KR102570842B1 - Heterogeneous Catalyst Complex for Carbon dioxide Conversion - Google Patents

Abstract

The present invention is a catalyst composite for a carbon dioxide conversion reaction, wherein the carbon dioxide conversion reaction is a reaction between carbon dioxide and a compound containing at least one hydroxy group, and the catalyst composite includes at least one noble metal as an active metal in the catalyst composite And, it relates to a catalyst composite for carbon dioxide conversion reaction, comprising at least one selected from nickel (Ni), iron (Fe), and cobalt (Co), and comprising a support.

Description

Heterogeneous Catalyst Complex for Carbon Dioxide Conversion}

The present invention relates to a catalyst composite for a carbon dioxide conversion reaction that converts carbon dioxide into a useful compound, and more particularly, through the reaction of carbon dioxide and/or an inorganic carbonate derived from carbon dioxide with a compound having at least one hydroxyl functional group in the molecule, to obtain a useful compound. It relates to a catalyst that promotes production and a method for converting carbon dioxide using the catalyst.

Coal and petroleum are fossil energies that account for more than 50% of total energy and have been used as important energy sources for mankind for the past several centuries. Since carbon dioxide acts as a greenhouse gas, efforts have been made to capture carbon dioxide and convert it into other useful compounds.

However, since carbon dioxide is a carbon compound with very low energy, a lot of energy must be input to convert it into a useful resource, which 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, carbon dioxide conversion technology is evaluated to be a very useful technology because added value is produced by treating carbon dioxide and reconverting it into a useful material at a low cost at the same time. .

One of the conversion processes of carbon dioxide is a process of converting carbon dioxide into 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, and rubber synthesis, and is in the spotlight as a hydrogen storage medium because of its low flammability and easy storage and transportation.

(Scheme 1)

ΔG˚aq (kcal/mol) = 13.4

As a prior art related to this, Korean Patent Publication No. 2014-0033491 discloses a formic acid production method using a heterogeneous catalyst containing gold and using silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. as a support, but the catalyst As shown in Scheme 1 above, the method of producing formic acid by directly hydrogenating carbon dioxide with low efficiency and having a high ΔG value of 13.4 requires a lot of external energy sources to proceed with 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 relatively low ΔG value, so the reaction can proceed thermodynamically much more easily than the reaction of Scheme 1 using 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 biodiesel production process, and is currently simply incinerated as waste. In this process, a lot of cost is required, which is a factor that deteriorates the economics of the biodiesel production process, and by-product incineration A large amount of carbon dioxide is generated during the treatment process, which causes secondary environmental pollution. Accordingly, research on how to utilize glycerol, which is produced as a by-product in the biodiesel production process, is being conducted together. can be a good alternative to solve both at the same time.

In addition, as a product of the above reaction, lactic acid obtained at the same time as formic acid is an industrially useful raw material, which is added in the food industry as an acidulant that gives a sour taste or in the early stage of fermentation of alcoholic beverages to prevent the growth of spoilage bacteria. , acidic mordant, deliming agent for leather, raw material for synthetic resin, etc., and recently, it is known to be used as a raw material for bioactive polymer materials in the bio field.

A process for obtaining formic acid and lactic acid from the reaction of glycerol and carbon dioxide can be represented by Reaction Formula 2 below.

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

However, in the case of a homogeneous catalyst, it requires a lot of energy to recover from the product solution by using expensive precious metals. In addition, the development of selective and efficient catalysts 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 of high purity because there are no residues of products derived from the homogeneous catalysts.

Therefore, the use of the heterogeneous catalyst complex as a catalyst for the carbon dioxide conversion reaction improves process efficiency, is recyclable and therefore environmentally friendly technology, has great research value, and can convert carbon dioxide with stable and high activity for this purpose. There is a demand for the development of heterogeneous catalysts.

Korean Patent Publication No. 10-2014-0033491 (published on March 18, 2014)

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

The present researchers completed the present invention while researching and developing a catalyst composite for the reaction of carbon dioxide and a compound containing at least one hydroxyl group in order to solve the above problems.

The present invention is a catalyst for converting carbon dioxide into a useful compound by reacting at least one of carbon dioxide and inorganic carbonate with a compound containing at least one hydroxy group, and two or more types of metals as active metals are supported on a support to provide a catalyst composite aims to do

In order to solve the above problems, the present invention is a catalyst composite for a carbon dioxide conversion reaction by reacting at least one of carbon dioxide and / or inorganic carbonate with a compound containing at least one hydroxy group, wherein the active metal in the catalyst composite is a noble metal It provides a catalyst composite for carbon dioxide conversion reaction, characterized in that at least one member selected from transition metals other than noble metals is supported on a support.

In one embodiment of the present invention, the noble metal may be at least one selected from ruthenium (Ru), iridium (Ir), rhodium (Rh), platinum (Pt), palladium (Pd), and gold (Au), Zinc (Zn), nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), titanium (Ti), chromium (Cr), copper (Cu), zirconium (Zr) as transition metals other than precious metals , molybdenum (Mo) and hafmium (Hf).

In another embodiment of the present invention, the support is a carbonaceous material; molecular sieve; ceramic materials; It may be at least one selected from metal oxides, and the compound containing at least one hydroxyl group may be one selected from monohydric alcohols and polyhydric alcohols, or a mixture thereof.

The compound containing at least one hydroxy group is glucose; mannose; galactose; xylose; sorbitol; mannitol; galactitol; xylitol; glycerol; 1,4-butanediol or an isomer thereof; 1,4-pentanediol or an isomer thereof; 1,2-propanediol or an isomer 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 by reacting at least one of carbon dioxide and/or inorganic carbonate with a compound containing at least one hydroxyl group to produce formic acid.

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 producing formic acid of the present invention may further include generating inorganic carbonate by reacting carbon dioxide with at least one selected from among metals, metal salts, and ammonium salts before reacting the inorganic carbonate with a compound containing at least one hydroxyl group. there is.

The present invention also relates to a compound containing at least one hydroxy group produced by dehydrogenation of a hydroxy group in a compound containing at least one hydroxy group by the reaction of at least one of carbon dioxide and/or inorganic carbonate with a compound containing at least one hydroxy group. A method for preparing the compound is provided.

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 carbon dioxide conversion reaction of carbon dioxide or inorganic carbonate.

In addition, the catalyst composite according to the present invention can be used as a heterogeneous catalyst, so that it is easy to separate from reaction products, and it provides an advantage that the catalyst can be recovered and used several times after being used as a catalyst.

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

Hereinafter, the configuration of the present invention, including a preferred embodiment, in which a person skilled in the art to which the present invention pertains can easily practice the present invention will be described in detail. In describing the principles of preferred embodiments of the present invention in detail, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

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

The active metal includes at least one noble metal, 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), , ruthenium (Ru), platinum (Pt) and palladium (Pd) are more preferred.

Examples of the ruthenium compound that is the ruthenium (Ru) precursor are, but are not limited to, 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 from the viewpoint of handling, Ru(NO)(NO ₃ ) ₃ , Ru(NO ₃ ) ₃ from the group consisting of It may be one selected type.

Examples of the iridium compound as the iridium precursor include, but are not limited to, (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 species selected from the group consisting of.

Examples of the rhodium compound that is the rhodium (Rh) precursor include, but are not limited to, 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.

Examples of the platinum compound that is the precursor of platinum (Pt) include, but are not limited to, 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 , and Pt(acac) ₂ .

Examples of the palladium compound as the precursor of palladium (Pd) include, but are not limited to, (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 compound as the gold (Au) precursor is, but is not limited to, HAuCl ₄ , AuCl ₃ , NaAuCl ₄ , KAuO ₂ , NaAuO ₂ , Au(OAc) ₃ , HAu(NO ₃ ) 1 selected from the group consisting of ₄ can be all day

In addition, as an active metal component in the catalyst composite, metals other than noble metals include zinc (Zn), nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), titanium (Ti), and chromium (Cr). ), copper (Cu), zirconium (Zr), molybdenum (Mo) and hafmium (Hf) is preferably included at least one selected from.

Although the catalyst according to the present invention can be used only with an active metal, it is generally used supported on a support. The support is a solid that stably maintains a substance having a catalytic function by dispersing it. It is a material that is highly dispersed and contained so that the exposed surface area of the catalytic function material is large, and usually means a material that is 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 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 applied reaction. can be chosen appropriately.

As the support according to the present invention, activated carbon; carbonaceous substances such as graphitic 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); , preferably graphitic carbon.

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

In order to prepare the catalyst composite according to the present invention, methods known in the art such as impregnation, co-precipitation, solidification paper, vapor deposition, wash coat, sol-gel, in-situ synthesis, etc. can be used and supported.

For example, the impregnation-based support includes supporting a precursor solution of an active metal on a support and drying the support on which the noble metal precursor solution is supported.

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 - It can be prepared using any known solvent capable of dissolving the precursor, such as glycol-based solvents such as hexanediol and trimethylol propane, or alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), and butanol.

Subsequently, it is preferable to prepare a composite catalyst by calcining the active metal-supported support at, for example, 500 to 1100 ° C. for 3 to 12 hours.

According to a preferred embodiment of the present invention, the content of the active metal included in the composite catalyst system for carbon dioxide conversion reaction preferably has 0.1wt% to 50wt%.

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 a sufficient active component in the carbon dioxide conversion reaction does not exist and the reactivity decreases. On the other hand, when the active metal exceeds 50 wt%, the activity decreases due to the 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 molar ratio of the noble metal and the transition metal excluding the noble metal is 1: 1 to 1: 200 It may be supported at a ratio of 1:10 to 1:100.

In the carbon dioxide conversion reaction, the compound containing one or more hydroxy groups may be one selected from monohydric alcohols or polyhydric alcohols or a mixture thereof, and the compounds containing one or more hydroxy groups may be glucose, mannose, galactose , xylose, sorbitol, mannitol, galactitol, xylitol, glycerol, 1,4-butanediol or its isomers, 1,4-pentanediol or its isomers, 1,2-propanediol or its isomers, butanol, pentanol and propanol It is preferably one selected from the group consisting of or a mixture thereof in terms of reactivity with carbon dioxide, and more preferably glucose, xylose, and glycerol, further including environmental and raw material supply and demand points.

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

Inorganic carbonates produced by combining 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 at least one selected from RbHCO ₃ , Rb ₂ CO ₃ , CsHCO ₃ and Cs ₂ CO ₃ , 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 are more preferred.

The carbon dioxide conversion reaction of the present invention may further include generating an inorganic carbonate by reacting carbon dioxide with a metal or metal salt before reacting the compound containing one or more hydroxyl groups with carbon dioxide or inorganic carbonate.

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

Illustratively, when the compound containing at least one hydroxyl group in the carbon dioxide conversion reaction is glycerol, the carbon dioxide conversion reaction is a reaction between carbon dioxide and glycerol represented by the following Reaction Scheme 2 and/or an inorganic carbonate represented by the following Reaction Scheme 3 It may be a reaction of glycerol.

(Scheme 2)

(Scheme 3)

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

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 triglycerides -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 by reacting at least one of carbon dioxide and inorganic carbonate with a compound containing at least one hydroxy group in the presence of the catalyst complex for carbon dioxide conversion reaction.

The reaction temperature in the method for producing formic acid is preferably from room temperature to 240° C., and the reaction is preferably performed at a pressure of 0 to 60 bar for 72 hours or less. Above 240 ℃, the reaction rate is very fast, and there is room for by-products to be formed.

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

In the method for preparing a compound produced by dehydrogenation of a hydroxy group in the formic acid and/or a compound containing at least one hydroxy group, the amount of the catalyst complex for carbon dioxide conversion reaction is a compound containing at least one hydroxy group It is preferably 0.01-10 wt% relative to. When the content of the catalyst is less than 0.01 wt%, a 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 carbon dioxide conversion reaction, it shows activity, so it can be efficiently 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

As follows, Ru(1)/ZIF-8 in which Ru(acac) ₃ (Ruthenium acetylacetonate) was encapsulated in the pores of ZIF-8 was prepared 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 one 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. for 4 hours. After cooling the reactor with cold water, the obtained solution was centrifuged at 7000 rpm for 10 minutes, washed with methanol three times, and the obtained powder was dried in a vacuum oven at 100 ° C for 12 hours to encapsulate Ru(acac) ₃ in the pores of ZIF-8. prepared Ru(1)/ZIF-8.

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

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

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 ° C at a rate of 5 ° C / min, carbonized at 900 ° C for 3 hours, and then cooled to room temperature to obtain Ru (1) in which Ru metal was highly dispersed in a graphite support /NC-900 was prepared.

The Zn was evaporated during the sintering process, so that only Ru actually existed as an active metal. The Ru content in the final prepared catalyst is 1.5 wt%.

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

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

As follows, Ru(1)/ZnCo-ZIF in which Ru(acac) ₃ (Ruthenium acetylacetonate) was encapsulated in the pores of ZnCo-ZIF was prepared by an in-situ method.

64 mmol of Zn(NO ₃ ) ₂ 6H ₂ O, 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 one 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. for 4 hours. After cooling the reactor with cold water, the obtained solution was centrifuged at 7000 rpm for 10 minutes, washed three times with methanol, and the obtained powder was dried in a vacuum oven at 100 ° C for 12 hours to obtain Ru (acac) ₃ 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 in a graphite support and Co nanoparticles were present was prepared.

Ru(1)/ZnCo-ZIF prepared in Production 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 was raised from room temperature to 900 degrees at a rate of 5°C/min, carbonized at 900°C for 3 hours, and then cooled to room temperature so that Ru metal was highly dispersed in the graphite support and Co nanoparticles were formed. The present Ru(1)Co/NC-900 was prepared. The Zn evaporated during the sintering process, and in fact, only Ru and Co were 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

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

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

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 one 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. for 4 hours. After cooling the reactor with cold water, the obtained solution was centrifuged at 7000 rpm for 10 minutes, washed with methanol three times, and the obtained powder was dried in a vacuum oven at 100 ° C for 12 hours to encapsulate Ru(acac) ₃ in the pores of ZIF-8. Ru(3)/ZIF-8 was prepared.

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

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

Ru(3)/ZIF-8 prepared in Preparation 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 ° C at a rate of 5 ° C / min, carbonized at 900 ° C for 3 hours, and then cooled to room temperature to obtain Ru (3) in which Ru metal was highly dispersed in the graphite support /NC-900 was prepared.

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

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

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

As follows, Ru(3)/ZnCo-ZIF-8 in which Ru ₃ (CO) ₁₂ (Ruthenium acetylacetonate) was encapsulated in the pores of ZnCo-ZIF-8 was prepared by an in-situ method.

64 mmol of Zn(NO ₃ ) ₂ 6H ₂ O, 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 one 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. for 4 hours. After cooling the reactor with cold water, the obtained solution was centrifuged at 7000 rpm for 10 minutes, washed with methanol three times, and the obtained powder was dried in a vacuum oven at 100 ° C for 12 hours to encapsulate Ru ₃ (CO) ₁₂ in the pores of ZnCo-ZIF prepared Ru(3)/ZnCo-ZIF.

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

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

Ru(3)/ZnCo-ZIF prepared in Preparation Example 4-1 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 degrees at a rate of 5°C/min, carbonized at 900°C for 3 hours, and then cooled to room temperature so that Ru metal was highly dispersed in the graphite support and Co nanoparticles were formed. The present Ru(3)Co/NC-900 was prepared. The Zn evaporated during the sintering process, and only Ru and Co actually existed as active metals. In the final prepared catalyst system, the Ru content was 2.7 wt% and the Co content was 11.2 wt%.

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

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

As follows, Ru(3)/ZIF-11 in which Ru(3) clusters ([Ru ₃ O(OAc) ₆ (H ₂ O) ₃ ]OAc) are encapsulated in the pores of ZIF-11 were prepared by an in-situ method. manufactured.

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 the 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 then 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 with methanol three times, and the obtained powder was dried in a vacuum oven at 100 ° C. for 12 hours to obtain 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.

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

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

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 ° C at a rate of 5 ° C / min, carbonized at 1100 ° C for 3 hours, and then cooled to room temperature to form Ru (3) in which Ru metal was highly dispersed in the graphite support /NC11-1100 was prepared. The Zn was evaporated during the sintering process, so that only Ru actually existed as an active metal. The content of Ru in the final prepared catalyst system is 0.9 wt%.

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

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

_{In- _ _ _} It was prepared by the in 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 the solution. Thereafter, 0.1 mmol of Ru(3) cluster was added to the solution, and then 5 mmol of Co(acet) ₂ ·4H ₂ O was added. The solution was stirred for 4 hours, centrifuged at 7000 rpm for 10 minutes, washed with methanol three times, and the obtained powder was dried in a vacuum oven at 100 ° C for 12 hours to obtain Ru (3) clusters 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 Ru metal was highly dispersed in a graphite support and Co nanoparticles were present was prepared.

Ru(3)/Co-ZIF-12 prepared in Preparation 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 was raised from room temperature to 1100 degrees at a rate of 5°C/min, carbonized at 1100°C for 3 hours, and then cooled to room temperature so that Ru metal was highly dispersed in the graphite support and Co nanoparticles were formed. The present Ru(3)Co/NC12-1100 was prepared.

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

Experimental example

Distilled water (35.38g) was added with glycerol, K ₂ CO ₃ , and, in some cases, KOH to the high-pressure reactor to have the concentrations in Tables 2 and 3, and then the catalyst (0.2g) prepared in Preparation Example was added. and filled with nitrogen to adjust the pressure to 26 bar. After raising the temperature of the reactor to the reaction temperature, the reaction was performed at a temperature of 180 °C or 220 °C for 12 hours. Thereafter, 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 simultaneous conversion reaction results 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-900 180 4 One 14.3 13.3 Experimental Example 4 Ru(3)/NC-900 180 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 active metal precursor was changed from the same metal. Although there is a slight difference in activity due to the difference in precursor, the activity is generally similar.

Experimental Example 3 and Experimental Example 4 are the results of using the same active metal precursor as Experimental Example 1 and Experimental Example 2, but using a single Ru metal that does not contain Co. Comparing the results of lactic acid when more Co is added to Ru, similar results are shown, but the yield of formic acid increases from 13.3% to 22.8% and from 11.0% to 25.1%.

Experimental Examples 5 and 6 are the experimental results at 220 ℃. Compared to the experimental results at 180 ° C (Experimental Examples 1 to 4), the yields of both lactic acid (LA) and formic acid (FA) tend to increase, but the yield of lactic acid increases more significantly than formic acid. can see.

Comparing the results of the experiment at 220 ° C, it can be seen that the yield of both lactic acid and formic acid increases when Ru and Co complex metals are used as active metals, but the yield of FA especially increases significantly.

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

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

The present invention has been described above with reference to the accompanying drawings, but this is only exemplary, and those skilled 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 claims below.

Claims (12)

In the catalyst composite for carbon dioxide conversion reaction,
The carbon dioxide conversion reaction is at least one of carbon dioxide and / or inorganic carbonate, glucose; mannose; galactose; xylose; sorbitol; mannitol; galactitol; xylitol; glycerol; 1,4-butanediol; 1,4-pentanediol; It is a reaction of one or a mixture thereof selected from butanol,
Catalyst composite for carbon dioxide conversion reaction, characterized in that at least one selected from noble metals and at least one selected from transition metals of Groups 3 to 12 excluding the noble metals are supported on a support as the active metal in the catalyst composite.
According to claim 1,
The noble metal is at least one selected from ruthenium (Ru), iridium (Ir), rhodium (Rh), platinum (Pt), palladium (Pd) and gold (Au) Catalyst complex for carbon dioxide conversion reaction.
According to claim 1,
As transition metals other than noble metals in the catalyst composite, zinc (Zn), nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), titanium (Ti), chromium (Cr), copper (Cu), A catalyst composite for carbon dioxide conversion reaction comprising at least one selected from zirconium (Zr), molybdenum (Mo) and hafmium (Hf).
According to claim 1,
The support may be a carbonaceous material; molecular sieve; ceramic materials; Catalyst composite for carbon dioxide conversion reaction, characterized in that at least one selected from metal oxides.
delete delete delete In the presence of the catalyst composite for carbon dioxide conversion reaction according to any one of claims 1 to 4,
at least one of carbon dioxide and/or inorganic carbonate, and glucose; mannose; galactose; xylose; sorbitol; mannitol; galactitol; xylitol; glycerol; 1,4-butanediol; 1,4-pentanediol; A process for producing formic acid by reacting one or a mixture thereof selected from butanol to produce formic acid.
According to claim 8,
The method for producing formic acid, characterized in that the temperature of the carbon dioxide conversion reaction is 180 to 240 ℃.
According to claim 9,
The inorganic carbonate is NaHCO ₃ Method for producing formic acid, characterized in that.
According to claim 8,
glucose; mannose; galactose; xylose; sorbitol; mannitol; galactitol; xylitol; glycerol; 1,4-butanediol; 1,4-pentanediol; A method for producing formic acid, which further comprises producing an inorganic carbonate by reacting carbon dioxide with at least one selected from among metals, metal salts, and ammonium salts before reacting one or a mixture thereof selected from butanol with the inorganic carbonate.
In the presence of the catalyst composite for carbon dioxide conversion reaction according to any one of claims 1 to 4,
at least one of carbon dioxide and/or inorganic carbonate, and glucose; mannose; galactose; xylose; sorbitol; mannitol; galactitol; xylitol; glycerol; 1,4-butanediol; 1,4-pentanediol; A method for producing a compound produced by dehydrogenation of a hydroxy group by reaction of one selected from butanol or a mixture thereof.