CN115974821A - 2,5-furandicarboxylic acid amplification production method - Google Patents
2,5-furandicarboxylic acid amplification production method Download PDFInfo
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- CN115974821A CN115974821A CN202310276712.5A CN202310276712A CN115974821A CN 115974821 A CN115974821 A CN 115974821A CN 202310276712 A CN202310276712 A CN 202310276712A CN 115974821 A CN115974821 A CN 115974821A
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- China
- Prior art keywords
- bicarbonate
- formate
- furandicarboxylic acid
- furoate
- furan
- Prior art date
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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 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000003321 amplification Effects 0.000 title abstract description 9
- 238000003199 nucleic acid amplification method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 34
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- VOZWCXPNEZWSAH-UHFFFAOYSA-N formic acid;furan Chemical compound OC=O.C=1C=COC=1 VOZWCXPNEZWSAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000000052 comparative effect Effects 0.000 claims abstract description 11
- 239000011949 solid catalyst Substances 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 230000001413 cellular effect Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- -1 potassium furan formate Chemical group 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- LWYJTCLDMYROHH-UHFFFAOYSA-M potassium;furan-2-carboxylate Chemical group [K+].[O-]C(=O)C1=CC=CO1 LWYJTCLDMYROHH-UHFFFAOYSA-M 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical group [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 7
- CKFRRDULRPAXQT-UHFFFAOYSA-M C1=COC(=C1)C(=O)[O-].[Cs+] Chemical compound C1=COC(=C1)C(=O)[O-].[Cs+] CKFRRDULRPAXQT-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000013341 scale-up Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- ORGWWLREDBVACT-UHFFFAOYSA-L calcium;furan-2-carboxylate Chemical compound [Ca+2].[O-]C(=O)C1=CC=CO1.[O-]C(=O)C1=CC=CO1 ORGWWLREDBVACT-UHFFFAOYSA-L 0.000 claims description 4
- 238000011031 large-scale manufacturing process Methods 0.000 claims description 4
- HDCRDACZYDHUQX-UHFFFAOYSA-M sodium;furan-2-carboxylate Chemical compound [Na+].[O-]C(=O)C1=CC=CO1 HDCRDACZYDHUQX-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 3
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical group [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 3
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 3
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- LBOHISOWGKIIKX-UHFFFAOYSA-M potassium;2-methylpropanoate Chemical compound [K+].CC(C)C([O-])=O LBOHISOWGKIIKX-UHFFFAOYSA-M 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 239000007789 gas Substances 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000178 monomer Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 238000004042 decolorization Methods 0.000 description 6
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OBSQZDSQVQLRQZ-UHFFFAOYSA-L copper;furan-2-carboxylate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CO1.[O-]C(=O)C1=CC=CO1 OBSQZDSQVQLRQZ-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- JOTDFEIYNHTJHZ-UHFFFAOYSA-N furan-2,4-dicarboxylic acid Chemical compound OC(=O)C1=COC(C(O)=O)=C1 JOTDFEIYNHTJHZ-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ZWKQEQLAWYCEQW-UHFFFAOYSA-L magnesium furan-2-carboxylate Chemical compound [Mg++].[O-]C(=O)c1ccco1.[O-]C(=O)c1ccco1 ZWKQEQLAWYCEQW-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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
Landscapes
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to an amplification production method of 2,5-furandicarboxylic acid. The method of the invention comprises the following steps: dissolving bicarbonate in low-melting-point molten salt to obtain a bicarbonate solid catalyst doped by the molten salt; dissolving furoate in methanol or ethanol solvent to obtain salt solution; adding a bicarbonate solid catalyst into a salt solution to obtain a porous cellular crystal structure reaction system with a high comparative area; or adding the furan formate, the alkaline catalyst and the low-melting-point molten salt into water, adding the inorganic carrier, and removing the water to obtain a uniformly mixed dry reactant system; and further reacting to obtain 2,5-furandicarboxylic acid. The method improves the reaction rate and promotes the high-efficiency removal of water generated in the reaction by pretreating the raw materials and the catalyst, thereby realizing the high-efficiency preparation of the 2,5-furandicarboxylic acid.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an amplification production method of 2,5-furandicarboxylic acid.
Background
5363 the synthesis of 2,5-furandicarboxylic acid mainly adopts the method of 5-hydroxymethylfurfural oxidation, and the problems of the method include: firstly, fructose is required to be used as a raw material for high-conversion synthesis of 5-hydroxymethylfurfural, and future large-scale production can compete with grain; secondly, the 5-hydroxymethylfurfural has an unstable structure and extremely good water solubility and is difficult to separate, so that the preparation of high-purity 5-hydroxymethylfurfural is difficult and the cost is high; in addition, when 5-hydroxymethylfurfural is oxidized to synthesize 2,5-furandicarboxylic acid, a noble metal catalyst with higher price is often used, the types of oxidation intermediates are multiple, the selective preparation is difficult, and the conversion rate is lower. Therefore, the 2,5-furandicarboxylic acid prepared by the existing 5-hydroxymethylfurfural oxidation method cannot be suitable for large-scale industrial production, and the large-scale application of 2,5-furandicarboxylic acid and downstream polyester products thereof is greatly limited.
Another method for synthesizing 2,5-furandicarboxylic acid adopts an addition reaction of furoic acid (salt) and carbon dioxide, the raw material furoic acid of the method is derived from non-grain biomass conversion, large-scale production is realized, the price is low, and the method has a commercial prospect. US20200157071 and WO2013096998 report a method for preparing 2,5-furandicarboxylic acid by disproportionation of furoic acid (salt) and carbon dioxide with a metal catalyst, wherein the yield of furandicarboxylic acid as a main product is low because furan dicarboxylic acid is obtained and is disproportionated to obtain an equivalent molar amount of furan monomer, and in addition, during the disproportionation reaction, a part 2,4-furandicarboxylic acid is generated, and is difficult to separate from 2,5-furandicarboxylic acid formic acid, the selectivity of the reaction is poor, and a pure 2,5-furandicarboxylic acid is difficult to obtain. WO2016153937 reports a method for preparing 2,5-furandicarboxylic acid by catalyzing carboxylation reaction of furanformate and carbon dioxide by cesium carbonate, and on the basis, WO2019214576 and WO2021061545 develop a method for synthesizing 2,5-furandicarboxylic acid under the condition of carbon dioxide gas from furanformate and an alkaline catalyst under a low-melting-point molten salt system. The essence of the reaction is that the furoate and the alkaline catalyst which are melted or dissolved in the low-melting-point molten salt are mixed with CO 2 Gas-liquid phase reaction of (2), but as the reaction proceeds, formation in the system continuesThe solid 2,5-furandicarboxylate severely retards the feed and catalyst and CO 2 Thereby inhibiting the efficient progress of the reaction, and this is now more pronounced during the reaction scale-up synthesis. Therefore, WO2021158890 proposes a reaction amplification device with shearing and crushing effects to crush the solid 2,5-furandicarboxylate generated in the system, thereby increasing the contact area of the gas and liquid phases in the reaction system and improving the conversion efficiency of the reaction. However, with the increasing proportion of 2,5-furandicarboxylate solid in the reaction system, it is thought that it is difficult to continue to increase the conversion rate of the reaction by merely pulverizing the solid matter produced in the system using equipment. Therefore, the development of a new process for continuously maintaining the high specific contact efficiency of the gas-liquid phase in the reaction system is important for the high-yield and large-scale production of 2,5-furandicarboxylic acid.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-yield amplification production process of 2,5-furandicarboxylic acid.
The technical scheme of the invention is a 2,5-furandicarboxylic acid amplification production method, which comprises the following steps:
step s1, raw material pretreatment: the operation is carried out by adopting one of the following a or b;
a. adding furan formate, an alkaline catalyst and low-melting-point molten salt into water, uniformly mixing, adding an inorganic carrier, removing water by spray drying to obtain a uniformly mixed dry reactant system, and drying and crushing under reduced pressure; the furan formate is potassium furan formate, sodium furan formate, copper furan formate, calcium furan formate or magnesium furan formate; the basic catalyst is carbonate, bicarbonate, phosphate or hydroxide base comprising an alkali metal or alkaline earth metal; the low-melting-point molten salt is potassium formate, sodium formate, potassium acetate/sodium acetate mixed molten salt, potassium isobutyrate or cesium acetate; the molar weight of the alkaline catalyst is 0.5 to 1.3 times of that of the furan formate, the mass of the low-melting-point molten salt is 0.2 to 0.4 times of the total mass of the furan formate and the alkaline catalyst, and the dosage of the inorganic carrier is 0.3 to 2 times of the total mass of the furan formate, the alkaline catalyst and the low-melting-point molten salt;
b. bicarbonate in vacuum or CO 2 Heating and dissolving in low-melting-point molten salt under the atmosphere, and cooling to room temperature to obtain a bicarbonate solid catalyst doped with the molten salt; dissolving furoate in methanol or ethanol solvent to obtain salt solution; adding a bicarbonate solid catalyst into a salt solution in a reactor, and heating to 150-280 ℃ to obtain a porous cellular crystal structure reaction system with a high comparative area; the furoate is potassium furoate, cesium furoate, sodium furoate and calcium furoate; the bicarbonate is cesium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, calcium bicarbonate or magnesium bicarbonate; the molar ratio of the bicarbonate to the furoate is 1: 1-4; the dosage of the low-melting-point molten salt is 0.2 to 3 times of the total mass of the furoate and the bicarbonate;
step s2, reaction: CO at a flow rate of 0.4 to 2MPa and 200 to 5000 mL/min 2 Raising the temperature of the reaction system to 220-320 ℃ under the air flow, and reacting for 1-6 hours; cooling to room temperature, adding deionized water for dissolving, adding activated carbon for decoloring, adding hydrochloric acid into the filtered water solution for acidifying, carrying out suction filtration on the solid to obtain an off-white solid, washing with ethanol, and drying to obtain 2,5-furandicarboxylic acid.
In the operation a of the step s1, the particle size of the crushed reactant system is controlled to be less than 1 micron; the water content of the reactant system after reduced pressure drying is less than 20ppm.
Further, in the operation a of the step s1, the molar weight of the basic catalyst is 1.1 to 1.2 times of that of the furoate; the mass of the low-melting-point molten salt is 0.3 times of the total mass of the furan formate and the alkaline catalyst.
In particular, in the operation b of the step s1, the molar ratio of the bicarbonate to the furoate is 1: 1.2 to 1.4; the dosage of the low-melting-point molten salt is 0.25 to 0.5 times of the total mass of the furoate and the bicarbonate.
Specifically, in the operation b of the step s1, heating to 200-220 ℃ to obtain a porous cellular crystal structure reaction system with a high comparative area.
Further, in step s2, the reactor for the reaction is a high-temperature high-pressure boiling bed, a spray drying device or a rotary drying device.
In particular, in step s2，CO 2 The airflow pressure is 0.8-1MPa, CO is in the range of 2 The airflow is 1500 mL/min, and the reaction is carried out for 2 hours at 293 ℃ to 305 ℃.
Wherein, in the step s2, the activated carbon is decolorized for 3 times.
The invention also provides 2,5-furandicarboxylic acid prepared by the method.
The invention has the beneficial effects that: the method aims at the problems that in the process of preparing 2,5-furandicarboxylic acid by catalyzing the reaction of furoic acid (salt) and carbon dioxide under a melting system by using an alkaline metal catalyst, along with the gradual generation of solid 2,5-furandicarboxylic acid salt, the contact area of the carbon dioxide, the furoate and a carbonate alkaline catalyst in a reaction system is blocked, so that the reaction rate is slowed, and side reactions are increased. According to the invention, raw materials and the catalyst are doped and designed into a core-shell structure, so that CO in the reaction process is ensured 2 Has continuous high contact area with dissolved reactants, improves the reaction rate, and simultaneously promotes the water generated in the reaction to be efficiently discharged from the system, thereby realizing the efficient preparation of the 2,5-furandicarboxylic acid. The invention quickly dissolves the bicarbonate of alkali metal or alkaline earth metal in the low-melting-point molten salt under the heating condition, then cools to room temperature to obtain the bicarbonate solid catalyst doped by the molten salt, takes the bicarbonate solid catalyst as a core, and further coats the bicarbonate catalyst with the core structure by taking furoate as a shell structure to prepare the reaction system with the core-shell structure. When the reaction temperature reaches or exceeds the decomposition degree of the bicarbonate, the temperature is maintained to ensure that the bicarbonate is gradually decomposed into carbonate, and simultaneously, water generated by thermal decomposition overflows from the surface of the core structure, so that the whole solid core-shell system is converted into a porous cellular crystal structure reaction system with a high comparative area. In addition, as the bicarbonate decomposition and the 2,5-furandicarboxylate generation form balance, the whole reaction system can continuously keep a hollow core-shell structure and can ensure that the carbon dioxide and CO can be ensured to form a hollow core-shell structure 2 The gases are maintained in intimate contact, thereby increasing the conversion of the furoate salt. The invention can ensure that the amplification process is scaled upThe furoate salt can be used for preparing 2,5-furandicarboxylic acid with high efficiency and high conversion.
Detailed description of the preferred embodiments
The preparation process is as follows, see table 1.
(1) Pretreatment of raw materials
Adding alkaline catalysts (including carbonates, bicarbonates, phosphates and hydroxide bases of alkali metals or alkaline earth metals) of alkali metals or alkaline earth metals in a molar amount of 1.1-1.3 times of furan formate (potassium furoate, sodium furoate, copper furoate, calcium furoate and magnesium furoate), low-melting-point molten salts (including potassium formate, sodium formate, potassium acetate/sodium acetate mixed molten salts, potassium isobutyrate, cesium acetate and the like) in an amount of 0.2-0.4 times of the total mass of furan formate and alkaline catalysts into water, mixing, adding a certain amount of inorganic carriers (including all commercial inorganic carriers, the using amount of the carriers being 0.3-2 times of the total mass of the materials) such as silicon oxide, kieselguhr, activated carbon, white carbon black, glass beads, titanium dioxide and the like, removing the aqueous solution by spray drying to obtain a dry reactant system with three uniformly mixed inorganic components, crushing the obtained solid material after reduced pressure drying, controlling the particle size of fine powder to be less than 1 micron, and the water content of the system to be less than 20ppm.
(2) Reaction of
Adding the mixture into 100L of fluidized bed system in dry carbon dioxide atmosphere to regulate and control CO of the system 2 The airflow is 200 to 5000 mL/min, the material powder is fully dispersed and reacted in a boiling reactor, the temperature of a reaction system is constantly set at 275 to 320 ℃, the reaction pressure is set at 0.4 to 2MPa, and a gas outlet of the boiling reactor is connected with a high-efficiency condensing device to ensure that CO 2 The gas flow can discharge the by-product water generated by the reaction out of the system, CO 2 And recycling the mixture through a dryer and a fan, wherein the reaction time is 1 to 5 hours.
(3) Purification of
Dissolving a solid material obtained after the reaction in water, filtering, rinsing the solid carrier, recycling, adding activated carbon into filtrate for decoloring, filtering to remove the activated carbon to obtain a clear and transparent aqueous solution, adding hydrochloric acid for acidification, performing suction filtration on the precipitated 2,5-furandicarboxylic acid to obtain a pure white solid, and washing with industrial ethanol to obtain a high-purity 2,5-furandicarboxylic acid monomer with the purity of 98-99.9% and the separation yield of 95-100%.
Table 1 examples 1-6 feedstock and parameter control
Comparative example 1 (comparison without load):
in a 100L fluidized bed reactor, adding 15.6 kg of 2-potassium furanformate and 16.5 kg of potassium carbonate, and adding 96.2 kg of anhydrous potassium formate to uniformly mix powder (the particle size of powder particles is 0.6-1 micron). CO of regulatory system 2 The gas flow is 1500 mL/min, the material powder is fully dispersed and reacted in the boiling reactor, the temperature of the reaction system is constantly set at 290 ℃, the reaction pressure is set at 0.9 MPa, and the gas outlet of the boiling reactor is connected with a high-efficiency condensing device to ensure that CO is condensed 2 The gas flow can discharge the by-product water generated by the reaction out of the system, CO 2 And (4) circulating and recycling the mixture through a dryer and a fan, and reacting for 6 hours. Dissolving the solid material obtained after the reaction in water, adding activated carbon for decoloring, filtering to remove the activated carbon to obtain a clear and transparent aqueous solution, adding hydrochloric acid for acidification, carrying out suction filtration on the separated 2,5-furandicarboxylic acid to obtain a pure white solid, and washing with industrial ethanol to obtain a high-purity 2,5-furandicarboxylic acid monomer with the purity of 98% and the separation yield of 57%. Note: a large amount of side reactants are produced in the reaction; the main byproducts are furan byproducts generated by disproportionation of furan formate, including furan and furan derivatives, HPLC detection of tail gas is carried out, existence of furan is found, and generation of acetate is found by nuclear magnetism detection.
A small experiment: in a 1L reactor, potassium 2-furancarboxylate (156 g), potassium carbonate (165 g), anhydrous potassium formate (96.2 g) were added, and the mixture was purged with dry carbon dioxide gas to remove air and water vapor. The reaction system is gradually heated to 285 ℃, and reacts for 6 hours under the condition of stirring and carbon dioxide gas flow of 8bar to obtain a solid system, the solid system is cooled and dissolved by adding water, activated carbon is added for decolorization (500 kg per time and 3 times of decolorization), and the obtained solution is filtered to obtain a transparent aqueous solution. Acidifying with hydrochloric acid, vacuum filtering to obtain off-white solid, washing with industrial ethanol to obtain 2,5-furandicarboxylic acid monomer with 97.8% purity and 65% separation yield.
Amplification experiment: in a 100L reactor, adding 15.6 kg of potassium 2-furanformate and 16.5 kg of potassium carbonate, adding 96.2 kg of anhydrous potassium formate, and uniformly mixing the powder, and blowing air and water vapor in the system by using dry carbon dioxide airflow. The reaction system is gradually heated to 285 ℃, and reacts for 6 hours under the condition of stirring and carbon dioxide gas flow of 8bar to obtain a solid system, the solid system is cooled and dissolved by adding water, activated carbon is added for decolorization (500 kg for each time and 3 times for decolorization), and the obtained solution is filtered to obtain a transparent aqueous solution. Acidifying with hydrochloric acid, vacuum filtering to obtain off-white solid, washing with industrial ethanol to obtain 2,5-furandicarboxylic acid monomer with 96% purity and separation yield of 40%.
Comparative example 3 (cesium furoate and cesium carbonate reaction system, see WO2021158890A1 patent):
A1000L high-temperature high-pressure reactor provided with a wall-mounted scraper anchor stirrer is added with powder formed by uniformly mixing cesium 2-furancarboxylate (156 kg) and potassium carbonate (115 kg), and air and water vapor in the system are blown out by dry carbon dioxide airflow. The reaction system is gradually heated to 252 ℃, and reacts for 1 hour under the condition of stirring and carbon dioxide gas flow of 0.8 MPa, the obtained solid system is cooled, water is added for dissolution, activated carbon is added for decolorization (500 kg for each time, 3 times for decolorization), and the obtained transparent aqueous solution is filtered. Acidifying with hydrochloric acid, vacuum filtering to obtain off-white solid, washing with industrial ethanol to obtain 2,5-furandicarboxylic acid monomer with 98.5% purity and separating yield of 69%.
The specific procedure was as follows (table 2):
mixing furoate (100 mol including alkali metal and alkaline earth metal furoate such as potassium furoate, cesium furoate, sodium furoate, and calcium furoate)Acid salt) is dissolved in a methanol or ethanol solvent to prepare a salt solution for standby. In a 100L high-temperature high-pressure boiling bed reactor, alkali metal or alkaline earth metal bicarbonate (including cesium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, calcium bicarbonate, magnesium bicarbonate, etc., the dosage is 1-4 times of mole of furoate) is put in vacuum or CO 2 Under the atmosphere, the mixture is heated and quickly dissolved in molten salt with low melting point (the dosage of the molten salt is 0.2 to 3 times of the total mass of the furoate and the bicarbonate), and then the reaction mixture is cooled to room temperature to obtain the bicarbonate solid catalyst doped with the molten salt. Then adding the solid catalyst and the prepared solid catalyst into an alcoholic solution of the furoate, heating and quickly evaporating to remove the alcoholic solvent to obtain a reaction system of the furoate coated bicarbonate catalyst. Then heating to make the temperature of the reaction system reach or exceed the decomposition degree of the bicarbonate (the heating temperature exceeds the decomposition temperature of the corresponding bicarbonate, 150-280 ℃), maintaining the temperature to gradually decompose the bicarbonate into the carbonate, and overflowing water generated by thermal decomposition from the surface of the core structure in the process to convert the whole solid core-shell system into a porous honeycomb crystal structure reaction system with a high comparative area.
CO sustained at 0.4-1.2 MPa 2 The temperature of the reaction system is raised to 220-305 ℃ under the air flow, and the reaction is carried out for 1-5 hours. Cooling the reaction system to room temperature, adding deionized water to dissolve the reaction system, adding activated carbon to decolor (1 kg of the decoloration is carried out for 3 times each time), adding hydrochloric acid into the filtered water solution to acidify, carrying out suction filtration on the solid to obtain off-white solid, washing the off-white solid with industrial ethanol, and drying the off-white solid to obtain the 2,5-furandicarboxylic acid monomer with the purity of 99.9 percent, wherein the reaction yield is 95-100 percent.
Comparative example 4
Cesium furoate (100 mol) and 75mol of cesium carbonate are added to a 100L autoclave reactor with a shear-effect paddle, under continuous CO 2 The temperature of the reaction system was raised to 250 ℃ under a gas flow, and the reaction was carried out for 1 hour. Cooling the reaction system to room temperature, adding deionized water for dissolving, adding activated carbon for decoloring (1 kg for each time and 3 times for decoloring), adding hydrochloric acid into the filtered water solution for acidification, filtering the solid to obtain off-white solid, washing the off-white solid with industrial ethanol, and drying to obtain 98% purity 2,5-furandicarboxylic acid monomer, reaction yield 80%.
Adding potassium furoate (100 mol), potassium carbonate (75 mol) and potassium formate (7.6 Kg, 0.3 times of the total mass of potassium furoate and potassium carbonate) into a 100L high-temperature high-pressure reaction kettle with a shear-effect stirring paddle, and continuously adding CO 2 The temperature of the reaction system was raised to 250 ℃ under a gas flow, and the reaction was carried out for 1 hour. Cooling the reaction system to room temperature, adding deionized water to dissolve the reaction system, adding activated carbon to decolor (1 kg of the decoloration is carried out for 3 times each time), adding hydrochloric acid into the filtered water solution to acidify, carrying out suction filtration on the solid to obtain off-white solid, washing the off-white solid with industrial ethanol, and drying the off-white solid to obtain the 2,5-furandicarboxylic acid monomer with the purity of 97.5 percent, wherein the reaction yield is 75 percent.
TABLE 2 preparation and Effect of examples 7 to 11 and comparative examples 4 and 5
Claims (9)
1. The method for amplifying production of 2,5-furandicarboxylic acid is characterized by comprising the following steps:
step s1, raw material pretreatment: the operation is carried out by adopting one of the following a or b;
a. adding furan formate, an alkaline catalyst and low-melting-point molten salt into water, uniformly mixing, adding an inorganic carrier, removing water by spray drying to obtain a uniformly mixed dry reactant system, and drying and crushing under reduced pressure; the furan formate is potassium furan formate, sodium furan formate, copper furan formate, calcium furan formate or magnesium furan formate; the basic catalyst is carbonate, bicarbonate, phosphate or hydroxide base comprising alkali metal or alkaline earth metal; the low-melting-point molten salt is potassium formate, sodium formate, potassium acetate/sodium acetate mixed molten salt, potassium isobutyrate or cesium acetate; the molar weight of the alkaline catalyst is 0.5 to 1.3 times of that of the furan formate, the mass of the low-melting-point molten salt is 0.2 to 0.4 times of the total mass of the furan formate and the alkaline catalyst, and the dosage of the inorganic carrier is 0.3 to 2 times of the total mass of the furan formate, the alkaline catalyst and the low-melting-point molten salt;
b. bicarbonate in vacuum or CO 2 Heating and dissolving in low-melting-point molten salt in the atmosphere, and cooling to room temperature to obtain a bicarbonate solid catalyst doped with the molten salt; dissolving furoate in methanol or ethanol solvent to obtain salt solution; adding a bicarbonate solid catalyst into a salt solution in a reactor, and heating to 150-280 ℃ to obtain a porous cellular crystal structure reaction system with a high comparative area; the furoate is potassium furoate, cesium furoate, sodium furoate and calcium furoate; the bicarbonate is cesium bicarbonate, potassium bicarbonate, sodium bicarbonate, rubidium bicarbonate, calcium bicarbonate or magnesium bicarbonate; the molar ratio of the bicarbonate to the furoate is 1: 1-4; the dosage of the low-melting-point molten salt is 0.2 to 3 times of the total mass of the furoate and the bicarbonate;
step s2, reaction: CO continuously flowing at the flow rate of 0.4 to 2MPa and 200 to 5000 mL/min 2 Raising the temperature of the reaction system to 220-320 ℃ under the air flow, and reacting for 1-6 hours; cooling to room temperature, adding deionized water for dissolving, adding activated carbon for decoloring, adding hydrochloric acid into the filtered water solution for acidifying, carrying out suction filtration on the solid to obtain an off-white solid, washing with ethanol, and drying to obtain 2,5-furandicarboxylic acid.
2. The process for the scale-up production of 2,5-furandicarboxylic acid as claimed in claim 1, wherein in step s1, the particle size of the reactant system after pulverization is controlled to <1 μm; the water content of the reactant system after reduced pressure drying is less than 20ppm.
3. The process for the scale-up production of 2,5-furandicarboxylic acid as claimed in claim 1, wherein in step s1, the molar amount of the basic catalyst is 1.1 to 1.2 times that of the furancarboxylic acid salt; the mass of the low-melting-point molten salt is 0.3 times of the total mass of the furan formate and the alkaline catalyst.
4. The method for large-scale production of 2,5-furandicarboxylic acid as in claim 1, wherein in step s1, the molar ratio of bicarbonate salt to furoate salt is 1: 1.2 to 1.4; the dosage of the low-melting-point molten salt is 0.25 to 0.5 times of the total mass of the furoate and the bicarbonate.
5. The method for producing 2,5-furandicarboxylic acid in an enlarged scale according to claim 1, wherein in the operation b of step s1, the temperature is raised to 200 to 220 ℃ to obtain a reaction system with a porous cellular crystal structure with a high comparative area.
6. The process for the scale-up production of 2,5-furandicarboxylic acid as claimed in claim 1, wherein in step s2, the reactor for the reaction is a high temperature high pressure ebullated bed, a spray drying apparatus or a tumble drying apparatus.
7. The process for the scaled-up production of 2,5-furandicarboxylic acid as claimed in claim 1, wherein in step s2, CO 2 The airflow pressure is 0.8-1MPa, CO is in the range of 2 The airflow is 1500 mL/min, and the reaction is carried out for 2 hours at 293 ℃ to 305 ℃.
8. The process for the scaled-up production of 2,5-furandicarboxylic acid of claim 1, wherein in step s2, activated carbon is decolorized 3 times.
9. 2,5-furandicarboxylic acid produced by the 2,5-furandicarboxylic acid scale-up process of any of claims 1 to 8.
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| WO2021158890A1 (en) * | 2020-02-06 | 2021-08-12 | The Board Of Trustees Of The Leland Stanford Junior University | Carbonate-promoted carboxylation at high rates |
| CN113461645A (en) * | 2021-08-06 | 2021-10-01 | 吉林省中科聚合工程塑料有限公司 | Method for synthesizing 2, 5-furandicarboxylic acid from furancarboxylic acid and carbon dioxide |
| US20230020051A1 (en) * | 2021-07-16 | 2023-01-19 | Kse, Inc. | Method and integrated process for the carboxylation of furan derived carboxylic acids to 2,5-furandicarboxylic acid |
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| CN108383814A (en) * | 2018-05-10 | 2018-08-10 | 中国科学院长春应用化学研究所 | A kind of preparation method of 2,5- furandicarboxylic acids |
| CN108558800A (en) * | 2018-05-10 | 2018-09-21 | 中国科学院长春应用化学研究所 | A kind of industrialized process for preparing of the 2,5- furandicarboxylic acids of low cost |
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