CN108383814A

CN108383814A - A kind of preparation method of 2,5- furandicarboxylic acids

Info

Publication number: CN108383814A
Application number: CN201810442704.2A
Authority: CN
Inventors: 周光远; 王瑞; 姜敏; 王国强; 张强
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Wuhu Wanlong New Material Co Ltd
Priority date: 2018-05-10
Filing date: 2018-05-10
Publication date: 2018-08-10

Abstract

The present invention provides a kind of preparation methods of 2,5 furandicarboxylic acids to obtain furoate after furancarboxylic acid, alkali compounds and water are carried out neutralization reaction first；Then under conditions of carbon dioxide gas, after the salt of furoate, melting that above-mentioned steps obtain and catalyst are reacted, 2,5 furandicarboxylic acid salt are obtained；The fusing point of the salt of the melting is less than or equal to 400 DEG C；The catalyst includes metal salt catalyst and/or organic alkali catalyst；2 that finally above-mentioned steps are obtained after 5 furandicarboxylic acid salt are acidified, obtain 2,5 furandicarboxylic acids.The present invention is using furancarboxylic acid as starting material; first prepare furoate; again using cheap and be easy to get common metal salt and/or organic base as catalyst; using the monomer or mixture of the organic salt of low melting point or inorganic salts as the salt of melting; it is simple for process, reaction temperature is low; it is economic and environment-friendly, it is suitble to scale industrial production.

Description

A kind of preparation method of 2,5- furandicarboxylic acids

Technical field

The invention belongs to 2,5-furandicarboxylic acid synthesis technical fields, are related to a kind of preparation side of 2,5-furandicarboxylic acid Method more particularly to a kind of industrialized process for preparing of the 2,5-furandicarboxylic acid of low cost.

Background technology

2,5-furandicarboxylic acid (FDCA), chemical formula C₆H₄O₅, structural formula isAs The important derivatives of furans, the biological based high molecular aromatic ring monomer with " rigidity " planar structure can be single with glycol, diamines etc. Body is polymerize, and the new bio based high molecular synthetic material haveing excellent performance is prepared, and is a kind of important industrial chemicals and organic Chemical intermediate.

Currently, as polyester product is widely applied, the high speed development of polyester raw material industry has been driven.Wherein, exploitation is used One of the hot spot of current polyester art research is had become in the biological poly ester monomer of substitution petroleum-based feedstock.Poly terephthalic acid Glycol ester (PET) has many advantages, such as that good-toughness, easy processing and the rate of recovery are high as a kind of important thermoplastic polyester, It is widely used for packaging field.Currently, the monoethylene glycol of the raw material of production PET can be using biomass material system It is standby, as the prior art has successfully prepared the biology base PET beverages that can be recycled completely using biological ethyl glycol as raw material Bottle.But another raw material terephthalic acid (TPA) for producing PET is the catalysis oxidation system from petroleum base raw material of industry paraxylene Standby and next, cause in obtained PET plastic product only containing 30% plant based ingredients.Although grinding energetically in recent years The biology base polyester starting monomer succinic acid studied carefully has the potential of partial alternative petroleum base diacid, but since it cannot be provided as right The fragrant benzene ring structure of the same rigidity of phthalic acid, dramatically limits the performance of corresponding polyester product.Therefore, how from It is an important development side in polyester raw material research and development field that being obtained in biomass, which has the polyester raw material binary acid of rigid ring structure, To.

In recent years the study found that 2,5-furandicarboxylic acid is that a kind of ideal polyester for substituting terephthalic acid (TPA) is former Material, first 2,5-furandicarboxylic acid have the rigid aromatic ring structure similar with terephthalic acid (TPA)；Secondly, 2,5-furandicarboxylic acid It is identical as glucose containing carbon number, and armaticity is weaker than phenyl ring, it is easier to degrade；More importantly 2,5- furandicarboxylic acids are A kind of bio-based monomer that can be prepared by biomass.Based on the above characteristic, furandicarboxylic acid receives more and more The concern of scientific research personnel and Corporation R ＆ D department.

Currently, the method for synthesis 2,5-furandicarboxylic acid mainly aoxidizes 5 hydroxymethyl furfural, this method has A large amount of document and patent are reported, but there is problems.First, raw material 5 hydroxymethyl furfural has reserves Less, difficult preparation, difficult the shortcomings of detaching, is unstable, cause cost sufficiently expensive；Second, it is synthesized using oxidation 5 hydroxymethyl furfural When 2,5-furandicarboxylic acid, the noble metal catalyst of higher price is often required to use, and conversion ratio is relatively low.So 5- hydroxyl first Base furfural oxidizing process can not also be suitable for large-scale industrialization into production at present, this also greatly limits 2,5-furandicarboxylic acid And its application of polyester product.

Although having in the recent period, some documents or patent report are a kind of to be using cheap organism-based raw material furancarboxylic acid The method that raw material prepares 2,5- furandicarboxylic acids.As ChemSusChem2013,6,47-50 report it is a kind of using zinc acetate as Catalyst is catalyzed furancarboxylic acid and carbon dioxide, the method for preparing 2,5-furandicarboxylic acid through disproportionated reaction, but this method is made Standby 2,5-furandicarboxylic acid poor selectivity, in reaction process, with part 2,3- furandicarboxylic acids and 2,4- furandicarboxylic acids It generates, 2,5-furandicarboxylic acid sterling can not be obtained.ARKIVOC, one kind is reported in 2013,405-412 is with furancarboxylic acid Raw material, lithium diisopropylamine are catalyst, under normal pressure, carbon dioxide are passed through into tetrahydrofuran solution and prepares 2,5- furans Dioctyl phthalate.The implementation of this method needs to use a large amount of organic solvent, and there is prodigious problem of environmental pollutions, in addition, reaction Used in lithium diisopropylamine price it is high, unstable, be not suitable for industrialized production.Also have document report it is a kind of with Furancarboxylic acid is starting material, using cesium carbonate as catalyst, under the conditions of normal pressure or the carbon dioxide gas of pressurization, prepares 2, The method of 5- furandicarboxylic acids.But since catalyst used in this method is high-cost cesium carbonate, again such that the party Method is difficult to industrialized production.

Therefore, how to develop efficient, cheap route and be used to prepare 2,5- furans diacid formic acid, will be that synthesising biological matter is come The important means of source bulk chemical and high added value high molecular material, has great application prospect and application potential, has become For widely one of the focus of attention of many forward-looking researchers in field.

Invention content

In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of 2,5-furandicarboxylic acid, Especially a kind of low cost is suitable for industrialized 2,5-furandicarboxylic acid preparation method, and preparation method provided by the invention is used Catalyst and raw material be cheap chemical products, reaction cost, and simple for process, reaction item greatly reduces Part is mild, is a kind of economic and environment-friendly, is suitble to the preparation method of scale industrial production.

The present invention provides a kind of preparation methods of 2,5-furandicarboxylic acid, include the following steps：

A after furancarboxylic acid, alkali compounds and water) are carried out neutralization reaction, furoate is obtained；

B) under conditions of carbon dioxide gas, the salt and catalyst of furoate, melting that above-mentioned steps are obtained After being reacted, 2,5-furandicarboxylic acid salt is obtained；

The fusing point of the salt of the melting is less than or equal to 400 DEG C；

The catalyst includes metal salt catalyst and/or organic alkali catalyst；

C after the 2,5-furandicarboxylic acid salt that) obtains above-mentioned steps is acidified, 2,5-furandicarboxylic acid is obtained.

Preferably, the salt of the melting includes single salt or salt-mixture；

The salt of the melting is the salt-mixture of sodium salt or sodium salt and sylvite.

Preferably, the salt of the melting includes the mixed of the fused salt mixts of sodium nitrate and potassium nitrate, sodium nitrate and potassium nitrite Close fused salt, sodium nitrate and the fused salt mixt of sodium nitrite, the fused salt mixt of sodium nitrite and potassium nitrate, sodium nitrite and nitrous acid Fused salt mixt, potassium acetate and the sodium formate of the fused salt mixt of potassium, the fused salt mixt of potassium acetate and sodium acetate, potassium acetate and potassium formate Fused salt mixt, the fused salt mixt of sodium acetate and potassium formate, the fused salt mixt of sodium acetate and sodium formate, potassium formate and sodium formate Fused salt mixt, the fused salt mixt of sodium bicarbonate and saleratus, the fused salt mixt of sodium hydroxide and potassium hydroxide, melting nitrous It is one or more in sour sodium and the sodium formate of melting；

The mass ratio of the salt-mixture is (5~95)：(95~5).

Preferably, the salt of the melting further includes that other can fused salt and/or can not fused salt；

The cation of the metal salt catalyst includes in potassium ion, sodium ion, lithium ion and alkaline-earth metal ion It is one or more；

The anion of the metal salt catalyst includes carbanion, phosphate anion, hydroxide ion, bicarbonate radical It is one or more in ion；

The organic alkali catalyst include 11 carbon -7- alkene of 1,8- diazabicylos, methylamine, urea, ethamine, ethanol amine, Ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA), three ethyl alcohol Amine, butylamine, isobutyl amine, tert-butylamine, hexylamine, octylame, cyclohexylamine, triethylene diamine, tetramethylethylenediamine, aniline and its derivative Object, benzylamine and its derivative, pyridine and its derivatives, pyrimidine, 4-dimethylaminopyridine, potassium tert-butoxide, sodium hydride, sodium ethoxide and It is one or more in sodium methoxide；

The furoate includes furancarboxylic acid sylvite and/or furancarboxylic acid sodium salt.

Preferably, the molar ratio of the furoate and the catalyst is 1：(0.5~50)；

The ratio of the gross mass of the furoate and catalyst and the quality of the salt of the melting is 1：(0.5~ 100)。

Preferably, the reaction time is 1~24 hour；

The reaction pressure is 0.1~25MPa；

The reaction temperature is 220~400 DEG C.

Preferably, the alkali compounds includes one kind or more in potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate Kind；

Further include dehydration after the neutralization reaction.

Preferably, further include post-processing step after the reaction.

The post-processing the specific steps are：

Into the reaction system after reaction plus water mixes, and removes the insoluble matter in reaction system, then decolourize.

Preferably, the decoloration includes adsorption bleaching；

The acid of the acidification includes one or more in hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and dust technology；

The pH value of the acidification is less than or equal to 3.0.

Preferably, after the acidification further include post-processing step again；

The post-processing again includes one or more in separation, drying and recrystallization.

The present invention provides a kind of preparation methods of 2,5-furandicarboxylic acid, include the following steps, first by furancarboxylic acid, After alkali compounds and water carry out neutralization reaction, furoate is obtained；It then, will be above-mentioned under conditions of carbon dioxide gas After the salt and catalyst for the furoate, melting that step obtains are reacted, 2,5-furandicarboxylic acid salt is obtained；The melting Salt fusing point be less than or equal to 400 DEG C；The catalyst includes metal salt catalyst and/or organic alkali catalyst；It finally will be upper State 2,5-furandicarboxylic acid salt that step obtains it is acidified after, obtain 2,5-furandicarboxylic acid.Compared with prior art, this hair There are cost of material height for the bright method for existing 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid, and using expensive Metallic catalyst, and the lower defect of conversion ratio.It is that raw material prepares 2,5- furandicarboxylic acids to be directed to existing furancarboxylic acid again Method, there are poor selectivities, and purity is low, and pollution is big, especially using high-cost cesium carbonate as catalyst, although can be sharp It is mixed with potassium carbonate and cesium carbonate, but cesium carbonate ratio is big, again such that this method is difficult to the defect of industrialized production.

The invention using furancarboxylic acid as starting material, first prepare furoate, then with cheap and easy Common metal salt and/or organic base are obtained as catalyst, the organic salt of low melting point or the monomer of inorganic salts or mixed is especially utilized Salt of the object as melting is closed, prepares 2,5-furandicarboxylic acid, catalyst and fused salt used in the present invention are cheap Chemical products, greatly reduce reaction cost, and it is simple for process, reaction temperature is low, be a kind of economic and environment-friendly, be suitble to scale The preparation method of chemical industry production, has pushed the process of industrialization of 2,5-furandicarboxylic acid.

The experimental results showed that 2,5-furandicarboxylic acid prepared by the present invention, purity and high income, purity is 99% or more, Yield can reach 70% or more.

Description of the drawings

Fig. 1 is 2,5- furandicarboxylic acid sterling nucleus magnetic hydrogen spectrum figures prepared by the embodiment of the present invention 1.

Specific implementation mode

For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention, rather than to invention claim Limitation.

All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art It is prepared by conventional method known to member.

All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or 2,5- furans two Formic acid synthesizes the conventional purity in field.

The catalyst includes metal salt catalyst and/or organic alkali catalyst；

After furancarboxylic acid, alkali compounds and water are carried out neutralization reaction by the present invention first, furoate is obtained.

The furancarboxylic acid is not particularly limited in the present invention, with furancarboxylic acid well known to those skilled in the art, Those skilled in the art can prepare according to the conventional method or commercially available purchase, and furancarboxylic acid of the present invention is preferably made a living Object base monomer furancarboxylic acid.

The alkali compounds is not particularly limited in the present invention, with conventional alkaline chemical combination well known to those skilled in the art Object, those skilled in the art can select and adjust according to practical condition, quality control and product requirement, Alkali compounds of the present invention preferably include it is one or more in potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, more Preferably potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate.

The dosage of the furancarboxylic acid and alkali compounds is not particularly limited in the present invention, ripe with those skilled in the art The conventional ratio known, those skilled in the art can carry out according to practical condition, quality control and product requirement Selection and adjustment, the molar ratio of furancarboxylic acid and alkali compounds of the present invention is preferably 1：(0.5~5), more preferably 1： (1.5~4), more preferably 1：(2.5~3).

The condition of the neutralization reaction is not particularly limited, with conventional neutralization reaction well known to those skilled in the art Condition, those skilled in the art can select and adjust according to practical condition, quality control and product requirement Whole, the time of neutralization reaction of the present invention is preferably 6~20h, more preferably 8~18h, more preferably 10~16h.

The present invention is then under conditions of carbon dioxide gas, the salt of furoate, melting that above-mentioned steps are obtained After being reacted with catalyst, 2,5-furandicarboxylic acid salt is obtained.

The salt of the melting is not particularly limited in the present invention, with the organic salt of low melting point well known to those skilled in the art And/or inorganic salts, those skilled in the art can select according to practical condition, quality control and product requirement It selects and adjusts, the fusing point of the salt of the melting is less than or equal to 400 DEG C, more preferably less than or equal to 350 DEG C, more preferably less than or equal to 300℃.Preparation method provided by the invention can allow reaction to carry out at low temperature, and have higher product quality, this hair The fusing point of the salt of the bright melting can be less than or equal to 290 DEG C, might be less that equal to 270 DEG C, might be less that equal to 250 DEG C, it might be less that equal to 230 DEG C.

The salt of melting of the present invention can be single salt, or salt-mixture is particularly preferred as sodium salt or sodium salt With the salt-mixture of sylvite, the mixing of the fused salt mixt, sodium nitrate and potassium nitrite of sodium nitrate and potassium nitrate is more specifically preferably included Fused salt mixt, sodium nitrite and the potassium nitrite of fused salt, the fused salt mixt of sodium nitrate and sodium nitrite, sodium nitrite and potassium nitrate Fused salt mixt, the fused salt mixt of potassium acetate and sodium acetate, the fused salt mixt of potassium acetate and potassium formate, potassium acetate and sodium formate Fused salt mixt, the fused salt mixt of sodium acetate and potassium formate, the fused salt mixt of sodium acetate and sodium formate, potassium formate and sodium formate it is mixed Close fused salt, sodium bicarbonate and the fused salt mixt of saleratus, the fused salt mixt of sodium hydroxide and potassium hydroxide, melting nitrous acid It is one or more in sodium and the sodium formate of melting, the more preferably fused salt mixt, sodium nitrate and nitrous of sodium nitrate and potassium nitrate Fused salt mixt, the sodium nitrite of the fused salt mixt of sour potassium, the fused salt mixt of sodium nitrate and sodium nitrite, sodium nitrite and potassium nitrate With fused salt mixt, the potassium acetate of the fused salt mixt of potassium nitrite, the fused salt mixt of potassium acetate and sodium acetate, potassium acetate and potassium formate With the fused salt mixt of the fused salt mixt of sodium formate, the fused salt mixt of sodium acetate and potassium formate, sodium acetate and sodium formate, potassium formate and The fused salt mixt, molten of the fused salt mixt of sodium formate, the fused salt mixt of sodium bicarbonate and saleratus, sodium hydroxide and potassium hydroxide The sodium formate of the sodium nitrite or melting that melt.

The ratio of the fused salt mixt is not particularly limited in the present invention, with conventional ratio well known to those skilled in the art , those skilled in the art can select and adjust according to practical condition, quality control and product requirement, this The mass ratio for inventing the fused salt mixt is preferably (5~95)：(95~5), more preferably (25~75)：(75~25), it is more excellent It is selected as (45~55)：(55~45).

Further include that other can fused salt and/or can not fused salt, more preferably other micro in the salt of melting of the present invention Can fused salt and/or can not fused salt, the present invention is not particularly limited, these it is micro can fused salt and/or can not fused salt this is also added In the salt for inventing above-mentioned melting, the mixture of a variety of salt is formed, the essence of technical solution is identical as the present invention, can also be formed The mixture of low melting point, be added these can fused salt and/or can not fused salt technical solution, also the present invention protection in.

The dosage of the salt of the melting is not particularly limited in the present invention, and those skilled in the art can be according to actual production Situation, quality control and product requirement are selected and are adjusted, the gross mass of furoate and catalyst of the present invention Ratio with the quality of the salt of the melting is preferably 1：(0.5~100), more preferably 1：(1~80), more preferably 1：(2~ 50), more preferably 1：(3~20), more preferably 1：(4~10), are specifically as follows 1：(0.5~10).

In the salt of melting of the present invention, further include other can fused salt and/or can not fused salt, the present invention do not do special limit System, these can fused salt and/or can not fused salt be also added in the salt of the above-mentioned melting of the present invention, form the mixture of a variety of salt, The essence of technical solution is identical as the present invention, be added these can fused salt and/or can not fused salt technical solution, also in this hair In bright protection.

The metal salt catalyst is not particularly limited in the present invention, with common metal salt well known to those skilled in the art Catalyst, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the present invention are to ensure that reaction can carry out at low temperature, further increase the quality of product, the metal salt catalyst Cation preferably include it is one or more in potassium ion, sodium ion, lithium ion and alkaline-earth metal ion, more preferably potassium from Son, sodium ion, lithium ion or alkaline-earth metal ion.The anion of the metal salt catalyst preferably include carbanion, It is one or more in phosphate anion, hydroxide ion and bicarbonate ion, more preferably carbanion, phosphate radical from Son, hydroxide ion or bicarbonate ion.

The organic alkali catalyst is not particularly limited in the present invention, with Conventional organic base well known to those skilled in the art Catalyst, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the present invention are to ensure that reaction can carry out at low temperature, further increase the quality of product, the organic alkali catalyst is excellent Choosing includes 11 carbon -7- alkene of 1,8- diazabicylos, methylamine, urea, ethamine, ethanol amine, ethylenediamine, dimethylamine, trimethylamine, three Ethamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA), triethanolamine, butylamine, isobutyl amine, tert-butylamine, oneself Amine, octylame, cyclohexylamine, triethylene diamine, tetramethylethylenediamine, aniline and its derivatives, benzylamine and its derivative, pyridine and its It is one or more in derivative, pyrimidine, 4-dimethylaminopyridine, potassium tert-butoxide, sodium hydride, sodium ethoxide and sodium methoxide, it is more excellent It is selected as 11 carbon -7- alkene of 1,8- diazabicylos, methylamine, urea, ethamine, ethanol amine, ethylenediamine, dimethylamine, trimethylamine, three second Amine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA), triethanolamine, butylamine, isobutyl amine, tert-butylamine, hexylamine, Octylame, cyclohexylamine, triethylene diamine, tetramethylethylenediamine, aniline and its derivatives, benzylamine and its derivative, pyridine and its spread out Biology, pyrimidine, 4-dimethylaminopyridine, potassium tert-butoxide, sodium hydride, sodium ethoxide or sodium methoxide.

The dosage of the catalyst is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings Condition, quality control and product requirement are selected and are adjusted, mole of furoate of the present invention and the catalyst Than being preferably 1：(0.5~50), more preferably 1：(1~40), more preferably 1：(2~20), more preferably 1：(2~20), more Preferably 1：(3~10), are specifically as follows 1：(0.5~5).

The temperature of the reaction is not particularly limited in the present invention, with the such reaction of routine well known to those skilled in the art Temperature, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the temperature of reaction of the present invention is preferably 220~400 DEG C, more preferably 250~350 DEG C, more preferably 270~330 DEG C, more preferably 290~310 DEG C.The present invention by using the salt of melting and specific metal salt and/or organic alkali catalyst, Reduce reaction temperature, can allow reaction carrying out at low temperature, and have higher product quality, reduce production risk and The temperature of energy consumption cost, the reaction can be 220~290 DEG C, can be 230~280 DEG C, can be 240~270 DEG C, It can be 250~260 DEG C.

The pressure of the reaction is not particularly limited in the present invention, with the such reaction of routine well known to those skilled in the art Pressure, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the pressure of reaction of the present invention is preferably 0.1~25MPa, more preferably 1~20MPa, more preferably 5~15MPa.

The time of the reaction is not particularly limited in the present invention, with the such reaction of routine well known to those skilled in the art Time, those skilled in the art can be selected according to practical condition, quality control and product requirement and Adjustment, the time of reaction of the present invention is preferably 1~24 hour, more preferably 5~20 hours, and more preferably 10~15 is small When.

The present invention is to ensure the purity and yield of final products, improves and optimizes preparation flow, after the reaction preferably also Including post-processing step.

The specific steps of the post-processing are not particularly limited in the present invention, with well known to those skilled in the art such anti- The post-processing step answered, those skilled in the art can according to practical condition, quality control and product requirement into Row selection and adjustment, the specific steps of post-processing of the present invention are preferably：

More specifically can be：

After reaction, a certain amount of water is added into reaction system, the insoluble matter being filtered to remove in system, filtrate is added Activated carbon decolorizing.

The present invention provides a kind of using cheap furancarboxylic acid and carbon dioxide as raw material, with raw material of industry carbonic acid Potassium etc. is catalyst, is dissolved to raw material and catalyst as fused salt using potassium acetate, sodium acetate etc., in certain pressure and At a temperature of, prepare the technology and methods of 2,5-furandicarboxylic acid.From a cost perspective, raw material used in the present invention is industry In easily prepare, the furancarboxylic acid of low cost, rather than expensive 5 hydroxymethyl furfural used in conventional method；In addition, Catalyst used in the present invention is cheap Industrial raw material potassium carbonate, rather than expensive caesium class catalyst, It efficiently solves the problems, such as that current 2,5-furandicarboxylic acid production cost is high, has invented a kind of with low cost preparation 2,5- furans The method of dioctyl phthalate, to pushing 2,5-furandicarboxylic acid industrialization to be of great significance.From environmentally protective and sustainable development Angle considers that furan starting material formic acid used in the present invention can derive from the biomaterials such as corncob, stalk, effectively realize Conversion and utilization to abandoned biomass；In addition, another kind feed carbon dioxide used in the present invention can be derived from industry The exhaust gas of discharge, this to reduce carbon dioxide discharge capacity, alleviate environmental problem caused by current greenhouse effects have it is important Meaning.

After 2,5-furandicarboxylic acid salt that the present invention finally obtains above-mentioned steps is acidified, 2,5- furans diformazans are obtained Acid.

The specific steps and parameter of the acidification are not particularly limited in the present invention, with well known to those skilled in the art normal The step of rule acidification and parameter, those skilled in the art can want according to practical condition, quality control and product It asks and is selected and adjusted, the acid of acidification of the present invention preferably includes in hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and dust technology It is one or more, more preferably hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid or dust technology.The pH value of the acidification, which is preferably less than, to be equal to 3.0, more preferably less than it is equal to 2.5, is more preferably less than equal to 2.0.

The present invention is to ensure the purity and yield of final products, improves and optimizes preparation flow, after the acidification preferably also Including post-processing step again.

The specific steps post-processed again are not particularly limited in the present invention, with it is well known to those skilled in the art this The conventional post-processing step of class reaction, those skilled in the art can be according to practical condition, quality control and production Product require to be selected and adjusted, post-processing again of the present invention preferably include separation, dry and one kind in recrystallization or It is a variety of, it more preferably detached, dried and is recrystallized successively, be specifically as follows and carry out suction filtration separation, drying and hot water successively Recrystallization.

The present invention is to ensure the purity and yield of final products, improves and optimize preparation flow, above-mentioned entirety preparation process It is specifically as follows：

The present invention first carries out neutralization reaction, wherein alkali packet using bio-based monomer furancarboxylic acid as raw material with the aqueous solution of alkali Containing all inorganic or organic bases that can carry out acid-base neutralization with furancarboxylic acid, preferably KOH, NaOH, K₂CO₃, Na₂CO₃, prepare Obtain the aqueous solution of furoate.Then, through being evaporated aqueous solvent, the solid powder of furoate is obtained.

Above-mentioned prepared solid powder is uniformly poured into high-temperature high-pressure reaction kettle, and is added and is equivalent to furan starting material The catalyst of 0.5~5 times of equivalent of formic acid, wherein the cation of metal salt catalyst can be potassium ion, sodium ion, lithium ion And alkaline-earth metal.The anion of metal salt catalyst can be carbonate, phosphate radical, hydroxyl, bicarbonate radical etc..Finally, Quality is added into kettle and is equivalent to raw material and the fused salt of 0.5~10 times of catalyst gross mass.

Addition finishes, and after mixing, body is excluded into line replacement at least 3 times to the air in reaction kettle with carbon dioxide Air in system and moisture；Then, certain pressure and at a temperature of reacted, after reaction, be added into reaction system A certain amount of water, the insoluble matter being filtered to remove in system, filtrate are added activated carbon decolorizing, are used in combination hydrochloric acid to be acidified, obtain White solid filters, dry, obtains product 2,5-furandicarboxylic acid, 2,5-furandicarboxylic acid sterling is recrystallized to give with hot water.

The present invention provides a kind of industrialized process for preparing of the 2,5-furandicarboxylic acid of low cost, are with furoate Having for low melting point is especially utilized using cheap and be easy to get common metal salt and/or organic base as catalyst in starting material Salt of the monomer or mixture of machine salt or inorganic salts as melting prepares 2,5-furandicarboxylic acid, the selected raw material of the present invention For cheap bio-based monomer furancarboxylic acid and carbon dioxide, and expensive 5- hydroxyls not commonly used in the prior art Methyl furfural, and using cheap inorganic base as catalyst, instead of expensive metallic catalyst, such as metal caesium Catalyst significantly reduces the manufacturing cost of product；The present invention is replaced with the small inorganic fused salt of cheap, pollution simultaneously Organic solvent realizes the process that green completely prepares 2,5-furandicarboxylic acid；In addition, used preparation method and post-processing Method is simple, it is easy to accomplish the large-scale industrial production of 2,5-furandicarboxylic acid has pushed the industry of 2,5-furandicarboxylic acid Change process.Integrated artistic of the present invention is simple, reaction temperature is low, is a kind of economic and environment-friendly, is suitble to the preparation of scale industrial production Method.

For a further understanding of the present invention, with reference to embodiment to a kind of 2,5-furandicarboxylic acid provided by the invention Preparation method illustrates, but it is to be understood that and these embodiments are to be implemented down based on the technical solution of the present invention, Detailed embodiment and specific operating process are given, are only the feature and advantage further illustrated the present invention, without It is limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiments.

Embodiment 1

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (potassium acetate is 1 with the mass ratio in sodium acetate to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).It has been added Finish, with the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, carbon dioxide is kept Pressure be 0.8MPa, react 24 hours under the conditions of 280 DEG C, conversion ratio 95%.

It waits for after reaction, the deionized water of 100ml is added into reaction system, amber transparent solution is obtained, to mother liquor The middle activated carbon that 0.2g is added is stirred 30 minutes, is filtered while hot, the colourless aqueous solution of gained is acidified to hydrochloric acid at 50 DEG C PH value is about 2, has a large amount of white precipitates to generate, and decompression filters, vacuum drying, with water recrystallize 2,5-furandicarboxylic acid is pure Product.

The 2,5-furandicarboxylic acid sterling prepared to the embodiment of the present invention 1 characterizes, and is solvent to institute using deuterated DMSO It obtains 2,5- furandicarboxylic acids and carries out nuclear magnetic resonance spectroscopy.

It is 2,5-furandicarboxylic acid sterling nucleus magnetic hydrogen spectrum figure prepared by the embodiment of the present invention 1 referring to Fig. 1, Fig. 1.It can by Fig. 1 To know, what the present invention was prepared 2,5-furandicarboxylic acid sterling does not find apparent impurity peaks, through nuclear-magnetism calculated purity >= 99%.

The yield of 2,5- furandicarboxylic acid sterlings prepared by the embodiment of the present invention 1 is 80%.

Embodiment 2

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 280 DEG C, conversion ratio 87%.

The 2,5-furandicarboxylic acid sterling prepared to the embodiment of the present invention 2 characterizes, and is solvent to institute using deuterated DMSO It obtains 2,5- furandicarboxylic acids and carries out nuclear magnetic resonance spectroscopy.

The result shows that the present invention was prepared 2,5-furandicarboxylic acid sterling, does not find apparent impurity peaks, through core Magnetic calculated purity >=99%.

The yield of 2,5- furandicarboxylic acid sterlings prepared by the embodiment of the present invention 2 is 70%.

Embodiment 3

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 3 hours under the conditions of 280 DEG C, conversion ratio 77%.

Embodiment 4

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 1 hour under the conditions of 280 DEG C, conversion ratio 42%.

Embodiment 5

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 270 DEG C, conversion ratio 73%.

Embodiment 6

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 4.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 270 DEG C, conversion ratio 71%.

Embodiment 7

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 7.4g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 270 DEG C, conversion ratio 58%.

Embodiment 8

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 9.9g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 270 DEG C, conversion ratio 53%.

Embodiment 9

Embodiment 10

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 12g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, and uses Air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept For 0.8MPa, reacted 6 hours under the conditions of 270 DEG C, conversion ratio 35%.

Embodiment 11

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 15g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, and uses Air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept For 0.8MPa, reacted 6 hours under the conditions of 270 DEG C, conversion ratio 27%.

Embodiment 12

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 0.7g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5g of (5mmol), potassium acetate and sodium acetate:1).Addition finishes, with two Carbonoxide replaces the air in cleared reaction kettle.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept to be 0.8MPa reacts 6 hours under the conditions of 270 DEG C, conversion ratio 42%.

Embodiment 13

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 1.38g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5g of (10mmol), potassium acetate and sodium acetate:1).Addition finishes, and uses Air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept For 0.8MPa, reacted 6 hours under the conditions of 270 DEG C, conversion ratio 53%.

Embodiment 14

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 2.76g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5g of (20mmol), potassium acetate and sodium acetate:1).Addition finishes, and uses Air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept For 0.8MPa, reacted 6 hours under the conditions of 270 DEG C, conversion ratio 42%.

Embodiment 15

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 4.14g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5g of (30mmol), potassium acetate and sodium acetate:1).Addition finishes, and uses Air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept For 0.8MPa, reacted 6 hours under the conditions of 270 DEG C, conversion ratio 77%.

Embodiment 16

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 5.5g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5g of (40mmol), potassium acetate and sodium acetate:1).Addition finishes, and uses Air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept For 0.8MPa, reacted 6 hours under the conditions of 270 DEG C, conversion ratio 72%.

Embodiment 17

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 250 DEG C, conversion ratio 26%.

Embodiment 18

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 260 DEG C, conversion ratio 41%.

It waits for after reaction, the deionized water of 100ml is added into reaction system, amber transparent solution is obtained, to mother liquor The middle activated carbon that 0.2g is added is stirred 30 minutes, is filtered while hot, the colourless aqueous solution of gained is acidified to hydrochloric acid at 50 DEG C PH value is about 2, has a large amount of white precipitates to generate, and decompression filters, and vacuum drying recrystallizes to obtain 2,5-furandicarboxylic acid sterling with water

Embodiment 19

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 265 DEG C, conversion ratio 64%.

Embodiment 20

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 275 DEG C, conversion ratio 82%.

Embodiment 21

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 6 hours under the conditions of 285 DEG C, conversion ratio 91%.

Embodiment 22

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.1MPa, is reacted 6 hours under the conditions of 280 DEG C, conversion ratio 70%.

Embodiment 23

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 10MPa, is reacted 6 hours under the conditions of 280 DEG C, conversion ratio 89%.

Embodiment 24

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.4MPa, is reacted 6 hours under the conditions of 280 DEG C, conversion ratio 80%.

Embodiment 25

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 3.45g (mass ratio of potassium acetate and sodium acetate is 55 to the fused salt mixt 5.0g of (25mmol), potassium acetate and sodium acetate:45).It has been added Finish, with the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, carbon dioxide is kept Pressure be 0.8MPa, react 24 hours under the conditions of 280 DEG C, conversion ratio 95%.

The 2,5-furandicarboxylic acid sterling prepared to the embodiment of the present invention 25 characterizes, and is solvent to institute using deuterated DMSO It obtains 2,5- furandicarboxylic acids and carries out nuclear magnetic resonance spectroscopy.

The yield of 2,5- furandicarboxylic acid sterlings prepared by the embodiment of the present invention 2 is 80%.

Embodiment 26

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 1.38g (mass ratio of potassium nitrate and sodium nitrite is 1 to the fused salt mixt 5.0g of (10mmol), potassium acetate and sodium acetate:1).It has been added Finish, with the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, carbon dioxide is kept Pressure be 0.8MPa, react 24 hours under the conditions of 270 DEG C, conversion ratio 63%.

Embodiment 27

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 1.38g (mass ratio of potassium nitrite and sodium nitrate is 1 to the fused salt mixt 5.0g of (10mmol), potassium acetate and sodium acetate:1).It has been added Finish, with the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, carbon dioxide is kept Pressure be 0.8MPa, react 24 hours under the conditions of 270 DEG C, conversion ratio 60%.

Embodiment 28

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 1.38g The fused salt mixt 5.0g sodium nitrites of (10mmol), potassium acetate and sodium acetate.Addition finishes, with the cleared reaction of carbon dioxide replacement Air in kettle.Then, in the case where maintaining certain air-flow, keep the pressure of carbon dioxide for 0.8MPa, under the conditions of 280 DEG C Reaction 24 hours, conversion ratio 83%.

Embodiment 29

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, Anhydrous potassium carbonate 1.38g The fused salt mixt 5.0g sodium formates of (10mmol), potassium acetate and sodium acetate.Addition finishes, with the cleared reaction kettle of carbon dioxide replacement Interior air.Then, in the case where maintaining certain air-flow, keep the pressure of carbon dioxide for 0.8MPa, it is anti-under the conditions of 270 DEG C It answers 24 hours, conversion ratio 80%.

Embodiment 30

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, anhydrous phosphoric acid potassium 2.12g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (10mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 24 hours under the conditions of 270 DEG C, conversion ratio 36%.

Embodiment 31

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, potassium hydroxide 0.56g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (10mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 24 hours under the conditions of 270 DEG C, conversion ratio 20%.

Embodiment 32

In the flask of 100ml, furancarboxylic acid 1.12g (10mmol), potassium carbonate 0.7g (5mmol) and 10ml are sequentially added Water.It is acquired that clear furancarboxylic acid sylvite aqueous solution, evaporated under reduced pressure moisture obtain the solid powder of white furancarboxylic acid sylvite End.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sylvite, sodium hydroxide 0.4g (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 5.0g of (10mmol), potassium acetate and sodium acetate:1).Addition finishes, With the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, the pressure of carbon dioxide is kept Power is 0.8MPa, is reacted 24 hours under the conditions of 270 DEG C, conversion ratio 20%.

Embodiment 33

In the flask of 100ml, sequentially add furancarboxylic acid 1.12g (10mmol), sodium carbonate 0.54g (5mmol) and The water of 10ml.It is acquired that clear furancarboxylic acid sodium-salt aqueous solution, evaporated under reduced pressure moisture obtain consolidating for white furancarboxylic acid sodium salt Body powder.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sodium salt, Anhydrous potassium carbonate (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 4.8g of 3.45g (25mmol), potassium acetate and sodium acetate:1).It is added It finishes, with the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, titanium dioxide is kept The pressure of carbon is 0.8MPa, is reacted 24 hours under the conditions of 280 DEG C, conversion ratio 95%.

The yield of 2,5- furandicarboxylic acid sterlings prepared by the embodiment of the present invention 33 is 80%.

Embodiment 34

In the flask of 100ml, sequentially add furancarboxylic acid 1.12g (10mmol), sodium carbonate 0.54g (5mmol) and The water of 10ml.It is acquired that clear furancarboxylic acid sodium-salt aqueous solution, evaporated under reduced pressure moisture obtain consolidating for white furancarboxylic acid sodium salt Body powder.In the high-temperature high-pressure reaction kettle of 100ml, it is separately added into above-mentioned prepared furancarboxylic acid sodium salt, Anhydrous potassium carbonate (mass ratio of potassium acetate and sodium acetate is 1 to the fused salt mixt 4.8g of 3.45g (25mmol), potassium acetate and sodium acetate:1).It is added It finishes, with the air in the cleared reaction kettle of carbon dioxide replacement.Then, in the case where maintaining certain air-flow, titanium dioxide is kept The pressure of carbon is 0.8MPa, is reacted 24 hours under the conditions of 275 DEG C, conversion ratio 93%.

A kind of industrialized process for preparing of the 2,5- furandicarboxylic acids of low cost provided by the invention has been carried out in detail above Thin introduction, principle and implementation of the present invention are described for specific case used herein, above example Illustrate to be merely used to help understand the method and its core concept of the present invention, including best mode, and but also this field Any technical staff can put into practice the present invention, including manufacture and use any device or system, and implement the side of any combination Method.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, may be used also With several improvements and modifications are made to the present invention, these improvement and modification are also fallen within the protection scope of the claims of the present invention. The range of patent protection of the present invention is defined by the claims, and may include those skilled in the art it is conceivable that other realities Apply example.If these other embodiments, which have, is not different from the structural element of claim character express, or if they Include with equivalent structural elements of the character express of claim without essence difference, then these other embodiments should also be included in In the scope of the claims.

Claims

1. a kind of preparation method of 2,5-furandicarboxylic acid, which is characterized in that include the following steps：

B) under conditions of carbon dioxide gas, the salt and catalyst of furoate, melting that above-mentioned steps are obtained carry out After reaction, 2,5-furandicarboxylic acid salt is obtained；

The catalyst includes metal salt catalyst and/or organic alkali catalyst；

2. preparation method according to claim 1, which is characterized in that the salt of the melting includes single salt or salt-mixture；

3. preparation method according to claim 1, which is characterized in that the salt of the melting includes sodium nitrate and potassium nitrate Fused salt mixt, sodium nitrite and the nitric acid of fused salt mixt, the fused salt mixt of sodium nitrate and potassium nitrite, sodium nitrate and sodium nitrite Fused salt mixt, potassium acetate and the first of the fused salt mixt of potassium, the fused salt mixt of sodium nitrite and potassium nitrite, potassium acetate and sodium acetate Fused salt mixt, sodium acetate and the formic acid of the fused salt mixt of sour potassium, the fused salt mixt of potassium acetate and sodium formate, sodium acetate and potassium formate The fused salt mixt of sodium, the fused salt mixt of potassium formate and sodium formate, the fused salt mixt of sodium bicarbonate and saleratus, sodium hydroxide and It is one or more in the sodium formate of the fused salt mixt of potassium hydroxide, the sodium nitrite of melting and melting；

The mass ratio of the salt-mixture is (5~95)：(95~5).

4. preparation method according to claim 3, which is characterized in that the salt of the melting further include other can fused salt and/ Or it can not fused salt；

The cation of the metal salt catalyst includes one kind in potassium ion, sodium ion, lithium ion and alkaline-earth metal ion Or it is a variety of；

The anion of the metal salt catalyst includes carbanion, phosphate anion, hydroxide ion, bicarbonate ion In it is one or more；

The organic alkali catalyst includes 11 carbon -7- alkene of 1,8- diazabicylos, methylamine, urea, ethamine, ethanol amine, second two Amine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3- propane diamine, 1,2- propane diamine, tripropyl amine (TPA), triethanolamine, fourth Amine, isobutyl amine, tert-butylamine, hexylamine, octylame, cyclohexylamine, triethylene diamine, tetramethylethylenediamine, aniline and its derivatives, benzylamine And its derivative, pyridine and its derivatives, pyrimidine, 4-dimethylaminopyridine, potassium tert-butoxide, sodium hydride, sodium ethoxide and sodium methoxide In it is one or more；

5. preparation method according to claim 1, which is characterized in that mole of the furoate and the catalyst Than being 1：(0.5~50)；

The ratio of the gross mass of the furoate and catalyst and the quality of the salt of the melting is 1：(0.5~100).

6. preparation method according to claim 1, which is characterized in that the reaction time is 1~24 hour；

The reaction pressure is 0.1~25MPa；

The reaction temperature is 220~400 DEG C.

7. preparation method according to claim 1, which is characterized in that the alkali compounds includes potassium hydroxide, hydrogen-oxygen Change one or more in sodium, potassium carbonate and sodium carbonate；

Further include dehydration after the neutralization reaction.

8. according to the preparation method described in claim 1~6 any one, which is characterized in that after further including after the reaction Manage step；

The post-processing the specific steps are：

9. preparation method according to claim 8, which is characterized in that the decoloration includes adsorption bleaching；

The pH value of the acidification is less than or equal to 3.0.

10. preparation method according to claim 1, which is characterized in that further include post-processing step again after the acidification；