Process for producing biomonomers and precursors of biomonomers

Abstract

A process for producing biomonomers and their precursors using a slurry phase reaction. The furoate carboxylation reaction is carried out in a hydrocarbon slurry containing carbon dioxide. The reaction produces a dicarboxylate that can be separated from the slurry and used to produce biomonomers such as furandicarboxylate methyl ester and furandicarboxylic acid.

Description

[Technical Field]

[0001] (Statement of priority) This application claims priority to U.S. Provisional Patent Application No. 63 / 477,857, filed December 30, 2022, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The present invention relates generally to processes for producing aromatic carboxylic acid compounds, including furandicarboxylic acid and furandicarboxylate methyl ester, and precursors thereof, from biomass. [Background technology]

[0003] Recently, processes have been developed for producing aromatic carboxylic acids and esters from sugars produced from biomass. These aromatic carboxylic acids and esters can be converted to dicarboxylates, which can then be used to produce monomers such as furandicarboxylate methyl ester (FDME) and furandicarboxylic acid (FDCA). As is known, these monomers are useful for making polymers and plastics and are sometimes referred to as biomonomers because they are derived at least in part from biomass.

[0004] These processes are desirable because they provide for the production of biomonomers, as opposed to producing chemicals and monomers from fossil fuel sources. Additionally, the processes are desirable because they can consume carbon dioxide, which is considered a greenhouse gas.

[0005] While generally effective for their intended purposes, these carboxylation reactions are carried out as solid-state melt reactions, which severely complicates the design of the necessary reactors.

[0006] Therefore, it is desirable to provide a process for producing biomonomers from biomass-derived components and carbon dioxide that does not require complex reactors. Summary of the Invention

[0007] The present inventors have invented a process for producing biomonomers and their precursors that utilizes a slurry-phase reaction. Specifically, the present invention addresses the shortcomings of conventional processes by conducting a furoate carboxylation reaction in a hydrocarbon slurry containing furoate, an alkali base, and carbon dioxide. A slurry-phase carboxylation reaction / process is advantageous because it allows for the use of a slurry bubble column reactor design. Furthermore, such a reaction can allow for the necessary heat of reaction to be added via hydrocarbon oil. Furthermore, heat can be recovered from used hydrocarbon oil via heat exchange. Similarly, exothermic heat that causes loss of selectivity can be removed. Finally, the reactor can have a countercurrent oil / gas flow design to facilitate the reaction.

[0008] Thus, in at least one aspect, the present invention can be characterized as providing a process for producing a precursor for producing a biomonomer by forming a slurry containing a furoate and an alkali base and heating the slurry in the presence of carbon dioxide to form a dicarboxylate.

[0009] The slurry may further include a carboxylate reaction accelerator.

[0010] The slurry can be heated to temperatures between 150°C and 360°C at pressures up to 6,895 kPa (1,000 psi).

[0011] The carbon dioxide may be provided as bubbles, which may flow countercurrently to the slurry.

[0012] The slurry can be formed in a hydrocarbon that has negligible solubility for the furoate and alkali base.

[0013] The process may also include recovering the dicarboxylate and converting the dicarboxylate to furandicarboxylate methyl ester or furandicarboxylic acid, or both.

[0014] The alkali base, the furoate counterion, or both, may be selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0015] The slurry may further include cesium.

[0016] The invention may also be broadly characterized in at least one aspect as providing a process for producing furandicarboxylate methyl ester or furandicarboxylic acid from biomass-derived compounds by transferring a slurry comprising furoate and an alkali base to a reaction zone vessel, transferring carbon dioxide into the vessel to contact the slurry, heating the slurry to form a dicarboxylate, recovering the dicarboxylate, and converting the dicarboxylate to furandicarboxylate methyl ester or furandicarboxylic acid, or both.

[0017] The slurry may also include a carboxylate reaction accelerator.

[0018] The alkali base or furoate counterion, or both, may be selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0019] The slurry may be heated to a temperature of 150°C to 360°C at a pressure up to 6,895 kPa (1,000 psi).

[0020] Carbon dioxide may be transported into the vessel by air bubbles flowing countercurrent to the slurry.

[0021] The slurry can be formed in a hydrocarbon having negligible solubility for the furoate and alkali base. The dicarboxylate can be recovered by separating the hydrocarbon from the dicarboxylate. The process can include recycling the separated hydrocarbon to form the slurry. The process can also include recovering heat from the separated hydrocarbon in a heat exchanger.

[0022] The slurry may further include cesium.

[0023] The furandicarboxylate methyl ester may be dimethyl furan-2,5-dicarboxylate, and the furandicarboxylic acid may be furan-2,5-dicarboxylate.

[0024] Further aspects, embodiments and details of the invention, all of which may be combined in any manner, are set out in the detailed description of the invention below. DETAILED DESCRIPTION OF THE INVENTION

[0025] As mentioned above, the present invention provides a process for producing furoate using a slurry-phase carboxylation reaction. Producing furoate from biomass is known. See U.S. Patent Nos. 7,572,925 and 8,772,515. As used herein, "biomass" includes, but is not limited to, lignin, plant parts, fruits, vegetables, plant processing waste, wood chips, rice husks, grains, grass, corn, corn husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and paper products, and any cellulose, lignin, or combinations thereof containing biological or biologically derived materials.

[0026] Thus, the process is intended to be used as part of an integrated facility for producing FDCA / FDME from C5 biomass, although other implementations may be utilized.

[0027] Generally, the process involves mixing a furoate, such as a furoic acid salt, an alkali base, and an optional promoter in a hydrocarbon oil to form a slurry. This slurry is heated to reaction temperature in the presence of carbon dioxide gas, optionally in a countercurrent slurry bubble column reactor. The furoate is converted to a dicarboxylate (FDCA salt) and then recovered from the oil slurry. The dicarboxylate can then be converted to either FDCA free acid or FDME in subsequent chemical steps, as is known.

[0028] With these general principles in mind, one or more embodiments of the invention are described below with the understanding that the description is not intended to be limiting.

[0029] The method according to the present invention includes forming a slurry containing furoate and an alkali base. The furoate counterions can include lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0030] The alkali base may be a metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and mixtures thereof.

[0031] The alkali base can be in a molar ratio of alkali base to furoate of 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.

[0032] The slurry may be formed in a hydrocarbon oil from hydrocarbon materials containing 5 to 30 carbon atoms per molecule and having paraffinic and / or aromatic functionality. Generally, the hydrocarbon oil selected for the slurry has negligible solubility for the furoate and alkali base.

[0033] The slurry may further include a carboxylate accelerant, such as a hydrocarbon having an alpha C—H bond, such as acetate, which may be selected from propionate, butyrate, isobutyrate, and lactate.

[0034] Carbon dioxide is provided to the slurry. For example, the carbon dioxide may be provided as gas bubbles in the slurry. The gas bubbles may flow countercurrently to the flow of the slurry.

[0035] With carbon dioxide, the slurry is heated to a temperature of 150-360°C or 270-330°C at a pressure from atmospheric up to 6,895 kPa (1,000 psi), or 4,826 kPa (700 psig), or 4,137 kPa (600 psig), with sufficient heat for a time sufficient to form dicarboxylates via a carboxylation reaction between the carbon dioxide and the furoate. The reaction time is sufficient to produce aromatic carboxylic acid compounds and is from 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.

[0036] The dicarboxylates made may include terephthalic acid, naphthalic acid, thiophenedicarboxylic acid, pyridinedicarboxylic acid, carbazoledicarboxylic acid, and dibenzothiophenedicarboxylic acid. In particular, the dicarboxylate may be a furandicarboxylate, specifically furan-2-dicarboxylate and / or furan-2,5-dicarboxylate.

[0037] The dicarboxylates can be recovered by separation from the slurry. The recovered decarboxylates can be converted to 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, dimethyl furan-2,5-dicarboxylate, dimethyl furan-2,4-dicarboxylate, and salts thereof. These biomonomers can be converted to polymers as known in the art.

[0038] After the decarboxylates are separated, the separated slurry can be recycled. Additionally, heat can be recovered from the separated slurry in a heat exchanger.

[0039] Compared to existing reactors and processes, the slurry reactor and reaction process is easier to implement and provides an effective and efficient means for producing biomonomers and their components.

[0040] experiment Three different slurries were formed based on the ingredients and proportions specified in Table 1 below.

[0041] [Table 1]

[0042] Examples 1, 2, and 3 were heated in the presence of carbon dioxide at temperatures of 315°C, 325°C, and 250°C for 5 hours.

[0043] The furoate conversion and FDCA yield of the examples are shown in Table 2 below.

[0044] [Table 2]

[0045] Specific Embodiments While the following will be described in conjunction with specific embodiments, it will be understood that this description is illustrative, but not intended to limit the scope of the preceding description and appended claims.

[0046] A first embodiment of the present invention is a process for producing a precursor for producing a biomonomer, the process comprising forming a slurry comprising furoate and an alkali base, and heating the slurry in the presence of carbon dioxide to form a dicarboxylate. An embodiment of the present invention is any one, any, or all of the preceding through first embodiments of this paragraph, in which the slurry further comprises a carboxylate reaction accelerator. An embodiment of the present invention is any one, any, or all of the preceding through first embodiments of this paragraph, in which the slurry is heated to a temperature of 150°C to 360°C at a pressure of up to 6,895 kPa (1,000 psi). An embodiment of the present invention is any one, any, or all of the preceding through first embodiments of this paragraph, in which the carbon dioxide is provided as gas bubbles. An embodiment of the present invention is any one, any, or all of the preceding through first embodiments of this paragraph, in which the gas bubbles flow countercurrently to the slurry. An embodiment of the invention is one, any, or all of the preceding through first embodiments of this paragraph, wherein the slurry is formed in a hydrocarbon having negligible solubility for the furoate and alkali base. An embodiment of the invention is one, any, or all of the preceding through first embodiments of this paragraph, further comprising recovering the dicarboxylate and converting the dicarboxylate to furandicarboxylate methyl ester or furandicarboxylic acid, or both. An embodiment of the invention is one, any, or all of the preceding through first embodiments of this paragraph, wherein the alkali base, furoate counterion, or both, is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. An embodiment of the invention is one, any, or all of the preceding through first embodiments of this paragraph, wherein the slurry further comprises cesium.

[0047] A second embodiment of the present invention is a process for producing furandicarboxylate methyl ester or furandicarboxylic acid from biomass-derived compounds, comprising: transferring a slurry comprising furoate and an alkali base into a reaction zone vessel; transferring carbon dioxide into the vessel to contact the slurry; heating the slurry to form a dicarboxylate; recovering the dicarboxylate; and converting the dicarboxylate to furandicarboxylate methyl ester or furandicarboxylic acid, or both. An embodiment of the present invention is one, any, or all of the preceding through second embodiments of this paragraph, wherein the slurry further comprises a carboxylate reaction accelerator. An embodiment of the present invention is one, any, or all of the preceding through second embodiments of this paragraph, wherein the alkali base, furoate counterion, or both, is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. An embodiment of the invention is any one, any, or all of the preceding through second embodiments of this paragraph, in which the slurry is heated to a temperature of 150°C to 360°C at a pressure of up to 6,895 kPa (1,000 psi). An embodiment of the invention is any one, any, or all of the preceding through second embodiments of this paragraph, in which carbon dioxide is transferred to the vessel by gas bubbles flowing countercurrently to the slurry. An embodiment of the invention is any one, any, or all of the preceding through second embodiments of this paragraph, in which the slurry is formed in a hydrocarbon having negligible solubility for furoate and alkali base. An embodiment of the invention is any one, any, or all of the preceding through second embodiments of this paragraph, in which recovering the dicarboxylate comprises separating the hydrocarbon from the dicarboxylate. An embodiment of the invention is any one, any, or all of the preceding through second embodiments of this paragraph, in which further comprising recycling the separated hydrocarbon to form the slurry.An embodiment of the present invention is one, any, or all of the previous through second embodiments of this paragraph, further comprising recovering heat from the separated hydrocarbons in a heat exchanger. An embodiment of the present invention is one, any, or all of the previous through second embodiments of this paragraph, wherein the slurry further comprises cesium. An embodiment of the present invention is one, any, or all of the previous through second embodiments of this paragraph, wherein the furandicarboxylate methyl ester comprises dimethyl furan-2,5-dicarboxylate and the furandicarboxylic acid comprises furan-2,5-dicarboxylate.

[0048] Without further elaboration, it is believed that, using the preceding description, one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of the present invention, and can make various changes and modifications to the present invention to adapt it to various uses and conditions, without departing from the spirit and scope of the present invention. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of 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.

[0049] Above, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight unless otherwise indicated.

[0050] While at least one exemplary embodiment has been presented in the foregoing detailed description of the present invention, it should be understood that numerous variations exist. It should also be understood that the exemplary embodiment(s) are merely examples and are in no way intended to limit the scope, applicability, or configuration of the present invention. Rather, the foregoing detailed description provides those skilled in the art with a convenient guide for implementing exemplary embodiments of the present invention, and it should be understood that various changes can be made in the functions and arrangement of elements described in the exemplary embodiment without departing from the scope of the present invention as set forth in the appended claims and their legal equivalents.

Claims

1. 1. A process for producing a precursor for producing a biomonomer, comprising: forming a slurry comprising furoate and an alkali base; heating the slurry in the presence of carbon dioxide to form a dicarboxylate; The process includes:

2. 10. The process of claim 1, wherein the slurry further comprises a carboxylate reaction accelerator.

3. 10. The process of claim 1, wherein the slurry is heated to a temperature of 150°C to 360°C at a pressure of up to 6,895 kPa (1,000 psi).

4. The process of claim 1 , wherein the carbon dioxide is provided in bubbles.

5. 5. The process of claim 4, wherein the air bubbles flow countercurrently to the slurry.

6. 6. The process of any one of claims 1 to 5, wherein the slurry is formed in a hydrocarbon having negligible solubility for the furoate and the alkali base.

7. recovering the dicarboxylate; and and converting the dicarboxylate to furandicarboxylate methyl ester or furandicarboxylic acid, or both.

8. 6. The process of any one of claims 1 to 5, wherein the alkali base, furoate counterion, or both is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

9. The process of any one of claims 1 to 5, wherein the slurry further comprises cesium.

10. 6. The process of any one of claims 1 to 5, wherein the dicarboxylate comprises dimethylfuran-2,5-dicarboxylate.

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