CN110437190A - The method that 2,5- furandicarboxylic acid is prepared by 5 hydroxymethyl furfural - Google Patents
The method that 2,5- furandicarboxylic acid is prepared by 5 hydroxymethyl furfural Download PDFInfo
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- 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
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Abstract
This application involves one kind by 5 hydroxymethyl furfural (5-HMF) preparation 2, the method of 5- furandicarboxylic acid (FDCA), this method comprises: 30~100 DEG C at a temperature of, in the in the mixed solvent of tert-alcohols and water, raw material 5 hydroxymethyl furfural (HMF) reacts in the presence of TEMPO catalyst, inorganic acid or solid acids co-catalyst, nitrite analog assistant and oxidant and is converted into 2,5-furandicarboxylic acid (FDCA).By utilizing method of the invention, raw material 5 hydroxymethyl furfural (5-HMF) conversion can be obtained by target product 2 with highly selective and high yield in a mild condition, 5- furandicarboxylic acid (FDCA), and process route is simple, has huge prospects for commercial application.
Description
Technical field
The present invention relates to the preparation methods of chemicals, more particularly to one kind is by 5 hydroxymethyl furfural (5-HMF) preparation 2,5-
The method of furandicarboxylic acid (FDCA).
Background technique
The reduction increasingly and global warming of petroleum resources require people to find the environmentally protective sustainable energy of one kind to subtract
Few dependence to fossil fuel.2,5-furandicarboxylic acid (FDCA) is stablized as novel paradigmatic structure monomer, performance itself.It can
To be used to prepare polyester, polyamide and polyurethane etc., the poly- furandicarboxylic acid glycol ester (PEF) that FDCA is prepared is considered
It is the important polyester material for replacing polyethylene terephthalate (PET), there are the advantages such as biodegradable, environmental protection.FDCA
Also there is important role in pharmacology, some researches show that furandicarboxylic acid diethylester and ***es seemingly have very strong anesthesia
Effect.Furandicarboxylic acid dicalcium has inhibiting effect to the growth of bacillus megaterium.
In view of the important function and purposes of furandicarboxylic acid, studying the carbohydrate especially conversion of HMF to FDCA is
It is very meaningful.Aoxidizing HMF to FDCA mainly includes noble metal catalyst and base metal catalysis using heterogeneous catalysis
Agent.Noble metal catalyst mainly includes Au base, Pd base, Pt base and Ru base catalyst.Research finds Au/CeO2's and Au/TiO2
Catalytic activity ratio Au/C and Au/Fe2O3 high, available quantitative FDCA yield (Applied Catalysis B:
Environmental, 2015,163:520-530).The participation of excess base is usually wanted in FDCA preparation process, is needed after reaction
Acid neutralizes, and can generate a large amount of inorganic salt waste in this way, therefore, can reduce nothing using the addition of basic supports substitution inorganic base
The use of machine soda acid.Yan etc. realizes the conversion of HMF to FDCA using Pt/PVP catalyst under alkali-free adding conditional, but urges
Agent content of metal is higher, recycling is poor, the reaction time it is long (Journal of Catalysis, 2014,315:67-
74).At present using base metal catalysts to the report of HMF to FDCA mainly include Fe-POP (Journal of Catalysis,
2013,299:316-32), nano-Fe3O4-CoOx (ACS Sustainable Chemistry&Engineering, 2015,3
) and CoxOy-N@C (ChemSusChem, 2014,7 (12): 3334-3340) etc. (3): 406-412.Although base metal catalysts
With cost advantage, but reaction condition is higher and selectivity of product is poor.Therefore realization mildly, under the conditions of alkali-free aoxidizes HMF
Preparation carboxylic acid product is of great significance.
Therefore, this field still need under mild reaction conditions (such as normal temperature and pressure) with simple low cost process simultaneously
And with highly selective and high yield by the new method of 5 hydroxymethyl furfural (5-HMF) preparation 2,5-furandicarboxylic acid (FDCA).
Summary of the invention
In view of above-mentioned, the object of the present invention is to provide under mild reaction conditions (such as normal temperature and pressure) with simple low
Cost process and with it is highly selective and in high yield by 5 hydroxymethyl furfural (5-HMF) prepare 2,5-furandicarboxylic acid (FDCA)
New method.
The present invention provides a kind of methods by 5 hydroxymethyl furfural preparation 2,5-furandicarboxylic acid, which comprises
30~100 DEG C at a temperature of, in the in the mixed solvent of tert-alcohols and water, raw material 5 hydroxymethyl furfural is catalyzed in TEMPO
It reacts in the presence of agent, inorganic acid or solid acids co-catalyst, nitrite analog assistant and oxidant and is converted into 2,5- furans
Dioctyl phthalate,
Wherein, the TEMPO catalyst is selected from one of catalyst 1-6 having following structure or a variety of:
In preferred embodiments, the inorganic acid or solid acids co-catalyst are selected from one of following or more
Kind: sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, Amberlite-15, phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid and silicomolybdic acid.
In preferred embodiments, the nitrite analog assistant is selected from one of following or a variety of: NaNO2 and
KNO2。
In preferred embodiments, the oxidant is selected from one of following or a variety of: air, oxygen, dioxygen
Water, peroxide salt and hypohalite;The preferably described reaction carries out under the air or oxygen atmosphere of 0.1~2.0MPa.
In preferred embodiments, it is described reaction 50~100 DEG C at a temperature of carry out;The reaction is at 50~70 DEG C
At a temperature of carry out.
In preferred embodiments, the time of the reaction is 1~96h;The time of the preferably described reaction be 1~
48h。
In preferred embodiments, the tert-alcohols are selected from one of following or a variety of: the tert-butyl alcohol, 2- first
The amyl- 2- alcohol of base-, 3- methyl-amyl- 3- pure and mild 2- methyl-butyl- 2- alcohol.
In preferred embodiments, the volume ratio of tert-alcohols described in the mixed solvent and water is 100: 1~1
∶1。
In preferred embodiments, the quality of the TEMPO catalyst and the raw material 5- hydroxymethylfurfural that use
Than being 0.01: 1~1: 1.
In preferred embodiments, the inorganic acid or solid acids co-catalyst that use and the raw material 5- hydroxyl first
The mass ratio of base furfural is 0.01: 1~5: 1.
In preferred embodiments, the nitrite analog assistant used and the raw material 5 hydroxymethyl furfural
Mass ratio is 0.01: 1~2: 1.
By the present invention in that with special catalyst cheap and easy to get, co-catalyst and nitrite analog assistant, with 5- hydroxyl first
Base furfural (5-HMF) is raw material, and in the in the mixed solvent of tert-alcohols and water, catalysis oxidation obtains 2,5-furandaldehyde
(DFF).Method of the invention can obtain 2,5-furandicarboxylic acid (FDCA) under the conditions of extremely mild (such as normal temperature and pressure).
The method of the present invention increases the dissolubility of product F DCA in tertiary alcohols solvent, avoids the inactivation of catalyst, while using
Inorganic acid and solid acid assistant can effectively promote the catalytic cycle of TEMPO, obtain highly selective and receive in a mild condition
Rate product, simple process have huge industrial application value.
Specific embodiment
The present invention provides a kind of methods by 5 hydroxymethyl furfural preparation 2,5-furandicarboxylic acid, which comprises
30~100 DEG C at a temperature of, in the in the mixed solvent of tert-alcohols and water, raw material 5 hydroxymethyl furfural is catalyzed in TEMPO
It reacts in the presence of agent, inorganic acid or solid acids co-catalyst, nitrite analog assistant and oxidant and is converted into 2,5- furans
Dioctyl phthalate.
In the method for the invention, the TEMPO catalyst used is one in the catalyst 1-6 having following structure
Kind is a variety of:
Such TEMPO catalyst is known in the art, and can be commercially available, and catalyst 1 as escribed above can
To derive from Ann Kyrgyzstan company (98% purity).Moreover, such TEMPO catalyst sometimes can also be respectively with activity below
Form (i.e. radical form) occurs, obtains or uses:
TEMPO catalyst is catalyst of the efficient catalysis oxidation alcohol to aldehyde, and the oxygen of the alcohol under temperate condition may be implemented
Change, exemplary catalyst is shown in the reaction mechanism is as follows:
In the method for the invention, it is preferable that the TEMPO catalyst is with raw material 5 hydroxymethyl furfural quality dosage
0.01~1 times of amount uses (i.e. the mass ratio of the two is 0.01: 1~1: 1).If catalyst amount is too low, can to react
Process is lasting too long, and damages its and industrialize meaning;If catalyst amount is too high, can process costs be increased, can also damage
Its industrialization meaning of evil.
In the method for the invention, in order to it is highly selective and in high yield by 5 hydroxymethyl furfural catalysis oxidation be target produce
Object 2,5-furandicarboxylic acid is needed using inorganic acid or solid acids co-catalyst.Inorganic acid or solid acids co-catalyst
Addition not only can assist dehydrating agent to form nitrogen oxides intermediate, but also be conducive to the aquation of intermediate aldehyde radical, from
And further promoting aldehyde radical to the conversion of carboxylic acid, this allows in preparation that is mild, realizing carboxylic acid under acid condition.
In the method for the invention, the inorganic acid or solid acids co-catalyst used is selected from one of following or more
Kind: sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, Amberlite-15, phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid and silicomolybdic acid.
In the method for the invention, it is preferable that the dosage of the inorganic acid or solid acids co-catalyst is with the raw material
0.01~5 times of amount of 5 hydroxymethyl furfural quality uses (i.e. the mass ratio of the two is 0.01: 1~5: 1).If inorganic acid is solid
Body acids co-catalyst dosage is too low, and reaction process can be made to continue too long and cannot obtain target acid product;If inorganic
Acid or solid acids co-catalyst dosage are too high, can process costs be increased, and can also damage it and industrialize meaning.
In the method for the invention, it is preferable that the nitrite analog assistant used can be NaNO2And KNO2.The nitrous
The effect of hydrochlorate analog assistant is the circulating ring for promoting TEMPO, the circulation of TEMPO is realized, to promote the generation of oxidation reaction.
In the method for the invention, it is preferable that the dosage of the nitrite analog assistant is with the raw material 5- methylol chaff
0.01~2 times of amount of aldehyde quality uses (i.e. the mass ratio of the two is 0.01: 1~2: 1).If nitrites auxiliary dosage
It is too low, it will cause slowing down for oxidation reaction speed;If nitrites auxiliary dosage is too high, cause the discharge of abraum salt higher,
The economy of atom is poor.
In the method for the invention, tertiary alcohols solvent not only remains alcohols solvent to the efficient molten of reaction substrate and product
Xie Xing, simultaneously because tertiary alcohols solvent is difficult to further be aoxidized, it is possible to reduce the toxic action to catalyst TEMPO, water
Added with conducive to aldehyde radical hydration reaction generation, promote the acquisition of carboxylic acid product.In the present invention, do not have for tert-alcohols
There is special limitation, it is preferable that the tert-alcohols used can be selected from one of following or a variety of: the tert-butyl alcohol, 2- methyl-
The pure and mild 2- methyl of amyl- 2- alcohol, 3- methyl-amyl- 3--butyl- 2- alcohol.It is highly preferred that the tert-alcohols of the in the mixed solvent with
The volume ratio of water is 100: 1~1: 1.
In the method for the invention, used oxidant is not particularly limited, it is preferable that the oxidant used can be with
It is selected from one of following or a variety of: air, oxygen, hydrogen peroxide, peroxide salt and hypohalite.Although in side of the invention
It refers in method and carrying out in the presence of an oxidizer, but in fact, since the method for the present invention completely can be in air atmosphere for example
The oxidant for carrying out in open reactor, therefore referring in the present invention is to a certain degree it is also assumed that be not present.It changes
Sentence is talked about, and the method for the present invention, which can be, to be carried out in the presence of anaerobic agent.
In the method for the invention, it is preferable that when using air or oxygen as when oxidant, the reaction can be direct
Directly carried out under air or oxygen atmosphere, can also by by oxygen or oxygen by bubbling mode be passed through in reaction system into
Row, or can also 0.1~2.0MPa air or oxygen atmosphere under (such as by utilize closed reactor) progress.
Method of the invention can 30~100 DEG C at a temperature of carry out, preferably react in 50~100 DEG C of temperature
Lower progress;More preferably it is described reaction 50~70 DEG C at a temperature of carry out.
In the method for the invention, the reaction time is not particularly limited, it is preferable that the time of the reaction be 1~
96h;It is preferred that the time of the reaction is 1~48h.
Implementation process of the present invention is described further combined with specific embodiments below.As described below is only that the present invention is preferable
Specific embodiment, but scope of protection of the present invention is not limited thereto.
In the examples below, if not otherwise specified, the raw materials and reagents used can be from traditional Chinese medicines Reagent Company
It buys, and is used as former state under not after further treatment with its;The reactor Shrek pipe used can be from Xin Weier company
It buys, high performance liquid chromatography detection can be bought from Shimadzu Corporation.
Embodiment 1
In 10mL Shrek pipe, it is packed into 126mg 5 hydroxymethyl furfural (5-HMF), 11 mg catalyst 1 and 24mg
NaNO2, 60mg H is then added3PO4, 0.2mL water and the 2mL tert-butyl alcohol (stir in magnetic agitation and in atmospheric oxygen atmosphere
It mixes rate and is heated to 55 DEG C of reaction 48h for water-bath under 800r/min).After the reaction was completed, it samples and is sent to efficient under stirring
Liquid chromatogram (HPLC) detection, wherein testing conditions are as follows: Hitachi L2000 HPLC System, Alltech C18
Column, mobile phase CH3OH∶H2O=20: 80;Flow velocity: 1.0mL/min, column temperature: 30 DEG C, detector: DAD, Detection wavelength: 264nm.
It is detected by HPLC, the yield of product 2,5-furandicarboxylic acid (FDCA) is 92.17%, and selectivity is 95%, and its purity
It is 99%.
Embodiment 2
Specific reaction process and detection method are same as Example 1, only will be that the tert-butyl alcohol is changed to 3- methyl-amyl- 3- alcohol,
Gained primary product is 2,5-furandicarboxylic acid (FDCA) as a result, and yield is 85.76%, and selectivity is 96%, and
Its purity is 99.3%.
Embodiment 3
Specific reaction process and detection method are same as Example 1, the tert-butyl alcohol are only changed to tert-pentyl alcohol, as a result institute
Obtaining primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 80.33%, and selectivity is 98%, and its purity is
98.6%.
Embodiment 4
Specific reaction process and detection method are same as Example 1, catalyst 1 are only changed to catalyst 2, as a result
Gained primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 85.08%, and selectivity is 95%, and its purity is
99.1%.
Embodiment 5
Specific reaction process and detection method are same as Example 1, catalyst 1 are only changed to catalyst 3, as a result
Gained primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 89%, and selectivity is 94%, and its purity is
98%.
Embodiment 6
Specific reaction process and detection method are same as Example 1, catalyst 1 are only changed to catalyst 5, as a result
Gained primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 76.76%, and selectivity is 96%, and its purity is
98.7%.
Embodiment 7
Specific reaction process and detection method are same as Example 1, phosphoric acid are only changed to hydrochloric acid, as a result winner, institute
Wanting product is 2,5-furandicarboxylic acid (FDCA), and yield is 77.59%, and selectivity is 96%, and its purity is 99.7%.
Embodiment 8
Specific reaction process and detection method are same as Example 1, phosphoric acid are only changed to sulfuric acid, as a result winner, institute
Wanting product is 2,5-furandicarboxylic acid (FDCA), and yield is 79.70%, and selectivity is 97%, and its purity is 98.6%.
Embodiment 9
Specific reaction process and detection method are same as Example 1, phosphoric acid are only changed to nitric acid, as a result winner, institute
Wanting product is 2,5-furandicarboxylic acid (FDCA), and yield is 80.47%, and selectivity is 93%, and its purity is 97.7%.
Embodiment 10
Specific reaction process and detection method are same as Example 1, and phosphoric acid is only changed to phosphotungstic acid, as a result gained
Primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 80%, and selectivity is 94%, and its purity is 97.7%.
Embodiment 11
Specific reaction process is same as Example 1 with detection method, and phosphoric acid is only changed to phosphomolybdic acid.Gained as a result
Primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 85.09%, and selectivity is 95%, and its purity is
98.3%.
Embodiment 12
Specific reaction process and detection method are same as Example 1, only by NaNO2It is changed to KNO2.Gained as a result
Primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 86.76%, and selectivity is 93%, and its purity is
99.3%.
Embodiment 13
Specific reaction process is same as Example 1 with detection method, and phosphoric acid is only changed to silicomolybdic acid.Gained as a result
Primary product is 2,5-furandicarboxylic acid (FDCA), and yield is 90.01%, and selectivity is 92%, and its purity is
97.3%.
Embodiment 14
Specific reaction process and detection method are same as Example 1, and oxidant is only changed to air from atmospheric oxygen, make
It is 2,5-furandicarboxylic acid (FDCA) for primary product obtained by result, and yield is 83.11%, selectivity is 93%, and its
Purity is 97.7%.
Embodiment 15
Specific reaction process and detection method are same as Example 1, and oxidant is only changed to hydrogen peroxide from atmospheric oxygen,
Gained primary product is 2,5-furandicarboxylic acid (FDCA) as a result, and yield is 81.87%, and selectivity is 91%, and
Its purity is 96.5%.
Embodiment 16
Specific reaction process and detection method are same as Example 1, and oxidant is only changed to 1MPa sky from atmospheric oxygen
Gas, gained primary product is 2,5-furandicarboxylic acid (FDCA) as a result, and yield is 88.29%, and selectivity is 86%, and
And its purity is 96.7%.
Embodiment 17
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction time of furandicarboxylic acid (FDCA) is changed to 12h from 48h, and gained primary product is 2,5-furandicarboxylic acid as a result
(FDCA), and yield is 80.90%, and selectivity is 83%, and its purity is 96.8%.
Embodiment 18
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction time of furandicarboxylic acid (FDCA) is changed to 72h from 48h, and gained primary product is 2,5-furandicarboxylic acid as a result
(FDCA), and yield is 93.11%, and selectivity is 92%, and its purity is 99.1%.
Embodiment 19
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction temperature of furandicarboxylic acid (FDCA) is changed to 80 DEG C from 55 DEG C, and gained primary product is 2,5-furandicarboxylic acid as a result
(FDCA), and yield is 80.03%, and selectivity is 86%, and its purity is 97.9%.
Embodiment 20
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction temperature of furandicarboxylic acid (FDCA) is changed to 70 DEG C from 55 DEG C, and gained primary product is 2,5-furandicarboxylic acid as a result
(FDCA), and yield is 84.44%, and selectivity is 91%, and its purity is 98.4%.
Embodiment 21
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The reaction temperature of furandicarboxylic acid (FDCA) is changed to 100 DEG C from 55 DEG C, and gained primary product is 2,5- furans diformazan as a result
Sour (FDCA), and yield is 94.54%, selectivity is 87%, and its purity is 98.7%.
Embodiment 22
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The oxygen reaction pressure of furandicarboxylic acid (FDCA) is changed to 0.5Mpa from normal pressure, and gained primary product is 2,5- furan as a result
Mutter dioctyl phthalate (FDCA), and yield is 92.33%, and selectivity is 93%, and its purity is 98.6%.
Embodiment 23
Specific reaction process and detection method are same as Example 1, only by 5 hydroxymethyl furfural (5-HMF) to 2,5-
The oxygen reaction pressure of furandicarboxylic acid (FDCA) is changed to 2Mpa from normal pressure, and gained primary product is 2,5- furans as a result
Dioctyl phthalate (FDCA), and yield is 95.09%, selectivity is 94%, and its purity is 99.4%.
Embodiment 24
Specific reaction process and detection method are same as Example 1, only by the body of the tertiary alcohol and the in the mixed solvent water of water
Product is changed to 2mL from 0.2mL, and gained primary product is 2,5- furandicarboxylic acid (FDCA) as a result, and yield is 82.87%,
Selectivity is 91%, and its purity is 96.8%.
Embodiment 25
Specific reaction process and detection method are same as Example 1, only by the body of the tertiary alcohol and the in the mixed solvent water of water
Product is changed to 20 μ L from 0.2mL, and gained primary product is 2,5-furandicarboxylic acid (FDCA) as a result, and yield is
80.99%, selectivity is 84%, and its purity is 96.3%.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright range is defined by the following claims.
Claims (10)
1. a kind of method by 5 hydroxymethyl furfural preparation 2,5-furandicarboxylic acid, which comprises in 30~100 DEG C of temperature
Under degree, in the in the mixed solvent of tert-alcohols and water, raw material 5 hydroxymethyl furfural is in TEMPO catalyst, inorganic acid or solid
It reacts in the presence of acids co-catalyst, nitrite analog assistant and oxidant and is converted into 2,5-furandicarboxylic acid,
Wherein, the TEMPO catalyst is selected from one of catalyst 1-6 having following structure or a variety of:
2. the method according to claim 1, wherein the inorganic acid or solid acids co-catalyst be selected from
It is one of lower or a variety of: sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, Amberlite-15, phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid
And silicomolybdic acid.
3. the method according to claim 1, wherein the nitrite analog assistant is selected from one of following
It is or a variety of: NaNO2And KNO2。
4. the method according to claim 1, wherein the oxidant is selected from one of following or a variety of:
Air, oxygen, hydrogen peroxide, peroxide salt and hypohalite;Air or oxygen atmosphere of the preferably described reaction in 0.1~2.0MPa
Enclose lower progress.
5. the method according to claim 1, wherein it is described reaction 50~100 DEG C at a temperature of carry out;It is described
React 50~70 DEG C at a temperature of carry out.
6. the method according to claim 1, wherein the time of the reaction is 1~96h;It is preferably described anti-
The time answered is 1~48h.
7. the method according to claim 1, wherein the tert-alcohols are selected from one of following or more
Kind: the pure and mild 2- methyl of the tert-butyl alcohol, 2- methyl-amyl- 2- alcohol, 3- methyl-amyl- 3--butyl- 2- alcohol;The preferably described in the mixed solvent
The volume ratio of the tert-alcohols and water is 100: 1~1: 1.
8. the method according to claim 1, wherein the TEMPO catalyst used and the raw material 5- hydroxyl
The mass ratio of methyl furfural is 0.01: 1~1: 1.
9. the method according to claim 1, wherein the inorganic acid or solid acids co-catalyst that use with
The mass ratio of the raw material 5 hydroxymethyl furfural is 0.01: 1~5: 1.
10. the method according to claim 1, wherein the nitrite analog assistant used and the raw material
The mass ratio of 5 hydroxymethyl furfural is 0.01: 1~2: 1.
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WO2023226181A1 (en) * | 2022-05-27 | 2023-11-30 | 上海沃凯生物技术有限公司 | Method for preparing 2,5-furandicarboxylic acid by using furfural |
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