CN111036200A - Catalyst and preparation method of 2, 5-furandicarboxylic acid - Google Patents
Catalyst and preparation method of 2, 5-furandicarboxylic acid Download PDFInfo
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- CN111036200A CN111036200A CN201811191617.0A CN201811191617A CN111036200A CN 111036200 A CN111036200 A CN 111036200A CN 201811191617 A CN201811191617 A CN 201811191617A CN 111036200 A CN111036200 A CN 111036200A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
The invention provides a catalyst and a preparation method of 2, 5-furandicarboxylic acid, wherein the preparation method of the catalyst comprises the following steps: mixing a carrier, an alkaline nitrogen-containing compound and an active component precursor, putting the mixture into a solvent, heating the mixture under the condition of water bath, and carrying out reflux stirring treatment; sequentially drying and roasting and reducing the carrier subjected to the reflux stirring treatment to obtain the catalyst; wherein the active component precursor is selected from one or more of ruthenium chloride, palladium chloride, chloroplatinic acid and rhodium chloride, and the carrier is selected from one or more of activated carbon, graphite, fullerene and graphene oxide. The catalyst can realize the high-efficiency conversion of the 5-hydroxymethylfurfural without adding an alkaline auxiliary agent to obtain the high-selectivity 2, 5-furandicarboxylic acid, and has the advantages of simple operation method, mild reaction condition, environmental protection, no pollution and good industrial application prospect.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method of a catalyst and a method for preparing 2, 5-furandicarboxylic acid by applying the prepared catalyst.
Background
Currently, fuels and chemicals needed by society are mainly derived from fossil fuels, and the increase of the cost, the reduction of the supply amount of the fossil fuels and the influence on the environment lead people to generate wide interest in sustainable alternative energy and chemical raw materials, especially biomass resources which have wide sources and high carbohydrate specific gravity and can produce liquid fuels and organic chemicals through processes of selective dehydration or hydrogenation and the like. 5-Hydroxymethylfurfural (HMF) is one of the important biomass-based platform compounds, which can be prepared by acid-catalyzed dehydration of carbohydrates such as fructose, glucose and cellulose, 2, 5-furandicarboxylic acid (FDCA) obtained by catalytic oxidation of 5-hydroxymethylfurfural. The FDCA contains aromatic rings in the molecular structure, can effectively improve the heat resistance and mechanical properties of a bio-based polymer material when used for synthesizing the bio-based polymer material, is considered to be an ideal substitute of petroleum-based monomer terephthalic acid (PTA), and can also be applied to the synthesis of bio-based polymers such as polyester, polyamide and epoxy resin instead of isophthalic acid, adipic acid, succinic acid, bisphenol A and the like. Therefore, the development of the synthetic method of the 2, 5-furandicarboxylic acid has important application value and biomass sustainable utilization significance.
In the process of preparing FDCA by selective oxidation of HMF, the generated FDCA can reduce the activity of a metal catalyst and even deactivate the metal catalyst, so that an alkaline compound is often added to generate a salt with the product FDCA, the catalyst is protected, the ring-opening degradation of the FDCA is prevented, and the selectivity of the product is improved. Some patents and literature reports methods for synthesizing FDCA, such as: CN 101891719A discloses a method for synthesizing 2, 5-furandicarboxylic acid, which adopts a catalyst to catalyze furan substances in an alkaline solution to synthesize the 2, 5-furandicarboxylic acid, but the reaction time is longer, and the alkaline solution is not easy to separate from the product after mixing; gupta et al (Greenchemistry, 2011, 13(4), p 824-827) load Au on alkaline Hydrotalcite (HT) to obtain an Au/HT catalyst, however, as the use frequency increases, the carrier HT gradually dissolves, so that the stability of the catalyst is reduced; CN104162422A discloses a preparation method of a basic carbonaceous solid catalyst carrier, which is used for catalytic synthesis of FDCA, however, the catalyst has a problem of reduced activity after multiple uses.
Therefore, it is desirable to provide a new catalyst and a method for synthesizing 2, 5-furandicarboxylic acid using the same, which solve the above problems in the prior art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst and a method for preparing 2, 5-furandicarboxylic acid by applying the prepared catalyst, so as to solve the problems that the traditional synthetic method or an alkaline solution is used as an alkali source, which brings difficulty to product separation, and the subsequent acidification treatment is complicated; or using basic compound as carrier, the loss of basic metal ion in the circulation process reduces the stability of catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a catalyst, which comprises the following steps:
mixing a carrier, an alkaline nitrogen-containing compound and an active component precursor, putting the mixture into a solvent, heating the mixture under the condition of water bath, and carrying out reflux stirring treatment;
sequentially drying and roasting and reducing the carrier subjected to the reflux stirring treatment to obtain the catalyst;
wherein the active component precursor is selected from ruthenium chloride (RuCl)3) Palladium chloride (PdCl)2) Chloroplatinic acid (H)2PtCl6) And rhodium chloride (RhCl)3) Is selected from Activated Carbon (AC), graphite (C), fullerene (C)60) And Graphene Oxide (GO).
According to one embodiment of the invention, the active component precursor is ruthenium chloride and the support is activated carbon.
According to one embodiment of the present invention, the basic nitrogen-containing compound is selected from one or more of a nitrogen-containing heterocyclic compound selected from one or more of pyridine, bipyridine, pyrrole, piperidine, imidazole, biimidazole and melamine, an aliphatic amine selected from one or more of ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, 1, 2-propylenediamine, 1, 3-propylenediamine and n-butylamine, and an aromatic amine selected from one or more of aniline, benzylamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-aminophenol, m-aminophenol and p-aminophenol.
According to one embodiment of the invention, the mass ratio of the metal element in the active component precursor to the carrier is 0.005-0.08: 1, preferably 0.035-0.08: 1, and more preferably 0.04-0.06: 1.
According to one embodiment of the invention, the mass ratio of the support to the basic nitrogen-containing compound is 1: 1-25; the mass ratio of the carrier to the solvent is 1: 20-150.
According to one embodiment of the present invention, the solvent is a mixed solution of ethanol and water, the ethanol accounts for 10% to 95% of the mass of the mixed solution, the water accounts for 5% to 90% of the mass of the mixed solution, preferably, the ethanol accounts for 20% to 50% of the mass of the mixed solution, and the water accounts for 50% to 80% of the mass of the mixed solution.
According to one embodiment of the invention, the reflux stirring treatment is carried out at a temperature of 40 ℃ to 95 ℃, preferably 50 ℃ to 75 ℃; the time of the reflux stirring treatment is 2 to 16 hours, preferably 6 to 10 hours.
According to one embodiment of the invention, the drying treatment is carried out at a temperature of between 80 ℃ and 200 ℃, preferably between 100 ℃ and 150 ℃; the drying time is 8-24 h, preferably 10-18 h.
According to one embodiment of the invention, the roasting reduction treatment comprises the step of subjecting the dried carrier to reduction roasting in a reducing atmosphere, wherein the reducing atmosphere comprises 10-100% of hydrogen and 0-90% of nitrogen or inert gas by volume percentage, preferably, the hydrogen is 20-50% by volume, and the nitrogen or inert gas is 50-80% by volume; the roasting reduction treatment is carried out at the temperature of 300-900 ℃, preferably 400-800 ℃; the time of the roasting reduction treatment is 1-6 h, preferably 2-4 h.
The invention also provides a catalyst prepared by the method.
The invention also provides a preparation method of the 2, 5-furandicarboxylic acid, which comprises the following steps:
contacting an aqueous solution of 5-hydroxymethylfurfural with a catalyst under the condition of air and/or oxygen to perform a catalytic oxidation reaction to prepare the 2, 5-furandicarboxylic acid, wherein the catalyst is the catalyst in claim 10.
According to one embodiment of the invention, the molar ratio of the 5-hydroxymethylfurfural to the metal elements in the catalyst is 40-200: 1, preferably 70-120: 1.
according to one embodiment of the present invention, the partial pressure of oxygen in the catalytic oxidation reaction is 0.05 to 2MPa, preferably 0.5 to 1 MPa; the reaction temperature is 50-170 ℃, and preferably 90-120 ℃; the reaction time is 0.5 to 24 hours, preferably 1 to 4 hours.
According to the technical scheme, the invention has the beneficial effects that:
according to the catalyst and the preparation method thereof provided by the invention, the active component precursor, the carrier and the basic nitrogen-containing compound are mixed, so that the interaction among the active component precursor, the carrier and the basic nitrogen-containing compound can be promoted, the surface chemical property of the carrier is changed, the obtained catalyst can catalyze the selective oxidation reaction of 5-hydroxymethylfurfural without adding an alkaline auxiliary agent, compared with the catalyst prepared without adding the basic nitrogen-containing compound, the activity is obviously improved, the preparation steps are simple, and the amplification production is convenient;
according to the preparation method of 2, 5-furandicarboxylic acid, the catalyst can be used for realizing efficient conversion of 5-hydroxymethylfurfural under mild conditions to obtain the high-selectivity 2, 5-furandicarboxylic acid, the operation method is simple, the post-treatment step of the product can be simplified without adding an alkaline auxiliary agent, and the condition that a large amount of wastewater is generated in the subsequent acidification process is avoided; in addition, in the preparation process, water is used as a solvent, and oxygen or air is used as an oxygen source, so that the preparation method is low in cost, green, environment-friendly, pollution-free and good in industrial application prospect.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a catalyst, which comprises the following steps:
mixing a carrier, an alkaline nitrogen-containing compound and an active component precursor, putting the mixture into a solvent, heating the mixture under the condition of water bath, and carrying out reflux stirring treatment;
sequentially drying and roasting and reducing the carrier subjected to the reflux stirring treatment to obtain the catalyst;
wherein the active component precursor is selected from ruthenium chloride (RuCl)3) Palladium chloride (PdCl)2) Chloroplatinic acid (H)2PtCl6) And rhodium chloride (RhCl)3) Is selected from Activated Carbon (AC), graphite (C), fullerene (C)60) And Graphene Oxide (GO).
According to the catalyst prepared by the method, the active component precursor, the carrier and the basic nitrogen-containing compound are mixed, so that the interaction among the active component precursor, the carrier and the basic nitrogen-containing compound can be promoted, the surface chemical property of the carrier is changed, the obtained catalyst can catalyze the selective oxidation reaction of the 5-hydroxymethylfurfural without adding the basic auxiliary agent, the activity is obviously improved compared with the catalyst prepared without adding the basic nitrogen-containing compound, the preparation steps are simple, and the large-scale production is facilitated.
In some embodiments, the active component precursor is ruthenium chloride (RuCl)3) And the carrier is Activated Carbon (AC). Research shows that the Ru/Ac catalyst prepared by the method can further improve the selectivity of the 2, 5-furandicarboxylic acid.
In some embodiments, the basic nitrogen-containing compound is selected from one or more of a nitrogen-containing heterocyclic compound selected from one or more of pyridine, bipyridine, pyrrole, piperidine, imidazole, biimidazole, and melamine, an aliphatic amine selected from one or more of ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, 1, 2-propanediamine, 1, 3-propanediamine, and n-butylamine, and an aromatic amine selected from one or more of aniline, benzylamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-aminophenol, m-aminophenol, and p-aminophenol.
In some embodiments, the mass ratio of the metal element in the active component precursor to the carrier is 0.005-0.08: 1, preferably 0.035-0.08: 1, and more preferably 0.04-0.06: 1.
In some embodiments, the mass ratio of the support to the basic nitrogen-containing compound is 1: 1-25; the mass ratio of the carrier to the solvent is 1: 20-150.
In some embodiments, the solvent is a mixed solution of ethanol and water, the ethanol accounts for 10% to 95% of the mixed solution, the water accounts for 5% to 90% of the mixed solution, preferably, the ethanol accounts for 20% to 50% of the mixed solution, and the water accounts for 50% to 80% of the mixed solution.
In some embodiments, the reflux agitation treatment is performed at a temperature of 40 ℃ to 95 ℃, preferably 50 ℃ to 75 ℃; the time of the reflux stirring treatment is 2 to 16 hours, preferably 6 to 10 hours.
In some embodiments, the drying treatment is carried out at a temperature of 80 ℃ to 200 ℃, preferably 100 ℃ to 150 ℃; the drying time is 8-24 h, preferably 10-18 h.
In some embodiments, the roasting reduction treatment includes subjecting the dried carrier to reduction roasting in a reducing atmosphere, wherein the reducing atmosphere includes 10-100% by volume of hydrogen (H)2) And 0% -90% of nitrogen (N)2) Or inert gases including, but not limited to, helium (He), argon (Ar), and the like. Preferably, the volume percentage of the hydrogen is 20-50%, and the volume percentage of the nitrogen or the inert gas is 50-80%; the roasting reduction treatment is carried out at the temperature of 300-900 ℃, preferably 400-800 ℃; the time of the roasting reduction treatment is 1-6 h, preferably 2-4 h.
The invention also provides a catalyst prepared by the method.
The invention also provides a preparation method of the 2, 5-furandicarboxylic acid, which comprises the following steps:
contacting an aqueous solution of 5-hydroxymethylfurfural with a catalyst under the condition of air and/or oxygen to perform a catalytic oxidation reaction to prepare the 2, 5-furandicarboxylic acid, wherein the catalyst is the catalyst in claim 10.
It will be appreciated by those skilled in the art that the catalytic oxidation reaction is carried out in a sealed environment.
In some embodiments, the molar ratio of the 5-hydroxymethylfurfural to the active components in the catalyst is from 40 to 200: 1, preferably 70-120: 1.
in some embodiments, the catalytic oxidation reaction has an oxygen partial pressure of 0.05 to 2MPa, preferably 0.5 to 1 MPa; specifically, the air and/or oxygen in the above pressure range can be injected into the reaction kettle at one time, and the operation is simpler and more convenient compared with a continuous aeration mode.
In some embodiments, the reaction temperature in the catalytic oxidation reaction is 50 ℃ to 170 ℃, preferably 90 ℃ to 120 ℃; the reaction time is 0.5 to 24 hours, preferably 1 to 4 hours. It can be seen that the catalyst of the invention is adopted to prepare 2, 5-furandicarboxylic acid, the reaction temperature is relatively mild, the catalytic activity is high, and the reaction time is short.
Therefore, the catalyst can realize the high-efficiency conversion of the 5-hydroxymethylfurfural under mild conditions without adding an alkaline auxiliary agent, and simplifies the post-treatment steps of the product. In addition, the method of the invention fills gas with certain pressure into the reaction kettle at one time, and the operation is simple; as water is used as a solvent and oxygen or air is used as an oxygen source in the whole preparation process, the preparation method is low in cost, green, environment-friendly and pollution-free, and has good industrial application prospects.
The following is illustrated by specific examples:
PREPARATION EXAMPLE 1 preparation of Ru/AC catalyst
2g of the support activated carbon AC, 6g of bipyridine, 120g of 25 wt% ethanol and 75 wt% water were mixed, and RuCl was added3Wherein the mass ratio of the metal Ru to the carrier active carbon AC is 0.05:1, refluxing and stirring the mixture for 8 hours under the condition of 70 ℃ water bath, separating the treated solid, drying the solid in a 120 ℃ oven for 16 hours, and then drying the dried solid in 20 percent of H by volume percentage2And 80% N2Is reduced and roasted for 4 hours at 650 ℃ to obtain the catalyst Ru/AC with the active component content (namely the metal element content) of 4.7wt percent.
PREPARATION EXAMPLE 2 preparation of Ru/AC catalyst
2g of the support activated carbon AC, 10g of melamine, 130g of 20% by weight ethanol and 70% by weight water are mixed, RuCl is added3Wherein the mass ratio of the metal Ru to the carrier active carbon AC is 0.06:1, refluxing and stirring for 10H under the condition of 60 ℃ water bath, separating the treated solid, drying in a 110 ℃ oven for 18H, and then drying in 30% H by volume percentage2And 70% N2Is reduced and roasted for 3 hours at 750 ℃ to obtain the catalyst Ru/AC with the active component content of 5.6 wt%.
PREPARATION EXAMPLE 3 preparation of Ru/AC catalyst
Mixing 2g of carrier activated carbon AC, 14g of 1, 3-propane diamine, 100g of 40 wt% ethanol and 60 wt% water, adding RuCl3, wherein the mass ratio of metal Ru to the carrier activated carbon AC is 0.04:1, and adding water at 65 DEG CRefluxing and stirring for 7H under bath conditions, separating the treated solid, drying in an oven at 130 deg.C for 14H, and then at 25% H by volume2And 75% N2The reduction roasting is carried out for 4 hours at 700 ℃, and the catalyst Ru/AC with the active component content of 3.7 wt% is obtained.
PREPARATION EXAMPLE 4 preparation of Ru/C catalyst
Mixing 2g of carrier graphite C, 2g of o-phenylenediamine, 150g of 10 wt% ethanol and 90 wt% water, adding RuCl3, wherein the mass ratio of metal Ru to the carrier graphite C is 0.05:1, carrying out reflux stirring treatment for 6H under the condition of 80 ℃ water bath, separating the treated solid, drying in an oven at 110 ℃ for 16H, and then carrying out drying at 35% H by volume percentage2And 65% N2The reduction roasting is carried out for 4 hours at the temperature of 600 ℃, and the catalyst Ru/C with the active component content of 4.7 wt% is obtained.
PREPARATION EXAMPLE 5 preparation of Rh/GO CATALYST
2g of graphene oxide as a support, 8g of biimidazole, 120g of 30 wt% ethanol and 70 wt% water were mixed, RhCl was added3Wherein the mass ratio of metal Rh to carrier graphene oxide GO is 0.05:1, refluxing and stirring for 8H under the condition of 55 ℃ water bath, separating the treated solid, drying for 12H in a 100 ℃ oven, and then adding 15% of H in percentage by volume2And reducing and roasting the mixture for 2 hours at 800 ℃ in the atmosphere of 85% He to obtain a catalyst Rh/GO with the active component content of 4.7 wt%.
PREPARATION EXAMPLE 6 preparation of Ru/AC catalyst
The catalyst Ru/AC was prepared as described in preparation 1, except that the basic compound added was piperidine, RuCl3The mass ratio of the metal Ru to the carrier active carbon AC in the aqueous solution is 0.08:1, and the catalyst Ru/AC with the active component content of 7.4 wt% is obtained.
PREPARATION EXAMPLE 7 preparation of Ru/AC catalyst
The catalyst Ru/AC was prepared as described in preparation example 1, except that the basic compound added was benzylamine, RuCl3The mass ratio of the metal Ru to the carrier active carbon AC in the aqueous solution is 0.03:1, and the catalyst Ru/AC with the active component content of 2.8 wt% is obtained.
Preparation example 8 preparation of Pd/AC catalyst
The catalyst Pd/AC was prepared by following the procedure of preparation example 1, except that triethylamine as a basic compound was added and PdCl was used2Aqueous solution instead of RuCl3Aqueous solution to obtain the catalyst Pd/AC with the active component content of 4.7 wt%.
PREPARATION EXAMPLE 9 preparation of Pt/AC catalyst
Catalyst Pt/AC was prepared as in preparation 1, except that the basic compound added was piperidine and H was used2PtCl6Aqueous solution instead of RuCl3And (4) obtaining a catalyst Pt/AC with the active component content of 4.7 wt% by using an aqueous solution.
PREPARATION EXAMPLE 10 preparation of Rh/AC catalyst
A catalyst Rh/AC was prepared as in preparation 1, except that the basic compound added was m-phenylenediamine and RhCl3The aqueous solution was substituted for the aqueous solution of RuCl3 to give a catalyst Rh/AC with an active component content of 4.7 wt%.
Preparation example 11 preparation of catalyst Pt/GO
Catalyst Pt/GO was prepared according to the method of preparation 1, except that the basic compound added was n-propylamine, H2PtCl6Aqueous solution instead of RuCl3And (3) obtaining a catalyst Pt/GO with the active component content of 4.7 wt% by using an aqueous solution.
Preparation example 12 Pd/C catalyst60Preparation of
Preparation of the catalyst Pd/C according to the method of preparation example 160In the difference, the basic compound added is pyrrole, with PdCl2Aqueous solution instead of RuCl3Aqueous solution to obtain catalyst Pd/C with active component content of 4.7 wt%60。
Comparative preparation example 1
The procedure of preparation example 1 was followed, except that RuCl was added without adding basic nitrogen-containing compound3Mixing activated carbon AC with 25 wt% ethanol and 75 wt% water, and stirring for 8h, wherein RuCl3The mass ratio of the metal Ru to the active carbon AC in the aqueous solution is 0.05: 1. The mixture was then dried at 120 ℃ for 16H at 20% H2And 80% N2Atmosphere(s)Reducing at 650 ℃ for 4h to obtain the catalyst Ru/AC with the active component content of 4.7 wt%.
Comparative preparation example 2
The procedure of preparation example 1 was followed except that RuCl was directly impregnated by an equal volume impregnation method3Mixing the aqueous solution with activated carbon AC, and stirring for 2h, wherein RuCl3The mass ratio of the metal Ru to the active carbon AC in the aqueous solution is 0.05: 1. The mixture was then dried at 120 ℃ for 16H at 20% H2And 80% N2Reducing for 4h at 650 ℃ in the atmosphere to obtain the catalyst Ru/AC with the active component content of 4.7 wt%.
Example 1
This example illustrates the synthesis of 2, 5-furandicarboxylic acid according to the present invention.
Adding 0.2g of 5-hydroxymethylfurfural into a 50mL stainless steel high-pressure reaction kettle, adding 10mL deionized water to dissolve the 5-hydroxymethylfurfural, adding 0.034g of Ru/AC (the content of active components is 4.7 wt%, namely the molar ratio of the 5-hydroxymethylfurfural to a catalyst calculated by metal elements is about 100: 1) obtained in the preparation example 1 into a reaction solution, filling oxygen to 0.8MPa without adding an alkaline assistant, sealing the reaction kettle, raising the reaction temperature to 120 ℃ by adopting an automatic temperature control program, keeping the temperature for 4 hours under continuous stirring, and keeping the pressure unchanged in the reaction process. After the reaction was completed, it was cooled to 25 ℃. And filtering and washing the reaction solution to collect the reaction solution. And (3) diluting the reaction solution with deionized water, fixing the volume to 100mL, and sampling for high performance liquid chromatography analysis. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 93.8 percent.
Example 2
This example illustrates the synthesis of 2, 5-furandicarboxylic acid according to the present invention.
Adding 0.2g of 5-hydroxymethylfurfural into a 50mL stainless steel high-pressure reaction kettle, adding 10mL deionized water to dissolve the 5-hydroxymethylfurfural, adding 0.024g of Ru/AC (the active component content is 5.6 wt%, namely the molar ratio of the 5-hydroxymethylfurfural to the catalyst calculated by metal elements is about 120: 1) obtained in the preparation example 2 into a reaction solution, filling oxygen to 1.0MPa without adding an alkaline assistant, sealing the reaction kettle, raising the reaction temperature to 90 ℃ by adopting an automatic temperature control program, keeping the temperature for 6 hours under continuous stirring, and keeping the pressure unchanged in the reaction process. After the reaction was completed, it was cooled to 25 ℃. And filtering and washing the reaction solution to collect the reaction solution. And (3) diluting the reaction solution with deionized water, fixing the volume to 100mL, and sampling for high performance liquid chromatography analysis. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 90.4 percent.
Example 3
This example illustrates the synthesis of 2, 5-furandicarboxylic acid according to the present invention.
Adding 0.2g of 5-hydroxymethylfurfural into a 50mL stainless steel high-pressure reaction kettle, adding 10mL deionized water to dissolve the 5-hydroxymethylfurfural, adding 0.06g of Ru/AC (the content of active components is 3.7 wt%, namely the molar ratio of the 5-hydroxymethylfurfural to a catalyst calculated by metal elements is about 70: 1) obtained in the preparation example 3 into a reaction solution, filling oxygen to 0.5MPa without adding an alkaline assistant, sealing the reaction kettle, raising the reaction temperature to 100 ℃ by adopting an automatic temperature control program, keeping the temperature for 2 hours under continuous stirring, and keeping the pressure unchanged in the reaction process. After the reaction was completed, it was cooled to 25 ℃. And filtering and washing the reaction solution to collect the reaction solution. And (3) diluting the reaction solution with deionized water, fixing the volume to 100mL, and sampling for high performance liquid chromatography analysis. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 87.7 percent.
Example 4
This example illustrates the synthesis of 2, 5-furandicarboxylic acid according to the present invention.
Adding 0.2g of 5-hydroxymethylfurfural into a 50mL stainless steel high-pressure reaction kettle, adding 10mL deionized water to dissolve the 5-hydroxymethylfurfural, adding 0.034g of Ru/C (the content of active components is 4.7 wt%, namely the molar ratio of the 5-hydroxymethylfurfural to a catalyst calculated by metal elements is about 100: 1) obtained in the preparation example 4 into a reaction solution, filling oxygen to 0.6MPa without adding an alkaline assistant, sealing the reaction kettle, raising the reaction temperature to 120 ℃ by adopting an automatic temperature control program, keeping the temperature for 2 hours under continuous stirring, and keeping the pressure unchanged in the reaction process. After the reaction was completed, it was cooled to 25 ℃. And filtering and washing the reaction solution to collect the reaction solution. And (3) diluting the reaction solution with deionized water, fixing the volume to 100mL, and sampling for high performance liquid chromatography analysis. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 82.6 percent.
Example 5
The procedure is as in example 1, except that 0.043g of the catalyst Rh/GO obtained in preparation 5 is used (active component content 3.7% by weight, i.e. the molar ratio of 5-hydroxymethylfurfural to catalyst calculated on metallic elements is approximately 100: 1). The conversion rate of the 5-hydroxymethylfurfural is 99 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 83.7 percent.
Example 6
The procedure of example 1 was followed except that 0.022g of the catalyst Ru/AC obtained in preparation example 6 was used (active component content 7.4 wt%, i.e., molar ratio of 5-hydroxymethylfurfural to the catalyst on a metal element basis was about 100: 1). The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 86.5 percent.
Example 7
The procedure of example 1 was followed except that 0.058g of the catalyst Ru/AC obtained in preparation example 7 (active component content: 2.8% by weight, i.e., the molar ratio of 5-hydroxymethylfurfural to the catalyst based on the metal element was about 100: 1) was used as the catalyst. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 83.9 percent.
Example 8
The procedure of example 1 was followed except that the catalyst Pd/AC obtained in preparation example 8 (active component content: 4.7% by weight, i.e., the molar ratio of 5-hydroxymethylfurfural to the catalyst on a metal element basis: about 100: 1) was used. The conversion rate of 5-hydroxymethylfurfural is 95% and the selectivity of the product 2, 5-furandicarboxylic acid is 79.5% through calculation.
Example 9
The procedure of example 1 was followed except that the catalyst Pt/AC obtained in preparation example 9 was used (active component content: 4.7% by weight, i.e., molar ratio of 5-hydroxymethylfurfural to the catalyst based on the metal element: about 100: 1). The conversion rate of the 5-hydroxymethylfurfural is 99 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 82.1 percent.
Example 10
The procedure of example 1 was followed, except that the catalyst Rh/AC obtained in preparation example 10 was used (active component content 4.7% by weight, i.e. the molar ratio of 5-hydroxymethylfurfural to the catalyst, calculated as metal element, was about 100: 1). The conversion rate of the 5-hydroxymethylfurfural is 97 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 84.9 percent.
Example 11
The procedure of example 1 was followed except that the catalyst Pt/GO obtained in preparation example 11 was used (active component content 4.7 wt%, i.e. the molar ratio of 5-hydroxymethylfurfural to catalyst calculated on the metallic element was about 100: 1). The conversion rate of the 5-hydroxymethylfurfural is 98 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 81.4 percent.
Example 12
The procedure of example 1 was followed, except that the catalyst Pd/C obtained in preparation example 12 was used60(active component content 4.7 wt%, i.e. the molar ratio of 5-hydroxymethylfurfural to catalyst, calculated as metallic element, is about 100: 1). The conversion rate of the 5-hydroxymethylfurfural is 92 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 73.8 percent.
Comparative example 1
The procedure of example 1 was followed except that the Ru/AC obtained in comparative preparation example 1 was used in place of the Ru/AC in example 1. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 67.2 percent.
Comparative example 2
The procedure of example 1 was followed except that the Ru/AC obtained in comparative preparation 2 was used in place of the Ru/AC in example 1. The conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the product 2, 5-furandicarboxylic acid is 64.9 percent.
Comparing the results of example 1 with those of comparative examples 1 and 2, it can be seen that, when 5-hydroxymethylfurfural is used to synthesize 2, 5-furandicarboxylic acid, the catalyst of the present invention can efficiently catalyze and oxidize 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid without adding an alkaline assistant, and can significantly improve the selectivity of 2, 5-furandicarboxylic acid.
In addition, the catalyst was recycled by the method of example 1, the conversion rate of HMF was 100% and the selectivity of 2, 5-furandicarboxylic acid was substantially maintained at 93.8% after 4 times of recycling, which shows that the stability and recycling performance of the catalyst prepared by the method of the present invention are improved.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (13)
1. A method of preparing a catalyst comprising:
mixing a carrier, an alkaline nitrogen-containing compound and an active component precursor, putting the mixture into a solvent, heating the mixture under the condition of water bath, and carrying out reflux stirring treatment;
sequentially drying and roasting and reducing the carrier subjected to the reflux stirring treatment to obtain the catalyst;
wherein the active component precursor is selected from one or more of ruthenium chloride, palladium chloride, chloroplatinic acid and rhodium chloride, and the carrier is selected from one or more of activated carbon, graphite, fullerene and graphene oxide.
2. The production method according to claim 1, wherein the active component precursor is ruthenium chloride, and the support is activated carbon.
3. The method according to claim 1, wherein the basic nitrogen-containing compound is selected from one or more of nitrogen-containing heterocyclic compounds selected from one or more of pyridine, bipyridine, pyrrole, piperidine, imidazole, biimidazole and melamine, aliphatic amines selected from one or more of ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, 1, 2-propylenediamine, 1, 3-propylenediamine and n-butylamine, and aromatic amines selected from one or more of aniline, benzylamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, o-aminophenol, m-aminophenol and p-aminophenol.
4. The preparation method according to claim 1, wherein the mass ratio of the metal element in the active component precursor to the carrier is 0.005-0.08: 1, preferably 0.035-0.08: 1, and more preferably 0.04-0.06: 1.
5. The production method according to claim 1, wherein the mass ratio of the carrier to the basic nitrogen-containing compound is 1: 1-25; the mass ratio of the carrier to the solvent is 1: 20-150.
6. The preparation method according to claim 1, wherein the solvent is a mixed solution of ethanol and water, the ethanol accounts for 10-95% of the mixed solution by mass, the water accounts for 5-90% of the mixed solution by mass, preferably, the ethanol accounts for 20-50% of the mixed solution by mass, and the water accounts for 50-80% of the mixed solution by mass.
7. The method according to claim 1, wherein the reflux-stirring treatment is performed at a temperature of 40 to 95 ℃, preferably 50 to 75 ℃; the time of the reflux stirring treatment is 2 to 16 hours, preferably 6 to 10 hours.
8. The method according to claim 1, characterized in that the drying treatment is carried out at a temperature of 80 ℃ to 200 ℃, preferably 100 ℃ to 150 ℃; the drying time is 8-24 h, preferably 10-18 h.
9. The preparation method according to claim 1, wherein the roasting reduction treatment comprises subjecting the dried carrier to reduction roasting in a reducing atmosphere, wherein the reducing atmosphere comprises 10-100% by volume of hydrogen and 0-90% by volume of nitrogen or an inert gas, preferably 20-50% by volume of hydrogen and 50-80% by volume of nitrogen or an inert gas; the roasting reduction treatment is carried out at the temperature of 300-900 ℃, preferably 400-800 ℃; the time of the roasting reduction treatment is 1-6 h, preferably 2-4 h.
10. A catalyst prepared by the method of any one of claims 1 to 9.
11. A process for the preparation of 2, 5-furandicarboxylic acid comprising:
contacting an aqueous solution of 5-hydroxymethylfurfural with a catalyst under the condition of air and/or oxygen to perform a catalytic oxidation reaction to prepare the 2, 5-furandicarboxylic acid, wherein the catalyst is the catalyst in claim 10.
12. The preparation method according to claim 11, wherein the molar ratio of the 5-hydroxymethylfurfural to the metal elements in the catalyst is 40 to 200: 1, preferably 70-120: 1.
13. the production method according to claim 11, wherein the partial pressure of oxygen in the catalytic oxidation reaction is 0.05 to 2MPa, preferably 0.5 to 1 MPa; the reaction temperature is 50-170 ℃, and preferably 90-120 ℃; the reaction time is 0.5 to 24 hours, preferably 1 to 4 hours.
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