CN111362892A - Method for preparing 2, 5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural on manganese-copper spinel catalyst - Google Patents
Method for preparing 2, 5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural on manganese-copper spinel catalyst Download PDFInfo
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- CN111362892A CN111362892A CN202010287843.XA CN202010287843A CN111362892A CN 111362892 A CN111362892 A CN 111362892A CN 202010287843 A CN202010287843 A CN 202010287843A CN 111362892 A CN111362892 A CN 111362892A
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- furandicarboxylic acid
- hydroxymethylfurfural
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 81
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 45
- 239000011029 spinel Substances 0.000 title claims abstract description 45
- 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 42
- 238000000034 method Methods 0.000 title claims abstract description 20
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims description 18
- 238000007254 oxidation reaction Methods 0.000 title claims description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 87
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 32
- 238000003980 solgel method Methods 0.000 claims description 18
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 16
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 150000002402 hexoses Chemical class 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000896 Manganin Inorganic materials 0.000 claims 9
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 37
- 229910052760 oxygen Inorganic materials 0.000 description 37
- 239000001301 oxygen Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 238000004128 high performance liquid chromatography Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 238000011160 research Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910016526 CuMn2O4 Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003172 MnCu Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- B01J23/005—Spinels
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural on a manganese-copper spinel catalyst, which comprises the steps of mixing an aqueous solution containing 5-Hydroxymethylfurfural (HMF) and a non-noble metal manganese-copper spinel catalyst, and reacting with an oxidant in the presence of alkali or no alkali to prepare the 2, 5-furandicarboxylic acid (FDCA). The method has the advantages of simple operation, mild conditions, high FDCA yield of over 90 percent, catalyst separation and recovery, good reusability and reproducibility and good industrial application prospect.
Description
Technical Field
The invention relates to a preparation method of 2, 5-furandicarboxylic acid, in particular to a method for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethyl furfural on a manganese-copper spinel catalyst.
Background
In the prior art, the related research of preparing the biomass platform compound 5-Hydroxymethylfurfural (HMF) from carbohydrate is a research hotspot. Currently, higher HMF yields and safe storage of HMF with high conversion of sugars can be achieved. In recent decades, the selective oxidation of HMF to 2, 5-furandicarboxylic acid (FDCA) has received widespread attention in various countries throughout the world. FDCA is an important downstream product of selective oxidation of HMF, and can obtain more fine chemicals with application potential and other furan derivatives through oxidation, hydrogenation, esterification, amidation and other reactions. Of particular interest is FDCA as a renewable polymer monomer with important potential application value in the synthesis of biodegradable fibers and polyesters.
In view of the importance of selectively oxidizing HMF to produce FDCA, many groups have conducted extensive research and development on this problem, and have gradually made major progress. Research has been conducted to develop from homogeneous catalysis systems to heterogeneous catalysis systems, from noble metal supported catalysis systems to transition metal oxide catalysis systems, and from conventional thermal catalysis to photo/electrocatalysis. Because of the problems of difficult separation of the homogeneous catalytic system product and the catalyst, poor carbon balance and the like, the development of a high-efficiency heterogeneous catalytic system becomes a hot point of research in recent years. Accordingly, the selective oxidation of HMF to FDCA in heterogeneous catalytic systems such as Pt-based, Au-based, Pd-based, and Ru-based systems has been greatly developed. Due to the storage of precious metals and cost issues, the selective oxidation of HMF to FDCA catalysts has gradually begun to move to transition metal oxide catalysts. Other spinel catalysts with excellent oxidation properties are still under development and exploration.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural on a manganese-copper spinel catalyst.
The technical scheme is as follows: the invention provides a method for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural on a manganese-copper spinel catalyst, which comprises the steps of mixing an aqueous solution containing 5-Hydroxymethylfurfural (HMF) and a non-noble metal manganese-copper spinel catalyst, and reacting with an oxidant in the presence of alkali or no alkali to prepare the 2, 5-furandicarboxylic acid (FDCA).
Further, the molar ratio of manganese to copper is 1: 2-2: 1.
Further, the non-noble metal manganese copper spinel catalyst is prepared by a hydrothermal method, a sol-gel method and a coprecipitation method.
Further, the HMF may be pure HMF or HMF obtained by dehydration of a hexose.
Further, the oxidant is molecular oxygen or air.
Further, the base is an inorganic base or an organic base.
Further, the inorganic base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium bicarbonate and sodium bicarbonate; the organic base is one or more of urea, pyridine, triethylamine or ethylenediamine.
Further, the molar ratio of the base to HMF is 0-4, preferably 2-3.
Further, the molar ratio of the non-noble metal manganese copper spinel catalyst to the HMF is 0.5-6.
Further, the reaction temperature is 90-130 ℃; the reaction time is 1-24 hours.
Has the advantages that: the invention takes non-noble metal manganese copper spinel as the catalyst, and has the following advantages: the reaction condition is mild, the conversion rate of HMF is high, and the yield of FDCA can reach 92%; non-noble metals are used as active components, so that the catalyst is low in cost; the catalyst prepared and used by the invention has good reusability.
Drawings
FIG. 1 shows CuMn2O4And (3) a cycle stability test chart of preparing FDCA by catalyzing and oxidizing HMF by using a spinel catalyst.
Detailed Description
Example 1
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution, 0.084g sodium bicarbonate, stainless steel autoclaveAnd (3) filling 1MPa of oxygen as an oxygen source into the reaction kettle, and reacting for 18 hours at 120 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.9% and FDCA yield was 90.1%.
Example 2
Mixing 300mg of CuMn prepared by sol-gel method2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 100% and the FDCA yield was 92.5%.
Example 3
378mg of CuMn prepared by a sol-gel method2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 100% and the FDCA yield was 93.2%.
Example 4
30mg of CuMn prepared by a sol-gel method2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 63.0% and FDCA yield was 32.5%.
Example 5
200mg of CuMn prepared by a precipitation method2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 0.5 hour at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 15.2% and FDCA yield was 5.3%.
Example 6
200mg of CuMn prepared by a hydrothermal method2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 6 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 63.7% and FDCA yield was 19.8%.
Example 7
Preparing CuMn by sol-gel method with the concentration of 200mg2O410mL of 0.05mol/L spinel catalyst, HMFHMF aqueous solution obtained by dehydrating hexose and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa oxygen is filled as an oxygen source, and the mixture reacts for 15 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.9% and FDCA yield was 83.4%.
Example 8
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 24 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 100% and the FDCA yield was 90.8%.
Example 9
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.5MPa of air is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 100% and the FDCA yield was 90.3%.
Example 10
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Adding spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate into a stainless steel high-pressure reaction kettle, filling 1.5MPa of oxygen as an oxygen source, magnetically stirring and simultaneously stirring at 90 DEG CThe reaction was carried out for 24 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 80.5% and FDCA yield was 23.8%.
Example 11
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.5MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 110 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 98.3% and the FDCA yield was 60.0%.
Example 12
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.5MPa of oxygen is filled as an oxygen source, and the mixture reacts for 14 hours at 130 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 98.9% and FDCA yield was 89.5%.
Example 13
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and no alkali are added into a stainless steel high-pressure reaction kettle, 1.0MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 37.8% and FDCA yield was 13.5%.
Example 14
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.0126g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.0MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 100% and the FDCA yield was 89.9%.
Example 15
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.0168g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.0MPa of oxygen is filled into the stainless steel high-pressure reaction kettle to serve as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 100% and the FDCA yield was 87.9%.
Example 16
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.100g of potassium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.0MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.7% and FDCA yield was 72.0%.
Example 17
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.106g of sodium carbonate are added into a stainless steel high-pressure reaction kettle, 1.0MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.7% and FDCA yield was 23.7%.
Example 18
Cyclic stability of the CuMn2O4 spinel catalyst catalyzed oxidation of HMF to FDCA (fig. 1).
Preparing CuMn by sol-gel method with the concentration of 200mg2O4Spinel catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium bicarbonate are added into a stainless steel high-pressure reaction kettle, 1.0MPa of oxygen is filled as an oxygen source, and the mixture reacts for 18 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. After the reaction is finished, performing centrifugal separation, analyzing the reaction solution to obtain the conversion rate of 5-HMF and the yield of FDCA, washing the catalyst with deionized water, and then continuing to perform the next reaction for 6 times, wherein the yield of FDCA is slightly reduced; however, by removing the surface adsorbate by calcination, the activity and FDCA yield were restored (fig. 1).
Example 19
MnCu prepared from 200mg of sol-gel2O4Catalyst, 10mL of 0.05mol/L HMF aqueous solution and 0.084g of sodium hydroxide are added into a stainless steel high-pressure reaction kettle, 1MPa of oxygen is filled as an oxygen source, and the mixture reacts for 10 hours at 120 ℃ while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 80.0% and FDCA yield was 54.0%.
Claims (10)
1. A method for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural on a manganese-copper spinel catalyst is characterized by comprising the following steps: mixing an aqueous solution containing 5-Hydroxymethylfurfural (HMF) and a non-noble metal manganese copper spinel catalyst, and reacting with an oxidant in the presence of alkali or no alkali to prepare 2, 5-furandicarboxylic acid (FDCA).
2. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the molar ratio of manganese to copper is 1: 2-2: 1.
3. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the non-noble metal manganese copper spinel catalyst is prepared by a hydrothermal method, a sol-gel method and a coprecipitation method.
4. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the HMF is pure HMF or HMF obtained by dehydrating hexose.
5. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the oxidant is molecular oxygen or air.
6. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the alkali is inorganic alkali or organic alkali.
7. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 6, characterized in that: the inorganic base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium bicarbonate and sodium bicarbonate; the organic base is one or more of urea, pyridine, triethylamine or ethylenediamine.
8. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the molar ratio of the base to the HMF is 0-4.
9. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the molar ratio of the non-noble metal manganese-copper spinel catalyst to the HMF is 0.5-6.
10. The method of selective oxidation of 5-hydroxymethylfurfural over a manganin spinel catalyst to 2, 5-furandicarboxylic acid of claim 1, characterized in that: the reaction temperature is 90-130 ℃; the reaction time is 1-24 hours.
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