CN118146180A - Method for synthesizing 2, 5-furandicarboxylic acid by carboxylation - Google Patents
Method for synthesizing 2, 5-furandicarboxylic acid by carboxylation Download PDFInfo
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- CN118146180A CN118146180A CN202410273615.5A CN202410273615A CN118146180A CN 118146180 A CN118146180 A CN 118146180A CN 202410273615 A CN202410273615 A CN 202410273615A CN 118146180 A CN118146180 A CN 118146180A
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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 174
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000006473 carboxylation reaction Methods 0.000 title claims abstract description 52
- 230000021523 carboxylation Effects 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 112
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 24
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 230000020477 pH reduction Effects 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 9
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 37
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 230000001360 synchronised effect Effects 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 239000010453 quartz Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- SXRACWYQVZMVMK-UHFFFAOYSA-N C(=O)O.C(=O)O.O1C=CC=C1 Chemical compound C(=O)O.C(=O)O.O1C=CC=C1 SXRACWYQVZMVMK-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007423 decrease 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
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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Classifications
-
- 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
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which belongs to the technical field of organic chemical synthesis, and comprises the following steps: in a rotary furnace, furoic acid and carbonate are mixed, then an X% Ru-Y% Cs/C catalyst is added, carbon dioxide is introduced to carry out carboxylation reaction, acidification treatment is carried out after the reaction, and FDCA is separated and collected; x in the X-Ru-Y Cs/C catalyst is Ru mol percent which is more than or equal to 0.5 and less than or equal to 20, Y is Cs mol percent which is more than or equal to 1 and less than or equal to 20. The prepared X-percent Ru-Y-percent Cs/C type catalyst has the advantages of larger specific surface area, simple preparation method, mild reaction conditions, high reaction efficiency, high yield, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing 2, 5-furandicarboxylic acid by carboxylation.
Background
2, 5-Furandicarboxylic acid (FDCA) is a biomass-derived compound with great potential for use, and is listed by the U.S. department of energy as one of twelve important biobased platform chemicals. The structure is similar to terephthalic acid, and is considered to replace terephthalic acid to be an important raw material for manufacturing polyester plastics, so as to manufacture a new generation of biodegradable plastics like polyethylene terephthalate (PET); the structure of the material has five-ring difunctional characteristics, and compared with a six-membered ring structure of terephthalic acid, the material has asymmetric molecular arrangement, so that the material can be used for synthesizing optical/gas-barrier special-function polymer materials; 2, 5-furandicarboxylic acid can also be used as an important intermediate for other fine chemicals, medicines and pesticides. Therefore, the preparation of 2, 5-furandicarboxylic acid is considered to be a very representative sustainable bioconversion process for replacing petroleum production, and has great application prospect and potential. The main synthesis method of the 2, 5-furandicarboxylic acid at present takes expensive 5-Hydroxymethylfurfural (HMF) as a raw material. The method has the defects of low total yield and high cost, and is difficult to realize large-scale industrialized application. The furoic acid is used as a low-cost bio-based raw material, and the carbon on the No. 5 furoic acid position is carboxylated by carbonate and CO 2 to prepare the FDCA, so that a new idea is provided for the synthesis of the FDCA. However, the reaction conditions are severe and the reaction efficiency is low, and the yield of the prepared FDCA is low, so that a catalyst with a large number of catalytic active sites is needed to improve the carboxylation reaction efficiency of furoic acid and carbon dioxide, thereby improving the yield of FDCA.
Disclosure of Invention
The invention aims to provide a method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which aims to solve the problems of low efficiency of carboxylation reaction of furoic acid and carbon dioxide and low yield of FDCA in the background technology.
The aim of the invention can be achieved by the following technical scheme:
a method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing an X% Ru-Y% Cs/C catalyst: sequentially adding the Ru/C catalyst into the cesium carbonate-containing aqueous solution stirred at 600-800rpm, stirring at 200-400rpm for 0.5-1.5h after the addition is finished, standing and aging for 3-6h; drying the black solid obtained after the concentration of the reaction liquid in an oven at 100-150 ℃ for 12-24 hours, grinding the black solid into powder, placing the powder in a rotary furnace, heating the powder to 300-600 ℃ at a constant speed of 5 ℃/min in a nitrogen atmosphere, calcining the powder for 1-10 hours, and naturally cooling the powder to room temperature (25-30 ℃); placing the calcined solid powder into a tube furnace, and reducing the solid powder for 1 to 10 hours at a constant speed of between 150 and 300 ℃ at a speed of 2 ℃ per minute under the hydrogen atmosphere; and cooling to room temperature after reduction, and aging for 2-4 hours to obtain the X% Ru-Y% Cs/C catalyst.
Further, in the X% Ru-Y% Cs/C catalyst, X is the mol percentage of Ru, and X is more than or equal to 0.5 and less than or equal to 20; y is the mole percent of Cs, and Cs is more than or equal to 1 and less than or equal to 20. The X-Ru-Y-Cs/C catalyst is specifically X-Ru/C loaded with Y-Cs, no essential relation exists between X values and Y values, the combined action of two metals promotes the immobilization of carbon dioxide to generate furan diformate, and the difference of the proportion of the two metals only affects the activity of the catalyst and the selectivity of a product.
S2, synthesizing 2, 5-furandicarboxylic acid: adding an X% Ru-Y% Cs/C catalyst after uniformly mixing furoic acid and carbonate, and introducing carbon dioxide at a flow rate of 100-1000mL/min after uniformly mixing so that the pressure of a reaction system is 0.1-2MPa; under the condition of rotating speed of 10-100rpm, the temperature is uniformly increased to 190-280 ℃ at the heating rate of 1-20 ℃/min for reaction for 2-24h; and naturally cooling to room temperature after the reaction is finished, taking out the solid after the reaction, suspending in water, adding an acid solution for acidizing, adjusting the pH to be not more than 1, precipitating a large amount of solid, filtering, drying and collecting FDCA.
Further, the carbonate in S2 includes sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate or lithium carbonate.
Further, the acid solution used in the acidification treatment in S2 includes one or any combination of a plurality of hydrochloric acid, sulfuric acid, dilute nitric acid, trifluoroacetic acid and trifluoromethanesulfonic acid.
Further, the molar ratio of the furoic acid to the carbonate is 1:1-10, the mass ratio of the catalyst to the furoic acid is 0.05-1:1.
Further, 2, 5-furandicarboxylic acid is carboxylated and synthesized in rotary furnace equipment, carbon dioxide is provided by a carbon dioxide generator, and the carbon dioxide generator comprises a generator air inlet and a generator air outlet; the rotary furnace equipment comprises a heating furnace, an equipment host, a cooling receiving tank and a rotating motor, wherein the heating temperature range of the heating furnace is 30-500 ℃, and the temperature of the cooling receiving tank is 5-30 ℃.
Further, the heating furnace comprises a heat preservation hearth, a special-shaped pipe baffle, an electric heating wire and a special-shaped pipe, wherein the heater in the equipment host is used for regulating and controlling the electric heating wire in the heating furnace, the temperature can be directly read out from a temperature control instrument, and the special-shaped pipe in the heating furnace is heated to a set temperature at a certain heating rate and then subjected to heat preservation reaction.
Further, the special tube is made of quartz.
Furthermore, two ends of the special-shaped tube are respectively connected with a special-shaped tube air inlet and a special-shaped tube air outlet through a furnace tube flange, and the special-shaped tube air outlet is connected with a cooling receiving tank air inlet through a pipeline.
Further, the equipment host is positioned at the lower part of the heating furnace and comprises a control button, a motor rotating speed driver and a temperature control instrument, and is electrically connected with the heater, and the temperature and time of the reaction system are controlled through the equipment host.
Further, the cooling receiving tank comprises a cooling receiving tank air inlet, a cooling receiving tank air outlet and a cooling receiving tank discharging port, and moisture generated in the reaction system can influence the conversion rate of the reaction, so that the cooling device is used for cooling mixed water vapor into water, and the cooling water is discharged through the cooling receiving tank discharging port; the carbon dioxide generator outputs carbon dioxide in a high-pressure state through a generator air outlet to reach a special pipe in the heating furnace for reaction, the generator air inlet is connected with a cooling receiving tank air outlet through a circulating pipe, the cooling receiving tank is used for cooling water mixed with water vapor in the reacted carbon dioxide, the water is discharged through a discharging port of the cooling receiving tank, and meanwhile, the residual carbon dioxide is returned to the carbon dioxide generator through the cooling receiving tank air outlet of the cooling receiving tank through the circulating pipe for recycling.
Further, the control button of the equipment host machine regulates and controls the driving belt synchronous device to enable the rotary furnace equipment to stably run at a certain rotating speed under the driving action of the motor rotating speed driver, wherein the motor rotating speed driver drives the rotating motor, the motor synchronous belt wheel connected with the rotating motor drives the synchronous belt to be transmitted to the main synchronous belt wheel, and the furnace tube gear on the outer surface of the special-shaped tube is in nested clamping connection with the main synchronous belt wheel so as to drive the special-shaped tube to run.
As a further scheme of the invention, the method for synthesizing the 2, 5-furandicarboxylic acid by carboxylation comprises the following steps of:
S1, preparing an X% Ru-Y% Cs/C catalyst: sequentially adding the Ru/C catalyst into the cesium carbonate-containing aqueous solution stirred at 600-800rpm, stirring at 200-400rpm for 0.5-1.5h after the addition is finished, standing and aging for 3-6h; drying the black solid obtained after the concentration of the reaction liquid in an oven at 100-150 ℃ for 12-24 hours, grinding the black solid into powder, placing the powder in a rotary furnace, heating the powder to 300-600 ℃ at a constant speed of 5 ℃/min in a nitrogen atmosphere, calcining the powder for 1-10 hours, and naturally cooling the powder to room temperature (25-30 ℃); placing the calcined solid powder into a tube furnace, and reducing the solid powder for 1 to 10 hours at a constant speed of between 150 and 300 ℃ at a speed of 2 ℃ per minute under the hydrogen atmosphere; and cooling to room temperature after reduction, and aging for 2-4 hours to obtain the X% Ru-Y% Cs/C catalyst. X in the X% Ru-Y% Cs/C catalyst is Ru mol percent which is more than or equal to 0.5 and less than or equal to 20; y is the mole percentage of Cs, and Cs is more than or equal to 1 and less than or equal to 20;
S2, after 1moL of furoic acid and 1-10moL of carbonate are physically mixed uniformly, adding an X-percent Ru-Y-percent Cs/C catalyst (X is more than or equal to 0.5 and less than or equal to 20, cs is more than or equal to 1 and less than or equal to 20), wherein the mass ratio of the X-percent Ru-Y-percent Cs/C catalyst to the furoic acid is 0.05-1:1, adding the mixed solid into a special pipe made of quartz material, clamping the special pipe into rotary furnace equipment, and introducing carbon dioxide into the special pipe at a flow rate of 100-1000mL/min through a carbon dioxide generator to ensure that the reaction pressure is 0.1-2MPa; regulating the rotating speed of the rotary furnace to 10-100rpm, heating to 190-280 ℃ at a heating rate of 1-20 ℃/min, reacting for 2-24 hours at a temperature, naturally cooling to room temperature after the reaction is finished, and taking out the solid. Placing the solid in water, adding acid to adjust the pH value to be less than or equal to 1, and filtering the precipitated filter cake to obtain a synthesized product FDCA.
The invention has the beneficial effects that:
1. The invention provides a method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, wherein the X% Ru-Y% Cs/C type catalyst has larger specific surface area, the preparation method is simple, the reaction condition is mild, and the FDCA synthesized by using the catalyst has the advantages of high reaction efficiency, high yield, low cost and the like.
2. The invention adopts the rotary furnace equipment with the carbon dioxide generator as a reaction device to carry out FDCA synthesis under proper reaction conditions, wherein the mixed vapor in the reacted carbon dioxide is condensed by the cooling receiving tank, and the rest carbon dioxide is sent back to the carbon dioxide generator for recycling through the circulating pipe, thereby not only timely removing the vapor generated in the reaction process and reducing the influence of the vapor on the reaction yield, but also removing the vapor in the carbon dioxide and recycling the carbon dioxide.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a chart of Fourier Transform Infrared (FTIR) analysis of a 5% Ru-10% Cs/C catalyst according to example 2 of the present invention;
FIG. 2 is a Raman spectrum of 5% Ru-10% Cs/C catalyst in example 2 of the present invention;
FIG. 3 is an XPS chart of a 5% Ru-10% Cs/C type catalyst according to example 2 of the present invention;
FIG. 4 is an XRD pattern for a 5% Ru-10% Cs/C type catalyst according to example 2 of the invention;
FIG. 5 is a front view of a rotary kiln in accordance with embodiment 3 of the present invention;
FIG. 6 is a top view of a rotary kiln in accordance with example 3 of the present invention;
FIG. 7 is a cross-sectional view of the rotary kiln of the present invention taken along line A-A;
In the figure: 1. a carbon dioxide generator; 2. a carbon dioxide generator air inlet; 3. a carbon dioxide generator gas outlet; 4. a special-shaped pipe air inlet; 5. a circulation pipe; 6. a heating furnace; 7. a special-shaped pipe air outlet; 8. cooling the receiving tank air inlet; 9. cooling the air outlet of the receiving tank; 10. cooling the receiving tank; 11. cooling the receiving tank discharge port; 12. a control button; 13. a motor rotation speed driver; 14. a temperature control instrument; 15. a device host; 16. furnace tube flange; 17. a primary synchronous pulley; 18. a furnace tube gear; 19. a heat preservation hearth; 20. a special-shaped pipe baffle; 21. an electric heating wire; 22. a special-shaped tube; 23. a heater; 24. a rotating motor; 25. a motor synchronous belt wheel; 26. a synchronous belt.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation of the 5% Ru/C catalyst adopts an impregnation method, and comprises the following steps:
Dissolving 25g of active carbon in 250mL of water, stirring for 0.5h to uniformly disperse the active carbon, slowly dripping 10mL of aqueous solution containing 2.6g of RuCl 3 into the dispersed active carbon aqueous solution at a rotation speed of 600rpm, continuously stirring for 1h, standing at room temperature, and fully aging overnight (12 h); concentrating to dry, vacuum drying at 80deg.C for 6 hr, taking out, and grinding into powder. Calcining for 3h under nitrogen flow at 400 ℃, and cooling. Reducing for 3h at 150 ℃ in a hydrogen atmosphere in a tube furnace, wherein the heating rate is 2 ℃/min. After the reduction, cooling to room temperature, opening the interfaces at the two ends, air aging for 3 hours under rotation, and taking out to obtain 20.0g of 5% Ru/C catalyst.
The same method prepares a 2 percent Ru/C catalyst, wherein the dosage of RuCl 3 is 1.0g;
A 6% Ru/C catalyst wherein RuCl 3 is used in an amount of 3.1g;
10% Ru/C catalyst, wherein RuCl 3.1 g was used.
Example 2
The preparation of the 5% Ru-10% Cs/C catalyst comprises the following steps:
18.8g of 5% Ru/C catalyst is added into 500mL of water solution containing 2.3g cesium carbonate under the stirring of 700rpm for 5 times, after the addition, the mixture is stirred for 1h at 300rpm, the stirring is stopped, and the mixture is stood for aging for 4h; concentrating the reaction solution to obtain a black solid, and placing the black solid in an oven to dry at 120 ℃ overnight (12 h), wherein 24.5g of the black solid is obtained after drying; grinding the dried catalyst into powder, placing the powder into a rotary furnace, introducing nitrogen flow, heating to 400 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature; the calcined catalyst was placed in a tube furnace, and reduced for 4 hours after being heated to 200 ℃ at a rate of 2 ℃/min in a hydrogen atmosphere. After reduction, the mixture was cooled to room temperature, both end ports were opened, and the mixture was aged for 3 hours to obtain 20.5g of 5% Ru-10% Cs/C catalyst.
Performance test is carried out on the 5% Ru-10% Cs/C catalyst prepared in the embodiment 2, wherein the specific surface area of the catalyst is 1050.7278m2/g, and the micropore volume is 0.372611cm 3/g, which shows that the catalyst has larger specific surface area, can increase the contact between an active site and a substrate, and is beneficial to the reaction;
Fourier Transform Infrared (FTIR) analysis of 5% Ru-10% Cs/C catalyst FIG. 1, from FIG. 1, the type of surface functional groups is known, the carbon support has carboxyl groups (C-O stretching vibration at 1178cm -1, C=O stretching vibration at 1630cm -1), alcohol functional groups (OH bending in the 1384cm -1, OH stretching vibration at 3417cm -1) and alkyl groups (C-H stretching vibration at 2922-2852cm -1);
The raman spectrum of the 5% ru-10% cs/C catalyst is shown in fig. 2, and structural information about the carbon material is known from fig. 2, showing two characteristic peaks at about 1340 and 1594cm –1 in the D and G bands, respectively. The D-band (sp 3 carbon) is associated with graphene defects caused by pentagons or heptagons, indicating the degree of surface defects and disorder in the carbon support, while the G-band corresponds to in-plane stretching vibration of sp 2 carbon atoms, indicating that the carbon support has a graphite structure in the order of C atoms;
The XPS diagram of the 5% Ru-10% Cs/C catalyst is shown in figure 3, and the catalyst comprises Ru (490-450, 288-278 eV), cs (746-718 eV), O (544-528 eV) and C (290-282 eV) elements as can be seen from figure 3;
XRD patterns of the 5% Ru-10% Cs/C catalyst are shown in figure 4, the main peak in figure 4 is a diffraction peak of carbon, no obvious diffraction peak of Ru and Cs is observed, and the active sites Ru and Cs in the catalyst are uniformly dispersed, so that the oxidation reaction is more facilitated. From the characterization results, the catalyst has a larger specific surface area from 5% Ru to 10% Cs/C, the catalyst contains Ru, cs, O, C elements, C in the catalyst is mainly graphene structural carbon which is beneficial to electron transfer, and meanwhile, the highly dispersed Ru and Cs are more beneficial to oxidation reaction.
Example 3
An apparatus for synthesizing 2, 5-furandicarboxylic acid, FIG. 5 is a front view of a rotary furnace apparatus, FIG. 6 is a top view of the rotary furnace apparatus, FIG. 7 is a cross-sectional view of the rotary furnace apparatus taken along line A-A, as shown in the drawing, when in use, 1mol of furoic acid and 1-10mol of carbonate are physically mixed uniformly, then X-Y% Cs/C catalyst (0.5-20, 1-20) is added, the mass ratio of X-Y% Cs/C catalyst to furoic acid is 0.05-1:1, the mixed solid is added into a special-shaped tube 22 made of quartz material, the special-shaped tube 22 is clamped and mounted into the rotary furnace apparatus by using a special-shaped tube baffle 20, a carbon dioxide generator gas outlet 3 in a carbon dioxide generator 1 is connected with a special-shaped tube gas inlet 4, and carbon dioxide is introduced into the special-shaped tube 22 at a flow rate of 100-1000mL/min, so that the pressure in the special-shaped tube 22 is 0.1-2MPa; the control button 12 of the equipment host 15 regulates and controls the driving belt synchronous device to enable the rotary furnace equipment to stably run at the rotating speed of 10-100rpm under the driving action of the motor rotating speed driver 13, wherein the motor rotating speed driver 13 drives the rotating motor 24, the motor synchronous pulley 25 connected with the rotating motor 24 drives the synchronous belt 26 to be transmitted to the main synchronous pulley 17, and the furnace tube gear 18 on the outer surface of the special-shaped tube 22 is nested and clamped with the main synchronous pulley 17 so as to drive the special-shaped tube 22 to run.
Meanwhile, the heater 23 in the equipment host 15 is used for regulating and controlling the electric heating wire 21 in the heating furnace 6, the temperature can be directly read out from a temperature control instrument, and the special-shaped pipe 22 in the heating furnace 6 is heated to 190-280 ℃ at the heating rate of 1-20 ℃/min and then subjected to heat preservation reaction for 2-24 hours by using the heat preservation hearth 19. After the reaction, naturally cooling to room temperature, and taking out the solid. Placing the solid in water, adding an acid solution to adjust the pH value to be less than or equal to 1, and filtering the precipitated filter cake to obtain a synthesized product FDCA.
The water vapor and the redundant carbon dioxide generated after the reaction enter a cooling receiving tank 10 through a cooling receiving tank air inlet 8 connected with a special pipe air outlet 7, the temperature of the cooling receiving tank 10 is controlled to be 5-30 ℃, at the moment, the water vapor is cooled into water through condensation, and the water vapor is discharged from a cooling receiving tank discharging opening 11, so that the reaction efficiency is effectively improved; the redundant carbon dioxide flows out from the air outlet 9 of the cooling receiving tank to the circulating pipe 5, and then returns to the carbon dioxide generator 1 from the air inlet 2 of the carbon dioxide generator to realize the recycling of the carbon dioxide.
Example 4
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, after 10g of furoic acid and 20g of potassium carbonate (the molar ratio of furoic acid to potassium carbonate is 1:1.6) are physically mixed uniformly, 1g of 5% Ru-10% Cs/C catalyst is added, the mixed solid is added into a special pipe made of quartz material, the special pipe is clamped in rotary furnace equipment, carbon dioxide is introduced into the special pipe at a flow rate of 1000mL/min through a carbon dioxide generator, and the reaction pressure is 0.1MPa; regulating the rotating speed of the rotary furnace to 100rpm, heating to 250 ℃ at a heating rate of 20 ℃/min, preserving heat for 6 hours, naturally cooling to room temperature after the reaction is finished, and taking out the solid. And (3) suspending the solid and 100mL of deionized water, adding hydrochloric acid to adjust the pH to be 0.8, and filtering the precipitated filter cake to obtain a synthesized product FDCA.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Sampling detection, detection conditions: hitachi L2000 HPLC SYSTEM, alltech C18 column; mobile phase methanol, 0.5wt% trifluoroacetic acid aqueous solution 20:80; flow rate: 1.0mL/min; column temperature: 30 ℃; a detector: DAD, detection wavelength: 264nm, the yield of FDCA was found to be 78% and the purity of FDCA was found to be 99.3%.
Example 5
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, only the equimolar amount of potassium carbonate is replaced by sodium carbonate, wherein the mass of the sodium carbonate is 15g, the rest components and steps are completely consistent, and the FDCA yield is 70% and the purity is 99.0% after the reaction is finished.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 6
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, only the equimolar amount of potassium carbonate is replaced by rubidium carbonate, wherein the mass of the rubidium carbonate is 33.4g, the rest components and steps are completely consistent, and the FDCA yield is 68% and the purity is 98.8% after the reaction is finished.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 7
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
s1, preparing a 5% Ru-5% Cs/C catalyst, wherein the preparation process is the same as that of example 2, except that the dosage of cesium carbonate is 1.2g, and the rest components and steps are completely consistent;
S2, the same as in example 4 is different in that the 5% Ru-5% Cs/C catalyst prepared by S1 is used, the rest components are completely consistent with the steps, and the FDCA yield is 70% and the purity is 99.1% after the reaction is finished.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 8
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-15% Cs/C catalyst, wherein the preparation process is the same as that of example 2, except that the dosage of cesium carbonate is 3.5g, and the rest components and steps are completely consistent;
s2, the same as in example 4 is different in that the 5% Ru-15% Cs/C catalyst prepared by S1 is used, the rest components are completely consistent with the steps, and after the reaction is finished, the FDCA yield is 72% and the purity is 99.4%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 9
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
s1, preparing a 5% Ru-20% Cs/C catalyst, wherein the preparation process is the same as that of example 2, except that the dosage of cesium carbonate is 4.6g, and the rest components and steps are completely consistent;
S2, the method is identical to example 4, except that the 5% Ru-20% Cs/C catalyst prepared by S1 is used, the rest components are completely identical to the steps, and after the reaction is finished, the FDCA yield is 69% and the purity is 98.9%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 10
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
s1, preparing a 2% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of the example 2, except that the 2% Ru/C catalyst is used, and the rest components and steps are completely consistent;
s2, the same as in example 4, except that the catalyst prepared by S1 is 2% Ru-10% Cs/C, and the rest components and steps are completely identical. After the completion of the reaction, the yield of FDCA was 73% and the purity was 98.7%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 11
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
s1, preparing a 6% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of the example 2, except that the 6% Ru/C catalyst is used, and the rest components and steps are completely consistent;
S2, the same as in example 4, except that the catalyst prepared by S1 is 6% Ru-10% Cs/C, and the rest components and steps are completely identical. After the completion of the reaction, the yield of FDCA was 79% and the purity was 99.1%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 12
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 10% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of the example 2, except that the 10% Ru/C catalyst is used, and the rest components and steps are completely consistent;
s2, the same as in example 4, except that the 10% Ru-10% Cs/C catalyst prepared by S1 is used, and the rest components and steps are completely identical. After the completion of the reaction, the yield of FDCA was 80% and the purity was 99.1%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 13
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the method is different in that the temperature is increased to 190 ℃, the reaction is carried out at the temperature, the other components and the steps are completely consistent, and after the reaction is finished, the FDCA yield is 68% and the purity is 99.0%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 14
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the method is different in that the temperature is increased to 230 ℃, the reaction is carried out at a temperature, the other components and the steps are completely consistent, and after the reaction is finished, the FDCA yield is 75% and the purity is 98.9%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 15
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
s2, compared with the example 4, the method is different in that the temperature is increased to 270 ℃, the reaction is carried out at a temperature, the other components and the steps are completely consistent, and after the reaction is finished, the FDCA yield is 73% and the purity is 99.1%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 16
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the reaction time is 8 hours, the rest components are completely consistent with the steps, the yield of FDCA is 79% after the reaction is finished, and the purity is 98.0%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 17
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the reaction time is 12 hours, the rest components are completely consistent with the steps, the FDCA yield is 80% after the reaction is finished, and the purity is 98.7%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 18
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
s2, compared with the example 4, the difference is that the reaction pressure is 1MPa, the rest components are completely consistent with the steps, the FDCA yield is 80% after the reaction is finished, and the purity is 99.4%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 19
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the reaction pressure is 2MPa, the rest components are completely consistent with the steps, the FDCA yield is 82% after the reaction is finished, and the purity is 99.0%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 20
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the flow rate of carbon dioxide is 400mL/min, the rest components are completely consistent with the steps, the yield of FDCA is 63% after the reaction is finished, and the purity is 99.1%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 21
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the flow rate of carbon dioxide is 700mL/min, the rest components are completely consistent with the steps, the yield of FDCA is 71% after the reaction is finished, and the purity is 98.7%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 22
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the rotating speed of the rotary furnace is 25rpm, the rest components and the steps are completely consistent, the FDCA yield is 62% after the reaction is finished, and the purity is 98.9%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 23
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the rotating speed of the rotary furnace is 50rpm, the rest components and the steps are completely consistent, the FDCA yield is 68% after the reaction is finished, and the purity is 99.1%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 24
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the rotating speed of the rotary furnace is 75rpm, the rest components and the steps are completely consistent, the FDCA yield is 70% after the reaction is finished, and the purity is 98.5%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 25
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the temperature rising rate is 10 ℃/min, the other components are completely consistent with the steps, the FDCA yield is 73% after the reaction is finished, and the purity is 99.2%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 26
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the temperature rising rate is 15 ℃/min, the other components are completely consistent with the steps, the FDCA yield is 75% after the reaction is finished, and the purity is 99.4%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 27
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with example 4, the difference is that the dosage of potassium carbonate is 62.2g, the rest components are completely consistent with the steps, the yield of FDCA is 70% after the reaction is finished, and the purity is 99.0%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 28
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
s2, compared with example 4, the difference is that the dosage of potassium carbonate is 124.0g, the rest components are completely consistent with the steps, the yield of FDCA is 65% after the reaction is finished, and the purity is 99.1%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 29
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with the example 4, the difference is that the dosage of the 5% Ru-10% Cs/C catalyst is 5g, the rest components are completely consistent with the steps, the FDCA yield is 65% after the reaction is finished, and the purity is 98.8%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 30
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2;
S2, compared with example 4, the difference is that the dosage of the 5% Ru-10% Cs/C catalyst is 9.5g, the rest components and steps are completely consistent, and the FDCA yield is 63% and the purity is 99.0% after the reaction is finished.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 31
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
s1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2, and the difference is that: heating to 400 ℃ at a speed of 5 ℃/min, calcining for 2 hours, and naturally cooling to room temperature; placing the calcined catalyst in a tube furnace, heating to 200 ℃ at a speed of 2 ℃/min in a hydrogen atmosphere, and reducing for 3 hours; the other components and the steps are completely consistent;
S2, compared with example 4, the difference is that the 5% Ru-10% Cs/C catalyst prepared in S2 is used, the rest components and steps are completely consistent, the FDCA yield is 80% and the purity is 99.1% after the reaction is finished.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 32
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2, and the difference is that: heating to 400 ℃ at a speed of 5 ℃/min, calcining for 5 hours, and naturally cooling to room temperature; placing the calcined catalyst in a tube furnace, heating to 200 ℃ at a speed of 2 ℃/min in a hydrogen atmosphere, and reducing for 5 hours; the other components and the steps are completely consistent;
S2, compared with example 4, the difference is that the 5% Ru-10% Cs/C catalyst prepared in S2 is used, the rest components and steps are completely consistent, the yield of FDCA is 79% after the reaction is finished, and the purity is 99.0%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 33
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2, and the difference is that: heating to 500 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature; placing the calcined catalyst in a tube furnace, heating to 250 ℃ at a speed of 2 ℃/min in a hydrogen atmosphere, and reducing for 4 hours; the other components and the steps are completely consistent;
S2, compared with example 4, the difference is that the 5% Ru-10% Cs/C catalyst prepared in S2 is used, the rest components and steps are completely consistent, the yield of FDCA is 79% after the reaction is finished, and the purity is 99.3%.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
Example 34
A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which comprises the following steps:
S1, preparing a 5% Ru-10% Cs/C catalyst, wherein the preparation process is the same as that of example 2, and the difference is that: heating to 300 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to room temperature; placing the calcined catalyst in a tube furnace, heating to 150 ℃ at a speed of 2 ℃/min in a hydrogen atmosphere, and reducing for 4 hours; the other components and the steps are completely consistent;
S2, compared with example 4, the difference is that the 5% Ru-10% Cs/C catalyst prepared in S2 is used, the rest components and steps are completely consistent, the FDCA yield is 77% and the purity is 99.3% after the reaction is finished.
The apparatus for synthesizing 2, 5-furandicarboxylic acid of this example is the same as that of example 3.
As can be seen from examples 4-6, the FDCA yield is best and reaches 78% under the condition of potassium carbonate when different bases (sodium carbonate and calcium carbonate) are used as reactants; examples 4 and 7-12 show that adjusting the mass fraction of Cs or Ru in the catalyst can affect the yield of FDCA; examples 4 and 13-15 show that FDCA yield increases with increasing temperature, but above 250 ℃, yield decreases with increasing temperature, mainly due to FDCA starting to decompose at a certain temperature, thereby affecting the yield of the reaction; as can be seen from examples 4 and 16-17, the longer the incubation time, the higher the reaction conversion rate, and the highest FDCA yield can reach 80% when the incubation time is 12 hours; it can be seen from examples 4 and 18-21 that controlling the reaction pressure and the carbon dioxide flow rate further improves the product yield; as can be seen from examples 4 and 22-24, the reaction yields were highest at 100rpm rates at different speeds of rotation of the rotary kiln (25 rpm, 50rpm, 75rpm, 100 rpm); it can be seen from examples 4 and 25 to 26 that the heating rate of the heating furnace has little influence on the reaction, and the FDCA yield is highest when the heating rate is 20 ℃/min; it can be seen from examples 4 and 27-28 that varying the equivalent weight of potassium carbonate affects the product yield, with an optimum equivalent weight of 1.65 for potassium carbonate and 78% for product yield; it can be seen from examples 4 and 29 to 30 that the product yield was the best when the catalyst input was 10% of furoic acid; it can be seen from examples 4 and 31 to 34 that the calcination, reduction time and temperature during the catalyst preparation process have little effect on the product yield, wherein the calcination and reduction time is shortened and the product yield is lowered. According to the embodiment, the type and the amount of carbonate, the catalyst amount, the temperature rise temperature and the rate of the catalyst, the rotating speed of the rotary furnace, the heat preservation time, the flow of carbon dioxide, the reaction pressure and the like are all factors influencing the yield of FDCA, and the method reasonably screens and optimizes experimental conditions, controls experimental variables and is beneficial to improving the conversion rate of the reaction.
The X% Ru-Y% Cs/C catalyst prepared by the invention has larger specific surface area, and the catalyst has the advantages of high yield, low cost and the like when being used for synthesizing FDCA by carboxyl. In addition, the rotary furnace equipment with the carbon dioxide generator can remove the water vapor generated in the reaction process in time, reduce the influence of the water vapor on the reaction yield, remove the water vapor in the carbon dioxide, recycle the carbon dioxide, and has the advantages of simple process, mild reaction condition, low energy consumption, high yield, cost saving and the like.
It is noted that relational terms such as first and second, and the like are 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. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus 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 apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for synthesizing 2, 5-furandicarboxylic acid by carboxylation, which is characterized by comprising the following steps:
In a rotary furnace, furoic acid and carbonate are mixed, then an X% Ru-Y% Cs/C catalyst is added, carbon dioxide is introduced to carry out carboxylation reaction, acidification treatment is carried out after the reaction, and FDCA is separated and collected; x in the X-Ru-Y Cs/C catalyst is Ru mol percent which is more than or equal to 0.5 and less than or equal to 20, Y is Cs mol percent which is more than or equal to 1 and less than or equal to 20.
2. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 1, wherein the x% Ru-y% Cs/C catalyst is prepared by the steps of:
adding Ru/C catalyst into cesium carbonate water solution stirred at 600-800rpm, stirring at 200-400rpm for 0.5-1.5h until uniform, standing and aging for 3-6h; drying the black solid obtained after the concentration of the reaction liquid in an oven at 100-150 ℃ for 12-24 hours, grinding the black solid into powder, heating the powder to 300-600 ℃ at a constant speed of 5 ℃/min in a nitrogen atmosphere, calcining the powder for 1-10 hours, and naturally cooling the powder to room temperature; heating the calcined solid powder to 150-300 ℃ at a constant speed of 2 ℃/min under the hydrogen atmosphere, and reducing for 1-10h; and cooling to room temperature after reduction, and aging for 2-4 hours to obtain the X% Ru-Y% Cs/C catalyst.
3. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 1, wherein the molar ratio of furoic acid to carbonate is 1:1-10, the dosage ratio of furoic acid to X% Ru-Y% Cs/C catalyst is 1:0.05-1.
4. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 1, wherein the carbonate comprises sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate or lithium carbonate.
5. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 1, wherein the carbon dioxide is introduced at a flow rate of 100-1000mL/min.
6. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 1, wherein the carboxylation reaction condition is that the pressure of a reaction system is 0.1-2MPa, and the reaction is carried out for 2-24 hours by uniformly heating to 190-280 ℃ at a heating rate of 1-20 ℃/min under the condition of rotating speed of 10-100 rpm.
7. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 1, wherein the acidification treatment is specifically to adjust the pH of the reaction system to not more than 1 by an acid solution.
8. The method for synthesizing 2, 5-furandicarboxylic acid by carboxylation according to claim 7, wherein the acid solution comprises one or any combination of a plurality of hydrochloric acid, sulfuric acid, dilute nitric acid, trifluoroacetic acid and trifluoromethanesulfonic acid.
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