(19) United States
`(12) Patent Application Publication (10) Pub. No.: US 2008/0103318 A1
`Lilga et al.
`(43) Pub. Date:
`May 1, 2008
`
`US 20080l03318A1
`
`(54) HYDROXYMETHYL FURFURAL OXIDATION
`METHODS
`
`Publication Classification
`
`(76)
`
`Inventors: Michael A. Lilga, Richland, WA (US);
`Richard T. Hallen, Richland, WA (US);
`Jianli Hu, Overland Park, KS (US);
`James E White, Richlanda WA (US);
`Michel J. Gray, Pasco, WA (US)
`
`Correspondence Address:
`WELLS ST. JOHN P.S.
`601 W. FIRST AVENUE, SUITE 1300
`SPOKANE, WA 99201 (US)
`
`(21) Appl. No.:
`
`11/932,436
`
`(22)
`
`Filed:
`
`Oct. 31, 2007
`
`Related U.S. Application Data
`
`(60) Provisional application No. 60/863,704, filed on Oct.
`31, 2006.
`
`(5 1)
`
`Int. Cl.
`(2006.01)
`C07D 307/68
`(200001)
`B01‘, 21/06
`(200601)
`3”” 23/42
`(200601)
`C07D 307/46
`(52) U.S. Cl.
`..........................
`
`’
`
`’
`
`ABSTRACT
`(57)
`(HMF)
`A method of oxidizing hydroxymethylfurfural
`includes providing a starting material which includes HMF in
`a solvent comprising water into a reactor. At least one of air
`and O2 is provided into the reactor. The starting material is
`contacted with the catalyst comprising Pt on a support mate-
`rial where the contacting is conducted at a reactor temperature
`of from about 50° C. to about 200° C. A method ofproducing
`an oxidation catalyst where ZrO2 is provided and is calcined.
`The ZrO2 is mixed with platinum (ll) acetylacetonate to form
`a mixture. The mixture is subjected to rotary evaporation to
`form a product. The product is calcined and reduced under
`hydrogen to form an activated product. The activated product
`is passivated under a flow of 2% O2.
`
`Petitioners‘ Exhibit 1008, Page 1 of 46
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`Petitioners' Exhibit 1008, Page 1 of 46
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`Patent Application Publication May 1, 2008 Sheet 2 of 39
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`Patent Application Publication May 1, 2008 Sheet 4 of 39
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`Patent Application Publication May 1, 2008 Sheet 26 of 39
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`US 2008/0103318 A1
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`Petitioners‘ Exhibit 1008, Page 27 of 46
`
`Petitioners' Exhibit 1008, Page 27 of 46
`
`
`
`

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`Patent Application Publication May 1, 2008 Sheet 27 of 39
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`US 2008/0103318 A1
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`Petitioners‘ Exhibit 1008, Page 28 of 46
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`Petitioners' Exhibit 1008, Page 28 of 46
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`Patent Application Publication May 1, 2008 Sheet 28 of 39
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`Petitioners' Exhibit 1008, Page 29 of 46
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`Patent Application Publication May 1, 2008 Sheet 29 of 39
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`US 2008/0103318 A1
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`Petitioners‘ Exhibit 1008, Page 30 of 46
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`Petitioners' Exhibit 1008, Page 30 of 46
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`Patent Application Publication May 1, 2008 Sheet 30 of 39
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`Petitioners‘ Exhibit 1008, Page 31 of 46
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`Petitioners' Exhibit 1008, Page 31 of 46
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`

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`Patent Application Publication May 1, 2008 Sheet 31 of 39
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`US 2008/0103318 A1
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`Petitioners‘ Exhibit 1008, Page 32 of 46
`
`Petitioners' Exhibit 1008, Page 32 of 46
`
`
`

`
`Patent Application Publication May 1, 2008 Sheet 32 of 39
`
`US 2008/0103318 A1
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`Petitioners‘ Exhibit 1008, Page 33 of 46
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`Petitioners' Exhibit 1008, Page 33 of 46
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`

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`Patent Application Publication May 1, 2008 Sheet 33 of 39
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`Petitioners' Exhibit 1008, Page 34 of 46
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`

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`Patent Application Publication May 1, 2008 Sheet 34 of 39
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`US 2008/0103318 A1
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`Petitioners' Exhibit 1008, Page 35 of 46
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`

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`Patent Application Publication May 1, 2008 Sheet 35 of 39
`
`US 2008/0103318 A1
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`Petitioners' Exhibit 1008, Page 36 of 46
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`

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`Patent Application Publication May 1, 2008 Sheet 36 of 39
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`US 2008/0103318 A1
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`Petitioners' Exhibit 1008, Page 37 of 46
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`Patent Application Publication May 1, 2008 Sheet 37 of 39
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`Petitioners' Exhibit 1008, Page 38 of 46
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`

`
`Patent Application Publication May 1, 2008 Sheet 38 of 39
`
`US 2008/0103318 A1
`
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`Petitioners‘ Exhibit 1008, Page 40 of 46
`
`Petitioners' Exhibit 1008, Page 40 of 46
`
`

`
`US 2008/0103318 A1
`
`May 1, 2008
`
`HYDROXYMETHYL FURFURAL OXIDATION
`METHODS
`
`RELATED PATENT DATA
`
`[0001] This patent claims priority under 35 U.S.C. § 119 to
`U.S. Provisional Application No. 60/863,704, which was
`filed Oct. 31, 2006.
`
`TECHNICAL FIELD
`
`[0002] The invention pertains to hydroxymethylfurfural
`oxidation methods, methods ofproducing diformyl furan and
`methods of producing an oxidation catalyst.
`
`BACKGROUND OF THE INVENTION
`
`is a compound
`(HMF)
`[0003] Hydroxymethylfurfural
`which can be produced from various hexoses or hexose-
`comprising materials. HMF can in mm be converted into a
`variety of derivatives, many of which are currently or are
`quickly becoming commercially valuable. Oxidation ofHMF
`can produce oxidation products including diformyl furan
`(DFF), hydroxymethyl furan carboxylic acid (HMFCA),
`formylfuran carboxylic acid (FFCA), and furandicarboxylic
`acid (FDCA). Uses for these oxidation products include but
`are not limited to adhesives, sealants, composites, coatings,
`binders, foams, curatives, monomers and resins.
`
`[0004] Although numerous routes and reactions have been
`utilized for preparing one or more of the oxidation products
`set forth above, conventional methodology typically results in
`low HMF conversion,
`low product selectivity and/or low
`product yield. It is desirable to develop alternative method-
`ologies for oxidation of HMF and production of HMF oxida-
`tion products.
`
`SUMMARY OF THE INVENTION
`
`In one aspect the invention pertains to a method of
`[0005]
`oxidizing hydroxymethylfurfural
`(HMF). The method
`includes providing a starting material which includes HMF in
`a solvent comprising water into a reactor. At least one of air
`and O2 is provided into the reactor. The starting material is
`contacted with the catalyst comprising Pt on a support mate-
`rial where the contacting is conducted at a reactor temperature
`of from about 50° C. to about 200° C.
`
`In one aspect the invention pertains to a method of
`[0006]
`producing diforrnylfuran. The method includes providing a
`mixture comprising HMF and an organic solvent. The mix-
`ture is contacted with a catalyst comprising active y—MnO2.
`The mixture is subjected to reflux temperature for a time of
`from about 6 hours to about 12 hours.
`
`In one aspect the invention includes a method of
`[0007]
`producing an oxidation catalyst. ZrO2 is provided and is cal-
`cined. The ZrO2 is mixed with platinum (II) acetylacetonate
`to form a mixture. The mixture is subjected to rotary evapo-
`ration to form a product. The product is calcined and reduced
`under hydrogen to form an activated product. The activated
`product is passivated under a flow of 2% O2.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`invention are
`the
`[0008] Preferred embodiments of
`described below with reference to the following accompany-
`ing drawings.
`
`FIG. 1 shows conversion of HMF and selective pro-
`[0009]
`duction of furan dicarboxylic acid and formylfuran carboxy-
`lic acid as a function of time on stream utilizing a continuous
`flow reactor with a 5% platinum supported on carbon catalyst
`and a base set of parameters in accordance with one aspect of
`the invention. The parameters included P = 150 psig, T = 100°
`C., 0.828% Na2CO3 added to 1% HMF, liquid hourly space
`velocity (LHSV)=7.5-15 h'1, air gas hourly space velocity
`(GHSV) =300 h’1, catalyst reduced at 30° C. wet.
`
`FIG. 2 shows HMF conversion and product selec-
`[0010]
`tivity as a function oftime on stream using the catalyst of FIG.
`1_at a decreased temperature (T=70° C.), LHSV=4.5-7.5
`h and air GHSV=300-600 h’1 (all other parameters and
`conditions being as set forth above with respect to FIG. 1).
`
`FIG. 3 shows HMF conversion and product selec-
`[0011]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 and the parameters as set forth for FIG. 2 except for
`temperature (T=50° C.).
`
`FIG. 4 shows HMF conversion and product selec-
`[0012]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 and the conditions as set forth at FIG. 2 with the
`
`exception of the temperature which was T=30° C.
`
`FIG. 5 shows HMF conversion and product selec-
`[0013]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 and the conditions of FIG. 2 with a decreased concen-
`
`tration of Na2CO3 of 0.414% and T=100° C.
`
`FIG. 6 shows HMF conversion and product selec-
`[0014]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 and the conditions of FIG. 1 except with an increased
`Na2CO3 concentration of 1.66%.
`
`FIG. 7 shows HMF conversion and product selec-
`[0015]
`tivity as a function oftemperature using the catalyst ofFIG. 1.
`P=150 psig, 0.828% Na2CO3 addedto 1% HMF, LHSV=7.5
`h’1 air, GHSV=300 h’1, data taken at time on stream= 140
`min.
`
`FIG. 8 shows HMF conversion and product selec-
`[0016]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 at the specified temperature and GHSV (either air or
`O2). P= 150 psig, T=100-115° C., 2.486% Na2CO3 added to
`3% HMF LHSV=4.5 h'1, air GHSV=300-600 h'1 or O2
`GHSV=600 h’1, catalyst reduced at 30° C. wet.
`
`FIG. 9 shows HMF conversion and product selec-
`[0017]
`tivity as a function of time on steam utilizing the catalyst of
`FIG. 1 under air or O2 at varied LHSV and/or GHSV. P=150
`psig, T= 130° C., 0.828% Na2CO3 added to 1% HMF,
`LHSV=7.5-15 h'1, air GHSV=300-600h'1 or O2 GHSV=
`600 h’1, catalyst reduced at 30° C. wet.
`
`FIG. 10 shows HMF conversion and product selec-
`[0018]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 at P=150 psig air, T=100° C., 1% HMF, LHSV=7.5-
`15 h’1,GHSV=300 h’1.
`
`FIG. 11 shows HMF conversion and product selec-
`[0019]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 1 and the conditions of FIG. 10 with the exception of
`0.8% added Na2CO3.
`
`FIG. 12 shows conversion of HMF and selective
`[0020]
`production of the indicated products as a function of time on
`stream utilizing a continuous flow reactor with a 5% Pt sup-
`ported on SiO2 catalyst and a base set of parameters in accor-
`
`Petitioners‘ Exhibit 1008, Page 41 of 46
`
`Petitioners' Exhibit 1008, Page 41 of 46
`
`

`
`US 2008/0103318 A1
`
`May 1, 2008
`
`dance with one aspect ofthe invention; 1% HMF, 150 psig air,
`60-100° C., LHSV=13-19.6 h’1,GHSV=261h’1.
`
`[0021] FIG. 13 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 12 in the presence of 0.8% Na2CO3. (1% HMF, 0.8%
`Na2CO3,150 psig air, 100° C., LHSV=13-6.5 h’1,GHSV=
`261 h'1.)
`
`[0022] FIG. 14 shows HMF conversion and product selec-
`tivity utilizing a 9.65% Pt supported on carbon catalyst. The
`conditions utilized were P=150 psig, T=100° C., 0.828%
`Na2CO3 added to 1% HMF LHSV=7.5-15 h’1, air GHSV=
`300 h'1, catalyst reduced at 30° C. wet.
`
`[0023] FIG. 15 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 14. P=150 psig, T=100° C., 2.414% Na2CO3 added to
`3% HMF LHSV=4.5 h'1, air GHSV=600 h'1, catalyst
`reduced at 30° C. wet.
`
`[0024] FIG. 16 shows HMF conversion and product selec-
`tivity as a function of time on stream for various air GHSV
`and LHSV. P=150 psig, T=100° C., 1% HMF LHSV=7.5-
`15 hl, air GHSV= 75-300 h” 1, catalyst reduced at 30° C. wet.
`
`[0025] FIG. 17 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 14 at varied temperature and LHSV. P =150 psig, T = 60-
`100° C., 1% HMF LHSV=3-7.5 hi, 1% O2 diluted air
`GHSV=300 hl, catalyst reduced at 30° C. wet.
`
`[0026] FIG. 18 shows HMF conversion and selective prod-
`uct production utilizing a 5% Pt on anAl2O3 support catalyst
`as a function on time on stream at varied LHSV. P =150 psig,
`T=100° C., 1% HMF LHSV=15-7.5 h'1, air GHSV=300
`h'1, catalyst reduced at 30° C. wet.
`
`[0027] FIG. 19 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst
`FIG. 18 at an increased temperature (130° C.) relative to FIG.
`18. P=150 psig, 1% HMF LHSV=7.5 h'1, air GHSV=300
`h'1, catalyst reduced at 30° C. wet.
`
`[0028] FIG. 20 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 in the presence of O2. P=150 psig, T=100° C., 1%
`HMF LHSV=7.5 h'1, 100% O2 GHSV=300 h'1, catalyst
`reduced at 30° C. wet.
`
`[0029] FIG. 21 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 and the conditions of FIG. 20 with the exception that
`P =300 psig.
`
`[0030] FIG. 22 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 and the conditions of FIG. 20 with the exception that
`100% O2 GHSV=600 h’1.
`
`[0031] FIG. 23 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 at varied LHSV. P= 150 psig, T=100° C., 1% HMF
`LHSV=7.5-4.5 h’1, air GHSV=600 h’1, catalyst reduced at
`30° C. wet.
`
`[0032] FIG. 24 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 at varied LHSV in the presence of O2. P=150 psig,
`
`T=l00° C., 0.828 weight % Na2CO3 added to 1% HMF
`LHSV=7.5-4.5 h’1,O2 GHSV=300 h’ 1, catalyst reduced at
`30° C. wet.
`
`FIG. 25 shows HMF conversion and product selec-
`[0033]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 at varied LHSV and GHSV. P=150 psig, T=100° C.,
`0.828% Na2CO3 added to 1% HMF LHSV=4.5-7.5 h'1, air
`GHSV=300-600 h’1, catalyst reduced at 30° C. wet.
`
`FIG. 26 shows HMF conversion and product selec-
`[0034]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 at varied LHSV and GHSV. P=150 psig, T=70° C.,
`0.828% Na2CO3 added to 1% HMF LHSV=4.5-7.5 h'1, air
`GHSV=300-600 h’1, catalyst reduced at 30° C. wet.
`
`FIG. 27 shows HMF conversion and product selec-
`[0035]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 18 in an 8 mL catalyst bed in the presence of air and then
`02. P=150 psig, T=100° C., 0.5% HMF LSHV=3.75 h’1,
`air then 02 GHSV= 150-263 h'1, catalyst reduced at 30° C.
`wet.
`
`FIG. 28 shows HMF conversion and selective prod-
`[0036]
`uct production as a function of time on stream utilizing a 5%
`Pt on a ZrO2 support catalyst at varied LHSV in a continuous
`flow reactor. P =150 psig air, T=100° C. 0.5% HMF LHSV=
`7.5-3 h’1,GHSV=300 h’1.
`
`FIG. 29 shows HMF conversion and product selec-
`[0037]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 at varied LHSV and HMF concentration. HMF =0.5-
`
`1%, P=150 psig air, T=120° C., LHSV=7.5-4.5 h’1,
`GHSV=300 h'1.
`
`FIG. 30 shows HMF conversion and product selec-
`[0038]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 at varied temperature. P=150 psig air, T=140-160°
`C., 0.5% HMF LHSV=7.5 h’1,GHSV=300 h’1.
`
`FIG. 31 shows HMF conversion and product selec-
`[0039]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 at varied LHSV at varied temperature and at varied
`psi air. P= 150-300 psig air, T=100-160° C., 0.5% HMF
`LHSV=7.5-15 h'1, GHSV=300 h'1.
`
`FIG. 32 shows HMF conversion and product selec-
`[0040]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28. P=150 psig air, T= 140° C., 0.5% HMF LHSV=7.5
`h'1, GHSV=300 h'1.
`
`FIG. 33 shows HMF conversion and product selec-
`[0041]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 and the condition of FIG. 32 with the exception of
`decreased GHSV (GHSV=150 h’1).
`
`FIG. 34 shows HMF conversion and product selec-
`[0042]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 and the condition of FIG. 32 with the exception that
`P=500 psig air.
`
`FIG. 35 shows HMF conversion and product selec-
`[0043]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 and the condition of FIG. 32 with the exception that
`GHSV=150 h'1 and P=150 psig O2.
`
`FIG. 36 shows HMF conversion and product selec-
`[0044]
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 after Na2CO3 wash; 0.5% HMF, P=150 psig air,
`T=100° C., LHSV=7.5 h'1, GHSV=300 h'1.
`
`Petitioners‘ Exhibit 1008, Page 42 of 46
`
`Petitioners' Exhibit 1008, Page 42 of 46
`
`

`
`US 2008/0103318 A1
`
`May 1, 2008
`
`[0045] FIG. 37 shows the concentration in weight % versus
`time on stream ofthe indicated starting material, products and
`by-products utilizing the catalyst of FIG. 28 after a carbonate
`wash. 0.5% HMF, P=150 psig air, T= 100° C., LHSV=7.5
`h'1, GHSV=300 h'1.
`
`[0046] FIG. 38 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 at varied temperature in the presence of either air or
`O2.1% HMF in 40% HOAc,150psigair/O2,T=100-140° C.,
`LHSV=7.5 h'1, GHSV=300 h'1.
`
`[0047] FIG. 39 shows HMF conversion and product selec-
`tivity as a function of time on stream utilizing the catalyst of
`FIG. 28 in the presence of either air or O2 at varied GHSV.
`0.5% HMF in 40% HOAc, P=150 psig air/O2, T=140° C.,
`LHSV=7.5 h’1, GHSV= 150-300 h’1.
`
`DETAILED DESCRIPTION OF THE PREFERRED
`EMBODIMENTS
`
`[0048] This disclosure of the invention is submitted in fur-
`therance of the constitutional purposes of the U.S. Patent
`Laws “to promote the progress of science and useful arts”
`(Article 1, Section 8).
`
`In general, the invention pertains to methods of oxi-
`[0049]
`dizing hydroxymethyl furfural (HMF) in an aqueous solu-
`tion. The oxidation process can be performed as a batch
`reaction or as a continuous flow process. A starting material is
`provided comprising HMF in water. Depending on the
`desired product, the mixture can be basic, neutral or acidic.
`Where an acidic aqueous solution solvent system is utilized,
`an appropriate acid can be added such as, for example, acetic
`acid. Due to the relatively low solubility of HMF oxidation
`products in neutral and acidic water, appropriate reactor
`designs can be utilized to accommodate solids formation.
`Feeds having up to 10% HMF have been successfully used in
`a batch reactor, and higher HMF concentrations are feasible.
`In a packed bed up-flow reactor the HMF concentration can
`preferably be less than or equal to about 3% by weight. Under
`mildly basic conditions, such as those created by providing
`Na2CO3 into the reaction mixture, products having carboxylic
`acid groups are present as the sodium salt and have increased
`solubilities. Solids formation and feed concentration are typi-
`cally not problematic under these conditions. The addition of
`a strong base, such as NaOH, can lead to undesirable side
`reactions such as the Cannizzaro reaction.
`
`[0050] The starting material comprising HMF is provided
`into a reactor and at least one of air or O2 is provided as
`oxidant. A pres sure offrom atmospheric to the pres sure rating
`of the equipment can be utilized depending upon the desired
`reaction rate. A preferred pressure can typically be in the
`range of 150-500 psi. Similarly an appropriate reaction tem-
`perature can be from about 50° C. to about 200° C., with a
`preferred range of from 100° C. through about 160° C.
`
`[0051] The starting material is contacted with a catalyst
`within the reactor. The catalyst typically comprises a metal on
`a support material. Preferably the metal comprises Pt. The
`support material can comprise, for example, C, ZrO2, A1203,
`SiO2, or TiO2. The particular support material utilized can
`depend upon, for example, the desired oxidation product(s)
`(discussed below).
`
`In particular instances, the reaction mixture can
`[0052]
`contain Na2CO3, or comparable weakbase. Where Na2CO3 is
`
`utilized, such can be present in the mixture at a molar ratio of
`from 0.25 to 2.0 moles Na2CO3 to HMF, preferably at a molar
`ratio of from 0.5 to about 1.0 relative to HMF. The use of
`
`Na2CO3 or alternative carbonate bases is advantageous rela-
`tive to conventional methodology. Other relatively weak
`bases (relative to NaOH) are contemplated such as those
`weaker than NaOH and stronger than the furan carboxylate
`product such that the furan carboxylate (FDCA, FFCA)
`remains in the soluble salt form. Possible alternative bases
`
`include metal carbonates, metal bicarbonates, metal phos-
`phates, and metal hydrogen phosphates. These relatively
`weak bases can be present in the feed and do not need to be
`added slowly over the course of the reaction to prevent side
`reactions that tend to occur with strong bases such as NaOH.