Process for producing biomonomers and precursors of biomonomers

Abstract

A process for the production of biomonomers and precursors thereof using slurry phase reactions. A furoate carboxylation reaction is performed within a hydrocarbon slurry comprising carbon dioxide. The reaction produces dicarboxylic acid esters that can be separated from the slurry and used to produce biomonomers, such as methyl furandicarboxylate and furandicarboxylic acid.

Description

[0001] Priority Claim

[0002] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 477,857, 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, and precursors thereof, including furandicarboxylic acid and methyl furandicarboxylate, from biomass. Background of the Invention

[0004] Recently, methods for producing aromatic carboxylic acids and esters from sugars derived from biomass have been developed. These aromatic carboxylic acids and esters can be converted to dicarboxylic esters, 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, since they are at least partially derived from biomass, can be referred to as biobased monomers.

[0005] These methods are desirable because they provide for the production of biobased monomers rather than the 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, these carboxylation reactions are carried out as solid-state melt reactions, which severely complicates the design of the required reactors.

[0007] Accordingly, there is a desire to provide methods for producing biobased monomers from biomass-derived components and carbon dioxide that do not require complex reactors. Summary of the Invention

[0008] The inventors have invented methods for producing biobased monomers and their precursors using slurry-phase reactions. Specifically, the present invention addresses the disadvantages of conventional methods by conducting a carboxylation reaction of a furan carboxylic acid ester in a hydrocarbon slurry containing the furan carboxylic acid ester, a base, and carbon dioxide. The slurry-phase carboxylation reaction / method is advantageous because it allows for the use of a slurry-bubble column reactor design. Additionally, this reaction allows for the application of the necessary reaction heat via a hydrocarbon oil. Further, heat can be recovered from the spent hydrocarbon oil by heat exchange. Similarly, the exotherm that causes selectivity loss can be removed. Finally, the reactor can have a countercurrent oil / gas flow design to facilitate the reaction.

[0009] Accordingly, the present invention can be characterized in at least one aspect as providing a method for producing a precursor for producing a biobased monomer, the method comprising the steps of: forming a slurry comprising a furan carboxylic acid ester and a base; and heating the slurry in the presence of carbon dioxide to form a dicarboxylic ester.

[0010] The slurry may also contain a carboxylic acid ester reaction promoter.

[0011] The slurry can be heated to a temperature between 150 °C and 360 °C at a pressure of up to 6,895 kPa (1,000 psi).

[0012] Carbon dioxide can be provided as bubbles, and the bubbles can flow countercurrently to the slurry.

[0013] The slurry can be formed in a hydrocarbon that has negligible solubility for the furanoate and the base.

[0014] The method can also include recovering the dicarboxylic acid ester and converting the dicarboxylic acid ester to methyl furandicarboxylate or furandicarboxylic acid, or both.

[0015] The base, the furanoate counterion, or both can be selected from: lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0016] The slurry may also contain cesium.

[0017] The present invention can also be generally characterized in at least one aspect as providing a method for producing methyl furandicarboxylate or furandicarboxylic acid from biomass-derived compounds, the method comprising the steps of: passing a slurry comprising a furanoate and a base through a vessel in a reaction zone; introducing carbon dioxide into the vessel to contact the slurry; heating the slurry to form a dicarboxylic acid ester; recovering the dicarboxylic acid ester; and converting the dicarboxylic acid ester to methyl furandicarboxylate or furandicarboxylic acid, or both.

[0018] The slurry may also contain a carboxylic acid ester reaction promoter.

[0019] The base, or the furanoate counterion, or both can be selected from: lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0020] The slurry can be heated to a temperature between 150 °C and 360 °C at a pressure of up to 6,895 kPa (1,000 psi).

[0021] Carbon dioxide can be introduced into the vessel as bubbles that flow countercurrently to the slurry.

[0022] The slurry can be formed in a hydrocarbon that has negligible solubility for the furanoate and the base. The dicarboxylic acid ester can be recovered by separating the hydrocarbon from the dicarboxylic acid ester. The method can include recycling the separated hydrocarbon to form the slurry. The method can also include recovering heat from the separated hydrocarbon in a heat exchanger.

[0023] The slurry may also contain cesium.

[0024] Methyl furandicarboxylate can be dimethyl furan-2,5-dicarboxylate, and furandicarboxylic acid can be furan-2,5-dicarboxylic acid.

[0025] Additional aspects, embodiments, and details of the present invention (all of which may be combined in any manner) are set forth in the following detailed description of the present invention. Detailed Description

[0026] As described above, the present invention provides a method for using a slurry-phase carboxylation reaction for furanoate. The production of furanoate 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, rice 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 bio-derived materials.

[0027] Accordingly, 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.

[0028] Generally, the method mixes a furanoate such as furfuryl formate, a base, and any promoter in a hydrocarbon oil to form a slurry. In the presence of carbon dioxide gas, possibly in a countercurrent slurry-bubble column reactor, the slurry is heated to a reaction temperature. The furanoate is converted to a dicarboxylate (FDCA salt), which is then recovered from the slurry. As is known, the dicarboxylate can then be converted to FDCA free acid or FDME in subsequent chemical steps.

[0029] With these general principles in mind, one or more embodiments of the present invention will be described without understanding the following description to be limiting.

[0030] The method according to the present invention includes forming a slurry comprising a furanoate and a base. The furanoate counterion can include lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

[0031] 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.

[0032] The molar ratio of the base to the furanoate can be from 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.

[0033] The slurry can be formed in a hydrocarbon oil, which is a hydrocarbon material having 5 to 30 carbon atoms per molecule and having alkane and / or aromatic functional groups. Generally, the hydrocarbon oil selected for the slurry has negligible solubility in the furanoate and the base.

[0034] The slurry may further comprise a carboxylic acid ester reaction promoter, such as a hydrocarbon having an α C-H bond, such as acetate. For example, the acetate may be selected from propionate, butyrate, isobutyrate, and lactate.

[0035] Carbon dioxide is provided to the slurry. For example, carbon dioxide may be provided into the slurry as bubbles. The bubbles may flow in a direction opposite to the flow of the slurry.

[0036] The slurry is heated with carbon dioxide at a pressure from 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) to a temperature of 150 °C to 360 °C, or 270 °C to 330 °C, and for a time sufficient to form a dicarboxylic acid ester via a carboxylation reaction between carbon dioxide and the furan carboxylic acid ester. The reaction time sufficient to produce the aromatic carboxylic acid compound 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 may be a continuous, semi-batch, or batch reaction process.

[0037] The prepared dicarboxylic acids may include terephthalic acid, naphthalenedicarboxylic acid, thiophenedicarboxylic acid, pyridinedicarboxylic acid, carbazoledicarboxylic acid, and dibenzothiophenedicarboxylic acid. Specifically, the dicarboxylic acid ester may be a furandicarboxylic acid ester, and specifically, furan-2-dicarboxylic acid ester and / or furan-2,5-dicarboxylic acid ester.

[0038] The dicarboxylic acid ester may be recovered by separation from the slurry. The recovered decarboxylated product may be converted to FDME, FDCA, or both. Specifically, the resulting biobased monomers may 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 their salts. These biobased monomers may be converted to polymers known in the art.

[0039] After the decarboxylated product has been separated, the separated slurry may be recycled. Additionally, heat may be recovered from the separated slurry in a heat exchanger.

[0040] Compared to existing reactors and methods, the slurry reactor and reaction method are easier to implement and provide an effective and efficient means for producing biobased monomers and their components.

[0041] Experiment

[0042] Three different slurries are formed based on the components and ratios specified in Table 1 below.

[0043] Table 1

[0044] Example 1 Example 2 Example 3 1 molar equivalent of M-furoate Potassium furoate Potassium furoate Cs-furoate <![CDATA[0.55 molar equivalents of M2-CO3]]> <![CDATA[Potassium carbonate]]> <![CDATA[Potassium carbonate]]> <![CDATA[Cs2CO3]]> 0.35 molar equivalent of M-acetate Potassium acetate Potassium acetate None

[0045] In the presence of carbon dioxide, Examples 1, 2, and 3 were heated at 315 °C, 325 °C, and 250 °C for 5 hours.

[0046] The conversion of the furoate and the FDCA yield of the examples are shown in Table 2 below.

[0047] Table 2

[0048] Example 1 Example 2 Example 3 Conversion rate of M-furoate, mol% 55 96 99 <![CDATA[M2-FDCA yield, wt%]]> 33 54 84

[0049] Specific implementation

[0050] 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.

[0051] A first embodiment of the present invention is a method for producing a precursor for producing a biobased monomer, the method comprising forming a slurry comprising a furoate and a base; and heating the slurry in the presence of carbon dioxide to form a dicarboxylate. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein the slurry further comprises a carboxylic acid ester reaction promoter. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein the slurry is heated to a temperature between 150 °C and 360 °C at a pressure of at most 6,895 kPa (1,000 psi). One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein carbon dioxide is provided as bubbles. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein the bubbles flow countercurrently to the slurry. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein the slurry is formed in a hydrocarbon having a negligible solubility for the furoate and the base. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, further comprising recovering the dicarboxylate; and converting the dicarboxylate to methyl furandicarboxylate or furandicarboxylic acid, or both. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein the base, the furoate counterion, or both are selected from lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. One embodiment of the present invention is one, any, or all of the first embodiment to the previous embodiments of this paragraph, wherein the slurry further comprises cesium.

[0052] A second embodiment of the present invention is a method for producing methyl furandicarboxylate or furandicarboxylic acid from a biomass-derived compound, the method comprising passing a slurry comprising a furanate and a base through a vessel in a reaction zone; introducing carbon dioxide into the vessel to contact the slurry; heating the slurry to form a dicarboxylate ester; and 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 second embodiment to the previous embodiments of this paragraph, wherein the slurry further comprises a carboxylic acid ester reaction promoter. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein the base, or the furanate counterion, or both are selected from lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein the slurry is heated to a temperature between 150 °C and 360 °C at a pressure of at most 6,895 kPa (1,000 psi). One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein carbon dioxide is introduced into the vessel as bubbles that flow countercurrently to the slurry. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein the slurry is formed in a hydrocarbon that has negligible solubility in the furanate and the base. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein recovering the dicarboxylate ester comprises separating the hydrocarbon from the dicarboxylate ester. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, further comprising recycling the separated hydrocarbon to form the slurry. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, further comprising recovering heat from the separated hydrocarbon in a heat exchanger. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein the slurry further comprises cesium. One embodiment of the present invention is one, any, or all of the second embodiment to the previous embodiments of this paragraph, wherein methyl furandicarboxylate comprises dimethyl furan-2,5-dicarboxylate, and wherein furandicarboxylic acid comprises furan-2,5-dicarboxylic acid.

[0053] Although no further elaboration 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.

[0054] In the foregoing, all temperatures are shown in degrees Celsius and all parts and percentages are by weight unless otherwise indicated.

[0055] Although at least one exemplary embodiment has been presented in the foregoing specific embodiments of the present invention, it should be understood that there are a large number of variations. It should also be understood that one exemplary embodiment or multiple 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 specific embodiments will provide those skilled in the art with a convenient roadmap for implementing the exemplary embodiments of the present invention, and 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 producing a biobased monomer, the method comprising: forming a slurry comprising a furanate and a base; and heating the slurry in the presence of carbon dioxide to form a dicarboxylate.

2. The method according to claim 1, wherein the slurry further comprises a carboxylic acid ester reaction promoter.

3. The method according to claim 1, wherein the slurry is heated to a temperature between 150 °C and 360 °C at a pressure of at most 6,895 kPa (1,000 psi).

4. The method according to claim 1, wherein the carbon dioxide is provided as bubbles.

5. The method according to claim 4, wherein the bubbles flow countercurrently to the slurry.

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

7. The method according to any one of claims 1 to 5, the method further comprising: recovering the dicarboxylate; and converting the dicarboxylate to methyl furan-2,5-dicarboxylate or furan-2,5-dicarboxylic acid, or both.

8. The method according to any one of claims 1 to 5, wherein the base, the furanate counterion, or both are selected from: lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

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

10. The method according to any one of claims 1 to 5, wherein the dicarboxylate comprises dimethyl furan-2,5-dicarboxylate.