CN108816226B - Preparation and application of a supported gold catalyst for 5-hydroxymethylfurfural oxidation to synthesize 2,5-furandicarboxylic acid - Google Patents
Preparation and application of a supported gold catalyst for 5-hydroxymethylfurfural oxidation to synthesize 2,5-furandicarboxylic acid Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010931 gold Substances 0.000 title claims abstract description 73
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 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 72
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 71
- 238000007254 oxidation reaction Methods 0.000 title abstract description 12
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 149
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 147
- 239000007787 solid Substances 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- -1 polytetrafluoroethylene Polymers 0.000 claims description 35
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 35
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000706 filtrate Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 18
- 239000005457 ice water Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种用于5‑羟甲基糠醛氧化合成2，5‑呋喃二甲酸的负载型金催化剂的制备和应用。该负载型金催化剂的载体是CeO2氧化物、ZrO2氧化物或不同配比的CexZr1‑xO复合氧化物(X值为0.7～0.9)，载体的质量分数为97％～99.5％，金组分的质量分数为0.5％～3％。该负载型金催化剂中金含量较低，利用效率较高，载体原料廉价易得，催化剂整体制备工艺简单。该负载型金催化剂用于催化5‑羟甲基糠醛氧化合成2，5‑呋喃二甲酸反应中，反应条件温和，对环境友好，催化活性较高，并且通过调节载体中Ce与Zr的配比以及活性金组分负载过程中的pH值，能够有效地调控2，5‑呋喃二甲酸的选择性。当反应温度为70～100℃，氧气压力为0.5～1.5MPa，反应时间为2～4小时，5‑羟甲基糠醛的转化率可达到100％，2，5‑呋喃二甲酸的选择性可达到97.3％。The invention relates to the preparation and application of a supported gold catalyst for 5-hydroxymethylfurfural oxidation to synthesize 2,5-furandicarboxylic acid. The carrier of the supported gold catalyst is CeO 2 oxide, ZrO 2 oxide or Ce x Zr 1-x O composite oxide with different ratios (X value is 0.7-0.9), and the mass fraction of the carrier is 97%-99.5 %, the mass fraction of the gold component is 0.5% to 3%. The supported gold catalyst has low gold content, high utilization efficiency, cheap and easy-to-obtain carrier raw materials, and simple overall preparation process of the catalyst. The supported gold catalyst is used in the reaction of catalyzing the oxidation of 5-hydroxymethylfurfural to synthesize 2,5-furandicarboxylic acid, the reaction conditions are mild, the environment is friendly, and the catalytic activity is high, and the ratio of Ce and Zr in the carrier is adjusted by adjusting the ratio of Ce and Zr. And the pH value during the loading process of the active gold component can effectively control the selectivity of 2,5-furandicarboxylic acid. When the reaction temperature is 70～100℃, the oxygen pressure is 0.5～1.5MPa, and the reaction time is 2～4 hours, the conversion rate of 5-hydroxymethylfurfural can reach 100%, and the selectivity of 2,5-furandicarboxylic acid can reach 100%. reached 97.3%.
Description
Technical Field
The invention relates to preparation and application of a supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural.
Background
The biomass resource has the advantages of rich source, low price, environmental protection, renewability and the like, and is an ideal fossil resource substitute. The 5-hydroxymethylfurfural is a biomass platform compound obtained by catalytic oxidation conversion of biomass carbohydrate, and can be subjected to reactions such as oxidation, reduction, polymerization, hydrolysis and the like to generate a series of products. Among them, 2, 5-furandicarboxylic acid, which is an oxidation product of 5-hydroxymethylfurfural, is an important intermediate for biopolymers, fine chemicals, and medicines. And 2, 5-furan dicarboxylic acid is similar to terephthalic acid in structure, is considered as a bio-based polyester monomer with application prospect, and can replace the traditional petroleum-based polyester monomer terephthalic acid to be used for synthesizing resin products commonly used in life production.
Potassium permanganate, potassium dichromate or high-valent lead compound and the like are generally adopted as oxidants in the traditional oxidation process, and the method belongs to metering oxidation reaction, needs to consume a large amount of oxidants, has low atom utilization rate and generates a large amount of toxic byproducts. Oxygen is used as an oxidant with wide sources, low price, easy obtaining and environmental protection in the catalytic oxidation process, can effectively solve the problems and is widely applied. The rapid development of gold catalysts has revolutionized the recognition that gold is chemically inert in recent years. Gold catalysts are widely studied for use in carbon monoxide oxidation, water gas shift, alcohol oxidation, oxidative esterification, and the like. The activity of the supported gold catalyst is mainly influenced by factors such as the size and morphology of the carrier and the gold particles, and the interaction between the gold and the carrier, and the factors are influenced by the preparation method.
Disclosure of Invention
The invention aims to provide preparation and application of a supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural.
The invention provides a preparation method of a supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural, which comprises the following conditions and steps:
(1) and (3) preparing a carrier. Weighing a certain mass of cerous nitrate hexahydrate (AR) or zirconyl nitrate (AR) or a mixture of the cerous nitrate hexahydrate and the zirconyl nitrate in 50mL of absolute ethyl alcohol, wherein the molar ratio of the cerous nitrate hexahydrate to the zirconyl nitrate in the mixture is (7: 3) - (9: 1). Slowly adding citric acid complexing agent with a molar ratio of citric acid to metal cation of 1: 1 under stirring, placing in water bath at 60 deg.C, stirring for 3 hr after temperature is stable, and cooling at room temperature for 30 min. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain CeO2、ZrO2Or Ce in different proportionsxZr1-xAn O composite oxide carrier (X value is 0.7 to 0.9).
(2) Preparing the supported gold catalyst. Weighing a certain mass of chloroauric acid to be dissolved in 50mL of secondary water according to the mass fraction of the gold component in the catalyst of 0.5-3%, adjusting the pH to 4.91-7.32 by using a NaOH solution, putting the solution into a water bath at 60 ℃, slowly adding a carrier with a corresponding mass while stirring, and continuously stirring for 1 hour after the temperature is stable. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst.
The invention provides an application of a supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural, and the conditions and the steps are as follows:
weighing a certain mass of 5-hydroxymethylfurfural, NaOH and a catalyst, adding the 5-hydroxymethylfurfural and the NaOH in a molar ratio of (1: 4) to (1: 1), adding 10mL of secondary water to dissolve the 5-hydroxymethylfurfural and the NaOH, and sealing the polytetrafluoroethylene lining in a high-pressure reaction kettle, wherein the molar ratio of the 5-hydroxymethylfurfural to the NaOH is (100: 1) to (1000: 1) and the molar ratio of the 5-hydroxymethylfurfural to the gold component in the catalyst is (100: 1). And (3) placing the reaction kettle in an oil bath at 70-100 ℃, filling 0.5-1.5 MPa of oxygen (99.999%) after the temperature is stable, and continuously stirring for reaction for 2-4 hours. And after the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then the pressure is slowly released, the reaction kettle is opened, the reacted liquid and the catalyst solid are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis to determine the conversion rate of the 5-hydroxymethylfurfural and the selectivity of the 2, 5-furandicarboxylic acid.
The invention has the beneficial effects that: the supported gold catalyst has the advantages of low gold content, high utilization efficiency, cheap and easily-obtained carrier raw materials and simple overall preparation process of the catalyst. The supported gold catalyst is used for catalyzing the oxidation synthesis of 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural, has mild reaction conditions, is environment-friendly and high in catalytic activity, and can effectively regulate and control the selectivity of the 2, 5-furandicarboxylic acid by regulating the ratio of Ce and Zr in the carrier and the pH value of an active gold component in the loading process. The conversion rate of 5-hydroxymethylfurfural can reach 100%, and the selectivity of 2, 5-furandicarboxylic acid can reach 97.3%.
Detailed Description
Example 1
(1) And (3) preparing a carrier. 6.5133g cerous nitrate hexahydrate (AR) is weighed and dissolved in 50mL absolute ethyl alcohol, 2.8818g citric acid complexing agent is slowly added under stirring, and then the mixture is placedThe mixture was put into a water bath at 60 ℃ and stirred for 3 hours after the temperature was stabilized, followed by cooling at room temperature for 30 minutes. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain CeO2An oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 5.92 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the mixture is continuously stirred for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst A.
Example 2
(1) And (3) preparing a carrier. 8.0930g of zirconyl nitrate (AR) is weighed and dissolved in 50mL of absolute ethyl alcohol, 6.725g of citric acid complexing agent is slowly added into the solution under stirring, the solution is put into a water bath at 60 ℃, the stirring is continuously carried out for 3 hours after the temperature is stabilized, and then the solution is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, and grinding into powder to obtain ZrO2An oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 5.92 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the mixture is continuously stirred for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst B.
Example 3
(1) And (3) preparing a carrier. 7.8160g of cerous nitrate hexahydrate (AR) and 0.4625g of zirconyl nitrate (AR) are weighed and dissolved in 50mL of absolute ethanol, 3.8424g of citric acid complexing agent is slowly added with stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stable, and then the mixture is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain Ce0.9Zr0.1O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 4.91 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the stirring is continued for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst C.
Example 4
(1) And (3) preparing a carrier. 7.8160g of cerous nitrate hexahydrate (AR) and 0.4625g of zirconyl nitrate (AR) are weighed and dissolved in 50mL of absolute ethanol, 3.8424g of citric acid complexing agent is slowly added with stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stable, and then the mixture is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain Ce0.9Zr0.1O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 5.39 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the stirring is continued for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst D.
Example 5
(1) And (3) preparing a carrier. 7.8160g of cerous nitrate hexahydrate (AR) and 0.4625g of zirconyl nitrate (AR) are weighed and dissolved in 50mL of absolute ethanol, 3.8424g of citric acid complexing agent is slowly added with stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stable, and then the mixture is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain Ce0.9Zr0.1O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 5.92 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the mixture is continuously stirred for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst E.
Example 6
(1) And (3) preparing a carrier. 7.8160g of cerous nitrate hexahydrate (AR) and 0.4625g of zirconyl nitrate (AR) are weighed and dissolved in 50mL of absolute ethanol, 3.8424g of citric acid complexing agent is slowly added with stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stable, and then the mixture is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. The solid obtained is placed in a muffle furnace and raised at a rate of 2 ℃/minHeating to 500 deg.C, calcining at 500 deg.C for 2 hr, naturally cooling to room temperature, taking out solid, grinding into powder to obtain Ce0.9Zr0.1O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 6.50 by using NaOH solution, the mixture is placed into a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the mixture is continuously stirred for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst F.
Example 7
(1) And (3) preparing a carrier. 7.8160g of cerous nitrate hexahydrate (AR) and 0.4625g of zirconyl nitrate (AR) are weighed and dissolved in 50mL of absolute ethanol, 3.8424g of citric acid complexing agent is slowly added with stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stable, and then the mixture is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain Ce0.9Zr0.1O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 7.32 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the stirring is continued for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst G.
Example 8
(1) And (3) preparing a carrier. 5.2107g of hexahydrate are weighed outCerium nitrate (AR) and 0.6938g of zirconyl nitrate (AR) were dissolved in 50mL of anhydrous ethanol, 2.8818g of citric acid complexing agent was slowly added with stirring, the mixture was placed in a water bath at 60 ℃ and stirred for 3 hours after the temperature stabilized, and then cooled at room temperature for 30 minutes. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain Ce0.8Zr0.2O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 5.92 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the mixture is continuously stirred for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst H.
Example 9
(1) And (3) preparing a carrier. 6.0791g of cerous nitrate hexahydrate (AR) and 1.3874g of zirconyl nitrate (AR) are weighed and dissolved in 50mL of absolute ethyl alcohol, 3.8424g of citric acid complexing agent is slowly added while stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stabilized, and then the mixture is cooled for 30 minutes at room temperature. The mixed solution was rotary evaporated at 50 ℃ and then dried at 100 ℃ to obtain a fluffy solid. Putting the obtained solid into a muffle furnace, heating to 500 ℃ at the speed of 2 ℃/min, roasting for 2 hours at 500 ℃, then naturally cooling to room temperature, taking out the solid, grinding into powder to obtain Ce0.7Zr0.3O2A composite oxide support.
(2) Preparing the supported gold catalyst. 0.0213g of chloroauric acid is weighed according to the mass fraction of the gold component in the catalyst being 1 percent, dissolved in 50mL of secondary water, the pH value is adjusted to 5.92 by using NaOH solution, the mixture is placed in a water bath at 60 ℃, 0.6g of carrier is slowly added under stirring, and after the temperature is stable, the mixture is continuously stirred for 1 hour. And then cooling for 40 minutes at room temperature, carrying out suction filtration, washing the obtained solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid at 65 ℃ for 12 hours after suction drying, and grinding the obtained solid into powder to obtain the supported gold catalyst I.
Example 10
0.1g of 5-hydroxymethylfurfural and 0.1269g of NaOH were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve the 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in an autoclave. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, so that the conversion rate of 5-hydroxymethylfurfural is 91.3%, and the selectivity of 2, 5-furandicarboxylic acid is 9.9%.
Example 11
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312gCe were weighed out0.9Zr0.1O2Adding the composite oxide carrier into a polytetrafluoroethylene lining, adding 10mL of secondary water to dissolve the 5-hydroxymethylfurfural and NaOH, and then sealing the polytetrafluoroethylene lining in a high-pressure reaction kettle. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, so that the conversion rate of the 5-hydroxymethylfurfural is 94.2%, and the selectivity of the 2, 5-furandicarboxylic acid is 5.5%.
Example 12
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst A were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 83.4%.
Example 13
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst B were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 62.3%.
Example 14
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst C were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 66.6%.
Example 15
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst D were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography, wherein the conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the 2, 5-furandicarboxylic acid is 87.5 percent.
Example 16
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst E were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of 5-hydroxymethylfurfural is 100%, and the selectivity of 2, 5-furandicarboxylic acid is 97.3%.
Example 17
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst F were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 69.6%.
Example 18
0.1G of 5-hydroxymethylfurfural, 0.1269G of NaOH and 0.0312G of supported gold catalyst G were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the 2, 5-furandicarboxylic acid is 43.6 percent.
Example 19
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst H were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the 2, 5-furandicarboxylic acid is 88.8 percent.
Example 20
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst I were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 85.3%.
Example 21
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst E were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 80 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, so that the conversion rate of the 5-hydroxymethylfurfural is 99.6%, and the selectivity of the 2, 5-furandicarboxylic acid is 90.5%.
Example 22
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst E were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 70 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, so that the conversion rate of the 5-hydroxymethylfurfural is 99.7%, and the selectivity of the 2, 5-furandicarboxylic acid is 42.1%.
Example 23
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst E were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, oxygen (99.999%) with 0.5MPa is filled after the temperature is stable, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100 percent, and the selectivity of the 2, 5-furandicarboxylic acid is 86.8 percent.
Example 24
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst E were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1.5MPa of oxygen (99.999%) is filled after the temperature is stable, and the reaction is continuously stirred for 3 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 97.8%.
Example 25
0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst E were weighed into a polytetrafluoroethylene liner, 10mL of secondary water was added to dissolve 5-hydroxymethylfurfural and NaOH, and the polytetrafluoroethylene liner was sealed in a high-pressure reaction vessel. The reaction kettle is put in an oil bath at 90 ℃, 1MPa of oxygen (99.999%) is filled after the temperature is stabilized, and the reaction is continuously stirred for 2 hours. After the reaction is finished, the reaction kettle is placed in an ice water bath to be cooled for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, and the filtrate is subjected to high performance liquid chromatography analysis, wherein the conversion rate of the 5-hydroxymethylfurfural is 100%, and the selectivity of the 2, 5-furandicarboxylic acid is 76.6%.
Claims (1)
1. The application of the supported gold catalyst in the synthesis of 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural is characterized in that the prepared catalyst has high activity when being applied to the synthesis of 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural: (1) 7.8160g of AR cerous nitrate hexahydrate and 0.4625g of AR zirconyl nitrate are weighed and dissolved in 50mL of absolute ethyl alcohol, 3.8424g of citric acid complexing agent is slowly added under stirring, the mixture is placed in a water bath at 60 ℃, the mixture is continuously stirred for 3 hours after the temperature is stabilized, then the mixture is cooled for 30 minutes at room temperature, the mixed solution is rotationally evaporated at 50 ℃, then the mixture is dried at 100 ℃ to obtain a bulky solid, the obtained solid is placed in a muffle furnace, the temperature is raised to 500 ℃ at the speed of 2 ℃/minRoasting at 500 deg.c for 2 hr, cooling naturally to room temperature, taking out the solid and grinding to obtain Ce powder0.9Zr0.1O2A composite oxide support; (2) 0.0213g of chloroauric acid was weighed to dissolve in 50mL of secondary water according to the mass fraction of 1% of the Au component in the catalyst, the pH was adjusted to 5.92 with NaOH solution, the mixture was placed in a water bath at 60 ℃, and 0.6g of Ce was slowly added with stirring0.9Zr0.1O2Continuously stirring the composite oxide carrier for 1 hour after the temperature is stable, then cooling the composite oxide carrier for 40 minutes at room temperature, carrying out suction filtration, washing the solid with ammonia water until no chloride ion exists in the filtrate, washing the solid with secondary water for 2-3 times, drying the solid for 12 hours at 65 ℃ after drying, and grinding the obtained solid into powder to obtain the supported gold catalyst; (3) 0.1g of 5-hydroxymethylfurfural, 0.1269g of NaOH and 0.0312g of supported gold catalyst are weighed and added into a polytetrafluoroethylene lining, the mol ratio of 5-hydroxymethylfurfural to Au component in the catalyst is 500: 1, 10mL of secondary water is added to dissolve 5-hydroxymethylfurfural and NaOH, then sealing the polytetrafluoroethylene lining in a high-pressure reaction kettle, putting the reaction kettle in an oil bath at 90 ℃, filling 99.999 percent oxygen with 1MPa after the temperature is stable, continuously stirring and reacting for 3 hours, after the reaction is finished, the reaction kettle is placed in an ice water bath for cooling for 40 minutes, then pressure is slowly released, the reaction kettle is opened, liquid and catalyst solid after the reaction are filtered and separated, the filtrate was subjected to high performance liquid chromatography, and the conversion of 5-hydroxymethylfurfural was 100%, the selectivity of 2, 5-furandicarboxylic acid was 97.3%, and the yield of 2, 5-furandicarboxylic acid was 97.3%.
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