KR20210061123A - Heterogeneous Catalyst Complex for Carbon dioxide Conversion - Google Patents

Abstract

The present invention relates to a catalyst complex for carbon dioxide conversion, wherein the carbon dioxide conversion is a reaction between carbon dioxide and hydrocarbons containing one or more hydroxyl groups, and the catalyst complex includes at least one type of noble metal as an active metal in the catalyst complex, contains at least one selected from nickel (Ni), iron (Fe) and cobalt (Co), and includes a support.

Description

Heterogeneous Catalyst Complex for Carbon dioxide Conversion}

The present invention relates to a catalyst complex for a carbon dioxide conversion reaction that converts carbon dioxide into a useful compound, and in detail, a useful compound is formed through the reaction of carbon dioxide and/or an inorganic carbonate derived from carbon dioxide and a hydrocarbon having one or more hydroxy functional groups It relates to a catalyst that promotes production and a method of converting carbon dioxide using the same.

Coal and petroleum are fossil energy that accounts for more than 50% of the total energy, and have been used as an important energy source for mankind for centuries, and mankind has used these fossil energy and discharged carbon dioxide generated without a separate post-treatment process. Since the carbon dioxide acts as a greenhouse gas, efforts have been made to capture carbon dioxide and convert it into other useful compounds.

However, carbon dioxide is a carbon compound having very low energy, and since a large amount of energy must be input to convert it to be used as a useful resource, it is an obstacle to commercial success of carbon dioxide conversion technology. Therefore, if a catalyst that minimizes energy use and improves the selectivity of the reaction is developed, the carbon dioxide conversion technology is evaluated to be a very useful technology because it produces added value by re-converting it into a useful material at low cost at the same time as the treatment of carbon dioxide. .

One of the processes of converting carbon dioxide is a process of converting carbon dioxide to formic acid through a hydrogenation reaction, and may be specifically represented by Reaction Formula 1 below. The formic acid is used in various industrial fields such as livestock feed processing, leather dyeing, rubber synthesis, and so on, and is in the spotlight as a hydrogen storage body because of its low flammability and easy storage and transport.

(Scheme 1)

ΔG˚aq (kcal/mol) = 13.4

ΔG˚aq (kcal/mol) = 13.4

As a related art, Korean Patent Publication No. 2014-0033491 discloses a method for producing formic acid using silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. as a support and a heterogeneous catalyst containing gold therein, but the catalyst In the method of producing formic acid by directly hydrogenating carbon dioxide using hydrogen and having low efficiency, as shown in Scheme 1 above, the ΔG value is high as 13.4, so many energy sources must be input from the outside in order to proceed the reaction.

However, the reaction of producing formic acid by reacting a hydrocarbon containing at least one hydroxy group such as glycerol with carbon dioxide has a low ΔG value, so the reaction can proceed more thermodynamically compared to the reaction of Scheme 1 using relatively direct hydrogen. Therefore, the carbon dioxide conversion technology using a hydrocarbon containing one or more hydroxy groups is expected to be an energy-saving carbon dioxide conversion technology if an innovative catalyst is developed so that the conversion efficiency is excellent and the conversion process cost is minimized.

The glycerol is generated as a by-product in the production process of biodiesel, and is currently being simply incinerated as a waste. In this process, a large cost is required to deteriorate the economic feasibility of the biodiesel production process, and by-product incineration In the process of treatment, a large amount of carbon dioxide is generated, causing secondary environmental pollution. Accordingly, research on the use of glycerol, which is produced as a by-product in the biodiesel production process, is being conducted together.If carbon dioxide to produce formic acid and lactic acid is converted from the reaction of carbon dioxide and glycerol, the treatment problem of glycerol and the conversion problem of carbon dioxide It can be a good alternative to solve the problem at the same time.

In addition, lactic acid obtained at the same time as formic acid as a product during the above reaction is an industrially useful raw material.It is also used in the food industry to prevent the growth of spoilage bacteria by adding acidity to the food industry at the beginning of fermentation or liquor fermentation. , Acidic mordants, demineralizers for leather, raw materials for synthetic resins, etc., as well as recently known to be used as a raw material for biopolymer materials in the bio field.

The process of obtaining formic acid and lactic acid from the reaction of glycerol and carbon dioxide may be represented by the following Reaction Formula 2.

Recently, a homogeneous organometallic catalyst (Ru-N-heterocyclic carbene) that promotes the reaction of producing lactic acid and formic acid from the reaction of glycerol and carbon dioxide has been developed (Non-Patent Document 1).

(Scheme 2)

ΔG˚_aq (kcal/mol) = -9.21

ΔG˚ _aq (kcal/mol) = -9.21

However, in the case of a homogeneous catalyst, a lot of energy is required to recover from the product solution by using expensive precious metals. In addition, the development of a selective and efficient catalyst is required for efficient production of useful products.

The use of a heterogeneous catalyst as the catalyst provides not only process convenience, but also the advantage of obtaining a product with high purity since there are no residues of products derived from homogeneous catalysts.

Therefore, using a heterogeneous catalyst complex as a catalyst for carbon dioxide conversion improves the efficiency of the process and is an eco-friendly technology that can be recycled, and its research value is great, and it is possible to convert carbon dioxide with a stable and high activity for this purpose. There is a need to develop a heterogeneous catalyst.

Korean Patent Publication No. 10-2014-0033491 (2014.03.18.Publication date)

Chem. Commun., 2018, 54, 6184 (2018.05.16)

In order to solve the above problems, the present researchers completed the present invention while researching and developing a catalyst composite for the reaction of carbon dioxide and a hydrocarbon containing at least one hydroxy group.

The present invention provides a catalyst complex in which two or more kinds of metals are supported on a support as an active metal as a catalyst for converting carbon dioxide into a useful compound by reacting one or more of carbon dioxide and an inorganic carbonate with a hydrocarbon containing one or more hydroxy groups. It aims to do.

In order to solve the above problems, the present invention is a catalyst complex for a carbon dioxide conversion reaction by reaction of at least one of carbon dioxide and/or inorganic carbonate and a hydrocarbon containing at least one hydroxy group, as an active metal in the catalyst complex. It provides a catalyst composite for carbon dioxide conversion reaction, characterized in that at least one of them and at least one selected from transition metals excluding the noble metal are supported on a support.

In one embodiment of the present invention, the noble metal may be one or more selected from ruthenium (Ru), iridium (Ir), rhodium (Rh), platinum (Pt), palladium (Pd), and gold (Au), As transition metals excluding precious metals, zinc (Zn), nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), titanium (Ti), chromium (Cr) , Copper (Cu), zirconium (Zr), molybdenum (Mo), indium (In), barium (Ba), hafmium (Hf), and may be at least one selected from cerium (Ce).

In another embodiment of the present invention, the support is a carbonaceous material; Molecular sieve; Ceramic material; It may be one or more selected from metal oxides, and the hydrocarbon containing one or more hydroxy groups may be one selected from monohydric alcohols or polyhydric alcohols, or a mixture thereof.

The hydrocarbon containing at least one hydroxy group is glucose; Mantous; Galactose; Xylose; Sorbitol; Mannitol; Calactitol; Xylitol; Glycerol; 1,4-butanediol or an isomer thereof; 1,4-pentanediol or isomer thereof; 1,2-propanediol or isomers thereof; Butanol; Pentanol; It may be one selected from propanol or a mixture thereof, preferably glycerol and/or glucose.

In addition, the present invention provides a method for producing formic acid for producing formic acid from the reaction of at least one of carbon dioxide and/or inorganic carbonate and a hydrocarbon containing at least one hydroxy group.

In the formic acid production method of the present invention, the temperature of the carbon dioxide conversion reaction may be 180 to 240 °C, and the inorganic carbonate may be _{NaHCO 3.}

In addition, the method for preparing formic acid of the present invention may further include generating an inorganic carbonate by reacting carbon dioxide with at least one selected from a metal, a metal salt, and an ammonium salt before the reaction of a hydrocarbon containing at least one hydroxy group with an inorganic carbonate. have.

The present invention is also produced by the reaction of at least one of carbon dioxide and/or inorganic carbonate, and a hydrocarbon containing at least one hydroxy group, from the hydrocarbon containing at least one hydroxy group by dehydrogenation in the hydroxy group. It provides a method for preparing the compound.

The catalyst composite according to the present invention can produce formic acid and formic acid derivatives in high yield even under relatively low temperature conditions from a carbon dioxide conversion reaction of carbon dioxide or inorganic carbonate.

In addition, since the catalyst composite according to the present invention can be used as a heterogeneous catalyst, it is easy to separate it from a reaction product, and after being used as a catalyst, the catalyst can be recovered and used several times.

1 shows an X-ray diffraction (XRD) graph according to an embodiment of the present invention.

Hereinafter, a detailed description will be given of the configuration of the invention, including preferred embodiments, by which a person of ordinary skill in the art to which the present invention pertains can easily implement the present invention. In describing the principle of the preferred embodiment of the present invention in detail, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

The present invention relates to a catalyst complex for a carbon dioxide conversion reaction, wherein the carbon dioxide conversion reaction is a reaction of at least one of carbon dioxide and an inorganic carbonate and a hydrocarbon containing at least one hydroxy group, and the catalyst complex comprises at least two types of active metals. It is characterized in that it is supported on this support.

The active metal includes at least one of noble metals, and at least one selected from other transition metals may be supported on the support.

As the active metal component in the catalyst complex, the noble metal is preferably at least one selected from ruthenium (Ru), iridium (Ir), rhodium (Rh), platinum (Pt), palladium (Pd), and gold (Au). , More preferably ruthenium (Ru), platinum (Pt) and palladium (Pd).

The ruthenium compound as the ruthenium (Ru) precursor is not limited thereto, but, for example, RuCl ₃ ㆍnH ₂ O, Ru(NO ₃ ) ₃ , Ru ₂ (OH) ₂ Cl ₄ ㆍ7NH ₃ ㆍ3H ₂ O, K ₂ (RuCl ₅ (H ₂ O)), (NH ₄ ) ₂ (RuCl ₅ (H ₂ O)), K ₂ (RuCl ₅ (NO)), RuBr ₃ ㆍnH ₂ O, Na ₂ RuO ₄ , Ru (NO)(NO ₃ ) ₃ , Ru ₃ (CO) ₁₂ , [Ru ₃ O(OAc) ₆ (ligand) ₃ ][X] (ligand = H ₂ O, alcohol, amine, X = anion) Ru(acac ) ₃ , [Ru( p- cymene)Cl ₂ ] ₂ , and the like, and preferably in the group consisting _{of Ru(NO)(NO 3} ) ₃ , Ru(NO ₃ ) _{3 from the viewpoint of handling} It may be one selected.

As the iridium precursor, the iridium compound, although not limited thereto, (NH ₄ ) ₂ IrCl ₆ , IrCl ₃ or H ₂ IrCl ₆ , Ir(acac) ₃ , [Ir(cod)Cl] ₂ , [Ir(coe) ₂ Cl] ₂ , Ir ₄ (CO) ₁₂ , [Ir ₃ O(OAc) ₆ (ligand) ₃ ][X] (ligand = H ₂ O, alcohol, amine, X = anion), [IrCp ^* Cl ₂ ] ₂ It may be one selected from the group consisting of.

The rhodium (Rh) precursor rhodium compound is not limited thereto, but Na ₃ RhCl ₆ , (NH ₄ ) ₂ RhCl ₆ , Rh(NH ₃ ) ₅ Cl ₃ , RhCl _3, Rh(acac) ₃ , [Rh( cod)Cl] ₂ , [Rh(coe) ₂ Cl] ₂ , Rh ₄ (CO) ₁₂ , [Rh ₃ O(OAc) ₆ (ligand) ₃ ][X] (ligand = H ₂ O, alcohol, amine, X = anion), Rh ₂ (OAc) ₄ , [RhCp ^* Cl ₂ ] _{2 It} may be one selected from the group consisting of.

The platinum (Pt) precursor platinum compound is not limited thereto, for example, PtCl ₄ , H ₂ PtCl ₄ , H ₂ PtCl ₆ , K ₂ PtCl ₄ , K ₂ PtCl ₆ , Pt(C ₅ H ₇ O ₂ ) ₂ , it may be one selected from the group consisting of Pt(acac) _2.

The palladium (Pd) precursor is not limited thereto, but (NH ₄ ) ₂ PdCl ₆ , (NH ₄ ) ₂ PdCl ₄ , Pd(NH ₃ ) ₄ Cl ₂ , PdCl ₂ , Pd(NO ₃ ) _{2 ,} Pd(OAc) ₂ , Pd(acac) _{2 It} may be one selected from the group consisting of.

The gold (Au) precursor gold compound is not limited thereto, but 1 selected from the group consisting of _{HAuCl 4} , AuCl ₃ , NaAuCl ₄ , KAuO ₂ , NaAuO ₂ , Au(OAc) ₃ , HAu(NO ₃ ) ₄ It can be a bell.

In addition, as an active metal component in the catalyst composite, metals other than precious metals include zinc (Zn), nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), magnesium (Mg), and aluminum (Al ), titanium (Ti), chromium (Cr), copper (Cu), zirconium (Zr), molybdenum (Mo), indium (In), barium (Ba), hafmium (Hf) and cerium (Ce) It is preferable to include one or more.

The catalyst according to the present invention may be used only with an active metal, but it is generally used by being supported on a support. The support is a solid that stably maintains a substance having a catalytic function by dispersing it. It refers to a material that is highly dispersed and contained so as to increase the exposed surface area of a catalytic function material. It is usually porous or has a large area, and is mechanically, thermally, and chemically stable. The support is selected in consideration of the diameter, volume, surface area, strength, chemical stability, shape, etc. of the pores in the support, and since the activity of the catalyst may vary depending on the type of support, it is appropriate for the type of active metal and the type of reaction applied. Can be chosen.

Activated carbon as a support according to the present invention; Carbonaceous substances such as graphite carbon; Molecular sieves such as zeolite and metal-organic framework (MOF); Ceramic materials such as hydrotalcite, perovskite, spinel (eg, CoAl ₂ O _{4 );} Metal oxides such as alumina and silica, sulfate-treated metal oxides (eg, ZrO ₂ -SO ₄ , SnO ₂ -SO ₄ ) and metal oxyhydroxides (eg, AlOOH, ZrO(OH)2, CoOOH), etc. , Preferably, it may be graphite carbon.

The support may be commercially purchased or manufactured and used. For example, a graphite carbon body as a support in a catalyst composite may use a metal organic skeleton as a starting material, and a graphite phase formed by firing at a high temperature may be used.

In order to prepare the catalyst composite according to the present invention, a known method in the technical field to which the present invention pertains, such as impregnation, coprecipitation, solid support, vapor deposition, washcoat, sol-gel, in-situ synthesis, etc., is used to prepare the catalyst composite according to the present invention. Can be used to support.

For example, a step of supporting a precursor solution of an active metal supported by impregnation on a support and a step of drying the support on which the noble metal precursor solution is supported are performed.

The precursor solution is water, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, 3-methyl-1,5-pentanediol, 1,6 -Any known solvent capable of dissolving the precursor, such as a glycol-based solvent such as hexanediol or trimethylol propane, or an alcohol-based solvent such as methanol, ethanol, isopropyl alcohol (IPA), and butanol, may be used.

Subsequently, the active metal-supported support is preferably calcined at 500 to 1100° C. for 3 to 12 hours to prepare a composite catalyst.

According to a preferred embodiment of the present invention, it is preferable that the content of the active metal contained in the complex catalyst system for carbon dioxide conversion reaction is 0.1 wt% to 50 wt%.

According to the present invention, when the content of the active metal is less than 0.1 wt% by weight, there is a problem in that the reactivity decreases because sufficient active ingredients in the carbon dioxide conversion reaction do not exist. On the other hand, when the amount of the active metal exceeds 50 wt%, the activity decreases due to an increase in the particle size of the active metal, and coking occurs more, so it is preferable to maintain the above range.

In addition, the ratio of the noble metal and the transition metal excluding the noble metal in a molar ratio of 1: 1 to 1: 200 It may be supported in a ratio of, and preferably may be in the range of 1: 10 to 1: 100.

In the carbon dioxide conversion reaction, the hydrocarbon containing at least one hydroxy group may be one selected from a monohydric alcohol or a polyhydric alcohol, or a mixture thereof, and the hydrocarbon containing at least one hydroxy group is glucose, mannose, Galactose, xylose, sorbitol, mannitol, calactitol, xylitol, glycerol, 1,4-butanediol or isomer thereof, 1,4-pentanediol or isomer thereof, 1,2-propanediol or isomer thereof, butanol, pentanol and One selected from the group consisting of propanol, or a mixture thereof, is preferable from the viewpoint of reactivity with carbon dioxide, and more preferably glucose, xylose, and glycerol, including the viewpoint of the environmental viewpoint and the supply and demand of raw materials.

In addition, in the carbon dioxide conversion reaction, the carbon dioxide may be in the form of a carbon dioxide molecule or a carbonate derived from carbon dioxide. The carbonate derived from carbon dioxide is an inorganic carbonate produced by combining carbon dioxide with a metal or ammonium, and may be preferably a metal carbonate or a metal bicarbonate compound.

The inorganic carbonate produced by bonding with the metal or ammonium ion, for example, MgCO ₃ , Mg(CO ₃ ) ₂ , CaCO ₃ , KHCO ₃ , K ₂ CO ₃ , NaHCO ₃ , Na ₂ CO ₃ , LiHCO ₃ , Li ₂ CO ₃ , FeCO ₃ , CuCO ₃ , Ag ₂ CO ₃ , BaCO ₃ , SrCO ₃ , MnCO ₃ , Mn(CO ₃ ) ₂ , KHCO ₃ , NaHCO _3, (NH ₄ ) ₂ CO ₃ , NH ₄ HCO _3, It may be one or more selected from _{RbHCO 3} , Rb ₂ CO ₃ , CsHCO ₃ and Cs ₂ CO _{3 , and KHCO 3} , K ₂ CO ₃ , NaHCO ₃ , Na ₂ CO ₃ , LiHCO ₃ , Li ₂ CO _3, (NH ₄ ) ₂ CO ₃ , NH ₄ HCO _3, RbHCO ₃ , Rb ₂ CO ₃ , CsHCO ₃ and Cs ₂ CO ₃ More preferable.

In the conversion reaction of carbon dioxide of the present invention, the step of reacting carbon dioxide and a metal or metal salt with carbon dioxide or a metal salt before the reaction of a hydrocarbon containing one or more hydroxy groups with carbon dioxide or inorganic carbonate to generate an inorganic carbonate may be further included.

In the carbon dioxide conversion reaction of the present invention, it can be seen that when the form of carbon dioxide is in the form of carbonate rather than molecular carbon dioxide, the ΔG value of the reaction is lower, so that the reaction can occur more easily.

Illustratively, if the hydrocarbon containing at least one hydroxy group in the carbon dioxide conversion reaction is glycerol, the carbon dioxide conversion reaction is performed by the reaction of carbon dioxide and glycerol represented by the following Scheme 2 and/or the inorganic carbonate represented by the following Scheme 3 It may be a reaction of glycerol.

(반응식 2)

(Scheme 2)

(반응식 3)

(Scheme 3)

Table 1 below shows the ΔG values in the conversion reaction of carbon dioxide and hydrocarbons containing at least one hydroxy group according to the present invention.

Substrates Products Source of alcohol ΔG (kcal/mol) Ethanol +
NaHCO3 (or CO2) Acetaldehyde +
Formic acid Biomass derived sugar fermentation 5.24 (7.94) Butanol +
NaHCO3 (or CO2) Butanone +
Formic acid Biomass derived sugar fermentation 5.76 (8.47) Glucose +
NaHCO3 (or CO2) Gluconic acid, Sorbitol + Formic acid Hydrolysis of cellulose -14.34 (-11.64) Mannose +
NaHCO3 (or CO2) Mannaric acid, Mannitol +
Formic acid Hydrolysis of cellulose -3.14 (-0.44) Galactose +
NaHCO3 (or CO2) Galactonic acid, Galactitol +
Formic acid Hydrolysis of hemicellulose -9.55 (-6.84) Xylose +
NaHCO3 (or CO2) Xylonic acid, Xylitol +
Formic acid Hydrolysis of hemicellulose -16.27 (-13.56) Sorbitol +
NaHCO3 (or CO2) Lactic acid +
Formic acid Hydrogenation of glucose -42.48 (-39.78) Mannitol +
NaHCO3 (or CO2) Lactic acid +
Formic acid Hydrogenation of mannose -40.40 (-37.10) Galactitol +
NaHCO3 (or CO2) Lactic acid +
Formic acid Hydrogenation of Galactose -43.56 (-40.86) Xylitol +
NaHCO3 (or CO2) Lactic acid +
Formic acid Hydrogenation of xylose -33.10 (-30.40) Glycerol +
NaHCO3 (or CO2) Lactic acid +
Formic acid Hydrolysis of triglyceride -19.48 (16.77) Ethylene glycol +
NaHCO3 (or CO2) Glycolic acid, Lactic acid +
Formic acid Cellulosic biomass cascade reaction 4.35 (7.05) 1,4-butane diol +
NaHCO3 (or CO2) γ-butyrolactone +
Formic acid Glucose fermentation/Succinic acid hydrogenation -3.68 (-0.97) 2,3- butane diol +
NaHCO3 (or CO2) Acetoin, Diacetyl +
Formic acid Cellulosic biomass fermentation 21.64 (24.35) 1,2-pentane diol +
NaHCO3 (or CO2) Tetrahydrofurfuryl alcohol +
Formic acid Furfural cascade reaction 17.98 (20.69) 1,5-pentane diol +
NaHCO3 (or CO2) delta-valerolactone +
Formic acid Furfural cascade reaction 29.74 (32.45) 1,4-pentane diol + NaHCO3 (or CO2) γ-Valerolactone +
Formic acid Hydrogenation of γ-Valerolactone (GVL) -0.06 (2.64) 1,6-hexane diol + NaHCO3 (or CO2) ε-caprolactone +
Formic acid Hydroxymethylfurfural (HMF) cascade reaction 31.02 (33.72)

In addition, the present invention provides a method for producing formic acid from the reaction of at least one of carbon dioxide and inorganic carbonate and a hydrocarbon containing at least one hydroxy group in the presence of the catalyst complex for carbon dioxide conversion reaction.

The reaction temperature of the method for producing formic acid is preferably room temperature to 240°C, and it is preferable to react for within 72 hours at a pressure of 0 to 60 bar. Above 240°C, the reaction rate is very fast, and there is room for by-products to be generated.

In addition, the present invention is a hydroxy group in a hydrocarbon containing at least one hydroxy group from the reaction of at least one of carbon dioxide and an inorganic carbonate and a hydrocarbon containing at least one hydroxy group in the presence of the catalyst complex for carbon dioxide conversion reaction. It provides a method for producing a compound produced by dehydrogenation in.

In the method for producing a compound produced by dehydrogenation of a hydroxy group from a hydrocarbon containing at least one formic acid and/or hydroxy group, the amount of the catalyst complex for carbon dioxide conversion is a hydrocarbon containing at least one hydroxy group It is preferably 0.01-10 wt% with respect to. When the content of the catalyst is less than 0.01 wt%, sufficient catalytic activity effect may not appear, and when the content of the catalyst exceeds 10 wt%, it is uneconomical in terms of increasing the catalytic activity effect according to the catalyst content.

Even when the catalyst composite according to the present invention is reused for the conversion reaction of carbon dioxide, it exhibits activity and can be effectively used as a heterogeneous catalyst. That is, the catalyst of the present invention can exhibit excellent catalytic activity even when used three or more times.

Preparation Example 1: Ru(1)/NC-900 catalyst

Preparation Example 1-1. Preparation of Ru(1)/ZIF-8

Ru(acac) ₃ (Ruthenium acetylacetonate) was encapsulated in the pores of ZIF-8 as follows to prepare Ru(1)/ZIF-8 by an in-situ method.

64 mmol of Zn(NO ₃ ) ₂ ·6H ₂ O and 4 mmol of Ru(acac) ₃ were dissolved in 480 mL of methanol by stirring for an hour. 256 mmol of 2-methylimidazole was dissolved in a solution of 96 mL of DMF and 64 mL of methanol. The two solutions were sequentially poured into a teflon-lined autoclave, and the reactor was placed in an oven and heated to 120°C, followed by heating for 4 hours. After cooling the reactor with cold water, the resulting solution was centrifuged at 7000 rpm for 10 minutes, washed three times with methanol, and dried in a vacuum oven at 100°C for 12 hours, and Ru(acac) ₃ was encapsulated in the pores of ZIF-8. Ru(1)/ZIF-8 was prepared.

Preparation Example 1-2. Preparation of Ru(1)/NC-900

Ru(1)/NC-900 in which Ru metal was highly dispersed in the graphite support was prepared as follows.

The Ru(1)/ZIF-8 prepared in Preparation Example 1-1 was placed in a boat-type alumina crucible, and the crucible was placed in a tube-type furnace. While injecting 5% H ₂ /Ar gas, the temperature was raised from room temperature to 800℃ at a rate of 5℃/min, carbonized at 900℃ for 3 hours, cooled to room temperature, and Ru (1) in which Ru metal was highly dispersed on the graphite support. /NC-900 was prepared.

The Zn evaporated during the firing process, so that only Ru was actually present as an active metal. In the finally prepared catalyst, the Ru content is 1.5 wt%.

Preparation Example 2: Ru(1)Co/NC-900 catalyst

Preparation Example 2-1. Preparation of Ru(1)/ZnCo-ZIF

Ru(acac) ₃ (Ruthenium acetylacetonate) was encapsulated in the pores of ZnCo-ZIF as follows to prepare Ru(1)/ZnCo-ZIF by the in-situ method.

64 mmol of Zn(NO ₃ ) ₂ ·6H ₂ O and 64 mmol of Co(NO ₃ ) ₂ ·6H ₂ O and 4 mmol of Ru(acac) ₃ were dissolved in 480 mL of methanol by stirring for an hour. 256 mmol of 2-methylimidazole was dissolved in a solution of 96 mL of DMF and 64 mL of methanol. The two solutions were sequentially poured into a teflon-lined autoclave, and the reactor was placed in an oven and heated to 120°C, followed by heating for 4 hours. After cooling the reactor with cold water, the resulting solution was centrifuged at 7000 rpm for 10 minutes, washed three times with methanol, and then dried in a vacuum oven at 100° C. for 12 hours _{, whereby Ru(acac) 3} was encapsulated in the pores of ZnCo-ZIF. Ru(1)/ZnCo-ZIF was prepared.

Preparation Example 2-2. Preparation of Ru(1)Co/NC-900

As follows, Ru(1)Co/NC-900 in which Ru metal was highly dispersed on the graphite support and Co nanoparticles were present was prepared.

The Ru(1)/ZnCo-ZIF prepared in Preparation Example 2-1 was placed in a boat-type alumina crucible, and the crucible was placed in a tube-type furnace. While injecting 5% H ₂ /Ar gas, the temperature is raised from room temperature to 900 degrees at a rate of 5℃/min, carbonized at 900℃ for 3 hours, cooled to room temperature, and the Ru metal is highly dispersed in the graphite support and Co nanoparticles are The present Ru(1)Co/NC-900 was prepared. The Zn was evaporated during the firing process, and only Ru and Co were actually present as active metals, and the content of Ru was 1 wt%, and the content of Co was 47 wt%.

Preparation Example 3: Ru(3)/NC-900 catalyst

Manufacturing Example 3-1. Preparation of Ru(3)/ZIF-8

Ru(3)/ZIF-8 in which Ru ₃ (CO) ₁₂ (Triruthenium dodecacarbonyl) was encapsulated in the pores of ZIF-8 was prepared by the in-situ method as follows.

64 mmol of Zn(NO ₃ ) ₂ ·6H ₂ O and 2.4 mmol of Ru ₃ (CO) ₁₂ were dissolved in 480 mL of methanol by stirring for an hour. 256 mmol of 2-methylimidazole was dissolved in a solution of 96 mL of DMF and 64 mL of methanol. The two solutions were sequentially poured into a teflon-lined autoclave, and the reactor was placed in an oven and heated to 120°C, followed by heating for 4 hours. After cooling the reactor with cold water, the resulting solution was centrifuged at 7000 rpm for 10 minutes, washed three times with methanol, and dried in a vacuum oven at 100°C for 12 hours, and Ru(acac) ₃ was encapsulated in the pores of ZIF-8. Ru(3)/ZIF-8 was prepared.

Manufacturing Example 3-2. Preparation of Ru(3)/NC-900

Ru (3)/NC-900 in which the Ru metal was highly dispersed in the graphite support was prepared as follows.

The Ru(3)/ZIF-8 prepared in Production Example 3-1 was placed in a boat-type alumina crucible, and the crucible was placed in a tube-type furnace. While injecting 5% H ₂ /Ar gas, the temperature was raised from room temperature to 900℃ at a rate of 5℃/min, carbonized at 900℃ for 3 hours, cooled to room temperature, and Ru metal was highly dispersed in the graphite support. /NC-900 was prepared.

The Zn evaporated during the firing process, so that only Ru was actually present as an active metal. The content of Ru in the finally prepared catalyst is 1.5wt%.

Preparation Example 4: Ru(3)Co/NC-900 catalyst

Preparation Example 4-1. Preparation of Ru(3)/ZnCo-ZIF

Ru ₃ (CO) ₁₂ (Ruthenium acetylacetonate) was encapsulated in the pores of ZnCo-ZIF-8 as follows to prepare Ru(3)/ZnCo-ZIF-8 by the in-situ method.

64 mmol of Zn(NO ₃ ) ₂ ·6H ₂ O and 64 mmol of Co(NO ₃ ) ₂ ·6H ₂ O and 2.4 mmol of Ru ₃ (CO) ₁₂ were dissolved in 480 mL of methanol by stirring for an hour. 256 mmol of 2-methylimidazole was dissolved in a solution of 96 mL of DMF and 64 mL of methanol. The two solutions were sequentially poured into a teflon-lined autoclave, and the reactor was placed in an oven and heated to 120°C, followed by heating for 4 hours. After cooling the reactor with cold water, the resulting solution was centrifuged at 7000 rpm for 10 minutes, washed three times with methanol, and then dried in a vacuum oven at 100° C. for 12 hours _{to encapsulate Ru 3} (CO) ₁₂ in the pores of ZnCo-ZIF. The prepared Ru(3)/ZnCo-ZIF was prepared.

Manufacturing Example 4-2. Preparation of Ru(3)Co/NC-900

As follows, Ru (3)Co/NC-900 in which the Ru metal was highly dispersed in the graphite support and Co nanoparticles were present was prepared.

The Ru(3)/ZnCo-ZIF prepared in Preparation Example 4-1 was placed in a boat-shaped alumina crucible, and the crucible was placed in a tube-shaped furnace. While injecting 5% H ₂ /Ar gas, the temperature is raised from room temperature to 900 degrees at a rate of 5℃/min, carbonized at 900℃ for 3 hours, cooled to room temperature, and the Ru metal is highly dispersed in the graphite support and Co nanoparticles are The present Ru(3)Co/NC-900 was prepared. The Zn evaporated during the firing process, so that only Ru and Co were actually present as active metals. In the finally prepared catalyst system, the content of Ru is 2.7 wt% and the content of Co is 11.2 wt%.

Preparation Example 5: Ru(3)/NC11-1100 catalyst

Manufacturing Example 5-1. Preparation of Ru(3)/ZIF-11

Ru(3) clusters ([Ru ₃ O(OAc) ₆ (H ₂ O) ₃ ]OAc) are encapsulated in the pores of ZIF-11 as follows by in-situ method. Was prepared.

After dissolving 10 mmol of benzimidazole in 48 g of methanol, 46 g of toluene and 1.3 ml of NH ₄ OH aqueous solution were added to this solution. Thereafter, 0.1 mmol of Ru(3) cluster ([Ru ₃ O(OAc) ₆ (H ₂ O) ₃ ]OAc) was added to the solution, and 5 mmol of Zn(acet) ₂ ·2H ₂ O was added. The solution was stirred for 4 hours, centrifuged at 7000 rpm for 10 minutes, washed three times with methanol, and dried for 12 hours in a vacuum oven at 100° C. for Ru(3) clusters ([Ru ₃ O(OAc) ₆ (H ₂ O) ₃ ]OAc) was encapsulated in the pores of ZIF-11 to prepare Ru(3)/ZIF-11.

Manufacturing Example 5-2. Preparation of Ru(3)/NC11-1100

Ru(3)/NC11-1100 in which the Ru metal was highly dispersed in the graphite support was prepared as follows.

The Ru(3)/ZIF-11 prepared in Production Example 5-1 was placed in a boat-type alumina crucible, and the crucible was placed in a tube-type furnace. While injecting 5% H ₂ /Ar gas, the temperature was raised from room temperature to 1100℃ at a rate of 5℃/min, carbonized at 1100℃ for 3 hours, cooled to room temperature, and Ru metal was highly dispersed in the graphite support. /NC11-1100 was prepared. The Zn evaporated during the firing process, so that only Ru was actually present as an active metal. The content of Ru in the finally prepared catalyst system is 0.9 wt%.

Preparation Example 6: Ru(3)Co/NC12-1100 catalyst

Manufacturing Example 6-1. Preparation of Ru(3)/Co-ZIF-12

Ru(3) clusters ([Ru ₃ O(OAc) ₆ (H ₂ O) ₃ ]OAc) encapsulated Ru(3)/Co-ZIF-12 in the pores of Co-ZIF-12 as follows. It was prepared by the situ method.

After dissolving 10 mmol of benzimidazole in 48 g of methanol, 46 g of toluene and 1.3 ml of NH ₄ OH aqueous solution were added to this solution. Thereafter, 0.1 mmol of Ru(3) cluster was added to the solution, and 5 mmol of Co(acet) ₂ ·4H ₂ O was added. The solution was stirred for 4 hours and then centrifuged at 7000 rpm for 10 minutes, and then the powder obtained by washing with methanol 3 times was dried in a vacuum oven at 100° C. for 12 hours, so that the Ru(3) cluster was formed in the pores of Co-ZIF-12. Encapsulated Ru(3)/Co-ZIF-12 was prepared.

Preparation Example 6-2. Preparation of Ru(3)Co/NC12-1100

As follows, Ru (3)Co/NC12-1100 in which the Ru metal was highly dispersed on the graphite support and Co nanoparticles were present was prepared.

The Ru(3)/Co-ZIF-12 prepared in Production Example 6-1 was placed in a boat-type alumina crucible, and the crucible was placed in a tube-type furnace. While injecting 5% H ₂ /Ar gas, the temperature is raised from room temperature to 1100 degrees at a rate of 5℃/min, carbonized at 1100℃ for 3 hours, cooled to room temperature, and the Ru metal is highly dispersed on the graphite support and Co nanoparticles are The present Ru(3)Co/NC12-1100 was prepared.

Ru and Co were present as active metals. In the finally prepared catalyst system, the content of Ru is 2.36 wt% and the content of Co is 47 wt%.

Experimental example

In distilled water (35.38g), glycerol and K ₂ CO ₃ , and optionally KOH were added to the high-pressure reactor so that the concentration in Table 2 and Table 3 was followed, and then the catalyst (0.2 g) prepared in Preparation Example was added. Then, the pressure was adjusted to 26 bar by filling with nitrogen. After raising the temperature of the reactor to the reaction temperature, it was reacted for 12 hours at a temperature of 180°C or 220°C. After cooling the reactor to room temperature, the solution obtained by filtering the catalyst was quantitatively analyzed through HPLC, and the obtained powder was washed with methanol and dried.

The results of the simultaneous conversion reaction are summarized in Tables 2 and 3 below.

No Cat Temp (℃) Glycerol (M) K ₂ CO ₃
(M) LA
Yield
(%) FA
Yield
(%) Experimental Example 1 Ru(1)Co/NC-900 180 4 One 14.2 22.8 Experimental Example 2 Ru(3)Co/NC-900 180 4 One 16.2 25.1 Experimental Example 3 Ru(1)/NC-800 180 4 One 14.3 13.3 Experimental Example 4 Ru(3)/NC-800 180 4 One 16.5 11.0

No Cat Temp
(℃) Glycerol (M) K ₂ CO ₃ (M) KOH
(M) LA/FA
Yield
(%) LA sel(%) 1,2-PDO Experimental Example 5 Ru(3)/NC11-1100 220 4 2 2 47.3/25.1 59.3 13.6 Experimental Example 6 Ru(3)Co/NC12-1100 220 4 2 2 55.5/41.4 57.3 5.8

In Experimental Example 1 and Experimental Example 2, the precursor of the active metal was different from the same metal. The activity is slightly different due to the difference between the precursors, but generally shows a similar degree of activity.

In Experimental Example 3 and Experimental Example 4, the same active metal precursors as those in Experimental Examples 1 and 2 were used, but a single Ru metal not containing Co was used. When Co was added to Ru, compared with the results of lactic acid, similar results were shown, but the formic acid yield increased from 13.3% to 22.8% and from 11.0% to 25.1%.

Experimental Examples 5 and 6 are experimental results at 220 ℃. Compared to the experimental results at 180°C (Experimental Examples 1 to 4), the yield of both lactic acid (LA) and formic acid (FA) showed a tendency to increase, but the yield of lactic acid was significantly increased than that of formic acid. can see.

Comparing the experimental results at 220°C, it can be seen that the yield of lactic acid and formic acid both increased when Ru and Co composite metal was used as the active metal, but in particular, the yield of FA increased significantly.

From the above results, it can be seen that when a transition metal, which is a non-precious metal, is included together with a noble metal, the yield of formic acid increases.

Therefore, when the catalyst according to the present invention is used, formic acid can be produced in a higher yield in the conversion of carbon dioxide by a reaction of at least one of carbon dioxide and/or inorganic carbonate and a hydrocarbon containing at least one hydroxy group. .

As described above, the present invention has been described with reference to the accompanying drawings, but this is only exemplary, and those of ordinary skill in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the technical protection scope of the present invention should be determined by the following claims.

Claims (12)

In the catalyst composite for carbon dioxide conversion reaction,
The carbon dioxide conversion reaction is a reaction of at least one of carbon dioxide and/or inorganic carbonate and a hydrocarbon containing at least one hydroxy group,
A catalyst complex for carbon dioxide conversion reaction, characterized in that at least one of noble metals and at least one selected from transition metals excluding the noble metals are supported on a support as the active metal in the catalyst complex.
The method of claim 1,
The noble metal is at least one selected from ruthenium (Ru), iridium (Ir), rhodium (Rh), platinum (Pt), palladium (Pd), and gold (Au).
The method of claim 1,
As transition metals excluding precious metals in the catalyst composite, zinc (Zn), nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), titanium (Ti), Characterized in that it contains at least one selected from chromium (Cr), copper (Cu), zirconium (Zr), molybdenum (Mo), indium (In), barium (Ba), hafmium (Hf) and cerium (Ce) A catalyst composite for carbon dioxide conversion reaction.
The method of claim 1,
The support is a carbonaceous material; Molecular sieve; Ceramic material; A catalyst composite for carbon dioxide conversion reaction, characterized in that at least one selected from metal oxides.
The method of claim 1,
The hydrocarbon comprising at least one hydroxy group is one selected from monohydric alcohols or polyhydric alcohols, or a mixture thereof.
The method of claim 5,
The hydrocarbon containing at least one hydroxy group is glucose; Mantous; Galactose; Xylose; Sorbitol; Mannitol; Calactitol; Xylitol; Glycerol; 1,4-butanediol or an isomer thereof; 1,4-pentanediol or isomer thereof; 1,2-propanediol or isomers thereof; Butanol; Pentanol; A catalyst complex for carbon dioxide conversion reaction, characterized in that one selected from propanol or a mixture thereof.
The method of claim 6,
The catalyst complex for carbon dioxide conversion reaction, characterized in that the hydrocarbon containing at least one hydroxy group is glycerol and/or glucose.
In the presence of the catalyst composite for carbon dioxide conversion according to any one of claims 1 to 7,
A method for producing formic acid for producing formic acid from the reaction of at least one of carbon dioxide and/or inorganic carbonate and a hydrocarbon containing at least one hydroxy group.
The method of claim 8,
The method for producing formic acid, characterized in that the temperature of the carbon dioxide conversion reaction is 180 to 240 ℃.
The method of claim 9,
The inorganic carbonate is NaHCO ₃ Method for producing formic acid, characterized in that.
The method of claim 8,
A method for producing formic acid, further comprising: reacting carbon dioxide with at least one selected from among metals, metal salts, and ammonium salts before the reaction of hydrocarbons containing one or more hydroxy groups with inorganic carbonates to produce inorganic carbonates.
In the presence of the catalyst composite for carbon dioxide conversion according to any one of claims 1 to 7,
Method for producing a compound produced by dehydrogenation in a hydroxy group from a hydrocarbon containing at least one hydroxy group by reaction of at least one of carbon dioxide and/or inorganic carbonate with a hydrocarbon containing at least one hydroxy group .

Images