KR102573854B1 - Catalyst for preparing dicarboxylic acid aromatic heterocyclic compound, and mehtod for preparing dicarboxylic acid aromatic heterocyclic compound - Google Patents

Abstract

A heterogeneous catalyst for producing a dicarboxylic acid aromatic heterocyclic compound, comprising an active metal and a basic metal oxide support supporting the active metal and capable of forming a complex by coordination with the dicarboxylic acid aromatic heterocyclic compound , providing a heterogeneous catalyst.

Description

Catalyst for producing dicarboxylic acid aromatic heterocyclic compound and method for producing dicarboxylic acid aromatic heterocyclic compound

The present invention relates to a catalyst for producing a dicarboxylic acid aromatic heterocyclic compound and a method for producing a dicarboxylic acid aromatic heterocyclic compound.

In order to reduce greenhouse gases, developed countries such as the United States and Europe are strengthening carbon dioxide emission regulations. Therefore, there is an increasing demand for the biochemical industry that can reduce dependence on existing fossil raw material resources and reduce greenhouse gases. In other words, the chemical industry is changing from petroleum-dependent to bio-dependent.

For example, technology for replacing polyethylene terephthalate (PET), which is mainly used as a beverage bottle or food storage container, with bio-PET is being actively researched.

A dicarboxylic acid aromatic heterocyclic compound useful as a monomer in the production of bio-PET is a derivative usually prepared by oxidizing 5-hydroxymethyl furfural (HMF). Since the 5-hydroxymethylfurfural is obtained from sugar, it is a derivative of a raw material widely available in nature.

For reference, as shown in Scheme 1, the oxidation reaction for 5-HMF is 2,5-furandicarboxylic acid (FDCA) and 2-carboxy-5-formyl furan (5-formyl-2- Aromatic heterocyclic compounds of monocarboxylic acids or dicarboxylic acids including furoic acid (FFCA) can be obtained as main products.

[Scheme 1]

The oxidation process of HMF by which the aromatic heterocyclic compound of the above monocarboxylic acid or dicarboxylic acid can be obtained as a main product is known in the literature. For example, U.S. Pat. No. 4,977,283 (Hoechst) describes a process for oxidation of HMF by means of a metal catalyst belonging to the platinum group in an aqueous environment.

In addition, US Patent Publication No. 2008-0103318 (Battelle) describes an oxidation method of HMF promoted by platinum supported on a carrier.

However, the above HMF oxidation methods have high manufacturing costs and are carried out as a batch reaction. It requires time unrelated to the process, and there is a problem that the productivity of the reactor is lowered. In addition, in order to repeatedly use the catalyst, a separation process between the catalyst and the product is required, and there is a problem in that the activity of the catalyst is deteriorated prematurely due to a change in temperature or the like.

US Patent No. 4,977,283 (December 11, 1990) US Patent Publication No. 2008-0103318 (May 1, 2008)

In one embodiment, in the reaction of producing FDCA by oxidizing HMF, when a continuous process is applied, the final product, FDCA, can be maintained in a liquid phase until the reaction is finished, and the reaction rate can be improved to improve process efficiency. Catalyst can contribute to the production of H ₂ O ₂ or reduce side reactions such as conversion to CO or CO ₂ to improve the yield, and to dissolve FDCA in water in the purification process, which can be recycled for producing dicarboxylic acid aromatic heterocyclic compounds provide a catalyst.

Another embodiment provides a method for producing a dicarboxylic acid aromatic heterocyclic compound.

According to one embodiment, as a heterogeneous catalyst for producing a dicarboxylic acid aromatic heterocyclic compound, an active metal and the active metal are supported, and the dicarboxylic acid aromatic heterocyclic compound is coordinately bonded to form a complex. A heterogeneous catalyst comprising a basic metal oxide support is provided.

The active metal may include Fe, Ni, Ru, Rh, Pd, Os, Ir, Au, Pt, or combinations thereof.

The heterogeneous catalyst may include 0.1 wt% to 10 wt% of the active metal based on the total weight of the heterogeneous catalyst.

The heterogeneous catalyst may further include a catalyst promoter including Bi, Na, Cu, Ce, K, or a combination thereof.

The heterogeneous catalyst may include a shell containing the catalyst enhancer on the surface of the active metal.

The basic metal oxide capable of forming a complex by coordinately bonding with the dicarboxylic acid aromatic heterocyclic compound is BaO, Nd ₂ O ₃ , Cs ₂ O, CsX (X is OH, Cl, Br, or I), basic It may include zeolite, basic composite metal oxide, metal-organic frameworks (MOFs), hydrotalcite, hydroxyapatite, or a combination thereof.

The basic zeolite is a silica/alumina (SiO ₂ /Al ₂ O ₃ ) molar ratio of 20 to 1000 high silica beta or mordenite acid zeolite hydrogen is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Or it may be a zeolite substituted with an ion containing a combination thereof.

The basic composite metal oxide is Mg ₂ Al ₂ O ₄ , ZnAl ₂ O ₄ , BaTiO ₃ , ZnTiO ₃ , MgO-SiO ₂ , CaO-SiO ₂ , SrO-SiO ₂ , BaO-SiO ₂ , MgO-Al ₂ O ₃ , CaO-Al ₂ O ₃ , SrO-Al ₂ O ₃ , BaO-Al ₂ O ₃ , MgO-TiO ₂ , CaO-TiO 2 , SrO-TiO ₂ , BaO-TiO _{2 ,} MgO-ZnO, CaO-ZnO, SrO-ZnO, BaO-ZnO, or a combination thereof.

The metal-organic framework may include Zr-based MOFs, Mg-based MOFs, Ca-based MOFs, Sr-based MOFs, Ba-based MOFs, or combinations thereof.

The hydrotalcite is [Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) 4H ₂ O], [Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) 4H ₂ O], [Mg ₄ Zn ₂ Al ₂ (OH) ₁₆ (CO ₃ ) 4H ₂ O], [Ca ₄ Al ₂ (OH) ₁₂ (NO ₃ ) ₂ xH ₂ O], [Ca ₆ Al ₂ (OH) ₁₆ (NO ₃ ) ₂ xH ₂ O], [Ca ₄ Zn ₂ Al ₂ (OH) ₁₆ (CO ₃ )·4H ₂ O], or a combination thereof.

The heterogeneous catalyst may produce a dicarboxylic acid aromatic heterocyclic compound represented by the following Chemical Formula 6 by oxidizing an aromatic heterocyclic compound represented by the following Chemical Formula 2 in a polar solvent.

[Formula 2]

[Formula 6]

According to another embodiment, a step of preparing a dicarboxylic acid aromatic heterocyclic compound by oxidizing a raw material of an aromatic heterocyclic compound in a polar solvent in the presence of a heterogeneous catalyst, wherein the heterogeneous catalyst reacts with an active metal and the active metal It provides a method for producing a dicarboxylic acid aromatic heterocyclic compound, including a basic metal oxide support capable of forming a complex by coordinating with the dicarboxylic acid aromatic heterocyclic compound.

The aromatic heterocyclic compound raw material may be represented by Formula 1 below.

[Formula 1]

In Formula 1, one of R ¹ and R ² is an aldehyde group, and the other is a hydrogen group, a hydroxyl group, an aldehyde group, an acetoxy group, a halogen group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or an unsubstituted C ₁ -C ₂₀ alkoxy group.

The raw material for the aromatic heterocyclic compound represented by Chemical Formula 1 includes a compound represented by Chemical Formula 2, a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5, or a combination thereof. can do.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

The dicarboxylic acid aromatic heterocyclic compound may be 2,5-furandicarboxylic acid (FDCA) represented by Formula 6 below.

[Formula 6]

In the reaction of preparing FDCA by oxidizing HMF, the catalyst for producing a dicarboxylic acid aromatic heterocyclic compound according to an embodiment maintains the final product FDCA in a liquid phase until the reaction is completed when a continuous process is applied, and increases the reaction rate It is possible to improve the process efficiency by improving the catalyst, and the yield can be improved by reducing side reactions such as the catalyst contributing to the production of H ₂ O ₂ or conversion to CO or CO ₂ , and recycling to dissolve FDCA in water in the purification process. It can be.

Advantages and features of the techniques described hereinafter, and methods of achieving them, will become clear with reference to the implementations described below in detail. However, the implemented form may be not limited to the embodiments disclosed below. Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used with meanings commonly understood by those skilled in the art. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined. When it is said that a certain part "includes" a component throughout the specification, this means that it may further include other components, not excluding other components unless otherwise stated. In addition, singular forms also include plural forms unless specifically stated otherwise in a phrase.

As used herein, unless otherwise specified, the term "alkyl" refers to a saturated monovalent aliphatic hydrocarbon radical, including straight and branched chains, having the specified number of carbon atoms. Alkyl groups typically contain from 1 to 20 carbon atoms (“C ₁ -C ₂₀ alkyl”), specifically from 1 to 12 carbon atoms (“C 1 -C 12 alkyl”), more specifically from 1 to 12 carbon atoms (“C ₁ -C ₁₂ alkyl”). 8 carbon atoms ("C ₁ -C ₈ alkyl"), or 1 to 6 carbon atoms ("C ₁ -C ₆ alkyl"), or 1 to 4 carbon atoms ("C ₁ -C ₄ alkyl" ) contains Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and the like. include Alkyl groups may be substituted or unsubstituted. In particular, unless otherwise specified, an alkyl group may be substituted with one or more halogens, up to the total number of hydrogen atoms present on the alkyl moiety. Thus, C ₁ -C ₄ alkyl is a halogenated alkyl group, for example a fluorinated alkyl group having 1 to 4 carbon atoms, such as trifluoromethyl (—CF ₃ ) or difluoroethyl (—CH ₂ CHF ₂ ).

As used herein, unless otherwise specified, the term "alkoxy" refers to a monovalent -O-alkyl group in which the alkyl moiety has the specified number of carbon atoms. Alkoxy groups typically contain 1 to 8 carbon atoms (“C ₁ -C ₈ alkoxy”), or 1 to 6 carbon atoms (“C ₁ -C ₆ alkoxy”), or 1 to 4 carbon atoms ( “C ₁ -C ₄ alkoxy”). For example, C ₁ -C ₄ alkoxy is methoxy (-OCH ₃ ), ethoxy (-OCH ₂ CH ₃ ), isopropoxy (-OCH(CH ₃ ) ₂ ), tert-butyloxy (-OC( CH ₃ ) ₃ ) and the like. The alkoxy group is unsubstituted or substituted on the alkyl moiety by the same groups described herein as suitable for alkyl. In particular, an alkoxy group may be optionally substituted with one or more halo atoms, in particular one or more fluoro atoms, up to the total number of hydrogen atoms present on the alkyl moiety. Such groups are referred to as “haloalkoxy” having the specified number of carbon atoms and substituted with one or more halo substituents, for example when fluorinated, more specifically “fluoroalkoxy” groups, typically such groups contain from 1 to 6 carbon atoms. atoms, specifically 1 to 4 carbon atoms, often 1 or 2 carbon atoms, and 1, 2 or 3 halo atoms (ie, "C ₁ -C ₆ haloalkoxy", " C ₁ -C ₄ haloalkoxy” or “C ₁ -C ₂ haloalkoxy”). More specifically, a fluorinated alkyl group is typically a fluoroalkoxy group substituted with 1, 2 or 3 fluoro atoms, such as C ₁ -C ₆ , C ₁ -C ₄ or C ₁ -C ₂ fluoroalkoxy. It can be specifically referred to as a group. Thus, C ₁ -C ₄ fluoroalkoxy is trifluoromethyloxy (-OCF ₃ ), difluoromethyloxy (-OCF ₂ H), fluoromethyloxy (-OCFH ₂ ), difluoroethyloxy ( -OCH ₂ CF ₂ H) and the like.

As used herein, the term "aromatic" or "aryl", unless otherwise specified, refers to an optionally substituted monocyclic or fused bicyclic or polycyclic ring system having the well-known character of aromaticity, wherein one or more The rings contain fully conjugated pi-electron systems. Typically, an aryl group has 6 to 20 carbon atoms ("C ₆ -C ₂₀ aryl") as a ring member, specifically 6 to 14 carbon atoms ("C ₆ -C ₁₄ aryl"), more specifically has 6 to 12 carbon atoms ("C ₆ -C ₁₂ aryl"). A fused aryl group can include an aryl ring (eg, a phenyl ring) fused to another aryl or heteroaryl ring or fused to a saturated or partially unsaturated carbocyclic or heterocyclic ring, provided that the base molecule on such a fused ring system is The point of attachment for is an atom of the aromatic portion of the ring system. For example, aryl groups include phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, indenyl or tetrahydronaphthyl. Aryl groups are unsubstituted or substituted as further described herein.

As used herein, unless otherwise specified, the term "aromatic heterocycle" or "heteroaryl" contains the specified number of ring atoms as a ring member in an aromatic ring and includes one or more heteroatoms selected from N, O and S. refers to monocyclic or fused bicyclic or polycyclic ring systems with the well-known character of aromaticity. The inclusion of heteroatoms allows for directionality in the 5- and 6-membered rings. Typically, a heteroaryl group has 5 to 20 ring atoms ("5- to 20-membered heteroaryl"), specifically 5 to 14 ring atoms ("5- to 14-membered heteroaryl"), more specifically has 5-12 membered ring atoms ("5-12 membered heteroaryl"). The heteroaryl ring is attached to the base molecule through a ring atom of the heteroaromatic ring such that the aromaticity is maintained. Thus, a 6-membered heteroaryl ring may be attached to the base molecule through a ring C atom, whereas a 5-membered heteroaryl ring may be attached to the base molecule through a ring C or N atom. Heteroaryl groups may also be fused to other aryl or heteroaryl rings, or fused to saturated or partially unsaturated carbocyclic or heterocyclic rings, wherein the point of attachment to the base molecule on such a fused ring system is at the heteroaromatic portion of the ring system. It is an atom. For example, unsubstituted heteroaryl groups include pyrrole, furan, thiophene, pyrazole, imidazole, isoxazole, oxazole, isothiazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazole. , pyridine, pyridazine, pyrimidine, pyridine, benzofuran, benzothiophene, indole, benzimidazole, indazole, quinoline, isoquinoline, purine, triazine, naphthyridine or carbazole. In various embodiments, the 5- or 6-membered heteroaryl group is pyrrolyl, furanyl, thiophenyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, triazolyl, pyridinyl and It is selected from the group consisting of pyrimidinyl, pyrazinyl or pyridazinyl rings. Heteroaryl groups are substituted or unsubstituted as further described herein.

As used herein, the term "halo" or "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), unless otherwise specified.

As used herein, the terms "optionally substituted" and "substituted or unsubstituted" mean that a particular group being described may have no non-hydrogen substituents (i.e., is unsubstituted), or that the group may have one or more non- They are used interchangeably to indicate that they may have hydrogen substituents (ie, substituted). Unless otherwise specified, the total number of substituents that may be present equals the number of H atoms present on the unsubstituted form of the described group. When an optional substituent is attached through a double bond (eg, an oxo (=0) substituent), the group occupies the available valency and the total number of other substituents included is reduced by two. When optional substituents are independently selected from a list of alternatives, the selected groups are the same or different. Throughout this specification, it will be understood that the number and nature of optional substituents will be limited to such extent that such substitutions satisfy chemical sense.

Suitable optional substituents for the alkyl, alkoxy, aryl, heteroaryl and heterocyclyl rings include, but are not limited to, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3-12 membered heterocyclyl, C ₆ -C ₁₂ aryl and 5-12 membered heteroaryl, halo, =O(oxo), =S(thiono), =N-CN, =N -OR ^x , =NR ^x , -CN, -C(O)R ^x , -CO ₂ R ^x , -C(O)NR ^x R ^y , -SR ^x , -SOR ^x , -SO ₂ R ^x , - SO ₂ NR ^x R ^y , -NO ₂ , -NR ^x R ^y , -NR ^x C(O)R ^y , -NR ^x C(O)NR ^x R ^y , -NR ^x C(O)OR ^x , - NR ^x SO ₂ R ^y , -NR ^x SO ₂ NR ^x R ^y , -OR ^x , -OC(O)R ^x and -OC(O)NR ^x R ^y , wherein each R ^x and R ^y is hydrogen (H), C ₁ -C ₈ alkyl, C ₁ -C ₈ acyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3 to 12 membered independently heterocyclyl, C ₆ -C ₁₂ aryl or 5-12 membered heteroaryl, or R ^x and R ^y together with the N atom to which they are attached represent a 3-12 membered heterocyclyl or 5-12 membered heteroaryl ring , each optionally containing 1, 2 or 3 additional heteroatoms selected from O, N and S(O) _q , where q is 0 to 2; Each of R ^x and R ^y is halo, =O, =S, =N-CN, =N-OR', =NR', -CN, -C(O)R', -CO ₂ R', -C (O)NR' ₂ , -SOR', -SO ₂ R', -SO ₂ NR' ₂ , -NO ₂ , -NR' ₂ , -NR'C(O)R', -NR'C(O) NR' ₂ , -NR'C(O)OR', -NR'SO ₂ R', -NR'SO ₂ NR' ₂ , -OR', -OC(O)R' and -OC(O)NR' optionally substituted with 1 to 3 substituents independently selected from the group consisting of ₂ , wherein each R' is independently hydrogen (H), C ₁ -C ₈ alkyl, C ₁ -C ₈ acyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3-12 membered heterocyclyl, C ₆ -C ₁₂ aryl or C ₅ -C ₁₂ heteroaryl; each of the above C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, 3-12 membered heterocyclyl, C ₆ -C ₁₂ aryl and A 5-12 membered heteroaryl may be optionally substituted as further defined herein.

In this specification, "metal precursor" is a concept that refers to a chemical substance prepared in advance to react a metal. For example, a “transition metal precursor” is a concept that refers to a chemical substance prepared in advance to react a transition metal.

A heterogeneous catalyst for producing a dicarboxylic acid aromatic heterocyclic compound according to an embodiment includes an active metal and a basic metal oxide support supporting the active metal.

The heterogeneous catalyst generates a dicarboxylic acid aromatic heterocyclic compound by an oxidation reaction of an aromatic heterocyclic compound raw material represented by the following formula (1).

[Formula 1]

The aromatic heterocyclic compound raw material represented by Chemical Formula 1 is a compound converted from wood, and is a compound that is first used in the production of dicarboxylic acid aromatic heterocyclic compounds. For example, the aromatic heterocyclic ring may be at least one selected from the group consisting of furan, thiophene, and pyrrole.

In Formula 1, one of R ¹ and R ² is an aldehyde group, and the other is a hydrogen group, a hydroxyl group, an aldehyde group, an acetoxy group, a halogen group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted Or it may be an unsubstituted C ₁ -C ₂₀ alkoxy group. That is, in Formula 1, when R ¹ is an aldehyde, R ² is a hydrogen group, a hydroxyl group, an aldehyde group, an acetoxy group, a halogen group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or unsubstituted It may be a C ₁ -C ₂₀ alkoxy group. Also, for example, a C ₁ -C ₂₀ alkyl group or a C ₁ -C ₂₀ alkoxy group may be unsubstituted or substituted with one or more halogen atoms.

Specifically, the aromatic heterocyclic compound raw material may include compounds represented by Formulas 2 to 5 below, or a combination thereof.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

More specifically, the heterogeneous catalyst oxidizes 5-hydroxymethyl furfural (HMF) represented by Chemical Formula 2, for example, through the same route as in Reaction Scheme 1, represented by Chemical Formula 6 below. 2,5-furandicarboxylic acid (FDCA) can be produced.

[Formula 6]

To this end, the heterogeneous catalyst includes an active metal and a basic metal oxide support supporting the active metal.

The active metal is a component supported on the basic metal oxide carrier and having an activity contributing to an improvement in product yield when the dicarboxylic acid aromatic heterocyclic compound is prepared from the aromatic heterocyclic compound raw material.

The active metal may include Fe, Ni, Ru, Rh, Pd, Os, Ir, Au, Pt, or a combination thereof, which may have various oxidation numbers, and for example, Ru, Pd, Pt, or Au can include

The heterogeneous catalyst may include 0.1 wt% to 10 wt% of the active metal, for example, 0.1 wt% to 5 wt%, based on the total weight of the heterogeneous catalyst. If the content of the active metal is less than 0.1% by weight, the oxidation reaction may not proceed, and if it exceeds 10% by weight, there may be economic loss due to the unnecessary amount because it is more than the amount required for the reaction in the continuous process reaction, The active metal may not be uniformly deposited on the carrier and may be aggregated with each other.

The heterogeneous catalyst may further include a catalyst promoter including Bi, Na, Cu, Ce, K, or a combination thereof together with the active metal. The catalyst promoter may be supported on the basic metal oxide carrier together with the active metal. In addition, the heterogeneous catalyst may include a shell containing the catalyst enhancer on the surface of the active metal. A shell containing the catalyst enhancer may also be placed on the basic metal oxide support.

The catalyst enhancer promotes the separation of carbon monoxide (CO) or carbon dioxide (CO ₂ ) on the surface of the heterogeneous catalyst, thereby preventing the activity of the heterogeneous catalyst from being lowered. In addition, the catalyst enhancer may have a limited effect on the particle size of the active metal, but can greatly increase the amount of adsorbed hydrogen, nitrogen, and ammonia. In particular, in the case of K, hydrogen, nitrogen, In addition to improving the adsorption characteristics of ammonia, etc., the adsorption strength of nitrogen and ammonia may be weakened.

The heterogeneous catalyst may include 0.1 wt% to 6 wt% of the catalyst enhancer based on the total weight of the heterogeneous catalyst. When the content of the catalyst enhancer is less than 0.1% by weight, the effect of preventing deterioration of the activity of the heterogeneous catalyst by promoting the separation of carbon monoxide (CO) or carbon dioxide (CO ₂ ) on the surface of the heterogeneous catalyst may be insignificant, and 6% by weight If it exceeds , the content of the active metal may decrease and the catalytic activity may decrease.

The basic metal oxide support includes a basic metal oxide capable of forming a complex through coordination with the dicarboxylic acid aromatic heterocyclic compound.

For example, the dicarboxylic acid aromatic compound may be prepared by oxidizing the aromatic heterocyclic compound raw material in a polar solvent in the presence of the heterogeneous catalyst, and the produced dicarboxylic acid aromatic heterocyclic compound is a white powder. , it must exist in a liquid phase during the reaction so that it does not precipitate in the reactor. At this time, the basic metal oxide coordinates with the dicarboxylic acid aromatic heterocyclic compound to maintain the final product in a liquid phase until the reaction is completed.

For example, the basic metal oxide maintains a reaction product including the aromatic heterocyclic compound raw material and a polar solvent in a basic pH of 6 to pH 8, so that the dicarboxylic acid aromatic heterocyclic compound is in the form of a salt. It can be maintained and maintained in a liquid state unless treated with an acid.

Scheme 2 below is a state structural formula representing metal salts of FDCA, wherein M ₁ (when the metal is divalent) or M ₂ (when the metal is trivalent), which is the metal of the basic metal oxide, is It is shown that the FDCA can be maintained in a liquid phase by coordinating with FDCA, which is an example of a levonic acid aromatic heterocyclic compound.

[Scheme 2]

In addition, when the active metal is supported on a carbon carrier as in the prior art, it undergoes oxidative loss during the oxidation reaction, resulting in loss of the carrier. Specifically, the carbon carrier may contribute to the generation of H ₂ O ₂ or be converted into CO or CO ₂ during an oxidation reaction. On the other hand, in the case of using the basic metal oxide, the yield may be improved by reducing the above side reactions.

In addition, when preparing the dicarboxylic acid aromatic compound, the reaction product may partially include 5-formyl-2-furoic acid (FFCA). In order to remove this, after dissolving the reaction product in water, the FFCA is removed by breaking the double bond of the furan ring through a hydrogenation reaction (hydrogenation reaction) to dissolve in water as a solvent, and then insoluble in water It goes through a purification process to obtain FDCA that does not In addition, it is necessary to dissolve the reaction product in water in order to filter Pd/C leaked from the batch reaction, and the basic metal oxide may serve to dissolve the dicarboxylic acid aromatic compound in water.

The basic metal oxide capable of forming a complex by coordinately bonding with the dicarboxylic acid aromatic heterocyclic compound is BaO, Nd ₂ O ₃ , Cs ₂ O, CsX (X is OH, Cl, Br, or I), basic It may include zeolite, basic composite metal oxide, metal-organic frameworks (MOFs), hydrotalcite, hydroxyapatite, or a combination thereof.

On the other hand, in the case of Mg oxide, it is difficult to mold into a spherical or granule type, and there is a problem that it is easily broken even after molding. Because of this, Mg oxide is difficult to utilize as a catalyst carrier in a continuous process.

For example, in the basic zeolite, the hydrogen of a high silica beta or mordenite acidic zeolite having a silica/alumina (SiO ₂ /Al ₂ O ₃ ) molar ratio of 20 to 1000 is Na, K, Rb, Cs, Mg, Ca, Sr , Ba, or a zeolite substituted with an ion containing a combination thereof.

For example, the basic composite metal oxide is Mg ₂ Al ₂ O ₄ , ZnAl ₂ O ₄ , BaTiO ₃ , ZnTiO ₃ , MgO-SiO ₂ , CaO-SiO ₂ , SrO-SiO ₂ , BaO-SiO ₂ , MgO-Al ₂ O ₃ , CaO-Al ₂ O ₃ , SrO-Al ₂ O ₃ , BaO-Al ₂ O ₃ , MgO-TiO ₂ , CaO-TiO ₂ , SrO-TiO ₂ , BaO-TiO ₂ , MgO-ZnO, CaO -ZnO, SrO-ZnO, BaO-ZnO, or combinations thereof.

The basic metal such as Na, Mg, or Ca reacts with some carriers at a high temperature to partially form a spinel structure. This allows the catalyst to have excellent durability and high catalytic activity for coke formation, thereby increasing reactivity and stability. In general, alumina has the properties of a Lewis acid, and this acidic property is a factor that increases coke formation during the reaction. Therefore, coke production can be suppressed by changing the acidic nature of the carrier to basic to have a spinel structure.

For example, the metal-organic framework may include Zr-based MOFs, Mg-based MOFs, Ca-based MOFs, Sr-based MOFs, Ba-based MOFs, or combinations thereof.

For example, the hydrotalcite is [Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) 4H ₂ O], [Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) 4H ₂ O], [Mg ₄ Zn ₂ Al ₂ (OH) ₁₆ (CO ₃ ) 4H ₂ O], [Ca ₄ Al ₂ (OH) ₁₂ (NO ₃ ) ₂ xH ₂ O], [Ca ₆ Al ₂ (OH) ₁₆ (NO ₃ ) ₂ ·xH ₂ O], [Ca ₄ Zn ₂ Al ₂ (OH) ₁₆ (CO ₃ )·4H ₂ O], or a combination thereof.

The amount of the heterogeneous catalyst used is not particularly limited, but may be used in an amount of 600 moles or less, or 50 to 600 moles based on the active metal in the catalyst, based on 1 mole of the aromatic heterocyclic compound raw material represented by Formula 1, for example. .

The heterogeneous catalyst may be prepared by supporting the active metal on the basic metal oxide carrier. For example, the method of supporting the active metal on the basic metal oxide carrier may be prepared by impregnating the basic metal oxide carrier in a solution containing the active metal precursor and then selectively calcining it.

Specifically, the active metal precursor is dissolved in a solvent to prepare a solution containing the active metal precursor, and the basic metal oxide carrier is impregnated therein. The solvent may include water, alcohol, or a combination thereof.

The active metal precursor is, for example, when the active metal is ruthenium, dimethyl ruthenium, diethyl ruthenium, ruthenium acetate, ruthenium acetate dihydrate, ruthenium acetylacetonate, ruthenium acetylacetonate hydrate, ruthenium iodide, ruthenium bromide, Ruthenium chloride, ruthenium fluoride, ruthenium fluoride tetrahydrate, ruthenium carbonate, ruthenium cyanide, ruthenium nitrate, ruthenium nitrate hexahydrate, ruthenium oxide, ruthenium peroxide, ruthenium perchlorate, ruthenium perchlorate hexahydrate, ruthenium sulfate, diphenyl It may be at least one selected from the group consisting of ruthenium, ruthenium naphthalate, ruthenium oleate and ruthenium stearate. In addition, the same can be applied to the case where the active metal is not ruthenium.

The impregnation may be performed at 40 °C to 80 °C, and the pressure may be maintained at normal pressure. Thereafter, the impregnated material may be optionally calcined at 40 °C to 800 °C, or 100 °C to 600 °C. At this time, the pressure may be maintained as it is.

A method for producing a dicarboxylic acid aromatic heterocyclic compound according to another embodiment includes preparing a dicarboxylic acid aromatic heterocyclic compound by subjecting an aromatic heterocyclic compound raw material to an oxidation reaction in a polar solvent in the presence of the heterogeneous catalyst.

The aromatic heterocyclic compound raw material may be an aromatic heterocyclic compound represented by Chemical Formula 1, and may include, for example, compounds represented by Chemical Formulas 2 to 5, or a combination thereof. Since the raw materials are as described above, repetitive descriptions are omitted.

The temperature of the oxidation reaction may be 80 °C to 200 °C, the pressure may be normal pressure conditions, and may be carried out for 2 hours to 10 hours.

A known polar solvent may be used as the polar solvent, and for example, dimethyl sulfoxide, ethanol, or acetonitrile may be used. The polar solvent may be used in an amount of 10 parts by weight to 100 parts by weight based on 100 parts by weight of the aromatic heterocyclic compound raw material, but the present invention is not limited thereto.

A reaction product obtained through the step of preparing the dicarboxylic acid aromatic heterocyclic compound may be a crude composition including the aromatic heterocyclic compound raw material and the dicarboxylic acid aromatic heterocyclic compound.

For example, the target compound as the dicarboxylic acid aromatic heterocyclic compound may be 2,5-furandicarboxylic acid (FDCA) represented by Formula 6 below.

[Formula 6]

In this case, the reaction product may inevitably include a raw material for an aromatic heterocyclic compound represented by Chemical Formula 1 (eg, a compound represented by Chemical Formulas 2 to 5).

That is, the above reaction is an oxidation reaction in the presence of a heterogeneous catalyst using the above-mentioned raw materials, and the oxide of an aromatic heterocyclic compound obtained from these reactions (hereinafter referred to as a dicarboxylic acid aromatic heterocyclic compound or reaction product) is unsaturated contained in the backbone. The group is oxidized, and as shown in Reaction Scheme 1, it may mainly include 2,5-furandicarboxylic acid (FDCA), 2-carboxy-5-formyl furan (FFCA) or levulinic acid. there is.

Since these products generally have higher melting points than the aromatic heterocyclic compound raw materials, they are difficult to take out from the reactor in a molten state and require post-processing such as purification or crystallization. For example, the 2-carboxy-5-formyl furan dissolves the reaction product in water, and the FFCA breaks the double bond of the furan ring through a hydrogenation reaction (hydrogenation reaction) Dissolving in water as a solvent It can be removed and subjected to a purification process to obtain water-insoluble FDCA.

Thereafter, the reaction product is titrated with an acid such as HCl, washed with water (DIW), and recrystallized to obtain a purified dicarboxylic acid aromatic heterocyclic compound.

Hereinafter, specific embodiments of the invention are presented. However, the embodiments described below are only intended to specifically illustrate or explain the invention, and the scope of the invention should not be limited thereto.

[Production Example: Preparation of Heterogeneous Catalyst]

(Preparation Example 1: Preparation of 5% Ru/BaO)

As active metal components, Ru precursor (RuCl ₃ 3H ₂ O) and BaO were stirred for 12 hours under N ₂ atmosphere, NaNH ₄ was dropped at 10 times the level of the Ru precursor and stirred at 500 rpm. A 5% Ru/BaO catalyst was obtained by reacting for 24 hours at room temperature in an N ₂ atmosphere.

(Preparation Example 2: 5% Ru/Nd ₂ O ₃ manufacturing)

As active metal components, Ru precursor (RuCl ₃ 3H ₂ O) and Nd ₂ O ₃ were stirred for 12 hours under N ₂ atmosphere, and NaNH ₄ was dropped therein at 10 times the level of the Ru precursor at a speed of 500 rpm. was stirred for 24 hours at room temperature in a N ₂ atmosphere to obtain a 5% Ru/Nd ₂ O ₃ catalyst.

(Preparation Example 3: Preparation of 5% Ru/Basic Zeolite)

As an active metal component, a Ru precursor (RuCl ₃ 3H ₂ O) and a basic zeolite (a zeolite in which hydrogen of a high silica beta acid zeolite is replaced with Mg ions) were stirred for 12 hours under a N ₂ atmosphere, and NaNH ₄ was added thereto. A 10-fold level of the Ru precursor was dropped and stirred at 500 rpm for 24 hours at room temperature in an N ₂ atmosphere to obtain a 5% Ru/basic zeolite catalyst.

(Preparation Example 4: Preparation of 5% Ru/Basic Zeolite Containing a Bi Shell)

A Ru precursor (RuCl ₃ 3H ₂ O) as an active metal component, a precursor of Bi (Bi(NO ₃ ) ₃ 5H ₂ O) as a catalyst enhancer, and a basic zeolite (hydrogen of high silica beta acidic zeolite converts to Mg ions). substituted zeolite) was stirred for 12 hours under an N ₂ atmosphere, where NaNH ₄ was dropped at 10 times the level of the Ru precursor and stirred at 500 rpm for 24 hours at room temperature in a N ₂ atmosphere to form a Bi shell. A 5% Ru/basic zeolite catalyst containing

After adding magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ 6H ₂ O) (Junsei), the mixture was stirred at 200 rpm for 1 hour. Subsequently, the stirred Bi(NO ₃ ) ₃ .5H ₂ O solution was adjusted to pH 11 using ammonia water, and the co-precipitated mixture was stirred at 200 rpm for 1 hour to prepare a uniform mixed solution. Then, for the hydrothermal process, the prepared mixed solution was put into a hydrothermal synthesizer and synthesized at 200 °C and 300 rpm for about 15 hours to obtain a precipitate.

(Comparative Preparation Example 1: 5% Ru/C Preparation)

A 5% Ru/C catalyst was obtained by reacting a Ru precursor (RuCl ₃ .3H ₂ O) and water-dispersed carbon as an active metal component under the same conditions as in Example 1.

[Example: Oxidation reaction experiment]

(Examples 1 to 4)

1.5 kg of the heterogeneous catalyst prepared in Preparation Examples 1 to 4 was packed in a column made of SUS material having a diameter of 20 cm and a height of 100 cm as a reactor. After filling, the reactor temperature was maintained in vacuum at 150 °C to remove adsorbed impurities.

As a raw material, 5-hydroxymethyl furfural (HMF) represented by Formula 2 was prepared by converting it from sugars, and it was dissolved in acetonitrile as a polar solvent at a concentration of 1% by weight to store raw materials. filled with 5 liters. After filling, it was pressurized to 3 bar with oxygen gas.

The raw material was transferred to a column and contacted with a catalyst in the column to obtain a crude composition containing an oxide.

(Comparative Example 1: Oxidation reaction experiment)

In Example 1, an oxidation reaction experiment was conducted in the same manner as in Example 1, except that the heterogeneous catalyst prepared in Comparative Preparation Example 1 was used as the heterogeneous catalyst.

[Experimental Example: Oxidation Reaction Evaluation]

Through component analysis of the crude composition prepared in Examples 1 to 4 and Comparative Example 1, the yield (%) of FDCA for each reaction time was measured, and the results are shown in Table 1 below. Table 1 shows the FDCA yield (%) according to the type of catalyst.

division catalyst type Response time (h) 3 4 5 6 Example 1 5% Ru/BaO 45.00% 50.00% 54.50% 60.50% Example 2 5% Ru/Nd ₂ O ₃ 35.50% 40.00% 45.00% 55.00% Example 3 5% Ru/basic zeolite 65.00% 69.00% 72.00% 73.00% Example 4 5% Ru/basic zeolite with Bi shell 90.00% 93.00% 95.00% 95.00% Comparative Example 1 5% Ru/C 0.14% 0.56% 0.90% 1.50%

Referring to Table 1, it can be seen that the yield of the reaction is remarkably low when Ru/C is used for FDCA synthesis. This is because crystallized FDCA precipitates on the catalyst layer inside the continuous reactor and adheres to the catalyst, Ru/C. As a result, the internal pressure of the reactor is significantly increased, and the yield is significantly lowered because FDCA in powder form does not escape out of the reactor.

However, when a basic metal oxide support is used, FDCA can be obtained in a liquid form without crystallization because it coordinates with FDCA to maintain a basic state of pH 6 or higher. The obtained FDCA liquid phase can be adjusted to pH 3 or less through acid titration to obtain a crystallized powder.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also made according to the present invention. falls within the scope of the rights of

Claims (16)

As a heterogeneous catalyst for producing a dicarboxylic acid aromatic heterocyclic compound,
active metal, and
A basic metal oxide support supporting the active metal and capable of forming a complex by coordinating with the dicarboxylic acid aromatic heterocyclic compound,
The basic metal oxide capable of forming a complex by coordinately bonding with the dicarboxylic acid aromatic heterocyclic compound is BaO, Nd ₂ O ₃ , Cs ₂ O, CsX (X is OH, Cl, Br, or I), basic Including zeolites, metal-organic frameworks (MOFs), or combinations thereof,
The basic zeolite is a silica/alumina (SiO ₂ /Al ₂ O ₃ ) molar ratio of 20 to 1000 high silica beta or mordenite acid zeolite hydrogen is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Or a zeolite substituted with an ion containing a combination thereof,
The metal-organic framework includes Zr-based MOFs, Mg-based MOFs, Ca-based MOFs, Sr-based MOFs, Ba-based MOFs, or a combination thereof. In paragraph 1,
wherein the active metal comprises Fe, Ni, Ru, Rh, Pd, Os, Ir, Au, Pt, or a combination thereof. In paragraph 1,
The heterogeneous catalyst comprises 0.1% to 10% by weight of the active metal based on the total weight of the heterogeneous catalyst. In paragraph 1,
The heterogeneous catalyst further comprises a catalyst promoter comprising Bi, Na, Cu, Ce, K, or a combination thereof. In paragraph 4,
wherein the heterogeneous catalyst comprises a shell comprising the catalyst promoter on the active metal surface. delete delete delete delete delete In paragraph 1,
The heterogeneous catalyst is a heterogeneous catalyst for producing a dicarboxylic acid aromatic heterocyclic compound represented by the following formula (6) by oxidizing an aromatic heterocyclic compound represented by the following formula (2) in a polar solvent:
[Formula 2]

[Formula 6]
A step of preparing a dicarboxylic acid aromatic heterocyclic compound by oxidizing a raw material for an aromatic heterocyclic compound in a polar solvent in the presence of a heterogeneous catalyst;
The heterogeneous catalyst includes an active metal and a basic metal oxide support supporting the active metal and capable of forming a complex by coordinately bonding with the dicarboxylic acid aromatic heterocyclic compound,
The basic metal oxide capable of forming a complex by coordinately bonding with the dicarboxylic acid aromatic heterocyclic compound is BaO, Nd ₂ O ₃ , Cs ₂ O, CsX (X is OH, Cl, Br, or I), basic Including zeolites, metal-organic frameworks (MOFs), or combinations thereof,
The basic zeolite is a silica/alumina (SiO ₂ /Al ₂ O ₃ ) molar ratio of 20 to 1000 high silica beta or mordenite acid zeolite hydrogen is Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Or a zeolite substituted with an ion containing a combination thereof,
Wherein the metal-organic framework comprises Zr-based MOFs, Mg-based MOFs, Ca-based MOFs, Sr-based MOFs, Ba-based MOFs, or a combination thereof. In paragraph 12,
The aromatic heterocyclic compound raw material is a method for producing a dicarboxylic acid aromatic heterocyclic compound represented by the following formula (1):
[Formula 1]

In Formula 1, one of R ¹ and R ² is an aldehyde group, and the other is a hydrogen group, a hydroxyl group, an aldehyde group, an acetoxy group, a halogen group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted or an unsubstituted C ₁ -C ₂₀ alkoxy group. In paragraph 13,
The raw material for the aromatic heterocyclic compound represented by Chemical Formula 1 includes a compound represented by Chemical Formula 2, a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, a compound represented by Chemical Formula 5, or a combination thereof. Method for producing a dicarboxylic acid aromatic heterocyclic compound:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]
In paragraph 12,
The dicarboxylic acid aromatic heterocyclic compound is 2,5-furandicarboxylic acid (FDCA) represented by the following formula (6), a method for producing a dicarboxylic acid aromatic heterocyclic compound.
[Formula 6]
As a heterogeneous catalyst for producing a dicarboxylic acid aromatic heterocyclic compound,
active metal, and
A basic metal oxide support supporting the active metal and capable of forming a complex by coordinating with the dicarboxylic acid aromatic heterocyclic compound,
The heterogeneous catalyst further comprises a catalyst promoter comprising Bi, Na, Cu, Ce, K, or a combination thereof, and the heterogeneous catalyst comprises a shell containing the catalyst promoter on the surface of the active metal. , a heterogeneous catalyst.