Exhibit 2022
`E.I. du Pont de Nemours & Co. and
`Acher-Daniels-Midland Co. v. Furanix Technologies B.V.
`IPR2015-01838
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`WO 2015/005942 A1 ||II||||||||||||||||||||||||||II|||I||||||||||||||||||||||||||||I||||||||||||||||I|
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`SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
`MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO,
`GW, KM, ML, MR, NE, SN, TD, TG).
`NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU,
`_
`RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH,
`TL TM TN‘ TR, T1.’ TZ, UA, UG’ US, UZ’ VC, VN, Declarations under Rule 4.17.
`ZA, ZM, ZW.
`— as to applicant’: entitlement to apply fbr and be granted
`(84) Designated States (unless otherwise indicated. fi)r every
`“pawn! (Rule 4'1""))
`kind gfpegiomt pmmg,-0,, am,-1a1,1e); AR1po(13w, on, — as to the applicant's entitlement to claim the priority of
`GM, KE, LR, Ls, MW, MZ, NA, RW, SD, SL, sz, TL
`the earlier application (Rule 4.I7(i1'z'))
`UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, Published,
`TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
`’
`E5, ES, [1, FR, GB, GR, 1-|R_ Hu, [13, [3, 11', L1‘, Lu, — with imemational search report (Art. 21(3))
`LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
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`WO 2015/005942
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`PCT/US20l3/067036
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`PROCESSES FOR MAKWG METHACRYLIC ACK3
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`
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`..............“¥‘-'i<=ii<1I0fth§.1.r.i:2e_a§i9n
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`[O001}The present appiication concerns processes for making
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`methacryiic acid via methacroiein from isobutene.
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`iggckgroasnd Art
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`{(3002} in this regard, isobutene is wideiy used for the production of a
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`variety of industriaiiy imporiant products, and has been used to make
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`methacryiic acid via metiiacroiein in one commerciaiiy known route.
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`isobutene has however been produced commerciaiiy to date through the
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`cataiytic or steam cracking of fossii feedstocks. As fossii rescurces are
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`depieted andior become more costiy to use. renewabie source-based routes
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`to isobutene are increasiragiy needed - especiaiiy in consideration of
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`increased demand for isobutene.
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`[G003}A harcfiempiafe method has previousiy been describeci for
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`synthesizing ZnxZr\,Oz mixed oxides for the direct and high yield conversion of
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`ethane! (from the fermentation of carbohydrates from renewabie source
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`materiais, inciuding biomass) to isobutene, wherein Zno was: added to ZrO2 to
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`seiectiveiy passivate zirconia‘s strong Lewis acidic sites and weaken Bréinsted
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`acidic sites while simuitaneousiy introducing basicity. The objectives of the
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`hard tempiate method were to suppress ethanoi dehydration and ace-tune
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`potymerization, whiie enabling a surface basic sitecataiyzed ethane:
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`dehydrogenation to acetaidehyde, an acetaldehycie to acetone canversion via
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`a1doi~condensationldehydrogenation, and a Brénsted and Lewis acidicfbasic
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`sitecatatyzed acatone~to~isobutene reaction pathway.
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`[06134] High isobutene yieids were in fact reaiized, but unfortunateiy. as
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`iater experieaced by Mizuno at at. {Mizuno et at. “One -path and Selective
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`Conversion of Ethane! to Propane on Scandiummodified indium Oxide
`
`Cataiysts", Chem. Lett., voi. 41, pp. 8924394 (2012)) in their efforts to produce
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`propyiene from ethanoi, it was found that further improvements in the
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`rsataiysfs stabiiiiy were needed.
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`PCT/US2013/067036
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`Summagg Of The invention
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`(00051 Our United States Patent Appticatiori Ser. No. 5t!720.433 (the
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`‘433 appiicaticnf’), flied October 31. 2012 for “Stable Mixed Oxide Cataiysts
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`fer Direct Conversion of Ethanot to isobutene and Process for tviaking” ,
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`concerns the discovery that these improvements couid be realized without
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`adding modifying metals and without a reduction in the initial high activity (100
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`percent ethanol canversion) that had been observed is these mixed oxide
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`catalysts. The ‘At-33 appiication thus in sum concerns an improved stabitity,
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`longer tifetime caiaiyst for converting etharmt to isobutene.
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`{G096} Separately‘ we discovered that acetic acid, rather than ethanol,
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`may be converted to a biobased isebuterie product using certain mixed oxide
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`cataiysts. inciuding a mixed oxide catalyst as made in the ‘433 appticatioh.
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`This discovery became the basis for United States Patent Appiication Ser. No.
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`tit!’/’i37,3t2 (the " ‘1312 application”), flied December 14, 2012 for “Process and
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`Cataiyst for Conversion of Acetic Acid to tsobutene“.
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`[D0011 Etuiirting on these discoveries, the present invention in one
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`aspect concerns a process for making methacrytic acid via methacrotein from
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`a biobased isobutene, wherein the biobasea‘ isobutene is prepared from
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`ethane! in the presence of a Zri,Zr.,0z mixed oxide catalyst, the biobased
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`isobuterie is oxidized to methacrolein and the methacroteirt is oxidized to
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`methacryiic acid.
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`[OO08]tri certain embodiments according to this first aspect, the
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`ZriKZr,,O,, mixed exicie cataiyst exhibits impreved stabitity for the conversien,
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`exhibiting tess than 16 percent toss, more preferabiy tess than 5 percent toss
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`and stiii more preferataiy tess than 2 percent less in isobutene seiectivity over
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`a period of 200 hours on stream.
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`in other embodiments, the Zn,.2§r,()2 mixed
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`oxide catatyst is made by a process as described in the ‘433 appticationt
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`broadly comprising forming a soiuticn of cine or more Zn compounds,
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`combining one or more zircontumeentaining solids with the soiution 0? one or
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`more Zn compounds. drying the wetter} sotids, then catcining the dried solids.
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`[00093in a second, related aspect, the present invention concerns a
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`process for making methacryiic acid via methacroiein from a biobesed
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`isobutehe. wherein the biobased isobutene is prepared from acetic acid in the
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`presence of a catalyst, the biobased isohutene is oxidized to meiilacroiein
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`and the methacroiein is oxidized to methaciyiic acid.
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`in certain embodiments.
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`the cataiyst is a Znxzryoz mixed oxide catalyst, especially a cataiyst made by
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`a process as described in the ‘433 application, and the process of making the
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`starting biobased isobutene is carried out as described in the ‘312 application.
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`§3_§i_¢,\3_§,__£)__g?,:_:;scri,:gtiz3n Of The Drawings
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`[001 0] Figure 1 schematically depicts a process for producing a wholly
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`biobased methacryiic acid from a whoiiy biobased isobutens made from
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`ethanol in the presence of a ZnxZr,.Oz mixed oxide catalyst, especialiy such a
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`cataiyst made by a process as described in the ‘4133 application.
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`[G011}Figure 2 schematihaiiy depicts a process for producing a
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`biohssed methacryiic acid, particufariy a wholly biobaseci methacryiic acid,
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`from a biobased and especially a wholly biobased isooutene made from acetic
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`acio‘, according to the second aspect of the present invention as summarized
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`above.
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`Descrigtion Of Embodimengg
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`[0£}‘l2}Referring now to Figuie 1. a process 10 is schemaiicaiiy
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`iiiustrated wherein ethanol '12 is converted to isobutene 1:: in the presence of
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`a catalyst, particularly, at Zh,.Zr,O, mixed oxide cataiyst. The isobotehe 14 is
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`then combined with oxygen from an oxygen source 18 and oxidized to yieid
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`methacroiein, which is then oxidized with oxygen from oxygen source 16 to
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`provide a methacryiic acid product 18.
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`{0013} The ethanol 12 is convsntionaiiy derived from biological carbon
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`sources. tor example. by fermentation of five» and especially six-carbon
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`sugals. so that the isobutene 14 and subsequent methacrylic acid product 18
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`are desirabiy wholly-biobased.
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`[£30141 Parentheticaiiy, by “biobased", we mean those materials whose
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`carbon content is shown by ASTM 96866 to be derived from or based in
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`significant part (at least 20 percent or more) upon bioiogicai products or
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`renewable agricultural materials (including but not being limited to plant,
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`animal and marine materials) or forestiy materiais. “Wholly biobased" thus will
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`be understood as referring to materials whose carbon content by ASTM
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`D6866 is entirety or substantiaiiy entirely (for example. 95 percent or more)
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`indicated as of bioiogicai origin.
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`{0015}ir: this respoctAST?v1 Method D8886, simiiar to radiocarbon
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`dating. compares how much of a decaying carbon isotope remains in a
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`sample to how much wouid be in the same sampio if it were made of entirety
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`rocantiy grown mate-riais. The percentage is caiieci the biobased content of
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`the product. Samoies are combusted in a quartz sampie tube and the
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`gaseous combustion products are transferred to a borosiiicate break seai
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`tube. in one merited, iiquid soiniiiiaiion is used to count the reiative amounts
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`of carbon isotopes in the carbon dioxide in the gaseous combustion products.
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`in a second method. i3Cf‘i2C and 14C:’1?.C isotope ratios are oounteri ( 140}
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`and measured {13C!‘i2C) using acceterator mass spectrometry. Zero percent
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`MC indicates the entire task of ‘MC atoms in a materiai, thus indicating a
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`iossii (for exarnpie, petroieum based} carbon source. One hundred percent
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`140, after correction for the post~1958 bomb injection of ‘MC into the
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`atmosphere. indicates a modem carbon source. ASTM D6868 effectiveiy
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`distinguishes between biobaseri materiais and petroieum derived maieriais in
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`part because isotopic fractionation due to physioiogioai processes. such as,
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`for oxampie, carbon dioxide transport within piants during photosynthesis.
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`roads to specific isotopic ratios in rraturai or biooased compounds. By
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`contrast, the 1301120 carbon isotopic ratio of pefroieum and potroieum
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`derived products is different from the isotopic ratios in natural or biocierived
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`compounds due to different chemicai processes and isotopic fractionation
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`during the generation of petroieum.
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`in addition, raciioactive decay of the
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`unstaoie 140 carbon radioisotope leads to different isotope ratios in biooaseo
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`products compared to petroieum products.
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`[9£3‘l6}Trre otizanoi ‘E2 can in this regard be derived from any known
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`process whereby five anolor six carbon sugars from convonrionai grain rrriiiirrg
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`operations or from processing of a iignoceiiuiosic biomass more genaraiiy
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`may be converted to one or more products inciusive of einanoi, at roast in
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`some part by fermentation means. Both aerobic and anaerobic processes are
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`thus contempiatod, using any of the variety of yeasts (e.g., Iriuyveromyces
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`ioctis, kiuyvemrnyces Iipolytica, saccharorrryoes cerevisiae, s. uvarum, s.
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`monacensis. s. pastorianus, s. bayanus, 5. eliipsoroues, candida shehata,
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`molibiosica,
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`£2.
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`intermedia) or any of the variety of bacteria ('a.g., ciostridium
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`sporogenes, c.
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`indolfs. c.
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`spironoidos,
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`£2.
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`sordefii. candida bracaransis.
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`candida dzzbrinierrsis, zymomonas mobiiis, z. pomaceas) that have ethano!~
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`producing capabiéity from five and/or six carbon sugars under aerobic or
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`anaerobic conditions and other appropriate conditions. The particuiar yeasts
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`(or bacteria} used and other particuiars of the fermentations empioying these
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`varicus yeasts {or bacteria) are a matter for routine seiection by those skilied
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`in the fermentation art.
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`[001 7} However obtained. the ethanoi 12 is then according tr: a first
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`aspect of the invention converted to isobutene 14 in the presence preferahiy
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`of a Znxzr,-Oz mixed oxide catalyst as described 5;‘; the ‘433 agzapiication, having
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`exceiient stabiiity for the conversion of ethane: to isobutene in exhibiting iess
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`man '30 percent toss in isobutene seiectivity over a period of 200 hours on
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`stream under atmospheric pressure (<5 psig) and 3% 450 °C. at fut: conversion
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`of the ethane! 32 re the isobutene 34. Preferabiy. however. the catatyst
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`exhibits iess than 5 percent ioss in isobutene selectivity over a period of 200
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`hours an stream, and more preferably Eess than 2 percent.
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`{0G18}These Znxzryoz mixed oxide cataiysts are generaéiy
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`charaaerize-ad by a Znlzr ratio ixzy) of from 3:100 to 30:1, preferabiy from 1:30
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`to 1:1, esgaeciafiy 1:20 to 1:5, and stiii mare preferably 1:32 to 1:10.
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`[G019}ParentheticaEiy, in the present appiication where any range of
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`varues is given for any aspect or feature of the mixed oxide caraiysts or any
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`process described for using the mixed oxide cataiysts, the given ranges wiii
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`be understood as disciosing and describing 33$ suhranges of vaiues inciudad
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`within the broader range. Thus, for exampie, the range of 1:100 to 10:1 wits
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`be understood as disctosing and describing not oniy the specific preferred and
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`more preferred subranges given above, but arse every other subrange
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`inctuding a vaiue for x between 3 and 10 and every other subrange inciuding
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`a vaiue for y between 1 and ‘£00.
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`[9020}The cataiysts made by the method cf the ‘433 appiication are
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`ccnsistent in their particie size with catatysts made by the hard remptafie
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`method ciescmbed in Sun at at, "Direct Conversion of Bimethanoi in Esobuterre
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`on Nanczsized ZnxZr;,—Oz Mixed Oxides with Baiamced A<:id«8ase Sites",
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`Joumaé of the American Chemicar Society, vot. 133, pp 11096-11099 (2011),
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`wherein carbon btack (BP 2000 carbon mack frum Cabot Corp.) was used as
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`a hard tempiate for the synthesis of nanosized Zn,<Zr,.0, mixed oxicies. En the
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`hard tempiate method of manufacture described in Sun, the BP 2000 temoiate
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`was dried at 188 “C overnight. Caicuiated amounts of zircooy! nitrate hydrate
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`(8igme~Atdrioh, greater than 99.8% purity) and Zn(NO3)2»€-H-30 isigma»
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`Aidrioh, greater than 99.8% purity} were dissolved in a given amount of water,
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`and sonicated for 15 minutes to produce a ciear soiution with desired
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`concentrations of Zn and Zr. About 25 grams of the obtained soiution were
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`then mixed with 6.0 grams of the preheated BP 2000 to achieve incipient
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`wetness, and the mixture was transferred to a ceramic orucibie and ceioined
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`at 400 degrees Cetsius for 4 hours. foliowed by ramoiog the temperature to
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`550 degrees Celsius {at a ramp rate of 3 degrees Cetsioslminute} and hoiding
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`at 550 degrees Ceisius for another 20 hours. Nanosized white powders were
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`obtained, having a mean particie size of less than 10 nanometers. The
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`oatafysts made by the method of the V433 appiication and used in the method
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`of Figure 2 (for converting ethane! 12 to isobutene 14) iikewise comprise
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`aggregates of tees thante ormsized oartictes, with a héghiy crystaiiirre
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`structure. The Zn oxide component is again highiy dispersed on the Zr oxide
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`component.
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`[0t}21]As summarized in the ‘433 eppiicetioo, some characteristic
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`differences have. however, aiso been observed between cataiysts of
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`equivaient Znizr ratios made by the prior hard temptate method and by the
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`method of the ‘433 application. For exampie, average crystaitite size as
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`caiortieteti based on the Scherer equation wiii typiceiiy be ierger. for exampie,
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`8.4 nanometers for 3 Zflgzfggoz mixed oxide oataiyst prepared according to
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`the ‘433 appiication as compared to 4.8 nanometers for a ZrtrZr.;aO2 mixed
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`oxide cataiyst prepared according to the former hard template method.
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`[0G22}A Zn;-Zr;g0g mixed oxide cataiyst prepared according to the
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`method of the ‘433 eppiioation eiso has a smaller surface area, roughty 49
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`square meters per gram, as compared to 338 square meters per gram for a
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`ZmZr..—,0g mixed oxide catalyst prepared according to the former herd
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`temoiate method.
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`[0023] One further, compositionat difference was aiso observed
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`between cataiysts prepared by the two methods, in that the Zn,Zr,O, mixed
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`oxide cetaiysts according to the ‘433 application preferebiy are substarztiaiiy
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`suiftmfree, containing fess than 6.14 weight percent of suifur. as compared to,
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`for exampie, 3.68 weight percent of suifur in the some ?.n¢Zr;gO;g mixed oxide
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`cetaiyet prepared according to the former hard tempiate method.
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`{(3924} The Zrr_,.Zr,,O, mixed oxide catatysts of the ‘433 application and
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`preferred for use herein have improved stabiiity for the conversion of ethane!
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`12 to isobutene 14; while the oomributions if any of the targer crystaiiite size
`
`and smarier surface area to this improved stabitéty are not presentiy
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`understood,
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`it is neverrheress believed that at ieast the much reduced suifur
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`content of the inventive catalysts does contribute materialiy to this improved
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`stability.
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`[0025] Based on infrared anarysr-2s of catatysts prepared according to
`
`the ‘433 apptécaltion and according to the hard tempiate method {which
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`anaryses are described more fuiiy in the incorporated ‘433 apprication}. the
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`presence of surfur in the former oataiysts - presumably reft behind from the
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`Cabot 8? 2000 furnace brack hard zemoiate after the rempEare‘s being
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`suostantiaiiy removed by a controlieo combustion ~ appeared to have
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`contributed to the presence of a number of stronger Lewis and Brorrsted
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`acidic sites on cataiysts made by the former method and in turn to a greater-
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`degree of acid ‘ac si’ce~cata¥yzeri coking of catalysts macro according to the
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`former hard tempfate method.
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`{0O26}According$y, whiie from one perspective the Zn,gZr.,.0z mixed
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`oxide oataiysts preferred for use in the present invention can be characterized
`
`in practice as having improved stabiiity for the conversion of ethanoi to
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`isoboterre, exhibiting toss than 30 percent rose in isoburono seiectivity over a
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`period of 203 hours on stream, from a different, compositiorzai perspective
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`the preferred more stable Zo,¢Zr_,.O, mixed oxide catatysts can be
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`characterézed as containing iess than 0.14 percent by weight of sulfur.
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`Preferabfiy, stiti more stabie cataiysts are provided, having a suifur content of
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`rose than 0.01 percent by weight, and aim more preferabiy the catarysts will
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`have a sulfur content of Iess than (3.001 percent by weight.
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`{G027} Such cataéysts may be made by a process broacity comprising,
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`in certain embodiments, forming a soiution of one or more Zn compounds.
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`combining one or more zirconiumoontainéng soiids with the soiution of one or
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`more Zn compounds so that the soiotion wets the zirconéumcorrtaining soiids
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`to a erate of incipient wetness, drying the wetted soiidsr then caroirring the
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`dried solids.
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`in other embodiments, 8 solution is formed of one or more Zr
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`compounds. the solution is combined with one or more Zmconlaining solids
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`so that the solution wets the Zn-containing solids to a state of incipient
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`wetness, the wetied solids are dried and then the dried solids are calcined.
`
`in principle, provided the zinc and zircorlium compounds and solids in these
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`embodiments do not contain sulfur, any combination of zinc and zirconium
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`materials and any solvent can be used that wili permit the zinc and zirconium
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`components to mix homogeneously whereby.
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`through incipient wetness
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`impregnation, one of the zinc or zirconium components are well dispersed on
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`a solid or the other component for subsequent drying and corlversion to line
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`oxide forms through calcining.
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`{(3028} The conditions and times for the drying and calcining steps will
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`depend, of course, on the particular zinc and zirconium materials and solvent
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`used, but in general terms, the drying step can be accomplished in a
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`temperature range of from 60 degrees Celsius to 200 degrees Celsius over at
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`leasi about 3 hours. while the calcining can take place at 3 temperature of
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`from 300 degrees Celsius to 1500 degrees Celsius, but more preferably a
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`temperature of from 400 to 600 «degrees Celsius is used. The caicinatiorl time
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`can be from 10 minutes to 48 hours, with from 2 to 10 hours being preferred.
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`i00291ln still other embodiments, suitable Zn,_.Zr.,O: mixed oxide
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`catalysts can also be prepared by a hard template method, except that a
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`suitable very low sulfur content carbon is used for the hard template such that
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`the finished catalyst will contain not more than 2 percent by weight of sulfur,
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`especially not more than 0.5 percent by weight of sulfur and still more
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`preferably will contain not more than 0.1 weight percent {by total weight of the
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`catalyst) of sulfur. A variety of such very low sulfur carbons are available
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`commercially from various suppliers;
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`in general, the lower the sulfur content.
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`the better for forming the highly active, stable mixed oxide catalysts preferred"
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`for use in a process of the present invention (whether based on eihanol as in
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`Figure 1 or acetic acid as in Figure 2).
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`{G936} Processes for converting the ethanol ‘i2 to isobulene ‘:4 using
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`these catalysts may be conriucieo in a manner and under conditions
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`described in the Sam ioumal article, or in a manner and under conditions
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`described in Mlzuno ei el or the several other prior publications concerned
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`with the production of products inclusive of isobutene from ethanoi.
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`in this
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`regard, while Mizuno et af. is particuiarry directed to the production of
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`propyrene from ethane}, it is nevertheiess considered to be war? within the
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`capabiiities of those skiiied in the art to determine what conditions embraced
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`by Mizune et or or other simiiar references win he most appropriate to
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`produce isoburene among the possible products, without undue
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`experimentation. Accordingéy, a detailed description of process detaiis for
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`using the more stabie mixed oxide cataiysts need not be undertaken herein.
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`Nevertneress. as an example, a continuous fixed bed reactor or new bed
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`reactor can be used. The reaction temperature may be in 3 range from 350 to
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`7'00 degrees Ceisius, preferabiy,
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`in a range from 400 to 500 degrees Ceisios,
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`and the WHSV can be in a range from 0.0? hr" to 10 hr“, preferably from
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`6.05 hr" to 2 hr’. Ethanol/water soiution vvith steam to carbon ratios from O to
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`20, preferably from 2 to 5 can be used.
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`[0831]Once the isobutene 14 is formed, the isobutene 14 is oxidized
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`with oxygen from an oxygen source 18 to yieid methacroiein according to any
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`known process and using any known cataiyst for this purpose, and the
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`mernacroiein is further oxidized to produce a methacryfic acid product 18,
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`again according to any known process and using any known oataiyst for the
`
`second oxidation step from methacrotein to methacryiic acid.
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`{0032}A number of parents have been issued describing methods for
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`producing methacrytic acid from isobutene via a methacroiein intermediate,
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`though those skirted in the art will be aware that the fofiowing are given as
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`merefy non-iémiiing exampies of the various processes and cataiysts that have
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`been and continue to be described in the patent and genera: scientific
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`literature reiating to a part of such a process or the process as a whoie.
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`[0033}US 8,133,313 to Garfoway describes a system and process for
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`separating rrzethacroiein from methacryiic acid and acetic acid in the gas
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`phase product from a partéai oxidation of isobutene én two oxidation steps,
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`purportedly maximizing recovery of ai! three components at minimum capital
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`and energy cost, under condérions minimizing poiymerizatéon and plugging by
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`solids deposition in compressors, commas and the Hire. A number of patents
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`and pubtications are recited for disciosing aspects of a process of partiatty
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`oxidizing isobutene or an isobutene equivaient §n:o metnacryiic acid in 23
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`singie step or multi-step oxidation process. for example. US 4,544,054; US
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`4,618_.?09: US 4,925,981; Us 4.8563493; Us 4,98?,252; US 5,356,466; US
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`5,780.67§ and WO 81345083.
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`{(3034}US 7,732,367’ to Stevenson et at. concerns a cataiysi for
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`accompiishing the gas~phase metrraororeén oxidation to methacryiic acid and
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`methods of making the cataiyst, where the cataiyst inorudes at ieast
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`moiybdenurrr, phosphorus, vanadium, bismuth and a first component setecteci
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`from potassium, rubidium, cesium, thaiiium or mixtures or combinations of
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`these, has at !east 57% medium pores and a nitric acid to motybdsrrum ratio
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`of at ieast 0.5 to 1 or a nitric acid to M012 ratio of at roast 6.0:1.
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`[0035]US 5,231,226 to Hammon et ai. aiso roiatos particuiariy to the
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`gas~phase oxidation of methacroiein to methacryiic acid, discéoséng a process
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`for the oataiytic gas-phase oxidation of methaoroiein to methacryiic acid in a
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`frxed~bed reactor at eievated temperature on oataiyticatiysctive oxides with a
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`singée pass conversion of from 4& to 95 percent. Because of the
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`exothermicity of the reaction, the reaction temperature is maintained from 280
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`to 340 degrees Ceésius untii a rneihacroieén conversion of from 20 to 46
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`percent is reached, at which pornt the reaction temperature is reduced at
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`once. irrcrementaiiy or continuously by from 5 to 40 degrees Cefsius rmtii a
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`conversion of from 45 to 95 percent has been acoompiished. with the proviso
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`that the reaction temperature as not !ess than 260 degrees Ceésius. Suitabie
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`oataéysts are indicated as those described in EP 265133, E? 102688 and DE
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`3010434.
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`{0036} US 5,155,262 to Etzkom st afi. concerns both processes for the
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`oxidation of isobutene to methaoroiein and for the oxidation of isobotene to
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`rrrethaoryric acid in two stages with methaoroiein as an intermediate, wherein
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`prior methods using steam in the starting reactant gas mixture to avoid
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`fiammabie gas mixtures and to improve reaction selectivity are assorteoiy
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`improved by using essentiaily inert, essenfraiiy anhydrous diiuent gases in
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`place of the steam. Reduced wastewater toad, improved seiectrvity and
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`reduced byproduct formation are said to resuit from the substitution. Etzkorr:
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`or at. recite that "many oxidation catalysis have been oisciosed for producing
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`meirracroreirr in high yierd by oxidizing isobutene”, cor. 1, tines 69452, giving
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`as examples oataiysts containing mixed oxides of moiybdsrrurrr, bismuth and
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`iron with phosphorus or tungsten or antimony, and commoniy incorporating
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`cohort andior nickei and alkafi metais as promoters, co}. 1, lines 6265. For
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`the secord stage oxidation of methacrotein to meihacryiic acid, mixed meta;
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`oxide catatysts are described which are said to typicaiiy contain motybdenum,
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`vanadium... tungsten, chromium, copper. niobium, tantaium and antimony.
`
`Etzkorn at at, refer in this regard to a number of additiortat publications
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`predating those listed in US 8,2?3,313, including US 4.141885; US
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`3,475,488; US 3.171.859‘. US 4,2£:‘s?',38S and US 4.26?’.385. as we}! as UK
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`2,058,943’ and US 4,618,709.
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`[0037}'¥‘urning now to Figure 2, a process is sohematicatty iiiustrated
`
`according to a second aspect of the present invention, providing biobased and
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`preferabiy whoiiy biobased methacryfic acid via methaorolein from a
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`corresponding biobased and preferably whoiiy béobased isobutene, wherein
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`the isobutene is prepared from acetic acid in the presence of a oataiyst, the
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`béobased isobutene is oxidized to methacroiein and the methacrotein is
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`oxédézed to methacrylic acid.
`
`in oertain embodiments, the oataiyst is a
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`zn_,zr,oz mixed oxide oatatyst, especially a catatyst made by a process as
`
`described in the ‘433 appiication, and the process of making the starting
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`biobased isobutene is carried out as described in the incorporated ‘$12
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`apptioatson.
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`[0638] More particulariy, a process 20 is shown wherein acetéo acid 22
`
`is converted to isobutene 24, and the isobutene 24 is oxidized {as described
`
`above in connection with Figure 1) using oxygen from an oxygen source 25 to
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`provide a mettracryiic acid product 28. As further described in the ‘312
`
`apptioation and as is wet! appreciated by those skirted in the art. the acetic
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`acid 22 can be obtained by various methods from a number of starting
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`materiais.
`
`if desired. at least a portéorr of the acetic acid that is conventionaiiy
`
`produced in the oxidation of isobutene 24 through methacroiein to the
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`mezhacrytic acid product 28 can be recovered and recycied to form a portion
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`of the acetic acid 22 that is used.
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`{G039} For exampie. the acetic acid 22 can he producer} from a source
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`30 of five and six carbon sugars by fermentation. {)8 6509.180 and US
`
`8,252,567 seek to improve upon known processes for making othanot and
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`butane?/hexanoi, respectivoiy. by means including the fermentation of five and
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`six carben sugars into acetic acid.
`
`in US 8,509,180, the acetic acid is
`
`esterified to form an acetate ester which may men he hydrogenated (using
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`hydrogen from, e.g.. steam reforming of naturai gas, eiectroiysis of water.
`
`gasification of biomass er partiai oxidation of hydrocarbons generaiiy) to
`
`ethanoi. §n US 8.252.567. the ethanoi formed in this marmer can be used to
`
`make butane; and hexanot, by subjecting the eihenot with acetate, acetic acid
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`or mixtures thereof to an acidogerric ferrnentation using, for example, species
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`of the bacteria Cxhstridium iclostridizrm irluyveri is mentioned}, to produce
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`butyrate, butyric acéd, caproate, capreic acid or mixtures thereof. These
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`materiais then in turn are acidified to convert butyrate and caproate to butyric
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`acid and caprok: acid, the butyric and caproic acids are esterified and then the
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`butyric and caproic acid esters undergo reduction by hydrogenation,
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`hydrogenoiysis or reduction by carbon monoxide to provide butane: and
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`ethanoi.
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`{8040]As reiated in these two patents and as is wefi known to these
`
`skiiied in the fermentation art, the fermentation of the five and six carbon
`
`sugars 30 ta form acetic acid 22 can be accompfished by various organésms.
`
`More particuiariy, homoacetegenic microorganisms are abie through
`
`fermentation to produce acetic acid with ‘$5096 carbon yieidg these
`
`micrerzrganisms intemaily convert carbon dioxide to acetate, in centres: to a
`
`process for producing ethane! from sugars obtained from biomass. wherein
`
`carbon dioxide is produced as a byproduct.
`
`[0043 Examptes of homoacetogens given by US 8252,56?’ are
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`microorganisms of the genus Moorelia and Ciostridium, especiafiy
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`microorganisms of the species Mooreiia thermoacericum (described as
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`fermeriy ctassified as Céostridium thermoaceticum) or Cfostriclirrm
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`formicuacetioum. US 8,252,567 represents that about one hundred known
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`acetogens in twentwwo genera were known as of 2009, and <:ross—--
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`references Stake, et 33., Ann. NY Asad. Sci. 1125: 100428 (2008) for a
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`review of aoetogenic microorganisms.
`
`{0042} Other references describing fermentation methods for producing
`
`acetic acid from five and six carbon sugars inctude US 4,935. 360; US
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`8,236,534; US 4,513,084; US 4.37’1.619 and US 4,506,812; bath onewstep
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`fermentatéorr processes from the sugars to acetic acid, acetates or both are
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`disciosed, as wet! as two—step processes Envoiving a first fermentation to iactio
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`acid (by iactobeciiios or known methods of hornoiactic fermentation,
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`oreferabiy) foiiowed by a second fermentation to convert lactic acid to acetic
`
`acid. for exampie. using Ciostridium forrnicoaoeticum.
`
`[0043}Any of the known fermentation methods may, in short. be used
`
`as described in the 1312 apoiication to produce acetic acid 22 for conversion
`
`to isooutone 24 in the presence of the Zn,;Zr,O; mixed oxide oataiysts, but
`
`homoaoetogeoic fermentation methods are considered preferabie in that
`
`carbon dioxide is not produced as a byproduct -— the carbon dioxide
`
`represents a yieid Eoss from the overaéi process to make isobutene and as a
`
`greenhouse gas is unciesirabie partiouiarty in the context of a process to make
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`a needed product more sustainabiy from renewabie resources.
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`{O0-44}As weii or in the aitemative, the acetic acid feedsiockr 22 can be
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`made from ethanoi 32, according to any of severe} known methods empioying
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`oxidative ferrnentarion with acetic acid bacteria of the genus Acetobaoter.
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`[0045}As weii or in the aitemative, the acetic acid feedstock 22 can be
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`made from methane: 34 through combination with carbon monoxide according
`
`to the most irrdusiriaiéy used more for making acetic acid. for example. in the
`
`presence of a caiaiyst under conditions effective for the carborryiation of
`
`methane}. A variety of carbonyiation cataiysts are known in this regard, see.
`
`for oxampio, US 5,672,743; US 5328, 8'?1; US 5,773,842; US 3883289; US
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`5.883.295,
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`[comm regard to the production of methane! 34, with increasing
`
`concerns for the abatement of greenhouse gases such as carbon dioxide in
`
`reoem years, a substantial amount of work has been reported on methods to
`
`convert carbon dioxide to metixanoi, see, for exampie, Wesselbaum et at,
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`"Hydrogenation of Carbon Dioxide to Methanoi by Using a Homogeneous
`
`Ruthenium-Phosphine Cataiyst”, Angew. Chem. int. Ed, voi. 51, pp ‘?499-
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`7502 (2012); Ma et ai., “A Short Review of Cataiysés for CO; Conversion”,
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`Ca.*oi_vsis Today, voi. 148, pp 221331 (2009); Borodko at at. "Cataiytic
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`Hydrogenation of Carbon Oxides - a 'i{)»Year Perspective”. Appiied C