CN117720490A - 2, 5-furandicarboxylic acid and purification method thereof - Google Patents
2, 5-furandicarboxylic acid and purification method thereof Download PDFInfo
- Publication number
- CN117720490A CN117720490A CN202311712966.3A CN202311712966A CN117720490A CN 117720490 A CN117720490 A CN 117720490A CN 202311712966 A CN202311712966 A CN 202311712966A CN 117720490 A CN117720490 A CN 117720490A
- Authority
- CN
- China
- Prior art keywords
- furandicarboxylic acid
- fdca
- aqueous solution
- acid
- purifying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 117
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000000746 purification Methods 0.000 title claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 38
- 230000020477 pH reduction Effects 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000010009 beating Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 25
- 239000012043 crude product Substances 0.000 description 22
- 239000012065 filter cake Substances 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 monomethyl ester Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 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
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000002834 transmittance Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses 2, 5-furandicarboxylic acid and a purification method thereof, which belong to the technical field of chemical industry, wherein the purification method comprises the following steps: and (3) carrying out alkali dissolution, oxidation, acidification, stirring, pulping, washing and drying on the crude 2, 5-furandicarboxylic acid product to obtain a pure 2, 5-furandicarboxylic acid product. In the acidification reaction crystallization process and the pulping washing process, the purity of the obtained FDCA can reach 99.99 percent by selecting proper conditions such as acidification reaction temperature, oxygen content of gas subjected to oxidation treatment, pulping washing temperature, pulping washing time and the like, and the requirement of a polymerization grade product can be met without adopting an organic solvent.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to 2, 5-furandicarboxylic acid and a purification method thereof.
Background
2, 5-furandicarboxylic acid (FDCA) is a very promising base material, which can replace petroleum-based monomer terephthalic acid (PX) to polymerize with ethylene glycol to produce high-performance polyester, and FDCA can be obtained by oxidizing 5-hydroxymethylfurfural (5-HMF), however, due to insufficient oxidation of 5-HMF, oxidation intermediates such as 5-formyl-2-furancarboxylic acid (FFCA), 2, 5-Diformylfuran (DFF) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) are usually generated, and in general, FFCA oxidation to form FDCA is a speed determining step, FFCA impurities are contained in the FDCA product obtained by oxidizing 5-HMF, and further due to the change of oxidation conditions, decarboxylation of FDCA can occur during the reaction to generate 2-furancarboxylic acid (FCA). Impurities of such mono-carboxylic acids (FFCA or FCA) terminate the growth of the polyester molecular chain in the polymerization reaction, affect the polymerization degree of the polymerization, and in addition, FFCA forms color bodies, which may cause the color of the polyester material to be not ideal, and affect the application of the polyester material in the beverage and food industries, so that the purification of FDCA is very necessary.
Patent CN115028610a discloses a process for purifying 2, 5-furandicarboxylic acid, which comprises mixing a crude FDCA product, a metal ion remover, and a recrystallization solvent, heating under the protection of inert gas to fully dissolve FDCA, cooling for crystallization, filtering, washing, and drying to obtain primarily refined FDCA; and then dissolving the preliminarily refined FDCA into a solvent under the protection of inert gas, carrying out hydrogenation reaction under the action of a hydrogenation catalyst and hydrogen, and then carrying out cooling crystallization, filtering, washing and drying to obtain a pure 2, 5-furandicarboxylic acid product, wherein the yield of the pure FDCA can reach more than 98 percent, and the light transmittance of the pure FDCA can reach 98.6 percent.
Patent CN116003354A reports a crystallization purification method of 2, 5-furandicarboxylic acid, which comprises the steps of dissolving a crude product of FDCA in a mixed solvent of glycol ether and water by heating, and then cooling and crystallizing to obtain 2, 5-furandicarboxylic acid crystals, wherein the purity of the FDCA product can reach 99.9%, the recovery yield can reach 70.3%, and the decoloring rate can reach 100%, but the process uses organic solvent glycol ether, which can cause solvent residues in the product and is unfavorable for downstream polymerization reaction.
Patent CN114787140a discloses a method for heat treatment of organic acids and purified 2, 5-furandicarboxylic acid, which process comprises the steps of: the method comprises the steps of adding the FDCA crude product into an aqueous solution containing acetic acid, carrying out heat treatment for 5-240min at 140-200 ℃, then cooling to 20-80 ℃, and separating to obtain an FDCA product, wherein the removal rate of two impurities, namely FDCA monomethyl ester (FDCA-Me) and 2-furancarboxylic acid, respectively reaches 83% and 75%, acetic acid is utilized in the method, and the purification process is carried out under the high-temperature condition, so that the system is corroded, the equipment is greatly damaged, the investment cost is increased if equipment made of corrosion-resistant materials is adopted, and in addition, decarboxylation reaction of the FDCA occurs under the high-temperature condition, so that the product is lost.
Patent CN103965146a discloses a method for purifying furandicarboxylic acid, which comprises dissolving furandicarboxylic acid to be purified in water by salifying, filtering, acidifying the filtrate, filtering out the solid obtained by precipitation, washing, and drying to obtain high-purity furandicarboxylic acid, adding activated carbon in the alkali dissolution process, and using the adsorption effect of the activated carbon to realize impurity removal and decolorization, wherein the adsorption of the activated carbon is usually non-selective, and can adsorb furandicarboxylic acid salt, thereby causing FDCA product loss and increasing the amount of solid waste.
FDCA products typically participate in downstream polymerization reactions in the form of solid particles, and thus the physical properties of the crystalline particle morphology, size distribution, bulk density, and flowability of the particles of FDCA have a large impact on the polymerization reaction. For example, low flowability of the FDCA product can cause uneven mixing of FDCA with other polymerization raw materials and catalysts, resulting in uneven concentrations of reactants, which can adversely affect the polymerization time and quality of the resulting polymer.
Patent CN116120264a discloses a method for regulating and controlling the grain size of 2, 5-furandicarboxylic acid crystal, which is to add an auxiliary agent into a raw material containing 2, 5-furandicarboxylic acid, and obtain 2, 5-furandicarboxylic acid crystal with a certain grain size range by regulating the types and the content of the auxiliary agent and controlling the technological parameters such as crystallization temperature. However, the use of organic solvents such as amide-based organic solvents, pyrrolidone-based organic solvents, sulfoxide-based organic solvents according to the patent may cause the organic solvents to remain in the FDCA product, thereby affecting the purity of the product; and the nucleating agents used in the patent are metal compounds, and even if the amount of the nucleating agents is in ppm level, the metals still remain in the product, so that the purity of the polymerization-grade monomer is affected.
Disclosure of Invention
The invention aims to provide 2, 5-furandicarboxylic acid and a purification method thereof, which are used for solving the problems of residual solvents, metals and the like after the purification of the 2, 5-furandicarboxylic acid.
The aim of the invention can be achieved by the following technical scheme:
a method for purifying 2, 5-furandicarboxylic acid, comprising the steps of:
s1, dissolving a crude 2, 5-furandicarboxylic acid product in an alkaline aqueous solution to prepare an alkaline aqueous solution of 2, 5-furandicarboxylic acid; the 2, 5-furandicarboxylic acid is present in the form of 2, 5-furandicarboxylic acid, 2, 5-furandicarboxylic acid monocarboxylate and/or 2, 5-furandicarboxylic acid dicarboxylic acid salt, the dissolving step involving the following reaction:
s2, adding the obtained 2, 5-furandicarboxylic acid alkaline aqueous solution into a high-pressure reaction kettle, and then carrying out oxidation treatment on the 2, 5-furandicarboxylic acid alkaline aqueous solution to obtain an oxidation solution after the oxidation treatment is finished;
step S3, adding an acidic aqueous solution into the oxidation solution for acidification treatment, and crystallizing 2, 5-furandicarboxylic acid monocarboxylate and/or 2, 5-furandicarboxylic acid dicarboxylic acid monocarboxylate through an acidification reaction to generate 2, 5-furandicarboxylic acid solid, thereby obtaining a mixed solution, wherein the acidification step involves the following reactions:
s4, filtering the 2, 5-furandicarboxylic acid solid obtained in the step S3 to obtain a wet 2, 5-furandicarboxylic acid solid, and then adding the wet solid into water for stirring, pulping and washing;
and S5, filtering to obtain a wet product of the pure 2, 5-furandicarboxylic acid after pulping and washing are finished, and finally drying the wet product of the pure 2, 5-furandicarboxylic acid to obtain the pure 2, 5-furandicarboxylic acid.
Further, the alkaline aqueous solution is one or more of sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium hydroxide aqueous solution and potassium carbonate aqueous solution.
Further, the conditions of the oxidation treatment include pure oxygen or an oxygen-containing gas+an oxidation catalyst.
Further, the oxidation catalyst is a palladium-based, ruthenium-based, manganese-based, cobalt-based, molybdenum-based, copper-based or composite metal oxide-based catalyst.
Further, the oxygen-containing gas is oxygen-enriched air having an oxygen content of greater than 21%.
Further, the acidic aqueous solution is an aqueous solution of an inorganic acid; the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Further, the pH value of the acidification reaction is less than or equal to 4; the acidification reaction temperature is in the range of 30-80 ℃.
Further, the stirring, beating and washing temperature is 80-160 ℃ in the pulp washing process, and the stirring, beating and washing time is 0.5-12h.
Further, the stirring, beating and washing temperature is in the range of 100-160 ℃ in the beating and washing process, and the stirring, beating and washing time is 1-4h.
The 2, 5-furandicarboxylic acid is purified by the method, the b value of the 2, 5-furandicarboxylic acid is less than 5, the repose angle is 32-45 degrees, and the bulk density is 0.58-0.82g/mL.
The invention has the beneficial effects that:
the invention provides a purification method of 2, 5-furandicarboxylic acid, wherein the 2, 5-furandicarboxylic acid crude product is subjected to alkali dissolution, oxidation, acidification, stirring, beating, washing and drying to obtain a pure 2, 5-furandicarboxylic acid product, the purity of the obtained FDCA can reach 99.99%, an organic solvent is not adopted, the requirement of a polymerization grade product can be met, and more importantly, the obtained FDCA product has good particle characteristics, higher flowability and bulk density, which is very favorable for downstream polymerization reaction and is also favorable for packaging and transportation of the FDCA product.
In the acidification reaction crystallization process and the pulping washing process, through selecting proper conditions such as acidification reaction temperature, gas oxygen content of oxidation treatment, pulping washing temperature, pulping washing time and the like, 99.99% purity FDCA can be obtained, b value of prepared FDCA particles is smaller than 1 through a color difference meter, the flowability of the particles is better (the repose angle can reach 32 degrees), the improvement of the characteristics of the solid particles benefits from the method to obtain the particles with the main irregular shape of the FDCA crystal particles, and the characteristics of the particles of the FDCA product prepared by the method are particularly favorable for a downstream polymerization process.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an HPLC chart of crude FDCA used in the present invention;
FIG. 2 is a photomicrograph of FDCA particles obtained in example 1 of the invention;
FIG. 3 is an HPLC chart of the FDCA pure product obtained in example 1 of the present invention;
FIG. 4 is an X-ray powder diffraction pattern of the FDCA crystalline particles obtained in example 1 of the invention;
FIG. 5 is a photomicrograph of FDCA particles obtained in comparative example 1 of the invention.
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.
The testing method comprises the following steps:
1. morphology of FDCA particle crystals
Shooting is carried out by adopting a transreflective digital polarized light microscope.
2. Fluidity of flow
The repose angle of the particles was determined using the test method specified in GB/T16913-2008.
3. Bulk density of
The bulk density of the particles was determined using the test method specified in GB/T16913-2008.
4. HPLC analysis
The purity of FDCA is analyzed by using Shimadzu LC-16 equipment, a chromatographic column is a C18 column, a detector is an ultraviolet detector, the wavelength is 264nm, a mobile phase A is methanol, a mobile phase B is 0.1% phosphoric acid aqueous solution, the column temperature is kept at 40 ℃, 10ul of sample is injected for analysis and test, and the peak position of FDCA is about 15 min.
The purification process of the present invention is described in more detail below and features of the present invention are demonstrated in conjunction with the examples.
The raw material used in the process step S1 is FDCA crude product, and is prepared by taking 5-hydroxymethylfurfural as raw material to carry out catalytic oxidation, wherein the oxidation process can be divided into homogeneous oxidation or heterogeneous oxidation, the former is catalytic oxidation carried out by taking Co/Mn/Br as a catalyst, the latter is catalytic oxidation carried out by taking ruthenium-based, manganese-based, cobalt-based and other heterogeneous catalysts, relevant impurities are generated due to incomplete oxidation, and the prepared FDCA crude product is shown in a HPLC analysis chart of the FDCA crude product as shown in figure 1. The alkaline solution used in step S1 may be prepared by mixing an alkaline solid with an aqueous solution, wherein the alkaline solid may be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, and preferably the alkaline solid is sodium hydroxide, or ammonia water may be used as the alkaline solution in step S1. Yongzhao Zhang et al in J.chem.Eng.Data 2018,63,5,1316-1324 report that FDCA is soluble in water, and even if 100g of water can only dissolve about 0.96g of FDCA at 90 ℃, 100g of alkaline aqueous solution can dissolve more than 20g of FDCA by the step S1 of the present invention, which is very advantageous for the improvement of production efficiency.
In the process step S2, the FDCA dissolved solution obtained in the step S1 is subjected to oxidation treatment by using oxygen-containing gas, and the oxidation process can remove chromogenic impurities in the FDCA crude product. The oxygen-containing gas may be air, preferably oxygen-enriched air having an oxygen content of greater than 21%, preferably having an oxygen content of greater than 50%, most preferably pure oxygen; the oxidation catalyst may be used in the oxidation treatment process, and the catalyst may be palladium-based, ruthenium-based, manganese-based, cobalt-based, molybdenum-based, copper-based, or composite metal oxide-based, and the effect of removing impurities and colors may be achieved without using a catalyst when pure oxygen is used as the oxidizing gas.
In the process step S3, the oxidation liquid obtained in the step S2 is acidified by using an acidic aqueous solution, and the process is an acidification reaction crystallization process, so that further purification of FDCA can be realized. The acid used in the step S3 is an inorganic acid or an organic acid, wherein the inorganic acid can be one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the organic acid can be a saturated organic acid with 2 to 4 carbon atoms, and hydrochloric acid is preferred. It is necessary to control the acidification reaction temperature in step S3, which is in the range of 30-80 ℃, preferably between 50-80 ℃; the amount of the acidic aqueous solution can be adjusted according to the pH value of the system, the pH value of the acidification reaction system can be selected to be smaller than 4, and the pH value of the acidification reaction system is preferably smaller than 2.
The beating of the solid obtained in step S3 in step S4 of the process according to the invention is very necessary, and it is well known that the product can be purified by a slurry wash process, and that the physical properties of the FDCA crystal particles can be improved by selecting suitable slurry wash conditions, which improvement is very advantageous for downstream polymerization applications, and that the FDCA particles obtained according to the invention can achieve a good result in mixing with alkylene glycol. According to the knowledge of the present inventors, the number of fine flaky FDCA particles gradually decreases and the number of large-sized FDCA particles gradually increases due to the aging effect of Ostwald, and further, the FDCA particle characteristics are further improved due to collisions between FDCA particles, collision friction with stirring paddles and the inner wall of the apparatus due to the stirring effect. The temperature in the sizing and washing process can be selected in the range of 80-160 ℃, preferably 100-160 ℃, and most preferably 120-160 ℃; the size washing time can be selected from 0.5-12h, preferably 1-10h, and most preferably 1-4h.
Example 1
Weighing 100g of FDCA crude product, and adding 500g of sodium hydroxide aqueous solution into the FDCA crude product to completely dissolve the FDCA crude product; then adding 1g ruthenium-carbon catalyst containing 5% active component into FDCA sodium hydroxide aqueous solution, introducing pure oxygen gas, setting the pressure to be 1Mpa, the temperature to be 130 ℃, carrying out oxidation treatment for 1h under stirring, filtering after the oxidation time is over to obtain oxidation liquid, heating the oxidation liquid to 80 ℃, then adding hydrochloric acid aqueous solution into the oxidation liquid to enable the pH value of an acidification reaction system to be 1, precipitating a large amount of FDCA solid at the moment, cooling to room temperature, and filtering to obtain FDCA wet filter cake; then adding 500g of water into the FDCA wet filter cake, and then heating to 160 ℃ for slurry washing for 4 hours; after the sizing is finished, the temperature of the system is reduced to room temperature, and then FDCA wet filter cake is obtained by filtration, and FDCA pure product is obtained after drying. The purity of FDCA was 99.993%, the repose angle was 32 degrees, the bulk density was 0.82g/mL, and the b value was 0.64 by color difference analysis.
The obtained micrograph of FDCA particles is shown in fig. 2;
the HPLC spectrum of the obtained FDCA pure product is shown in figure 3;
the X-ray powder diffraction pattern of the obtained FDCA crystal particles is shown in fig. 4.
Example 2
Example 1 was repeated; except that no catalyst was added to the aqueous solution of FDCA sodium hydroxide and oxidation treatment was carried out by introducing pure oxygen gas. The obtained pure FDCA was analyzed to obtain a purity of 99.991%, a repose angle of 33 degrees, a bulk density of 0.81g/mL, and a b value of 0.66 as determined by a color difference meter.
Example 3
Example 1 was repeated; except that oxygen-enriched air having an oxygen content of 50% was introduced to perform the oxidation treatment. The obtained pure FDCA was analyzed to obtain a purity of 99.94%, a repose angle of 34 degrees, a bulk density of 0.78g/mL, and a b value of 1.32 as analyzed by a color difference meter.
Example 4
Example 1 was repeated; except that air was introduced for oxidation treatment. The obtained FDCA was analyzed to obtain a purity of 99.92%, a repose angle of 33 degrees, a bulk density of 0.84g/mL, and a color difference analysis b value of 2.43.
Example 5
Example 1 was repeated; except that the beaten wash temperature was 80 ℃. The obtained FDCA pure product was analyzed, the purity of FDCA was 99.95%, the repose angle was 45 degrees, the bulk density was 0.58g/mL, and the b value was 0.92 by a color difference meter analysis.
Example 6
Example 1 was repeated; except that the beaten washing time was 0.5h. The obtained FDCA pure product was analyzed, the purity of FDCA was 99.98%, the repose angle was 39 degrees, the bulk density was 0.61g/mL, and the b value was 0.71 by a color difference meter analysis.
Example 7
Example 1 was repeated; except that the acidification reaction temperature was 30 ℃. The obtained pure FDCA was analyzed to obtain a purity of 99.91%, a repose angle of 36℃and a bulk density of 0.71g/mL, and a value of 1.01 was analyzed by a color difference meter.
Comparative example 1
Weighing 100g of FDCA crude product, adding 500g of sodium hydroxide aqueous solution into the FDCA crude product to completely dissolve the FDCA crude product, then adding hydrochloric acid aqueous solution into FDCA alkaline aqueous solution at 30 ℃ to enable the pH value of an acidification reaction system to be 1, separating out a large amount of FDCA solids at the moment, and then filtering to obtain an FDCA wet filter cake; then 500g of water was added to the FDCA wet cake, followed by slurry washing at 25℃for 4 hours; and filtering after the slurry washing is finished to obtain an FDCA wet filter cake, and drying to obtain an FDCA pure product. The purity of FDCA was 98.87%, the repose angle was 55 degrees, the bulk density was 0.34g/mL, and the b value was 7.81 as determined by a color difference meter. The obtained micrograph of FDCA particles is shown in FIG. 5.
Comparative example 2
Weighing 100g of FDCA crude product, adding 500g of sodium hydroxide aqueous solution into the FDCA crude product to completely dissolve the FDCA crude product, then adding hydrochloric acid aqueous solution into FDCA alkaline aqueous solution at 80 ℃ to enable the pH value of an acidification reaction system to be 1, separating out a large amount of FDCA solids at the moment, and then filtering to obtain an FDCA wet filter cake; then 500g of water was added to the FDCA wet cake, followed by slurry washing at 25℃for 4 hours; and filtering after the slurry washing is finished to obtain an FDCA wet filter cake, and drying to obtain an FDCA pure product. The purity of FDCA was 99.84%, the repose angle was 53 degrees, the bulk density was 0.36g/mL, and the b value was 5.27 by color difference analysis.
Comparative example 3
Weighing 100g of FDCA crude product, adding 500g of sodium hydroxide aqueous solution into the FDCA crude product to completely dissolve the FDCA crude product, then adding hydrochloric acid aqueous solution into FDCA alkaline aqueous solution at 30 ℃ to enable the pH value of an acidification reaction system to be 1, separating out a large amount of FDCA solids at the moment, and then filtering to obtain an FDCA wet filter cake; then 500g of water was added to the FDCA wet cake, followed by slurry washing at 160℃for 4 hours; and filtering after the slurry washing is finished to obtain an FDCA wet filter cake, and drying to obtain an FDCA pure product. The purity of FDCA was 99.53%, the repose angle was 34 degrees, the bulk density was 0.79g/mL, and the b value was 6.23 by color difference analysis.
Comparative example 4
Weighing 100g of FDCA crude product, and adding 500g of sodium hydroxide aqueous solution into the FDCA crude product to completely dissolve the FDCA crude product; then adding 1g ruthenium-carbon catalyst containing 5% active component into FDCA alkaline aqueous solution, introducing pure oxygen gas, setting pressure to be 1Mpa, setting temperature to be 130 ℃, carrying out oxidation treatment for 1h under stirring, filtering after the oxidation time is over to obtain oxidation solution, then adding hydrochloric acid aqueous solution into FDCA alkaline aqueous solution at 30 ℃ to enable the pH value of an acidification reaction system to be 1, precipitating a large amount of FDCA solid at the moment, cooling to room temperature, and filtering to obtain FDCA wet filter cake. Then 500g of water was added to the FDCA wet cake, followed by slurry washing at 25℃for 4 hours; and filtering after the slurry washing is finished to obtain an FDCA wet filter cake, and drying to obtain an FDCA pure product. The purity of FDCA was 99.96%, the repose angle was 54 degrees, the bulk density was 0.35g/mL, and the b value was 0.87 by color difference analysis.
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 (10)
1. A method for purifying 2, 5-furandicarboxylic acid, comprising the steps of:
s1, dissolving a crude 2, 5-furandicarboxylic acid product in an alkaline aqueous solution to prepare an alkaline aqueous solution of 2, 5-furandicarboxylic acid;
s2, oxidizing the 2, 5-furandicarboxylic acid alkaline aqueous solution to obtain an oxidation solution after the oxidation treatment is completed;
s3, adding an acidic aqueous solution into the oxidation solution for acidizing treatment to generate 2, 5-furandicarboxylic acid solid, so as to obtain a mixed solution;
s4, filtering the mixed solution obtained in the step S3 to obtain wet solid 2, 5-furandicarboxylic acid, and then adding the wet solid into water to stir, slurry and wash;
and S5, filtering to obtain a wet product of the pure 2, 5-furandicarboxylic acid after pulping and washing are finished, and finally drying the wet product of the pure 2, 5-furandicarboxylic acid to obtain the pure 2, 5-furandicarboxylic acid.
2. The method for purifying 2, 5-furandicarboxylic acid according to claim 1, wherein the alkaline aqueous solution is one or more of aqueous sodium hydroxide, aqueous sodium carbonate, aqueous potassium hydroxide and aqueous potassium carbonate.
3. The method for purifying 2, 5-furandicarboxylic acid according to claim 1, wherein the conditions for the oxidation treatment comprise pure oxygen or an oxygen-containing gas+oxidation catalyst.
4. A process for purifying 2, 5-furandicarboxylic acid according to claim 3, wherein the oxidation catalyst is a palladium-based, ruthenium-based, manganese-based, cobalt-based, molybdenum-based, copper-based, composite metal oxide-based catalyst.
5. A process for purifying 2, 5-furandicarboxylic acid according to claim 3, wherein the oxygen-containing gas is oxygen-enriched air having an oxygen content of greater than 21%.
6. The method for purifying 2, 5-furandicarboxylic acid according to claim 1, wherein the acidic aqueous solution is an aqueous solution of an inorganic acid; the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
7. The method for purifying 2, 5-furandicarboxylic acid according to claim 1, wherein the pH of the acidification treatment is less than or equal to 4; the acidification temperature is in the range of 30-80 ℃.
8. The method for purifying 2, 5-furandicarboxylic acid according to claim 1, wherein the stirring and beating washing temperature is 80-160 ℃ in the process of beating washing, and the stirring and beating washing time is 0.5-12h.
9. The method for purifying 2, 5-furandicarboxylic acid according to claim 1, wherein the stirring and beating washing temperature is in the range of 100-160 ℃ in the process of beating washing, and the stirring and beating washing time is 1-4h.
10. 2, 5-furandicarboxylic acid, characterized in that it is purified by the purification process according to any one of claims 1 to 9, the b value of 2, 5-furandicarboxylic acid being less than 5, the angle of repose being 32 to 45 degrees and the bulk density being 0.58 to 0.82g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311712966.3A CN117720490A (en) | 2023-12-13 | 2023-12-13 | 2, 5-furandicarboxylic acid and purification method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311712966.3A CN117720490A (en) | 2023-12-13 | 2023-12-13 | 2, 5-furandicarboxylic acid and purification method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117720490A true CN117720490A (en) | 2024-03-19 |
Family
ID=90210019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311712966.3A Pending CN117720490A (en) | 2023-12-13 | 2023-12-13 | 2, 5-furandicarboxylic acid and purification method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117720490A (en) |
-
2023
- 2023-12-13 CN CN202311712966.3A patent/CN117720490A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MXPA06011559A (en) | Purification of carboxylic acids by complexation with selective solvents. | |
| EP4077293B1 (en) | Thermal treatment of purified 2,5-furandicarboxylic acid resulting carboxylic acid composition | |
| JP5428942B2 (en) | Method for producing N-tert-butylacrylamide with reduced coloring | |
| WO2021123189A1 (en) | Process for producing 2,5-furandicarboxylic acid from ethers of 5-hydroxymethylfurfural | |
| CN117720490A (en) | 2, 5-furandicarboxylic acid and purification method thereof | |
| CN110054561A (en) | A kind of oxidative decoloration technique of long-chain biatomic acid | |
| US20220324718A1 (en) | Method for preparing basic copper carbonate | |
| US20230002338A1 (en) | Water and thermal treatment of purified 2,5-furandicarboxylic acid | |
| CN107129446B (en) | Process for reducing sulfate ions in synthetic process of 2-acrylamido-2-methylpropanesulfonic acid | |
| JP7186313B2 (en) | Production of malic acid | |
| CN109970548B (en) | Long-chain dibasic acid oxidation decoloring process | |
| JP2019081742A (en) | Manufacturing method of 2,6-naphthalenedicarboxylic acid | |
| CN111690166A (en) | Method for recovering polyphenylene sulfide synthetic solvent NMP | |
| EP4077295B1 (en) | Water and thermal treatment of purified 2,5-furandicarboxylic acid | |
| CN112538012A (en) | Method for purifying 2, 6-naphthalenedicarboxylic acid or dimethyl 2, 6-naphthalenedicarboxylate | |
| CN105218358B (en) | A kind of process for purification of thick trimesic acid | |
| TW202242018A (en) | Process for extracting aromatic dicarboxylic acids from their metal salts | |
| CN113929632B (en) | Acipimox calcium salt and preparation method thereof | |
| JPH1053557A (en) | Production of 2,6-naphthalenedicarboxylic acid having high purity | |
| CN115286593B (en) | Preparation method of dibenzothiazyl disulfide serving as rubber vulcanization accelerator | |
| US20230322575A1 (en) | Preparation method for electronic-grade copper chloride dihydrate | |
| JP3282642B2 (en) | Method for producing high-purity 2-acrylamide-2-methylpropanesulfonic acid | |
| WO2023242151A1 (en) | Producing 2,5-furandicarboxylic acid with recovery of acid | |
| JPH1180074A (en) | Production of highly pure 2,6-naphthalene dicarboxylic acid | |
| CN112694397A (en) | Method for purifying 2, 6-naphthalene dicarboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |