CN115772143B - Method for preparing 2, 5-furandicarboxylic acid - Google Patents
Method for preparing 2, 5-furandicarboxylic acid Download PDFInfo
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- CN115772143B CN115772143B CN202111048690.4A CN202111048690A CN115772143B CN 115772143 B CN115772143 B CN 115772143B CN 202111048690 A CN202111048690 A CN 202111048690A CN 115772143 B CN115772143 B CN 115772143B
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- 238000000034 method Methods 0.000 title claims abstract description 65
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 53
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 46
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 21
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
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- 238000005470 impregnation Methods 0.000 description 8
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
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- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a method for preparing 2, 5-furandicarboxylic acid, which comprises the following steps: in a mixed solvent consisting of an organic solvent and water, reacting 5-hydroxymethylfurfural with oxygen in the presence of an oxidation catalyst to obtain the 2, 5-furandicarboxylic acid; wherein the oxidation catalyst is a supported catalyst containing bismuth and a noble metal. The invention uses the mixed solvent composed of water and organic solvent, avoids the introduction of alkaline compound and the complex processes of acidification treatment and the like brought by the alkaline compound in the traditional method; meanwhile, the invention uses the noble metal catalyst loaded by the carbon-containing carrier with high specific surface area and containing bismuth as the oxidation catalyst, so that the catalytic efficiency is high, and the reaction process is green.
Description
Technical Field
The invention relates to the field of preparation of oxygen-containing compounds, in particular to a method for preparing 2, 5-furandicarboxylic acid.
Background
The fuels and chemicals required by the current society are mainly derived from fossil fuels, and the influence of fossil fuels on the environment has led to a great deal of interest in sustainable alternative energy sources and chemical raw materials, especially biomass resources, which are widely available and have high carbohydrate specific gravity, and liquid fuels and organic chemicals can be produced through a variety of chemical catalytic processes. 5-Hydroxymethylfurfural (HMF) is one of the important biomass-based platform compounds that can be produced by acid-catalyzed dehydration of carbohydrates such as fructose, glucose, and cellulose, and 2, 5-furandicarboxylic acid (FDCA) obtained from the catalytic oxidation of HMF. FDCA can be used for synthesizing bio-based polymer materials, can effectively improve the heat resistance and mechanical property of the bio-based polymer materials, is considered as an ideal substitute of petroleum-based monomer terephthalic acid (PTA), and can be widely applied to synthesis of bio-based polymers such as polyester, polyamide, epoxy resin and the like. Therefore, the development of a synthetic method of 2, 5-furandicarboxylic acid has important application value and biomass sustainable utilization significance.
In the preparation of FDCA by HMF selective oxidation, researchers often increase the single pass throughput of the process by adding basic compounds with the product FDCA during the reaction to form soluble salt compounds of FDCA due to the low solubility of FDCA in water (< 1g/100mL water, 100 ℃). However, the salt compounds of FDCA obtained by these methods cannot be directly used in processes for producing polymers and the like, but must be subjected to acidification (ph≡1) to be reconverted into FDCA products, which undoubtedly increases the complexity of the overall production process of FDCA and reduces the environmental friendliness thereof.
Therefore, there is a need to provide a method for synthesizing 2, 5-furandicarboxylic acid which is simple, inexpensive and environmentally friendly, so as to solve the above problems in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of 2, 5-furandicarboxylic acid, which uses a mixed solvent composed of water and an organic solvent, so that the complex processes of introducing an alkaline compound and acidizing treatment and the like brought by the alkaline compound in the traditional method are avoided; meanwhile, the supported catalyst containing bismuth and noble metals is used as an oxidation catalyst, so that the catalyst has high catalytic efficiency, high FDCA yield and green and concise reaction process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for preparing 2, 5-furandicarboxylic acid comprising:
in a mixed solvent consisting of an organic solvent and water, reacting 5-hydroxymethylfurfural with oxygen in the presence of an oxidation catalyst to obtain the 2, 5-furandicarboxylic acid; wherein the oxidation catalyst is a supported catalyst containing bismuth and a noble metal.
The organic solvent is selected from tetrahydrofuran or 1, 4-dioxane.
In the mixed solvent composed of the organic solvent and water, the mass ratio of the organic solvent to the water is 5:1-0.5:1, preferably 3:1-1:1.
In the solution formed by the mixed solvent of the 5-hydroxymethylfurfural and the organic solvent and water, the mass percentage of the 5-hydroxymethylfurfural is 0.1-30%, preferably 0.5-20%, and more preferably 1-10%.
In the supported catalyst containing bismuth and noble metal, the molar ratio of the noble metal to bismuth is 1:0.1-10, preferably 1:0.5-4.
In the supported catalyst containing bismuth and noble metal, the molar ratio of the noble metal to the 5-hydroxymethylfurfural is 1:1 to 1000, preferably 1:5 to 500, more preferably 1:5 to 250.
The oxygen can be derived from pure oxygen, air or a mixed gas of oxygen and nitrogen, and the partial pressure of the oxygen is 1 MPa-5 MPa, preferably 1-3 MPa.
The reaction temperature of the oxidation reaction is 50-170 ℃, preferably 90-150 ℃.
The preparation method of the supported catalyst containing bismuth and noble metals comprises the following steps:
(1) Dissolving a precursor containing bismuth in a certain amount of acid solution to prepare an acidic solution containing bismuth;
(2) Dispersing a supported noble metal catalyst in water, stirring to obtain a suspension, and continuously introducing hydrogen (the ventilation amount of the hydrogen is 10-100 mL/min) into the suspension;
(3) And (3) adding a certain amount of acid solution into the suspension in the step (2) to adjust the pH value to be acidic, dropwise adding the bismuth-containing acidic solution in the step (1), and filtering and drying to obtain the bismuth-and-noble-metal-containing supported catalyst.
The bismuth-containing precursor in the step (1) is selected from one or more of bismuth nitrate, bismuth trichloride and bismuth acetate.
The acid solution in the steps (1) and (3) is nitric acid, hydrochloric acid, acetic acid or aqueous solution prepared from one or more of nitric acid, hydrochloric acid and acetic acid, and the pH value of the solution is 0-4.
In the step (2), the system is kept in a hydrogen-rich environment, and the ventilation amount of hydrogen is preferably 10-100 mL/min.
The supported noble metal catalyst in the step (2) comprises a carrier and noble metals supported on the carrier, wherein the noble metals are preferably Ru, pt, au or a combination of Ru, pt and Au, and the loading amount of the noble metals is 0.1-10%, preferably 1-5% based on the total mass of the carrier.
The carrier of the supported noble metal catalyst in the step (2) is selected from carbon-containing materials, including one or more of activated carbon, carbon nanotubes, graphene or graphene oxide, preferably activated carbon.
When the carrier is activated carbon, the specific surface area of the activated carbon is 1000m 2/g-1500 m2/g.
The supported noble metal catalyst can be prepared according to the existing method, such as an isovolumetric impregnation method, a incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method, a vacuum impregnation method, or the like. In the specific preparation, after the noble metal is deposited, solid powder is placed in a baking oven at 100-140 ℃ for drying for about 6-24 hours, the obtained supported catalyst precursor is calcined for a period of time at 300-800 ℃ in nitrogen, and then reduced for about 6-24 hours in a reducing atmosphere (such as a mixed atmosphere of H 2 or H 2 and N 2) at 200-500 ℃ to obtain the supported noble metal catalyst.
According to the description of the technical scheme, the beneficial effects of the invention are as follows:
1. According to the invention, the bismuth component is introduced on the surface of the supported noble metal catalyst by a specific method, so that the oxidation efficiency of the catalyst can be further improved.
2. According to the invention, the mixed solution of water and an organic solvent in a proper proportion is used as a solvent, so that the solubility of the product 2, 5-furandicarboxylic acid is increased, the introduction of alkaline compounds is avoided, the post-treatment step of the product is simplified, and the condition that a large amount of waste acid and waste water are generated in the subsequent acidification process is avoided;
3. The high specific surface area carbonaceous material used by the invention is used as a carrier, has high catalytic efficiency and high FDCA yield, is green and concise in reaction process, is convenient for large-scale production, and has good industrial application prospect.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Wherein the source of the 5-hydroxymethylfurfural is Beijing Inocai technology Co., ltd; the source of the activated carbon is Beijing Dali macro industry science and technology Co., ltd (analytically pure, hereinafter referred to as "Dali macro industry") and the specific surface area is 1286m 2/g; the specific surface area of the Kabot (China) investment Co., ltd. (trade mark: VXC 72) is 258m 2/g.
Preparation example 1
The primary wet impregnation method is used for preparing 2% Pt/C of supported noble metal catalyst:
Mixing 1.1mL of 0.05g/mL H 2PtCl6 solution and 10.0mL of deionized water, stirring uniformly, adding 0.98g of high specific surface area active carbon carrier (the specific surface area is 1286m 2/g in the great macro industry) into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and drying in a baking oven at 110 ℃ for 12 hours to obtain a catalyst precursor. The Pt loading was 2% (mass percent). The precursor prepared by the steps is placed in a quartz tube, calcined for 4 hours at 500 ℃ in nitrogen, and reduced for 3 hours at 500 ℃ in 20% H 2+N2, so as to obtain the supported 2% Pt/C catalyst.
Ru and Au catalysts 5% Ru/C and 1% Au/C with different loadings were prepared on the activated carbon support in a similar manner.
Preparation example 2
Preparation of supported catalyst containing bismuth and noble metals 2% bi-2% pt/C:
The method comprises the steps of (1) weighing bismuth acetate (Bi (CH 3COO)3) 36.9mg, adding 2mL of glacial acetic acid, fully stirring to enable the bismuth acetate to be fully dissolved, adding 10mL of water to prepare an acetic acid aqueous solution containing the bismuth acetate, (2) weighing 1.0g of a 2% Pt/C catalyst, adding 150mL of deionized water, fully stirring to obtain a suspension, continuously introducing hydrogen (with the flow rate of 10 mL/min) into the suspension for 0.5h, (3) adding a certain amount of glacial acetic acid into the suspension in the step (2), adjusting the pH to be approximately equal to 2, dropwise adding the acetic acid aqueous solution containing the bismuth acetate prepared in the step (1) into the suspension, fully stirring for 1h, keeping continuous introduction of the hydrogen (with the flow rate of 10 mL/min), filtering the suspension, and drying at room temperature to obtain a supported catalyst containing the Bi and the 2% Bi-2% Pt/C of noble metal, wherein the load of the Bi is 2% (mass fraction), and the molar ratio of the Pt to the Bi is approximately 1:1.
Based on the supported Pt catalyst obtained in preparation example 1, supported catalysts containing bismuth and noble metal were prepared in a similar manner with different molar ratios of Pt to Bi, 1% Bi-2% Pt/C (molar ratio of Pt to Bi about 1:0.5) and 8% Bi-2% Pt/C (molar ratio of Pt to Bi about 1:4).
Preparation example 3
A supported catalyst containing bismuth and noble metal was prepared as per preparation example 2, 5% Bi-5% Ru/C, except that the Bi precursor used was bismuth trichloride (BiCl 3), the acid solution used was dilute hydrochloric acid, the Bi loading was 5% (mass fraction), and the molar ratio of Ru to Bi was 1:0.5.
Preparation example 4
A supported catalyst containing bismuth and noble metal was prepared as in preparation example 2, 2% Bi-1% Au/C, except that the Bi precursor used was bismuth nitrate (Bi (NO 3)3), the acid solution used was dilute nitric acid, the Bi loading was 2% (mass fraction), and the Au to Bi molar ratio was 1:2.
Comparative preparation example 1
The supported catalyst containing bismuth and noble metals, 2% Bi-2% Pt/C, was prepared in one step using a incipient wetness impregnation.
Weighing 36.9mg of bismuth acetate (Bi (CH 3COO)3), adding 2mL of glacial acetic acid, stirring fully to dissolve bismuth acetate completely, adding 10mL of water to prepare an aqueous acetic acid solution containing bismuth acetate, adding 1.1mL of 0.05g/mL of H 2PtCl6 solution into the aqueous acetic acid solution, stirring uniformly, adding 0.98g of a high specific surface area active carbon carrier (the specific surface area is 1286m 2/g) into the mixed solution, stirring and soaking at room temperature for 10 hours, evaporating to dryness, and drying in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor, wherein the Bi loading is 2% (mass fraction), and the Pt loading is 2% (mass percent), placing the precursor prepared in the steps into a quartz tube, calcining for 4 hours at 500 ℃ in nitrogen, and reducing for 3 hours at 500 ℃ in 20% H 2+N2 to obtain the supported catalyst containing bismuth and noble metal, namely 2% -Bi-2%Pt/C (marked as 2%Bi-2%C) and Pt with the Pt loading ratio of about 1:1 molar ratio of 1.
Comparative preparation example 2
The supported catalyst containing bismuth and noble metals, 2% Bi-2% Pt/C, was prepared stepwise using incipient wetness impregnation.
First, a supported 2% Pt/C catalyst was prepared according to the method of preparation example 1. Then weighing 36.9mg of bismuth acetate (Bi (CH 3COO)3), adding 2mL of glacial acetic acid, stirring thoroughly to dissolve bismuth acetate, adding 10mL of water to prepare an aqueous solution of bismuth acetate-containing acetic acid, adding 1.0g of 2% Pt/C catalyst to the aqueous solution, stirring and impregnating at room temperature for 10 hours, evaporating to dryness, and drying in a 110 ℃ oven for 12 hours to obtain a catalyst precursor, wherein the Bi loading amount is 2% (mass fraction), placing the precursor prepared in the steps in a quartz tube, and reducing for 3 hours at 300 ℃ in 20% H 2+N2 to obtain the supported catalyst containing bismuth and noble metal, namely 2% Bi-2% Pt/C (marked as 2% Bi-2% Pt/C) by a molar ratio of Pt to Bi being about 1:1.
As can be seen from comparison, in preparation example 2, hydrogen was continuously introduced into a solution containing bismuth to allow bismuth ions in the solution to be reduced in situ on the surface of Pt to form a Pt-Bi alloy, while in preparation example 2, bismuth ions were deposited on the surface of PtC catalyst (not necessarily in contact with Pt) by using an impregnation method, and then reduced in a hydrogen atmosphere after drying, so that Bi and Pt did not interact well with each other on the prepared catalyst.
Comparative preparation example 3
Preparation of Supported catalyst containing bismuth and noble metals on Low specific surface area active carbon Carrier 2% Bi-2% Pt/C
Supported catalyst containing bismuth and noble metals 2% Bi-2% Pt/C3 was prepared on a low specific surface area activated carbon support according to the procedure of preparation 2, except that the catalyst support used was a low specific surface area activated carbon (cabot VXC72, specific surface area 258m 2/g).
Example 1
This example illustrates the synthesis of 2, 5-furandicarboxylic acid according to the present invention.
In a 50mL autoclave, 0.5g of 5-hydroxymethylfurfural, 0.2g of the 2% Bi-2% Pt/C oxidation catalyst prepared in preparation example 2, 10g of a mixed solvent composed of water and 1, 4-dioxane (the mass ratio of water to 1, 4-dioxane is 1:1) were added, the autoclave was closed, 1MPa of oxygen was filled to replace the residual air in the autoclave, the autoclave was repeatedly used three times, 1MPa of oxygen was filled to the autoclave, and the autoclave was heated to a reaction temperature of 100℃in a heating furnace and stirred at a rotation speed of 700rpm for 10 hours. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, filtering, washing a filter cake by using the mixed solvent which is the same as the reaction solvent, finally fixing the volume to 100mL, and taking a liquid sample for high performance liquid chromatography analysis. The reaction results are shown in Table 1.
Example 2
The procedure of example 1 was followed except that 0.2g of the 1% Bi-2% Pt/C catalyst prepared in preparation example 2 was used as the oxidation catalyst, and the reaction results are shown in Table 1.
Example 3
The procedure of example 1 was followed except that 0.2g of the oxidation catalyst was used as the 8% Bi-2% Pt/C catalyst prepared in preparation example 2, and the reaction results are shown in Table 1.
Example 4
The procedure of example 1 was followed except that 0.2g of the 5% Bi-5% Ru/C catalyst prepared in preparation example 3 was used as the oxidation catalyst, and the reaction results are shown in Table 1.
Example 5
The procedure of example 1 was followed except that 0.2g of the 2% Bi-1% Au/C catalyst prepared in preparation example 4 was used as the oxidation catalyst, and the reaction results are shown in Table 1.
Example 6
The procedure of example 1 was followed except that the pressure of oxygen charged into the reaction vessel at the start of the reaction was 2MPa, and the reaction results are shown in Table 1.
Example 7
The procedure of example 1 was followed except that the pressure of oxygen charged into the reaction vessel at the start of the reaction was 3MPa, and the reaction results are shown in Table 1.
Example 8
The procedure of example 1 was followed except that the reaction temperature was 120℃and the reaction results are shown in Table 1.
Example 9
The procedure of example 1 was followed except that the reaction temperature was 140℃and the reaction results are shown in Table 1.
Example 10
The procedure of example 1 was followed except that the reaction solvent was a mixed solvent of water and tetrahydrofuran (mass ratio of water to tetrahydrofuran: 1:1). The reaction results are shown in Table 2.
Example 11
The procedure of example 1 was followed except that the reaction solvent was a mixed solvent of 1, 4-dioxane and water (mass ratio of 1, 4-dioxane to water: 3:1). The reaction results are shown in Table 2.
Example 12
The procedure of example 1 was followed except that only 10% Ru/C catalyst supported on activated carbon from the macro industry was used as the oxidation catalyst, and the total mass of the reaction solvent was 20g. The reaction results are shown in Table 2.
Comparative example 1
The procedure of example 1 was followed except that 0.2g of the 2% Pt/C catalyst prepared in preparation example 1 was used as the oxidation catalyst, and the reaction results are shown in Table 1.
Comparative example 2
The procedure of example 1 was followed except that 0.2g of the oxidation catalyst was used as 2% bi-2% pt/C1 catalyst prepared in comparative preparation 1, and the reaction results are shown in table 1.
Comparative example 3
The procedure of example 1 was followed except that 0.2g of the oxidation catalyst was used as 2% bi-2% pt/C2 catalyst prepared in comparative preparation 2, and the reaction results are shown in table 1.
Comparative example 4
The procedure of example 1 was followed except that 0.2g of the oxidation catalyst was used as 2% bi-2% pt/C3 catalyst prepared in comparative preparation 3, and the reaction results are shown in table 1.
Comparative example 5
The procedure of example 1 was followed except that the reaction solvent was water only, and the reaction results are shown in Table 2.
Comparative example 6
The procedure of example 1 was followed except that the reaction solvent was 1, 4-dioxane only, and the reaction results are shown in Table 2.
Comparative example 7
The procedure of example 1 was followed except that the reaction solvent was dimethyl sulfoxide alone, and the reaction results are shown in Table 2.
TABLE 1 reaction results for examples 1-9 and comparative examples 1-4
TABLE 2 reaction results for examples 10-12 and comparative examples 5-7
From the data in Table 1, examples 1-3, it is seen that the molar ratio of Pt to bismuth in the supported Pt catalyst containing bismuth affects the performance of the catalyst, but the molar ratio of noble metal to bismuth is in the range of 1:0.5 to 1:4, with FDCA yield greater than 85%; 2. from examples 4 and 5, the supported Ru or Au catalyst containing bismuth shows higher activity of oxidizing HMF to FDCA under the test condition of the method, the conversion rate of HMF reaches 100%, and the yield of FDCA is more than 90%; 3. from examples 6-9, it is clear that the partial pressure of oxygen and the reaction temperature also affect the performance of the 2% Bi-2% Pt/C oxidation catalyst, and that too high partial pressure of oxygen and reaction temperature will result in a certain reduction in FDCA yield; 4. as can be seen from comparative example 1, compared with the catalyst containing bismuth prepared by the method, the catalyst without bismuth has significantly reduced HMF oxidation activity and FDCA yield, which indicates that the catalyst performance can be significantly improved after the catalyst surface is modified with bismuth; 5, as can be seen from comparative examples 2 and 3, compared with the supported catalyst containing bismuth and noble metal prepared by the conventional catalyst preparation method, such as an impregnation method, whether the supported catalyst is prepared in one step or step, the supported catalyst has obviously lower HMF oxidation activity and FDCA yield compared with the supported catalyst prepared by the method, which indicates that the catalyst preparation method used by the method can better promote the promotion effect of bismuth element on the oxidation activity of the catalyst and effectively improve the FDCA yield; 6, as is clear from comparative example 4, the specific surface area of the carrier significantly affects the activity of the catalyst, and when the specific surface area of the carrier is reduced, the FDCA yield is significantly reduced.
From the data in Table 2, 1, it is known from examples 10 to 12 that solvents composed of water and 1, 4-dioxane or tetrahydrofuran in different mass ratios can better realize the reaction process of preparing FDCA by oxidizing HMF within the limit of the invention; the total addition of the solvent affects the performance of the catalyst, and the increase of the total addition of the solvent, namely, the reduction of the concentration of the 5-hydroxymethylfurfural is beneficial to the improvement of the FDCA yield, but the single-pass treatment capacity of the method is correspondingly reduced; 2. as is clear from comparative examples 5 to 7, pure water, or 1, 4-dioxane or dimethyl sulfoxide solvent alone, caused a small amount of FDCA generated in the reaction to adhere to the surface of the oxidation catalyst and poisoned the catalytic active center due to the inability to effectively dissolve FDCA generated in the reaction, resulting in a significant decrease in the activity of the oxidation catalyst and the yield of FDCA.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (16)
1. A process for preparing 2, 5-furandicarboxylic acid comprising: in a mixed solvent consisting of an organic solvent and water, reacting 5-hydroxymethylfurfural with oxygen in the presence of an oxidation catalyst to obtain the 2, 5-furandicarboxylic acid; wherein the oxidation catalyst is a supported catalyst containing bismuth and noble metal, and the preparation method of the supported catalyst containing bismuth and noble metal comprises the following steps: (1) Dissolving a precursor containing bismuth in an acid solution to prepare an acid solution containing bismuth; (2) Dispersing a supported noble metal catalyst in water, stirring to obtain a suspension, and continuously introducing hydrogen into the suspension; (3) Adding an acid solution into the suspension in the step (2), regulating the pH value to be acidic, adding the bismuth-containing acidic solution in the step (1), and filtering and drying to obtain the bismuth-and-noble-metal-containing supported catalyst; the supported noble metal catalyst comprises a carrier and noble metals supported on the carrier, wherein the noble metals are one or more of Ru, pt and Au, the loading amount of the noble metals is 0.1-10% based on the total mass of the carrier, the molar ratio of the noble metals to bismuth is 1:0.1-10, the organic solvent is selected from tetrahydrofuran or 1, 4-dioxane, the mass ratio of the organic solvent to water is 5:1-0.5:1, and the temperature of the oxidation reaction is 90-150 ℃.
2. The method according to claim 1, wherein the mass ratio of the organic solvent to water in the mixed solvent of the organic solvent and water is 3:1 to 1:1.
3. The method according to claim 1, wherein the mass percentage of the 5-hydroxymethylfurfural in the solution formed by the mixed solvent of the 5-hydroxymethylfurfural and the organic solvent and water is 0.1-30%.
4. The method according to claim 1, wherein the mass percentage of the 5-hydroxymethylfurfural in the solution formed by the mixed solvent of the 5-hydroxymethylfurfural and the organic solvent and water is 0.5-20%.
5. The method according to claim 1, wherein the mass percentage of the 5-hydroxymethylfurfural in the solution formed by the mixed solvent of the 5-hydroxymethylfurfural and the organic solvent and water is 1-10%.
6. The process according to claim 1, wherein the molar ratio of noble metal to bismuth in the supported catalyst comprising bismuth and noble metal is from 1:0.5 to 4.
7. The process according to claim 1, wherein the molar ratio of noble metal to 5-hydroxymethylfurfural in the supported catalyst containing bismuth and noble metal is from 1:1 to 1000.
8. The process according to claim 1, wherein the molar ratio of noble metal to 5-hydroxymethylfurfural in the supported catalyst containing bismuth and noble metal is 1:5-500.
9. The process according to claim 1, wherein the molar ratio of noble metal to 5-hydroxymethylfurfural in the supported catalyst containing bismuth and noble metal is from 1:5 to 250.
10. The method of claim 1, wherein the bismuth-containing precursor in step (1) is selected from one or more of bismuth nitrate, bismuth trichloride, bismuth acetate.
11. The method of claim 1, wherein the acid solution in steps (1) and (3) is nitric acid, hydrochloric acid, acetic acid, or an aqueous solution formulated from one or more thereof.
12. The method according to claim 1, wherein in the step (2), the ventilation amount of hydrogen is 10 to 100mL/min.
13. The method according to claim 1, wherein the noble metal loading is 1% to 5% based on the total mass of the support.
14. The method of claim 1, wherein the carrier of the supported noble metal catalyst is selected from one or more carbonaceous materials of activated carbon, carbon nanotubes, graphene or graphene oxide.
15. The method of claim 14, wherein the activated carbon has a specific surface area of 1000m 2/g～1500m2/g.
16. The method according to claim 1, wherein the oxygen is derived from pure oxygen, air or a mixed gas of oxygen and nitrogen, and the partial pressure of the oxygen is 1MPa to 5MPa.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277020A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diformic acid by water phase catalysis of 5-hydroxymethylfurfural |
| CN105026383A (en) * | 2013-03-14 | 2015-11-04 | 阿彻丹尼尔斯米德兰德公司 | Process for making 2,5-furandicarboxylic acid |
| CN105555774A (en) * | 2013-09-19 | 2016-05-04 | 花王株式会社 | 2,5-furan dicarboxylic acid production method |
| CN106999917A (en) * | 2014-12-18 | 2017-08-01 | 花王株式会社 | The modulator approach of catalyst |
| CN107365287A (en) * | 2016-05-11 | 2017-11-21 | 中国石油化工股份有限公司 | A kind of method of synthesis 2,5- furandicarboxylic acids |
| CN108779088A (en) * | 2016-01-13 | 2018-11-09 | 斯道拉恩索公司 | The preparation method of 2,5- furandicarboxylic acids and its intermediate and derivative |
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026383A (en) * | 2013-03-14 | 2015-11-04 | 阿彻丹尼尔斯米德兰德公司 | Process for making 2,5-furandicarboxylic acid |
| CN104277020A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diformic acid by water phase catalysis of 5-hydroxymethylfurfural |
| CN105555774A (en) * | 2013-09-19 | 2016-05-04 | 花王株式会社 | 2,5-furan dicarboxylic acid production method |
| CN106999917A (en) * | 2014-12-18 | 2017-08-01 | 花王株式会社 | The modulator approach of catalyst |
| CN108779088A (en) * | 2016-01-13 | 2018-11-09 | 斯道拉恩索公司 | The preparation method of 2,5- furandicarboxylic acids and its intermediate and derivative |
| CN107365287A (en) * | 2016-05-11 | 2017-11-21 | 中国石油化工股份有限公司 | A kind of method of synthesis 2,5- furandicarboxylic acids |
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