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    METHOD OF PRODUCTION OF ONE OR MORE FURANODICARBOXYLATES, METHOD OF SYNTHESIS OF A FURAN DIESTER AND METHOD OF PROCESSING FURANODICARBOXYLIC ACID The present invention describes a method for making a furanodicarboxylate by reacting a 2,5-furanodicar acid (or 2,5-furanicaric acid) or mixture of alcohols in an atmosphere with a predominance of CO2, without the presence of any other acid catalyst. The reaction is carried out under conditions that correspond to supercritical, critical or quasi-critical temperatures and pressures for alcohol and / or CO2 gas species.
    公开号:BR112015014183B1
    申请号:R112015014183-8
    申请日:2013-12-09
    公开日:2021-03-16
    发明作者:Kenneth Stensrud；Padmesh Venkitasubramanian
    申请人:Archer Daniels Midland Company；
    IPC主号:
    专利说明:

    [001] This application claims the priority benefit of North American Provisional Application No. 61 / 739,761, filed on December 20, 2012, the contents of which are incorporated into the present invention. FIELD OF THE INVENTION
    [002] The present invention relates to an esterification process. In particular, the invention relates to the conversion of furanodicarboxylic acid to esters with an alcohol and CO2. BACKGROUND OF THE INVENTION
    [003] Biomass contains carbohydrates or sugars (ie hexoses and pentoses) that can be converted into value-added products. The production of products derived from biomass for non-food uses is a growing industry. Biofuels are an example of an application with growing interest. Another application of interest is the use of biomass as a raw material for the synthesis of various other chemicals from renewable hydrocarbon sources.
    [004] In recent years, a growing effort has been devoted to finding ways to use biomass as a raw material for the production of organic chemicals, due to its abundance, capacity for renewal and worldwide distribution. When considering possible downstream chemical processing technologies, converting sugars into value-added chemicals is very important. Recently, the production of furan derivatives from sugars has become fascinating in chemical and catalysis studies because it assists one of the main routes to achieve a sustainable energy supply and the production of chemicals. As illustrated in figure 1, which shows a schematic representation of a process for converting biomass into useful final products, furan intermediates: 5-hydroxymethylfurfural (5-HMF), 2,5-furanedicarboxylic acid (2,5-FDCA) and 2,5-dimethylfuran (2,5-DMF) were called "sleeping giants" of renewable intermediate chemicals. These intermediates are green building blocks for a variety of materials, chemicals and fuels. As building blocks that have been extensively studied and have enormous potential for use in the production of green plastics and chemicals, the US Department of Energy has recognized furan intermediates as one of the most important green building blocks with high potential. 5-HMF is a hexose dehydration product and a potential substitute for petroleum-based building blocks of various polymers. 2,5-FDCA is derived from the oxidative dehydration of hexoses, and is considered to be one of the 12 main compounds made from sugar, in an added-value chemical. 2,5-DMF is produced through the hydrogenation of HMF, is less volatile and has 40% more energy density than ethanol. (See, for general reference, T. Werpy, G. Petersen, TOP VALUE ADDED CHEMICALS FROM BIOMASS: Vol. I - Results of Screening for Potential Candidates from Sugars and Synthesis Gas, August 2004. (Available electronically at http: / /www.osti.gov/bridge))
    [005] Despite the fact that there is a lot of interest to develop better ways to make building blocks for the emerging market for green materials and renewable energies, until recently, furanics have not been commercialized because the large-scale production of furan intermediaries has not been shown profitable. Several different processes have advanced towards the catalytic conversion of sugar into furan-derived chemicals. (See, for a general reference, X. Tong et al., “Biomass into Chemicals: Conversion of Sugars to Furan Derivatives by Catalytic Processes,” APPLIED CATALYSIS A: GENERAL 385 (2010) 1-13.)
    [006] Among furan intermediates, furanedicarboxylic acid (FDCA) is a commercially valuable material that can be used as a precursor to various plasticizers, or a substitute for purified terephthalic acid (PTA) or other value-added products. Over the years, chemical manufacturers have been looking for a simpler way to produce and handle FDCA, due to the known problems associated with working with FDCA, such as its poor solubility in common organic solvents, and being soluble in solvents with a high boiling point, such as DMSO. Another problem that arises when using FDCA in the polymerization of molten material is the tendency of an FDCA molecule to decompose at temperatures above about 180 ° C in furoic acid, producing a product of poor quality. All of these challenges can be solved by derivating the FDCA into an ester. Current acid-catalyzed esterification, however, usually requires about 20 hours or more to produce diester molecules. This process is very time consuming and is not profitable for mass production of large volumes of esters. In addition, the purification of the resulting esters requires base washing to remove the residual acid catalyst which can affect the quality of the FDCA esters in downstream processing. Other alternatives for the esterification of the FDCA require its activation as a diacyl chloride, which makes the process unsustainable or not economical.
    [007] The preparation of an acyl chloride (that is, a COCl portion) requires treatment of an acid with thionyl chloride in stoichiometric amount and then its conversion into an ester. Safety concerns arise when using thionyl chloride on a large scale, as the by-products of the acylation reaction are HCl and SO2, and HCl for esterification. SO2 and HCl are captured on a weak basis and then discarded as waste. In addition, the conversion of FDCA to the corresponding furan-2,5-dicarbonyl dichloride could generate a mixture of by-products after esterification with alcohols, due to unstable intermediates. In addition, acyl chloride is sensitive to water and would require special storage conditions.
    [008] WO 2011/023590 A1, by Grass et al., Describes, in part, methods for the production of mixtures of 2,5-furanedicarboxylic acid ester derivatives (FDCA) and the use of the derived material (furanedicarboxylate) isononyl) as a plasticizer. In particular, the disclosure relates to a method of using an acid, or a metal catalyst, to prepare esters of FDCA with isomeric C-9 alcohols in particular mixtures of linear and branched nonanois (e.g., furan-2 , 5- isononyl dicarboxylate). The method largely follows a conventional esterification process. According to Grass et al, an ester can be prepared using FDCA or a reactive derivative, such as the corresponding dichloride with a strong mineral acid. In addition, the method unfortunately has certain disadvantages, such as: FDCA at temperatures above 190 ° C tends to eliminate CO2 and form monocarboxylic acids (for example, furoic acid) that cannot be converted into the desired product, and to avoid color formation and decomposition of FDCA at reaction temperatures, it may be necessary to use dimethyl furanedicarboxylate as a precursor.
    [009] In view of these problems of conversion or synthesis of esters of the FDCA, according to current techniques, there is a need for a simple, clean and economical process to convert carbohydrates into building blocks of materials and fuels for commercial use. SUMMARY OF THE INVENTION
    [010] The present invention relates to a method of producing one or more furanodicarboxylates. The method involves, in a first modality: reacting 2,5-furanedicarboxylic acid (FDCA) with at least one alcohol or a mixture of different alcohols in a CO2 atmosphere in the substantial absence of any other extrinsic catalyst, according to the following reaction:
    to produce a mixture of esters, where the group R is at least one saturated, unsaturated, cyclic or aromatic group. CO2 functions as an acid catalyst autogenerated in situ and regenerates again in a reagent during the synthesis of the ester. The esterification reaction of the FDCA with an alcohol in CO2 is carried out under operating conditions that correspond to supercritical, critical or quasi-critical reaction temperatures or pressures for at least the type of alcohol or CO2. In certain embodiments, the synthesis is carried out at a reaction temperature between about 150 ° C and 250 ° C, at a reaction pressure of about 400 psi (2.76 MPa) to about 3,000 psi (20.68 MPa). The method can also comprise the reaction of the ester product in a second esterification reaction to regenerate the alcohol reagent and recycle it back to react with more FDCA.
    [011] In another aspect, the disclosure relates to a method of processing furanodicarboxylic acid (FDCA). The method involves: reacting FDCA with a first alcohol in a CO2 atmosphere in the substantial absence of any other catalyst to produce a first ester mixture; reacting said first ester mixture with a second alcohol in a transesterification reaction to produce a second ester mixture. You can regenerate the first alcohol and recycle it back to react with more FDCA. The method can be adapted for any batch or continuous processing operations.
    [012] Additional features and advantages of the present methods will be disclosed in the detailed description below. It should be understood that both the above summary and the detailed description below, as well as the examples, are merely representative of the invention and are intended to provide an overview for understanding the invention, as claimed. BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a schematic overview of the general steps involved in refining biomass in furan intermediates, which can be further processed along value chains for polymer molecules used in materials or fuels. Figure 2 is a general illustration of an esterification reaction of the FDCA and the subsequent transesterification reaction of the ester products, according to an embodiment of the present invention. Figure 3 is a schematic representation of a continuous esterification and recovery process, according to an embodiment of the present invention. Figure 4 shows an esterification reaction of the FDCA with methanol according to an example of the present method. DETAILED DESCRIPTION OF THE INVENTION Section I - Description
    [013] The present invention involves the verification, in a simple and effective way, of production of esters from furanodicarboxylic acid (FDCA). One aspect of the method of the invention uses carbon dioxide (CO2) as an acid catalyst in esterification reactions, without the presence of any other acid catalyst. The present method is an ecological way of producing mono- and / or dialkylfuranedicarboxylates. The method involves a liquid reaction system.
    [014] The method allows the use of the resulting mono- or dialkylfuranedicarboxylates as a precursor to compounds useful for polymeric, plasticizing or combustible materials, in the downstream routes, as shown in figure 1. For example, dimethylfuranedicarboxylates can be precursors for plasticizers such as terephthalic acid or isononyl furanedicarboxylate, or for various polymers, such as polyethylene furanedicarboxylate or FDCA esters of isosorbide, for polymers with high glass transition temperature (Tg). Monomethyl furanedicarboxylates can be a precursor to higher alcoholic alkyl esters that can be used as cationic surfactants, chelators and corrosion inhibitors. Alternatively, some monoalkyl esters made by the present invention can be used directly as fungicides in wood preservation.
    [015] An advantageous feature of the method of the invention is that the activation of free carboxylic acid, such as an acyl halide (eg fluoride, chloride, bromide) or by the use of strong mineral acids, is unnecessary, unlike some other techniques . Acyl halides are inconvenient to use because these species are inherently reactive, have problems with stability and waste treatment, and their syntheses can be complicated and expensive. An acyl chloride is a more reactive species than FDCA.
    [016] Conventionally, the mechanism for the formation of an ester from an acid and an alcohol is the reverse of the steps for an acid-catalyzed hydrolysis of an ester, and the reaction can occur in any direction, depending on the conditions used. In a typical esterification process, a carboxylic acid does not react with an alcohol, unless a strong acid is used as a catalyst. The catalyst is usually concentrated sulfuric acid or hydrogen chloride. Protonation makes the carbonyl group more electrophilic and allows it to react with alcohol, which is a weak nucleophile.
    [017] In general terms, the present esterification process involves a reaction of FDCA with an alcohol in a CO2 atmosphere in the substantial absence of any other acid catalyst to produce esters. As used in the present invention, the term "substantial absence" refers to a condition in which an acid catalyst is, to a large extent or completely, absent, or is present in trace or minimal proportions, less than the amounts of catalytic efficacy. In other words, no other acid catalyst is present, or is present at a level below 10%, 5%, 3%, or 1% w / w in relation to the carboxylic acid in the reaction. The esterification reaction is carried out in solution, under conditions that are supercritical, critical or almost critical pressures and / or temperatures for alcohol and / or CO2. Under such conditions, we believe that CO2 is self-generated or works in situ, as an acid catalyst, and subsequently regenerates in situ again in a reagent. Carbonic acid is much weaker than the usual strong acids. However, a reactive intermediate (monoalkylcarbonic acid) is being made in situ in large quantities sufficient to conduct esterification and carry out ester production. The observed trend towards greater ester conversion at higher temperatures presents a relatively high activation energy for this process.
    [018] Figure 2A is an equation that represents certain modalities of the present esterification method. The FDCA reacts with an alcohol (ROH) in a CO2 atmosphere, at an elevated temperature, such as between 180 ° C and 240 ° C, and under pressure, from 950 psi (6.55 MPa) to 3000 psi (20.68 MPa) ) (scale). Typically, the resulting ester products can be monoesters or diesters, or a mixture of both. The reaction can be controlled to conduct esterification towards the formation of monoesters or diesters, or a certain mixture of mono and diesters. For example, it is possible to select a reaction temperature and pressure that preferentially direct the reaction towards the formation of diester molecules. It is possible to separate the monoalkyl esters from the dialkyl esters by means of crystallization, distillation, ion exchange resin or acid-base extraction techniques.
    [019] Figures 2B and 2C, respectively, show the subsequent transesterification of monoalkyl and dialkyl esters by means of base catalyzed or enzymatic reactions, such as by means of an enzymatic reaction with lipase. Lipase can be derived from a variety of microbes, such as Candida antartica, which is commercially available under the trade name Novozym ™ 435.
    [020] Figure 3 illustrates another aspect of the present invention that relates to a method of processing the FDCA. The method involves: reacting the FDCA 1 with a first alcohol (R-OH1) in an atmosphere of CO2 2 in the substantial absence of any other catalyst to produce a first mixture of ester 3; reacting the first ester mixture with a second alcohol (R-OH2) in a transesterification reaction 4 to produce a second ester mixture 5. The monoalkyl and dialkyl esters produced in the reaction with the first alcohol species (for example, methanol) they are transesterified with the second type of alcohol (for example, ethanol). The first mixture of esters can include monoesters or diesters, such as, according to certain modalities, any of the following species: methylfuranedicarboxylate, ethylfuranedicarboxylate, propylfuranedicarboxylate, etc.
    [021] Transesterification reaction 4 can be carried out at a lower temperature than the first esterification reaction, for example, from about 80 ° C to about 90 ° C, and under reduced pressure, at the boiling point of first kind of alcohol. That is, negative pressure, a partial vacuum, can be applied to reduce the pressure in the reactor. The boiling point of the second alcohol must be at least 10 ° C to 20 ° C (for example, 12 ° C, 15 ° C) greater than the boiling point of the first alcohol. This will help to release and separate the first and second alcohol species 6. Alcohol, such as methanol, released during the condensation reaction of monoalkyl or dialkyl esters, can be recycled 7 back to the synthesis of more mono- and / or dialkylfuranedicarboxylate, as shown in figure 3. This feature allows the present process to be carried out in continuous or batch mode. The monoesters and diesters in the second mixture of esters 5 can then be separated from each other.
    [022] In the present esterification process, both the catalyst (CO2) and the esterification reagent (alcohol) are present in great excess in relation to the amount of organic acid. CO2 must be in the gaseous phase during the reaction phase, regardless of its origin (for example, gas tank or dry ice), since the reaction is carried out under high temperatures. The addition of solid CO2 is strategic in the case of the use of pressurized reactors, as it allows the slow sublimation of the formation of gaseous CO2, as the reaction apparatus is assembled. This can minimize the loss of CO2. In a CO2 atmosphere (i.e., containing CO2), the concentration of CO2 in the reaction atmosphere can be at least 10% or 15% by volume, favorably about 25% or 30%, and preferably greater than 50%. To achieve a reaction with better results, the CO2 concentration must be maximized. Desirable concentrations of CO2 are from about 75% or 80% to about 99.9% by volume, typically between about 85% and about 98%. The presence of nitrogen gas (N2) or air is allowed in the reactor, but preferably, the concentration of gases other than CO2 is maintained in a lower percentage (<50%) or in a minimum amount.
    [023] Any liquid alcohol with a group R equal to C1-C20 can serve as the solvent reagent or the first type of alcohol. The group R can be at least one saturated, unsaturated, cyclic or aromatic species. A mixture of different types of alcohols (for example, C1-C12) can also be used in the reaction, but will produce a corresponding mixture of different esters, depending on the particular R group. Certain species of lower alcohols with C1-C6 alkyl groups are preferred as the reagent in the first CO2 esterification, in view of their common availability, low cost and mechanistic simplicity in the esterification reaction. In addition, alcohols such as methanol, ethanol, propanol or butanol are preferred due to parameters such as their relatively simple structures and the fact that reactions are more easily controlled in relation to the supercritical, critical or quasi-critical pressures and temperatures of these species. alcohol. Alternatively, in some embodiments, the alcohol may also be a C2-C6 diol. Esterification with a diol can generate low molecular weight monomers or oligomers that can be readily polymerized.
    [024] When processing ester products from CO2 esterification in the second or subsequent transesterification reaction, any type of liquid alcohol with at least one RC2 group formula can be used as the second alcohol reagent. The group R can be at least one saturated, unsaturated, cyclic or aromatic species. Depending on the desired ester compounds, higher alcohol species, with longer carbon chains, such as C3-C10 or C12-C18 alkyl groups, may be preferred. Typically, however, alcohols with R groups of C2-C6 or C8 are more convenient and easier to use as reagents. Alcohol can also be a C2-C6 diol.
    [025] In general, the esterification process is carried out at a reaction temperature between about 160 ° C and about 250 ° C, at a reaction pressure between 400 psi (2.76 MPa) or 500 psi (3.45 MPa ) and 2,500 psi (17.24 MPa) or 2,800 psi (19.31 MPa) (scale), for a period of at least 4 hours or up to about 12 hours. Particular reaction times may vary, but are generally shorter, such as between about 5 or 6 hours and about 8 or 10 hours. Typically, the reaction temperature can range from about 170 ° C or 190 ° C to about 230 ° C or 245 ° C (for example, 175 ° C, 187 ° C, 195 ° C or 215 ° C) , and the reaction pressure is between about 900 psi (6.21 MPa) or 950 psi (6.55 MPa), and about 2,200 psi (15.17 MPa) or 2,400 psi (16.55 MPa) (for example , 960 psi (6.62 MPa), 980 psi (6.76 MPa), 1020 psi (7.03 MPa) or 1050 psi (7.24 MPa). Alternatively, the temperature can be in the range of about 180 ° C to about 240 ° C (for example, from about 185 ° C or 200 ° C to about 220 ° C or 235 ° C), and the reaction pressure is between about 1,000 psi (6.89 MPa) and 2,350 psi (16.20 MPa) (e.g., 1,100 psi (7.58 MPa), 1,250 psi (8.62 MPa), 1,500 psi (10.34 MPa), 1,700 psi (11.72 MPa), 1,820 psi (12.55 MPa) or 1,900 psi (13.10 MPa) Other reaction temperatures may be within a range, for example, of about 160 ° C or 175 ° C to about 210 ° C or 225 ° C , and other reaction pressures may be within a range, for example, of about 1,200 psi (8.27 MPa) or 1,630 psi (11.24 MPa) to about 1,800 psi (12.41 MPa) or 2,100 psi (14.48 MPa).
    [026] These reaction temperatures and pressures correspond to supercritical, critical or quasi-critical conditions for alcohol / alcohols or CO2. Table 1 lists, for purposes of illustration, the critical parameters for some common solvents (ie, methanol, ethanol, 1-propanol, 1-butanol, water and CO2).

    [027] Under conditions above the critical point (ie, temperature and / or critical pressure), the fluid exists in a supercritical phase in which it has properties that are between those of a liquid and a gas. More specifically, supercritical fluids have a liquid-like density and gas-like transport properties (i.e., diffusivity and viscosity). This can be seen in Table 2, in which the typical values of these properties are compared between the three types of fluids - conventional liquids, supercritical fluids and gases.

    [028] Likewise, "quasi-critical" refers to conditions in which the temperature or pressure of at least the species of alcohol or CO2 gas is below, but within 150K (for example, between 50 and 100K) or 220 psi (1.52 MPa) (for example, between 30 psi (0.21 MPa) and 150 psi (1.03 MPa) of their respective critical points. critical, critical or supercritical, the solubility of the reagents increases, promoting the esterification reaction. In other words, CO2 gas, and acid and alcohol species are more capable of interacting under quasi-critical, critical or supercritical conditions than under conditions The reaction does not require that the species of alcohol and CO2 are in almost critical, critical or supercritical conditions, on the contrary, the reaction is functional as long as one of the species satisfies this condition.
    [029] If the present esterification reactions occur at higher temperatures and higher pressures, up to about 250 ° C or 3000 psi (20.68 MPa), respectively, and for reaction times of at least 4 hours, significant quantities of the ester product are produced at relatively higher levels of selectivity and purity. At lower reaction temperatures (<190 ° C), the formation of monoester molecules is more prevalent, while reactions at temperatures> 190 ° C or 195 ° C will preferentially convert carboxylic acids to diesters. When selecting a temperature over a larger range, from about 190 ° C or 195 ° C or 200 ° C to about 245 ° C or 250 ° C, it is preferable to conduct the reaction up to a higher diester conversion rate. The esterification can produce a minimum of about 50%, desirably at least 65% or 70% of an organic acid diester. Reactions that are carried out at or near supercritical operating conditions appear to provide better results. When working at or near critical conditions of about 250 ° C for methanol and about 31 ° C / 1000 psi (6.89 MPa) for CO2, conversion rates of at least 90% or more, typically about 93% or 95%, for example, up to 98% or 99% conversion.
    [030] Using an excess of the alcohol solvent in excess of the carboxylic acid gas, a very pure esterification can be obtained. The present synthesis process produces very clean ester products (for example, with about 70% to 72% of initial purity) without generating significant amounts of secondary products, such as low molecular weight acids - acetic acid or formic acid - rearrangements molecular or cyclic products, which could normally be seen in standard acid catalyzed esterification under high temperatures. Esters can be refined to reach about 90% to 99% purity. Purification can be carried out, for example, by means of crystallization, chromatography or distillation.
    [031] As noted earlier, conventional acid-catalyzed esterification typically requires about 20 hours to generate diester molecules. Further purification of the resulting esters requires base washing to remove the residual acid catalyst which can affect the quality of the FDCA esters in downstream processing. Other alternatives for the esterification of the FDCA require its activation as a diacyl chloride, which makes the process unsustainable. In contrast, the advantages of this approach allow manufacturers to produce diesters in relatively short reaction periods (eg <6 or 7 hours) and with higher yields (eg ~ 55 to 90%) without using strong mineral acids , thus being able to eliminate the associated purification steps.
    [032] In addition, unlike other approaches, the process described in the present invention is a more environmentally friendly way of producing esters. As it is believed that carbon dioxide can self-generate an acid catalyst in situ in the presence of alcohol during the esterification reaction, the present process does not require the use or addition of another species of acid catalyst. In other words, reaction kinetics with CO2 alone can drive esterification in the substantial absence of any other acid catalyst. Therefore, the process does not require the activation of the FDCA as acyl chloride, which is another savings in terms of costs and process conversion. Section II - Examples
    [033] The following examples demonstrate the production of furanodicarboxylate esters and an alcohol under a CO2 atmosphere, without any other acid catalyst, carried out under supercritical, critical or quasi-critical conditions for alcohol and / or CO2.
    [034] Table 1 shows some esterification reactions according to the modalities of the present method, under the reaction conditions listed therein. The FDCA reacts with an alcohol and CO2: methanol is used in examples 1 to 3, ethanol in examples 4 to 6, propanol in examples 7 and 8 and 1-butanol in examples 9 and 10. In general, all reactions showed good yields of the corresponding diester. A higher temperature, a higher pressure and a longer reaction time tend to generate a better performance. Species of shorter or shorter alcohols tend to produce a better yield of the corresponding diester than longer or longer alcoholic solvents.


    [035] Figure 4 is an equation for an esterification of the FDCA with methanol assisted by CO2, as example 1 in table 1. The yield of diester was good in about 45% to 90%, indicating that this new protocol is viable for esterification and can lead to more practical manipulation of the FDCA. Table 1 suggests that, together with dimethyl esters, esterification reactions can be optimized to convert furanedicarboxylic acid into its corresponding diester species of higher alcohols (eg, diethyl, dipropyl, dibutyl esters) with relatively high yield (eg , ~ 60-90%), according to the present method.
    [036] The following examples are generated by the reaction with methanol and ethanol used as a solvent, but other alcohols, such as propanol or butanol, also react in a similar way. 1. Synthesis of the mixture of monomethyl furanedicarboxylate and dimethyl furanedicarboxylate: Example 1.
    [037] A 1L autoclave reactor containing 2,5-furanedicarboxylic acid (5 g) and methanol (300 mL) was purged with N2 gas and then initially pressurized with 400 psig (2.76 MPa) CO2 gas . The reaction mixture was heated to 180 ° C and maintained at that temperature for 5 hours. During that time, the reaction pressure inside the reactor increased from 400 psig (2.76 MPa) to 1600 psig (11.03 MPa). After 5 hours at 180 ° C, the reactor vessel was cooled to room temperature and depressurized. The reactor contents were filtered, and dried overnight under vacuum. The samples of the solid material and the solution were quantitatively analyzed for conversion, using gas chromatography coupled with mass spectrometry (GC / MS). The reaction mixture contained dimethyl ester (~ 23.4% by weight), monomethyl ester (~ 50.6% by weight) and unreacted FDCA (~ 32.8% by weight). Example 2.
    [038] In a 12 mL SS316 reactor, 0.5 g of FDCA and 5 mL of methanol were placed, along with some dry ice (CO2) crystals, which sublimate. The reactor was closed and heated to 180 ° C for 4 hours in a sand bath. The internal reaction pressure was between about 1300 psig (8.96 MPa) and 1700 psig (11.72 MPa). After 4 hours, the reactor was cooled. The contents were filtered, dried overnight and analyzed for dimethyl ester and other reaction intermediates. The reaction mixture included dimethyl ester (~ 49.8% by weight), monomethyl ester (~ 35.5% by weight) and unreacted FDCA (~ 14.8% by weight). In a second reaction repeated under the same parameters, the reaction mixture contained dimethyl ester (~ 51.7% by weight), monomethyl ester (~ 31.9% by weight) and unreacted FDCA (~ 12.4% by weight) ). Example 3.
    [039] As in Example 2, 0.5 g of FDCA and 5 ml of methanol were placed in a 12 ml SS316 reactor. The reactor was closed, purged with N2 gas and then initially pressurized to 400 psig with CO2 and heated to 190 ° C for 4 hours in a sand bath. The internal reaction pressure was between about 1400 psig (9.65 MPa) and 1800 psig (12.41 MPa). After 4 hours, the reactor was cooled. The content was filtered, dried and analyzed for dimethyl ester and other reaction intermediates. The reaction mixture included dimethyl ester (~ 62.3% by weight), monomethyl ester (~ 31.6% by weight), and unreacted FDCA (~ 6.7% by weight). Example 4.
    [040] 0.5 g of FDCA and 5 ml of methanol were placed in a 12 mL SS316 reactor. Some dry ice crystals were added to the reactor, which was closed and heated to 200 ° C for 4 hours in a sand bath. The internal reaction pressure was between about 1600 psig (11.03 MPa) and 1900 psig (13.10 MPa). After 2 hours, the reactor was cooled. The content was filtered, dried overnight and analyzed using GS / MC. The reaction mixture included dimethyl ester (~ 70.3% by weight), monomethyl ester (~ 29.1% by weight) and unreacted FDCA (~ 2.4% by weight). Example 5.
    [041] In a repeat of Example 4, 0.5 g of FDCA and 5 ml of methanol were placed in a 12 ml SS316 reactor. Some dry ice crystals were added to the reactor, which was heated to 200 ° C for 4 hours in a sand bath. The internal reaction pressure was between about 1500 psig (10.34 MPa) and 2000 psig (13.79 MPa). After 4 hours, the reactor was cooled. The contents were filtered, dried overnight and analyzed. The reaction mixture contained dimethyl ester (~ 81.3% by weight), monomethyl ester (~ 24.56% by weight) and unreacted FDCA (~ 0.92% by weight). Example 6.
    [042] 0.5 g of FDCA and 5 ml of methanol were placed in a 12 mL SS316 reactor. Some dry ice crystals were added to the reactor, which was closed and heated to 200 ° C for 6 hours in a sand bath. The internal reaction pressure was between about 1200 psig (8.27 MPa) and 1800 psig (12.41 MPa). After 6 hours, the reactor was cooled. The contents were filtered, dried overnight and analyzed. The reaction mixture included dimethyl ester (~ 89.2% by weight), monomethyl ester (~ 10.3% by weight), and unreacted FDCA (~ 0.67% by weight). 2. Synthesis of monoethyl furanedicarboxylate and diethyl furanedicarboxylate: Example 7.
    [043] In a 1 liter (L) autoclave reactor, 5 g of 2,5-furanedicarboxylic acid and 300 mL of ethanol were placed and the reactor was initially pressurized with 400 psig (2.76 MPa) of CO2. The reaction mixture was heated to about 180 ° C and maintained at that temperature for 4 hours. During that time, the pressure inside the reactor increased from 400 psig (2.76 MPa) to about 1600 psig (11.03 MPa). After 4 hours at 180 ° C, the reactor was cooled to room temperature and depressurized. The reactor contents were filtered, dried overnight under vacuum and analyzed for conversion using GC / MS. The reaction mixture contained diethyl ester (~ 22.7% by weight), monoethyl ester (~ 51.6% by weight) and unreacted FDCA (~ 25.8% by weight). Example 8.
    [044] 0.5 g of FDCA and 5 ml of ethanol were placed in a 12 mL stainless steel reactor, along with several medium-sized dry ice crystals. The reactor was closed and heated to 190 ° C for 5 hours in a sand bath. The internal reaction pressure was between about 1100 psig (7.58 MPa) and 1700 psig (11.72 MPa). After 5 hours, the reactor was cooled. The contents were dried under vacuum and analyzed using GC / MS for dimethyl FDCA and other intermediates. The reaction mixture contained diethyl ester (~ 54.8% by weight), monoethyl ester (~ 27.5% by weight), and unreacted FDCA (~ 17.8% by weight). In a second reaction repeated under the same parameters, the reaction mixture contained dimethyl ester (~ 55.6% by weight), monoethyl ester (~ 29.2% by weight) and unreacted FDCA (~ 15.3% by weight) ). Example 9.
    [045] A 12 mL stainless steel reactor containing 0.5 g of FDCA, 5 mL of ethanol and an excess of dry ice crystals was used. The reactor was closed and heated to 200 ° C for 4 hours in a sand bath. The internal reaction pressure was between about 1400 psig (9.65 MPa) and 1800 psig (12.41 MPa). After 4 hours, the reactor was cooled, the reaction mixture was extracted, dried overnight and analyzed using GS / MS. The reaction mixture contained diethyl ester (~ 63.9%), monomethyl ester (~ 31.7%) and unreacted FDCA (~ 4.6%). In a second reaction repeated under the same parameters, the reaction mixture contained diethyl ester (~ 69.3%), monoethyl ester (~ 28.3%) and unreacted FDCA (~ 2.5%). Example 10.
    [046] As in Example 9, 0.5 g of FDCA, 5 ml of ethanol and an excess of dry ice crystals were placed in a 12 ml stainless steel reactor. The reactor was closed and heated to 210 ° C for 5 hours in a sand bath. The internal reaction pressure was between about 1600 psig (11.03 MPa) and 2200 psig (15.17 MPa). After 5 hours, the reactor was cooled. The contents were dried and analyzed as described above. The reaction mixture contained diethyl ester (~ 82.1%), monoethyl ester (~ 15.6%) and unreacted FDCA (~ 2.4%). 3. Purification of dimethyl furanedicarboxylate:
    [047] To purify the ester, the crude reaction mixture was resuspended in ethyl acetate and washed with sodium bicarbonate. The unreacted FDCA and monoethyl esters were washed away. The ethyl acetate layer was concentrated to produce the dimethyl ester. Likewise, the unreacted FDCA and monoethyl esters were washed away, and the ethyl acetate layer was concentrated to produce the diethyl ester. Other cost-effective separation and purification techniques may include crystallization.
    [048] The present invention has been described in general lines and in detail, by way of examples. The person skilled in the art understands that the invention is not necessarily limited to the specifically disclosed modalities, but that modifications and variations can be made without departing from the scope of the invention, as defined by the following claims or their equivalents, including other equivalent components currently known , or to be developed, which can be used within the scope of the present invention. Therefore, unless the changes cause a departure from the scope of the invention, the changes should be interpreted as being included in the present invention.
    权利要求:
    Claims (14)
    [0001]
    1. METHOD OF PRODUCTION OF ONE OR MORE FURANODICARBOXYLATES, characterized by the method comprising: reacting furanodicarboxylic acid (FDCA) with at least one alcohol or a mixture of different alcohols in a CO2 atmosphere, according to the following reaction:
    [0002]
    2. METHOD according to claim 1, characterized in that said synthesis is carried out at a temperature between 150 ° C and 250 ° C, at a pressure of 2758 KPa (400 psi) up to 20684 KPa (3000 psi).
    [0003]
    3. METHOD, according to claim 1, characterized by further comprising reacting said mixture of esters in a second esterification reaction to regenerate said alcohol, and recycling it back to react with more FDCA.
    [0004]
    METHOD according to claim 1, characterized in that said alcohol is a C2-C6 diol.
    [0005]
    5. SYNTHESIS METHOD OF A FURAN DIESTER, characterized by the method comprising: reacting furanodicarboxylic acid (FDCA) with an alcohol in a CO2 atmosphere in the substantial absence of any other acid catalyst under operational conditions that are at supercritical, critical temperatures and pressures or almost critical for alcohol or CO2 gas.
    [0006]
    6. METHOD, according to claim 5, characterized in that said operating conditions, temperatures and pressures are selectively modified to conduct said synthesis reaction towards the formation of diester molecules.
    [0007]
    7. METHOD OF PROCESSING FURANODICARBOXYLIC ACID, characterized by comprising: reacting FDCA with a first alcohol, in particular a C1 to C20 alcohol, in a CO2 atmosphere in the substantial absence of any other catalyst to produce a first ester mixture; reacting said first ester mixture with a second alcohol, in particular a C2 to C12 alcohol, in a transesterification reaction, in particular by means of base-catalyzed or enzymatic reactions, to produce a second ester mixture.
    [0008]
    METHOD, according to claim 7, characterized in that it further comprises regenerating said first alcohol and recycling said first alcohol back, to react with more FDCA.
    [0009]
    Method according to claim 7, characterized in that said first mixture of esters may include monoesters or diesters, according to any of the following species: methyl furanedicarboxylate, ethyl furanedicarboxylate or propyl furanedicarboxylate.
    [0010]
    10. METHOD, according to claim 7, characterized by said FDCA reaction with an alcohol in CO2 being carried out under operating conditions at supercritical, critical or almost critical temperatures and pressures for said alcohol or CO2.
    [0011]
    11. METHOD, according to claim 7, characterized in that said FDCA reaction with an alcohol in CO2 is carried out at a reaction temperature between about 150 ° C and 250 ° C and at a reaction pressure of 2758 KPa (400 psi) up to 20684 KPa (3000 psi) or at a reaction temperature between 170 ° C and 230 ° C, at a reaction pressure of about 6343 KPa (920 psi) to about 17237 KPa (2500 psi).
    [0012]
    12. METHOD, according to claim 7, characterized in that said transesterification reaction is carried out from 80 ° C to 90 ° C.
    [0013]
    13. METHOD according to claim 7, characterized in that a boiling point of said second alcohol is equal to at least 10 ° C to 20 ° C greater than that of said first alcohol.
    [0014]
    14. METHOD, according to claim 7, characterized in that said transesterification reaction occurs by means of an enzymatic reaction with lipase, in particular, in which said lipase is from Candida antartica.
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    同族专利:
    公开号 | 公开日
    CN105246958A|2016-01-13|
    WO2014099438A2|2014-06-26|
    SG11201503646TA|2015-07-30|
    EP2935229B1|2017-06-28|
    AU2013363501B2|2016-12-01|
    EP2935229A2|2015-10-28|
    AU2013363501A1|2015-05-28|
    CA2895186C|2019-10-22|
    US9765045B2|2017-09-19|
    US10155736B2|2018-12-18|
    CN105246958B|2018-02-02|
    WO2014099438A3|2015-07-16|
    MX2015007903A|2015-10-05|
    KR101963478B1|2019-03-28|
    US20170369463A1|2017-12-28|
    EP2935229A4|2016-01-27|
    BR112015014183A2|2017-07-11|
    CA2895186A1|2014-06-26|
    JP2016506407A|2016-03-03|
    US20150315166A1|2015-11-05|
    MX362292B|2019-01-10|
    ES2642005T3|2017-11-14|
    JP6370307B2|2018-08-08|
    KR20150095931A|2015-08-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5071754A|1990-01-23|1991-12-10|Battelle Memorial Institute|Production of esters of lactic acid, esters of acrylic acid, lactic acid, and acrylic acid|
    CN100594220C|2003-03-05|2010-03-17|伊士曼化工公司|Polymer blends|
    NZ549320A|2004-01-29|2010-10-29|Zeachem Inc|Recovery of organic acids|
    DE102004008042A1|2004-02-19|2005-09-01|Goldschmidt Gmbh|Process for the preparation of amino acid esters and their acid addition salts|
    DE102004047869A1|2004-10-01|2006-04-06|Goldschmidt Gmbh|Process for the enzymatic synthesis of pyroglutamic acid esters|
    WO2007038496A2|2005-09-27|2007-04-05|Chemic Laboratories, Inc.|Synthesis of fatty alcohol esters of hydroxy carboxylic acids, the use of the same as percutaneous permeation enhancers|
    US7772414B1|2006-11-14|2010-08-10|Aerophase, Inc.|Process for producing biodiesel fuel products|
    CA2625511A1|2008-03-13|2009-09-13|Dilum Dunuwila|Process for the direct production of esters of carboxylic acids from fermentation broths|
    US8105809B2|2008-07-03|2012-01-31|Accera, Inc.|Enzymatic synthesis of acetoacetate esters and derivatives|
    WO2010090965A2|2009-02-03|2010-08-12|David Miller|Method of producing biodiesel with supercritical alcohol and apparatus for same|
    DE102009028975A1|2009-08-28|2011-03-03|Evonik Oxeno Gmbh|Ester derivatives of 2,5-furandicarboxylic acid and their use as plasticizers|
    CA2775319C|2009-10-07|2018-08-28|Furanix Technologies B.V.|Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid|
    CN102648191B|2009-10-07|2015-08-19|福兰尼克斯科技公司|Prepare the method for FDCA and ester thereof|
    EP2481733A1|2011-01-28|2012-08-01|Süd-Chemie AG|Process for manufacturing esters of 2,5-furandicarboxylic acid|
    US8658810B2|2012-06-22|2014-02-25|Eastman Chemical Company|Method for producing purified dialkyl-furan-2,5-dicarboxylate vapor|
    US8859788B2|2012-06-22|2014-10-14|Eastman Chemical Company|Esterification of furan-2,5-dicarboxylic acid to a dialkyl-furan-2,5-dicarboxylate vapor with rectification|WO2014070415A1|2012-10-29|2014-05-08|Archer Daniels Midland Company|Alcohol-mediated esterification of carboxylic acids with carbonates|
    MX2016002618A|2013-08-30|2016-06-06|Furanix Technologies Bv|Process for purifying an acid composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furandicarboxylic acid.|
    US9573120B2|2014-05-08|2017-02-21|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    US9944615B2|2014-05-08|2018-04-17|Eastman Chemical Company|Purifying crude furan 2,5-dicarboxylic acid by hydrogenation and a purge zone|
    US10010812B2|2014-05-08|2018-07-03|Eastman Chemical Company|Furan-2,5-dicarboxylic acid purge process|
    JP6452428B2|2014-12-18|2019-01-16|花王株式会社|Plasticizer for halogen resin|
    DE112016001317T5|2015-03-20|2018-01-04|Stanford University|Carbonate-assisted carboxylation reaction for the synthesis of valuable organic compounds|
    US10538499B2|2015-04-14|2020-01-21|Dupont Industrial Biosciences Usa, Llc|Processes for producing 2,5-furandicarboxylic acid and derivatives thereof and polymers made therefrom|
    US20190084952A1|2015-07-24|2019-03-21|E I Du Pont De Nemours And Company|Process for producing 2,5-furandicarboxylic acid dialkyl ester|
    WO2017091435A1|2015-11-24|2017-06-01|Archer Daniels Midland Company|Oligomerizations of fdca and glycols in a one-pot esterification-transesterification process catalyzed by homogeneous organometallic lewis acids|
    WO2017123763A1|2016-01-13|2017-07-20|Rennovia Inc.|Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof|
    EP3606664A1|2017-04-05|2020-02-12|Archer Daniels Midland Co.|Novel esterification catalyst and uses thereof|
    EP3642190A4|2017-06-22|2021-04-28|Archer Daniels Midland Company|Process for making esters of 2,5-furandicarboxylic acid|
    BR112020000611A2|2017-07-12|2020-07-14|Stora Enso Oyj|purified products via 2,5-furanedicarboxylic acid pathway|
    US10421736B2|2017-07-20|2019-09-24|Eastman Chemical Company|Production of purified dialkyl-furan-2,5-dicarboxylatein a retrofitted DMT plant|
    WO2019214576A1|2018-05-10|2019-11-14|中国科学院长春应用化学研究所|Method for preparing 2,5-furandicarboxylic acid|
    US20190389820A1|2018-06-25|2019-12-26|Eastman Chemical Company|Process for producing 5-furan-2-carboxylic acids and compositions containing same|
    US20190390004A1|2018-06-25|2019-12-26|Eastman Chemical Company|Oxidation process to produce 5 methyl 5-methylfuran-2-carboxylate |
    JP2020022377A|2018-08-06|2020-02-13|三菱ケミカル株式会社|High acid-resistant microorganism having glucaric acid-producing ability, and method for producing glucaric acid using the same|
    CN112585123A|2018-08-31|2021-03-30|伊士曼化工公司|Production of purified dialkyl furan-2, 5-dicarboxylatein modified DMT plant|
    US10526301B1|2018-10-18|2020-01-07|Eastman Chemical Company|Production of purified dialkyl-furan-2,5-dicarboxylatein a retrofitted DMT plant|
    WO2021045927A1|2019-09-05|2021-03-11|Eastman Chemical Company|Efficient process for producing 5--furan-2-carboxylic acids|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2021-02-23| B09A| Decision: intention to grant|
    2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261739761P| true| 2012-12-20|2012-12-20|
    US61/739,761|2012-12-20|
    PCT/US2013/073821|WO2014099438A2|2012-12-20|2013-12-09|Esterification of 2,5-furan-dicarboxylic acid|
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