TWI564074B - Oxidation catalyst for furfural compound and applying method thereof - Google Patents

Description

Oxidation reaction catalyst composition of furfural compound and application method thereof

The invention relates to an oxidation reaction catalyst composition and a application method for preparing a derivative of a furfural compound, and particularly relates to an oxidation reaction catalyst composition which can be used for oxidizing a furfural compound and a application method thereof.

2,5-Furandicarboxylic acid (FDCA), 2,5-diformylfuran (DFF), 5-formylfuran-2-carboxylic acid (5-Formyl) -2-furancarboxylic acid, FFCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), which is derived from six carbon (C6) fructose or glucose to form 5-hydroxyl A compound produced by an oxidation reaction based on furfural (HMF). Among them, 2,5-furandicarboxylic acid is a dicarboxylic acid structure, which can be used in the polyester industry as a diacid monomer of polyester, and is esterified with various diols to be polymerized. A series of polyester compounds and elastomer materials. 2,5-furandicarboxylic acid can form in addition to its furan five ring Special properties of polyester materials are suitable for use in various industries or other new fields. 2,5-furandicarboxylic acid can also be reacted with various diamines to polymerize into a series of nylon materials. In addition to the ability to derivatize polymeric materials, 2,5-furandicarboxylic acid can also be derived from other applications for new applications in the field of surfactants and plasticizers.

In general, the preparation of 2,5-furandicarboxylic acid from 5-hydrocarbylmethylfurfural can be roughly divided into two processes, an alkali process and an acid process. Among them, the process of preparing 2,5-furandicarboxylic acid by alkali method has a high yield, but the catalyst is mostly precious metal, such as platinum (Pt), which is expensive, and produces a large amount of salty wastewater. . In contrast, the process for preparing 2,5-furandicarboxylic acid by the acid method is relatively inexpensive, and the solvent used can be recovered, so that it is more commercially valuable and competitive. However, in the process of preparing 2,5-furandicarboxylic acid by an acid method (for example, an acetic acid method), since the bromine concentration in the catalyst used is high, for example, higher than 2000 ppm, corrosion of the reaction system is liable to occur, thereby affecting subsequent processes. Going on.

Accordingly, there is a need to provide an advanced oxidation reaction catalyst composition and method of use thereof for oxidizing a furfural compound to overcome the problems faced by the prior art.

One embodiment of the present specification provides an oxidation reaction catalyst composition of a furfural compound including a nickel (Ni)-containing material, a manganese-containing (Mn) material, and a bromine-containing (Br) material. Wherein the mole number of bromine element in the composition of the oxidation reaction catalyst is divided by the molar number of nickel element in the composition of the catalyst containing oxidation reaction and the molar number of manganese element The sum of the two values is substantially between 0.01 and 7.5.

Another embodiment of the present specification provides a method of oxidizing a furfural compound comprising the steps of first providing an oxidation reaction catalyst composition comprising a nickel-containing material, a manganese-containing material, and a bromine-containing material. Wherein, the number of moles of bromine in the composition of the oxidation reaction catalyst is divided by the total number of moles of nickel element in the composition of the catalyst containing the oxidation reaction and the number of moles of manganese element, which is substantially between 0.01 and 7.5. Thereafter, at least one furfural compound is oxidized in an oxygen atmosphere.

In accordance with the above, an embodiment of the present invention discloses a composition of an oxidation reaction catalyst for oxidizing a furfural compound and a method for oxidizing a furfural compound using the composition of the oxidation reaction catalyst. The oxidation reaction catalyst composition comprising a material containing three elements of nickel, manganese and bromine is used to replace the oxidation reaction catalyst composition containing a precious metal, thereby oxidizing the furfural compound. Further, the concentration of the bromine element in the composition of the oxidation reaction catalyst is controlled within a specific range to reduce the corrosion of the reaction system. It ensures the application of the catalyst composition is not disturbed, increases the process yield, and greatly reduces the process cost.

S11‧‧‧ provides a catalyst consisting of a nickel-containing material, a manganese-containing material, and a bromine-containing material oxidation reaction catalyst

S12‧‧‧ The oxidation reaction catalyst composition is placed in an organic acid solution to form a first solution

S13‧‧‧ Mixing the furfural compound into the first solution to form a second solution

S14‧‧‧ The second solution is placed in an oxygen atmosphere to oxidize the furfural compound

The above-described embodiments and other objects, features and advantages of the present invention will become more apparent from the embodiments of the invention. a pair of furfural compounds A method in which an object undergoes an oxidation reaction.

The present invention provides a catalyst composition for oxidizing a furfural compound and a method for oxidizing a furfural compound by using the catalyst composition, which can improve the oxidation cost of a conventional catalyst for oxidizing a furfural compound and interfere with the composition. The problem of the reaction system. The above-described embodiments, as well as other objects, features and advantages of the present invention will be more apparent from the description of the appended claims.

However, it must be noted that these specific embodiments and methods are not intended to limit the invention. The invention may be practiced with other features, elements, methods and parameters. The preferred embodiments are merely illustrative of the technical features of the present invention and are not intended to limit the scope of the invention. Equivalent modifications and variations will be made without departing from the spirit and scope of the invention. In the different embodiments and the drawings, the same elements will be denoted by the same reference numerals.

Referring to FIG. 1 , a first embodiment of a method for oxidizing a furfural compound according to an embodiment of the present invention includes the following steps: First, referring to step S11, an oxidation reaction catalyst composition is first provided. It includes nickel-containing materials, manganese-containing materials, and bromine-containing materials. If the number of moles of bromine in the composition of the oxidation reaction catalyst is represented by [Br]; the number of moles of nickel in the composition of the oxidation reaction catalyst is represented by [Ni]; and the manganese element in the composition of the oxidation reaction catalyst is The number of ears is expressed as [Mn]. Then the molar number of bromine [Br] divided by the molar number of nickel elements [Ni] and the molar number of manganese elements [Mn] (ie [Br] / ([Ni] + [Mn])) The essence is between 0.01 and 7.5.

In some embodiments of the invention, the bromine molar number [Br] divided by the nickel element molar number [Ni] (ie [Br] / [Ni]) is substantially between 0.01 and 20; The molar number of bromine elements [Br] divided by the molar number of manganese elements [Ni] (ie [Br] / [Mn]) is substantially between 0.01 and 20. In still other embodiments of the present invention, the molar number of bromine elements [Br] divided by the molar number of nickel elements [Ni] (ie, [Br] / [Ni]) is substantially between 0.01 and 5; The molar number of bromine elements [Br] divided by the molar number of manganese elements [Mn] (ie [Br] / [Mn]) is substantially between 0.01 and 5; and the molar fraction of bromine [Br] is divided by The sum of the nickel element molar number [Ni] and the manganese element molar number [Mn] (ie, [Br] / ([Ni] + [Mn]))) is substantially between 0.01 and 0.5.

In some embodiments of the invention, the bromine molar number [Br] divided by the nickel element molar number [Ni] (ie [Br] / [Ni]) is substantially between 0.01 and 15; The bromine molar number [Br] divided by the manganese element molar number [Ni] (ie [Br] / [Mn]) is substantially between 0.01 and 15; and the bromine molar number [Br] is divided by The sum of the nickel element molar number [Ni] and the manganese element molar number [Mn] (ie, [Br] / ([Ni] + [Mn]))) is substantially between 0.01 and 5.

In still other embodiments of the present invention, the molar number of bromine elements [Br] divided by the molar number of nickel elements [Ni] (ie, [Br] / [Ni]) is substantially between 0.01 and 10; The molar number of bromine elements [Br] divided by the molar number of manganese elements [Mn] (ie [Br] / [Mn]) is substantially between 0.01 and 10; and the molar fraction of bromine [Br] is divided by Nickel element The sum of the number [Ni] and the molar number of manganese elements [Mn] (i.e., [Br] / ([Ni] + [Mn]))) is substantially between 0.01 and 1.

In some embodiments of the invention, the nickel-containing material may be nickel acetate, nickel bromide, nickel sulfate, nickel chloride, nickel oxalate. Nickel carbonate or any combination of the above compounds; the manganese-containing material may be manganese acetate, manganese bromide, manganese sulfate, manganese chloride, Manganese oxalate, manganese carbonate or any combination of the above; the bromine-containing material may be nickel bromide, manganese bromide, hydrogen bromide, sodium bromide or Any combination of the above compounds.

Thereafter, referring to step S12, the oxidation reaction catalyst composition is placed in an organic acid solution in which the moisture content is substantially between 0 and 30 weight percent (wt%) of the first solution. In some embodiments of the invention. Preferably, it may be acetic acid, propanoic acid, butyric acid or any combination of the above compounds.

Then, the furfural compound is further mixed into the first solution to form a second solution having a moisture content substantially in the range of 0 to 30% by weight (as shown in step S13). In some embodiments of the invention, the aforementioned furfural compound has a general formula as follows:

Wherein R is H, CH ₃ , C ₂ H ₅ , COCH ₃ , COCH ₂ CH ₃ or COCH ₂ CH ₂ CH ₃ or the like. A preferred furfural compound may be 5-hydroxymethylfurfural.

The second solution is then placed in an oxygen atmosphere to oxidize the furfural compound (as depicted in step S14). Wherein, the reaction temperature is substantially between 40 ° C and 200 ° C; the reaction pressure is substantially between 1 kg / cm ² and 100 kg / cm ² ; in some embodiments of the invention, the oxygen atmosphere comprises a concentration substantially between 1 and 100 mole percent (mol%) of oxygen (O ₂ ), and selected from nitrogen (N ₂ ), carbon dioxide (CO ₂ ), helium (He), helium (Ne), argon (Ar) or the like Other auxiliary gases in any combination. The reaction temperature is substantially between 80 ° C and 180 ° C; the reaction pressure is substantially between 5 kg/cm ² and 30 kg/cm ² . In some embodiments of the present invention, the multi-stage heating method may be used to adjust the reaction temperature or pressure during the oxidation reaction, or to adjust the flow rates of different reaction gases in the oxygen atmosphere to obtain a better reaction effect.

The oxidation reaction can be carried out to include 2,5-furandicarboxylic acid (FDCA), 2,5-diformylfuran (DFF), 5-methylmercaptofuran-2. -5-Formyl-2-furancarboxylic acid (FFCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) or any mixture of the above. Subsequently, the product is filtered, washed, dried and purified to obtain pure 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-carboxylfuran-2-carboxylic acid, 5- Hydroxymethyl-2-furancarboxylic acid or any mixture of the above, and the yield thereof is calculated (as depicted in step S14).

The detailed description of the specific embodiments is as follows

Example 1

In the first embodiment, the oxidation reaction of the furfural compound was carried out by using the above-mentioned oxidation reaction catalyst composition containing three elements of nickel, manganese and bromine, and the composition of the oxidation reaction catalyst containing only two elements of manganese and bromine was used as a comparative example for comparison. The detailed operation is as follows: First, 12 g (g) of nickel acetate, 5.9 g of manganese acetate, and 2.02 g of an aqueous hydrogen bromide solution are placed in a Par reactor having a capacity of 1 liter (L) and containing acetic acid (Par reactor In order to form the first solvent. In the present embodiment, the molar number of bromine elements [Br] in the composition of the oxidation reaction catalyst is divided by the molar number of nickel elements [Ni] and the molar number of manganese elements [Mn], and the total value is about 0.167 ([ Br] / ([Ni] + [Mn]) = 0.167). Thereafter, 52 g of 5-hydroxymethylfurfural (HMF) was dissolved in 150 ml (ml) of aqueous acetic acid (water content of about 2%), and fed to the reactor at a feed rate of 3.5 g per minute. To form a second solvent. The reaction was carried out in an oxygen atmosphere at a reaction temperature of 150 ° C, and the pressure was maintained at 20 kg/cm ² , and after one hour, the temperature was pulled up to 180 ° C for one hour to precipitate the product, and the reactor temperature was returned to the chamber. After the temperature is removed, the pressure is removed and filtered, and the resultant wet cake is washed with water. After drying, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran- 2-carboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid or any mixture of the above.

Comparative example 1

5.9 g of manganese acetate and 2.02 g of an aqueous hydrogen bromide solution were placed in a Par reactor having a capacity of 1 liter and containing acetic acid. Among them, the molar number of bromine elements [Br] in the composition of the oxidation reaction catalyst is divided by the molar number of manganese elements [Mn] of about 0.5 ([Br] / [Mn] = 0.5). Thereafter, 52 g of 5-hydroxymethylfurfural was dissolved in 150 ml of aqueous acetic acid (water content of about 2 by weight), and fed to the reactor at a feed rate of 3.5 g per minute to form the first Two solvents. The reaction was carried out in an oxygen atmosphere at a reaction temperature of about 150 ° C, and at the same time, the pressure was maintained at about 20 kg/cm ² , and after one hour, the temperature was pulled up to 180 ° C for one hour to precipitate the product, and the reaction was carried out. After the temperature of the device returns to room temperature, the pressure is removed and filtered, and the resulting wet cake is washed with water. After drying, 2,5-furandicarboxylic acid, 2,5-dimethylmercaptofuran, 5-- Mercaptofuran-2-carboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid or any mixture of the above.

For the detailed reaction results, please refer to Table 1: wherein Ni(II) & Mn(II) & Br and Mn(II) & Br(I) are used to represent the oxidation reaction catalyst compositions used in Example 1 and Comparative Example 1, respectively; HMF, FDCA, DFF, FFCA and HMFCA are used to represent 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5- Hydroxymethyl-2-furancarboxylic acid.

According to the reaction results in Table 1, it is shown that the oxidation reaction of 5-hydroxymethylfurfural is carried out by using an oxidation reaction catalyst composition containing three elements of nickel, manganese and bromine or an oxidation reaction catalyst containing two elements of manganese and bromine. A mixture of 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid can be produced. However, when the oxidation reaction is carried out by using an oxidation reaction catalyst containing three elements of nickel, manganese and bromine, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan and 5-methylmercaptofuran-2 can be greatly improved. The overall yield of the mixture of formic acid and 5-hydroxymethyl-2-furancarboxylic acid. In particular, the yield of 2,5-furandicarboxylic acid can be increased from 7.1% to 38%.

In some embodiments, the oxidation reaction catalyst composition containing the three elements of nickel, manganese and bromine may be used to oxidize the furfural compound, and the oxidation reaction catalyst composition containing three elements of cobalt, manganese and bromine is used as a comparative example. For comparison, for example, please refer to the following Examples 2-1, 2-2 and 2-3 and Comparative Example 2:

Examples 2-1, 2-2, and 2-3

First, 5.36 g of nickel acetate, 2.64 g of manganese acetate, and 0.9 g of an aqueous hydrogen bromide solution were placed in a Par reactor having a capacity of 1 liter and containing acetic acid to form a first solvent. In the present embodiment, the molar number of bromine elements [Br] in the composition of the oxidation reaction catalyst is divided by the molar number of nickel elements [Ni] and the molar number of manganese elements [Mn], and the total value is about 0.167 ([ Br] / ([Ni] + [Mn]) = 0.167). Thereafter, 11.55 g of 5-hydroxymethylfurfural was dissolved in 150 ml of an aqueous acetic acid solution (water content of about 2 by weight) and added to the reactor to form a second solvent. The reaction was carried out in an oxygen atmosphere at a reaction temperature of about 150 ° C (the reaction temperatures of Examples 2-2 and 2-3 were about 180 ° C), and the pressure was maintained at about 20 kg/cm ² , and the temperature was pulled after one hour. When the temperature is raised to 180 ° C for one hour, the product is precipitated. When the temperature of the reactor returns to room temperature, the pressure is removed and filtered, and the resulting wet cake is washed with water. After drying, 2,5-furan can be obtained. Dicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid or any mixture of the above.

Comparative example 2

5.36 g of cobalt acetate, 2.64 g of manganese acetate, and 0.9 g of an aqueous hydrogen bromide solution were placed in a Par reactor having a capacity of 1 liter and containing acetic acid. Thereafter, 11.55 g of 5-hydroxymethylfurfural was dissolved in 150 ml of an aqueous acetic acid solution (water content of about 0.7 by weight) and added to the reactor to form a second solvent. The reaction was carried out in an oxygen atmosphere at a reaction temperature of about 150 ° C, and at the same time, the pressure was maintained at 20 kg/cm ² , and after one hour, the temperature was pulled up to 180 ° C for one hour, and the product was precipitated as a reactor. After the temperature returns to room temperature, the pressure is removed and filtered, and the resulting wet cake is washed with water. After drying, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-A can be obtained. Mercaptofuran-2-carboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid or any mixture of the above.

For the detailed reaction results, please refer to Table 2: wherein Ni(II) & Mn(II) & Br and Co(II) & Mn(II) & Br represent the oxidation reaction catalyst compositions used in Example 2 and Comparative Example 2, respectively; HMF, FDCA, DFF, FFCA and HMFCA are used to represent 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine Furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid.

According to the reaction results in Table 2, when the oxidation reaction of 5-hydroxymethylfurfural is carried out by using an oxidation reaction catalyst composition containing three elements of nickel, manganese and bromine, 2,5-furandicarboxylic acid, 2,5 The overall yield of the mixture of dimethyl decyl furan, 5-methyl decyl furan-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid is significantly higher than that of the oxidation reaction catalyst containing three elements of cobalt, manganese and bromine. The yield of the oxidation reaction carried out is composed. In particular, the yield of 2,5-furandicarboxylic acid can be increased by at least 10%.

In some embodiments of the invention, the initial concentration of the furfural compound can be moderately increased to achieve better process efficiency. For example, please refer to Embodiments 3-1 and 3-2. Since the process methods and parameters used in Examples 3-1 and 3-2 are similar to Examples 2-1, 2-2 and 2-3, the difference lies only in the initial concentration of 5-hydroxymethylfurfural, so The operation content will not be described again. In Examples 3-1 and 3-2, the initial concentration of 5-hydroxymethylfurfural was increased to a weight percent concentration of 6.6.

For the detailed reaction results of Examples 3-1 and 3-2, refer to Table 3: Ni(II) & Mn(II) & Br are used to represent the oxidation reaction catalyst compositions used in Examples 3-1 and 3-2; HMF, FDCA, DFF, FFCA and HMFCA are used to represent 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5- Hydroxymethyl-2-furancarboxylic acid.

In some embodiments of the invention, the initial concentration of the furfural compound can also be increased, while the ratio of the three elements of nickel, manganese, and bromine in the oxidation catalyst composition is more varied. For example, please refer to Examples 4-1, 4-2 and 4-3:

Example 4-1

First, 12 g of nickel acetate, 5.9 g of manganese acetate, and 2.02 g of an aqueous hydrogen bromide solution were placed in a Par reactor having a capacity of 1 liter and containing acetic acid to form a first solvent. In the present embodiment, the bromine element concentration [Br] in the oxidation reaction catalyst composition is divided by the nickel element concentration [Ni] and the manganese element concentration [Mn], and the total value is about 0.167 ([Br]/([Ni ]+[Mn])=0.167). Thereafter, 11.55 g of 5-hydroxymethylfurfural (HMF) was dissolved in 150 ml of an aqueous acetic acid solution (having a moisture content of about 1.8%) and charged into the reactor to form a second solvent. The reaction was carried out in an oxygen atmosphere at a reaction temperature of 150 ° C, and the pressure was maintained at 20 kg/cm ² . After one hour, the temperature was pulled up to 180 ° C for one hour to precipitate the product, and the reactor temperature was returned to the chamber. After the temperature is removed, the pressure is removed and filtered, and the resultant wet cake is washed with water. After drying, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran- 2-carboxylic acid, 5-hydroxymethyl-2-furancarboxylic acid or any mixture of the above.

Examples 4-2 and 4-3

The process methods and parameters used in Examples 4-2 and 4-3 were similar to those in Example 4-1 except that the ratio of the three elements of nickel, manganese and bromine in the composition of the reaction catalyst was different. Wherein, the bromine element concentration [Br] in the composition of the oxidation reaction catalyst used in Examples 4-2 and 4-3 is divided by the nickel element concentration [Ni] and the manganese element concentration [Mn], and the total value is about 0.33. ([Br]/([Ni]+[Mn])=0.33)). Since other operation contents have been described in detail in Embodiment 4-1, they will not be described again.

For detailed reaction results, please refer to Table 4: HMF, FDCA, DFF, FFCA and HMFCA are used to represent 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylmercaptofuran, 5-A. Mercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid.

Table 4

In some embodiments of the invention, the concentration of bromine in the oxidation catalyst composition may also be more varied. For example, please refer to Examples 5-1 to 5-8: the process methods and parameters used in Examples 5-1 to 5-8 are similar to Examples 2-1, 2-2 and 2-3, except that the oxidation is only in the oxidation. The concentration of the bromine element in the composition of the reaction catalyst, and the reaction pressure was substantially 30 kg/cm ² . Since the other operation contents have been detailed as before, they will not be described again.

For the detailed reaction results of Examples 5-1 to 5-8, refer to Table 5: wherein only Br (ppm) is used to represent the bromine molar number in the oxidation catalyst composition used in Examples 5-1 to 5-8. ; HMF, FDCA, DFF, FFCA and HMFCA are respectively represented by 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid.

Table 5

According to the results of the reaction in Table 5, when the concentration of bromine in the oxidation catalyst composition [Br] is reduced to 22 ppm, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran The overall yield of the mixture of 2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid was still 76.7%. The yield of the 2,5-furandicarboxylic acid mixture was as high as 76.6% (see Example 5-3). Although the overall yield of a mixture of 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid will follow the bromine element The concentration [Br] increases and increases, but the increase is not obvious; when the bromine concentration [Br] increases to 1080 ppm, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylhydrazine The overall yield of the mixture of kifuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid reached a maximum of about 89.3% (see Examples 5-7); After the concentration [Br] exceeds 1080 ppm, the mixture of 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid as a whole The yield will drop significantly to 68.2% (see Examples 5-8).

It can be seen that the whole production of the mixture of 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid is not affected. Under the condition of the ratio, the bromine element concentration [Br] in the oxidation reaction catalyst composition can be controlled to a lower range, so as to avoid corrosion of the reaction system due to excessive bromine element concentration [Br], thereby affecting the progress of the reaction. In the present embodiment, the bromine element concentration [Br] in the composition of the oxidation reaction catalyst is preferably between 20 ppm and 1100 ppm.

In some embodiments of the invention, the concentration of manganese in the oxidation reaction catalyst composition may also be more varied. For example, please refer to Examples 6-1 to 6-6: The process methods and parameters used in Examples 6-1 to 6-6 are similar to Examples 2-1, 2-2 and 2-3, except that the oxidation is only in the oxidation. The concentration of the manganese element in the composition of the reaction catalyst, and the reaction pressure was substantially 30 kg/cm ² . Since the other operation contents have been detailed as before, they will not be described again.

For the detailed reaction results of Examples 6-1 to 6-6, refer to Table 6 in which Mn (ppm) is used to represent the concentration of manganese in the oxidation catalyst composition used in Examples 6-1 to 6-6; HMF, FDCA, DFF, FFCA and HMFCA are used to represent 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5- Hydroxymethyl-2-furancarboxylic acid.

Table 6

According to the results of the reaction in Table 6, when the concentration [Mn] of the manganese element in the oxidation catalyst composition is reduced to 158 ppm, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran The overall yield of the mixture of 2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid was still about 40.1% (see Example 6-2). When the concentration [Mn] of the manganese element in the oxidation catalyst composition is increased to 1586 ppm, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid, and 5-hydroxyl The overall yield of the mixture of methyl-2-furancarboxylic acid was the highest, about 89.3% (see Example 6-4). In the present embodiment, the manganese element concentration [Mn] in the composition of the oxidation reaction catalyst is preferably between 500 ppm and 5000 ppm.

In some embodiments of the invention, the concentration of nickel in the oxidation reaction catalyst composition may also be more varied. For example, please refer to Examples 7-1 to 7-8: the process methods and parameters used in Examples 7-1 to 7-8 are similar to Examples 2-1, 2-2 and 2-3, except that the oxidation is only in the oxidation. The concentration of the nickel element in the composition of the reaction catalyst, and the reaction pressure was substantially 30 kg/cm ² . Since the other operation contents have been detailed as before, they will not be described again.

For the detailed reaction results of Examples 7-1 to 7-8, refer to Table 7 in which only Ni (ppm) is used to represent the concentration of nickel element in the composition of the oxidation reaction catalyst used in Examples 7-1 to 7-8; HMF, FDCA, DFF, FFCA and HMFCA are used to represent 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5- Hydroxymethyl-2-furancarboxylic acid.

According to the results of the reaction in Table 7, when the concentration of nickel element [Ni] in the composition of the oxidation reaction catalyst was reduced to 171 ppm, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran The overall yield of the mixture of 2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid was still about 65.2% (see Example 7-2). Oxidation catalyst group When the concentration of nickel in the element [Ni] is increased to 3388 ppm, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2 The overall yield of the mixture of furancarboxylic acid was the highest, about 89.3% (see Examples 7-5). In the present embodiment, the concentration of the nickel element [Ni] in the composition of the oxidation reaction catalyst is preferably between 100 ppm and 12,000 ppm.

Additionally, in some embodiments of the invention, the magnesium oxide (Mg) containing material may also be included in the oxidation reaction catalyst composition. Wherein, the bromine molar number [Br] in the oxidation reaction catalyst composition divided by the magnesium element molar number (expressed as [Mg]) is substantially between 0.01 and 20; preferably substantially between 0.01 and 7.5; Better in substance between 0.01 and 5. The magnesium-containing material may be magnesium acetate, magnesium bromide, magnesium sulfate, magnesium chloride, magnesium oxalate, magnesium carbonate or the above. Any combination of objects.

Referring to Examples 8-1 and 8-2, the process methods and parameters used in Examples 8-1 and 8-2 are similar to those of Examples 2-1, 2-2 and 2-3, except that the oxidation reaction is only The catalyst composition has a different magnesium element concentration, and the reaction pressure is substantially 30 kg/cm ² . Among them, the magnesium element concentration [Mg] in the oxidation reaction catalyst compositions employed in Examples 8-1 and 8-2 was about 244 ppm and 480 ppm, respectively. Since other operation contents have been described in detail as before, they will not be described again.

For the detailed reaction results of Examples 8-1 and 8-2, refer to Table 8 in which only Mg (ppm) is used to represent the magnesium element concentration in the oxidation reaction catalyst compositions used in Examples 8-1 and 8-2; With HMF, FDCA, DFF, FFCA and HMFCA stands for 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid.

According to the results of the reaction in Table 8, when the composition of the oxidation catalyst is increased, the magnesium-containing material is added. When the concentration of 5-hydroxymethylfurfural is 3.3 by weight, the concentration of magnesium in the composition of the oxidation catalyst is [Mg] of about 244 ppm. The overall yield of the mixture of 2,5-furandicarboxylic acid, 2,5-dimethylhydrazine furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid can be 87.56. %. If the initial concentration of 5-hydroxymethylfurfural is increased to 5 by weight, and the concentration of magnesium in the composition of the oxidation catalyst [Mg] is about 480 ppm, 2,5-furandicarboxylic acid, 2,5-di can be obtained. The overall yield of the mixture of formazan furan, 5-methylmercaptofuran-2-carboxylic acid and 5-hydroxymethyl-2-furancarboxylic acid may be 79.5%.

In accordance with the above, an embodiment of the present invention discloses a composition of an oxidation reaction catalyst for oxidizing a furfural compound and a method for oxidizing a furfural compound using the composition of the oxidation reaction catalyst. It is composed of an oxidation reaction catalyst containing a material containing three elements of nickel, manganese and bromine instead of the conventional one. A heavy metal oxidation reaction catalyst composition for oxidizing a furfural compound. Further, the concentration of the bromine element in the composition of the oxidation reaction catalyst is controlled within a specific range to reduce the corrosion of the reaction system. It ensures the application of the catalyst composition is not disturbed, increases the process yield, and greatly reduces the process cost.

While the invention has been described above in the preferred embodiments, it is not intended to limit the invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

S11‧‧‧ provides a catalyst consisting of a nickel-containing material, a manganese-containing material, and a bromine-containing material oxidation reaction catalyst

S12‧‧‧ The oxidation reaction catalyst composition is placed in an organic acid solution to form a first solution

S13‧‧‧ Mixing the furfural compound into the first solution to form a second solution

S14‧‧‧ The second solution is placed in an oxygen atmosphere to oxidize the furfural compound

Claims (14)

An oxidation reaction catalyst composition of a furfural compound, comprising: a nickel-containing (Ni) material, a manganese-containing (Mn) material, and a bromine-containing (Br) material; wherein the oxidation reaction catalyst composition has a monobromo element molar number (mole) divided by the composition of the nickel oxide element and the molar number of one manganese element in the composition of the oxidation reaction catalyst, the total value is substantially between 0.01 and 7.5. An oxidation reaction catalyst composition of a furfural compound according to claim 1, wherein the furfural compound has a general formula as follows: Wherein R is H, CH ₃ , C ₂ H ₅ , COCH ₃ , COCH ₂ CH ₃ or COCH ₂ CH ₂ CH ₃ . The oxidation reaction catalyst composition of the furfural compound according to claim 1, wherein the molar number of the bromine element divided by the molar number of the nickel element is substantially between 0.01 and 20; and the molar amount of the bromine element is divided The molar amount of the manganese element is substantially between 0.01 and 20. An oxidation reaction catalyst composition of a furfural compound according to claim 1, wherein the molar number of the bromine element is divided by the molar amount of the nickel element Between 0.01 and 5; the number of moles of bromine element divided by the molar number of the manganese element is substantially between 0.01 and 5; and the number of moles of the bromine element is divided by the number of moles of the nickel element and the manganese element The sum of the molar numbers is substantially between 0.01 and 0.5. The oxidation reaction catalyst composition of the furfural compound according to claim 1, wherein the nickel-containing material is selected from the group consisting of nickel acetate, nickel bromide, nickel sulfate, A group consisting of nickel chloride, nickel oxalate, nickel carbonate, and any combination thereof. The oxidation reaction catalyst composition of the furfural compound according to claim 1, wherein the manganese-containing material is selected from the group consisting of manganese acetate, manganese bromide, manganese sulfate, A group consisting of manganese chloride, manganese oxalate, manganese carbonate, and any combination thereof. The oxidation reaction catalyst composition of the furfural compound according to claim 1, wherein the bromine-containing material is selected from the group consisting of nickel bromide, manganese bromide, hydrogen bromide, and sodium bromide. And a combination of any of the above. The oxidation reaction catalyst composition of the furfural compound according to claim 1, further comprising a magnesium-containing (Mg) material, wherein the number of moles of the bromine element is divided by the number of moles of the magnesium element in the composition of the oxidation reaction catalyst The value is essentially between 0.01 and 20. The oxidation reaction catalyst composition of the furfural compound according to claim 8, wherein the molar number of the bromine element divided by the molar number of the magnesium element is substantially between 0.01 and 5. An oxidation reaction catalyst composition of a furfural compound according to claim 8 wherein the magnesium-containing material is selected from the group consisting of magnesium acetate, magnesium bromide, magnesium sulfate, magnesium chloride. (magnesium chloride), magnesium oxalate, magnesium carbonate, and any combination of the above. A method of oxidizing a furfural compound, comprising: providing an oxidation reaction catalyst composition as described in one of claims 1 to 10; and oxidizing at least one furfural compound in an oxygen atmosphere. The method of oxidizing a furfural compound according to claim 11, wherein before oxidizing the furfural compound, the method further comprises: placing the oxidation catalyst composition in an organic acid solution to form a first solution, The first solution has a moisture content substantially between 0 and 30 weight percent (wt%); and the furfural compound is mixed into the first solution to form a second solution, such that the second solution has substantial A moisture content of 0 to 30 weight percent. The method of claim 12, wherein the organic acid solution is selected from the group consisting of acetic acid, propanoic acid, butyric acid, and any combination thereof. a group of people. The method of claim 1, wherein the oxygen atmosphere comprises: an oxygen gas (O ₂ ) having a concentration substantially between 1 and 100 mole percent (mol%); and an auxiliary gas system It is selected from the group consisting of nitrogen (N ₂ ), carbon dioxide (CO ₂ ), helium (He), helium (Ne), argon (Ar), or any combination thereof.