CATALYST FOR MAKING DICARBOXYL ACID AROMATIC HETEROCYCLIC COMPOUND, AND METHOD FOR PREPARING DICARBOXYL ACID AROMATIC HETEROCYCLIC COMPOUND

Abstract

The present invention relates to a heterogeneous catalyst for making a dicarboxyl acid aromatic heterocyclic compound and a method for preparing a dicarboxyl acid aromatic heterocyclic compound, and according to the present invention, an oxide with improved yield and purity can be produced by an oxidation reaction of a bio-based aromatic heterocyclic compound under a heterogeneous catalyst.

Claims

1. A heterogeneous catalyst, comprising a catalyst for preparing dicarboxyl acid aromatic heterocyclic compound, wherein a structure in which cations of a metal catalyst component are bonded to a porous central metal-organic framework material.

2. The heterogeneous catalyst of claim 1, wherein the metal catalyst component is one or more selected from Fe, Ni, Ru, Rh, Pd, Os, Ir, Au, and Pt.

3. The heterogeneous catalyst of claim 1, wherein the porous central metal is one or more types selected from a skeleton support material, an active metal, and an activity-promoting metal.

4. The heterogeneous catalyst of claim 1, wherein the organic framework material is an anion provided from an anionic crosslinking agent.

5. The heterogeneous catalyst of claim 4, wherein the anionic crosslinking agent is one or more polyanionic substances selected from citric acid, tartaric acid, malic acid, malonic acid, and tartaric acid.

6. The heterogeneous catalyst of claim 1, wherein the heterogeneous catalyst produces a dicarboxyl acid aromatic heterocyclic compound by oxidizing an aromatic heterocyclic raw material having a structure represented by Chemical Formula 1: ##STR00022## (wherein, in above chemical formula, any one of R1 and R2 is an aldehyde and the other is a substituted or unsubstituted (C1-C20) alkyl, acetoxy, or aldehyde, the substituted (C1-C20) alkyl is substituted with one or more functional groups selected from bromine, chlorine, fluorine, and iodine).

7. The heterogeneous catalyst of claim 1, wherein the heterogeneous catalyst is prepared by oxidizing one or more compounds selected from a compound having a structure represented by Chemical Formula 2, a compound having a structure represented by Chemical Formula 3, and a compound having a structure represented by Chemical Formula 4 in a polar solvent to obtain an oxide having the structure represented by Chemical Formula 5: ##STR00023##

8. The heterogeneous catalyst of claim 6, wherein the heterogeneous catalyst one or more selected from Ru/MnCO.sub.2O.sub.4, Au/CeO.sub.2, Ru/C and Pt/C at a molar ratio of 0.4 to 1.0 based on 1 mole of the aromatic heterocyclic compound having the structure represented by Chemical Formula 1.

9. A method for preparing a heterogeneous catalyst comprising preparing a solution including a porous central metal oxide; preparing a porous central metal-organic framework material by reacting the porous central metal oxide solution with an anionic crosslinking agent; and impregnating the porous central metal-organic framework material with a precursor solution of the metal catalyst component to provide a structure in which cations of the metal catalyst component are bonded.

10. The method of claim 9, wherein the second step includes a 2-1 step of mixing the porous central metal oxide solution and an anionic crosslinking agent; a 2-2 step of heating the mixed solution after the step 2-1 to a first temperature and then performing a primary reaction of the mixed solution; and a 2-3 step of heating the mixed solution after the step 2-2 to a second temperature higher than the first temperature and then subjecting the mixed solution to a secondary reaction

11. The method of claim 9, wherein the third step includes a 3-1 step of impregnating the reactant after the second step with a precursor solution of the metal catalyst component obtained by dissolving the precursor of the metal catalyst component in a solvent; and a 3-2 step of firing the impregnated product after step 3-1 at a third temperature lower than the second temperature.

12. The method of claim 10 or claim 11, wherein the solvent used to prepare the porous central metal oxide solution and the precursor solution of the metal catalyst component is water, alcohol, or a combination thereof.

13. The method of claim 9, wherein the anionic crosslinking agent is citric acid, tartaric acid, malic acid, malonic acid, tartaric acid, and a combination thereof.

14. The method of claim 10, wherein the first temperature is in the range of 40 to 200? C., the second temperature is in the range of 400 to 1000? C., and the step 2-3 is performed for 3 to 12 hours.

15. The method of claim 11, wherein the step 3-1 is performed in the range of 40 to 80? C., and the third temperature is in the range of 40 to 800? C.

16. A method for preparing a dicarboxyl acid aromatic heterocyclic compound, comprising subjecting the above-described aromatic heterocyclic compound raw material to an oxidation reaction in a polar solvent in the presence of a heterogeneous catalyst to prepare a dicarboxyl acid aromatic heterocyclic compound, wherein the heterogeneous catalyst is the catalyst of any one of claim 1 to claim 8, and the aromatic heterocyclic compound raw material is a hydroxyl-free compound having a structure represented by Chemical Formula 1: ##STR00024## (wherein, in the above chemical formula, any one of R1 and R2 is an aldehyde, and the others are substituted or unsubstituted (C1 to C20) alkyl, acetoxy, or aldehyde, and the substituted (C1 to C20) alkyl is substituted with one or more functional groups selected from bromine, chlorine, fluorine and iodine).

17. The method of claim 16, wherein the aromatic heterocyclic compound having the structure represented by Chemical Formula 1 is used in a state modified to the structure represented by Chemical Formula 3 or the structure represented by Chemical Formula 4: ##STR00025##

18. The method of claim 16, wherein the oxidation reaction is performed by a catalyst-free oxidation step of oxidizing an aromatic heterocyclic compound having a structure represented by Chemical Formula 2 at a fourth temperature in a polar solvent in the presence of a halogen-based ammonium compound and an ion activator to produce an aromatic heterocyclic compound having a structure represented by Chemical Formula 3; and an oxidation step of oxidizing an aromatic heterocyclic compound having the structure represented by Chemical Formula 3 in a polar solvent in the presence of a basic material and a heterogeneous catalyst at a fifth temperature higher than the fourth temperature to produce a dicarboxyl acid aromatic heterocyclic compound: ##STR00026##

19. The method of claim 16, wherein the oxidation reaction is performed by a first catalyst-free oxidation step of oxidizing an aromatic heterocyclic compound raw material having a structure represented by Chemical Formula 2 at a sixth temperature in a polar solvent; a second catalyst-free oxidation step of substituting the polar solvent with another type of polar solvent and performing an oxidation reaction at a seventh temperature lower than the sixth temperature to produce an aromatic heterocyclic compound having a structure represented by Chemical Formula 4; and an oxidation step of oxidizing an aromatic heterocyclic compound having the structure represented by Chemical Formula 4 in a polar solvent at an eighth temperature lower than the sixth temperature in the presence of a heterogeneous catalyst to produce a dicarboxyl acid aromatic heterocyclic compound: ##STR00027##

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0168] Hereinafter, the present invention will be described with reference to examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited to these only.

EXAMPLES

[0169] Preparation Example 1: Preparation of Raw Material 1 having the structure represented by Chemical Formula 1

[0170] Among compounds having the structure represented by Chemical Formula 1 as raw materials, a compound with R1=aldehyde and R2=ChH2Cl (corresponding to a compound having a structure represented by Chemical Formula 2) was prepared through conversion from wood.

[0171] Preparation Example 2: Preparation of Raw Material 2 having the structure represented by Chemical Formula 1

[0172] Among compounds having the structure represented by Chemical Formula 1 as raw materials, a compound with R1=R2=aldehyde (corresponding to 5-hydroxymethyl furfural that does not meet the proviso@@@of Chemical Formula 1) was prepared.

[0173] Preparation Example 3: Preparation of Heterogeneous Catalyst (4 wt % RuMnCO.sub.2O.sub.4)

[0174] An Mn precursor (Mn(CH.sub.3COO).sub.2 and a Co precursor (Co(CH.sub.4COO).sub.3) were taken in a weight ratio of 1:1 and respectively dissolved in a DIW solvent with a weight 50 times that of each precursor to prepare an Mn precursor solution and a Co precursor solution.

[0175] The prepared precursor solutions were mixed each other and then, mixed with a citric acid solution as an anionic crosslinking agent to prepare a porous central metal-organic framework material.

[0176] The porous central metal-organic framework material was activated to have a spherical shape to obtain spherical RuMnCO.sub.2O.sub.4 as a framework material in which binding sites were generated.

[0177] Subsequently, the MnCO.sub.2O.sub.4 was stirred with a Ru precursor (RuCl.sub.3*3H.sub.2O) as a metal catalyst component for 12 hrs under a N.sub.2 atmosphere, and NaBH.sub.4 was dropped thereto at 10 times as much as that of the Ru precursor and then, reacted by stirring at 500 rpm under an N.sub.2 atmosphere at room temperature for 24 hours to obtain 4% Ru/MnCO.sub.2O.sub.4.

[0178] Preparation Example 4: Preparation of Heterogeneous Catalyst (2 wt % AuCeO.sub.2)

[0179] A Ce precursor (Ce(CH.sub.3COO).sub.2) was taken and dissolved in 20 g of a H.sub.2O solvent and 0.01 mole of an NaOH aqueous solution to prepare a Ce precursor solution. The prepared Ce precursor solution was stirred at room temperature under a nitrogen atmosphere for 12 hours to obtain a spherical CeO.sub.2 support.

[0180] The CeO.sub.2 support was stirred with an Au precursor (AuCl.sub.3*3H.sub.2O) as an inactive catalyst component for 12 hr under a N.sub.2 atmosphere, and NaNH.sub.4 was dropped thereto at 10 times as much as that of the Au precursor and then, reacted by stirring at 500 rpm under a N.sub.2 atmosphere at room temperature for 24 hours to obtain a 2 wt % AuCeO.sub.2 catalyst.

[0181] Preparation Example 5: Preparation of Heterogeneous Catalyst (4 wt % RuMnCO.sub.2O.sub.4)

[0182] An Mn precursor (Mn(CH.sub.3COO).sub.2 and a Co precursor (Co(CH.sub.4COO).sub.3) were taken in a weight ratio of about 1:1 and dissolved in a DIW solvent at a weight of 50 times as much as that of each precursor to prepare an Mn precursor solution and a Co precursor solution.

[0183] The prepared precursor solutions were mixed and then, stirred at room temperature under a N.sub.2 atmosphere for 12 hours to obtain a framework material.

[0184] Subsequently, the MnCO.sub.2O.sub.4 was stirred with a Ru precursor (RuCl.sub.3*3H.sub.2O) as a metal catalyst component for 12 hrs under a N.sub.2 atmosphere, and NaBH.sub.4 was dropped thereto at about 10 times as much as that of the Ru precursor and then, reacted by stirring at 500 rpm under a N.sub.2 atmosphere at room temperature for 24 hours to obtain 4% Ru/MnCO.sub.2O.sub.4.

Example 1: Oxidation Reaction Experiment

[0185] After connecting two types of columns including a reacting region, having a diameter of 20 cm and a height of 100 cm, and made of a SUS material to a reactor, the reacting region in the rear column, which was used as an oxidation reactor, was filled with 1.5 kg of RuMnCO.sub.2O.sub.4 as a heterogeneous catalyst, while using the front column as a catalyst-free oxidation reactor.

[0186] Herein, the RuMnCO.sub.2O.sub.4, which was prepared in Preparation Example 3, was filled. After the filling, impurities absorbed thereon were removed by maintaining the reactor at 150? C.

[0187] In the storage tank of the raw material aromatic heterocyclic compound, 5 L of a solution prepared by dissolving the aromatic heterocyclic compound (the compound of Chemical Formula 1, wherein R1=aldehyde, R2=CH.sub.2Cl, corresponding to the material prepared in Preparation Example 1) in acetonitrile at a concentration of 1 wt % as a polar solvent was filled. After the filling, oxygen gas was used for pressurization to 3 bar. Herein, since the applied pressure is proportional to an amount of the oxygen dissolved in the aromatic heterocyclic compound, a higher pressure may improve a reaction rate.

[0188] The front column was supplied with the raw material in a solution state pressurized by the oxygen from the top of the column by using a liquid mass feeder, and an internal pressure of the column was adjusted within a range of 1 to 5 bar. The supplied aromatic heterocyclic compound solution flew to the bottom of the column, wherein 15 g of tetrabutylammonium chloride (TBAC) as an onium-based compound and 10 g of NaOAc as an ion activator were added therewith to the front column.

[0189] Herein, when a portion of the reactant was extracted to check a structure, a compound turned out to have a structure represented by Chemical Formula 3.

##STR00019##

[0190] Subsequently, the reactant was transported to the rear column to contact with the catalyst therein, while NaHCO.sub.3 was intermittently added to satisfy pH of the reaction solution within a range of 7 to 11, to cause an oxidation reaction, from which 3 wt % NaHCO.sub.3(in DIW solution) was three times washed at three times as much as the reactant to obtain a crude composition including oxides.

Example 2: Oxidation Reaction Experiment

[0191] An oxidation reaction was performed in the same manner as in Example 1 by using the same method as in Example 1, except that 4 wt % RuMnCO.sub.2O.sub.4 according to Preparation Example 3 and 2 wt % AuCeO.sub.2 according to Preparation Example 4 were used.

[0192] Specifically, used was a reactor in which two types of columns including a reacting region, having a diameter of 20 cm and a height of 100 cm, and made of a SUS material were connected, wherein the front column was used as a catalyst-free oxidation reactor, while the rear column was used as an oxidation reactor, and the reacting region of the rear column was filled with 1.5 kg of AuCeO.sub.2 as a heterogeneous catalyst.

[0193] Herein, the AuCeO.sub.2, which was prepared in Preparation Example 4, was filled. After the filling, impurities absorbed thereon were removed by maintaining the reactor at 150? C. under vacuum.

[0194] In the storage tank of the raw material aromatic heterocyclic compound, 5 L of a solution prepared by dissolving an aromatic heterocyclic compound (a compound of Chemical Formula 1, wherein R1-aldehyde, R2=CH.sub.2Cl, corresponding to the material prepared in Preparation Example 1) in DMSO at a concentration of 1 wt % as a polar solvent was filled. After the filling, oxygen gas was used for the pressurization to 3 bar. Herein, since the applied pressure is proportional to an amount of the oxygen dissolved in the aromatic heterocyclic compound, a higher pressure may improve a reaction rate.

[0195] The front column was supplied with the raw material in a solution state pressurized by the oxygen from the top of the column by using a liquid mass feeder, and an internal pressure of the column was adjusted within a range of 1 to 5 bar. The supplied aromatic heterocyclic compound solution flew to the bottom of the column, wherein as a result of checking a structure by extracting a portion of the catalyst-free oxidation reactant, a compound with the structure represented by Chemical Formula 4 was confirmed.

##STR00020##

[0196] Subsequently, the solvent (DMSO) in the front column was substituted with tertiarybutyl hypochlorite and then, proceeded with a reaction at room temperature for 24 hours.

[0197] Additionally, as a result of checking a structure by extracting a portion of the reactant, a compound with the structure represented by Chemical Formula 4 was confirmed.

[0198] Subsequently, the obtained reactant was transported to the rear column to contact with the catalyst in the column, and NaHCO.sub.3 was intermittently added thereto to satisfy the reaction solution within a range of pH 7 to 11 to cause an oxidation reaction, from which 3 wt % NaHCO.sub.3 in DIW solution was washed with water at three times as much as the reactant to obtain a crude composition including oxides.

Comparative Example 1: Oxidation Reaction Experiment

[0199] A crude composition including oxides was obtained by repeating the same process as in Example 1 except that the raw material of Preparation Example 1 was replaced with the raw material of Preparation Example 2.

Comparative Example 2: Oxidation Reaction Experiment

[0200] A crude composition including oxides was obtained in the same manner as in Example 1 by using the same method as used in Example 1, except that 4 wt % RuMnCO.sub.2O.sub.4 of Preparation Example 5 was used instead of 1 wt % RuMnCO.sub.2O.sub.4 of Preparation Example 3.

[0201] Specifically, used was a reactor in which two types of columns including a reacting region, having a diameter of 20 cm and a height of 100 cm, and made of a SUS material were connected, wherein the front column was used as a catalyst-free oxidation reactor, while the rear column was used as an oxidation reactor, and the reacting region of the rear column was filled with 1.5 kg of RuMnCO.sub.2O.sub.4, a heterogenous catalyst.

[0202] Herein, the RuMnCO.sub.2O.sub.4, which was prepared in Preparation Example 5, was filled. After the filling, impurities absorbed thereon were removed by maintaining the reactor at 150? C.

[0203] In the storage tank of the raw material aromatic heterocyclic compound, 5 L of a solution prepared by dissolving an aromatic heterocyclic compound (a compound of Chemical Formula 1, wherein R1=aldehyde, R2=CH.sub.2Cl, corresponding to the material prepared in Preparation Example 1) in acetonitrile at a concentration of 1 wt % as a polar solvent was filled. After the filling, oxygen gas was used for the pressurization to 3 bar. Herein, since the applied pressure is proportional to an amount of the oxygen dissolved in the aromatic heterocyclic compound, a higher pressure may improve a reaction rate.

[0204] The front column was supplied with the raw material in a solution state pressurized by the oxygen from the top of the column by using a liquid mass feeder, and an internal pressure of the column was adjusted within a range of 1 to 5 bar. The supplied aromatic heterocyclic compound solution flew to the bottom of the column by gravity, wherein 15 g of tetrabutylammonium chloride (TBAC) as an onium-based compound and 10 g of NaOAc as an ion activator were added therewith to the front column.

[0205] Herein, when a portion of the reactant was extracted to check a structure, a compound turned out to have the structure represented by Chemical Formula 3.

##STR00021##

[0206] Subsequently, the reactant was transported to the rear column to contact with the catalyst in the column, while NaHCO.sub.3 was intermittently added to satisfy the reaction solution within a range of pH 7 to11 to cause an oxidation reaction, from which 3 wt % NaHCO.sub.3(in DIW solution) was three times washed at three times as much as the reactant to obtain a crude composition including oxides.

<Evaluation>

1) Yield Evaluation

[0207] Each content of the compound with the structure represented by Chemical Formula 5, the compound with the structure represented by Chemical Formula 6, and the compound with the structure represented by Chemical Formula 7 was measured through component analysis of the crude compositions synthesized in each method shown in Examples 1 to 2 and Comparative Examples 1 to 2, and the results are shown in Table 1.

TABLE-US-00001 TABLE 1 Compara- Compara- Exam- Exam- tive tive ple 1 ple 2 Example 1 Example 2 Chemical Formula 5 99 98 65.5 73.5 structure compound (wt %) Chemical Formula 6 0.3 0.4 30 23 structure compound (wt %) Chemical Formula 7 0.7 1.6 4.5 3.5 structure compound (wt %)

[0208] As shown in Table 1, when the raw material of Preparation Example 1 according to the present invention was used, a yield of 98 wt % or more was confirmed for both of the heterogeneous catalysts of Preparation Examples 3 to 4.

[0209] On the contrary, when the raw material of Comparative Example 1 was used, an inferior yield of 65.5% was confirmed for each heterogeneous catalyst of Preparation Examples 3 to 5.

[0210] In addition, when the catalyst of Preparation Example 5 was used without using the appropriate crosslinking agent of Comparative Example 2, an inferior yield of 73.5% was also confirmed.

2) Purity Evaluation

[0211] The compound with the structure represented by Chemical Formula 5, which was confirmed in the yield evaluation, also was evaluated with respect to purity by using a sample obtained in Example 1 and a standard material in the related art, which is manufactured by Sigma Aldrich Co., Ltd. as a control example, and measuring with HPLC, and the purity comparison analysis results are shown in Table 2.

TABLE-US-00002 TABLE 2 Example 1 Control Purity 97.5 95

[0212] As shown in Table 2, the corresponding compound excessively synthesized by using the raw material provided in the present invention turned out to exhibit high purity.

3) Evaluation of Conversion Rate

[0213] When the crude compositions according to Examples 1 to 2 were measured with respect to a conversion rate according to a temperature and a reaction pressure during the oxidation reaction, the compound having the structure represented by Chemical Formula 5 exhibited an excellent conversion rate within a range of 100? C. to 180? C. under a pressure of 1 to 4 atm.

4) Evaluation of Effect of Pressure

[0214] During the conversion rate evaluation of the 3), an effect of the pressure at the same temperature was evaluated. The corresponding pressure turned out to affect adsorption power of carbon and platinum onto oxygen or adsorption power of a central metal, a transition metal, and a metal catalyst component onto the oxygen and exhibited an excellent conversion rate at a pressure of 1 to 5 atm, particularly, 2 atm.

[0215] The features, structures, effects, etc. illustrated in each of the above-described embodiments can be combined or modified for other embodiments by those skilled in the art. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

INDUSTRIAL APPLICABILITY

[0216] The present invention provides a method for preparing a dicarboxyl acid aromatic heterocyclic compound that is environmentally friendly and has Improved production efficiency by using bio-based raw materials as the aromatic heterocyclic compound raw material.