US008519167B2
`
`(12) United States Patent
`Mufioz De Diego et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 8,519,167 B2
`Aug. 27, 2013
`
`(54)
`
`(75)
`
`METHOD FOR THE PREPARATION OF
`2,5-FURANDICARBOXYLIC ACID AND
`ESTERS THEREOF
`
`(58) Field of Classification Search
`USPC ........................................................ .. 549/485
`
`See application file for complete search history.
`
`Inventors: Cesar Mufioz De Diego, Amsterdam
`(NL); Wayne Paul Schammel, San
`Francisco, CA (US); Matheus Adrianus
`Dam, Amsterdam (NL); Gerardus
`Johannes Maria Gruter, Amsterdam
`(NL)
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`2,628,249 A
`3,173,933 A
`4,977,283 A
`2012/0059178 A1*
`
`2/1953 Bruno, Jr.
`3/1965 Hay
`12/1990 Leupold et al.
`3/2012 Sanborn ...................... .. 549/485
`
`(73)
`
`Assignee:
`
`Furanix Technologies B.V., Amsterdam
`(NL)
`
`(*)
`
`Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`
`GB
`WO
`WO
`WO
`
`FOREIGN PATENT DOCUMENTS
`621971
`10/1947
`01/72732 A2
`10/2001
`2007/104514 A2
`9/2007
`2009/030509 A2
`3/2009
`
`OTHER PUBLICATIONS
`
`(21)
`
`Appl. No.:
`
`13/497,682
`
`(22)
`
`PCT Filed:
`
`Oct. 6, 2010
`
`PCT No.:
`
`PCT/NL2010/050653
`
`§ 371 (C)(1),
`(2), (4) Date:
`
`Jul. 11, 2012
`
`PCT Pub. No.: WO2011/043660
`
`PCT Pub. Date: Apr. 14, 2011
`
`Prior Publication Data
`
`US 2012/0283452 A1
`
`Nov. 8,2012
`
`Related U.S. Application Data
`
`(86)
`
`(87)
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`(65)
`
`(60)
`
`(30)
`
`(51)
`
`(52)
`
`W. Partenheimer, “Methodology and scope of metal/bromide
`autoxidation of hydrocarbons”, Catalysis Today 23 (1995), pp.
`69-15 8.
`
`Walt Partenheimer et a1., “Synthesis of2,5 -Diformylfuran and Furan-
`2,5-Dicarboxylic
`Acid
`by
`Catalytic
`Air-Oxidation
`of
`5-Hydroxymethylfurfural. Unexpectedly Selective Aerobic Oxida-
`tion of Benzyl Alcohol to Benzaldehyde with Metal/Bromide Cata-
`lysts” Adv. Synth. Catal., 343, No. 1, Jan. 1, 2001, p. 102-111.
`Taarning et al., “Chemicals from Renewablesz Aerobic Oxidation of
`Furfural
`and Hydroxyrnethylfurfural
`over Gold Catalysts”
`ChemSusChem 2008 1, 1-5.
`
`* cited by examiner
`
`Primary Examiner — Kristin Vajda
`(74) Attorney, Agent, or Firm — Hoffmann & Baron, LLP
`
`Provisional application No. 61/249,400, filed on Oct.
`7, 2009.
`
`(57)
`
`ABSTRACT
`
`Foreign Application Priority Data
`
`Oct. 7, 2009
`
`(NL) .................................... .. 2003607
`
`Int. Cl.
`C07D 307/68
`U.S. Cl.
`USPC ........................................................ .. 549/485
`
`(2006.01)
`
`A method for the preparation of 2,5-furandicarboxylic acid
`(“FDCA”) and/or an alkyl ester of FDCA includes the step of
`contacting a feed comprising a starting material selected from
`5-alkoxymethylfurfural, 2,5-di(alkoxymethyl)furan and a
`mixture thereof with an oxidant in the presence of an oxida-
`tion catalyst. The feed may also comprise 5-hydroxymethyl-
`furfural as a further starting material.
`
`17 Claims, No Drawings
`
`Petitioners‘ Exhibit 1029, Page 1 of 9
`
`Petitioners' Exhibit 1029, Page 1 of 9
`
`

`
`US 8,519,167 B2
`
`1
`METHOD FOR THE PREPARATION OF
`2,5-FURANDICARBOXYLIC ACID AND
`ESTERS THEREOF
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`This application is the National Stage of International
`Application No. PCT/NL2010/050653, filed Oct. 6, 2010,
`which claims the benefit of Netherlands Application No.
`2003607, filed Oct. 7, 2009, and U.S. Provisional Application
`No. 61/249,400, filed Oct. 7, 2009, the contents of all of
`which are incorporated by reference herein.
`
`FIELD OF THE INVENTION
`
`The present invention relates to a method for the prepara-
`tion of 2,5-furandicarboxylic acid and esters thereof, in par-
`ticular 2,5-furandicarboxylic acid (“FDCA) and/or alkyl
`esters ofFDCA from alkyl ethers of 5-hydroxymethylfurfural
`(“HMF”), also known as 5-(alkoxymethyl)-2-furaldehyde,
`from 2,5-bis(alkoxymethyl)furan or from a mixture thereof.
`Mixtures of one or more ofthese starting materials with HMF
`may also be used.
`
`BACKGROUND OF THE INVENTION
`
`2,5-Furandicarboxylic acid is a furan derivative. This
`organic compound was first obtained by Fittig and Heinzel-
`mann in 1876. The first review, by Henry Hill was published
`in 1901 (Am. Chem. Journ. 25, 439). FDCA was more than
`125 years later identified by the US Department of Energy as
`one of 12 priority chemicals for establishing the “green”
`chemistry industry of the future. However, to date, no com-
`mercial process exists for its production. On the laboratory
`scale it is often synthesized from HMF, which in mm can be
`obtained from carbohydrate-containing sources such as glu-
`cose, fructose, sucrose and starch. From fructose and glucose
`HMF is obtained by acidic elimination of three moles of
`water.
`
`The derivatives of HMF are identified as potential and
`versatile fuel components and precursors for the production
`of plastics. The polyester from 2,5-furandicarboxylic acid
`dimethyl ester and ethylene glycol was first reported in 1946
`(GB 621,971).
`WO 01/72732 describes the oxidation of HMF to FDCA.
`
`The maximum FDCA yield reported is 59%, obtained at 105°
`C. The oxidation of HMF in an aqueous medium with oxygen
`using a catalyst from the Pt-group is described in U.S. Pat.
`No. 4,977,283. Taaming et al. described the oxidation of
`HMF over gold based catalysts (ChemSusChem, 1, (2008),
`75-784).
`Partenheimer et al describe the synthesis of furan-2,5-di-
`carboxylic acid by catalytic air-oxidation of 5-hydroxymeth-
`ylfurfural with the metal/bromide catalyst Co/Mn/Br in Adv.
`Synth. Catal. 2001, 343, pp 102-11.
`In WO 2007/ 104514, the synthesis of ethers of HMF such
`as 5-methoxymethylfurfural (MMF) and 5-ethoxymethylfur-
`fural (EMF) from biomass sources is described. Given the
`higher stability than HMF and hence improved production
`pathways and given the green reputation of these ethers, they
`were considered by the present inventors as interesting start-
`ing point in the preparation of furan-based monomers that
`could be used for the production of furandicarboxylic acid-
`based polyesters, for instance as an alternative for PET or
`FDCA-based polyamids (nylons). One of the most important
`conventional, oil-based, polyester monomers is Purified
`
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`2
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`Terephthalic Acid (PTA) and their alkyl esters such as DiM-
`ethyl Terephthalate (DMT). The di-esters are ofinterest in the
`polymerization process, as methanol is liberated as conden-
`sation product in the reaction of DMT with a diol instead of
`higher boiling water that is liberated in the reaction of PTA
`with a diol. The lower boiling point ofmethanol facilitates the
`required removal during the polycondensation step, facilitat-
`ing the formation of high molecular weight polymers.
`Oxidation of the HMF ethers has not been reported. When
`using prior art techniques such as the above described catalyst
`systems, the desired FDCA could be obtained in moderate
`yield. Surprisingly, it was found that when using a bromide-
`containing cobalt and manganese-based catalyst, under spe-
`cific reaction conditions, not only FDCA was obtained but
`that also significant amounts of esters could be obtained from
`direct oxidation of the ether function of HMF ethers. The
`
`FDCA+FDCA ester combined yields are with 70-85% very
`high. From a process point of view this is very interesting.
`Thus for 5-(methoxymethyl)furfural or MMF the formation
`of the mono methyl ester of FDCA was observed.
`
`SUMMARY OF THE INVENTION
`
`In conclusion, the present inventors have now found that
`HMF alkyl ethers or 2,5-bis(alkoxymethyl)furan can be oxi-
`dized to FDCA and alkyl esters thereof. Thus, in a first aspect
`the invention provides a method for the preparation of 2,5-
`furandicarboxylic acid or an alkyl ester of 2,5-furandicar-
`boxylic acid comprising the step of contacting a feed com-
`prising a starting material selected from 5-alkoxymethyl
`furfural, 2,5-bis(alkoxymethyl)furan and a mixture thereof
`with an oxidant in the presence of an oxidation catalyst.
`Optionally, the feed may also comprise HMF as a further
`starting material. As an example, the oxidation catalyst pref-
`erably comprises at least one metal selected from cobalt and
`manganese, more preferably both, and suitably further com-
`prises a source of bromine, preferably a bromide.
`
`DETAILED DESCRIPTION OF THE INVENTION
`
`5-Alkoxymethyl furfural can be obtained from biomass
`sources as described in WO 2007/ 1045 14. Depending on the
`process conditions the product obtained in accordance with
`the process of this reference may also contain HMF. 2,5-Bis
`(alkoxymethyl)furan, can be produced from HMF and from
`5-alkoxymethyl furfural as described in WO 2009/030509.
`The product of the reaction of the current invention with
`5-(alkoxymethyl)furfural can be FDCA, or a mixture of
`FDCA and the monoalkylester
`(hemi-ester) of FDCA,
`depending on the process conditions and the catalyst selec-
`tion and concentration. For example, when a Co/Mn/Br based
`catalyst is used, the Co/Mn/Br stoichiometry and concentra-
`tion of the catalyst has a significant impact. Likewise, when
`the feed comprises 2,5-bis(alkoxymethyl)furan, the product
`of the reaction can be FDCA, a mixture of FDCA and the
`monoalkylester (hemi-ester) of FDCA, or a mixture of
`FDCA, the monoalkylester (hemi-ester) of FDCA and the
`dialkyl ester of FDCA, again depending on the process con-
`ditions and the catalyst selection and concentration.
`The alkyl group in 5-(alkoxymethyl)furfural or in 2,5-bis
`(alkoxymethyl)furan can suitably be C1 -C5 alkyl, i.e. methyl,
`ethyl, propyl, isopropyl, butyl, 2-butyl, tert-butyl, pentyl,
`2-pentyl, neopentyl or 3-pentyl. There is a preference for
`methyl, and to a lesser extent, also ethyl, as explained here-
`after. For HMF, 5 -(methoxymethyl)furfural and 5 -(ethoxym-
`ethyl)furfural, the products contain FDCA (R:H), FDCA
`
`Petitioners‘ Exhibit 1029, Page 2 of 9
`
`Petitioners' Exhibit 1029, Page 2 of 9
`
`

`
`US 8,519,167 B2
`
`3
`and the monomethylester (hemi-ester) of FDCA (R:Me), or
`FDCA and the monoethylester (hemi-ester) ofFDCA (R:Et),
`respectively.
`
`RO
`
`0
`
`\
`
`/
`
`OH
`
`R:H,MeorEt
`
`The product of the reaction can be used in the preparation
`of a polyester, by reaction thereof with a suitable diol. Such
`polyester preparations are preferably performed by transes-
`terification, whereby the di-methyl ester or di-ethyl ester of
`FDCA is used and wherein the methyl or ethyl groups are
`exchanged in the form of a volatile alcohol during the trans-
`esterification with the diol. Accordingly, there is a preference
`for methyl, and to a lesser extent, also ethyl as alkyl group.
`In case a bromine containing catalyst is used, the bromine
`source can be any compound that produces bromide ions in
`the reaction mixture. These compounds include hydrogen
`bromide, sodium bromide, elemental bromine, benzyl bro-
`mide, tetrabromoethane. Also other bromine salts, such as an
`alkali or earth alkali metal bromine or another metal bromide
`
`such as ZnBr2 can be used. There is a preference for hydro-
`bromic acid or sodium bromide. The amount of bromine
`mentioned in here relates to the amount measured as Br
`
`relative to cobalt. The oxidation catalyst, as mentioned above,
`preferably comprises at least one metal selected from the
`group consisting of Co and Mn, preferably both.
`In the processes according to the current invention that
`make use of cobalt, manganese and bromide catalyst, a cobalt
`compound and a manganese compound and a bromine-con-
`taining compound are used. These compounds are preferably
`soluble in the reaction mixture.
`
`The bromide catalyst that also contains Co and Mn can
`optionally contain one or more additional metals, in particular
`Zr and/or Ce. Alternative and suitable catalysts are described
`in W. Partenheimer, Catalysis Today 23(2), 69-158 (1995) in
`particular on pages 89-99, included herein by reference.
`Each of the metal components can be provided in any of
`their known ionic forms. Preferably the metal or metals are in
`a form that is soluble in the reaction solvent. Examples of
`suitable counterions for cobalt and manganese include, but
`are not limited to, carbonate, acetate, acetate tetrahydrate and
`halide, with bromide being the preferred halide.
`As described in Partenheimer, ibid, pages 86-88, suitable
`solvents for use in the processes of the present invention,
`described above, preferably have at least one component that
`contains a monocarboxylic acid functional group. The sol-
`vent may also function as one of the reagents. The processes
`may be run in a solvent or solvent mixture that does not
`contain an acid group. In that case, preferably one of the
`reagents does contain a monocarboxylic acid functional
`group. Suitable solvents can also be aromatic acids such as
`benzoic acid and derivatives thereof. A preferred solvent is an
`aliphatic C2-C6 monocarboxylic acid, such as but not limited
`to acetic acid, propionic acid, n-butyric acid, isobutyric acid,
`n-valeric acid, trimethylacetic acid, and caproic acid and mix-
`tures thereof. Said mixtures may also include benzene, aceto-
`nitrile, heptane, acetic anhydride, chlorobenzene, o-dichlo-
`robenzene, and water. Most preferred as solvent is acetic acid
`(“AcOH”).
`The oxidant in the processes of the present invention is
`preferably an oxygen-containing gas or gas mixture, such as,
`
`4
`
`but not limited to air and oxygen-enriched air. Oxygen by
`itself is also a preferred oxidant.
`The processes ofthe instant invention described above can
`be conducted in a batch, semi-continuous or continuous
`mode. Especially for the manufacture of FDCA, operation in
`the batch mode with increasing temperature at specific times,
`increasing pressure at specific times, variation of the catalyst
`concentration at the beginning of the reaction, and variation
`of the catalyst composition during the reaction is desirable.
`For example, variation of the catalyst composition during
`reaction can be accomplished by addition of cobalt and/or
`manganese and/or zirconium, and/or cerium, and/or bromide
`at specified times.
`The temperature and pressure in a commercial process can
`be selected from wide ranges. When the reaction is conducted
`in the presence of a solvent the reaction temperature and
`pressure are not independent. The pressure is determined by
`the solvent (e.g., acetic acid) pressure at a certain tempera-
`ture. The pressure of the reaction mixture is preferably
`selected such that the solvent is mainly in the liquid phase. In
`practice this means that pressures between 5 and 100 bar can
`be used with a preference for pressures between 10 and 80
`bars, depending on the desired product (diacid or (hemi)
`ester). In case the oxidant is an oxygen-containing gas, such
`as air, the gas can be continuously fed to and removed from
`the reactor, or the gas can be supplied all at the start of the
`reaction. In the latter case, the pressure of the system will
`depend on the headspace volume and the amount of gas
`required to convert the starting material. It is clear that in the
`latter case, the pressure of the system may be significantly
`higher than when an oxygen containing gas is continuously
`fed and removed.
`
`The temperature of the reaction mixture is suitably
`between 60 and 220° C., preferably between 100 and 210° C.,
`more preferably between 150 and 200° C., most preferably
`between 160 and 190° C. Temperatures higher than 180° C.
`tend to lead to decarboxylation and to other degradation prod-
`ucts. Good results (FDCA+FDCA esters) have been achieved
`at a temperature of about 180° C.
`In the preferred oxidation catalysts, molar ratios of cobalt
`to manganese (Co/Mn) are typically 1/ 1000-100/ 1, prefer-
`ably 1/ 100-10/1 and more preferably 1/ 10-4/ 1.
`Likewise, in the preferred oxidation catalysts, molar ratios
`of bromine to metals (e.g. Br/(Co+Mn)) are typically from
`0.001 to 5 .00, preferably 0.01 to 2.00 and more preferably 0.1
`to 0.9.
`
`Catalyst concentration (calculated on the metal, e.g.,
`Co+Mn) is preferably between 0.1 and 10 mol % relative to
`the starting material, with a preference for loads between 2
`and 6 mol %. Good results were obtained in general with
`catalyst loads of around 4 mol %.
`In another aspect, the monoester ofthe present invention or
`the mixture of FDCA and mono- and/or diester of FDCA can
`
`be transformed using common esterification reactions to a
`diester by contacting the starting material(s) under appropri-
`ate conditions with the relevant alcohol. Thus, in one aspect,
`the invention also relates to the use of the monoalkylester of
`2,5-furandicarboxylic acid or the mixture of FDCA and
`mono- and/or diester of FDCA in the preparation of a dialky-
`lester of 2,5-dicarboxylic acid by reaction ofthe monomethy-
`lester of 2,5-furandicarboxylic acid or the mixture of FDCA
`and mono- and/or diester of FDCA with a C1-C5 alkyl alco-
`hol, preferably the alcohol required to prepare the symmetric
`alkylester of 2,5-furandicarboxylic acid (i.e. both alkyl
`groups are identical) and more preferably to the use of the
`monomethylester of 2,5-furandicarboxylic acid or the mix-
`
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`Petitioners‘ Exhibit 1029, Page 3 of 9
`
`Petitioners' Exhibit 1029, Page 3 of 9
`
`

`
`US 8,519,167 B2
`
`5
`ture of FDCA and mono- and/or dimethyl ester of FDCA in
`the preparation of a dimethyl ester of FDCA.
`
`0
`
`MeOH
`
`OH
`
`\o
`
`O
`
`\
`
`/
`
`0/
`
`Accordingly, the present invention also provides a method
`for the preparation of a dialkylester of 2,5-furandicarboxylic
`acid, comprising preparing 2,5-furandicarboxylic acid or an
`alkyl ester of 2,5-furandicarboxylic acid in a method as
`described above to obtain a reaction product, and reacting the
`reaction product with a C1-C5 alkyl alcohol to obtain the
`dialkyl ester of2,5-furandicarboxylic acid. The alkyl group in
`the latter C1-C5 alkyl alcohol is preferably the same as the
`alkyl group in the starting material so that a symmetrical
`dialkyl ester of 2,5-furandicarboxylic acid is obtained. The
`alkyl groups are preferably methyl groups. The reaction may
`be performed as described in U.S. Pat. No. 2,628,249, in the
`presence of sulphuric acid or a sulphonic acid, with optionally
`activated carbon being present as well.
`In a further aspect of the invention, the esters of the inven-
`tion and in particular the di-methylester can be used in the
`preparation of polyester polymers by reaction with a diol.
`Reacting the di-methylester with a diol will result in the
`formation of methanol that quickly vaporises. In 1946 the
`polymerization of FDCA dimethyl ester with ethylene glycol
`was described as a first example of such a polymerization in
`GB 621,971.
`The starting materials for the production of FDCA may
`originate from a carbohydrate source as described above.
`Examples of such disclosures are WO 2007/ 104515 and WO
`2009/030509. Accordingly, the invention also provides a
`method for the preparation of 2,5-furandicarboxylic acid and
`an alkyl ester of 2,5-furandicarboxylic acid, wherein a carbo-
`hydrate source is converted into products comprising
`5-alkoxymethyl furfural and optionally 5-hydroxymethyl
`furfural, from which is isolated a feed comprising 5-alkoxym-
`ethyl furfural and optionally 5-hydroxymethyl furfural, and
`which method further comprises the subsequent step of con-
`tacting the feed with an oxidant in the presence of an oxida-
`tion catalyst, in particular a cobalt and manganese and bro-
`mide-containing
`catalyst,
`under
`appropriate
`reaction
`conditions. The subsequent step is preferably carried out in a
`method as described above.
`
`Indeed, polyesters are generally made by a combined
`esterification/polycondensation reaction between monomer
`units of a diol (e.g., ethylene glycol (EG)) and a dicarboxylic
`acid. Additives such as catalysts and stabilizers may be added
`to facilitate the process and stabilize the polyester towards
`degradation.
`
`EXAMPLES
`
`Experiments were carried out in parallel 12 ml magneti-
`cally stirred stainless steel batch reactors. The reactors are
`grouped in blocks containing 12 batch reactors. The standard
`procedure for all the reactions was as follows: 0.5 ml of feed
`stock solution in acetic acid (1.56 M) were added into a
`reactor lined with a Teflon insert.
`1 ml of a catalyst stock
`
`6
`solution in acetic acid was subsequently added to the reactor.
`In a typical experiment, a catalyst composition Co/Mn/Br
`with a relative 1-x-y ratio,
`the concentration of Co
`(OAc)2 *4H2O was 0.78 mg/ml (0.31 mmol/ml). As a Mn
`source, Mn(OAc)2*4H2O was used and as a bromine source
`NaBr was used. The reactors were closed with a rubber sep-
`tum, after which the reactors were sealed and pressurized to
`the desired air pressure, ranging from 20-60 bars. After pres-
`surization, the block with 12 reactors was placed in the test
`unit which was preheated at the desired temperature, ranging
`from 100 to 220° C. After the desired reaction time, ranging
`from 0.5 hr to 24 hrs, the block is placed into an ice bath for
`20 minutes. When the block had cooled down, it was depres-
`surized. After opening, HPLC samples were prepared. First 5
`ml of a saccharine solution in DMSO (11.04 mg/ml) was
`added to the each reactor and the mixture was stirred for 5
`
`10
`
`15
`
`minutes. Then 10 pl of this mixture was diluted to 1000 p.l
`with water in a HPLC vial. The samples were analyzed using
`HPLC.
`
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`
`Example 1
`
`Example 1 shows the combined yield (“y”) of FDCA+
`FDCA mono-alkyl ester in the oxidation of EMF, MMF, a 1 :1
`mixture of HMF+EMF and a 1:1 mixture of HMF+MMF,
`respectively with 0.78 mol % Co catalyst (relative to the
`feed), 0.52 M feed concentration and Co/Mn/Br ratios of
`1/5/5, 1/5/20 and 1/3/20 at 180° C. for 1 hrwith 60 bar air. The
`oxygen to feed ratio was 8.07 mol of 02 per mole feed. Under
`these conditions, higher Br amounts give higher yields but
`when Br/(Co+Mn)>1, corrosion may become a problem on
`commercial scale. Surprisingly, MMF gives slightly higher
`yields than EMF.
`Example 1 further shows the selectivity (“s”) to FDCA and
`to FDCA monoalkyl ester (FDCA1/2R) for the EMF and
`MMF oxidations. Under these conditions, MMF showed
`higher ester selectivities than EMF and the lower bromine
`amounts show higher ester selectivities. The data of these
`experiments are given in Table 1.
`It is surprising that the oxidations of EMF and MMF are
`also complete after 1 hour, and provide almost the same yield
`on furandicarboxylics as HMF. This is contrary to the teach-
`ings of the prior art that indicates that a significantly lower
`amount of products may be expected in the oxidation of an
`ether. InU.S. Pat. No. 3,173,933 the oxidation ofalcohols and
`ethers over a cobalt and bromine-containing catalyst has been
`described. It appeared that the yield of oxidation products
`such as a carboxylic acid and the corresponding ester is sig-
`nificantly higher when an alcohol is oxidised compared to the
`oxidation of an ether.
`
`Example 2
`
`Example 2 shows the effect of absolute catalyst amounts on
`the combined yield of FDCA+FDCA mono-methyl ester in
`the oxidation ofMMF with 0.1, 0.78, 1.56 and 1.85 mol % Co
`catalyst (relative to the feed), 3.7 wt/wt % feed concentration
`and Co/Mn/Brratios of 1/5/5, 1/3/20 and 1/5/20 at 180° C. for
`1 hr with 60 bar air. The oxygen to feed ratio was 8.07 mol of
`02 per mole feed. Under these conditions, the lowest catalyst
`concentration (0.1 mol % Co) gives 25-45% yields of FDCA+
`FDCA methyl ester. With 0.78 mol % Co, the low bromine
`catalyst system (1/5/5) gives a 60% yield of FDCA+FDCA
`methyl ester, while the higher Br catalysts (1/3/20 and 1/5/20)
`give 70-80% yields of FDCA+FDCA methyl ester. Higher
`catalyst concentrations (1.56 mol % and 1.95 mol %) give
`
`Petitioners‘ Exhibit 1029, Page 4 of 9
`
`Petitioners' Exhibit 1029, Page 4 of 9
`
`

`
`US 8,519,167 B2
`
`7
`FDCA+FDCA methyl ester yields of 70-80%, independent of
`Mn or Br amount (within the range tested).
`Example 2 further shows the selectivity to FDCA monom-
`ethyl ester (FDCA1/2R) for MMF oxidations. Under these
`conditions, the low Br catalyst (1/5/5) showed higher ester
`selectivities than the higher Br catalysts (1/3/20 and 1/5/20).
`The Co/Mn ratio’s 1/5 and 1/3 give identical results. The 0.78
`mol % Co catalyst system gives the highest ester yields. The
`data of these experiments are given in Table 2.
`
`Example 3
`
`Example 3 shows the effect of air pressure (20, 40 and 60
`bar air pressure in the headspace of the reactor at room tem-
`perature, translated to the molar ratio of oxygen to feed) on
`the combined yield of FDCA+FDCA mono-methyl ester in
`the oxidation of MMF with 0.78 mol % and 0.10 mol % Co
`
`catalyst (relative to the feed), and Co/Mn/Br ratios of 1/5/5,
`1/3/20 and 1/5/20. The feed concentration in all experiments
`was 3.7 wt/wt %, the temperature was 180° C. and the experi-
`ments lasted 1 hr. A pressure of 20 bar air corresponded to an
`oxygen to feed ratio of 2.69 mole/mole; a pressure of 40 bar
`corresponded to an O2/feed ratio of 5.68 mole/mole; and a
`pressure of 60 bar corresponded with an O2/feed ratio of 8.07
`mole/mole. Under these conditions, the lowest air pressure
`(20 bar) gives 73-82% yields of FDCA+FDCA methyl ester.
`The higher pressures show lower yields. The 1/5/20 catalyst
`shows highest combined FDCA+FDCA methyl ester yields.
`The lowest combined yields were observed for the low Br
`catalyst (1/5/5). This low Br catalyst is also most affected by
`the pressure. The data of these experiments is also given in
`Table 3.
`
`Table 3 further shows the selectivity to FDCA monomethyl
`ester (FDCA1/2R) for the MMF oxidations. Under these
`conditions, the higher pressures give higher FDCA methyl
`ester yields (and consequently lower FDCA yields) and the
`lower Br catalyst (1/5/5) shows highest methyl ester yields.
`Table 3 also shows the results of experiments with a low
`catalyst loading (0.10 mol % Co). The pressure effect on the
`FDCA+FDCA methyl ester yield is different than what was
`observed for the higher catalyst concentration of FIG. 5.
`
`Example 4
`
`Example 4 shows the effect of reaction time (0.5, 0.75 and
`1 hour) on the combined yield of FDCA+FDCA mono-me-
`thyl ester in the oxidation of MMF with 0.78 mol % Co
`catalyst (relative to the feed), 3.7 wt/wt % feed concentration
`at 180° C. and 60 bar air. The air pressure corresponded to an
`O2/feed ratio of 8.07 mole/mole. The catalyst composition
`was varied having Co/Mn/Br ratios of 1/5/5, 1/3/20 and 1/5/
`20. Under these conditions it was found that the reaction time
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`has hardly any effect on the combined FDCA+FDCA methyl
`ester yields. The data of these experiments are given in Table
`4.
`
`55
`
`Example 5
`
`Example 5 shows the effect of temperature (160, 180, 200
`and 220° C.) on the combined yield of FDCA+FDCA mono-
`methyl ester in the oxidation of MMF with 0.78 mol % Co
`catalyst (relative to the feed), 3.7 wt/wt % feed concentration
`for 1 hr. and Co/Mn/Br ratios of 1/5/5, 1/3/20 and 1/5/20 at 20
`bars and at 60 bars. Under these conditions, the highest com-
`bined yield of FDCA+FDCA methyl ester is observed at
`180° C. The data of these experiments are given in Table 5.
`
`60
`
`65
`
`8
`Example 6
`
`Example 6 shows the effect of feed concentration (3.7, 7.4
`and 1'1.1 wt %) on the combined yield of FDCA+FDCA
`mono-methyl ester in the oxidation of MMF with 0.78 mol %
`Co catalyst (relative to the feed) at 180° C. and 20 bar for 1 hr.
`The catalyst composition was varied having Co/Mn/Br ratios
`of1/5/5, 1/3/20 and 1/5/20. Under these conditions, the yields
`of FDCA+FDCA methyl ester decrease slightly with increas-
`ing feed concentration. The data of these experiments are
`given in Table 6.
`
`Example 7
`
`Example 7 shows the effect of feed concentration (3.7, 7.4
`and 11.1 wt %) on the yield of the intermediate 5-formyl-
`furancarboxylic acid (FFCA) in the oxidation of MMF with
`0.78 mol % Co catalyst (relative to the feed) at 180° C. and 20
`bar for 1 hr. The catalyst composition was varied having
`Co/Mn/Br ratios of 1/5/5, 1/3/20 and 1/5/20. Under these
`conditions, the yield of FFCA is negligible at 3.7 wt % feed
`concentration but increases slightly with increasing feed con-
`centration. FFCA is undesired as it acts as a chain stopper in
`polycondensation reactions. The data of these experiments
`are given in Table 7.
`
`Example 8
`
`Example 8 shows the effect of the Co/Mn ratio (0/1 (only
`Mn), 1/60, 1/40, 1/20, 1/15, 1/10, 1/8, 1/6, 1/4, 3/2, 2/3 and
`4/1) on the combined yield of FDCA+FDCA mono-methyl
`ester in the oxidation of MMF with 4 mol % Co+Mn catalyst
`(relative to the feed) and a fixed Br/(Co+Mn) ratio of 0.7. In
`all experiments the feed concentration was 3.7 wt/wt %, the
`temperature was 180° C., the air pressure was 20 bar and
`lasted 1 hr. The air pressure corresponded with an O2/feed
`ratio of 2.69 mole/mole. Under these conditions, it is obvious
`that Co is required to get relevant FDCA+FDCA methyl ester
`yields but that even very low amounts of Co (Co/Mn of
`0.0167) result in desired product formation. The data ofthese
`experiments are given in Table 8.
`
`Example 9
`
`Example 9 shows the effect of the Mn/Co ratio (0/1 (only
`Co), 1/80, 1/60, 1/40, 1/20, 1/10, 1/4, 2/3, 3/2 and 4/1) onthe
`combined yield of FDCA+FDCA mono-methyl ester in the
`oxidation of MMF with 4 mol % Co+Mn catalyst (relative to
`the feed) and a fixed Br/(Co+Mn) ratio of 0.7. In all experi-
`ments the feed concentration was 3.7 wt/wt %, the tempera-
`ture was 180° C., the air pressure was 20 bar and lasted 1 hr.
`The air pressure corresponded with an O2/feed ratio of 2.69
`mole/mole. Under these conditions, it is obvious that also Mn
`is required to get relevant FDCA+FDCA methyl ester yields
`but that in this case, at the lowest amounts of Mn (Co/Mn<20/
`1) only low amounts of the desired products were observed.
`The highest FDCA+FDCA methyl ester yields were observed
`for Mn/Co 1/4. The data of these experiments are given in
`Table 9.
`
`Example 10
`
`Example 10 shows the effect of the Br amount (Br/(Co+
`Mn):0.1, 0.25, 0.4, 0.5, 0.7 and 0.9) on the combined yield of
`FDCA+FDCA mono-methyl ester in the oxidation of MMF
`with 4 mol % Co+Mn catalyst (relative to the feed). In all
`
`Petitioners‘ Exhibit 1029, Page 5 of 9
`
`Petitioners' Exhibit 1029, Page 5 of 9
`
`

`
`US 8,519,167 B2
`
`9
`experiments the feed concentration was 3.7 wt/wt %, the
`temperature was 180° C., the air pressure was 20 bar and
`lasted 1 hr. The air pressure corresponded with an O2/feed
`ratio of 2.69 mole/mole. Under these conditions, it is obvious
`
`10
`that the yield of FDCA+FDCA methyl ester increases from
`57-63% at the lowest amount of Br (Br/Co+Mn):0.1) to
`71-77% at the highest amount of Br (Br/(Co+Mn):0.9). The
`data of these experiments are given in Table 10.
`TABLE 1
`
`Example 1
`
`Experiment
`No.
`
`Feed
`
`Catalyst
`Composition
`Co/Mn/Br
`
`Feed
`concentration
`[Wt %]
`
`Conversion
`%]
`
`s
`s
`FDCA FDCA1/2R
`[%]
`[%]
`
`s
`Furandicarboxylics
`[%]
`
`a
`b
`c
`d
`e
`f
`g
`h
`i
`j
`k
`1
`
`EMF
`MMF
`EMF/HMF
`MMF/HMF
`EMF
`MMF
`EMF/HMF
`MMF/HMF
`EMF
`MMF
`EMF/HMF
`MMF/HMF
`
`1/5/5
`1/5/5
`1/5/5
`1/5/5
`1/3/20
`1/3/20
`1/3/20
`1/3/20
`1/5/20
`1/5/20
`1/5/20
`1/5/20
`
`4
`3.7
`3.6
`3.5
`4
`3.7
`3.6
`3.5
`4
`3.7
`3.6
`3.5
`
`00
`00
`00
`00
`00
`00
`00
`00
`00
`00
`00
`00
`
`42.68
`32.49
`53.31
`56.04
`58.23
`57.48
`65.10
`68.31
`59.31
`60.47
`66.49
`71.50
`
`15.08
`28.40
`7.38
`10.48
`9.34
`15.80
`4.54
`5.62
`9.91
`16.20
`5.22
`6.11
`
`57.76
`60.89
`60.69
`66.52
`67.57
`73.28
`69.63
`73.93
`69.21
`76.66
`71.70
`77.61
`
`TABLE 2
`
`Example 2
`
`Experiment
`No.
`2a
`2h
`2c
`2d
`2e
`2f
`2g
`2h
`2i
`2j
`2k
`21
`
`Catalyst
`concentration
`[Co mol %]
`0.10
`0.10
`0.10
`0.78
`0.78
`0.78
`1.5 6
`1.5 6
`1.5 6
`1 .95
`1 .95
`1 .95
`
`Catalyst
`Composition Conversion
`Co/Mn/Br
`[%]
`1/5/5
`100.00
`1/3/20
`100.00
`1/5/20
`100.00
`1/5/5
`100.00
`1/3/20
`100.00
`1/5/20
`100.00
`1/5/5
`100.00
`1/3/20
`100.00
`1/5/20
`100.00
`1/5/5
`100.00
`1/3/20
`100.00
`1/5/20
`100.00
`
`s
`s
`FDCA FDCA1/2R
`[%]
`[%]
`13.99
`10.86
`15.50
`10.60
`18.90
`12.10
`31.42
`28.38
`58.13
`15.42
`60.77
`16.17
`46.01
`26.90
`68.07
`9.60
`67.89
`9.82
`51.93
`24.93
`67.29
`8.91
`66.10
`9.10
`
`s
`Furandicarboxylics
`[%]
`24.84
`26.11
`31.00
`59.80
`73.54
`76.94
`72.91
`77.67
`77.71
`76.86
`76.21
`75.20
`
`Feed
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`MMF
`
`TABLE 3
`
`Example 3
`
`Experiment
`No.
`3a
`3h
`3c
`3d
`3e
`3f
`3g
`3h
`31
`3j
`3k
`31
`3m
`3n
`30
`3p
`3r
`3s
`
`Catalyst
`Catalyst
`concentration Composition O2/Feed
`[Co mol %]
`Co/Mn/Br
`[mol/mol]
`0.78
`/5/5
`2.69
`0.78
`/3/20
`2.69
`0.78
`/5/20
`2.69
`0.78
`/5/5
`5.68
`0.78
`/3/20
`5.68
`0.78
`/5/20
`5.68
`0.78
`/5/5
`8.07
`0.78
`/3/20
`8.07
`0.78
`/5/20
`8.07
`0.10
`/5/5
`2.69
`0.10
`/3/20
`2.69
`0.10
`/5/20
`2.69
`0.10
`/5/5
`5.68
`0.10
`/3/20
`5.68
`0.10
`/5/20
`5.68
`0.10
`/5/5
`8.07
`0.10
`/3/20
`8.07
`0.10
`/5/20
`8.07
`
`Fee
`MM 7
`MM 7
`MM 7
`MM7
`MM 7
`MM 7
`MM 7
`MM 7
`MM 7
`MM 7
`MM 7
`MM7
`MM 7
`MM 7
`MM7
`MM 7
`MM 7
`MM 7
`
`Conversion
`[%]
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`00.00
`
`s
`s
`FDCA FDCA1/2R
`[%]
`[%]
`54.98
`9.07
`69.83
`8.57
`72.20
`0.07
`41.17
`26.98
`64.13
`1.93
`67.07
`2.36
`31.42
`28.38
`58.13
`5.42
`60.77
`6.17
`4.66
`6.83
`8.88
`3.33
`8.27
`8.18
`15.22
`3.07
`16.66
`2.56
`21.66
`3.01
`13.99
`0.86
`15.50
`0.60
`26.76
`7.63
`
`s
`Furandicarboxylics
`[%]
`74.05
`78.40
`82.27
`68.15
`76.06
`79.43
`59.80
`73.54
`76.94
`11.49
`22.21
`16.44
`28.29
`29.22
`34.67
`24.84
`26.11
`44.38
`
`Petitioners‘ Exhibit 1029, Page 6 of 9
`
`Petitioner