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Title:
USE OF CARBOXYLIC ACIDS IN THE PRODUCTION OF 2,5-FURANDICARBOXYLIC ACID
Document Type and Number:
WIPO Patent Application WO/2016/057676
Kind Code:
A1
Abstract:
Methods for providing effective, efficient and convenient ways of producing 2-5-furandicarboxylic acid are presented. In addition, compositions of 2-5-furandicarboxylic acid including 2-5-furandicarboxylic acid, and at toast one byproduct are preserved, in some aspects, 4-deoxy-S-dehydroglucaric acid is dehydrated to obtain the 2-5-furandicarboxylic acid, A solvents catalyst, and/or reactant may he combined with the 4-deoxy-S-dehydroglucaric acid to produce a reaction product Including the 2-5-furandicarboxylic acid. In some arrangements, the reaction product may additionally include water and/or byproducts.

Inventors:
ADAMIAN, Victor, A. (150 W. Warrenville Road, Mc 200-1wNaperville, IL, 60563, US)
BINDER, Joseph, B. (150 W. Warrenville Road, Mc 200-1, Naperville IL, 60563, US)
SHEA, Ryan (150 W. Warrenville Road, Mc 200-1, Naperville IL, 60563, US)
Application Number:
US2015/054504
Publication Date:
April 14, 2016
Filing Date:
October 07, 2015
Export Citation:
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Assignee:
BP CORPORATION NORTH AMERICA INC. (501 Westlake Park Boulevard, Houston, TX, 77079, US)
International Classes:
C07D307/56
Domestic Patent References:
WO2013049711A12013-04-04
WO2014047510A12014-03-27
Attorney, Agent or Firm:
FUZAIL, Kalim (BP America Inc, 150 W. Warrenville Road,MC 200-1, Naperville IL, 60563, US)
Download PDF:
Claims:
CLAIMS

WA S a;AlMEDJS:

1 , A method of producing 2,S~iurandicatboxylic acid com ri ing:

mixing 4--deoxy~S"dehydroghtearie acid with a earboxyiie acid and a solvent to form a reaction mixture;

allowing the 4-deo:x;y-5~dehy:drogIucanc acid to react in the presence of the carboxybc acid to produce 2 ~iunmdica?boxylle acid, water, and iryproducis: and

removing the 2.5-fufandiear oxIic acid, horn the react on product

whereto the earboxyiie acid is selected from, the group consisting of acetic acid, trill unroaceiic acid, propionic acid, butyric acid, formic acid, and eonfoinations thereof,

wherein t e solvent is selected from the group consisting of. water, methanol, ethanoi i-propanol, 2-propanol, .1 -butane L, N-me hyi nOlid nCi ionic liquids, and combinations thereof,, and

wherein the byproducts produced include lactones.

2, The method of claim 1, further comprising dissolving 4-deoxy-5~dehydroglucatic acid in water prior to mixing the 4"deoxy~S~ ehydroghicade acid with the catboxylie acid and the solvent,

3, The method of claim L wherein the 2,5-fnrandicarboxylie acid has a yield of greater than 50 m s¾,

4, The method of claim I , farther comprising adding a catalyst to the reaction mixture,

5, The method of claim 4, wherein the catalyst is selected from the group consisting of a bali.de salt a hydrohaiie acid, elemental iotn and combinations thereof,

6, The method of claim. 4, wherein the catalyst is selected from, the group consisting of sodium chloride, potassium chloride, lithium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, Fe(¾, Aids, Ni¾£h B lMjCl, sodium .fluoride, potassium fluoride, lithium fluoride, rubidium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, sn-outium fluoride, barium fluoride, !¾¾,, A!F¾ NRjF, p iMJF, sodium iodide, potassium iodide, lithium iodide, rubidium, iodide, cesium iodide, magnesium iodide, calcium Iodide, strontium iodide, barium iodide*. Fefj, Alls, N!¾b [EMlM]b sodium bromide, potassium bromide, lithium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, barium romides Fe i¾, A.1B¾ ¾Br, [EiVOMJB memarsesuiibnie acid, rIiliK¾rometh »es I&m c acid, sulfuric acid, ydrobtomio &ci $ hydroiodlo acid, irydroftuorie acid, hydrochloric add. and comb na ions thereof.

7, The method of claim 15: wherein th 25S-ft mdiearboxyiie acid has a yield of greater thai 70 mo .%.

8, A method of producing 2,S nra5idlearhoxylle acid comprising:

mixing 4-deoxy-5~dchydxogiuearic mid wit a eafboecylic acid to form a .reaction nmluro; and

allowing "deoxy-5*dehydroglnoaric acid to react in tfc presence of the carboxylie acid to produce a reaction product including 255--forandicarboxyiie acid, water and byproducts,

9, The: method of claim. S, further comprising dissolving the 4-deoxy-3~dehydroghicarie aeid. in water prior to mixing with a oarboxylic acid.

10, The method of claim 8, .f her eonmrismg adding a catalyst to the reaction .mixture,

1 L The method of claim 10s wherein die catalyst is selected from die group consisting of haiide salt, a hydrohalic acid, elemental ion, and combinations thereof

.1.2. lire method of claim 10, wherein the catalyst is a haiide salt selected fern the group consisting of alkali metal Inwddes, alkaline earth metal bromides, transition metal, bromides, rare earth .metal bromides, alkali metal ch rides* alkaline earth metal chlorides, transition metal chlorides, rare earth metal chlorides, alkali metal, imorldes, alkaline earth .metal fluorides, transition metal fluorides, rare earth metal fluorides, alkali metal iodides, alkaline eart metal iodides, transition- metal iodides, rare earth, metal, iodides, and combinations thereof

13, Ί/he method of claim 1.0, wherein die catalyst is a haiide salt selected from die group consisting of organic cations In combination with chloride, organic cations in combination with fluoride, organic cations in combination with iodide, and combinations thereof

14. The method of claim 13, wherein the organic cation Is selected from the group consisting of quaternary ammonium ions, tertiary ammonium ions, secondary ammonium ions, primary ammonium ions, phosphonium ions, and combinations thereof 15, The method of claim 10, wherein the catalyst is selected from the group, consisting of sodium chloride., p tassi m chloride, lirihum chloride, rubidium chloride, eesiimi chloride, magnesium chloride, calcium chloride, strorbium chloride, barium chloride, Fe€.l.¾ A ¾. NEtCJ, [EM }Cis sodium fluoride, potassium fluoride, lithium fluoride, rubidium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, Fel¾, A.IF3, NbUF, paMiMjF, sodium iodide, potassium iodide, Lithium iodide, rubidhan iodide, cesium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, Pe s; A¾ N¾I, piMI ]!, sodium bromide, potassium broraide, lithium bromide, rubidium bromide, cesium bromide, magnesium bromide, calcium, bromide, strontium bromide, barium bromide, FeRtj, Α1Β¾ N¾B.r, [B lM]Br, med anesulfbnle acid, trifluoromoihanesuiibirie acid, sulfuric acid, hydrohromie acid, hydroiodsc acid, hydrofluoric acid, hydrochloric acid, and combinations thereof.

Id, The metho of claim. 1.0, whereirs the carboxylic acid, includes acetic acid and triiluoroacebc acid, and the catalyst includes hydrobromle acid.

17. The method of claim 8, wherein the carboxyiie acid is selected from the group c nsisting of acetic acid, tr fluoroaeetie acid, propionic acid, butyric acid, formic acid, and combinations thereof

18. The method of claim 8, wherein the carboxylk acid is a lri.fi uoroacetic acid.

19. The method of claim 8, wherein the carboxylk acid has a pKa of less than 3,5,

20. The method of claim 8, further comprising adding a solvent to the reaction mixture.

21. The .method of claim 20, wherein, the solvent Is selected from the group consisting of water, methanol, ethanol, 1-p.ropan.o!., 2-propanol, 1-butanoi, N-methylpyrrohdone, ionic liquids, and combinations thereof

22. The method of claim 8, wherein the byproducts include lactones selected bom the

.. and combinations thereof 23:, The method of cl im 8. wherein the 2$S-&randiearbo¾lic acid has a yield of greater thai! 50 mol%,

24, A method of producin 2,5~furandicarboxylic add comprising:

mixing 4~deoxy~5~dehydrog1i:eadc acid with a carboxylic acid, and solvent to form a. reaction mixture; and

allo wing the 4-deoxy -dehydroginearle acid to react in t e presence of fee earboxylk ask! to produce ^.S- urandiearboxyiic acid, water, and byproducts,

wherein the carboxylic acid i¾ selected from the group consisting of acetic acid, triiiuoroacetie acid, propionic acid, butyric acid, ibrrnic acid, and combinations thereof, and wherein the solvent ¾ selected iom the group consisting of water, methanol, etbaaoi, i --propanoL 2-propanoh 1 -bntanoL H-methy!pyrrelidone, ionic liquids, and combinations thereof

25 , A. method of producing 2s5~romndicarboxylic acid comprising;

mixing a solution including 4-deoxy-5-dehydrogiucaric acid and water with a carbox lic acid and a solvent to form a reaction .mixture;

allowing the 4wieoxy-5~deh drog rrcarle acid to react in the presence of the carbox lic acid to produce 2i5-iurandicarboxylie acid, water, and byproducts; and

removing the 2,5 urandicarboxlic acid .from the reaction product,

wherein, the carboxylic acid is selected, from the group consisting of acetic acid, trifiuoroaeetic acidf propionic acid, buiy.no acid, ibrrnic acid, and combinations thereof, and wherein the sol vent is selected from the group consisting of water, methanol, ethano!, !.~propanoh 2-propanoi, l~bofemol, N-methyipyrrohdone. ionic Iliads, and combinations thereof

26. A method of producing 2,S brandicarboxylie acid comprising: mixing a solutio including d-deoxy-S-dnhydrogluearie acid and water with a carboxylic acid, a catalyst and a solvent in a reaction vessel to form a -reaction mixture;

heating the reaction, mixture to a temperature no greater than 150*€;

allowing the 4-deoxy-5-delr droglucario acid to react in tire presence of the carboxylic acid, the catalyst, and the solvent to produce a reaction product including 2,5- mrandiearboxylie acid, byproducts, and water;

removing the water produced during the reaction continuously or periodically and add: from the reaction product,

wherdxs the sol es! is selected ironr the group consisting of water, methanol, ethane I, 2-pro£>anoL hbutanol K~niethyl pyrrol idone, iomio liquids, and combinations thereof,

wherein the catalyst is selected from the group consisting, of sodiom chloride,, potassium cliioride, lithium chloride, tobidium chloride, cesium chloride, magnesium chloride, calem . chloride, strontium, chloride, barioro chloride, Fe<¾, Al€¾, Ni¾Ci, [E iMJCL sodhna fluoride,, potassium fluoride, lithium f xoride, rubid m fluoride, cesium fluoride, magnesium fluoride, e&lciunr fluoride, stmntf fluoride, barium fluoride, 1¼1¾, Ad¾, N¾F, pMIMIP, sodium iodide, potassium iodide, lithium, iodide, rubidium iodide, cesium iodide;, magnesium iodide, c¾3cium iodide, stroorhim iodide, barium iodide, Fe¾, A¾ l4i, [EMlMji, sodium bromide, potassium bromide, !ithiuaa bromide, rubidium bromide, cesium bromide, magnesium romide, .calcium hromide, strontium bromide, barium bromide, PeB¾ A1B¾ NRfBr, B'MlMJBr, methanesuiib iic acid, bii uoromodrauesutf uic acid, sulfuric acid, hydrobroraic acid, hydroiodic acid, hydrofluoric add, hydrochloric acid, and combinations tliereoi

wherein me eatboxylie acid is selected f om the group consisting of acetic acid, irifluoroacetic acid, propionic acid, butyric acid, formic acid, and eomhimmons thereof aud wherein the byproducts produced include lactones.

27, The met od of claim 26, further comprising preheating the reaction vessel to a temperature of 60* C 'before mixing the solution including the 4~deoxy-5-dehydrogiuearic aoid and water with the cathoxy!ie acid, the catalyst,, and the sol vent in the reaction vessel ,

28.. The method of claim 26, wherein the 2fS~furandicarboxylie add has a yield of greater than 50 ra.oi%.

29, The method of claim. 26, wherein the earboxyiic acid is acetic aeid and the soiyent is water.

30, The method of claim. 26, whereiu the carboxylic acid is acetic acid, a d the solvent is hydrochloric, acid,

31 , The method of claim 26, wherein the 2,5-furandk3iboxy lie acid has a yield of greater than ?0 mol%.

32. A composition of 2J-i½a dlc rb x ic acid kcladkg :al least 85 wt 2,5- &randcarjCJ}£lie add. and. at least orse byproduct selected from on or .more of 2-furoie acid and lactoses, prepared by a. mehod comprising:

nlkmg; 4~deoxy"5~d.eliydr«iiucaric acid wth a carbcmyiio acd to orrrs. a reaction ml¾ re; and allowing 4~d:eo¾y-5-dehydiOghieark acid to react in the presence of the earboxyBc acid to produce a reaction product diclading 2>5"fursiid5car oxy!ic acid, water md. byproducts:.

Description:
USE 01? CAKBOX¥LIC AC!BS IN ' THE .PRODUCTION OF 2,S~

FURA JMCMBCDCYLIC AC:O>

CROSS-REFB EHCE

(¾00XJ This application claims the benefit of S * provisional p lest application Serial No, mim filed. October % 2014, and mlltk4 of. (¾r x>xy!ic Adds in the Production of:2,5 ¾t¾»dicar o?i ¾ Acid " which is ' hereby incorporated herein by reference in its entirety .

BACKGROUND .0002] 2: S 5-&randiear oxylie acid (FDCA)- and FDCA esters are recognized as potential intermediates in numerous chemical fields. For instance, FDCA is idendfied as a prospective precursor in the productloo of plasties, fuel, polymer materials, pharnniceotieals, agricultural chemicals, and enhancers of comestibles, among others. Moreover, FDCAs ar highlighted by the U.S. Department of Energ as a priority chemical for developing future " men" chemis r .

SUMMARY

[ 0031 The following presents a simplified summary in order to provide a basic understanding of some aspects of die disclosure. The summary is not an extensive overview of the disciosirre. It is neither intended to identify key or cndea! elements of the diseiosare nor to delineate the scope of the disclosure. The following summar presents some concepts of the disclosure in. a simplified form as a prelude to the description below,

[0004] Aspects of the disclosure provide effective, efficient, and convenient ways of prodironig 2 5 S~ibrandicarboxyite acid. (FDCA), In particular, certain aspects of the disclosure provide techniques for dehydrating 4-deoxy-S~dehydrogluearie acid (DDG) to obtain FDCA, The dehydration reaction proceeds by combining one or .more catalysts and/or one or more solvents with a DDG starling material In some instances, the catalyst ma act as a dehydrating agent and may interact with hydroxy! poops on the DDG thereby encouraging elim nation reactions to form FDCA, The catalyst and/or solvents may assist the dehydration reaction thereby producing increased yields of FDCA.

[0005] In a. first embodiment, a. method of producing .FDCA includes hrittgkg DDG into contact with a solvent in the presence of a catalyst ie,g. s combining DDG, a solvent, and a catalyst in a reactor), wherein the catalyst is selected from the group consisting of a bromide salt, a hydrobmraie ao¾ elemental ' bromlao,. and combina ions hereof, ami. allowing D.DO to react to produce F DCA S any by roduct and water. 0 tt 1 I» other embodiments, a method of producing FDCA includes bringing DDG into contact w th a solvent i the presence of a catalyst (e,g. s combining DDG, a sol en , and a catalyst in a. reactor),, wherein the catalyst is selected fcaa the group consistin of a hahde salt, a Iwdrohahc acid, elemental Ion, and combinations thereof, and allowing DDG to react to produce FDCA, any byproducts, and water,

|0I)I)7| In another embodiment a method of producing FDCA includes bringing DDG into contact with a acidic solvent In the presence of water, and allowing DDG, the acidic solvent, and water to react with each other in produce FDCA, any byproducts, and water.

[QOftQ in some embodiments, a method of producing FDCA Includes bringing DDG into contact with a carboxylic aei.d ? and allowing DDG and the eatboxyiic acid to react with each other to produce FDCA. any byproducts, and water.

[W&9\ These features, along wi th nmuy others, are discussed In greater detail below,

BMBF DESCRIPTION OF THE DRAWINGS i1 j The present disclosure Is illustrated by way of example and not limited, in the accompanying figures in which Eke referen e numerals indicate similar elements and in which;

POIIJ FIG. I Illustrates graph that depicts the benefit of using water with an acidic solvent according to- one or more embodiments,

DETAILED DESCRIPTION

[0§12| Various examples, aspects, and embodiments of the subject matter disclosed here are possible and will be apparent to the person of ordinary skill in the art, given the benefit of this disclosure. In this disclosure reference to "eerbim exemplary embodiments" or aspects (and similar phrases) means that those embodiments or aspects are merely non-limiting examples of the subject matter and thai there likely are other alternative eoibodimeots or aspects which are not excluded. Unless otherwise indicated or unless otherwise clear from the context in which it is described, alternative elements or features in the mbodiments and examples below and in the Summary above are interchangeable with each other. An element described, in one example may be interchanged or substituted for one or n¾ne corresponding elements described in another example, Sim larly, optional or non-esseuijai features disclosed «* connection with a particular endmdiment or example should be understood, to be disclosed for use in any other embodiment of the disclosed subject matter. More generally, the elements of the examples should be understood to be disclosed generally fo use with oilier aspects and ex m les of be products and methods disclosed herein. A reference to a component or Ingredient being operative, i.e., able to perform one or more fractions, tasks and/or operations or the like, Is intended to mean that, it can perform the expressly recited nmelion(s), task(s) and/or operailoufs) ia at least certain embodi errts, and may well be operat ve t perform also one or more other .foneti os, tasks and/dr operations.

While this disclosure Includes specific examples, including presently preferred modes or embodiments, those skilled in the art will appreciate thai there are numerous variations and modifications: within the spirit and scope of the Invention as set forth.3» die appended claims. Bach word and phrase used, in the claims i intended to include all Its dictionary meanings consistent with its usage in this disclosure aud/ot with its technical and industry usage In say relevant technology area. Indefinite articles, such as "a," and "a " and the definite article "the" and other such words and phrases are used in the claims in the usual and traditional way in patents,, to mean, "at least one" or "one or more." The word "comprising" is used in the claims to have its traditional, open-ended meaning, that is, to mean that the product or process defined by die claim may optionally also have, additional features, elements, steps, etc. beyond those expressly recited.

De!wdratk s reaction of M>G to FDCA

[1)014] The present invention Is directed to syndicating 2,S~disubsututed furans (which may include,, e.g., FDCA) b the dehydration of oxidized sugar products (which ma include, e.g., DDG), In accordance with some aspects of foe invention, the dehydration methods produce higher yields and/or higher purity 2,5-di fctiiuted furans than previously known dehydration, reactions. f fJt.1.5] in certain aspects, the DDG may be a. DDG salt and/or a. DDG ester. For example, esters of DDG- may include dibntyl. ester (DOO-DBE), Salts of DDG- may Include DDG 2K, which is a DDG dlpotassinm salt. The FDCA. may be au FDCA ester (e.g., FDCA-DB!s), For example, a starting material of DDG-D8E may be dehydrate to produce FDCA-DBE. For ease of discussion, "DDG" and "FDCA" as used herein refer to DDG and FDCA generieaily (Including but not limited to esters thereof), and not to any specific chemical form. of DDG md FDCA, Specific chemical forms, suefe as esters of FDCA and DDG, are identified specifically .

[ 0161 DDG s dehydrated, to produce FDCA, The dehydmiion reaction, may additionally produce various byproducts in addition to the FDCA. in some aspects, DDG is combi ed with a solvent (e.g., an acidic solvent) uu /or a. catalyst, and allowed to react to produce FDCA. DDG may be d ssolved in a first solvent prior to adding the DDG to a catalyst, In some aspects, DD may be dissolved in a first solvent prio to adding the DDG (i.e,, the dissolved DDG and the flrsi solvent:} to a catalyst aud/or a second solvent. In certain aspects, DDG is dissolved In water prior to adding the DDG to a catalyst and/or an acidic solvent. It is generally understood that by dissolving the DDG in water prior to adding my other component (e.g., a catalyst) causes a more efficient reaction from FDCA to DBG, A few reasons for why more efficient reaction may occur iaelude s by dissolv&g BDG~2 i water prior to adding a catalyst or acidic solvent, the DDG-2.K is more effective in solution; DDG m adopt its preferred form whets first dissolved in water; and DDG in solution may increase yields of FDCA. j lTj In certain aspects, the catalyst is a solvent, I» some aspects, the catalys also acts as a dehydrating agen . Hie catalyst may be a salt, gas, elemental ion, and/or an acid. In certai aspects, the catalyst and/or solvent is selected from one or more of an elemental halogen (e.g., elemental bromine, elemental chlorine, elemental fluorine, elemental iodine, and tile like), hydrohaiie acid (e.g., hydrohronrie acid, hydrochloric acid, hydrofluoric acid, hydroiodie acid, and the like), alkali and. alkaline earth metal salts (e.g., sodium, bromide, potassium bromide,, lithium bromide, rubidium hmmide, cesium bromide, .magnesium bromide, calcium bromide, strontium bromide barium bromide, sodium chloride,, potassium chloride, lithium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, sodium fluoride, potassium fluoride, lithium fluorides rubidium, fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, stmotinm. fluoride, barium fluoride, , sodium iodide, potassium iodide, lithium iodide, rubidium iodide, , cesium iodide, magnesium Iodide, calcium iodide, strontium, iodide, barium iodide, other alkali or alkaline earth metal sabs, other salts in which at least some of the negative ions are haiides. and the like), acetyl chloride, other acid, halides or activated species, other heterogeneous acid catalysts, tri.fi uoroaeedc acid, acetic acid, water, methanol, ethanoi, 1- ropa oi c 2~pOpariol, l-bmanob n-Kmihylpyrrolldone acid, propionic acid, butyric acid, formic acid, other ionic liquids, nitric acid, sulfuric acid, phosphoric acid, methanesnifimlc add, p-tnlnenesulfonk acid, other supported sulfonic acids (e.g., nation, Anrberiyst%1 , other s fhnie acid resins, and t¾ like), heteropoly acids <e,g ;> Mn stoS ek aeid, pbosphornolybdie ac-ki phosphMungstlc acid, aofi the like), adds with a firs! pKa less than 2„ and other supported organic,, or inorganic acids, and supported or solid acids, A catalyst may be obtained firor my source thai produces that catalyst in a reaction mixture (e.g . ,, a bromine containing catalyst may bo obtained from ny compound that produces bromide ions in. me reaction mixture). f ' 00I8 ' ) Acetic acid is a particularly desirable solvent as the ultimate FDCA product has a lower color value, e.g. it Is whiter than products rod ced with other ol ents. r ooroaceiic acid and water arc additional pr fer ed lve ts for the production of F.DCA. Addldonaiiy, the combina ions of itiiluoroacede acid with water and acetic acid with water are particularly desirable for being low cost solvents.

[ 191 It is generally understood that the. dehydration of DDG to FDCA by the methods discussed herein provide molar yields of FDCA larger than those obtained from previously known, dehydration reactions. In some aspects, the dehydration reaction yields at: least 20%, at least 30:%, at least 40% 5 at least 50%, at least 55% . , at least 60 , at least 65%, at least 70%, at least 75%, at least §0%, at least 83% s at least 90%, at least 95%, or at least 99% molar yieid of FDCA that may be produced from DDG as the starting Material In other aspects, the dehydration reaction yields betwee 20% ami. 100%, between 20% and 90%. between: 20% and. 80%, between 30% and 1 0%, between 30% and 90%, between: 30% and 80%, between 40% and 100%, between 40% and. 90%, between 40% and §0%, between 40% and 70%, between 40% and 60%, beiweera $0% and 100%, between 50% md 90%, between. 50% and 80 , between 50% and 70%, between 55% and 95%, between 55%. and 90%, between 55% and 85%, between 55% and 80%, between 55% and 75%, between, 55% and 70%, between 60% and 99%, between 60% and 95%, between 60% and. 90%, between 60% and 85%, between 60% and 80%, between 65% and 99%, between 65% and 95%, between 65% and 90%, between 65% and 85%, between 65 and 80%, between 70% and 99%, between. 70% and 95%, between 70% and 90%, between 70% and 85%, between, 75% aod 99%, between 75% and. 95%, between 75 md. 90%, between 75% and 85%, between 80% and. 99%, between 80% and 95%, between 85% and 99%, or between 90% and 99% molar yield of FDCA that may be produced from DDG as the starting material f HEOJ The- FDCA prodnced via the dehydration reaction may be isolated and/or purified. Suitable isolation or purification techniques include filtrating and washing tire PDCA product with water or reorystaill ing the FDCA. from water. ίϊΐί] Hie pu ified F X. A .«%ay have multiple uses in the : Industry such as an alternative to terephthalie acid in producing olyethyle e ierephOialaie (PET), PET is eomrsonby used to manufacture polyeste fabrics, , bottles, and other packaging, PDCA .may also be a precursor for adipie acid, jet f elSj other dial ' s, dianilrsc., or dialdehyde based chemicals, fCK llJ in one aspect, the process described, above is conducted by adding DDG and a catalyst and/or a solvent Into a reaction vessel provided with a slirr g nreehanism and then stirring the resulting mixture, ' lire reaction vessel may be a batch o a continuous reaotor. A continuous reactor may be a ping tlow reactor, continuous stirred tank, reactor, and o tinuous stirred tank reacto in series, In some aspects, the reaction vessel may be selected tor a dehydration reaction based on its metallurgy (e.g.. a aireotunm reactor may be selected over a teflon reactor for reactions utilizing bromine), A reaction vessel may be a xireoniom reactor, a teflon reactor, glass-lined reactor, or the like, lire temperature and pressure within the re ction vessel may be adjusted as appropriate. The 1>DG may be dissolved in water or another solvent prior to adding the DDG (ie. s the dissolved DD© and solvent) to the reaction vessel, in certain aspects, DDG Is .mixed with tire solvent at a temperature in the range of 5° C to 40* C, and in more specific aspects at about 25° (1 to ensure dissolution in the solvent before the catalyst is added and reaction is initiated. Additionally and/or alternatively, the catalyst may be mixed with the solvent at room temperature to ensure dissolution i the solvent before being added to the DDG. j¾02 ' 3.| in some aspects, the process includes removing water produced daring the. reaction. Reducing at least some of the water produced may reduce or eliminate side reactions and reactivate the catalysts, As a consequence higher product yields may be obtained, Any suitable means ma be used to regulate the amount of water in the reaction vessel such as use of a water content regulator, t ' 0024] The manufacturing process of FDCA may be conducted in a batch, a serai- continuous, or a continuous mode, i certain aspects, the manufacture of PDCA operates in a hatch mode with increasing temperatures at predefined times, increasing pressures at predefined times, and variations of the catalyst composition durin the reaction, Fo exam le, variation of the catalyst composition during react on can he accomplished by the addition of one or m re catalysts at predefined times.

|0(£2SJ The. tem erature sad pressure typically can he selected from wide range, Bowever, when the reaction is conducted Irs. the presence of a solvent, the reaction temperature and pressure may not be independent. For example, the pressure of a reaction mixture may be determined by the solvent pressure at a certain temperature, irrsorne aspects, the p essure of the reaction mixture is selected, such that the sol vent m maia!y in. the liquid phase. flh26J T e: temperature of the reaction mixture ma fee within the range of 0° C to 180° C, and in certain aspects may he within the range of 20 s C to 1(KP C, and in more specific aspects within, the range of ό ' Ο* C to 100 e C. A temperature above l W C may lead to decarboxylation to other degradation products and. thus such h g er temperatures may need, to he avoided, pM)27J In some aspects, a dehydration reaction may run fo lip to 48 .hoars, in alternative aspects, a dehydration.. reaction may run for less than S minutes (i.e., the dehydration reaction, is at least 95% complete within. 5 minutes). In certain preferred examples, a dehydration, reaction may occur within ' the time range of 1 minute to 4 hours, (i.e., the dehydration reaction of the reaction mixture is at least 95% complete within 1 .minute to 4 hours), in some aspect the reaction of the reaction mixture is at least 95% complete within no more than 1 .minute, 5 minvnes, 4 hours, 8 hours or 24 hours, lire length of the reaction process may be dependent on. the temperature of the reaction mixture, the concentration of DDG, the concentration of the catalyst and the couceuimdon of other reagents. For example, at low temperamres (e.g., at or near the freezing point of the selected solvent) the .reaction may run for up to two days, hut at high temperatures (e.g <s , above 1.CKF C) the .reaction .may run for less than ive minutes to achieve at least 95% completion. 281 " Upon, completion of the reaction process, a reaction product ma he formed irieiudm F0CA and various byproducts. The terui ^hyproducis" as used herein includes all substances other than 2,5-fnrandiearboxylic acid and water, . In some- aspects, the number, amount, and type of byproducts obtained in me reaction products ma he different than those produced using other dehydration processes. Undesirable byproducts, such as 2-furoie acid and lactones, may he produced in limited amounts. For example, byproducts may melode,

and the lik , In certain aspects, d dtfabie byproducts may also include DDG-eienved organic compounds containing at least one bromine tom, A reaction product may contain less l¾an 15 %, alternatively less than 13%, alternatively W% to 12%. or preferably less than 10% byproducts. The reaction product may contain at least 0.5%, about 0,5%, less than ?% : , 0,5% to ?% > 5 to /%, or about 5% ketone byproducts. "Lactone byproducts" or "lactones" as used herein include the ' one or ore lactone byproducts (e.g... LI, L¾ h% and/or 1,4) presen In the reaction product Additionally or alternatively, the reaction product may contain less t m. 10 , 5% to 10% ; or about 5% 2-&roic acid.

| ' ffi)29| In certain aspects, the resulting F.DCA ma be Isolated and/or purified, from the reaction product For example, the re-suiting FDCA may be purified and οτ Isolated by recrystaD!¾ation techniques or soiicFIiqoid separation. In som aspects * the isolated and/or purified FDCA still includes small amounts of byproducts, The purified product may contain at least 0.1% (1000 ppm) ketone byproducts. In some aspects, the purified product contains less than 0.5% (5000 ppm), or preferably less than 0,25% (2500 ppm) lactone byproducts:. In. some aspects, the isolated and/or purified FDCA product May cont n between about 0,1% to 0,5% lactone byproducts, or between about 0.1% to 0,25% lactone byproducts.

Sy»tte«s of FDC A using a iakgeu catalyst

|0030J in an aspect, F.DCA is synthesized from DDG by oonfolniog DDG with a solvent and. a halogen catalyst. The DDG undergoes a dehydration .reaction, removing two water groups. For example, DDG dipotassium salt may be dehydrated, to Form FDCA:-

| ' 0 3i] The catalyst may ' be a haiide (e,g. } a haiide ion, which may be combined with cations in salts or with protons in acid) or a halogen (e.g., a halogen in Its elemental form), in some aspects, the catalyst may be a hydr lraOc acid, an alkali or alkaline earth metal salt, a transition metal sal t a rare earth metal salt, a salt n which at least some oft.be negative ions are ha!ides (eg,, ammonium salts, ionic liquids, ion. exchange resins which are exchanged with balides, or salts of other ittetals), or ekmeatal h logem When a. halide sail Includes cations in combination with a halide, the i& may be selected from quatern ry ammooiiirn ions >: tertiary ammonitmi ns, secondary annnoninm ions, primary ammoBium iom > plmsplioniuni ions,: or soy combination thereof. Elemental halogens may be reduced in situ into halide ions, The catalyst may contain one or more of bromine, chlorine, t¾orme, and Iod ne ^ For example, a halogen catalyst may be selected from hydtobromie acid, hydrochloric acid, frydrofiuoraie dd. hydrolodic acid, sodium bromide, potassium bromide, lithium bromide, rubidium bromide, caesium b omide, magnesiam bromide, calcium komMo, strontium bromide, barium bromide, sodium chloride, potassium, chloride, lithium chloride, rubidium, chloride, caesium chloride, nnrgBes rn chloride, calcium chloride, strontium cbloride, barium chloride, sodium fluoride, potassium fluoride, lithium fluoride, rubidium fluoride, caesium fluoride, mngnesinm. fluoride, calcium tluoride > strontium fluoride, barium tiuoride, sodium iodide, potassium Iodide, lithium iodide, rabidiisui iodide, caesium iodide, nmgoesittro iodide, calcium iodide, strontium Iodide, harfara iodide, ekaieatai bromine, elemental chlorine, elemental iluorme, elemental iodine, FeB¾ A ¾, idik, [E iMJBr, i¾<¾, A.ICi ¾ N!¾CL EMl jClr, FeF ¾ AIF 3s Ni¾F, [EMlMjF, Fek. A¾ NB 4 I,. [EMI ji, or any combination thereof In certain aspects, the catalyst includes a hydrohailc acid and a ha!ide salt, I32J In certain aspects, the hydro!ialk acids or halide salts may be used as a solvent in the reaction mixture. In other aspects, the hydrohr-he acid or hailde salts may mixtures with DDG at room temperature. Additionally or alternatively, m some aspects, DDG may he treated with gaseous hydrohalie acids. In some aspects, DDG- and the halide compound are eonibiued with other solveni(s). In preferred aspects, a halide salt is combined with an acid, such as a hydrohalie acid. By using both a halide salt and a Irydrohalic acid the reaction may be catalyzed both with acid and with the beneficial effect of the halide Ions, In certain preferred aspects, a catalyst and a solvent are the same compound. For example, a catalyst and a solvent may both be hydrobromic acid, may both be a hydrochloric acid, may both be hydroiodie acid, or may both, be hydrofluoric aeid. O033| A solvent that may he combined with a halogen catalyst may be selected, from water, acetic acid, propionic acid, butyric acid, i lfinoroaeetic acid, mema¾nsulfenk aeid, su!rnric acid, methanol, ethanol, l-propaoo!, 2-propanol, !-butanol, fermlo acid, ~ nrethylpytrohdone, other Ionic liquids, or any combination thereof Various co.mliinab.ons of solvents may include a er and. acetic acid, -w ter aad proprionic acid, and water and Iriil oro&cet!e acid, β05 ) T&e reagents (e.g. 5 DDG, catalyst sol en ) may fee combined, toge&er in any suitable reaction vessel such as a batch or a continuous reactor, A. continuous reactor may be a plug flow reactor, continuous stirred tank reactor, and a continuous stirred tank reactor In series. A reactor may be selected: based, on. its metdlnrgy. For example, a reactor may be a zirconium reactor, a teflon reactor, a glass-hoed reactor, or the hke. A preferred reactor may be selected based upon corrosion and chemical compatibility with die halogen being utilised in the dehydration reaction., In some aspects, the reaction vessel is preheated (e.g, 5 preheated to a temperature of 60* C) prior to initiating a. dehydration, reaction,

[005S] i some aspects, DDG Is dissolved in water and then combined with, a halogen containin catalyst to form a reacdon mixture, l¾e reaction of the reaction mixture ma proceed at a temperature within a range of 0 s C to 20 * C > akematively within a. range of 30 " ' C to I SO* C, or preferably within a range of 60 s C to 100" (1 The pressure in the reaction vessel may be auto generated by the reaction components at the reaction, temperate-. In some aspects, hydrobrorrsic acid may- be combined with water in the reaction vessel and the pressure in. the reaction vessel may range from ! bar to 50 bar. In some as ec s, the reacdon may proceed (Le, ; reach ' 95% completion) for up to two days if die reaction temperature is low, or the reaction may proceed for less than five minutes if the temperature is 100* C or higher. A. preferred reaction, time for the reactio mixture is within†&.e range of one -minute to four hours. The reaction may proceed to yield a reaction product including FDCA, water, and other byproducts. (e,g., lactones). The FDCA may be filtered and removed from, the reaction product

[IH136} In some aspects, die reaction may proceed at a fixed temperature, in alternative aspects, the temperature of the reaction mixture may be increased rapidly after the reaction inixtum is formed. For example, the temperature of the reaction mfxinre may be increased ifom a ambient temperature or from no more than 30* C to 6.0°€ or to at least 6{Y" (3 within two minutes, alternatively within 5 .m nutes, or within 20 minutes. In another example, the iernperature of d e reaction mixture, ma be increased from an ambient temperature or from no more than 30* C to 1.00 (3 or to at least 100° C within two minutes, alternatively within 5 nhnutes, or within 20 minutes. A hist heal up time, as compared to a slow or gradual temperature increase, can limit and/or prevent side reactions ..from occurring during the reaction process. By reducing the master of side reactions that occur during the reaction process, the number of byproducts pro uced during th reaction Is reduced. In c r n as e ts, any byproducts produced by die dehydration reaction, arc present at below 15%, aUematively less- than. 12%, alternatively 1.0% to 12%, or preferably less than 10%. fOCI37j In some aspects, the halogen catalyst may b added to the reaction ' m ture in high concentrations. For exa pl * the halogen catalyst added to the reaction, mk&re may have halide eonoentradon of greater than. ! % by weight, greater than 45% by weight, between 45% to 70% by weight, greater than 55% by eight, between 55% to 70% b weight, or .at. least 65% by weight of the reaction mixture (including the halide}.. In some aspects, tits halide concentration is 50 by weight, and in other aspects the hahde concentration is 62% by weight, with a preferred halide concentration of around 58 by weigh of the reaction mixture, including th halide. If both a. halide salt and a hydrohalle aeid are added to a reaction, the combined halide concentration may be within, the range of 55% lis 70% by wei ht of the reacdon mixture, including the halide sad and hydrohalie aeid, iBSI to preferred aspects, the halogen catalyst and/or solvent contains bromine. In. some aspects, the catalyst is selected from a bromide salt, a hydrobromic acid, an elemental bromine Ion. or any combination- thereof In certain aspects, the catalyst is hydrobromic acid, Alternatively, ie catalyst includes Irydrobrornic acid and bromide salt, A reaction mixture- may contain 1. M to 13 M hydrobromie aeM, or in. some aspects 2 to 6 M hydrobromic acid. For example, a reaction mixture may include 40% to 70% water, o alternatively about 38% water, and 10 M to 1.5 M hydrobromic acid, or alternatively about 12 M hydrobronne acid. The reaction mixture including water and hydrobromic acid may produce a reaction product including FDCA, water and byproducts. The reaction product may include up to 15% byproducts,, and 70 to 05% molar yield FDCA,

( 1139} In other examples, a reacdon mixture may include 0% to 30% water, or alternatively about 8% water, 40% to 67% acetic acid, and I M to 6 M hydrohromic acid, or alternatively about 5 M hydrohromic aeid. The reacdon mixture including water, acetic acid, and hydrohromic aeid may produce reaction, product innlnding FDCA, water and byproducts, ' The reaction product may include up to 15% byproducts, and 70% to 95% molar yield FDCA,.

( ' 00 0J Exemplary sol enboaialyst combinations include, but are not limited to, 1} acetic aeid, water, and hydrobromic aeid; 2) acetic acid. and. hydrobromic acid; and 3) hydrobromic acid and water. Examples of exemplary process- parameters, inc,I«t¾g a DUG starting material, a solvent, a ca lyst, molarity of an acid molarity of the MXi, fac ion time, reaction temperature, molar yield of the FDCA, and any additional oomments, such as the v lume percent of any water added to the reaction mixture, can be seen in Table. 1 , IWIJ TABLE ! :

|fi 42] I other aspects, the- halogen catalyst and/or solvent contains chlorine, fluorine, and/or iodine. In some aspects, the catalyst is selected from a hal e sail, hydrohalic acid, an elemental halogen ion, or any combination thereof In certain, aspects, the catalyst is hydrochloric acid. Alternatively, the catalyst includes hydrohalic acid and haiide salt, A reaction mm te may contain 1 M to- 12 M hydrochloric acid. For -ex m le, a reaction mixture may include 63% to 97% water, or alternatively about 70% water, aad 1 M to. 12 hydrochloric acid, or alternatively about 1 1 M hydrochloric acid. The reaction, .mixture may als contain acetic acid, The- reaction mixture ¼ciiK¾ng water aad hydrochloric acid -.may produce a reacdon product inc udin FD£A„ byproducts, and water. The reaction product may include u to 1 S% by ro uc s, and 30% to d0% molar yield FDCA,

[80431 in <«¾ar aspects, the catalyst Is hydroiodie aeki A rea ion mixture may contain I M to 8 M hydroiodle acid. I» $om examples, a reaction mkta e may kcktde 40% to 97% water, or ahemativefy about 50% water, and 3 M to § M hydroiodle acid, or alternatively about 7 M hydroiodie acid. The reaction mixture ma als contain acetic acid. Tim reaction rnixtore mcindlng water and hydroiodie acid may produce a. reaction prodiro iaelorilng DCA, water .and byproducts. The reaction product inay include up to 15%. byproducts, and 3( % to 60% molar yield FDCA.

[0.044] Exemplary solvent/catalyst combinations iaclade* but are not limited to, !) acetic acid and hy rochloric acid, 2) water and hydroehlorfc acid, 3} acetic aeld f water, and hydroiodle acid, and 4) wate and Irydrolodle acid. Examples of exemplar process parameters. Including & DDG starting material, a solvent a catal se molarity of an aeidj molarity of the DDG, reaction time, reaction temperature, molar yield, of the FDCA, and any additional comments, such as the volume percent of any water added to the reaction oii¾ture f can he seen In Table 2. I4S] TABLE 2:

2k Water Hi .57 0.05 4 60 41 ,25:

[f!Mdf Although not wishing to be bound fey any particular theory, It Is possible that the halogen displaces ' hydroxy! groups -of the DDG, thereby aiding in the required, dehydration and/of dimi«atk>¾ reaction of the DDCJ due to its enhanced uue opMiieity . AJternati vely, It Is possible that the halogen m&y initiate additional dehydration m.ee¾amsms that n ke he halogen. oxidation states. In an event, it as discovered thai d e yield of.FDCA- increases if a halogen catalyst is used with the dehydrati n reaction of 000 t ' form f 0CA.

Symthesis of I¾CA «.si«g:-a» aeidic solves i a : ».d wafer

[0(i47j In an bo ent of the hiverndon J¾CA is synthesized by combining B0G wi th water and an acidic solv n and/or catalyst. In some as ects, the water may be used as the principal solvent for the maciion, in other aspects, die water may he added to other sol ents, such as acetic acid, to enhance the .reaction. In some aspects, aa acidic solvent acts as a catalyst (e,g. f hydrobromie aeid). An acidic solvent may be selected from hydrochloric acid, bydroiodic acid., hydrobromie acid, hydrofluoric acid, acetic acid, sulfate aeid, phosphoric acid, nitric acid, irifluoroaeeiic aeid, methanesul: mac acid, etbaaiesulfouie acid, benxenesnltmic acid, acidic ion exchange resins, other supported sulfonic acids (which may include, e.g., Nation, Amberiys .5, other sulfonic aeid. resins, and. the like), other heterogeneous acid catalysts, hetetopoly acids (which may include, e.g., tungsloslliele acid, pimsphomoiybdic acid, phosphoinugstlc acid, and the like), acids with a first pKa of less tha 2, other supported, organic, inorganic, and supported, or solid acids, and combinati ns thereof.

| 0 $ ' | In certai aspects, DOG is combined with water and. an acidic solvent- to form a reaction mixture. Is some aspects, a catalyst is added to the reaction mixture. The catalyst may be selected from. a halids salt (e.g., alkali metal !ides, alkaline earth metal ha!kles, transition metal halides, rare earth -metal halides, or organic canons (e,g. ? quaternary ammonium ions, tertiary ammonium ions, secondary ' aaunooium ions, primary ammonium ions, or phosphoninru ions) in combination with halids ions), a hydrohalie acid, an elemental ion, and any combination thereof The catalyst may be selected if orn sodium chloride, potassium chloride, lithium chloride, rtibidiem chloride, caesium chloride, mapcslum chloride, calcium chloride, strontium chloride, barium, chloride, Fe(¾, AK¾ ' N¾Ci 5 [BMJMjCI, sodium fluoride, potassium fluoride, lithium fluoride, rubidium flimride, caesium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium, fluoride, l½f¾, AlFs, M1¾F, [E IMJF, sodium iodide, potassium: iodide, lithium iodide, rubidium iodide, caesium iodide, magnesium iodide, calcium iodide, strontium iodide, barium Iodide, Pe¾ A¾, hh¾L p IMJL sodium bromide, potassium bromide, lithium bromide, rubidium. bromide., c esium brom de, magnesium bromide, calcium bromide, strontium bromide, barium bromide, FeBr ¾ A1B¾, N¾Br> |BMIM B¾ and eombioaiiom thereoi jddd j The reagents (e.g, 5 DDG,. water, acidic solvent) may be cmnhined together in any suitable reaction vessel such as a batch or a. continuous reactor. A continuous reactor may be a plug flow reactor, continuous, stirred tank reactor, and a -co»tinuo«s stirred, tank reactor in series, A reactor may be selected based on its ntetaihitgy. For example, a reactor may be a :sireoniuui reactor, a teflon reactor, a glass-hdred reactor, or the like, A preferred reactor may be selected based u on corrosion and chemical compatibility with, the reaction mixture of the dehydration reaction. In some aspects, the reaction vessel is preheated (e,g<, preheated, to a temperature of 60° C) prior to Initiating a dehydration reaction. jl0S§| In some aspects, DDG Is dissolved in water and then combined with an aeidie solvent and an additional volume of water. The reaction of the reaction mixture roceed at a temperature withi a range of 0° CI to 20(P C, alternatively within a range of 3d" C to 150 's C, or preferably within a range of 60° C to 100* C, The pressure in the reaction vessel m b -auto generated by the reaction com one ts at the reaction temperature. The pressure in the reaction vessel may range from I bar to 17 bat, In some aspects, the reaction, may proceed (i.e.,. achieve 95% cornpiedon) tor up to two days if the reaction temperature is low, or the reaction, may proceed, for less than live minutes if the temperature is 100°€ or higher, A. preferred reaction time for the reaction mixture is within the range of one minute to four hours. The reaction may proceed to yield reaction product including FDCA, water, and other byproducts (e.g.,. lactones), T he FDCA. may be filtered, and removed trom the /reaction product, 0OSI ' | In some aspects, the reaction may proceed at a fixed temperature. In alternative aspects, the temperature of the reaction -mixture may be Increased rapidly after the reaction mixture is ionised. For example, die temperature of the reaction mixture may be increased from an ambient temperature or from no more than 30° C to 60* C or to at least 60° C within two minutes, alternatively within 5 minutes, or within 20 minutes. In another example, the temperature of the reaction mixture may be increased from an ambient temperature or from no more than 30° C to 100* C or to at least 100° C within two minutes, alternatively within 5 minutes, o within 20 minutes, A fast heat op time, as compared, to a slow or gradual temperature increase, can limit and/or prevent side reactions from occurring during the reaction process. By reefneing the number of side reactions that occur during the reaction process, the number of byproducts produced daring the reaction Is reduced. ¾ certain aspec s, any ' byproducts- produced by the dehydration reacti n arc present at below 15%, alternatively less than 12%, alternatively 10% to 1 or preferably less than 10%,

£0052] In some aspects, water ma be added to the reaction -mi ture The including of water can have a significant impact on. the reaction and yield. For example, water can be in the reaction mixture in an amount (by volume) of at least 10 ' %,. at least 20%, at least 30%, 1 % to 70% s . 1.0% to 30%, or 30% to 65%. In preferred embodiments, the reaction mixture includes water and bydrobr mie acid. The reaction mixture may contain I M to 13 M hydrobro ic acid, or in some aspects 2 M to 6 M hydr - ' bromie acid. For example, a reaction, mixture may include 10% to 70% water, or ah¾rnatlyely 30% to 6-5% water, and 10 M to 1$ hydrobromic acid, or alternatively about 12 M I diobromie acid. The reaction mixture including w te : and hydrobromie aeid .may produce a reaction, product Including FDCA, byproducts, and water. The reaction product may include up to 1.5% byproducts, and. 40% to 9S% molar yield FDCA..

[0053] Exemplary solvent/catalyst combinations include, but are not limited to, i) ator- and hydrobromie acid; 2) wate and hydrochloric acid; 3) water and nydroiodic acid 4) water and methanes !i mc aeid; and 5) water, acetic acid aod sulfuric acid. Examples of exemplary process parameters, meloding a DDO starting material, a solvent, a catalyst, molarity of an. acid, rnrdarity of the DDG, reaction time, reaction temperature, molar yield of the FDCA, and- any additional comments, such as the volume percent of any water added to the reaction mixture, can. be seen in Table 3.

S0O 4I TABLE 3.

Id

I00S5J Conditions for various alternative dehydmdon reactions utO ng DDG-2K as the s arting material are provided Irs Table 4, The first line for each oold provides a: working range tor eac reaction condition and the subsequent M»e(s) provides examples of specific reaction conditions. As seer? in FIG, 1 , higher molar yields of F DC A may ho obtained when utOiEmg both water and hydrobromk acid in dehydration reaedons.

0856] TABLE 4

ptJS7) It. was unexpected that the addition of water to the reaction m xtur would increase the yield of a product in a. dehydration reaction because water is the product of dehydration,, and by Le Chatetiers * principle increased concentrations of water would be expected to disfavor dehydration chemistry, Although, not wishing to be bound by any particular tkeory, possible reasons fo the advantageous effect of water may be good solubility of DDO and acids in wafer,, low solubility of FDCA i water, stabilisation of transition states for dehydration chemistry by tbe polar solveat, and the p r eference of DDG for imanoid forms in water, which are pre-disposed for dehydration Into f DCA,

| )0S8} Additionally, water may be an advantageous solvent for the dehydration of DDG to FDCA because th water causes the DDO to assume a fhranoid form thai is ' bete for dehydration, reactions. The furanoid fer s of DDG are S-nicrnbered rings -which may be easy to dehydrate Into PDOA. When tbe DDG assumes- its preferred form it produces fewer byproducts during the dehydration reaction, as well as encouraging a more efficient (e.g.. faster) reaction, 0O5tJ FDCA. may be further isolated at a Mgh purit (eg., about 99%) irons tbe above described reactions by filtrating and washing the FDCA prod net with, water only.

Synthesis of D A using a carhoxylic M (<HM$1 In as embo i ent of the invention, FDCA Is : sy thesized tto . DDG in combination with a carbsxyiie acid. For e&amplivDDG may be dehydrated to form. EPCA m a carbox lic acid solvent:

l&Mil] A e&rboxyile acid may be combined with DDG to produce a reaction product Including FDCA. Br ame spects, the carboxylic add id DDG are combined with: solvent and/or: a catalyst, in other aspects, the carboxylic acid acts as both a solvent and a catalyst. For example, a carboxylic acid with a low pKa (e.g.. less than 3,5) may act as both, a solvent and a catalyst in the reaction. In some aspects, a cat ly t may be added to the carboxylic aeid having a low pK to speed ιψ the reaction of DDG to FDCA. In another example, a. carboxylic acid with a high pKa (e.g., greater than 3,5) may be combined with a catalyst, and In some aspects a solvent. In some aspects . , a carboxylic acid .may be selected from, trill uoroacetic acid, acetic acid, acetic acid, propionic acid, butyric acid, other carboxylic acids with a low pKa (e.g., less tha 3,5 or a pKa less than 2.0), other carboxylic acids with a high. pKa (e.g., greater than 3.5), and any combination thereof.

£0062] In some aspects, a solvent is added to the reaction mixture in addition to the carboxylic acid. Solvents ma he selected .. from water, methanol ethanal, l-propanol, 2~ propane!, lAnmmol, N-methylpyrro!ldono, other ionic liquids, or any combination thereof In certain aspects, the dehydration reaction may utilize three sobvents In combination. la alternative aspects, the dehydration rea tion may utilize two solvents in combination. In still other aspects, the dehydration reaction may utilize a single solvent.

In certain aspects, a catalyst is added to the reaction mixture. The catalyst may be selected from a hahde salt (e.g., alkali metal halides, alkaline earth metal halides, ttaiisrhon metal, halides, rare earth metal halides, or organic cations (e,g,, quaternary anrnroniurn ions, tertiary ammonium loos, secondary ammonium ions, primary ammonium, ions, or phosphonium ions) In combination with halide ions), a hydrobalic acid, elemental ions, a strong acid, or an combination thereof For example, the catalyst may be selected from sodium chloride, potassium, chloride, lithium chloride, rubidium chloride, caesium chloride, .magnesium chloride, calcium cMaride, strontium chloride, bariu chloride, Pe€I¾ AK¾ i¾Cl, pMi jCL sodium lluorlde, potassium fluoride, lithium fluoride, rubidium. iluoride s caesium fluoride, magnesiu fluoride, -calcium fluoride, strontium fluoride, barium fluoride, Pel¾ > A!F 3i ¾F, -Mi :jF 5 s dium iodide, potassium Iodide, lithium iodide, mbidi n iodide, caesium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, Fe¾, Al¾,. Nl¾h [EMIMjl, sodium bromide, potassium hmuride, lithium hrouiide, rubidium bromide, , caesium bromide, magnesium bromide, eaieiuro. bromide, stondnm. brom d , barium bromide, FeBr ¾ ΑΙΒ¾, K¾Br 4 [EMiM]Br, hydrphromle add, hydroiodle acid, Irydre loorlc acid, hydrochloric acid, elemental bromine, elemental ehi.ori.ue, elemental fluorine, elemerrtal iodirje s , SBefhanesuifbriio acid, trifinoromethanesul bmc acid., sulfuric acid, and cornbinadous hrereof

[0064] The reagents (e,g., BDQ, catalyst, solvent) may be combined together In arr suitable reaction vessel such as a batch or a continuous reactor, A continuous reactor may be a plug flow reactor, co i uous stirred tank reactor,, and a continuous stirred tank, reactor in series, A reactor may be selected, based, on its metallurgy. For example, ¾ reactor may be a. zirconium reactor, a teflon reaeior, glass-lifted reactor or the like. A preferred reactor may be selected based upon corrosion, and chemical compatibility with the carboxylie acid being utilized in the dehydration reaction. In some aspects, the reaction vessel is preheated (e.g,, preheated to a. temperature of 60° G) prior to Initiating a dehydration reaction,

[006-5] Is some aspects,. DDG is dissolved in water and then combined with a carboxylie acid, and In s me Instances ' catalyst and/or solvent, to .term, a reaction mixture. The reaction of the reaction mixture may proceed at a: temperature within a range of 0° C to 200° €, alternatively within a range of 30* C to IW C * or preferably within a range of 60* C to 100° C, The pressure in the reaction vessel .may be auto generated by the reaction components at the reaction temperature, m some- asp cts, acetic acid may be used in the reaction, vessel and the pressure in the reaction vessel may range from 1 bat to 10 bar. In some aspects, the reaction may proceed for up to two days if the reaction temperature is low, or the reaction ma proceed tor less than five minute if the temperature is 1.00°€ or higher, A preferred reaction, time (i.e., time to achieve 95% completion.) for the reaction mixture is within the range of one minute to four hours. The reaction may proceed to yield a reaction product including FDCA, water, and. other byproducts (e.g., lactones). The FDCA. may fee filtered, and removed from the reaction product,

[10M6J In some aspects, the reaction may proceed at a feed temperature. In alternative aspects, the temperature of the reaction, mixture may he increased rapidly after the reaction mixture is formed. For exam le, ihe temperature of the reaction mixture m y be increased from, arr arab!errt temperature or from no more (ba 30° G to 60° C or to at least 6(P C imk two minutes, alternatively within 5 minutes, or within 20 .minutes. In another example, the temperature of the reaction mixture may be increased from m ambient temperature or from no more than 30° C to 100° C or to at least 1:00° C within two minutes, aheraatively within 5 minutes, or within 26 minutes. A fast heat ixp time, as compared, to stow or gradual tempemlore increase, ca t limit and/or prevent side reactions from occurring d rmg the reaction process. By redneing the number of side reactions that occur during the reaction process, the number of byproducts produced, during the reaction is reduced. In certain aspects, any byproducts produced by the dehydration reaction are present at below 15%, alternatively less than. 1.2%, alternatively 10% to 12%, or preferably less than 10%,

|0067j In preform! aspects, tire carboxylie acid is tdrluoroaeetie acid. A. reaction mixture may contain triiluoroaceiic acid, and hydrohronric acid. For example, a reaction mixture may include 0 M to 6.0 M hydrobromic acid, or alternatively about 3 M hydrobromic acid. The reaction mixture including hydrobromic acid and trill uoroacetlc acid may produce a reaction product including FDCA, byproducts, and water, The reaction product may include up to 15% byproducts, and 50% to 80% molar yield FDCA. In some additional examples, water may be added to the reaction mixture. In certain aspects, 5 vol.% to 30 vol.% of the reaction mixture is water.

Exemplary catalyst or not limited to, 1.) txifluoroaeetic acid, and sulluric acid; 2} acetic acid, and hydrobromic acid; 3) hydrobromic acid, triiluoroaeet!c acid, and water; and 4) hydrobromic acid, tri loo oacelic acid, acetic acid, and water. Examples of exemplary process parameters, including a DDG starting material a solvent, a catalyst, molarity of an acid, molarity of the DDG, -reaction time, reaction temperature, molar yield of the FDCA, and any additional comments, such as the volume perceat of any water added to the reaction mixture, can be seen in Table 5,

[ 1 69] TABLE 5:

10070 . 1 Conditions for various alternative dehydration reactions utilising DDO-2K as the starting material, in combinatio with trirlnoroaeetie acid, acetic acid, or trifiiroroanede acid and acetic acid in combination are provided in Table 6. iOOTIi TABLE 6:

strong acid

| 072| It was unexpected for carboxyiic acids to. act as an effective medium tor the dehydration reactio of DDG to FDCA. Although not wishing to be bound by an particular theory, carboxyiic acids may bo an advantageous solvent aad/or catalyst for the dehydration of DDG to FDCA because the carboxyiic acid causes the DDG to ass me ihranold forms that are better for dehydration reactions. The luraoold forms of DDG are S-metnbered rings which may be easy to dehydrate into FDCA. When the DDG assumes its preferred form it produces fewer byproducts dar ng he dehydration reaction * as well as enco¾i¾gmg a more efficient (e.g., faster) reaction.

[0873J Acetic acid may be aa advantageous solvent for the dehydration of DDG to FDCA. because DDG and other acids have good solubility in acetic acid, FDCA has low solubility in acetic acid, transition states for dehydration chemistry are stabilized by the polar solvent, nd DDG prefers furimokl forms in acetic acid, which are predisposed for -dehydration into FDCA- Other earboxyiie acids exhibit similar characteristics. Additionally, it is believed that earboxyiie acid, solvents enhance the acidity of other acids (e.g., hydrobroinie acid, hydrochloric acid, and the like) which are used as acid catalysts in conihination with these solvents. Further, earboxyiie acids having a low . p a (e.g.., less than 3.-5), such as tritluoroaeetic acid, form a distinct class within the earboxyiie acids, in contrast to acetic acid (pKa of 4.76), these acids have enhanced acidity which. Is un e stood as accelerating the dehydration reaction of DDG to FDCA.

EXAMPLES

[111174] ft will be appreciated that ma r changes may be mads to ie following examples, while still obtainin similar results. Accordingly, the following example , illustrating embodiments of processing DDG to obtain FDCA utilizin various reaction conditions ami reagents, are intended to illustrate and .not to limit the invention.

[O075J Bxmtpk I: DDG dipotassiuru salt is combined, with (US M 0 2 $0 I acetic acid. The reaction proceeds at 60* C for 4 hours yielding 1% FDCA molar yield.

[mm] Example 2; DDG dipotaashrm salt is combined wi h 0,25 M ¾S0 4 in acetic acid with NaBr (S wt%). The reaction proceeds at 60° C for 4 hours yielding 19% FDCA molar yield,

{W77\ Example 3: DDG dipotasHinft salt is combined with 0.25 M ¾S0 4 acetic acid. The reaction, proceeds at 1 0° C for 3 hours to produce 20% FDCA molar yield,

[0078] Exampk 4 DDG dvpotassium salt is combined with 0.25 M 1¾80 4 i acetic acid with NaBr (0,7 wD¾). The reaction proceeds at 160° C for 3 hours to produce 31% FDCA. molar yield,

$079] Example 3; DDG dibotyl ester is combined with 0 M ¾SD 4 in Dbutaaol. The reaction proceeds at 60 s " -C for 2 hours yielding 53% FDCA nolar yield. [0Q88J Example 6. DDG dibutyt ster is combmed with 9 M I-¾S0 in acetic acid. l¾e reaction proceeds at 60°€ for ! tor yielding 22% FDCA-DBE mete yield.

[00811 Example- 7: DDG dibuiy! ester is combined with I M BCi m acetic acid.. The tmatwti proceeds at .6(P C for 4 hoars ylel ding 43% FDCA- DBE molar yield.

|WS ' 2j Example 8: Xi dihmyl ester is combined, with 2.9 M, HBr in acetic acid.. The- reaction proceeds at £0* C for 4 hours yielding 61% FDCA-DBE molar yield. i i Example 9: 0,1 M DDG 2K is combined with, 5,7 M HBr in aee e acid. The reaction proceeds at 60" C fhr 4 horns yielding 33% FDCA molar yield.

[0084] Exa ple TO: 0,1 M DDG 2K is combined with 23 M HBr in acetic acid, The reaction proceeds at 60° C for 4 Fours to produce 82% FDCA molar yield. «8S| Exampk EI: ill M DDG 2 is combmed with 5.7 M HBr fa acetic acid with 10 vol water. The reaction proceeds at 6IF C for 4 hoars yielding 89% FDCA molar yield,

[008$ Example 12: 0Λ hi DDG 2 s comb ned with 5.1 M HBr in acetic acid with 10 ¥ø!:% water. The reaction proceeds at 6iF€ For 4 hours yielding 9! % FDCA molar yield.

Example 13: 0.05 M DDG 2K is combmed with 12,45 M HBr in water. The reaction proceeds at 100° C for 1 hour yielding 77% FDCA: molar yield, lW \ Emmpk 14: 0.05 M DDG 2 is combined with 5.2 M HBr in acetic - add with 8,2 vol% water. live reaction proceeds at 100° C for 4 hours yielding 71% FDCA molar yield,

|iK 89) Example 15: DDGAQBB is combined, with 9 M ¾.S0 4 w ί -butane.!. The reacdon proceeds at 6CPC for 2 hours yielding 53% FDCA-DBE molar yield.

10090 . 1 Example 16: DDG-DBE is combined with 2.9 M HBr in acetic acid.. lire reaction proceeds at 60 s C for 4 hours yielding 52% FDCA-DBE molar yield,

(00911 Example 17: DDG-DBE is combined with 9 M ¾S0 4 ¾ l~b(rtanoi 1¾e reaction proceeds at C for 2 hours yielding 53% FD€A~DBB. molar yield,

[ 092J Example IS: DDG-DBE is combined with 2, M HBr in acetic acid. The reaction proceeds at 6 ° C br 4 hours yieldirig 52% DCA-DBB molar yield,

[6093] E mpk 19: DDG-DBB is combined with iriiluoroacetlc acid, lire reaction proceeds at 60° C for 4 hours yielding 77% FDCA-DBE molar yield. I )94J Aspects of .the discl sure have been described k teims of i!H raiivs embodiments thereof. Numerous othe embodimeats, modifcatk s,. aad variations within the scope: and spirit of the appended claims will, occur to persons of ordinary skill in the art from a review of this disclosure. For exai&p e* the steps described may be performed hi other than the recited order unless stated otherwise, and orse or .more steps illustrated may be options in accordance with aspects of the disclosure,