon dioxide is 1.0 ⁇ 0.2, the amount of unreacted circulating gas is minimized, so that an optimum reaction condition can be obtained.
  • the carbon dioxide supplied to the formate generating unit 200 may be simply absorbed in a solution, dissolved in water, or combined with an amine-based compound. Therefore, the molar ratio of hydrogen to carbon dioxide can be determined by Equation 1 below.
  • the hydrogenation reaction of carbon dioxide may be carried out at a reaction temperature of 30 to 200 degrees (specifically, 40 to 150 degrees) and a reaction pressure of 20 to 200 atm (specifically, 30 to 150 atm).
  • a reaction temperature of 30 to 200 degrees (specifically, 40 to 150 degrees)
  • a reaction pressure of 20 to 200 atm (specifically, 30 to 150 atm).
  • the reaction temperature is less than 30 degrees
  • the catalytic activity may be lowered, and when the reaction temperature exceeds 200 degrees, the catalyst may be reduced and deactivated.
  • the reaction pressure is less than 20 atmospheres
  • the catalytic activity may be lowered, and when the reaction pressure exceeds 200 atmospheres, a lot of energy is consumed for the reaction, and the process efficiency may decrease.
  • the catalyst provided in the formate generating unit 200 may be supported on a porous carrier including at least one of nitrogen and phosphorus as an active metal.
  • the active metal may include at least one selected from the group consisting of iridium (Ir), ruthenium (Ru), palladium (Pd), gold (Au), iron (Fe), and cobalt (Co).
  • Such an active metal may be derived from a compound containing an active metal.
  • the compound containing the active metal may be in a form in which an active metal and a salt thereof are combined.
  • the salt of the active metal may be a chlorine salt, acetate, acetylacetonate, nitrate, hydroxide, sulfate, or sulfide. .
  • the compound containing the active metal may be an oxide, an oxide in which they are hydrated, an oxide in which they are mixed, a reduced metal, or a metal in which they are mixed.
  • porous carrier containing at least one of nitrogen and phosphorus is porous organic frameworks (POFs), covalent organic frameworks (COFs), and covalent triazine frameworks (CTFs).
  • Porous aromatic frameworks (porous aromatic frameworks, PAFs) and porous organic polymers (porous organic polymer, POP) may include one or more selected from the group consisting of.
  • Such a porous carrier may include a triazine structure or a heptazine structure.
  • the porous carrier containing at least one of nitrogen and phosphorus may be a pyridine bonded nitrogen (pyridinic-N), a pyrrole bonded nitrogen (pyrrolic-N), a pyrazole bonded nitrogen (pyrazole-N) and a graphite bonded nitrogen. It may include one or more selected from the group consisting of (graphitic-N).
  • the porous carrier containing at least one of nitrogen and phosphorus includes at least one selected from the group consisting of titania, alumina, gallia, zirconia, and silica. can do.
  • the catalyst provided in the formate generation unit 200 may exhibit high catalytic activity due to nitrogen and/or phosphorus contained in the lattice of the porous carrier, and may exhibit improved catalytic stability.
  • the product including formate generated through the A-2 process may be discharged from the formate generating unit 200 as a stream 3 and supplied to the formic acid separating unit 300.
  • the stream 3 may contain formate (amine-formic acid adduct), carbon dioxide, hydrogen, and water.
  • the stream 3 may contain a mixture of free amine or free formic acid together with formate.
  • the formate generating unit 200 may include a formate generating reactor for generating formate.
  • the formate generating reactor may include at least one selected from the group consisting of a stirred reactor, a fixed bed reactor, and a fluidized bed reactor.
  • the A-5 process is a process of gas-liquid separating a product containing formate, and may be performed by supplying a product containing formate to the gas-liquid separation unit 500 to separate carbon dioxide and hydrogen. This A-5 process may be selectively performed as needed.
  • the product containing formate may be separated into gas and liquid (or liquid + solid) components.
  • the gaseous components separated from the formate-containing product may include carbon dioxide (unreacted carbon dioxide) and hydrogen, which may be supplied back to the formate generating unit 200 as a stream 4.
  • the liquid or liquid + solid component separated from the formate-containing product may include formate (formic acid-amine adduct), which may be supplied to the formic acid separation unit 300 as a stream 5.
  • gas-liquid separation may be performed at a temperature of 25 to 150 degrees (specifically, 40 to 100 degrees).
  • the pressure may be the same as the reaction pressure of the carbon dioxide hydrogenation reaction.
  • the gas-liquid separator 200 may include a gas-liquid separator.
  • the A-3 process is a process of separating formic acid from formic acid salt, and may include distillation and purification by supplying the formic acid salt to the formic acid separation unit 300.
  • the stream 5 supplied to the formic acid separation unit 300 may contain water, amine-based compounds, etc., along with formate, and the separated water and amine-based compounds among them are a carbon dioxide collection unit as a stream 6 Can be supplied to 400.
  • the formic acid separated in the stream 5 may be separated from formic acid through distillation and purification processes, and the separated formic acid may be obtained as the stream 10.
  • the formic acid separation unit 300 may include an evaporator, a distiller, a purifier, and the like.
  • the present invention produces formic acid by obtaining carbon dioxide and hydrogen, which are raw materials for producing formic acid through syngas, economical efficiency can be improved compared to the conventional formic acid production process using purified carbon dioxide and hydrogen.
  • the heterogeneous catalyst is used, the amine compound used in the reaction can be easily recovered, and the recovered amine compound is recycled back to the formic acid production process to capture carbon dioxide. It is possible to obtain a carbon dioxide reduction effect while increasing the efficiency of the manufacturing process.
  • RuCl 3 0.777 g was dissolved in 300 ml of methanol, and 9.23 g of the synthesized bpyTN-30-CTF carrier was dispersed in a methanol solution in which RuCl 3 was dissolved. Then, the mixture was boiled while refluxing for about 48 hours, washed with methanol at room temperature, and dried to prepare a Ru-bpyTN-30-CTF catalyst.
  • FIG. 2A shows the EDX mapping result
  • FIG. 2B shows the HAADF-STEM image result. It was confirmed that Ru was well dispersed in the carrier.
  • Fig. 2C shows that Ru is mainly present as Ru(III) as a result of XPS
  • Fig. 2D shows that Ru is well bound to the triazine structure as a result of XAFS spectra.
  • the synthesized POP carrier was dispersed in 160 ml of methanol, and RuCl 3 was dissolved in 40 ml of methanol, put into a solution in which the POP carrier was dispersed, and boiled under reflux for 24 hours while stirring, followed by drying, and an argon atmosphere at 160 degrees.
  • a catalyst was prepared through a process of heat treatment under (see FIG. 3 for a specific manufacturing process). At this time, three types of catalysts (Ru-POP1, Ru-POP2, and Ru-POP3) as shown in Table 1 below were prepared by controlling the amount of Ru supported.
  • an Ir-POP3 catalyst was prepared through the same procedure as above, except that IrCl 3 was used instead of RuCl 3.
  • the POP carrier had a triazine structure while having porosity with a specific surface area of 810 m 2 /g.
  • the specific surface area and average pore volume decrease, and through this, it was confirmed that Ru was well supported.
  • Example 2 The same as in Example 1, except that 2wt% of RuCl 3, 2wt% AuCl 3, 2wt% PdCl 2, 2wt% FeCl 3 and 2wt% CoCl 3 were supported by using an NGN carrier instead of the bpyTN-30-CTF carrier.
  • Ru-NGN, Au-NGN, Pd-NGN, Fe-NGN, and Co-NGN catalysts were prepared, respectively.
  • Adenine and magnesium hydrochloride (MgCl 2 ⁇ 6H 2 O) were added to mortar at a weight ratio of 1:10 and mixed to obtain a mixture.
  • the obtained mixture was put in a ceramic boat and fired for 1 hour in a nitrogen atmosphere to obtain a fired product.
  • the resulting fired product was treated with a 2 M HCl solution to remove residual magnesium components, washed with water, and dried to obtain a carrier containing pyrrole-bonded nitrogen and pyridine-bonded nitrogen.
  • two types of carriers (C800A and C1000A) were synthesized, respectively, by adjusting the firing temperature to 800 degrees and 1000 degrees. Referring to FIG. 4, it was confirmed that nitrogen was contained in carbon grids such as pyrollic-N and piridinic-N in each of the prepared carriers.
  • 4 is an analysis result of a carrier by X-ray photoelectron spectroscopy (XPS).
  • Adenine and metal salts AuCl 3 , PdCl 2 , FeCl 3 and CoCl 3 were each added to mortar at a weight ratio of 1:10 and mixed to obtain a mixture.
  • Each of the obtained mixtures was placed in a ceramic boat and fired at 800 degrees for 1 hour under a nitrogen atmosphere to obtain fired products.
  • Each obtained fired product was treated with 0.1M HCl solution to remove residual metal components, washed with water, dried, and Pd-C800A, Au-800A, Fe in which each metal was supported on a carrier containing nitrogen of pyrrole bonds and nitrogen of pyridine bonds.
  • -800A and Co-800A catalysts were prepared respectively.
  • Ti(OH) 4 1 g and melamine were mixed, ground with a mortar, and then calcined at 550 degrees for 8 hours to obtain a nitrogen-doped titanium dioxide carrier. At this time, the amount of melamine was adjusted to 1g, 2g, 3g, and 4g to synthesize four types of titanium dioxide carriers.
  • Figure 5 is an XPS analysis of four types of titanium dioxide carriers,
  • Figure 5 in Figure 5 (a) is a survey spectrum
  • (b) is a narrow spectrum of the N1s peak of the carrier to which melamine 2g is applied
  • (c) is melamine 3g
  • the narrow spectrum of the N1s peak of the carrier to which this was applied it was found that nitrogen in the form of Ti-N-0 in the lattice was present in each titanium dioxide carrier prepared. It could be confirmed by X-ray photoelectron spectroscopy.
  • Each synthesized titanium dioxide carrier and 2 wt% of RuCl 3 were added to distilled water, stirred at 100° C. for 24 hours, distilled water was removed, and vacuum dried at 100° C. for 24 hours to prepare 4 types of catalysts, respectively.
  • the activities of the catalysts prepared in Examples 1 to 5 were evaluated under the conditions of Table 2 below using a 150 ml stainless steel high-pressure stirred reactor. Specifically, after Et3N (Triethylamine) was introduced into a stirred reactor, the catalysts prepared in Examples 1 to 5 were put into a stirred reactor and purged with carbon dioxide to remove air. After making the pressure of carbon dioxide to be 40 atm, hydrogen was supplied to maintain the pressure at 80 atm, and the reaction temperature was raised to 120 degrees to proceed with the reaction at 120 atm. Subsequently, a product obtained through the reaction was obtained, and the amount (concentration) of formate in the product was analyzed by liquid chromatography (HP LC, high performance chromatography), and the results are shown in Table 2 below. At this time, the amount of the solvent used in the reaction was 40 ml. In addition, TOF h -1 means the molar ratio of formic acid converted for 1 hour to the total moles of active metal.
  • Ir-bpyTN-30-CTF catalyst was prepared through the same procedure as in Example 1, except that IrCl 3 was used instead of RuCl 3.
  • Ir1-POP catalyst was prepared in the same manner as in Example 2, except that IrCl 3 was used instead of RuCl 3.
  • Ir-NGN catalyst was prepared through the same procedure as in Example 3, except that IrCl 3 was used instead of RuCl 3.
  • Ir-C800A catalyst was prepared through the same procedure as in Example 4, except that IrCl 3 was used instead of RuCl 3.
  • a Ru-bpyTN-30-CTF catalyst was prepared in the same manner as in Example 1, except that a combination of Ru and acetate was used instead of RuCl 3.
  • a Ru-bpyTN-30-CTF catalyst was prepared in the same manner as in Example 1, except that a combination of Ru and acetylacetonate was used instead of RuCl 3.
  • Example 6 The activity of the catalyst prepared in Example 6 was evaluated according to the reaction process of Experimental Example 1 and the conditions in Table 5 below, and the results are shown in Table 5 below. At this time, evaluation was carried out by adding a catalyst prepared using a titanium dioxide carrier (no nitrogen doped) synthesized with a melamine amount of 0 g.
  • the catalyst prepared using the titanium dioxide carrier doped with nitrogen has higher activity compared to the titanium dioxide carrier not doped with nitrogen.
  • RuO (OH) x -N-TiO 2 catalyst was prepared in the same manner as in Example 6, except that ruthenium oxide was used instead of RuCl 3. At this time, a process of dispersing 2 g of a titanium dioxide carrier supported with Ru in 60 ml of an aqueous solution, slowly adding 1 M NaOH aqueous solution, stirring for 24 hours while adjusting the pH of the solution to 13.2, filtering, washing with water, and drying. I went through additionally.
  • a RuO(OH) x -N-TiO 2 catalyst was prepared in the same manner as in Example 6, except that iridium oxide (hydrous ruthenium) was used instead of RuCl 3.
  • iridium oxide hydrogenous ruthenium
  • the reaction was carried out under the following conditions. At this time, the unreacted gas was not recycled. Specifically, 1.5 g of the Ru-bpyTN-30-CTF catalyst prepared in Example 1 was fixed in the middle of a fixed bed reactor (diameter: 1/2 inch, length: 60 cm) to form a catalyst layer. Beads were filled. A preheater was placed at the tip of the reactor. The temperature of the preheater was maintained to be the same as the reaction temperature. Water and Et3N were quantified by a separate liquid transfer pump and introduced into the reactor, and hydrogen was introduced into the reactor by raising the pressure to the reaction pressure with a compressor.
  • Carbon dioxide maintained in liquid form in a vessel maintained at 60 atmospheres was introduced into the reactor by a liquid transfer pump, and carbon dioxide was vaporized before the reaction.
  • the reaction temperature was maintained by a temperature controller, and a pressure controller was placed at the rear end of the vessel for collecting the reaction product to maintain the reaction pressure.
  • reaction proceeded under these conditions, but the reaction was proceeded by adjusting the reaction pressure, reaction temperature, the molar ratio of H 2 /CO 2 of the feed solution, the molar ratio of Et3N/CO 2 and the concentration of Et3N, and the productivity of formate was evaluated after the reaction was completed. It is shown in FIG. 7.
  • (A) of FIG. 7 shows the productivity of formate according to the reaction temperature under the reaction conditions in which the molar ratio of H 2 /CO 2 in the feed solution is 1.0, the molar ratio of Et3N/CO 2 is 1.0, and the concentration of Et3N is 3M at a reaction pressure of 100 atm.
  • the productivity of formate increased as the reaction temperature increased.
  • the productivity of formate was 355.1 gHCOOH/gcat/d, and the conversion rate of carbon dioxide was confirmed to be 71.3% under this reaction condition.
  • (B) of FIG. 7 shows the productivity of formate according to the reaction pressure under the reaction conditions in which the molar ratio of H 2 /CO 2 in the feed solution is 1.0, the molar ratio of Et3N/CO 2 is 1.0, and the concentration of Et3N is 3M at a reaction temperature of 120 degrees. As shown, it was confirmed that the productivity of formate increased as the reaction pressure increased.
  • (C) of FIG. 7 shows formic acid according to the change in concentration of Et3N under a reaction condition in which the molar ratio of H 2 /CO 2 in the feed solution is 1.0 and the molar ratio of Et3N/CO 2 is 1.0 at a reaction pressure of 120 atm and a reaction temperature of 120 degrees.
  • the productivity of the salt it was confirmed that the productivity of formate was the highest at 340 gHCOOH/gcat/d under the reaction condition of the Et3N molar ratio of 3.0.
  • (D) of FIG. 7 shows that the molar ratio of Et3M/CO 2 is changed under the reaction conditions in which the H 2 /CO 2 molar ratio of the feed solution is 1.0 and the concentration of Et3N is 3M at a reaction temperature of 120 degrees and a reaction pressure of 120 atm.
  • the higher the molar ratio of Et3N / CO 2 increase with decreasing the contact time of CO 2 it was confirmed that the formate salt increase productivity. Further more the molar ratio of Et3N / CO 2 increases with increasing the contact time of CO 2 was confirmed that the CO 2 conversion decreases.
  • the reaction was carried out under the following conditions. Specifically, 3 g of the Ru-bpyTN-30-CTF catalyst prepared in Example 1 was dispersed in a fluidized bed reactor (diameter: 3/8 inch, length: 1 m).
  • the tube for separating the catalyst at the top has a diameter of 1 inch and a length of 30 cm.
  • the tube was made to be able to control the temperature by using a tubular band heater.
  • the reactor was filled with Et3N with a gas sparger to prevent liquid from entering the lower end of the reactor.
  • the reaction was carried out while supplying 761.6 ml/min of carbon dioxide, 761.6 ml/min of hydrogen, 3.0 ml/min of water, and 2.34 ml/min of Et3N at a reaction temperature of 120 degrees and a reaction pressure of 120 atm.
  • Formic acid was prepared using methane (synthetic gas) through a process chart as shown in FIG. 9.
  • methane (3,196.8 kg/h) and steam (12,603 kg/h) were supplied to the methane reforming reactor (R2) maintained at 850 degrees and 20 atmospheres to react. After the reaction, heat was recovered through a heat exchanger, and then methane (184.0 kg/h), carbon monoxide (3398.3 kg/h), carbon dioxide (2979.3 kg/h), and hydrogen (1267.3 kg) were passed through conditions of 450 degrees and 20 atmospheres. /h) and steam (7980 kg/h). The amount of heat recovered here was 4.9 M*kcal/h.
  • the reformer product was subjected to a water gas reaction through a high temperature water gas reactor (R3) at 450°C and a low temperature water gas reactor (R4) at 210°C, through this reaction, methane (184.0 kg/h) and carbon monoxide (71.5 kg/h) h), carbon dioxide (8208 kg/h), hydrogen (1504.6 kg/h) and steam (5840 kg/h).
  • This water gas composition (stream (3)) was pressurized from 20 atm to 120 atm by a compressor to remove water, and then supplied to a formate generating reactor (R1).
  • the product (stream (7)) in which CO 2 supplied from the carbon dioxide absorption tower (A) is absorbed is composed of CO 2 (25080 kg/h), Et3N (95725 kg/h), and water (183412 kg/h). It was supplied to the formate generating reactor (R1). In addition, unreacted methane (7868 kg/h), carbon monoxide (2876 kg/h), carbon dioxide (47654 kg/h), hydrogen (2421 kg/h) and water in the gas stream (2745 kg/h) are formate. It was cycled through the production reactor (R1). As a result, stream (3), stream (7) and stream (4) were supplied to the formate generating reactor (R1).
  • the formate generating reactor (R1) was filled with 400 kg of the catalyst Ru-bpyTN-30-CTF prepared in Example 1, and the CO 2 conversion rate was about 40%. Methane (8557 kg/h), carbon monoxide (3132 kg/h), carbon dioxide (50401 kg/h), hydrogen (2555 kg/h), water (183614 kg/h) to the bottom of the formate generating reactor (R1) , Et3N (95725 kg/h) and formic acid (35331 kg/h) were discharged.
  • Et3N (95725 kg/h) and formic acid (35331 kg/h) were discharged.
  • the amount of formic acid was calculated through the amount of the additive compound in which formate and Et3N were combined. Specifically, additional compounds Et3NH +: HCOO - (1: 0.81) , and the one in parentheses: 0.81 is added at HCOO compound indicates the molar ratio of Et3NH + for.
  • the reactant (Stream (5)) was gas-liquid separation in vessel GL and was maintained to have a temperature of about 80 degrees. Of the separated gas component is refluxed in formic acid generation reactor (R1) Et3NH +: HCOO - : it was supplied to the addition compound 131056 kg / h water, and 186333 kg / h is evaporated tower (Ev) of (1 0.81). The evaporation tower (Ev) was 1.2 m in height and was filled with a lash ring, and the pressure was maintained at 150 mmHg.
  • formic acid generation reactor (R1) Et3NH +: HCOO - it was supplied to the addition compound 131056 kg / h water, and 186333 kg / h is evaporated tower (Ev) of (1 0.81).
  • the evaporation tower (Ev) was 1.2 m in height and was filled with a lash ring, and the pressure was maintained at 150 mmHg.
  • Et3N and water discharged from the top of the evaporation tower (Ev) are phase-separated, and these are mixed in the vessel (V4) together with 33791 kg/h of Et3N discharged from the top of the distillation column (D1) and phase-separated. It was supplied to the feed tank (T2).
  • the distillation column (D1) was 2.5 m in height and was filled with structured packing. Thereafter, Et3N and water (Stream (6)) were supplied to the carbon dioxide absorption tower (A), and the carbon dioxide contained in the combustion exhaust gas was absorbed by the carbon dioxide absorption tower (A) as a product in which CO 2 was absorbed (stream (7)). , Was recycled to the formate generating reactor (R1).
  • 1:0.81 in parentheses represents the molar ratio of nBIMH + to HCOO- in the adduct compound
  • nBIM represents n-butylimidazole.

Abstract

La présente invention concerne un procédé et un appareil de fabrication d'acide formique à partir d'un gaz synthétique et, plus particulièrement, un procédé et un appareil de fabrication d'acide formique, comprenant : l'utilisation d'un gaz mixte (mélange) d'hydrogène préparé par une réaction de conversion eau-gaz d'un gaz de synthèse et de dioxyde de carbone, et un composé à base d'amine en tant que milieu de réaction ; et l'introduction d'un produit d'addition d'amine ayant capturé du dioxyde de carbone à partir d'un gaz d'échappement évacué par une combustion dans un réacteur pour fabriquer de l'acide formique.
PCT/KR2020/015152 2019-11-04 2020-11-02 Procédé de fabrication d'acide formique et appareil de fabrication utilisant un gaz synthétique WO2021091182A1 (fr)

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