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    • 专利摘要:
    The present invention relates to a composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furanedicarboxylic acid which is purified in a process comprising: contacting the acid composition with an alcohol to obtain an esterified composition; and separating the 2-formyl-furan-5-carboxylic acid ester from the esterified composition to obtain an esterified purified product; and contacting the purified esterified composition with water for saponification or hydrolysis, to obtain a product composition, comprising 2,5-furanedicarboxylic acid and a reduced amount of 2-formyl-furan-5-carboxylic acid.
    公开号:BR112016003938B1
    申请号:R112016003938-6
    申请日:2014-08-29
    公开日:2021-02-23
    发明作者:Ana Sofia Vagueiro De Sousa Dias；Benjamin Mckay；Bing Wang；Gerardus Johannes Maria Gruter；Jagdeep Singh；Matheus Adrianus Dam
    申请人:Furanix Technologies B.V；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for purifying a composition comprising 2-formyl-furan-5-carboxylic acid (FFCA) and 2,5-furanedicarboxylic acid (FDCA).
    [0002] US 2012/0302768 discloses an oxidation process to produce a crude product and / or a purified carboxylic acid product. The product is a carboxylic acid composition comprising 2,5-furan-dicarboxylic acid. It was obtained with a process comprising the oxidation of a raw material containing 5-hydroxymethylfurfural in the presence of oxygen, a saturated organic acid solvent, containing 2 to 6 carbon atoms, and a catalyst system. The raw material can also comprise 5-hydroxymethylfurfural ethers, such as 5-ethoxymethylfurfural. It is reported that the oxidation reaction leads to the formation of a mixture of 2,5-furan-dicarboxylic acid, 2-formyl-furan-5-carboxylic acid and, optionally, some other furan derivatives, such as alkyl esters of acid 2-formyl-furan-5-carboxylic. The amount of 2-formyl-furan-5-carboxylic acid can vary from 0.1% by weight to about 4% by weight. After oxidation, the crude product obtained is washed with the organic acid solvent, for example, acetic acid, and water. Although it is indicated that the purified 2,5-furan-dicarboxylic acid can be obtained, it has been found that the purified product also still contains an amount of 2-formyl-furan-5-carboxylic acid. It is recognized in US 2012/0302768 that significant concentrations of mono-functional molecules such as 2-formyl-furan-5-carboxylic acid in the 2,5-furan-dicarboxylic acid product are particularly harmful to polymerization processes in which they can act as terminator chains during a polyester condensation reaction.
    [0003] The present inventors have found that the additional washing does not produce any purer product. It is believed that 2-formyl-furan-5-carboxylic acid is included in the crystals of 2,5-furan-dicarboxylic acid in which washing purification is not feasible.
    [0004] Therefore, there is a need for a process that allows for the reduction of the amount of 2-formyl-furan-5-carboxylic acid in a carboxylic acid composition comprising 2,5-furan-dicarboxylic acid. It has now been found that the amount of 2-formyl-furan-5-carboxylic acid in such compositions can be considerably reduced by esterifying the composition and subsequently separating the esterified product thus obtained.
    [0005] Accordingly, the present invention provides a process for purifying a composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furanedicarboxylic acid, which process comprises: contacting the acid composition with an alcohol for obtaining an esterified composition; separating the 2-formyl-furan-5-carboxylic acid ester from the esterified composition to obtain an esterified purified product; and contacting the purified esterified composition with water for saponification or hydrolysis, to obtain a product composition, which comprises 2,5-furanedicarboxylic acid and a reduced amount of 2-formyl-furan-5-carboxylic acid.
    [0006] The process according to the invention uses the surprising fact that the esterified composition allows easier separation of 2-formyl-furan-5-carboxylic acid ester compounds from the esterified product than the corresponding acid from of the acid composition. The 2-formyl-furan-5-carboxylic acid ester molecules are believed not to be, or at least to a lesser extent, incorporated into the crystals of the 2,5-furan-dicarboxylic acid diester. The process product is a composition that comprises an increased content of 2,5-furan-dicarboxylic acid compounds, as compared to the content thereof in the acid composition. By compounds of 2,5-furan-dicarboxylic acid is understood 2,5-furan-dicarboxylic acid, but also the mono and diesters of 2,5-furan-dicarboxylic acid.
    [0007] Although the recrystallization of the starting material, that is, the acid composition, can be used to obtain a purer product, the inclusion of 2-formyl-furan-5-carboxylic acid in the form of 2-acid crystals , 5-furan-dicarboxylic has the drawback that purer products can only be obtained at a considerable loss of yield. It is surprising that esterification allows for a simpler and more efficient purification method, since the mixture after esterification tends to be more complex in that not only the 2,5-furan-dicarboxylic acid mono- and diester will be present in this mixture, but also small amounts of 2,5-furan-dicarboxylic acid. Despite the complexity of this mixture, the separation of the 2-formyl-furan-5-carboxylic acid ester is simplified, which results in a pure product, with an increase in yield, in comparison with, for example, the recrystallization of the composition of the acid.
    [0008] The figure shows a simplified flow chart of a modality of the process according to the present invention.
    [0009] The acid composition that is used as a raw material for the process according to the present invention can be produced in a similar manner to that described in US 2012/0302768. This means that the acid composition can be produced by oxidizing 5-hydroxymethylfurfural. Also, as described in US 2012/0302768 the starting material can be a 5-hydroxymethylfurfural ether, or an ester, such as 5-acetoxymethylfurfural. Preferably, the acid composition originates from the oxidation of 5-alkoxymethylfurfural, 5-hydroxymethylfurfural or a mixture thereof. When the acid composition originates from the oxidation of a feed containing 5-alkoxymethylfurfural, the oxidized product may comprise FDCA and FFCA, but also the FDCA mono- and diester and the FFCA alkyl ester. The process according to the present invention provides an elegant procedure for purifying the complex mixture in pure FDCA.
    [0010] The oxidation of 5-hydroxymethylfurfural or its derivatives can be carried out as described in US 2012/0302768. A suitable way to oxidize 5-alkoxymethylfurfural has also been described in WO 2011/043660. The conditions according to the last application include a reaction temperature of 60 to 220 ° C, preferably 100210 ° C, more preferably 150-200 ° C, more preferably 160-190 ° C, and a pressure of 0.5 MPa to 10 MPa, preferably from 1 MPa to 8 MPa. The catalysts that can be used in this oxidation reaction are similar to those described in US 2012/0302768. They suitably include cobalt and manganese. In addition, they contain a source of bromide. The molar ratios of cobalt to manganese (Co / Mn) are typically 1/1000 - 100/1, preferably 1/100 - 10/1 and more preferably 1/10 - 4/1. Molar ratios of bromide to metals (e.g., Br / (Co + Mn)) are typically 0.001-5.00, preferably 0.01-2.00, and more preferably 0.1-0.9. Oxygen is adequately supplied by air, although oxygen enriched air or oxygen depleted air can also be used. It is surprising that the main oxidation product according to WO 2011/043660 provides furan-2,5-dicarboxylic acid as the main product, instead of the monoester thereof.
    [0011] As shown in US 2012/0302768 the acid composition obtained by such oxidation reactions can contain up to a significant level of 2-formyl-furan-5-carboxylic acid. When the starting material for the oxidation reaction comprises an ether, the product of the same can also comprise a 2-formyl-furan-5-carboxylic acid ester. However, the main by-product is the acid compound, also in the case of the oxidation of an ether. The amount of 2-formyl-furan-carboxylic acid in the acid composition can be of the same order of magnitude as described in US 2012/0302768. Typically, the acid composition comprises from 0.1 to 4.0% by weight of 2-formyl-furan-5-carboxylic acid, based on the weight of the acid composition. The composition may have been washed, as described in US 2012/0302768. It is, however, observed that by such a washing step no significant reduction in the content of 2-formyl-furan-5-carboxylic acid occurs. Suitable washing liquids include acetic acid, water, and mixtures thereof.
    [0012] The process according to the present invention comprises a step of contacting the acid composition with an alcohol. Alcohol can be selected from a wide range of alcoholic compounds. Such compounds include alcoholic mono-alcohols, but also polyols, such as ethylene glycol, propylene glycol, glycerol, pentaerythritol and the like. Preferably, the alcohol has from 1 to 16, more preferably from 1 to 8 carbon atoms. Alcohol is suitably a mono-alcohol. Such alcohols include linear and branched aliphatic, cycloaliphatic and aromatic alcohols. The alcohol is suitably an alkanol having 1 to 16, more preferably 1 to 8 carbon atoms. Such alcohols can be easily used in the esterification reaction and provide a suitable behavior different from the resulting esters to facilitate the separation of the resulting esters. The alkanols can be straight or branched, and include n-propanol, isopropanol, n-butanol, iso-butanol, tert-butanol, ethylhexyl alcohol, n-octanol and the like. Most preferred are methanol and ethanol.
    [0013] Alcohol can be present in a wide range of proportions in relation to the acid functions in the acid composition. Since esterification is an equilibrium reaction, it is preferable to use a molar excess of alcohol in view of the acid functions in the acid composition. Suitably, the alcohol is present in a molar excess of the acid composition, the molar ratio between the alcohol and the acid composition preferably being from 2: 1 to 100: 1. It has been surprisingly found that 2-formyl- furan-5-carboxylic can be easily esterified, and the balance for this esterification is measured towards the ester side. Therefore, esterification of the 2-formyl-furan-5-carboxylic acid ester can be achieved virtually quantitatively. It is not necessary to remove the water that is generated by the esterification reaction. If the removal of water is considered to be feasible, the use of dry molecular sieves, or other conventional desiccants, such as anhydrous calcium chloride, sodium sulfate, calcium sulfate, magnesium sulfate and mixtures thereof. The desiccant can be added to the mixture to the acid composition, and the alcohol and water that is generated can be adsorbed by the desiccant. It is also possible to use a Soxhlet apparatus or similar equipment, in which the alcohol, containing a little water, is refluxed, and the liquid is passed through the desiccant that adsorbes the water that is incorporated into the flow of water. reflux. Another method for removing water can be carried out in a manner similar to that described in EP 2481733, that is, by means of a purge gas. Therefore, a purge gas can be present in the process according to the invention; the purge gas is preferably an inert gas, that is, a gas which is non-reactive with the educts, the intermediates, and the process apparatus according to the present invention. The useful inert gases are nitrogen, carbon dioxide, and all noble gases, such as neon and argon and their mixtures. Particularly preferred is a purge gas which is or comprises nitrogen gas. Thus, water can be removed from the purge gas after leaving the reaction chamber, such as by condensation or by adsorption. The purge gas is preferably recycled. As indicated before, water removal is not necessary. It may even be possible to add diluents to the mixture of the acid composition and the alcohol. Such thinners can include water. Other diluents can include organic solvents, such as sulfoxides, for example, dimethyl sulfoxide, and ketones, for example, acetone.
    [0014] In order to increase the esterification rate, the contact of the acid composition with alcohol can be properly conducted in the presence of an esterification catalyst. A suitable esterification catalyst is an acid catalyst. Many acid catalysts are suitable for catalyzing the esterification reaction of the present invention. Suitable catalysts include inorganic mineral acids, organic Bronsted acids, Lewis acids, acid ion exchange resins and acid zeolites. The catalyst can be homogeneous, heterogeneous, but also, including the catalysts described in EP 2481733. Examples of inorganic mineral acids include hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid. Suitable organic Bronsted acids comprise methane sulfonic acid, toluene sulfonic acid and trichloroacetic acid. Suitable Lewis acids include boron trifluoride and aluminum trichloride. Preferably, the acid catalyst is selected from the group consisting of acids, zeolites, ion exchange resins, inorganic minerals and mixtures thereof. Examples of mineral inorganic acids are those mentioned above. Examples of ion exchange resins are divinylbenzene / styrene polymer resins containing sulfonic groups. Suitable zeolites are crystalline aluminosilicates and aluminophosphates. Examples of suitable zeolites include zeolite X, zeolite Y, beta zeolite, ferrierite, mordenite, chabazite, ZSM-5, ZSM-11, ZSM-23, SAPO-5, SAPO-11 and SAPO-34. Preferably, zeolites are in their H form, indicating that they have undergone ion exchange to replace metal cations, such as alkali metal ions, with protons, thereby increasing their acidity. Examples of suitable ion exchange resins include sulfonated polymer resins, for example, sulfonated styrene-divinylbenzene copolymers, such as Amberlyst resins (ex Rohm and Haas), and sulfonated copolymer-fluoropolymer-based tetrafluoroethylene resins, such as Nafion (from DuPont). A particularly suitable ion exchange resin is Amberlyst 70, a styrene-divinylbenzene copolymer containing groups of sulfonic acid and which is reported to be halogenated and is indicated to have a high thermal stability.
    [0015] Heterogeneous catalysts are suitably used in continuous processes. In such processes, impurities in the reaction mixtures or by thermal degradation can be deactivated, for example. It was found that especially ion exchange resins can be easily regenerated by washing a solution of sulfuric acid in an alcohol, in particular methanol or ethanol, on the deactivated catalyst, thus restoring the acidic sites of the ion exchange resin.
    [0016] The esterification reaction can be carried out in a batch or continuous reactor. In a batch reactor, the reaction mixture can be maintained substantially until equilibrium has been reached. Preferably, the esterification is carried out in a continuous reactor. Suitable reactors include a tank reactor with continuous agitation and a buffer flow reactor. Advantageously, the esterification is carried out in a reactive separation column. In such a column, a liquid containing the acid composition, for example, a solution of the acid composition in a C1-C4 alcohol, such as methanol or ethanol, is passed through a heterogeneous catalyst bed, and in reverse a gas is passed over the catalyst. The gas may comprise an inert gas, such as nitrogen, noble gases or carbon dioxide. In such a case, the alcohol can be passed along with the acid composition in the liquid phase over the catalyst. However, when alcohol is vaporous under the prevailing conditions, it is preferred to use alcohol vapor. The acid-containing liquid is usually passed down through the catalyst bed and the gas is usually passed upwards. The gas will entrain at least part of the water formed during esterification, in order to influence the degree of ester formation. The use of reactive pickling is particularly advantageous in the present process, since the removal of water will reduce the amount of monoester formed while improving the formation of the diester. Thus, the esterified composition obtained in the process of the present invention then comprises 2-formyl-furan-5-carboxylic acid ester and 2,5-furan-dicarboxylic acid diester as main products. The separation between these two compounds is relatively easy.
    [0017] Since the mixture of the acid composition and the alcohol already contains the acid compounds, in other words, 2-formyl-furan-5-carboxylic acid and 2,5-furan-dicarboxylic acid, the mixture is already acidic. Therefore, it is not necessary that an additional acid esterifying catalyst be added to the mixture. It has been found that a satisfactory degree of esterification of especially 2-formyl-5-carboxylic acid is obtained when the esterification according to the invention is carried out in the absence of an esterification catalyst so that the esterification is catalyzed by automobile. By esterification catalyst is meant any catalyst in addition to any of the acids in the acid composition. It is advantageous to perform the esterification by autocatalysis, since in this way there are no other acid components introduced in the reaction mixture. That may render any subsequent neutralization and / or purification step superfluous.
    [0018] The esterification reaction can be carried out in a wide range of conditions such as temperature and pressure. The temperature can be as low as the reflux temperature of the alcohol with which the acid composition is contacted. This would mean that an adequate minimum temperature is in the order of 65 ° C. The pressure can be atmospheric. In order to increase the reaction rate, the temperature and pressure are suitably elevated. Suitably, the acid composition is contacted with an alcohol at a temperature of 100 to 250 ° C, preferably 120 to 180 ° C. The pressure is appropriately selected in such a way that the alcohol is in the liquid phase at the prevailing temperature. This typically means that the minimum pressure is suitably at least the vapor pressure of the alcohol. Maximum pressure is determined by practical considerations. Typically, this implies that the pressure can vary between 0.1 and 10 MPa, preferably from 0.1 to 5 MPa.
    [0019] Due to the different properties of the 2-formyl-furan-5-carboxylic acid ester compounds on the one hand and 2,5-furan-dicarboxylic acid on the other hand, it is possible to separate the 2-formyl-furan ester 5-carboxylate from the esterified product. Suitable separation technologies include dissolution, distillation and crystallization. Thanks to the difference in solubilities, it is possible to wash the esterified product with a washing liquid that provides greater solubility for the 2-formyl-furan-5-carboxylate ester than for the acid mono- and / or di-ester 2, 5- furan-dicarboxylic. A suitable washing liquid can be an alcohol, such as methanol. The use of acids, such as acetic acid, is also feasible. Alcohol and / or acid can also be mixed with water. Such a washing treatment is especially suitable when the esterified product is obtained as a solid product and can be subjected to a washing step. Suitably, the esterified composition is subjected to crystallization and / or distillation.
    [0020] A very suitable separation technique is crystallization. This is very convenient when the esterification is carried out at an elevated temperature and in solution. Upon cooling the reaction mixture in which the contact between the acid composition and the alcohol takes place, the esterified composition tends to crystallize. Due to the difference in solubilities, the crystallized product contains a reduced content of compounds containing the 2-formyl-furan-5-carboxylate group. The crystallized solid material consists mainly of furan-2,5-dicarboxylic acid and the corresponding mono- and diester. Since this represents a very convenient method for separating the purified esterified product obtained in the process according to the invention, the process is preferably conducted in such a way that the esterified composition is allowed to crystallize by cooling to a temperature of -10 to 30 ° Ç.
    [0021] Another suitable crystallization technique is fusion crystallization. Fusion crystallization is considered appropriate when two or more substances of comparable melting points must be separated by a certain degree of cooling. The degree of integrity of such separations may depend on phase equilibrium relationships. When the crystals must be refined to remove clogged substances, the recovered material can leave the process in the molten form. Subsequently, it can be solidified in the form of powdered flakes or granules. Fusion crystallization (sometimes referred to as extractive crystallization) is based on the principle that when an impure molten material is cooled to its freezing point and after the heat is removed, some of the material will solidify. In most cases, the solidified material is pure. Impurities tend to be concentrated in the melt. The purified product is recovered by separating the solidified material from its melting and re-melting. The fusion crystallization can be performed in suspension crystallization equipment and static drop film, as known in the art.
    [0022] Another separation technique that can be properly applied is distillation. Generally, the alcohol will first be removed by distillation; then, the esterified product will be subjected to fractionation. Typically, the 2-formyl-furan-5-carboxylic acid ester, the diester and 2,5-furan-dicarboxylic acid monoester and any remaining 2,5-furan-dicarboxylic acid will be fractionated into one or more columns fractionation. Distillation will generally be carried out under vacuum in order to allow a temperature that is practically low. The person skilled in the art will be able to select the appropriate distillation conditions, including reflux ratio, the use of re-boiling, etc. It has been found that the compounds are not thermally affected if the temperature remains below 200 ° C, preferably below 180 ° C. Suitable distillation conditions therefore comprise a lower column temperature in the range 150 to 200 ° C, preferably 150 to 180 ° C, and a top column temperature in the range 120 to 150 ° C, and a column pressure in the range of 0.1 to 3 kPa.
    The purified esterified product obtained in the process of the present invention has a reduced ester content of 2-formyl-furan-5-carboxylic acid. The amount of the 2-formyl-furan-5-carboxylic acid ester may be dependent on the severity with which the ester has been separated from the esterified product. The separation may suitably have been carried out by means of crystallization and / or distillation. The person skilled in the art will realize that, by repeating the separation steps, for example, the recrystallization of the purified esterified product one or more times, the purity of the resulting product can be further increased. Typically, the purified esterified product has an ester content of 2-formyl-furan-5-carboxylic acid in the range of 0 to 200 ppmp by weight. By repeated distillation and / or recrystallization the amount of 2-formyl-furan-5-carboxylic acid ester can be reduced to values between 0 and 100 ppmp by weight, suitably from 0 to 50 ppmp.
    [0024] In accordance with the present invention, the purified esterified composition is brought into contact with water for hydrolysis or saponification, to obtain a product composition, which comprises 2,5-furan-dicarboxylic acid and a reduced amount of 2-formyl-furan-5-carboxylic acid in comparison to the acid composition, which was used as a starting material in the process of the present invention.
    [0025] By saponification is understood the basic catalyzed hydrolysis of an ester, in which an alcohol and the acid salt are formed. The process usually involves reacting an aqueous alkali metal base, such as NaOH or KOH, with an ester to form an alkali metal salt. The alkali metal base is generally present in at least a stoichiometric amount to allow the formation of the salt.
    [0026] Ester hydrolysis is well known in the art. The reaction is to make contact with the ester in question with water. Suitably, the water has been acidified or made alkaline. Acids and bases tend to catalyze the hydrolysis of the ester. Therefore, the purified esterified product is suitably brought into contact with water in the presence of a hydrolysis catalyst. The catalyst can be selected from a wide range of acidic or alkaline compounds. It is more convenient to apply inorganic acids, such as sulfuric acid, hydrochloric acid, nitric acid and the like. In addition, the use of Lewis acids, such as aluminum trichloride, can be used. Suitable alkaline catalysts include alkali metal hydroxides, such as potassium or sodium hydroxide, but salts of weak organic acids can also be used. Salts of formic acid, acetic acid, propionic acid or butyric acid are suitable examples. The cation can be any metal ion, such as an alkali metal ion or an alkaline earth metal ion. Other metal salts of weak organic acids such as zinc salts can also be used. It is advantageous if the salts are soluble in water. The person skilled in the art will appreciate that the nature of the hydrolysis catalyst is not of critical importance.
    [0027] Although the hydrolysis catalyst may increase the reaction rate of the hydrolysis, it may have the disadvantage that with the introduction of the catalyst a foreign compound is added which can contaminate the resulting acids. Therefore, hydrolysis of the purified esterified composition, i.e., contact of the purified esterified composition with water, is conveniently carried out in the absence of a hydrolysis catalyst. It has been found that the conversion of the esters to the purified esterified composition is also working smoothly, without an additional hydrolysis catalyst. Since the risk of contamination is being avoided by carrying out hydrolysis in the absence of an additional hydrolysis catalyst, such a process is preferred.
    [0028] Hydrolysis conditions are well known in the art. It is conventional to heat the ester in water in the presence or absence of an acid or a base. A suitable temperature range can be 100 to 200 ° C. Since in the present case, it has been found that it is advantageous to carry out the hydrolysis at temperatures above 100 ° C, it is desirable to apply a pressure above 0.1 MPa. Therefore, the composition is preferably esterified purified in contact with water at a temperature of 120 to 180 ° C, and a pressure of 0.5 to 3 MPa.
    [0029] The saponification conditions can be the same as those for hydrolysis. However, the temperature can be even lower, for example, from 60 to 200 ° C. The pressure can also vary from about 0.1 to 3 MPa.
    [0030] The process according to the present invention can be carried out in batch mode. This would allow the qualified person to apply the ideal conditions for each stage separately from any subsequent stage. The conditions include the contact time of the alcohol with the acid composition, the residence time in any crystallizer, and the contact time of the esterified composition purified with water, if such composition is subjected to hydrolysis or saponification. The process according to the invention, however, is preferably conducted as a continuous process. The continuous process can be carried out in a tank reactor with continuous agitation or any other continuous reactor. The contact time of alcohol with the composition of acids can, for example, also be carried out in a reactor operating smoothly.
    [0031] Referring to the Figure, for a filtration unit A of a feed stream 1, which comprises a composition with 2-formyl-furan-5-carboxylic acid and 2,5-furan-dicarboxylic acid, and a diluent , such as acetic acid, is introduced. The filtration unit results in a mother liquor, which comprises the diluent, which is removed via a line 3, and the acid composition which is removed from the filtration unit A via a line 2. The acid composition is introduced into a unit Wash B, in which the acid composition is washed with a washing liquid, such as water, provided via a line 4, to remove impurities, for example, the remaining acetic acid. The washing can be carried out by stirring the acid composition with the washing liquid at an elevated temperature, for example, 80 ° C, for a certain period, for example, between 0.25 and 1.0 hours. Then, the remaining suspension is filtered. It is possible to dry the filter cake, that is, the acid composition, by treating it additionally (not shown).
    [0032] The washing liquid used is discharged via line 5 and the washed acid composition is passed through line 6 to an esterification unit C. The acid composition is brought into contact with an alcohol, for example, methanol, which is introduced via a line 7, optionally in combination with a homogeneous catalyst, for example, sulfuric acid, which is included in alcohol. The contact time of the acid composition with alcohol can be, for example, 10 hours at a pressure of up to 0.5 MPa and a temperature of about 80 ° C. Alternatively, contact is made under atmospheric reflux conditions (ie 0.1 MPa (one bar) and, for example, 65 ° C) for up to 24 hours. The resulting esterified product is removed via line 8 and passed to a crystallization unit D. In unit D, the compounds from line 8 are cooled to a temperature of about 20 ° C whereby the acid mono- and diester 2,5-furanicarboxylic precipitate. The product obtained is then filtered, obtaining a mother liquor, which contains alcohol, 2-formyl-furan-5-carboxylic acid ester and, optionally, some 2,5-furan acid mono- and diester -dicarboxylic, which is removed by means of a line 9, and a purified esterified composition, which mainly comprises the compounds of 2,5-furan-dicarboxylic acid which is recovered through a line 10.
    [0033] By means of this line 10, the purified esterified product can be passed to a hydrolysis unit E. In unit E the purified product is dissolved in an aqueous solution of sodium hydroxide, for example, supplied through a line 11 for unit E, where hydrolysis occurs under reflux conditions. When hydrolysis is complete, for example, after two hours, an aliquot of aqueous hydrochloric acid is added via a line 12 to unit E to neutralize the solution. This results in the precipitation of 2,5-furan-dicarboxylic acid. The precipitate is filtered from the remaining mother liquor and through a line 13, passed to a recrystallization unit F. Water is added to the recrystallization unit F through a line 14 in quantities such that the precipitate from the unit E dissolves completely. This may imply a weight ratio of 2,5-furan-dicarboxylic acid to water of about 1 to 10. The compounds in the recrystallization unit F can be maintained under reflux conditions, that is, a temperature of about 100 °. C at atmospheric pressure. When all solids are dissolved the solution obtained is allowed to cool to a temperature of about 20 ° C, resulting in the precipitation of the purified 2,5-furan-dicarboxylic acid. The precipitate is filtered and recovered through a line 15. The remaining aqueous phase is discharged through a line 16. The recovered purified 2,5-furan-dicarboxylic acid product can be dried before further use.
    [0034] The invention will be further illustrated by means of the following examples. EXAMPLE 1
    [0035] In the following experiments an acid composition was used, which was obtained from the oxidation of 5-methoxymethylfurfural to acetic acid in the presence of a catalyst containing cobalt, manganese and bromide. The acid composition was precipitated, and the solid product was filtered to remove acetic acid. Subsequently, the acid composition was mixed with water, stirred for 30 minutes at 80 ° C, filtered and dried at room temperature under a vacuum of 5 kPa. The acid composition comprised about 1% by weight of 2-formyl-furan-5-carboxylic acid (“FFCA”), and about 3% by weight of 2,5-furan-dicarboxylic acid monomethyl ester (“FDCA -Me ”), some ppm of the FFCA methyl ester (“ FFCA-Me ”), the remainder being 2,5-furan-dicarboxylic acid (“ FDCA ”).
    [0036] One part, by weight, of the acid composition was removed in four parts, by weight, from methanol, and sulfuric acid was added as an esterification catalyst. The mixtures obtained were subjected to different conditions of esterification such as pressure, temperature and the amount of sulfuric acid. After the esterification reaction reached equilibrium, the mixtures were allowed to cool to room temperature and left overnight. A precipitate was crystallized. The precipitate was filtered and dried overnight at 50 ° C and 10 kPa. Their composition was determined by HPLC. The products contained FFCA, FFCA-ME and compounds of 2,5-furan-dicarboxylic acid (FDCA-C), that is, the acid, the monomethyl ester and the dimethyl ester. The amounts of FFCA and FFCA-ME were determined, the balance being FFDA-c.
    [0037] The results of the experiments are shown in Table 1 below.
    [0038] Table 1

    [0039] The results show that esterification and crystallization resulted in a purified esterified product that contained considerably significantly lower amounts of FFCA derivatives than the initial acid product. COMPARATIVE EXPERIMENT 1
    An acid product, obtained in a similar manner to that described in Example 1, was washed with water, and the amount of FFCA present there was determined. The product was subsequently collected in water at 90 ° C and completely dissolved. The weight ratio of the acid product to water was about 1: 150. The solution was allowed to cool to 20 ° C, and a precipitate was formed. The precipitate was filtered off and dried. This precipitate was recrystallized twice more, using this procedure. The yield of the obtained solids, based on the weight of the acid product, was determined. The amount of FFCA in the final precipitate was also determined. The results are shown in Table 1C, below.
    [0041] The recrystallization experiment was repeated with the same acid product as the starting material, but the product was dissolved in acetic acid at 100 ° C. The weight ratio of the acid product to acetic acid was about 1: 150. The solution was allowed to cool to 5 ° C, and a precipitate was formed. The precipitate was filtered off and dried. The yield of the solids obtained after three recrystallizations, based on the weight of the acid product, was determined. The amount of FFCA in the final precipitate was also determined. The results are shown in Table 1C, below.
    [0042] The recrystallization experiment was repeated with the same acid product as the starting material, but the product was dissolved in methanol at 60 ° C. The weight ratio of acid product to methanol was about 1:26. The solution was allowed to cool to -20 ° C, and a precipitate was formed. The precipitate was filtered off and dried. The yield of the solids obtained after three recrystallizations, based on the weight of the acid product, was determined. The amount of FFCA in the final precipitate was also determined. The results are shown in Table C1, below. Table C1

    [0043] These results show that recrystallization has only a modest effect on the removal of FFCA from the acid product, while the product loss is considerable. EXAMPLE 2
    [0044] This experiment shows that the esterification reaction can also be carried out in a continuous way.
    [0045] In a continuous mode, a feed solution of 1% by weight of an FDCA composition containing about 1% by weight of FFCA, based on FDCA, in methanol was passed through a piston flow reactor of 15 ml at different temperatures and different feeding speeds, resulting in different residence times. To ensure steady state conditions, a product sample is not collected until at least three times the volume of the unit has been purged with the supply. The pressure in the reactor was 10 MPa. The feed solution contained a small amount of sulfuric acid as an esterification catalyst. The effect of water was investigated by adding a little water to the feed solution. The product contained the esterified product.
    [0046] Reaction conditions and results are shown in Table 2.Table 2

    [0047] The results show that the esterification can be effectively carried out in a continuous process. The product thereof can subsequently be subjected to separation from any FFCA derivative present therein. EXAMPLE 3
    [0048] In a similar manner to the process of Example 2, a feed solution of 1% by weight of an FDCA acid composition containing 1% by weight of FFCA, based on FDCA, in methanol, was passed in a continuous manner through a 15 ml piston flow reactor at various temperatures and various feed rates, resulting in different residence times. To ensure steady state conditions, a product sample is not collected until at least three times the volume of the unit has been purged with the supply. The product sample is analyzed by liquid chromatography. The pressure in the reactor was 10 MPa and the temperature was maintained at 200 ° C. The reactor was charged with a heterogeneous catalyst, as indicated in Table 3. The product contained the esterified product. The residence time in each experiment was 2 min.
    [0049] The catalysts used were HY zeolite (Cat. No. 1), ultra-stable HY zeolite (Cat. No. 2), very ultra-stable HY zeolite (Cat. No. 3), de-illuminated HY zeolite (Cat. N ° 4) and SAPO-34 (Cat. N ° 5).
    [0050] Reaction conditions and results are shown in Table 3.Table 3

    [0051] These results show that the esterification of a product in a very effective way from FDCA can be achieved by means of a zeolitic catalyst. The esterified product can be subjected to separation by, for example, crystallization or distillation.
    [0052] EXAMPLE 4
    [0053] Similar to the experiments in Example 3, a series of experiments using a halogenated sulfonated polystyrene-divinylbenzene ion exchange resin, marketed under the brand name Amberlyst 70, was carried out.
    [0054] The pressure in the reactor was 10 MPa. The temperature varied between 130 and 160 ° C. The residence time was varied by adjusting the flow rate of the feed solution.
    [0055] The results are shown in Table 4 below.Table 4.

    [0056] These results show that esterification can also be performed effectively using an ion exchange resin as a catalyst. EXAMPLE 5
    [0057] Two acid products, obtained from two separate oxidations of methoxymethylfurfural on a manganese / cobalt / bromide catalyst, were isolated. The amounts of 2-formyl-furan-5-carboxylic acid and furan-2,5-dicarboxylic acid in both products were determined. An acid product was washed with water in an amount of ten times the weight of the acid product. The other acid product was washed with acetic acid, also in an amount of ten times the weight of the acid product.
    [0058] The acid products were subsequently collected in methanol (in a 20% slurry) and in a batch reactor maintained at 160 ° C and 4 MPa, over a period of 6 hours. The amounts of the resulting compounds were determined. The washing agent, the composition of the starting materials and the amounts of the resulting compounds are shown in Table 5, where AcOH = acetic acid and FDCA-DME = FDCA dimethyl ester. The quantities are indicated in molar percentages, based on the starting material and resulting compounds, respectively. Table 5

    [0059] (1) Due to experimental analysis actions, the percentages do not exactly add up to 100%.
    [0060] Experiments show that esterification can be adequately performed without the use of an additional catalyst. EXAMPLE 6
    [0061] In a series of batch experiments the 2,5-furan-dicarboxylic acid dimethyl ester was taken up in water, in the absence or in the presence of a catalyst. The catalyst was sulfuric acid (catalyst A) or zinc acetate (catalyst B). At various temperatures, pressures and for different contact times the mixture obtained was subjected to hydrolysis. Reaction conditions and results are shown in Table 6.Table 6

    [0062] These results show that, if the esterified product has been purified, hydrolysis can be easily achieved to recover the acid from the FDCA, if such a product is desired. EXAMPLE 7
    [0063] An FDCA composition ("Composition A") was taken up in methanol and sulfuric acid in a closed container. The weight ratio of the FDCA composition to methanol was 1: 4. The resulting mixture was subjected to esterification at 80 ° C for about 12 hours, under autogenous pressure. A precipitate was formed, which was filtered. The filter cake was redissolved in methanol at 60 ° C and recrystallized by cooling to 25 ° C. The product thus recrystallized containing mainly FDCA-DME was recovered by filtration and dried ("Composition B").
    [0064] Composition B was mixed with an aqueous sodium hydroxide solution; the equivalent ratio of sodium hydroxide to the FDCA dimethyl ester was 2.41. The diester was saponified to the disodium salt by heating the mixture to about 80 ° C at about atmospheric pressure. The amount of water was sufficient to completely dissolve the disodium salt.
    [0065] The disodium salt was neutralized by the addition of a small excess of sulfuric acid by means of precipitated FDCA released. The precipitated FDCA was recovered by filtration, and washed with water. The washed FDCA product was removed from the filter and placed in water at 150 ° C and 0.5 MPa to completely dissolve the FDCA product. The obtained solution was cooled to room temperature, while recrystallized FDCA precipitated. This recrystallized FDCA product was obtained by filtration and subsequently dried under vacuum at 70 ° C ("Composition C"). The yield of Composition C was about 65 mole%, based on composition A.
    [0066] The components of Compositions A, B and C are shown in Table 7.Table 7


    The results show that the esterification sequence of an FDCA product with subsequent recrystallization and saponification leads to a satisfactory yield of the pure FDCA product.
    权利要求:
    Claims (15)
    [0001]
    1. Process for the purification of a composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furanedicarboxylic acid characterized by comprising: contacting the acid composition with an alcohol to obtain an esterified composition; separating the 2-formyl-furan-5-carboxylic acid ester from the esterified composition to obtain an esterified purified product; and contacting the esterified composition purified with water for saponification or hydrolysis, to obtain a product composition, comprising 2.5 furanedicarboxylic acid and a reduced amount of 2-formyl-furan-5-carboxylic acid, wherein the composition of acid is contacted with an alcohol in the presence of an esterification catalyst, where the esterification catalyst is an acid catalyst; or in which acid composition to be contacted with an alcohol in the absence of an esterification catalyst.
    [0002]
    Process according to claim 1, characterized in that the acid composition originates from the oxidation of 5-acoxymethylfurfural, 5-hydroxymethylfurfural or a mixture thereof.
    [0003]
    Process according to claim 1 or claim 2, characterized in that the acid composition comprises from 0.1 to 4.0% by weight of 2-formyl-furan-5 carboxylic acid, based on the weight of the composition of acids.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that the acid composition is contacted with a mono-alcohol.
    [0005]
    Process according to claim 4, characterized in that the mono-alcohol is an alkanol having from 1 to 8 carbon atoms, preferably ethanol or methanol.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the alcohol is present in a molar excess of the acid composition, the molar ratio between the alcohol and the acid composition is preferably 5: 1 to 100: 1.
    [0007]
    Process according to claim 1, characterized in that the acid catalyst is selected from the group consisting of inorganic mineral acids, zeolites, ion exchange resins and mixtures thereof.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that the acid composition is contacted with an alcohol at a temperature of 60 to 250 ° C, preferably 70 to 200 ° C, and a pressure of 0, 1 MPa to 10 MPa, preferably 0.1 MPa to 7 MPa.
    [0009]
    Process according to any one of claims 1 to 8, characterized in that the esterified composition is subjected to crystallization and / or distillation.
    [0010]
    Process according to claim 9, characterized in that the esterified composition is allowed to crystallize by cooling to a temperature of -30 ° C to 40 ° C.
    [0011]
    Process according to claim 10, characterized in that the purified esterified composition is allowed to crystallize by cooling to a temperature of -10 ° C to 30 ° C.
    [0012]
    Process according to any one of claims 1 to 11, characterized in that the purified esterified composition is brought into contact with water in the presence of a hydrolysis catalyst.
    [0013]
    Process according to any one of claims 1 to 11, characterized in that the purified esterified composition is brought into contact with water, in the absence of a hydrolysis catalyst.
    [0014]
    Process according to any one of claims 1 to 13, characterized in that the purified esterified composition is brought into contact with water at a temperature of 120 to 180 ° C and a pressure of 0.5 MPa to 3 MPa.
    [0015]
    Process according to any one of claims 1 to 14, characterized in that it is conducted as a continuous process.
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    法律状态:
    2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    NL2011362|2013-08-30|
    NL2011362|2013-08-30|
    PCT/NL2014/050589|WO2015030590A1|2013-08-30|2014-08-29|Process for purifying an acid composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furandicarboxylic acid|
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