CN115555029A - Application of manganese dioxide modified copper manganese spinel catalyst in production of 2, 5-furan diformaldehyde - Google Patents
Application of manganese dioxide modified copper manganese spinel catalyst in production of 2, 5-furan diformaldehyde Download PDFInfo
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- CN115555029A CN115555029A CN202211218364.8A CN202211218364A CN115555029A CN 115555029 A CN115555029 A CN 115555029A CN 202211218364 A CN202211218364 A CN 202211218364A CN 115555029 A CN115555029 A CN 115555029A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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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- 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
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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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the field of biomass recycling, and relates to a preparation method of a manganese dioxide modified copper manganese spinel catalyst, which comprises the following steps: a. preparing the copper-manganese spinel. b. Dissolving copper-manganese spinel in deionized water, wherein the molar ratio of the copper-manganese spinel to the deionized water is (1.5-6): 1, and obtaining a solution A. c. Dissolving potassium permanganate into the solution A, wherein the molar ratio of the potassium permanganate to the deionized water is (1.2-2) to 1, and obtaining solution B. d. Dissolving an HCl solution in the solution B, wherein the volume ratio of HCl to deionized water is 1:30 to 40 percent to obtain solution C. e. And putting the solution C into a hydrothermal kettle with polytetrafluoroethylene as an inner lining for hydrothermal for 8-18 h at the temperature of 120-180 ℃, rinsing with deionized water in the suction filtration process, and drying in vacuum. The manganese dioxide modified copper manganese spinel catalyst provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process, wide application range and recycling, and has the performance of preparing 2, 5-furandicarboxaldehyde with high selectivity.
Description
Technical Field
The invention belongs to the field of biomass recycling, and particularly relates to an application of a manganese dioxide modified copper manganese spinel catalyst in the production of 2, 5-furandicarboxaldehyde.
Background
Under the stimulation of the ever-increasing material culture demands of people, petrochemical energy is consumed in large quantities. As an important platform compound, the directional oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxaldehyde is one of the key points for realizing the conversion from biomass energy to energy for producing high-value chemicals and fuels. However, in the conventional thermal catalytic system, the aldehyde functional group is easily over-oxidized, so that the selectivity of 2, 5-furandicarboxaldehyde is low. In addition, compared with the catalyst, the traditional noble metal catalyst has high cost and high activity, and is difficult to realize the controllable preparation of the 2, 5-furan dicarbaldehyde; non-metallic catalysts rely on the addition of nitrogen-containing promoters such as nitric acid and do not achieve efficient conversion of high concentrations of substrate. Thus, designing and developing catalysts for HMF-directed catalysis at low cost, high selectivity, and stability remains a challenging endeavor.
The invention content is as follows:
the invention aims to provide a preparation method of a manganese dioxide modified copper manganese spinel catalyst with high catalytic activity and good stability, which is applied to the production of 2, 5-furandicarboxaldehyde and is characterized by comprising the following steps:
a. preparing the copper-manganese spinel.
b. Dissolving copper-manganese spinel into deionized water, wherein the molar ratio of the copper-manganese spinel to the deionized water is (1.5-6): 1, and obtaining a solution A
c. Dissolving potassium permanganate into the solution A, wherein the molar ratio of the potassium permanganate to the deionized water is (1.2-2) to 1, and obtaining solution B.
d. Dissolving an HCl solution into the solution B, wherein the volume ratio of HCl to deionized water is 1:30 to 40 percent to obtain solution C.
e. And putting the solution C into a hydrothermal kettle with polytetrafluoroethylene as an inner lining for hydrothermal for 8-18 h at the temperature of 120-180 ℃, rinsing with deionized water in the suction filtration process, and drying in vacuum.
Further, the preparation method of the copper manganese spinel in the step a comprises the following steps: dissolving copper salt and manganese salt into deionized water, wherein the molar ratio of the copper salt to the manganese salt to water is (1). Dissolving NaOH in deionized water, wherein the molar ratio of the NaOH to the deionized water is 1 (800-1200), and obtaining a solution E. And slowly pouring the solution E into the solution D, continuously stirring, and stopping adding the solution E when the pH of the solution is = 11-14 to obtain a suspension F. And stirring the suspension F for 6-18 h in air atmosphere, carrying out suction filtration, drying and grinding, and roasting the ground powder in a muffle furnace at 250-600 ℃ for 2-5 h.
Furthermore, the copper salt in the preparation process of the copper-manganese spinel is one or more of copper nitrate trihydrate, copper sulfate and copper chloride dihydrate. The manganese salt is one or more of manganese nitrate, manganese sulfate monohydrate and manganese chloride tetrahydrate.
Further, the molar amount of the deionized water in the step c and the step d is the same.
Detailed Description
The present invention is further described in the following examples, but the technical content described in the examples is illustrative and not restrictive, and the scope of the present invention should not be limited thereby.
Example 1
a. Dissolving 7.158g of manganese nitrate aqueous solution (50 wt%) and 2.416g of copper nitrate trihydrate into deionized water, wherein the molar ratio of the copper nitrate trihydrate, the manganese nitrate and the water is 1; dissolving NaOH in deionized water, wherein the molar ratio of the NaOH to the deionized water is 1; adding the solution B into the solution A until the pH of the solution is =12 to obtain a suspension B; and stirring the solution B for 8 hours in the air atmosphere, carrying out suction filtration and drying, and roasting in a muffle furnace at 500 ℃ for 4 hours to obtain the copper-manganese spinel.
b. And (3) taking 0.200g of copper manganese spinel to disperse in deionized water, wherein the molar ratio of the copper manganese spinel to the deionized water is 1.8.
c. 1.454g of potassium permanganate was dissolved in solution C to obtain solution D.
d. Adding 3.000ml of HCl solution into the solution D, and stirring for 30min to obtain a mixed solution E.
e. And putting the solution E into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 12 hours at the temperature of 140 ℃, and performing suction filtration and drying.
The performance of the manganese dioxide modified copper-manganese spinel catalyst is evaluated by adopting a rock sign YZ-MR high-temperature high-pressure reactor, 5-hydroxymethylfurfural of 20ml and 2000mg/L is used as a substrate, a solvent is dimethyl sulfoxide, the prepared catalyst is taken as 100mg, the oxygen pressure is controlled to be 2Mpa, the temperature is 120 ℃, the reaction time is controlled to be 6h, and the yield of 2, 5-furandicarboxaldehyde is 88%.
Example 2
a. 3.957g of manganese chloride tetrahydrate and 1.705g of copper chloride dihydrate were dissolved in deionized water, and the molar ratio of copper chloride dihydrate to manganese chloride tetrahydrate to water was 1. NaOH solution was added to solution a until solution pH =11 to give suspension B. And stirring the solution B for 10 hours in the air atmosphere, filtering, drying, and roasting in a muffle furnace at 300 ℃ for 5 hours to obtain the copper-manganese spinel.
b. And (3) taking 0.400g of copper manganese spinel to disperse in deionized water, wherein the molar ratio of the copper manganese spinel to the deionized water is 2.
c. And dissolving 1.010g of potassium permanganate in the solution C to obtain a solution D.
d. Adding 2.280ml of HCl solution into the solution D, and stirring for 30min to obtain a mixed solution E.
e. And putting the solution E into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 11 hours at the temperature of 160 ℃, and performing suction filtration and drying.
The performance of the manganese dioxide modified copper-manganese spinel catalyst is evaluated by adopting a rock sign YZ-MR high-temperature high-pressure reactor, 5-hydroxymethylfurfural of 20ml and 2000mg/L is used as a substrate, a solvent is dimethyl sulfoxide, the prepared catalyst is taken as 100mg, the oxygen pressure is controlled to be 2Mpa, the temperature is 120 ℃, the reaction time is controlled to be 6h, and the yield of 2, 5-furandicarboxaldehyde is 84%.
Example 3
a. 3.380g of manganese sulfate monohydrate and 1.596g of copper sulfate are dissolved in deionized water, and the molar ratio of copper nitrate trihydrate, manganese nitrate and water is 1. NaOH solution was added to solution a until solution pH =14 resulting in suspension B. And stirring the solution B for 8 hours in the air atmosphere, carrying out suction filtration and drying, and roasting in a muffle furnace at 350 ℃ for 4 hours to obtain the copper-manganese spinel.
b. And (3) taking 0.600g of copper manganese spinel to disperse in deionized water, wherein the molar ratio of the copper manganese spinel to the deionized water is 3.
c. 0.727g of potassium permanganate is dissolved in the solution C to obtain a solution D.
d. Adding 1.520ml of HCl solution into the solution D, and stirring for 30min to obtain a mixed solution E.
e. And putting the solution E into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 17 hours at the temperature of 150 ℃, and performing suction filtration and drying.
The performance of the manganese dioxide modified copper-manganese spinel catalyst is evaluated by adopting a rock sign YZ-MR high-temperature high-pressure reactor, 5-hydroxymethylfurfural of 20ml and 2000mg/L is used as a substrate, a solvent is dimethyl sulfoxide, the prepared catalyst is taken as 100mg, the oxygen pressure is controlled to be 2Mpa, the temperature is 120 ℃, the reaction time is controlled to be 6h, and the yield of 2, 5-furandicarboxaldehyde is 83%.
Example 4
a. 7.158g of an aqueous solution of manganese nitrate (50 wt%) and 2.416g of copper nitrate trihydrate were dissolved in deionized water, and the molar ratio of copper nitrate trihydrate, manganese nitrate and water was 1. NaOH solution was added to solution a until solution pH =12 to give suspension B. And stirring the solution B for 8 hours in an air atmosphere, carrying out suction filtration and drying, and roasting in a muffle furnace at 400 ℃ for 3 hours to obtain the copper-manganese spinel.
b. And (3) taking 0.900g of copper manganese spinel to disperse in deionized water, wherein the molar ratio of the copper manganese spinel to the deionized water is 4.
c. 0.091g of potassium permanganate is dissolved in the solution C to obtain a solution D.
d. Adding 1.000ml of HCl solution into the solution D, and stirring for 30min to obtain a mixed solution E.
e. And putting the solution E into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 14 hours at the temperature of 150 ℃, and performing suction filtration and drying.
The performance of the manganese dioxide modified copper-manganese spinel catalyst is evaluated by adopting a rock sign YZ-MR high-temperature high-pressure reactor, 5-hydroxymethylfurfural of 20ml and 2000mg/L is used as a substrate, a solvent is dimethyl sulfoxide, the prepared catalyst is taken as 100mg, the oxygen pressure is controlled to be 2Mpa, the temperature is 120 ℃, the reaction time is controlled to be 6h, and the yield of 2, 5-furandicarboxaldehyde is 69%.
Claims (2)
1. An application of a manganese dioxide modified copper manganese spinel catalyst in the production of 2, 5-furandicarboxaldehyde is characterized in that 5-hydroxymethylfurfural is used as a substrate to prepare the 2, 5-furandicarboxaldehyde, and the preparation method of the manganese dioxide modified copper manganese spinel catalyst comprises the following steps:
a. preparing copper-manganese spinel: and (2) dissolving copper salt and manganese salt into deionized water, wherein the molar ratio of the copper salt to the manganese salt to the deionized water is 1 (40-100), obtaining a solution D, dissolving NaOH into the deionized water, and the molar ratio of the NaOH to the deionized water is 1 (800-1200), obtaining a solution E. Slowly pouring the solution E into the solution D and continuously stirring, stopping adding the solution E when the pH of the solution is = 11-14 to obtain a suspension F, stirring the suspension F for 6-18 h under an air atmosphere, performing suction filtration, drying and grinding, and roasting the ground powder for 2-5 h at 250-600 ℃ in a muffle furnace;
b. dissolving copper-manganese spinel in deionized water, wherein the molar ratio of the copper-manganese spinel to the deionized water is (1.5-6): 1, so as to obtain a solution A;
c. dissolving potassium permanganate into the solution A, wherein the molar ratio of potassium permanganate to deionized water is (1.2-2) to 1, and obtaining a solution B;
d. dissolving an HCl solution in the solution B, wherein the volume ratio of HCl to deionized water is 1: 30-40 to obtain a solution C;
e. and (3) putting the solution C into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal for 8-18 h at the temperature of 120-180 ℃, rinsing with deionized water in the suction filtration process, and drying in vacuum.
2. The use of a manganese dioxide modified copper manganese spinel catalyst according to claim 1 in the production of 2, 5-furandicarboxaldehyde, characterized in that: the copper salt in the preparation process of the copper-manganese spinel is one or more of copper nitrate trihydrate, copper sulfate and copper chloride dihydrate. The manganese salt is one or more of manganese nitrate, manganese sulfate monohydrate and manganese chloride tetrahydrate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211218364.8A CN115555029A (en) | 2022-10-05 | 2022-10-05 | Application of manganese dioxide modified copper manganese spinel catalyst in production of 2, 5-furan diformaldehyde |
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| CN202211218364.8A CN115555029A (en) | 2022-10-05 | 2022-10-05 | Application of manganese dioxide modified copper manganese spinel catalyst in production of 2, 5-furan diformaldehyde |
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