CN103965146B - The purification process of furandicarboxylic acid - Google Patents
The purification process of furandicarboxylic acid Download PDFInfo
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- CN103965146B CN103965146B CN201410134671.7A CN201410134671A CN103965146B CN 103965146 B CN103965146 B CN 103965146B CN 201410134671 A CN201410134671 A CN 201410134671A CN 103965146 B CN103965146 B CN 103965146B
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- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000000746 purification Methods 0.000 title claims abstract description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 49
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000002845 discoloration Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000010992 reflux Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 19
- 239000000178 monomer Substances 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000004383 yellowing Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- -1 poly-furandicarboxylic acid glycol ester Chemical class 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a kind of purification process of furandicarboxylic acid.The method is by salt-forming reaction, and by soluble in water for furandicarboxylic acid to be purified, acidified filtrate again after filtration, and leach precipitating the solid obtained, wash and dry, obtains high purity furandicarboxylic acid.Meanwhile, in order to lower for furandicarboxylic acid purity to be purified, be not suitable for the situation of preceding method, the invention also discloses and reflux and recrystallization two kinds of prepurification processes in water in acetic acid.Present invention process flow process is simple, reaction conditions is gentle, do not adopt organic solvent.Prepared high purity furandicarboxylic acid is applied in polymerization, effectively can suppress polymer discoloration, be conducive to the polymerisate obtaining high molecular simultaneously.
Description
Technical field
The present invention relates to chemical field, particularly relate to a kind of purification process of furandicarboxylic acid
Background technology
Along with petering out and the aggravation of Greenhouse effect of petroleum resources, how to strengthen the utilization of reproducible biomass resource, become focus with Nonrenewable resources such as petroleum replacings.
Furandicarboxylic acid is as a kind of bio-based monomer newly developed, can be prepared by the maximum biomass resource-Mierocrystalline cellulose of output and half fiber, there are the potentiality becoming large breed organism base monomer, just day by day be subject to investigator to pay attention to, and be classified as one of the 12 kinds of module compounds from biomass processing by USDOE.Because the chemical structure of furandicarboxylic acid is similar to petroleum base monomers terephthalic acid; so terephthalic acid can be substituted to prepare the material of polyester; thus realize biomass resource substituting petroleum resources, contribute to the use of environment protection and minimizing Nonrenewable resources.
There is lot of documents to report and adopted furandicarboxylic acid to substitute as monomer the preparation that terephthalic acid carries out polyester, but furandicarboxylic acid base polyester still exists a lot of defect compared to terephthalic acid groups polyester to be waited to solve, and one of them is the Yellowing of polymkeric substance.Research before the present inventor has reported and has adopted furandicarboxylic acid can produce significant metachromatism as monomer synthesize polyester, polymerisate color is deepened to be brown (WuL by yellow by the additional proportion of furandicarboxylic acid monomer gradually, MinchevaRP, XuY, RaquezJ-M, DuboisP.Biomacromolecules).In order to address this problem, CN102516513A reports a kind of preparation method of low-yellowing 2,5-furandicarboxylic acid-based polyester, can Yellowing effectively in inhibited reaction process.But the method needs first furandicarboxylic acid to be converted into acyl chlorides, then adopts solution polycondensation to be polymerized, and process is loaded down with trivial details, long reaction time, cost are high, and needs to use highly toxic compound as solvent, and this makes the application of the method greatly be restricted.
The present inventor also expands large quantifier elimination to how suppressing the Yellowing of furandicarboxylic acid base polyester.Research is surprised to find that, reduces the content of the foreign matter content, particularly aldehydes in furandicarboxylic acid, effectively can suppress Yellowing, the remarkable color and luster improving polymkeric substance, also contributes to the molecular weight improving polymkeric substance simultaneously, and and then the mechanical property of lifting polymkeric substance.If can highly purified furandicarboxylic acid be prepared, then directly can adopt the direct esterification-melt-polycondensation be widely used in industry, prepare the furandicarboxylic acid base polyester of low-yellowing high molecular at low cost.
But the technique preparing furandicarboxylic acid at present also cannot obtain low impurity content, the particularly high purity furandicarboxylic acid of low aldehyde content, how furandicarboxylic acid is further purified, making it be applicable to synthesize the furandicarboxylic acid base polyester of low-yellowing, high molecular, is a problem demanding prompt solution.
Summary of the invention
The object of this invention is to provide a kind of purification process of furandicarboxylic acid, the method has the advantage that technical process is simple, reaction conditions is gentle, do not adopt organic solvent, furandicarboxylic acid after the method purifying, directly can prepare the furandicarboxylic acid base polyester of low-yellowing, high molecular by esterification-melt-polycondensation.
Technical solution of the present invention:
The invention provides a kind of purification process of furandicarboxylic acid, the steps include:
(1) alkali, furandicarboxylic acid to be purified and gac are added to the water, fully stir and solids is dissolved completely, obtain the aqueous solution of furandicarboxylic acid salt;
Described furandicarboxylic acid to be purified, the purity that its purity is greater than in 95.0%(the present invention all refers to quality purity), wherein contained 2-carboxyl furfural content is less than 15000ppm, and acetic acid content is less than 15000ppm;
(2) furandicarboxylic acid salt brine solution step (1) obtained under agitation adds acid, the pH to 0-5 of regulator solution, obtains solid sediment simultaneously after filtering in filtrate;
(3) solid sediment that step (2) obtains is leached, and wash with water, dry, obtain highly purified furandicarboxylic acid;
Described highly purified furandicarboxylic acid, its purity is greater than 99.9%, and wherein contained 2-carboxyl furfural content is less than 100ppm, and acetic acid content is less than 50ppm.In above-mentioned step,
Alkali can select the highly basic of sodium hydroxide or potassium hydroxide or other types, from the preferred sodium hydroxide of cost consideration;
Acid can select the strong acid of hydrochloric acid, sulfuric acid or other type, considers, preferred hydrochloric acid from the complexity of cost and removing acid ion;
The mol ratio of alkali and furandicarboxylic acid to be purified is 1.8-3.5:1, is difficult to dissolve completely, and can strengthens the consumption of highly basic when mol ratio is too high owing to can cause furandicarboxylic acid when mol ratio is too low, therefore preferred 1.95-2.5;
Add gac and play adsorbing contaminant, the mass ratio of gac and furandicarboxylic acid to be purified is 0.01-1:1, because impurity is difficult to by active adsorption when the quality of gac is too low, then increase the consumption of gac when the quality of gac is too high, therefore be preferably 0.1-0.5:1;
The aqueous solution of the furandicarboxylic acid salt that step (1) obtains, the concentration of furandicarboxylic acid salt is 10-150 grams per liter, decline owing to can make the purification effect of the method when the concentration of aqueous solution of furandicarboxylic acid salt is too high, the purity drop of the high-purity furandicarboxylic acid obtained, and make the production efficiency of the method decline when the concentration is too low, the yield of high-purity furandicarboxylic acid can be reduced simultaneously, therefore be preferably 70-100 grams per liter;
In step (2), the PH to 0-5 of regulator solution, because the yield of monomer can decline when pH is too high, and can affect the acidity of high-purity furandicarboxylic acid when pH is too low, therefore is preferably 1-2;
The party's ratio juris is, when furandicarboxylic acid has under acidity and neutral environment, the solubleness in water is less, and understands the feature that solubleness enlarges markedly owing to there is salt-forming reaction under alkaline environment.Present method is exactly according to this feature, after first making furandicarboxylic acid generation salt-forming reaction soluble in water, and elimination insoluble impurities, then by souring soln, furandicarboxylic acid is precipitated, remove soluble impurity, thus obtain highly purified furandicarboxylic acid.
By above method, finally highly purified furandicarboxylic acid can be obtained by purifying.The purity of this high-purity furandicarboxylic acid is greater than 99.9%, and wherein contained acetic acid content is less than 50ppm, and 2-carboxyl furfural content is less than 100ppm, if repeat above-mentioned steps, then the purity of gained furandicarboxylic acid can improve further.Due in the course of the polymerization process, these two kinds of impurity can play and suppress polymericular weight to uprise, the effect of aggravation oxidation stain, so when the purity of furandicarboxylic acid is improved, after particularly these two kinds of foreign matter contents significantly reduce, be conducive to the furandicarboxylic acid base polyester being prepared low-yellowing, high molecular by direct esterification-melt phase polycondensation
Especially, the purity of the furandicarboxylic acid of the raw material selected by above-mentioned purification process-to be purified can affect the purification effect of the method.Generally speaking, the material purity selected by the method is higher, and the purity of the high-purity furandicarboxylic acid finally obtained is also higher.
In order to when the purity of raw material is lower, the purification effect that above-mentioned purification process also can obtain, the present inventor additionally provides the method for two kinds of prepurifications, effectively can improve the purity of raw material, and then improve the purification effect of above-mentioned purification process.It should be noted that, when the two kinds of methods provided below are used alone, effectively cannot remove aldehyde type impurities, so when purifying object is to prepare polymerization monomer used, can only as the prepurification processes of above-mentioned purifying aspect, and when purifying object is other, also can be used as the method for independent purifying furandicarboxylic acid.
The step of the first prepurification processes is as follows:
(A) after being mixed with acetic acid by furandicarboxylic acid to be purified, under the condition of backflow, 30-300 minute is stirred;
(B) solid insoluble is leached, and wash with water, obtain the furandicarboxylic acid after purifying.
Described furandicarboxylic acid to be purified, its purity is greater than 80.0%.
By before purification steps, carry out prepurification process, can process the furandicarboxylic acid that purity is lower, especially when the purity of furandicarboxylic acid to be purified is below 95.0%, increase the operation of a prepurification, purification effect is significantly good.
Wherein, the furandicarboxylic acid to be purified that the method is used and acetic acid, its mass ratio is 1:1-10, because when the ratio of furandicarboxylic acid is excessive, the purification effect of the method can decline, and when the ratio of furandicarboxylic acid is too small, purification efficiency decline cost increase, therefore preferred 1:4-6.Churning time needed for step 1 is 30-300 minute, can reduce purification effect time too short upon agitation, and upon agitation between long time can affect purification efficiency, raise the cost.
Especially, a certain amount of water can also be added to reduce the viscosity of system in the mixture of furandicarboxylic acid and acetic acid.
The party's ratio juris is that furandicarboxylic acid solubleness in acetic acid is very little, and partial impurities has certain solubleness in acetic acid, therefore by the acetic acid partial impurities in backflow, thus can improve the purity of furandicarboxylic acid.
The step of the second prepurification processes is as follows:
(1) by after furandicarboxylic acid to be purified and water mixing, under agitation heat, furandicarboxylic acid is dissolved completely;
(2) after the furandicarboxylic acid aqueous solution being filtered, cool under fast stirring, obtain white solid precipitation.Solid sediment is leached, and washes with water, obtain the furandicarboxylic acid after purifying;
Described furandicarboxylic acid to be purified, its purity is greater than 80.0%.
The party's ratio juris is, the rising of the solubility with temperature of furandicarboxylic acid in water and increasing.Especially, when water is close to boiling point under normal temperature, the solubleness of furandicarboxylic acid in water can occur to increase very significantly.Therefore the method can be utilized first to be dissolved in the water of high temperature by furandicarboxylic acid, after the insoluble impurity of elimination, then obtain the furandicarboxylic acid after purifying by cooling.It should be noted that, CN103408421A provides a kind of method of purification of terephthalic acid, have employed the means comparatively similar with prepurification processes of the present invention.But through the present inventor's checking, the solubleness of terephthalic acid in high-temperature water is very low, and the increase of solubility with temperature in water changes not obvious, the method is applicable to Alkali reduction trade effluent and reclaims field simultaneously.This prepurification processes relies on the present inventor to find the " rising of the solubility with temperature of furandicarboxylic acid in water and increasing.Especially, when water is close to boiling point under normal temperature, the solubleness of furandicarboxylic acid in water can occur to increase very significantly " principle and realize, the purification of terephthalic acid method provided with CN103408421A has remarkable difference.
By above-mentioned purification process, effectively can improve the purity of furandicarboxylic acid, particularly reduce the content of aldehydes and acetic acid, obtain high-purity furandicarboxylic acid.This high-purity furandicarboxylic acid is specially adapted to prepare furandicarboxylic acid base polyester by esterification-melt-polycondensation, is conducive to reducing the Yellowing of polyester, promoting the molecular weight of polyester.
Beneficial effect of the present invention is embodied in:
The purification process of furandicarboxylic acid provided by the invention, technical process is simple, and reaction conditions is gentle, does not adopt organic solvent;
The purification process of furandicarboxylic acid provided by the invention, can make furandicarboxylic acid reach the purity of more than 99.9%, does not need further process namely to can be applicable to the reactions such as polymerization and organic synthesis;
The high purity furandicarboxylic acid that the purification process of the furandicarboxylic acid that the application of the invention provides obtains, final polymkeric substance Yellowing can be made to alleviate, and molecular weight effectively promotes.
Accompanying drawing explanation
Fig. 1 be embodiment 3 with embodiment 5 purifying before and after furandicarboxylic acid
1hNMR composes.
Embodiment
The purification process of furandicarboxylic acid provided by the present invention, effectively can improve the purity of furandicarboxylic acid, particularly reduces the content of aldehydes and acetic acid, obtains high-purity furandicarboxylic acid.This high-purity furandicarboxylic acid is specially adapted to prepare furandicarboxylic acid base polyester by esterification-melt-polycondensation, is conducive to reducing the Yellowing of polyester, promoting the molecular weight of polyester.The method technical process is simple, and reaction conditions is gentle, does not adopt organic solvent.
Below by embodiment, the present invention is specifically described, but the invention is not restricted to these embodiments.
Different way of purification is adopted to carry out purifying to the furandicarboxylic acid of different purity:
Embodiment 1:
(1) by the sodium hydroxide of 12 grams, the furandicarboxylic acid (purity 96.5% to be purified of 20 grams, wherein 2-carboxyl furfural content 12000ppm, acetic acid content 8000ppm) and 1 gram of gac be added to the water, fully stir and solids dissolved completely, obtain the aqueous solution of furandicarboxylic acid salt.
(2), after furandicarboxylic acid salt brine solution being filtered, under agitation in filtrate, add concentrated hydrochloric acid, make the pH=2 of solution, obtain solid sediment.
(3) solid sediment is leached, and wash with water, dry, obtain highly purified furandicarboxylic acid.
After testing, in high-purity furandicarboxylic acid that purifying obtains, inclusion-free remains, and its purity is 100.0%.
Embodiment 2:
Repeat the method for embodiment 1.Difference is, raw material adopts furandicarboxylic acid (purity 90.3%, wherein 2-carboxyl furfural content 23000ppm, acetic acid content 9500ppm) to be purified.
After testing, high-purity furandicarboxylic acid purity 99.9% that purifying obtains, wherein 2-carboxyl furfural content 450ppm, acetic acid content 100ppm.
Embodiment 3:
(1), after 100 grams of furandicarboxylic acids (purity 90.3%, wherein 2-carboxyl furfural content 23000ppm, acetic acid content 9500ppm) to be purified being mixed with 500 grams of acetic acid, under the condition of reflux, stir 240 minutes;
(2) solid insoluble is leached, and wash with water, obtain the furandicarboxylic acid after purifying.
After testing, the furandicarboxylic acid purity 97.6% that purifying obtains, wherein 2-carboxyl furfural content 22000ppm, acetic acid content 2000ppm.
Embodiment 4:
(1) by after 20 grams of furandicarboxylic acids (purity 90.3%, wherein 2-carboxyl furfural content 23000ppm, acetic acid content 9500ppm) to be purified and 500 grams of water mixing, under agitation heat, when water is close to boiling, furandicarboxylic acid dissolves completely;
(2) after the furandicarboxylic acid aqueous solution being filtered, cool under fast stirring, obtain white solid precipitation.Solid sediment is leached, and washes with water, obtain the furandicarboxylic acid after purifying.
After testing, the furandicarboxylic acid purity 97.7% that purifying obtains, wherein 2-carboxyl furfural content 23000ppm, does not detect acetic acid.
Embodiment 5:
Repeat the method for embodiment 1.Difference is, the furandicarboxylic acid (purity 97.6%, wherein 2-carboxyl furfural content 22000ppm, acetic acid content 2000ppm) that raw material adopts embodiment 3 to obtain.
After testing, in high-purity furandicarboxylic acid that purifying obtains, inclusion-free remains, and its purity is 100.0%.
Fig. 1 gives furandicarboxylic acid before and after embodiment 3 and the purifying of embodiment 5
1hNMR composes, as can be seen from spectrogram, not purified furandicarboxylic acid
1containing a large amount of impurity peaks in HNMR spectrogram, illustrating containing a large amount of impurity in not purified furandicarboxylic acid, is low-purity furandicarboxylic acid.
When passing through embodiment 3, after purifying is carried out to low-purity furandicarboxylic acid, quantity and the peak area of impurity peaks all significantly decline, but not completely dissolve, illustrate after the method purifying, the purity of furandicarboxylic acid has had and has improved very significantly, but is not removed completely by impurity, is moderate purity furandicarboxylic acid.
When passing through embodiment 5, after the moderate purity furandicarboxylic acid of embodiment 3 gained is further purified, impurity peaks thoroughly disappears, and illustrates and carries out after two-step purifying through method provided by the invention, can be high purity furandicarboxylic acid by low-purity furandicarboxylic acid purifying effectively.
The molecular weight of the preparation-obtained polyester of furandicarboxylic acid monomer of different purity and discoloration:
Embodiment 6:
Add to be purified 2 in the reactor, 5-furandicarboxylic acid 156 grams of (purity 90.3%, wherein 2-carboxyl furfural content 23000ppm, acetic acid content 9500ppm), ethylene glycol 124 grams, tetrabutyl titanate 340 milligrams, carries out esterification at 190 DEG C, and being warming up to 220 DEG C gradually, esterification carries out four hours altogether.Then vacuumize at 220 DEG C and carry out polycondensation, temperature rises to 240 DEG C gradually from 220 DEG C, and pressure drops to 80Pa from 500Pa gradually, and polycondensation carries out eight hours altogether, finally obtains poly-furandicarboxylic acid glycol ester.
The poly-furandicarboxylic acid glycol ester of gained is brownish black, and weight-average molecular weight is less than 10,000, and recording its b value by colour-difference meter is 45.3.
Embodiment 7:
Repeat the method for embodiment 6.Difference is, the purity 96.5% of furandicarboxylic acid, wherein 2-carboxyl furfural content 12000ppm, acetic acid content 8000ppm.
The poly-furandicarboxylic acid glycol ester of gained is light brown, and weight-average molecular weight is less than 10,000, and recording its b value by colour-difference meter is 19.6.
Embodiment 8:
Repeat the method for embodiment 6.Difference is, high-purity furandicarboxylic acid that furandicarboxylic acid adopts embodiment 1 to obtain, purity 100.0%.
The poly-furandicarboxylic acid glycol ester of gained is in white, and weight-average molecular weight 8.3 ten thousand, recording its b value by colour-difference meter is 5.9.
Embodiment 9:
Repeat the method for embodiment 6.Difference is, the furandicarboxylic acid that furandicarboxylic acid adopts embodiment 2 to obtain, purity 99.9%, wherein 2-carboxyl furfural content 450ppm, acetic acid content 100ppm.
The poly-furandicarboxylic acid glycol ester of gained is faint yellow, weight-average molecular weight 7.6 ten thousand, and recording its b value by colour-difference meter is 9.3.
Embodiment 10:
Repeat the method for embodiment 6.Difference is, the furandicarboxylic acid that furandicarboxylic acid adopts embodiment 3 to obtain, purity 97.6%, wherein 2-carboxyl furfural content 22000ppm, acetic acid content 2000ppm.
The poly-furandicarboxylic acid glycol ester of gained is brownish black, weight-average molecular weight 2.3 ten thousand, and recording its b value by colour-difference meter is 47.2.
Embodiment 11:
Repeat the method for embodiment 6.Difference is, the furandicarboxylic acid that furandicarboxylic acid adopts embodiment 4 to obtain, and purity 97.7%, wherein 2-carboxyl furfural content 23000ppm, does not detect acetic acid.
The poly-furandicarboxylic acid glycol ester of gained is brownish black, weight-average molecular weight 3.8 ten thousand, and recording its b value by colour-difference meter is 50.1.
Embodiment 12:
Repeat the method for embodiment 6.Difference is, high-purity furandicarboxylic acid that furandicarboxylic acid adopts embodiment 5 to obtain, purity 100.0%.
The poly-furandicarboxylic acid glycol ester of gained is in white, and weight-average molecular weight 9.5 ten thousand, recording its b value by colour-difference meter is 6.1.
Table 1 gives in embodiment 1-5, adopts different way of purification to carry out the effect after purifying to the furandicarboxylic acid of different purity.From embodiment 1, by purification process provided by the invention, the impurity in furandicarboxylic acid effectively can be removed.From embodiment 2, when furan starting material dioctyl phthalate purity is very low, although purification process provided by the invention can remove impurity effectively, but still have portion of residual.From embodiment 3,4, by prepurification processes provided by the invention, the most of impurity in furandicarboxylic acid very low for purity can be removed, but still can remaining a large amount of aldehydes.From embodiment 5, by using prepurification of the present invention, purification process simultaneously, even if when furan starting material dioctyl phthalate purity is very low, the impurity in furandicarboxylic acid still effectively can be removed.
Table 2 gives in embodiment 6-12, the molecular weight of the preparation-obtained polyester of furandicarboxylic acid monomer of different purity and discoloration.From embodiment 6-7, when adopting not purified furandicarboxylic acid monomer to be polymerized, the polymkeric substance that number molecular weight is very low, variable color is serious can only be obtained.From embodiment 8,9,12, when adopting highly purified furandicarboxylic acid monomer to be polymerized, the polymkeric substance of high molecular, low-yellowing can be obtained.From embodiment 10,11, when adopting the furandicarboxylic acid monomer that obtains of prepurification to be polymerized, the polymkeric substance that intermediate molecular weight, variable color are serious can be obtained.From embodiment 6-12, in the molecular weight of polymkeric substance and discoloration and monomer, the content of 2-carboxyl furfural and acetic acid is closely related, by purification process provided by the invention, effectively can remove the impurity in furandicarboxylic acid, particularly remove 2-carboxyl furfural and acetic acid, and then improve polymkeric substance color and luster, raising polymerizable molecular amount significantly.
Table 1
Table 2
Note: b value is recorded by colour-difference meter.B value is larger, and the xanthochromia of polymkeric substance is more remarkable.
Claims (4)
1. a purification process for furandicarboxylic acid, is characterized in that, comprises the following steps:
(1) alkali, furandicarboxylic acid to be purified and gac are added to the water, fully stir and solids is dissolved completely, obtain the aqueous solution of furandicarboxylic acid salt;
Described furandicarboxylic acid to be purified, its purity is greater than 95.0%, and wherein contained 2-carboxyl furfural content is less than 15000ppm, and acetic acid content is less than 15000ppm;
(2), after the aqueous solution filtration of furandicarboxylic acid salt step (1) obtained, under agitation in filtrate, add acid, regulate the pH to 1-2 of described filtrate, obtain solid sediment;
(3) solid sediment that step (2) obtains is leached, and wash with water, dry, obtain highly purified furandicarboxylic acid;
Described highly purified furandicarboxylic acid, its purity is greater than 99.9%, and wherein contained 2-carboxyl furfural content is less than 100ppm, and acetic acid content is less than 50ppm;
Described alkali is sodium hydroxide or potassium hydroxide; Described acid is hydrochloric acid or sulfuric acid;
The mol ratio of described alkali and furandicarboxylic acid to be purified is 1.8-3.5:1; The mass ratio of gac and furandicarboxylic acid to be purified is 0.01-1:1;
In the aqueous solution of described furandicarboxylic acid salt, the concentration of furandicarboxylic acid salt is 10-150 grams per liter.
2. the purification process of furandicarboxylic acid as claimed in claim 1, it is characterized in that, described furandicarboxylic acid to be purified adopts following step to carry out prepurification:
(A) after being mixed with acetic acid by furandicarboxylic acid to be purified, under the condition of backflow, 30-300 minute is stirred;
(B) solid insoluble in step (A) is leached, and wash with water, obtain the furandicarboxylic acid after prepurification and enter in step (1) and carry out further purifying;
Described furandicarboxylic acid to be purified, its purity is greater than 80.0%.
3. the purification process of furandicarboxylic acid as claimed in claim 2, it is characterized in that, described furandicarboxylic acid to be purified and the mass ratio of acetic acid are 1:1-10.
4. the purification process of furandicarboxylic acid as claimed in claim 1, it is characterized in that, described furandicarboxylic acid to be purified adopts following step to carry out prepurification:
(A) by after furandicarboxylic acid to be purified and water mixing, under agitation heat, furandicarboxylic acid is dissolved completely and obtains the furandicarboxylic acid aqueous solution;
(B) after furandicarboxylic acid aqueous solution filtered while hot step (A) obtained, the filtrate obtained under agitation cools, obtain white solid precipitation, described white solid precipitation is leached, and wash with water, obtain the furandicarboxylic acid after prepurification and enter in step (1) and carry out further purifying;
Described furandicarboxylic acid to be purified, its purity is greater than 80.0%.
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| CA2979589C (en) * | 2015-03-17 | 2020-04-28 | Purac Biochem Bv | Method for manufacturing furan-2,5-dicarboxylic acid (fdca) from a salt solution |
| SG11201805514VA (en) | 2016-01-13 | 2018-07-30 | Stora Enso Oyj | Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof |
| JP2017190316A (en) * | 2016-04-15 | 2017-10-19 | 三菱ケミカル株式会社 | Method of purifying 2,5-furandicarboxylic acid |
| CN105732551B (en) * | 2016-04-18 | 2017-12-15 | 张玲 | A kind of method for purifying the furandicarboxylic acid of bio-based 2,5 |
| CN106905145A (en) * | 2017-04-07 | 2017-06-30 | 云南省药物研究所 | A kind of preparation method of high-purity crocetin |
| US11192872B2 (en) | 2017-07-12 | 2021-12-07 | Stora Enso Oyj | Purified 2,5-furandicarboxylic acid pathway products |
| TWI650318B (en) | 2017-10-30 | 2019-02-11 | 財團法人工業技術研究院 | Method for purifying crude product of 2,5-furandicarboxylic acid by crystallization method and method for forming polyester |
| CN109721577A (en) * | 2017-10-30 | 2019-05-07 | 中国科学院宁波材料技术与工程研究所 | A kind of purification process of furans dicarboxylic acids |
| CN109797434A (en) * | 2017-11-16 | 2019-05-24 | 中国科学院宁波材料技术与工程研究所 | A kind of 2,5- furandicarboxylic acid monocrystalline and preparation method thereof |
| CN108558799B (en) * | 2018-04-25 | 2022-03-22 | 徐州奥格曼新材料科技有限公司 | Method for extracting 2, 5-furandicarboxylic acid from fermentation liquor |
| TWI697487B (en) * | 2019-07-02 | 2020-07-01 | 遠東新世紀股份有限公司 | Purification method of crude 2,5-furandicarboxylic acid |
| CN113121480B (en) * | 2019-12-31 | 2022-09-09 | 中国石油化工股份有限公司 | Method for purifying and refining 2, 5-furandicarboxylic acid |
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