WO2015076156A1 - Catalyseur de déshydrogénation de l'acide formique, procédé de déshydrogénation de l'acide formique, et procédé de production d'hydrogène - Google Patents

Catalyseur de déshydrogénation de l'acide formique, procédé de déshydrogénation de l'acide formique, et procédé de production d'hydrogène Download PDF

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WO2015076156A1
WO2015076156A1 PCT/JP2014/079860 JP2014079860W WO2015076156A1 WO 2015076156 A1 WO2015076156 A1 WO 2015076156A1 JP 2014079860 W JP2014079860 W JP 2014079860W WO 2015076156 A1 WO2015076156 A1 WO 2015076156A1
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formic acid
ion
catalyst
dehydrogenation
hydrogen
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English (en)
Japanese (ja)
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雄一郎 姫田
万輝 王
有紀 砂
雄一 眞中
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独立行政法人産業技術総合研究所
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas

Definitions

  • the present invention relates to a catalyst used for dehydrogenation of formic acid, a method for dehydrogenating formic acid using the catalyst, a method for producing atmospheric pressure and high pressure hydrogen, and hydrogen production from an aqueous solution.
  • Hydrogen (H 2 ) is produced about 500 billion Nm 3 worldwide, and is used for various purposes such as petroleum refining and ammonia production, and attracts attention as a future clean energy.
  • a fuel cell can efficiently supply power by supplying hydrogen from the outside.
  • hydrogen is a highly reactive gas, it is difficult to transport and store, and a safe and low-cost transport and storage technique is required for its stable supply.
  • poisoning by-products on the surface of the electrode catalyst due to carbon monoxide is a problem, so it is generally required to supply high-purity hydrogen whose carbon monoxide is 10 ppm or less. .
  • a method for storing hydrogen As a method for storing hydrogen, a method of storing in a cylinder or the like as a high-pressure gas is generally used. However, this method has problems such as safety during high-pressure gas transportation and hydrogen embrittlement of the container. In addition, there is a method of storing hydrogen gas in the form of liquid hydrogen at a very low temperature. However, there are problems in that a large amount of energy is consumed in the liquefaction process and liquid hydrogen is lost due to vaporization of 3 to 6% per day.
  • Patent Documents 1 and 2 In recent years, many dehydrogenation reactions of formic acid using metal complex catalysts have been reported (Patent Documents 1 and 2, Non-Patent Documents 1 to 8). These hardly generate carbon monoxide as a by-product when hydrogen is generated by dehydrogenation of formic acid. However, most of these required organic solvents and amine additives. On the other hand, in a reaction example in water without using an organic additive, low catalyst activity and durability were problems (Patent Documents 3 to 7, Non-Patent Documents 9 to 12). Apart from these reports, the catalyst for dehydrogenation of formic acid in water free from organic additives found by the present inventors shows high catalytic performance, while the durability of the catalyst in high-concentration formic acid solution and high-temperature reaction conditions is high. There was a problem with sex. (Patent Documents 12 to 14, Non-Patent Documents 13 to 22).
  • Hull, Jonathan F .; Himeda, Yuichiro Wang, Wan-Hui; Hashiguchi, Brian; Periana, Roy; Szalda, David J .; Muckerman, James T .; Fujita, Etsuko, Nature Chemistry 2012, 4, 383-388.
  • the present invention provides a catalyst that can produce atmospheric or high-pressure hydrogen by dehydrogenation of formic acid in a solution such as water with high efficiency, high energy efficiency, high selectivity, and high durability. Is an issue.
  • the present invention also provides a method for producing hydrogen by dehydrogenation of formic acid in a solution such as water that can be carried out with high efficiency, simple operation, and low cost using the catalyst, and hydrogen consumption of a fuel cell or the like. It is an object of the present invention to provide a method for producing pressurized hydrogen such as high-pressure hydrogen that does not contain carbon monoxide so that the amount of hydrogen necessary for the apparatus can be stably and continuously supplied.
  • Patent Documents 8 to 11 and Non-Patent Documents 13 to 16 and 22 describe metal complexes including those represented by the following formula (1).
  • the metal complexes include carbon dioxide and hydrogen. It is only described as a catalyst for producing formic acid and the like from it, and is not described at all as a catalyst for dehydrogenation of formic acid. This is because metal complexes including those represented by the following formula (1) are generally known to be extremely poorly soluble in acidic aqueous solutions (Non-patent Document 22).
  • a catalyst for use in a dehydrogenation reaction of formic acid containing a mononuclear complex represented by the formula (1), an isomer or a salt thereof as an active ingredient.
  • X is any ligand or absent
  • n is a positive integer, 0, or a negative integer.
  • X is a water molecule, hydrogen atom, alkoxide ion, hydroxide ion, halide ion, carbonate ion, trifluoromethanesulfonate ion, sulfate ion, nitrate ion, formate ion, or acetate ion, or
  • [4] A method for dehydrogenating formic acid by reacting with a solution containing formic acid in the presence of the catalyst according to any one of [1] to [3].
  • [5] A method for producing hydrogen by dehydrogenating formic acid by reacting with a solution containing formic acid in the presence of the catalyst according to any one of [1] to [3].
  • [6] A method for producing high-pressure hydrogen by dehydrogenating formic acid by reacting with a solution containing formic acid in a closed reaction vessel in the presence of the catalyst according to any one of [1] to [3].
  • the present invention can include the following aspects.
  • [7] The method according to any one of [4] to [6], wherein the reaction is performed at a formic acid concentration of 2 M or more.
  • the mononuclear complex of the present invention its isomer or salt is used as a catalyst, it is highly efficient, high energy efficient, at a constant speed even under high temperature reaction conditions and in high-concentration formic acid solution.
  • High-pressure hydrogen gas not containing carbon monoxide by dehydrogenation of formic acid in solution can be provided for a long time. Further, by using the dehydrogenation method of the present invention, it is possible to easily regenerate hydrogen from formic acid, which is a liquid fuel suitable for transportation and storage.
  • the mononuclear catalyst of the present invention has extremely high durability compared to the complex catalysts described in Patent Documents 12 to 14, and can maintain high catalytic performance that is stable for a long period of time in a high concentration formic acid solution under high temperature reaction conditions. Excellent catalyst performance.
  • Fig. 1 depends on the formic acid concentration of the dehydrogenation reaction of formic acid with various concentrations of formic acid aqueous solution (20 mL) using a mononuclear complex (2) sulfate (2 ⁇ mol) as a catalyst at a reaction temperature of 60 ° C.
  • 5 is a graph showing TOF (catalyst rotation efficiency (h ⁇ 1 ) and gas generation amount.
  • Figure 2 shows the time course of the amount of gas generated by the dehydrogenation reaction of formic acid at a reaction temperature of 60 ° C and an 80% aqueous formic acid solution (20 mL) using the mononuclear complex (2) sulfate (2 ⁇ mol) as a catalyst. It is the graph which showed.
  • Figure 3 shows the gas chromatographic analysis of carbon monoxide in the gas generated from the dehydrogenation reaction of formic acid at a reaction temperature of 60 ° C using the mononuclear complex (2) sulfate (2 ⁇ mol) as a catalyst. It is a graph.
  • FIG. 4 is a graph showing the time course of the amount of gas generated from a 50% (12.9 M) aqueous solution of formic acid (200 mL) using a mononuclear complex (2) sulfate (1 ⁇ mol) as a catalyst.
  • FIG. 5 shows the amount of gas generated in the dehydrogenation reaction of formic acid depending on pH in a 1M formic acid solution (20 mL) to which sulfuric acid or a base was added using sulfate (2 ⁇ mol) of mononuclear complex (2) as a catalyst. It is the graph which showed progress of time.
  • Figure 6 shows the gas evolution when 50% formic acid solution was added dropwise at 5ml / h to 8M formic acid solution (50mL) at 80 ° C using sulfate (5 ⁇ mol) of mononuclear complex (2) as a catalyst. It is the graph which showed the time passage (solid line) of quantity, and the change (dotted line) of the gas generation rate per minute.
  • FIG. 7 shows a reaction pressure of 80 ° C in a closed glass autoclave equipped with a back pressure valve, generated from an 8M formic acid aqueous solution (50mL) containing sulfate (5 ⁇ mol) of the mononuclear complex (2) and set to a pressure of 2MPa.
  • 6 is a graph showing the time course of the amount of gas passing through the back pressure valve (solid line) and the pressure in the glass autoclave (dotted line).
  • FIG 8 shows a reaction in a closed glass autoclave fitted with a back pressure valve, generated from an 8M aqueous formic acid solution (50mL) containing sulfate (5 ⁇ mol) of mononuclear complex (2) at a reaction temperature of 80 ° C, and set to a pressure of 2MPa 5 is a graph showing the time passage of the ratio of carbon dioxide and hydrogen gas that has passed through the back pressure valve.
  • Figure 9 shows various pressures generated from 6M aqueous formic acid solution (50mL) containing sulfate (5 ⁇ mol) of mononuclear complex (2) at a reaction temperature of 80 ° C in a closed glass autoclave equipped with a back pressure valve. It is the graph which showed the time passage of the gas amount which passed the made back pressure valve.
  • hydrogen and carbon dioxide are efficiently generated by the dehydrogenation reaction of formic acid represented by the following formula.
  • carbon monoxide and water may be by-produced by the decarbonylation reaction of formic acid.
  • the formic acid dehydrogenation catalyst of the present invention is highly reactive in a solution such as water under mild reaction conditions. Only the dehydrogenation reaction of formic acid proceeds with selection and high efficiency, and only hydrogen gas containing no carbon monoxide can be produced.
  • the ligand represented by X includes a water molecule, a hydrogen atom, an alkoxide ion, a hydroxide ion, a halide ion, a carbonate ion, a trifluoromethanesulfonate ion, It may or may not be a ligand of sulfate ion, nitrate ion, formate ion, or acetate ion.
  • the alkoxide ion is not particularly limited.
  • alkoxide ions derived from methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, or the like can be used.
  • X is preferably a water molecule in order to be easily dissolved in water at the start of the reaction. Further, once dissolved in water, X is not limited as shown below.
  • the ligand X becomes a water molecule (—OH 2 ) in an acidic aqueous solution and becomes —OH in an alkaline aqueous solution. Also, it easily becomes a hydrogen atom in the presence of hydrogen gas or formic acid molecules. In an alcohol solvent, it becomes an alkoxide ion and may be desorbed by light or heat.
  • this description is only an example of a possible mechanism and does not limit the present invention.
  • n is a positive integer, 0, or a negative integer.
  • the counter ion is not particularly limited, but examples of the anion include hexafluorophosphate ion (PF 6 ⁇ ) and tetrafluoroborate ion. (BF 4 -), hydroxide ions (OH -), acetate ion, carbonate ion, phosphate ion, sulfate ion, nitrate ion, halide ion (e.g.
  • hypohalous acid ion e.g. hypofluorite ion, hypochlorite ion, hypobromous acid ion, hypoiodous acid ion, etc.
  • Halogen acid ions for example, fluorite ion, chlorite ion, bromate ion, iodate ion, etc.
  • halogen acid ions for example, fluorine acid ion, chlorate ion, bromate ion, iodate ion) Etc.
  • perhalogenate ions (For example, perfluoric acid ion, perchloric acid ion, perbromate ion, periodate ion, etc.), trifluoromethanesulfonic acid ion (OSO 2 CF 3 ⁇ ), tetrakispentafluorophenylborate ion [B (C 6 F 5 ) 4 -], and the like.
  • the cation is not particularly limited, but various metal ions such as lithium ion, magnesium ion, sodium ion, potassium ion, calcium ion, barium ion, strontium ion, yttrium ion, scandium ion, lanthanoid ion, hydrogen ion, etc. Can be mentioned. These counter ions may be one type, but two or more types may coexist. However, this description is only an example of a possible mechanism and does not limit the present invention.
  • the catalyst of the present invention contains, as an active ingredient, a mononuclear complex represented by any one of the general formulas (1) to (2), a tautomer or stereoisomer thereof, or a salt thereof, It is a catalyst used for the hydrogenation method (or hydrogen production method) and the hydrogen production method.
  • the active component of the catalyst is at least one selected from the group consisting of mononuclear complexes represented by any one of the general formulas (1) to (2), tautomers, stereoisomers, and salts thereof. It consists of the compound.
  • one or a plurality of compounds of the active ingredient may be used as they are as the mononuclear catalyst of the present invention, or a mixture of these isomers may be used.
  • other components may be added as appropriate (preferably, less than 10 wt%).
  • the formic acid dehydrogenation method of the present invention is a solution comprising a mononuclear complex of the present invention, a tautomer or stereoisomer thereof, or a salt thereof as an active ingredient and formic acid. And at least one step selected from the group consisting of a step of heating the solution. That is, for example, the mononuclear catalyst of the present invention may be added to a solution containing formic acid and stirred as it is or heated as necessary. In the case of heating, the temperature is not particularly limited, but is, for example, 0 to 300 ° C, preferably 20 to 120 ° C, more preferably 60 to 100 ° C.
  • the method for collecting the generated hydrogen is not particularly limited, and a known method such as water replacement or upward replacement can be appropriately used.
  • formic acid can be dehydrogenated under pressure using a sealable reaction vessel.
  • the gas pressure in the reaction vessel is not particularly limited, but is, for example, 0 to 100 MPa, preferably 1 to 10 MPa.
  • high-pressure hydrogen gas can be supplied spontaneously without being pressurized by external energy.
  • the concentration of the mononuclear catalyst has no particular upper and lower limits, but depends on the reaction rate, the solubility of the complex in the reaction solution, and the economic efficiency. .
  • Suitable catalyst concentrations are 1x10 -9 to 1x10 -1 M, preferably 1x10 -7 to 1x10 -4 M.
  • the formic acid concentration has no particular upper and lower limits.
  • a feature of the present invention is that, even with a high concentration formic acid aqueous solution (8 M or more), formic acid can be dehydrogenated without deterioration of the catalyst. Under normal pressure conditions, it is possible to completely convert formic acid into hydrogen and carbon dioxide.
  • a suitable formic acid concentration is 0.1 to 20M, preferably 2 to 8M.
  • the substance amount ratio (number ratio) of the complex molecule and formic acid molecule is not particularly limited.
  • the formic acid molecule: complex molecule is 100. : 1 to 1: 100000000, but is not limited to this.
  • continuous hydrogen production is possible by adding additional formic acid molecules during the reaction or continuously dropping them.
  • formate may be contained, but it is generally preferred that the pH be 0 to 3, particularly preferably 0.5 to 2 during the reaction. It is particularly preferable to use an aqueous formic acid solution that does not require pH adjustment.
  • formic acid may be dehydrogenated outside this range by adding an acid or a base.
  • the cation includes lithium ion, magnesium ion, sodium ion, potassium ion, calcium ion, barium ion, strontium ion, yttrium ion, scandium ion, or lanthanoid ion.
  • examples include various metal ions or ammonium ions, tetramethylammonium, tetraethylammonium and the like. These counter ions may be one kind, but may be two or more kinds.
  • the mononuclear complex of the present invention, its tautomer or stereoisomer, or a salt thereof can be used as a formic acid dehydrogenation catalyst, for example, in a formic acid fuel cell.
  • the formic acid dehydrogenation catalyst of the present invention may be contained inside the cell, and a mechanism for dehydrogenating formic acid by the above method to generate hydrogen may be included.
  • the specific structure is not particularly limited, and for example, a known fuel cell structure or the like can be appropriately applied.
  • the use of the formic acid dehydrogenation catalyst of the present invention is not limited to the above, and can be used in, for example, any technical field that requires supply of hydrogen (H 2 ).
  • the reaction solvent used in the formic acid dehydrogenation method of the present invention is not particularly limited.
  • water or an organic solvent may be used, or only one kind may be used or two or more kinds may be used in combination.
  • the mononuclear catalyst of the present invention is soluble in water, it is preferable to use water because it is simple.
  • the organic solvent is not particularly limited, but is preferably a highly polar solvent from the viewpoint of the solubility of the complex, etc., nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile, methanol, ethanol, n-propyl alcohol, n-butyl alcohol Primary alcohols such as isopropyl alcohol, secondary alcohols such as s-butyl alcohol, tertiary alcohols such as t-butyl alcohol, polyhydric alcohols such as ethylene glycol and propylene glycol, tetrahydrofuran, dioxane, dimethoxyethane, Examples include ethers such as diethyl ether, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, and esters such as ethyl acetate.
  • the raw material formic acid may be in the form of, for example, a solution or a salt.
  • the mononuclear complex represented by the general formula (1) or (2) of the present invention is compared with the complex represented by the general formula (3) composed of a bipyridine ligand having a hydroxyl group shown in Non-Patent Document 18.
  • the reaction efficiency and durability of the formic acid dehydrogenation reaction in water are significantly improved.
  • the mononuclear catalyst represented by the general formula (3) exhibits only about 70% of the reaction rate and about 100,000 catalyst rotation speeds of the mononuclear catalyst represented by the general formula (2).
  • phenanthroline-based ligands have extremely low water solubility under acidic conditions suitable for formic acid dehydrogenation reaction compared to bipyridine-based ligands (Non-patent Document 16).
  • Example 2 Dehydrogenation reaction of formic acid A catalyst solution in which a mononuclear complex sulfate represented by the general formula (2) was dissolved in water was degassed. Aqueous formic acid solutions (20 mL or 40 mL) with various concentrations were degassed, the catalyst solution prepared above was added, and the mixture was heated and stirred. The amount of gas generated was measured with a gas meter (Shinagawa W-NK-05).
  • the TOF here is measured for 30 minutes after the start of the reaction. Calculated) and the amount of gas generated.
  • the sulfate of the mononuclear complex represented by the general formula (2) has the highest reaction rate in the 3M aqueous formic acid solution, but exhibits a high reaction rate in the concentration range of 1M to 8M. Further, formic acid can be completely decomposed even with an aqueous formic acid solution of 12.9M (50%) or 20.3M (80%). At this time, the reaction rate is low when the formic acid concentration at the initial stage of the reaction is high, but the reaction rate increases when the formic acid concentration decreases to the optimum condition.
  • the time course of gas generation with 20.3M (80%) formic acid aqueous solution is shown in FIG.
  • Example 3 The sulfate (1 ⁇ mol) of the mononuclear complex represented by the general formula (2) was dissolved in an aqueous solution (200 mL) of 50% (12.9M) formic acid and vacuum degassed. The reaction solution was heated and stirred in an oil bath at 40 to 110 ° C., and the time course of gas generation is shown in FIG. Since the catalytic reaction proceeded for 200 hours or more and the formic acid was completely decomposed after the reaction, the rotational speed of the catalyst exceeded 2.5 million. If the formic acid concentration is above a certain level, the gas generation rate corresponding to the reaction temperature is indicated. After 200 hours, the gas generation rate decreased due to a decrease in formic acid concentration in the reaction solution.
  • Example 4 (Effect of adding other acid or base) A catalyst solution in which a sulfate of a mononuclear complex represented by the general formula (2) was dissolved in water was degassed. Degas the 1M formic acid aqueous solution (pH 1.6) or 1M formic acid / sodium formate aqueous solution (pH1.7, 2.0, 3.5) (20mL) with sulfuric acid, and add the catalyst solution (2 ⁇ mol) prepared earlier. And stirred at 60 ° C. The time course of the gas generation amount depending on pH is shown in FIG. As a result, it was found that 1M aqueous formic acid solution (pH 1.7) had the fastest reaction rate (gas generation amount per unit time) and completely decomposed formic acid.
  • the formic acid / formate solution (pH 2.0, 3.5) containing formate increases in pH with the progress of the reaction, and the mononuclear catalyst (2) precipitates, so that the reaction rate decreases rapidly. Moreover, even if it was made acidic (pH 1.6) by adding sulfuric acid, the reaction rate was not improved.
  • Example 5 An 8 M aqueous formic acid solution (50 mL) containing a mononuclear complex sulfate (5 ⁇ mol) represented by the general formula (2) was degassed and stirred at 80 ° C. After 1 hour, a degassed 50% formic acid solution was added dropwise at 5 mL / h for 10 hours.
  • Example 6 An 8 M aqueous formic acid solution (50 mL) containing a mononuclear complex sulfate (5 ⁇ mol) represented by the general formula (2) was degassed, placed in a glass autoclave equipped with a back pressure valve, and stirred at 80 ° C.
  • FIG. 7 shows the time passage of the amount of gas passing through the back pressure valve set to 2 MPa and the pressure in the glass autoclave
  • FIG. 8 shows the passage of time of the ratio of hydrogen and carbon dioxide in the gas passing through the back pressure valve.
  • Example 7 A 6M aqueous formic acid solution (50 mL) containing a mononuclear complex sulfate (5 ⁇ mol) represented by the general formula (2) is degassed and placed in a glass autoclave surrounded by a safety polycarbonate container and equipped with a back pressure valve. A gas of carbon dioxide: hydrogen (1: 1) was charged to a predetermined pressure and stirred at 80 ° C. in a water bath. The amount of gas that passed through the back pressure valve set to a predetermined pressure was measured (FIG. 9). Table 2 shows a summary of TOF (h -1 ) from 1 hour to 4 hours after the start of the reaction and the residual formic acid concentration in the reaction solution after the reaction for 7 hours. As a result, it was found that TOF and residual formic acid concentration were not significantly affected by the pressure in the reaction vessel. In particular, at pressures up to 3 MPa, it was found that formic acid was converted to gas by 99.8% or more.
  • Example 2 in the dehydrogenation reaction of formic acid using the similar mononuclear catalysts represented by the general formulas (3) and (4), the TOFs were 2060 and 1360, respectively.
  • the catalyst represented by the general formula (1) or (2) composed of a ligand in which a hydroxyl group is substituted on phenanthroline is effective in improving the reaction efficiency of formic acid dehydrogenation in water. Is shown.
  • the metal complex represented by the general formula (1) or (2) has an extremely high catalytic activity even in high-temperature reaction conditions and a high-concentration formic acid aqueous solution in hydrogen production by dehydrogenation of formic acid in water. Shows durability. Therefore, if the metal complex of the present invention is used, hydrogen can be easily produced from formic acid that is easy to store and transport.
  • the selective formic acid dehydrogenation reaction can generate high-pressure hydrogen without carbon monoxide by-product, so that hydrogen can be supplied as fuel for a fuel cell without using a gas reformer. .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

La présente invention aborde le problème consistant à pourvoir à un catalyseur pouvant produire de l'hydrogène à pression normale ou à haute pression avec une efficacité, une efficacité énergétique, une sélectivité, et une durabilité élevées par déshydrogénation de l'acide formique dans une solution telle que de l'eau. Le catalyseur est caractérisé en ce qu'il comprend un complexe mononucléaire représenté par la formule (1), un isomère ou un sel associé en tant que principe actif. Dans la formule (1), X représente un ligand arbitraire tel qu'une molécule d'eau, un atome d'hydrogène, un ion alkoxyde, un ion hydroxyde, un ion halogénure, un ion carbonate, un ion trifluorométhane sulfonate, un ion sulfate, un ion nitrate, un ion formate, ou un ion acétate, ou est absent, et n est un entier positif, 0, ou un entier négatif.
PCT/JP2014/079860 2013-11-19 2014-11-11 Catalyseur de déshydrogénation de l'acide formique, procédé de déshydrogénation de l'acide formique, et procédé de production d'hydrogène WO2015076156A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN110228791A (zh) * 2019-05-29 2019-09-13 安徽青木子德慧能源发展有限公司 一种用于去除甲酸制氢反应产物中的微量甲酸和水汽的装置
JP2021016832A (ja) * 2019-07-22 2021-02-15 国立研究開発法人産業技術総合研究所 脱水素化触媒
JP7370040B2 (ja) 2019-07-22 2023-10-27 国立研究開発法人産業技術総合研究所 脱水素化触媒
JP2021091567A (ja) * 2019-12-09 2021-06-17 日東電工株式会社 水素貯蔵方法、水素ガスの製造方法及び水素ガス製造システム
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CN114957339A (zh) * 2022-03-25 2022-08-30 大连理工大学 一类新型配合物的合成方法及其催化甲酸储放氢应用
CN114957339B (zh) * 2022-03-25 2023-11-24 大连理工大学 一类新型配合物的合成方法及其催化甲酸储放氢应用

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