CN113198512A - Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate - Google Patents
Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate Download PDFInfo
- Publication number
- CN113198512A CN113198512A CN202110511244.6A CN202110511244A CN113198512A CN 113198512 A CN113198512 A CN 113198512A CN 202110511244 A CN202110511244 A CN 202110511244A CN 113198512 A CN113198512 A CN 113198512A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- catalyst
- preparation
- hours
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a nitrogen-carbon-doped cobalt-based bimetallic catalyst and a preparation method thereof, and the preparation method comprises the following steps: mixing: mixing a nitrogen source compound, cobalt nitrate, a second metal element nitrate and a carbon source compound, stirring at 90-120 ℃ for more than 8 hours, filtering and drying to obtain a solid compound containing Co, the second metal element and N, C elements; and (3) calcining: and calcining the solid compound under the nitrogen condition to obtain the composite catalyst containing Co, the second metal element and N, C element. The invention also provides a preparation method of the 2, 5-furan dicarboxylic acid dimethyl ester, which comprises the following steps: mixing 5-hydroxymethylfurfural, methanol and the nitrogen-carbon-doped cobalt-based bimetallic catalyst, and reacting for 3-5h in an oxygen environment under the conditions of pressure of 0.1-0.5MPa and temperature of 70-90 ℃ under stirring to obtain the dimethyl 2, 5-furandicarboxylate. The catalyst of the invention has simple preparation method, is suitable for industrial production, and can obtain 96% of yield of 2, 5-furan dicarboxylic acid dimethyl ester. At a HMF concentration of 10 wt%, a yield of 92% dimethyl-2, 5-furandicarboxylate was obtained.
Description
Technical Field
The invention relates to the field of synthesis of dimethyl 2, 5-furandicarboxylate, in particular to a nitrogen-carbon-doped cobalt-based bimetallic catalyst, a preparation method thereof and a preparation method of dimethyl 2, 5-furandicarboxylate by using the catalyst.
Background
The conversion of renewable biomass resources into high-added-value carbon-based chemicals is an important way for sustainable development of chemical industry in the future. In recent years, 2, 5-furandicarboxylic acid (FDCA) synthesized by selective oxidation of cellulose with biomass-based platform molecule 5-Hydroxymethylfurfural (HMF) has received much attention. The bio-based FDCA has the molecular structure and chemical properties of petroleum-based terephthalic acid (PTA), and the FDCA-based polyester shows gas barrier properties and mechanical properties significantly superior to those of conventional PET, so FDCA is considered as the most ideal biomass-based substitute monomer for PTA.
Many noble metal-based (such as gold, platinum, palladium and ruthenium) and non-noble metal-based (such as manganese, cobalt and cerium) catalysts have excellent performance for synthesizing FDCA by oxidizing HMF, and the yield of FDCA can reach 95-99% (ACS Catal.2015,5, 6529-.However, the solubility of FDCA in most conventional solvents such as water is very low, and the boiling point of FDCA exceeds 400 ℃, so that HMF can be converted only at a low concentration and the separation and purification of FDCA are difficult. In addition, the synthesis of FDCA by catalytic oxidation of HMF needs to be carried out under harsher conditions (130-150 ℃, 30-50bar O)2). These factors all contribute to the failure of FDCA to be synthetically prepared on a pilot or industrial scale.
Recent studies have found that the direct oxidative esterification of HMF to dimethyl Furandicarboxylate (FDMC) can be carried out at 60-80 ℃ and 2-5bar O2The method is carried out under mild conditions, and the FDMC has better solubility in solvents such as methanol and the like, thereby being beneficial to the high-efficiency conversion, separation and purification of the FDMC. To date, several gold, palladium, or cobalt containing materials have been successfully used in the oxidative esterification of HMF (CN 110799504A). For example, AuPd-Fe3O4The catalytic HMF oxidation esterification can obtain the FDMC yield of 92% (1equiv. KCO)3，1atm O2Room temperature,24h) (ChemSusChem 2019,12, 2310-2317.). At present, only nitrogen-doped carbon-supported cobalt catalysts in non-noble metal catalysts have excellent activity for efficiently catalyzing the synthesis of FDMC through HMF oxidation and esterification.
The methods of developing Co-based catalysts have been too cumbersome. For example, the preparation method of the catalyst involved in patent CN111346659A is as follows: ZIF-67@ SiO2，Zn(NO3)2·6H2Sequentially adding O and 2-methylimidazole into methanol, stirring at room temperature, washing with ethanol, and centrifugally drying to obtain ZIF-67@ SiO2@ ZIF-8, followed by ZIF-67@ SiO2@ ZIF-8 is calcined at high temperature (900 +/-10 ℃,5 ℃/min, 3-4h) under the condition of nitrogen, the calcined product is etched (48h) by using sodium hydroxide solution (0.5M), the obtained calcined product is centrifuged, cleaned by ethanol and dried in vacuum (80 ℃,12 h), the hollow yolk-shell structure cobalt carbon material is prepared, and the catalytic effect of the catalyst under the optimized condition is 95%.
In addition, in alkaline promoters (e.g. K)2CO3) By CoX-N @ C catalyst and cocatalyst (. alpha. -MnO)2or Ru/C) can be used to obtain 95-99% (1-6bar O)2Air, 50-100 ℃, 12-16 hours) FDMC yield (ChemCatchem 2016,8, 2907-2911; ACS Sustainable chem. Eng.2019,7, 12061-12068). However, the additional addition of alkali additives not only causes environmental problems, but also requires a great deal of cost for product purification and waste disposal.
In addition, the preparation process of most of the prior non-noble metal catalysts is too complicated, and has the defect of difficult scale-up (CN 111408392A; CHEMSOSCHEM.13 (2020) 4151-4158.). For example, Liu et al, a CoCu bimetallic catalyst, was prepared as follows: respectively dissolving 2-methylimidazole and Zn salt in methanol, mixing and stirring the two solutions at room temperature for 24 hours, centrifuging to obtain ZIF-8 (white solid), and drying at 80 ℃ for 12 hours for later use. ZIF-8 is uniformly dispersed in normal hexane by adopting a double-solvent method, and then a small amount of water containing cobalt and copper nitrate with different molar ratios is dropwise added under continuous and violent stirring. And then the mixture is continuously stirred for 12 hours, and then the mixture is filtered and separated to obtain the ZIF-8 nitrate containing cobalt and copper. The resulting cobalt and copper containing ZIF-8 nitrate was then dried in a vacuum oven at 80 ℃ for 12 hours and then calcined in nitrogen at 900 ℃ for 2 hours.
Disclosure of Invention
Therefore, a preparation method of the nitrogen-carbon doped cobalt-based bimetallic catalyst, which is simple and easy to amplify, needs to be provided, only a proper nitrogen source, a proper carbon source and a proper active metal salt are selected, and the high-activity catalyst can be prepared by mixing, drying and calcining, so that the defect that the existing preparation method of the HMF oxidative esterification catalyst is complex and difficult to amplify is overcome. The Co-based bimetallic catalyst designed and synthesized in the invention can overcome the difficulties that the existing HMF oxidation esterification catalyst is difficult to prepare in an amplification way and needs a large amount of alkali assistants.
The invention provides a preparation method of a nitrogen-carbon-doped cobalt-based bimetallic catalyst, which comprises the following steps:
mixing: mixing a nitrogen source compound, cobalt nitrate, a second metal element nitrate and a carbon source compound, stirring at 90-120 ℃ for more than 8 hours, filtering and drying to obtain a solid compound containing a Co element, a second metal element, an N element and a C element;
and (3) calcining: and calcining the solid compound under the nitrogen condition to obtain the composite catalyst containing the Co element, the second metal element, the N element and the C element.
Preferably, the nitrogen source compound comprises ammonium chloride, urea, chitosan, dicyandiamide, or a combination thereof.
Preferably, the carbon source comprises activated carbon, formaldehyde, glyoxal, or a combination thereof.
Preferably, the mixing step, the stirring temperature is 105 ℃.
Preferably, in the calcining step, the calcining temperature is 800-900 ℃, and the calcining time is 1-3 h.
Preferably, the second metal element includes Cu, Ni, Fe, Ce, or Cr element.
Preferably, the method comprises the following steps:
mixing: mixing 2.5018g dicyandiamide, 0.0705g cobalt nitrate hexahydrate, 0.0242g (or other second metal element nitrate with equal molar quantity) and 15.0228mL water, adding 2.2mL formaldehyde, stirring at 105 ℃ for more than 8h, filtering and drying to obtain a solid compound containing Co element, second metal element, N element and C element;
and (3) calcining: calcining the solid compound for 2 hours at 900 ℃ under the nitrogen condition to obtain Co7Cu3-NC composite catalyst.
The second aspect of the present invention provides a nitrogen-carbon-doped cobalt-based bimetallic catalyst produced by the preparation method according to the first aspect of the present invention.
The third aspect of the invention provides a preparation method of dimethyl 2, 5-furandicarboxylate, which comprises the following steps:
5-hydroxymethylfurfural, methanol and the nitrogen-carbon-doped cobalt-based bimetallic catalyst provided by the second aspect of the invention are mixed and then react for 3-5h in an oxygen environment under the conditions of 0.1-0.5MPa of pressure and 70-90 ℃ of temperature, and dimethyl 2, 5-furandicarboxylate is obtained.
Both the reaction temperature and the reaction time have an influence on the reaction conversion. Too low temperature and too short reaction time can cause insufficient reaction, while too high temperature can cause the HMF substrate to deteriorate, and too long reaction time can cause reverse reaction, and the conversion rate is reduced on the contrary.
Preferably, the mass ratio of the 5-hydroxymethylfurfural to the methanol is 1: 100; the pressure is 0.2MPa, the temperature is 80 ℃, and the reaction is carried out for 4 hours under the stirring condition.
Preferably, the method comprises the following steps: mixing 0.0287g of 5-hydroxymethyl furfural, 3ml of methanol and 0.0410g of Co7Cu3And (3) mixing the-NC composite catalyst, and reacting for 4 hours in an oxygen environment under the conditions of 0.2MPa of pressure, 80 ℃ of temperature and 500rpm of stirring to obtain the dimethyl 2, 5-furandicarboxylate.
Preferably, the reaction concentration of the 5-hydroxymethylfurfural is 10 wt%, and the yield of the dimethyl 2, 5-furandicarboxylate is 92%.
Different from the prior art, the technical scheme at least comprises the following beneficial effects: the nitrogen-carbon-doped cobalt-based bimetallic catalyst Co of the inventionXBYThe preparation method of the-NC catalyst is simple and is suitable for industrial production. Wherein Co prepared7Cu3The NC catalyst can obtain 96% yield of 2, 5-furan dicarboxylic acid dimethyl ester under the alkali-free condition. At a HMF concentration of 10 wt%, a yield of 92% dimethyl-2, 5-furandicarboxylate was obtained.
Drawings
Fig. 1 is a reaction scheme for producing FDMC from HMF in an embodiment.
FIG. 2 is a graph showing the results of qualitative analyses of the reactants in example 2 by an Agilent 7890 series gas chromatograph according to the embodiment.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
Examples 1 to 22 (Nitrogen-carbon-doped cobalt-based bimetallic catalyst Co)XBY-NC catalyst, x, y representing their molar ratio; )
1. 2.5047g of dicyandiamide, 0.0912g of cobalt nitrate hexahydrate, 0.0090g of copper nitrate trihydrate and 15.0716ml of water are mixed and dissolved in a 50ml beaker, followed by dropwise addition of 2.2ml of formaldehyde, mixing and stirring at 105 ℃ overnight andremoving water, drying to obtain solid, grinding into powder, calcining at 900 deg.C under nitrogen for 2 hr to obtain Co9Cu1-NC catalyst.
0.0292g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0371g of Co was added9Cu1NC catalyst, sealing the reaction kettle, filling 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the number 1 in the table 1.
2. 2.5018g of dicyandiamide, 0.0705g of cobalt nitrate hexahydrate, 0.0242g of copper nitrate trihydrate and 15.0228mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, thus obtaining Co7Cu3-NC catalyst.
0.0287g of 5-hydroxymethyl furfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0410g of Co was added7Cu3NC catalyst, sealing the reaction kettle, filling 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the number 2 in the table 1.
3. 2.5005g of dicyandiamide, 0.0515g of cobalt nitrate hexahydrate, 0.0441g of copper nitrate trihydrate and 15.0283mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained5Cu5-NC catalyst.
0.0291g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0377g of Co was added5Cu5NC catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, stirring vigorously at 500rpm, heating to 80 ℃ and maintaining for 4h to finish the reaction, and the detection result is shown as number 3 in Table 1.
4. 2.5027g of dicyandiamide, 0.0316g of cobalt nitrate hexahydrate, 0.0591g of copper nitrate trihydrate and 15g of copper nitrate1300mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, thus obtaining Co3Cu7-NC catalyst.
0.0286g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0330g of Co was added3Cu7NC catalyst, sealing the reaction kettle, filling 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the number 4 in the table 1.
5. 2.5030g of dicyandiamide, 0.0132g of cobalt nitrate hexahydrate, 0.0757g of copper nitrate trihydrate and 15.2177mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, a solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained1Cu9-NC catalyst.
0.0287g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0275g of Co was added1Cu9-NC-D1-F1The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number of 5.
6. 0.1g of 5-hydroxymethylfurfural and 1ml of methanol were added to a reaction vessel (20ml), and 0.1336g of Co was added7Cu3NC (prepared in example 2) catalyst, sealed reaction vessel and charged with 0.5MPa oxygen, stirred vigorously at 500rpm and heated to 80 ℃ for 5h to terminate the reaction, the reaction mass was cooled to room temperature and sampled for detection, and the detection result is shown in Table 1 as number 6.
7. 3.0025g of dicyandiamide, 0.0719g of cobalt nitrate hexahydrate, 0.0246g of copper nitrate trihydrate and 15.0818mL of water are mixed and dissolved in a 50mL beaker, 2.2mL of formaldehyde is then added dropwise, the mixture is stirred overnight at 105 ℃ and the water is removed, the solid obtained after drying is ground into a powder and then the powder is placed under nitrogen in a nitrogen atmosphereCalcining at 900 ℃ for 2h to obtain Co7Cu3-NC-1 catalyst.
0.0290g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0375g of Co was added7Cu3NC-1 catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the serial number 7 in the table 1.
8. 4.0104g of dicyandiamide, 0.0724g of cobalt nitrate hexahydrate, 0.0246g of copper nitrate trihydrate and 15.0860mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, thus obtaining Co7Cu3-NC-2 catalyst.
0.0290g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0326g of Co was added7Cu3NC-2 catalyst, sealing the autoclave and charging 0.2MPa of oxygen, stirring vigorously at 500rpm, heating to 80 ℃ and maintaining for 4h to finish the reaction, cooling the reactant to room temperature and sampling for detection, wherein the detection result is shown as the serial number 8 in the table 1.
9. 5.0180g of dicyandiamide, 0.0740g of cobalt nitrate hexahydrate, 0.0254g of copper nitrate trihydrate and 15.0215mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC-3 catalyst.
0.0290g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0328g of Co was added7Cu3And (3) sealing the reaction kettle, filling 0.2MPa of oxygen into the reaction kettle, violently stirring the reaction kettle at 500rpm, heating the reaction kettle to 80 ℃ and maintaining the reaction kettle for 4 hours, finishing the reaction, cooling the reactants to room temperature, sampling and detecting, wherein the detection result is shown as the serial number 9 in the table 1.
10. 0.5056g of dicyandiamide, 0.0722g of cobalt nitrate hexahydrate, 0.0244g of copper nitrate trihydrate and 15.0515mL of water are mixed and dissolvedAdding 2.2ml formaldehyde into a 50ml beaker, mixing and stirring at 105 ℃ overnight, removing water, drying to obtain a solid, grinding into powder, and calcining at 900 ℃ for 2h under the condition of nitrogen to obtain Co7Cu3-NC-4 catalyst.
0.0288g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0212g of Co was added7Cu3And (3) sealing the reaction kettle, filling 0.2MPa of oxygen into the reaction kettle, violently stirring the reaction kettle at 500rpm, heating the reaction kettle to 80 ℃ and maintaining the reaction kettle for 4 hours, finishing the reaction, cooling the reactants to room temperature, sampling and detecting, wherein the detection result is shown as the serial number 10 in the table 1.
11. 1.0084g of dicyandiamide, 0.0721g of cobalt nitrate hexahydrate, 0.0247g of copper nitrate trihydrate and 15.1426mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC-5 catalyst.
0.0288g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0254g of Co was added7Cu3NC-5 catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, stirring vigorously at 500rpm, heating to 80 ℃ and maintaining for 4h to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as serial number 11 in Table 1.
12. 2.0126g of dicyandiamide, 0.0716g of cobalt nitrate hexahydrate, 0.0243g of copper nitrate trihydrate and 15.1936mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, a solid obtained after drying is ground into powder, and the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC-6 catalyst.
0.0289g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0214g of Co was added7Cu3-NC-6 catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, the detection results are listed in Table 1The medium number is 12.
13. 2.5011g of dicyandiamide, 0.0715g of cobalt nitrate hexahydrate, 0.0244g of copper nitrate trihydrate and 15.0085mL of water are mixed and dissolved in a 50mL beaker, then 3.0mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC-7 catalyst.
0.0286g of 5-hydroxymethyl furfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0419g of Co was added7Cu3And (3) sealing the reaction kettle, filling 0.2MPa of oxygen into the reaction kettle, violently stirring the reaction kettle at 500rpm, heating the reaction kettle to 80 ℃ and maintaining the reaction kettle for 4 hours, finishing the reaction, cooling the reactants to room temperature, sampling and detecting, wherein the detection result is shown as a serial number 13 in the table 1.
14. 2.5046g of dicyandiamide, 0.0720g of cobalt nitrate hexahydrate, 0.0249g of copper nitrate trihydrate and 15.0065mL of water are mixed and dissolved in a 50mL beaker, 4.0mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC-8 catalyst.
0.0286g of 5-hydroxymethyl furfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0500g of Co was added7Cu3NC-8 catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, stirring vigorously at 500rpm, heating to 80 ℃ and maintaining for 4h to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as a serial number of 14 in Table 1.
15. 2.5017g of dicyandiamide, 0.0723g of cobalt nitrate hexahydrate, 0.0251g of copper nitrate trihydrate and 15.1050mL of water are mixed and dissolved in a 50mL beaker, 5.0mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, a solid obtained after drying is ground into powder, and the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC-9 catalyst.
0.0285g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0505g of Co was added7Cu3-NC-9 catalyst, sealed reaction kettleAnd 0.2MPa oxygen was charged, vigorously stirred at 500rpm and heated to 80 ℃ for 4 hours to terminate the reaction, and the reaction was cooled to room temperature and sampled for detection, the detection results being given in Table 1 as number 15.
16. 5.0000g of ammonium chloride, 5.000g of citric acid, 0.0700g of cobalt nitrate hexahydrate, 0.0240g of copper nitrate trihydrate and 15.1000mL of water are mixed and dissolved in a 50mL beaker, 5.0mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cu3-NC[b]A catalyst.
Adding 0.0290g of 5-hydroxymethylfurfural and 3ml of methanol into a reaction kettle (20ml), and adding 0.0405g of Co7Cu3-NC[b]The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number of 16.
17. 2.5000g of urea, 0.0701g of cobalt nitrate hexahydrate, 0.0240g of copper nitrate trihydrate and 15.0000mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, thus obtaining Co7Cu3-NC[c]A catalyst.
0.0298g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0485g of Co was added7Cu3-NC[c]The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number 17.
18. 1.0000g of urea, 2.5017g of dicyandiamide, 0.0700g of cobalt nitrate hexahydrate, 0.0240g of copper nitrate trihydrate, 1.000g of zinc nitrate hexahydrate and 15.0000mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is added dropwise, the mixture is stirred overnight at 105 ℃ and the water is removed, the solid obtained after drying is ground into powder and then the powder is placed under nitrogenCalcining at 900 deg.C for 2h to obtain Co7Cu3-NC[d]A catalyst.
0.0301g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0308g of Co was added7Cu3-NC[d]The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number of 18.
19. Mixing and dissolving 0.5000g of chitosan, 2.0000g of dicyandiamide, 0.0708g of cobalt nitrate hexahydrate, 0.0247g of copper nitrate trihydrate and 15.0018mL of water in a 50mL beaker, then dropwise adding 2.2mL of formaldehyde, mixing and stirring at 105 ℃ overnight, removing water, grinding the obtained solid into powder, calcining at 900 ℃ for 2 hours under the condition of nitrogen, and thus obtaining Co7Cu3-NC[e]A catalyst.
0.0291g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0388g of Co was added7Cu3-NC[e]The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number 19.
20. Mixing and dissolving 0.1000g of activated carbon, 2.5000g of dicyandiamide, 0.0728g of cobalt nitrate hexahydrate, 0.0245g of copper nitrate trihydrate and 15.0018mL of water in a 50mL beaker, then dropwise adding 2.2mL of formaldehyde, mixing and stirring at 105 ℃ overnight, removing water, grinding a solid obtained after drying into powder, and then calcining at 900 ℃ for 2 hours under the condition of nitrogen to obtain Co7Cu3-NC[f]A catalyst.
0.0281g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0343g of Co was added7Cu3-NC[f]The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number of 20.
21. 2.5000g of dicyandiamide, 0.0700g of cobalt nitrate hexahydrate, 0.0240g of copper nitrate trihydrate and 15.0258mL of water are mixed and dissolved in a 50mL beaker, then 3.5mL of glyoxal is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, thus obtaining Co7Cu3-NC[g]A catalyst.
0.0293g of 5-hydroxymethylfurfural and 3ml of methanol were charged into a reaction vessel (20ml), and 0.0243g of Co was further charged7Cu3-NC[g]The catalyst, sealed reaction kettle and charged 0.2MPa oxygen, in 500rpm vigorously stirring and heating to 80 ℃ and maintaining for 4 hours after finishing the reaction, the reactant cooling to room temperature and sampling detection, the detection results are listed in Table 1 in the number of 21.
22. 2.5002g of dicyandiamide, 0.0709g of cobalt nitrate hexahydrate, 0.0245g of copper nitrate trihydrate and 15.0258mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 800 ℃ under the condition of nitrogen, thus obtaining Co7Cu3-NC[h]A catalyst.
0.0281g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0313g of Co was added7Cu3-NC[h]The catalyst, sealing the reaction kettle and charging 0.2MPa oxygen, stirring vigorously at 500rpm and heating to 80 ℃ and maintaining for 4h to finish the reaction, cooling the reactant to room temperature and sampling for detection, wherein the detection result is listed as number 22 in Table 1.
23. 2.5009g of dicyandiamide, 0.1016g of cobalt nitrate hexahydrate and 15.0277mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that the Co-NC catalyst is obtained.
Adding 0.0300g of 5-hydroxymethylfurfural and 3ml of methanol into a reaction kettle (20ml), adding 0.0277g of Co-NC catalyst, sealing the reaction kettle, filling 0.2MPa of oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactants to room temperature, sampling and detecting, wherein the detection result is shown as a serial number 23 in Table 1.
24. 2.5004g of dicyandiamide, 0.0704g of cobalt nitrate hexahydrate, 0.0416g of ferric nitrate nonahydrate and 15.0175mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dropwise added, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Fe3-NC catalyst.
0.0309g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction kettle (20ml), and 0.0363g of Co was added7Fe3NC catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the number 24 in the table 1.
25. Mixing 2.5003g dicyandiamide, 0.0702g cobalt nitrate hexahydrate, 0.0443g cerous nitrate hexahydrate and 15.0323mL water, dissolving in a 50mL beaker, then dropwise adding 2.2mL formaldehyde, mixing and stirring at 105 ℃ overnight, removing water, drying to obtain a solid, grinding into powder, calcining at 900 ℃ for 2h under the condition of nitrogen to obtain Co7Ce3-NC catalyst.
0.0307g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0406g of Co was added7Ce3NC catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the serial number of 25 in the table 1.
26. 2.5004g of dicyandiamide, 0.0701g of cobalt nitrate hexahydrate, 0.0414g of chromium nitrate nonahydrate and 15.0119mL of water are mixed and dissolved in a 50mL beaker, then 2.2mL of formaldehyde is dripped, the mixture is stirred overnight at 105 ℃, water is removed, the solid obtained after drying is ground into powder, and then the powder is calcined for 2 hours at 900 ℃ under the condition of nitrogen, so that Co can be obtained7Cr3-NC catalyst.
0.0309g of 5-hydroxymethylfurfural and 20ml of a reaction kettle were charged3ml of methanol was added, and 0.0407g of Co were added7Cr3NC catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the number 26 in the table 1.
27. Mixing 2.5006g dicyandiamide, 0.0707g cobalt nitrate hexahydrate, 0.0308g nickel nitrate hexahydrate and 15.0122mL water, dissolving in a 50mL beaker, then dropwise adding 2.2mL formaldehyde, mixing and stirring at 105 ℃ overnight, removing water, drying to obtain a solid, grinding into powder, calcining at 900 ℃ for 2h under the condition of nitrogen to obtain Co7Ni3-NC catalyst.
0.0308g of 5-hydroxymethylfurfural and 3ml of methanol were added to a reaction vessel (20ml), and 0.0407g of Co was added7Ni3NC catalyst, sealing the reaction kettle, charging 0.2MPa oxygen, violently stirring at 500rpm, heating to 80 ℃ and maintaining for 4 hours to finish the reaction, cooling the reactant to room temperature, sampling and detecting, wherein the detection result is shown as the serial number 27 in the table 1.
TABLE 1 examination results of examples 1 to 27 and comparative example
[a]: the substrate (HMF) concentration in example 6 was 10 wt%; [ b ] a]The nitrogen source is ammonium chloride; [ c ] is]The nitrogen source is urea; [ d]The nitrogen source is urea and dicyandiamide; [ e ] a]The nitrogen source is chitosan and dicyandiamide; [ f ] of]The carbon source is activated carbon and formaldehyde; [ g ]]The carbon source is glyoxal; [ h ] of]The calcining temperature is 800 ℃; comparative examples 1, 2 reference [ i ]]0.2equiv.K2CO3(ChemSusChem 2014,7,3334–3340；ACS Sustainable Chem.Eng.2019,7,12061–12068.)
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (10)
1. The preparation method of the nitrogen-carbon-doped cobalt-based bimetallic catalyst is characterized by comprising the following steps of:
mixing: mixing a nitrogen source compound, cobalt nitrate, a second metal element nitrate and a carbon source compound, stirring at 90-120 ℃ for more than 8 hours, filtering and drying to obtain a solid compound containing a Co element, a second metal element, an N element and a C element;
and (3) calcining: and calcining the solid compound under the nitrogen condition to obtain the composite catalyst containing the Co element, the second metal element, the N element and the C element.
2. The method of claim 1, wherein the nitrogen source compound comprises ammonium chloride, urea, chitosan, dicyandiamide, or a combination thereof.
3. The method of claim 1, wherein the carbon source comprises activated carbon, formaldehyde, glyoxal, or a combination thereof.
4. The method according to claim 1, wherein the mixing step is carried out at a stirring temperature of 105 ℃.
5. The preparation method according to claim 1, wherein in the calcining step, the calcining temperature is 800-900 ℃ and the calcining time is 1-3 h.
6. The production method according to claim 1, wherein the second metal element includes Cu, Ni, Fe, Ce, or Cr element.
7. A nitrogen-carbon-doped cobalt-based bimetallic catalyst produced by the production method according to any one of claims 1 to 6.
8. A preparation method of dimethyl 2, 5-furandicarboxylate is characterized by comprising the following steps:
mixing 5-hydroxymethylfurfural, methanol and the nitrogen-carbon-doped cobalt-based bimetallic catalyst disclosed by claim 7, and reacting for 3-5 hours in an oxygen environment at the pressure of 0.1-0.5MPa and the temperature of 70-90 ℃ under stirring to obtain the dimethyl 2, 5-furandicarboxylate.
9. The method of claim 8, comprising the steps of: mixing 0.0287g of 5-hydroxymethyl furfural, 3ml of methanol and 0.0410g of Co7Cu3And (3) mixing the-NC composite catalyst, and reacting for 4 hours in an oxygen environment under the conditions of 0.2MPa of pressure, 80 ℃ of temperature and 500rpm of stirring to obtain the dimethyl 2, 5-furandicarboxylate.
10. The method according to claim 8, wherein the reaction concentration of 5-hydroxymethylfurfural is 10 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110511244.6A CN113198512B (en) | 2021-05-11 | 2021-05-11 | Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110511244.6A CN113198512B (en) | 2021-05-11 | 2021-05-11 | Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113198512A true CN113198512A (en) | 2021-08-03 |
| CN113198512B CN113198512B (en) | 2022-06-24 |
Family
ID=77030801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110511244.6A Active CN113198512B (en) | 2021-05-11 | 2021-05-11 | Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113198512B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768856A (en) * | 2022-05-18 | 2022-07-22 | 中国科学技术大学 | Heterogeneous catalyst and preparation method and application thereof |
| CN116396249A (en) * | 2023-04-11 | 2023-07-07 | 中国科学院山西煤炭化学研究所 | Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120059178A1 (en) * | 2009-05-14 | 2012-03-08 | Archer Daniels Midland Company | Oxidation of furfural compounds |
| CN108084123A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters |
| CN110590721A (en) * | 2019-09-29 | 2019-12-20 | 厦门大学 | Method for preparing 2, 5-furan dicarboxylic acid diester compound from 5-hydroxymethylfurfural |
| CN111253353A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural |
-
2021
- 2021-05-11 CN CN202110511244.6A patent/CN113198512B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120059178A1 (en) * | 2009-05-14 | 2012-03-08 | Archer Daniels Midland Company | Oxidation of furfural compounds |
| CN108084123A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters |
| CN111253353A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural |
| CN110590721A (en) * | 2019-09-29 | 2019-12-20 | 厦门大学 | Method for preparing 2, 5-furan dicarboxylic acid diester compound from 5-hydroxymethylfurfural |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114768856A (en) * | 2022-05-18 | 2022-07-22 | 中国科学技术大学 | Heterogeneous catalyst and preparation method and application thereof |
| CN116396249A (en) * | 2023-04-11 | 2023-07-07 | 中国科学院山西煤炭化学研究所 | Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran |
| CN116396249B (en) * | 2023-04-11 | 2023-11-21 | 中国科学院山西煤炭化学研究所 | Application of Co/NC-DA-x hollow structure catalyst and preparation method of 2, 5-dimethylolfuran |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113198512B (en) | 2022-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113198512B (en) | Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate | |
| CN111604055B (en) | Catalyst for preparing acetophenone by oxidizing ethylbenzene and preparation method thereof | |
| CN111187238B (en) | Synthetic method of 2, 5-furandicarboxylic acid | |
| CN110590721B (en) | Method for preparing 2, 5-furan dicarboxylic acid diester compound from 5-hydroxymethylfurfural | |
| CN112742482A (en) | Catalyst for catalytic hydrogenation, preparation method and application thereof | |
| CN113198472B (en) | Magnetic catalyst and preparation and application thereof | |
| CN110078601A (en) | The method that polyoxometallate efficient catalytic paraxylene prepares p-tolyl aldehyde | |
| CN113996296A (en) | Silver catalyst for preparing bio-based 2,5-furandicarboxylic acid and preparation method and application thereof | |
| CN112920041B (en) | Method for preparing hydroxy dibasic acid by catalyzing acetyl acid raw material to oxidize | |
| CN112371150B (en) | Nickel-aluminum bimetal nitrogen-carbon doped catalyst, preparation method thereof and application thereof in catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone | |
| CN109603837B (en) | Preparation method of Cu/Ce/Co catalyst for furfural liquid-phase hydrogenation | |
| CN113121481A (en) | Ruthenium-based catalyst and method for preparing 2, 5-furandicarboxylic acid by using same | |
| CN114345337B (en) | Lactic acid preparation method | |
| CN114602477B (en) | For CO 2 Double-shell hollow copper-zinc-based catalyst for preparing methanol at low temperature and preparation method thereof | |
| CN113318730B (en) | δ-MnO2Catalyst, preparation method and application thereof | |
| CN115430418A (en) | Catalyst, preparation method thereof and method for preparing acetic acid by using catalyst | |
| CN112246240B (en) | Preparation and application of dimethyl carbonate catalyst | |
| CN111974409B (en) | Flaky porous manganese-doped nickel oxide catalyst, preparation method and application thereof | |
| CN114621166A (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN116574076B (en) | Solvent-free method for synthesizing 2, 5-furandicarboxylic acid | |
| CN112958155B (en) | Phthalocyanine polymer catalyst and preparation method and application thereof | |
| CN118217980A (en) | RuO (Ruo) devicex/MnOyCatalyst, preparation method and method for catalytic synthesis of 2, 5-furandicarboxylic acid | |
| CN115073404B (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN113117705B (en) | Modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of modified ruthenium-based catalyst | |
| CN115814814B (en) | Preparation method of ruthenium-loaded iron-chromium bimetallic oxide catalyst and method for synthesizing 2, 5-furandicarboxylic acid by using catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |