Process for producing biomonomers and precursors for biomonomers

Abstract

The invention relates to a method for producing a biomonomer and a precursor for the biomonomer. A furoate carboxylation reaction is carried out with particles formed from a furoate and a base, and optionally a reaction accelerator. The particles may be in a slurry. The particles are exposed to gaseous carbon dioxide and heated. The reaction produces dicarboxylic acid esters that can be isolated and used to produce biomonomers, such as methyl furandicarboxylate and furandicarboxylic acid.

Description

[0001] Priority Claim

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 477,859, filed Dec. 30, 2022, the entire disclosure of which is incorporated herein by reference. Field of the Invention

[0003] The present invention generally relates to methods for producing aromatic carboxylic acid compounds including furandicarboxylic acid and methyl furandicarboxylate from biomass, as well as precursors therefor. Background of the Invention

[0004] Recently, methods have been developed for producing aromatic carboxylic acids and esters from sugars derived from biomass. These aromatic carboxylic acids and esters can be converted into dicarboxylic acid compounds, which in turn can be used to produce monomers such as methyl furandicarboxylate (FDME) and furandicarboxylic acid (FDCA). As is known, these monomers can be used to prepare polymers and plastics, and because they are at least partially derived from biomass, they can be referred to as biobased monomers.

[0005] These methods are desirable because they provide production of biobased monomers rather than production of chemicals and monomers from fossil fuel sources. Additionally, the methods are desirable because they may consume carbon dioxide, which is considered a greenhouse gas.

[0006] While generally effective for their intended purposes, there has been a continuing desire and need to provide effective and efficient methods for producing biobased monomers from biomass-derived components and carbon dioxide. Summary of the Invention

[0007] The inventors have found that the particle size and interparticle crystallization of the furoate ester, base, and promoter components play an important role in controlling the reactivity. In particular, smaller particle sizes and intergrown crystals result in significantly faster carboxylation reactions compared to reactions utilizing blended powders. Thus, forming small furoate ester feed particles prior to the carboxylation reactor facilitates the ability to provide a smaller reactor and / or achieve higher conversion rates.

[0008] Accordingly, in at least one aspect, the present invention can be characterized as providing a method for producing a precursor for a biobased monomer by: mixing a furoate ester and a base to form a mixture; forming particles from the mixture, the particles comprising the furoate ester and the base; and heating the particles in the presence of carbon dioxide to form a dicarboxylate ester.

[0009] The particles can have an average particle size between 20 microns and 200 microns.

[0010] The particles can further comprise a carboxylic ester reaction promoter.

[0011] The particles may be spherical.

[0012] The particles may be formed in hydrocarbon oils.

[0013] The particles may be formed by drying a portion of the effluent from the oxidation reaction zone. The drying may include spray drying and / or aqueous evaporation.

[0014] The mixture may be heated to a temperature between 150°C and 360°C at a pressure of up to 6,895 kPa (1,000 psi).

[0015] The mixture may be a slurry and the carbon dioxide may be provided as bubbles flowing countercurrently with the slurry and with the particles.

[0016] The process may further comprise recovering the dicarboxylic acid ester and converting the dicarboxylic acid ester to dimethyl furandicarboxylate or furandicarboxylic acid, or both.

[0017] In another aspect, the present invention can be broadly characterized as providing a method for producing methyl furandicarboxylate or furandicarboxylic acid from a biomass-derived compound by: mixing a furoate ester and a base to form a mixture; forming particles from the mixture, the particles comprising the furoate ester and the base; heating the particles in the presence of carbon dioxide to form a dicarboxylate ester; recovering the dicarboxylate ester; and converting the dicarboxylate ester to methyl furandicarboxylate or furandicarboxylic acid, or both.

[0018] The particles may also contain a carboxylate reaction accelerator.

[0019] The particles may be spherical.

[0020] The base, the furoate counterion, or both can be selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0021] The furoate particles may have an average particle size between 20 microns and 200 microns.

[0022] The mixture is heated to a temperature between 150°C and 360°C at a pressure of up to 6,895 kPa (1,000 psi).

[0023] The mixture may be a slurry. The slurry may be formed in a hydrocarbon having negligible solubility for the furoate and the base.

[0024] Further aspects, embodiments and details of the invention (all of which may be combined in any manner) are set forth in the following detailed description of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] One or more exemplary embodiments of the present invention will be described below with reference to the following drawings, in which:

[0026] Figure 1 is a photograph of a conventional powder mixture for the carboxylation reaction;

[0027] Figure 2 is a photograph of a conventional co-evaporated material for the carboxylation reaction; and

[0028] Figure 3 is a photograph of the particles according to the invention for the carboxylation reaction. DETAILED DESCRIPTION

[0029] As described above, the present invention provides a method for the carboxylation reaction of furanoate esters. The production of furanoate esters from biomass is known. See, U.S. Patent No. 7,572,925 and U.S. Patent No. 8,772,515. As used herein, "biomass" includes, but is not limited to, lignin, plant parts, fruits, vegetables, plant processing waste, wood chips, husks, grains, grasses, corn, corn husks, waste, aquatic plants, hay, paper stock, paper products, recycled paper and paper products, and any cellulose, lignin or combination thereof containing biological materials or materials of biological origin. Thus, the method is intended to be used as part of an integrated C5 biomass to FDCA / FDME production facility; however, other embodiments may be utilized.

[0030] Generally speaking, the method mixes a furanoate ester (such as a furanate salt), a base, and optionally any carboxylic ester reaction promoter to form particles. These particles are heated to a reaction temperature in the presence of carbon dioxide gas. The furanoate ester is converted to a dicarboxylate ester (FDCA salt), and can subsequently be converted to FDCA free acid or FDME in subsequent chemical steps.

[0031] With these general principles in mind, one or more embodiments of the present invention will be described, understanding that the following description is not intended to be limiting.

[0032] The method according to the present invention includes: forming a mixture containing a furanoate ester and a base, and subsequently drying the mixture to form particles. The mixture may also contain a carboxylic ester reaction promoter, such as a hydrocarbon having an αC-H bond, such as an acetate.

[0033] The base can be a metal hydroxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and mixtures thereof.

[0034] The furanoate counterions can include lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0035] The base can be in a molar ratio of base to furanoate ester that can be 1:1 to 2:1, 1:0.1 to 1:1, 1:0.1 to 1:0.5, or 0.1:1 to 1:1.

[0036] It is expected that furanate esters are formed in an oxidation zone where biomass-derived components undergo a selective oxidation reaction process to produce furanate esters. The furanate esters can be separated from other parts of the effluent, mixed with a base and an optional reaction promoter, and then dried to form particles. The drying can include spray drying and / or aqueous evaporation. The particles can be formed in a hydrocarbon oil or may not be formed in a hydrocarbon oil.

[0037] Once formed, the particles preferably have an average particle size between 20 microns and 200 microns, or between 40 microns and 100 microns, such as 60 microns. The particles are preferably spherical.

[0038] The components of the particles (furanate esters and base) are uniformly dispersed or distributed throughout the individual particles such that each particle is generally homogeneous in composition. This is in contrast to methods in which two different types of particles are formed simultaneously and one type of particle can contact the other type of particle. Thus, at least 10 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt% of the particles are formed from a mixture of at least furanate esters and a base.

[0039] The particles can be provided in a hydrocarbon oil (e.g., a hydrocarbon material containing between 5 and 30 carbon atoms per molecule and having alkane and / or aromatic functional groups) to form a slurry. Generally, the hydrocarbon oil selected for the slurry has negligible solubility for the furanate esters and the base. It should be understood that the use of a slurry phase reaction is only preferred, and other reactors, such as solid-state reactors, can be used. If the promoter is not included in the particles, it can be provided with the slurry or otherwise provided to the particles.

[0040] The formed particles are exposed to carbon dioxide gas and heated. If a slurry is used, carbon dioxide can be provided as bubbles into the slurry. The bubbles can flow countercurrently to the slurry stream and particularly to the particle stream.

[0041] The particles are heated with carbon dioxide to a temperature of between 150° C. and 360° C., or between 270° C. and 330° C., at a pressure of atmospheric pressure up to 6,895 kPa (1,000 psi), or up to 4,826 kPa (700 psig), or up to 4,137 kPa (600 psig), and for a sufficient time to form the dicarboxylic acid ester via a carboxylation reaction between the carbon dioxide and the furoate. The reaction time sufficient to produce the aromatic carboxylic acid compound is 1 second to 24 hours, 1 minute to 12 hours, 1 minute to 6 hours, or 1 minute to 1 hour. The process can be a continuous, semi-batch, or batch reaction process.

[0042] The prepared dicarboxylic acid may include terephthalic acid, naphthalene dicarboxylic acid, thiophene dicarboxylic acid, pyridine dicarboxylic acid, carbazole dicarboxylic acid, and dibenzothiophene dicarboxylic acid. In particular, the dicarboxylic acid ester may be furandicarboxylate, and specifically, furan-2,4-dicarboxylate and / or furan-2,5-dicarboxylate.

[0043] The dicarboxylic acid ester can be recovered, for example, by separation from the slurry. The recovered decarboxylate can be converted into FDME, FDCA, or both. In particular, the biomonomers produced can include one or more of furan-2,5-dicarboxylic acid, furan-2,4-dicarboxylic acid, furan-2,5-dicarboxylic acid dimethyl ester, furan-2,4-dicarboxylic acid dimethyl ester, and salts thereof. These biomonomers can be converted into polymers as known in the art.

[0044] Any separated slurry may be recycled, and heat may be recovered from the separated slurry in a heat exchanger.

[0045] Particles formed from both the furoate and the base provide an effective and efficient means for producing biomonomers and precursors to the biomonomers.

[0046] Experiment

[0047] The particles according to the present invention ( Figure 3 ) is used in carboxylation reactions and mixed with conventional powders ( Figure 1 ) and co-evaporated materials ( Figure 2 ) were compared. The feed for the carboxylation reaction was 1 molar equivalent of K-furoate, 0.55 molar equivalent of K2CO3 and 0.35 molar equivalent of KO-acetate. The feed was heated to a temperature of 300°C in the presence of carbon dioxide for five hours. It was found that the conventional powder mixture ( Figure 1 ) had a conversion of 69%, and the co-evaporated material was found to have a conversion of 79%. The particles according to the invention were found to have a conversion of 96%.

[0048] Specific implementation

[0049] Although the following is described in connection with specific embodiments, it should be understood that the description is intended to illustrate and not limit the scope of the foregoing description and the appended claims.

[0050] A first embodiment of the present invention is a method for producing a precursor for a biobased monomer, the method comprising: mixing a furan carboxylic acid ester and a base to form a mixture; forming particles from the mixture, the particles comprising the furan carboxylic acid ester and the base; and heating the particles in the presence of carbon dioxide to form a dicarboxylic acid ester. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the particles have an average particle size between 20 microns and 200 microns. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the particles further comprise a carboxylic acid ester reaction promoter. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the particles are spherical. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the particles are formed in a hydrocarbon oil. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the particles are formed by drying a portion of the effluent from an oxidation reaction zone. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the drying comprises spray drying. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the drying comprises aqueous evaporation. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the mixture is heated to a temperature between 150 °C and 360 °C at a pressure up to 6,895 kPa (1,000 psi). An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the mixture comprises a slurry. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, wherein the carbon dioxide is provided as bubbles flowing countercurrently to the slurry and to the particles. An embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the first embodiment in this paragraph, further comprising recovering the dicarboxylic acid ester; and converting the dicarboxylic acid ester to dimethyl furandicarboxylate or furandicarboxylic acid, or both.

[0051] A second embodiment of the present invention is a method for producing methyl furandicarboxylate or furandicarboxylic acid from biomass-derived compounds, the method comprising: mixing a furanate ester and a base to form a mixture; forming particles from the mixture, the particles comprising the furanate ester and the base; heating the particles in the presence of carbon dioxide to form a dicarboxylate ester; recovering the dicarboxylate ester; and converting the dicarboxylate ester to methyl furandicarboxylate or furandicarboxylic acid, or both. One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the particles further comprise a carboxylic acid ester reaction promoter. One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the particles are spherical. One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the base, the furanate counterion, or both are selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the furanate ester particles have an average particle size between 20 microns and 200 microns. One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the mixture is heated to a temperature between 150 °C and 360 °C at a pressure up to 6,895 kPa (1,000 psi). One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the mixture comprises a slurry. One embodiment of the present invention is one, any, or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, wherein the slurry is formed in a hydrocarbon having a negligible solubility for the furanate salt and the base.

[0052] Although no further detailed description is provided, it is believed that those skilled in the art can make the most of the present invention by using the foregoing description and can easily determine the basic features of the present invention without departing from the essence and scope of the present invention to make various changes and modifications thereto and adapt it to various uses and conditions. Therefore, the foregoing preferred specific embodiments should be understood as being merely illustrative and not limiting the remainder of the disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0053] In the foregoing, all temperatures are shown in degrees Celsius, and all parts and percentages are by weight unless otherwise indicated.

[0054] Although at least one exemplary embodiment has been presented in the foregoing detailed description of the present invention, it should be understood that there are numerous variations. It should also be understood that one exemplary embodiment or a plurality of exemplary embodiments are merely examples and are not intended to limit the scope, applicability, or construction of the present invention in any way. On the contrary, the foregoing detailed description will provide those skilled in the art with a convenient roadmap for implementing the exemplary embodiments of the present invention. It should be understood that various changes can be made to the functions and arrangements of the elements described in the exemplary embodiments without departing from the scope of the present invention as set forth in the appended claims and their legal equivalents.

Claims

1. A method for producing a precursor for a biological monomer, the method comprising: Mixing a furoate and a base to form a mixture; Forming particles from the mixture, the particles comprising the furoate and the base; And Heating the particles in the presence of carbon dioxide to form a dicarboxylate.

2. The method according to claim 1, wherein the particles have an average particle size between 20 microns and 200 microns.

3. The method according to claim 1, wherein the particles further comprise a carboxylic ester reaction promoter.

4. The method according to claim 1, wherein the particles are spherical.

5. The method according to any one of claims 1 to 4, wherein the particles are formed in a hydrocarbon oil.

6. The method according to any one of claims 1 to 4, wherein the particles are formed by drying a portion of the effluent from an oxidation reaction zone.

7. The method according to claim 6, wherein the drying comprises spray drying.

8. The method according to claim 6, wherein the drying comprises aqueous evaporation.

9. The method according to any one of claims 1 to 4, wherein the mixture is heated to a temperature between 150 °C and 360 °C at a pressure up to 6,895 kPa (1,000 psi).

10. The method according to any one of claims 1 to 4, wherein the mixture comprises a slurry.

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