CN111362892A - Method for preparing 2,5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural over manganese-copper spinel catalyst - Google Patents
Method for preparing 2,5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural over 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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- hydroxymethyl furfural
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- 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 106
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 78
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 43
- 239000011029 spinel Substances 0.000 title claims abstract description 43
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims description 9
- 238000007254 oxidation reaction Methods 0.000 title claims description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 86
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000003980 solgel method Methods 0.000 claims description 18
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 15
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000010970 precious metal Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 235000011116 calcium hydroxide Nutrition 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
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 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
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 235000007686 potassium Nutrition 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000004575 stone Substances 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 19
- 239000010935 stainless steel Substances 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910016526 CuMn2O4 Inorganic materials 0.000 description 1
- 229910003172 MnCu Inorganic materials 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
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- -1 carbohydrate compounds Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction 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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Abstract
本发明公开了锰铜尖晶石催化剂上选择氧化5‑羟甲基糠醛制备2，5‑呋喃二甲酸的方法，将包含5‑羟甲基糠醛(HMF)的水溶液、非贵金属锰铜尖晶石催化剂混合，碱或无碱存在条件下，与氧化剂反应制得2，5‑呋喃二甲酸(FDCA)。该方法操作简单，条件温和，FDCA收率可达90％以上，并且催化剂可分离和回收，重复使用性和再生性好，具有良好的工业化应用前景。
The invention discloses a method for preparing 2,5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethyl furfural on a manganese-copper spinel catalyst. 2,5-furandicarboxylic acid (FDCA) is prepared by reacting with an oxidant in the presence of alkali or without alkali by mixing with a stone catalyst. The method has simple operation, mild conditions, FDCA yield can reach more than 90%, and the catalyst can be separated and recovered, with good reusability and regeneration, and has a good industrial application prospect.
Description
技术领域technical field
本发明涉及2，5-呋喃二甲酸的制备方法，特别涉及锰铜尖晶石催化剂上选择氧化5-羟甲基糠醛制备2，5-呋喃二甲酸的方法。The invention relates to a method for preparing 2,5-furandicarboxylic acid, in particular to a method for preparing 2,5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural on a manganese-copper spinel catalyst.
背景技术Background technique
现有技术中由糖类化合物制备生物质平台化合物5-羟甲基糠醛(HMF)的相关研究为研究热点。目前，能够实现糖在高转化的情况下HMF收率较高和HMF的安全储存。近十几年来，由HMF选择氧化制2，5-呋喃二甲酸(FDCA)，受到世界各国的普遍关注。FDCA是HMF选择氧化的重要的下游产品，可通过氧化、加氢、酯化、酰胺化等反应得到更多的具有应用潜质的精细化学品和其它呋喃衍生物。尤其值得关注的是，FDCA可作为可再生聚合物单体，在合成可生物降解纤维和聚酯中具有重要的潜在应用价值。In the prior art, the related research on the preparation of biomass platform compound 5-hydroxymethylfurfural (HMF) from carbohydrate compounds is a research hotspot. Currently, higher yields of HMF and safe storage of HMF can be achieved with high sugar conversion. In the past ten years, the selective oxidation of HMF to 2,5-furandicarboxylic acid (FDCA) has attracted widespread attention from all over the world. FDCA is an important downstream product of HMF selective oxidation, and more fine chemicals and other furan derivatives with application potential can be obtained through oxidation, hydrogenation, esterification, amidation and other reactions. Of particular interest is that FDCA can be used as a renewable polymer monomer and has important potential applications in the synthesis of biodegradable fibers and polyesters.
鉴于选择氧化HMF制FDCA的重要性，已有不少研究小组对此开展了大量探索研究，且逐步取得了重大进展。已有研究从均相催化体系发展为多相催化体系，从贵金属负载型催化体系发展为过渡金属氧化物催化体系，由传统热催化发展为光/电催化。由于均相催化体系产物与催化剂不易分离、碳平衡较差等问题，开发高效多相催化体系成为近年来研究的一个热点。随之，Pt基、Au基、Pd基、Ru基等多相催化体系中HMF选择氧化制FDCA取得了巨大进展展。鉴于贵金属的储存量和成本问题，HMF选择氧化制FDCA催化剂逐渐开始转向过渡金属氧化物催化剂。对于具有优异氧化性能的其他尖晶石催化剂，目前还有待开发探索。In view of the importance of selectively oxidizing HMF to produce FDCA, many research groups have carried out a lot of exploration and research, and have gradually made significant progress. Existing studies have developed from homogeneous catalytic systems to heterogeneous catalytic systems, from noble metal supported catalytic systems to transition metal oxide catalytic systems, and from traditional thermal catalysis to photo/electrocatalysis. The development of efficient heterogeneous catalytic systems has become a hot research topic in recent years due to the problems of difficult separation of products and catalysts in homogeneous catalytic systems and poor carbon balance. Subsequently, great progress has been made in the selective oxidation of HMF to FDCA in heterogeneous catalytic systems such as Pt-based, Au-based, Pd-based, and Ru-based catalysts. In view of the storage capacity and cost of precious metals, selective oxidation of HMF to FDCA catalysts has gradually begun to turn to transition metal oxide catalysts. Other spinel catalysts with excellent oxidative properties are yet to be explored.
发明内容SUMMARY OF THE INVENTION
发明目的：本发明目的是提供锰铜尖晶石催化剂上选择氧化5-羟甲基糠醛制备2，5-呋喃二甲酸的方法。Purpose of the invention: The purpose of the present invention is to provide a method for preparing 2,5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethyl furfural on a manganese-copper spinel catalyst.
技术方案：本发明提供锰铜尖晶石催化剂上选择氧化5-羟甲基糠醛制备2，5-呋喃二甲酸的方法，将包含5-羟甲基糠醛(HMF)的水溶液、非贵金属锰铜尖晶石催化剂混合，碱或无碱存在条件下，与氧化剂反应制得2，5-呋喃二甲酸(FDCA)。Technical scheme: The present invention provides a method for selectively oxidizing 5-hydroxymethyl furfural to prepare 2,5-furandicarboxylic acid on a manganese-copper spinel catalyst, comprising an aqueous solution containing 5-hydroxymethyl furfural (HMF), a non-precious metal manganese copper The spinel catalyst is mixed and reacted with an oxidant in the presence of alkali or without alkali to obtain 2,5-furandicarboxylic acid (FDCA).
进一步地，所述锰和铜摩尔比为1∶2～2∶1。Further, the molar ratio of manganese and copper is 1:2-2:1.
进一步地，所述非贵金属锰铜尖晶石催化剂通过水热法、溶胶凝胶法、共沉淀方法制备。Further, the non-precious metal manganese copper spinel catalyst is prepared by a hydrothermal method, a sol-gel method and a co-precipitation method.
进一步地，所述HMF可以是纯的HMF，也可以是由六碳糖脱水后得到的HMF。Further, the HMF can be pure HMF or HMF obtained by dehydration of six-carbon sugars.
进一步地，所述氧化剂为分子氧或空气。Further, the oxidant is molecular oxygen or air.
进一步地，所述碱为无机碱或有机碱。Further, the base is an inorganic base or an organic base.
进一步地，所述无机碱为氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钾、碳酸氢钠中的一种或几种；有机碱为尿素、吡啶、三乙胺或乙二胺中的一种或几种。Further, the inorganic base is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, potassium bicarbonate, and sodium bicarbonate; the organic base is urea, pyridine, triethyl One or more of amine or ethylenediamine.
进一步地，所述碱与HMF的摩尔比为0-4，优选为2-3。Further, the molar ratio of the base to HMF is 0-4, preferably 2-3.
进一步地，所述非贵金属锰铜尖晶石催化剂与HMF的摩尔比为0.5-6。Further, the molar ratio of the non-precious metal manganese-copper spinel catalyst to HMF is 0.5-6.
进一步地，反应温度为90-130℃；反应时间为1-24小时。Further, the reaction temperature is 90-130°C; the reaction time is 1-24 hours.
有益效果：本发明以非贵金属锰铜尖晶石作为催化剂，具有以下优点：反应条件温和，HMF的转化率高，FDCA收率可达到92％；使用非贵金属作为活性组分，催化剂成本低；本发明制备并使用的催化剂重复使用性好。Beneficial effects: the present invention uses non-precious metal manganese copper spinel as catalyst, which has the following advantages: mild reaction conditions, high conversion rate of HMF, FDCA yield can reach 92%; non-precious metal is used as active component, and catalyst cost is low; The catalyst prepared and used in the present invention has good reusability.
附图说明Description of drawings
图1为CuMn2O4尖晶石催化剂催化氧化HMF制FDCA的循环稳定性测试图。Figure 1 shows the cycle stability test diagram of CuMn 2 O 4 spinel catalyst for catalytic oxidation of HMF to FDCA.
具体实施方式Detailed ways
实施例1Example 1
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为99.9％，FDCA收率为90.1％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and while magnetic stirring The reaction was carried out at 120°C for 18 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 99.9% and the FDCA yield was 90.1%.
实施例2Example 2
将300mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为100％，FDCA收率为92.5％。Add 300 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate into a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, while magnetic stirring The reaction was carried out at 120°C for 18 hours. 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%.
实施例3Example 3
将378mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1 MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为100％，FDCA收率为93.2％。378 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. 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%.
实施例4Example 4
将30mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1 MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为63.0％，FDCA收率为32.5％。Add 30 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate into a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 63.0% and the FDCA yield was 32.5%.
实施例5Example 5
将200mg沉淀法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应0.5小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为15.2％，FDCA收率为5.3％。200 mg of CuMn 2 O 4 spinel catalyst prepared by the precipitation method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and magnetically stirred at 120 ℃. The reaction was carried out at °C for 0.5 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 15.2% and the FDCA yield was 5.3%.
实施例6Example 6
将200mg水热法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1 MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应6小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为63.7％，FDCA收率为19.8％。200 mg of CuMn 2 O 4 spinel catalyst prepared by hydrothermal method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and while magnetic stirring The reaction was carried out at 120°C for 6 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 63.7% and the FDCA yield was 19.8%.
实施例7Example 7
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L由六碳糖脱水后得到的HMFHMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应15小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为99.9％，FDCA收率为83.4％。Add 200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMFHMF aqueous solution obtained by dehydration of six-carbon sugar, and 0.084 g of sodium bicarbonate, into a stainless steel autoclave, and fill with 1 MPa of oxygen. As an oxygen source, the reaction was carried out at 120° C. for 15 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 99.9% and the FDCA yield was 83.4%.
实施例8Example 8
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1 MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应24小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为100％，FDCA收率为90.8％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 24 hours. 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%.
实施例9Example 9
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1.5MPa的空气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为100％，FDCA收率为90.3％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1.5 MPa of air as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. 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%.
实施例10Example 10
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1.5MPa的氧气作为氧源，磁力搅拌的同时在90℃下反应24小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为80.5％，FDCA收率为23.8％。Add 200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate into a stainless steel autoclave, filled with 1.5 MPa of oxygen as an oxygen source, and magnetically stirred. At the same time, the reaction was carried out at 90°C for 24 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 80.5% and the FDCA yield was 23.8%.
实施例11Example 11
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1.5MPa的氧气作为氧源，磁力搅拌的同时在110℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为98.3％，FDCA收率为60.0％。Add 200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate into a stainless steel autoclave, filled with 1.5 MPa of oxygen as an oxygen source, and magnetically stirred. At the same time, the reaction was carried out at 110° C. for 18 hours. 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%.
实施例12Example 12
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1.5MPa的氧气作为氧源，磁力搅拌的同时在130℃下反应14小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为98.9％，FDCA收率为89.5％。Add 200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium bicarbonate into a stainless steel autoclave, filled with 1.5 MPa of oxygen as an oxygen source, and magnetically stirred. At the same time, the reaction was carried out at 130°C for 14 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 98.9% and the FDCA yield was 89.5%.
实施例13Example 13
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，无碱，加入不锈钢高压反应釜，充入1.0MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为37.8％，FDCA收率为13.5％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, without alkali, were added to a stainless steel autoclave, filled with 1.0 MPa of oxygen as the oxygen source, and magnetically stirred at 120 The reaction was carried out at °C for 18 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 37.8% and the FDCA yield was 13.5%.
实施例14Example 14
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.0126g碳酸氢钠，加入不锈钢高压反应釜，充入1.0MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为100％，FDCA收率为89.9％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, 0.0126 g of sodium bicarbonate, were added to a stainless steel autoclave, filled with 1.0 MPa of oxygen as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. 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%.
实施例15Example 15
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.0168g碳酸氢钠，加入不锈钢高压反应釜，充入1.0MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为100％，FDCA收率为87.9％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.0168 g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1.0 MPa of oxygen as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. 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%.
实施例16Example 16
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.100g碳酸氢钾，加入不锈钢高压反应釜，充入1.0MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为99.7％，FDCA收率为72.0％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.100 g of potassium bicarbonate were added to a stainless steel autoclave, filled with 1.0 MPa of oxygen as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 99.7% and the FDCA yield was 72.0%.
实施例17Example 17
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.106g碳酸钠，加入不锈钢高压反应釜，充入1.0MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为99.7％，FDCA收率为23.7％。200 mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.106 g of sodium carbonate were added to a stainless steel autoclave, filled with 1.0 MPa of oxygen as the oxygen source, and while magnetic stirring The reaction was carried out at 120°C for 18 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 99.7% and the FDCA yield was 23.7%.
实施例18Example 18
CuMn2O4尖晶石催化剂催化氧化HMF制FDCA的循环稳定性(图1)。Cycling stability of the CuMn2O4 spinel catalyst for the catalytic oxidation of HMF to FDCA (Fig. 1).
将200mg溶胶凝胶法制备的CuMn2O4尖晶石催化剂，10mL 0.05mol/L HMF水溶液，0.084g碳酸氢钠，加入不锈钢高压反应釜，充入1.0MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应18小时。最后反应液通过HPLC分析底物转化率和产物收率。反应结束后，离心分离，对反应液进行分析得到5-HMF的转化率和FDCA的收率，催化剂用去离子水洗涤后继续做下一个反应，反应共套用6次，FDCA收率略微降低；但经过焙烧除去表面吸附物，活性和FDCA收率可恢复(图1)。200mg of CuMn 2 O 4 spinel catalyst prepared by sol-gel method, 10mL of 0.05mol/L HMF aqueous solution, and 0.084g of sodium bicarbonate were added to a stainless steel autoclave, filled with 1.0MPa of oxygen as the oxygen source, and the mixture was stirred magnetically. At the same time, the reaction was carried out at 120°C for 18 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. After the reaction is finished, centrifugation, the reaction solution is analyzed to obtain the conversion rate of 5-HMF and the yield of FDCA, the catalyst is washed with deionized water and continues to do the next reaction, the reaction is applied 6 times in total, and the yield of FDCA is slightly reduced; However, after calcination to remove the surface adsorbate, the activity and FDCA yield could be recovered (Fig. 1).
实施例19Example 19
将200mg溶胶凝胶制备的MnCu2O4催化剂，10mL 0.05mol/L HMF水溶液，0.084g氢氧化钠，加入不锈钢高压反应釜，充入1MPa的氧气作为氧源，磁力搅拌的同时在120℃下反应10小时。最后反应液通过HPLC分析底物转化率和产物收率。HMF转化率为80.0％，FDCA收率为54.0％。200 mg of MnCu 2 O 4 catalyst prepared by sol-gel, 10 mL of 0.05 mol/L HMF aqueous solution, and 0.084 g of sodium hydroxide were added to a stainless steel autoclave, filled with 1 MPa of oxygen as the oxygen source, and stirred at 120 °C while magnetically stirring. The reaction was carried out for 10 hours. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 80.0% and the FDCA yield was 54.0%.
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