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    Paten Utama

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    Muhammad Gian Novaldi
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    2 'US009193661B. 2) United States Patent (10) Patent Noz US 9,193,661 B2 Peterson et al. (45) Date of Patent: Nov. 24, 2015 (64) PROCESSES FOR PRODUCING ACRYLIC SRA 21m Gator endian 6.232352 BL $2001. Vidalin eta (71) Applica: Celanese international Corperaton, Siar7m BL 920m Cheung tal Irving, TX U5) fseasret be "23000 img ta Soossat 823200 Cheaters (72) Inventors: Craig. Peterson, Hebron, KY (US); Ths m2 b2000 Pant eal Josefina T. Chapman, Hooston, TX Fone ee (US); Mas. Kotsianis, Houston, 1X iat Bee (Us); Sean Mier, Ds Plaine So. m2 02012 Gacgeal (US); Dick Nagakl, The Woodlands, TX Shmooe0 B ADa012 Gracy tal {Us Tianshu Pan Houston 1X (8) as Dene ct Shuoet Disa al (03) Assignee: Celanese International Corporati Resiazt Bat 22014 Meron al sean Teving, TX (US) 200910048354 Al 2/2009 Bell etal Soaoorieas Ale 3012 Hey eal se2s0 (*) Notice: Subject to any disclaimer, the term of this 201410039225 Al 2/2014 Daniel etal. Patents extended or adised under 35 TIS. 1540) by 28 cays. POREIGN PATENT DOCUMENTS. 5 tous 4.2008 (21) Appl. Nos 14112 @ pose sane ih Sais ato (22) Filed: San, 9, 2014 5 eee ih Streams amo (os) Prior Pubticaton Data i» dorset ‘US 2014/0128636 Al May 8, 2014 te gaa iene OTitER PUBLICATIONS Related U.S. Application Data .. Applied Catalysis, 36, pp. 221-230 (1988). (63) Contiaation of aptication No, 137251623, filed on = Api Cty 252: 203. 18191 (Oct 3, 2011, Pat. No, 8.658.823 “nwa of Caayte 1,000 pp. 29-96 Soka. 2,222 C98, woah onlin GI) Ine. eon we ema Core SU353 (2006.01) International Search Report and Written Opinion for PCT/US20121 carestas (200601) A569 me eb O13 coresiaa (200801) NowFind Oice Aton for soneaponding US. Appl. No eres veo {SEs1e dal un 262003 ena ea ees NOt. App 8.182168 C07C 51377 (2006.01), ick 2 oo) Oe Fi Of ton fr sonepndig US Ap 0,151.6 ce CO7C $1444 2013.01}: CO7CS1383 Repeal Oise Acton for 'S. App No. 1925163, a Giison.careS1A77 eoOL; CoC NOES ory SUAZ QUIS), CO7C SL6 2013.01), COTE Oe Aton or U'S App. No, [1632.20 dated. 25,2014 S148 201301) ee Acton or US AML No. [082299 dt 25-2014 (58) Field of Casscation Search 2 CPC ...., COTE S1/42; COTE 51/353, COFC 51/377; ‘cited by examiner Core sis: Cove sas; CO7C SAE . ‘See application file for complete search history. a 6) References Cited 0 ABSTRACT " Ione embodiment, he invention so a proces fr prode- US. PATENT DOCUMENTS ‘ing an acrylate product. The process comprises the step of . oT wrovicing a crude product stream comprising the acrylate 4,040,913 A * 8/1977 Clovis etal serisox i evee ee Frodvet alan alkylenaing agent. The prowess farther com GUT 2 Moar Ban ta Prive the stp of sporting tls portion ofthe erie Gooteas A Boot Toes eta Product seam to frm an allenating agent sream and an $0012 A 31591. Smith ta intermediate product stream. The alkylenating agent stream. anemia | Geel Saket ‘comprises atleast 1 1% alkylenating agent and the interme- pee ree teeneat iat podut steam compres arya pr Resta TLboe Sein ca Soon A ‘Zier Scart 22 Claims, 2 Drawing Sheets U.S. Patent Nov. 24, 2015 Sheet 1 of 2 US 9,193,661 B2 HAcA 118 8 \ 120 Alkylenating Agent ¢ 132 L_ FIG. 1 P a Sz| 2 Zs] 5 <2|z US 9,193,661 B2 Sheet 2 of 2 Noy. 24, 2015 U.S, Patent ae 802 ¥OH waby Buyeuayiyy oz US 9,193,661 B2 1 PROCESSES FOR PRODUCING ACRYLIC "ACIDS AND ACRYLATES, (CROSS REFERENCE TO RELATED "APPLICATION ‘This application i » contineation of U.S. patent appli tion Ser. No, 13251,623, ied Oct. 3, 2011, which has issved as US. Pat. No. 8658823, the entirety of which is hereby incomporated by relerence. FIELD OF THE INVENTION ‘Te present invention relates generally tothe production of ‘serylic acid. More specifically the presen invention rlatesto the production of erudo acrylic acid via the condensation of acetic acid and formaldelyde and the subsequent purifiation thersof, BACKGROUND OF THE INVENTION .f-unsitursted seids, particularly acrylic acid and meth- scrylic acid, and the ester derivatives thereo! are wsefil ‘organic compounds in the chemical industry. These acids and ‘esters are known to readily polymerize or co-polymerze to orm homopolymers or copolymers. Often the polymerized js are use in applications such as superabsorbents, dis- persints, loeculats, and thickeners. The polymerized ester ‘rivatives are used in coatings (including Intex paints), ex tiles, adhesives, plastics, fibers, and synthetic resins ‘ecause aerylie acid and is esters have lang been valued ‘commercially, many methods of prluction have been devel- ‘oped. One exemplary acrylic acid ester production process uilzes: (1) the reation of acetylene with water and earbon ‘monoxide: andor (2) the reaction of an alcoho] and carbon ‘monoxide, in the presence of an eid, ex, hydrochloric acid, and nick tetracarbony, to yield a erude product comprising the acrylate ester as well 38 hydrogen and nickel chloride. Another conventional process involves the reaction of ketene (often obtained by the pyrolysis of acetone or aeeti acid) ‘with formaldehyde, which yields a crode prodact comprising acrylic acid and either waiee (when acetic acid js used 38 8 pyrolysis reactant) or methane (when acetone i used as 2 pyrolysis reactant). These processes have become obsolete Tor economic, eavironmenta, or other reasons ‘More recent acrylic acid production processes have relied ‘onthe gas phase oxidation of propylene via acroten, to form ‘acrylic acid, The ration can be eared out in single oF two-step processes bit the latter fivored becase of higher yells, The oxidation of propylene produces serolein, acrylic id, acetaldebiyde and carbon oxides, Acrylic acid from the Primary oxidation can be recovered while the aerolein is fed toa second sep to yield the erade aerylic cid product, which ‘comprises acrylic acid, water smallamountsof acetic acid as, well as impurities such as furfural, arolein, and propionic ‘cid, Porfiation ofthe crude product may be eatried out hy azeotropie distillation. Ahough this process may show some improvement over ealior processes this process suffers from produetion andr separation ineffitieneies. In addition, this ‘oxidation reaction is highly exothermic and, as such erates ‘anexplosion risk, Asa rest, more expensive reacior design and metallurgy are raquired. Also, the east of propylene is ‘often prohibitive ‘The aldo condensation rection of formaldehyde and ace tic acid andor carboxylic acd esters has been disclosed in feature, This reaction forms aerylic acid and is often con- Iucted over a catalyst. For example, condensation eatalysts 0 o 2 ‘consisting of mixed oxideso vanadium and phosphorus were investigated and described in M. Ai, Ji Catal, 107, 201 (1987):M.AiJ. Catal, 124,293 (1990): M. Ai, Ap. Catal 36, 221 (L088); and M. Ai, Shokubai, 29, $23 (1987). The ‘aceticucid conversions in these reactions, however, may leave ‘mom for improvement, hough this reaction is disclose there has boon litle if any disclosure relating to separation schemes that may be employed to effectively provide purified acrylic aid fom the aldol condensation crude pret. Thus, the need exists for processes for producing purified scrylicacid and, particular, for separation schemes to effee- tively purify unique aldol condensation enide products to {orm the purified acrylic cid. The relerences mentioned above are hereby incorporated by reference BRIEP DESCRIPTION OF DRAWINGS The invention is described in detail below with reference to the appended drawings, whorein like numerals designate similar pans FIG. T is @ process flowsheet showing an acrylic acid eactow/Separation system in accordance with an embod- ‘ment of the present invention FIG. 2s a schematic diagram of an arylie acid reaction! separation system in accordance with one embodiment ofthe present invention, SUMMARY OF THE INVENTION In one embodiment, the invention is to a process for pro ducing acrylic acid, methacrylic acid, and/or the salts and esters thereof. Preferably, the inventive process yields an ‘erylc ocd product. The provess comprises the step of pro- viding a erude product stream comprising acrylic aid andor other ery late produits and an alkylenating agent. The ene product stream may comprise atleast 1 wt % alkylensting ‘gent, The alkylenating agent may be, for example, formal- {dehy de. In preferred embodiments, the crude product stream is formed by contacting acetic acid snd formaldehyde over a catalyst and under conditions effective t form the enude product stream, In one embodiment, the iaventive process further comprises the sep of separating atleast a portion of there praduct stream to form analkyenating agent stream land an intemediate acrylic product stream. Preferably, the alkylenating stream comprises at least 1 wt 6 alkylemating ‘agent and te intermediate acrylic product stream comprises acrylic eid andor other aerylate products in high concentra- tions. DETAILED DI ‘RIPTION OP THE INVENTION Introduction Production of unsaturated carboxylic acids such as ae acidand methserylie aid andthe ester derivatives thereo! via ‘ost conventional processes have been limited by eeonom and environmental constraints. Ihe interest of finding 2 ness action path the aldol condeasation reaction of acetie acid and an alkylenating agent, eg. formaldehyde, sss been vestigated. This reaction may yield a unique ene product that comprises, imer alia, a higher amount of (residual) form- aldehyde, which is generally known to ad unpredictability ‘nd problems to separation schemes. Although the aol con- ‘ensstion reaction of acetic acid and formaldehyde is known, there has boon little if any disclosure relating to separation schemes that may be employed to effectively purify the US 9,193,661 B2 3 unique crude product that is produced. Other conventional reactions, eg, propylene oxidation or ketene/formaldchyde. ‘do not yield crude prodvets that comprises highee amounts of ormaldehyel. Theprimaryreectionsand the side reactions in propylene oxidation do no erate formaldehyde. Ta the reae- tion of ketene and formaldehyde, a two-step reaction is ‘employed and the formadelyde is confined tthe first stage. Also, the ketene is highly reactive and converts substantially allofthe reactant formaldehyde. Asa result of these features, ver tle, iTany, formaldehyde remains inthe erude product ‘exiting the reaction zone, Beeause no formaldehyde present Jncrude products formed by these conventional reactions, the separation schemes associated therewith have not addressed the problems and unpredictability that accompany crude products that have higher formaldehyde content Inone embodiment, the present invention is toa process for producing aerylic acid, methaerylic acid, andor the salts and ‘esters thereof. As used herein, acrylic acid, methacrylic acid, andlor te salts and esters thereo collectively or inividue ally, may be refered 1 as “aerylaté products” The use ofthe terms aerylie acid, methaerylie acid, or the salts and esters thereof, individualy, does not exclude the other aerylate products, and the use ofthe term acrylate predict does not require the presence of acrylic aeid, methacrylic acid and the salts and esters there The inventive process, in one embodiment, includes the step of providing a enude product steam comprising the acrylic acid andr other acrylate products, The crude product stream of the present invention, unlike most conventional acrylic acid-containing crude products, further comprises 3 ‘lgnificant portion of atleast ane allylenating agent. Prefer ably, the at leat one alkylenating agent is formaldehyde. For ‘example, the ede product stream may comprise at lest 0.5 wt %alkylenating apent(s) eg. at east 1 wt %, at least S wt 6, at least 7 wt %, at least 10 wt %, oF at least 25 wt %. In ‘eemis of ranges, the crude product stream may comprise from (055 % to 50 wt Yo alkylenating azen(s),e-.from I wt % to 45 wt % fom 1 wt 6 t0 25 wo, fom 1 wt 2610 10 8% ‘or from Sw eto 1Ow1 %. In terms of upper limits, the rade produc stream may comprise ess than 50 wt % alkylenating agent(s),eg less than 4S wt% less than 251 %,orless than Tw %, Inoneembodiment, the crude product stream ofthe present Jnvention further compeses water. For example, the crude product stream may comprise less than 60 wi water, ea. Jess than 50-wt 9% less than 40 w1 %, of less than 30 wt 9 Ia terms of ranges, the crude product steam may comprise from wt % t0 60 wt % water, eg, from $ w1% 10 50 Ww %, from 101% t0 40 1%, or from 15 wt % to 40.1%, In terms of ‘upper limits, the crude product stream may comprise at least wt % water, eat least Sw %,at east 10 wt %,orat least 150%, Inoneembodiment, the crude produet stream ofthe present invention comprises very litle, it any ofthe impurities found jn most conventional aerylie acid erude product steams. For ‘example, the eride product stream ofthe present invention ‘may comprise less than 1000 wppm of such impurities (ether 2 individual components or collectively). less than 500 ‘ppm, ess than 100 wppm, less than 50 wppea, oF Fess than 10 wppm. Exemplary impurities include acetylene, ketene, beta-propiolacione, higher alcabols, eg, Cys Cy OF Cage and combinations thereof. Importantly, the enad® prodact ‘ream of the peeseat invention comprises very il, i any, furfural and/or aceon. In one embodiment, the erude prod uct stream comprises substantially’ no furfiral andlor sctolein,¢g..n0frfral and/or aerate, Inone embodiment, the erude pret steam comprises less than less than 500 0 o 4 ‘wpm aerolein,¢ 2 less than 100 wppm, es tha $0 ppm, cress than 10 wppsn. In one embodiment, the erude product ‘stream connprises less than less than 500 wppm ffl, eg Jess than 100 wppm, less than 50 wppm, or less than 10 ‘wpm. Furfural and aerotein are known to ae a detrimental chain terminators in acrylic acid polymerization reactions. ‘Also, furfural andior acrolein are known to have adverse effects on the olor of purified precact andor to subsequent polymerized products In ation to the acrylic acid and the alkylenating agent the erude produet stream may further comprise aectie acid, water, propionie acid. and ligt ends such as oxygen, nitro” zen, carbon monoxide, carbon dioxide, methanol, methyl faeeiate, methyl serylate, acetaldehyde, hydrogen, and acetone. Exemplary compositional data forthe era product stream are shown in Table 1. Components other than those Tisted in Table 1 may also be present in the erode product TABLE L Aewlcan Tes tes) ses) Wea Aipking Ags) 0st tas 110 Asso id Tem tem aes) Neer ies) Stes Isioa) Prope Acid ONTO aA 81D oxen Siete ater Ninwsen item aren CarbonDonde OMNI Ate Oiler LigeEnis OUTIL O10 The unique erode product stream of the present invention may be separated in # separation zane to for final proc, eg, a final aeryic aeid product. In one embodiment, the inventive process comprises the step of separating atleast a portion of the ene product stream to form an alkylenating fagent stream and an intermediate product stream. This ses "ating step maybe reeered to as an “akylenating agent spit none embodiment, the alkylensting agent stream comprises significant amounts of alkylenating agents). For example, the alkylenating agent stream may comprise at least 1 wt % alkylenating agent(s), gat least 5 w1%, atleast 10 wt %, at Teast 15 w1 2%, or a least 28 wi %. In terms of ranges, the alkylenating stream may comprise from 1 wt % to 75 wt % alkylenating aent(s) eg. from 3 to SO wi %, fom 3 W1% 10 25.61%, oF from LOWw1% to 20.61%. Inteems of pe ii the alkylenating stream may comprise less than 75 wt % alkylenatingagent(s), e.g. less than 50 wt % or less than 40 wt preferred embodiments, the alkylenating azent is form aldehyde ‘As noted above, the presence of alkylenating agent inthe «nice product stream adds unpredictability and problems to separation schemes. Without being bound by theory, itis believed that formaldehyde resets in many side reactions with ‘Water (0 form by-products. The following sie reactions are exemplary a0+1,0—t0c1Lo1 O10 eOCHOH-OH,O ENO ‘Without being bound by theory, itis believed that in some embodiments, as a result ofthese reactions, the alkylenating ‘agent, eg, formaldehyde, acts as “light” component st US 9,193,661 B2 5 higher temperatures and as & “heavy” component at lover temperatures. The reaction(s) are exothermic. Accordingly, the equilibrium constant increases as temperature decreases and decreases as temperature inereases. Nt lower temper- tures, thelarger equilibrium constant favors methylene glycol and oligomer production and formaldehyde becomes limited, and, a such, belaves as a heavy component. At higher tem- peratures, the smaller equilibrium constant favors formalde- hyde production and methylene glycol hecomes limited. As such, formaldehyde behaves as alight componeat In view of these difficulties, as well as others, the separation of steams that comprise water and formaldeiyde cannot be expected to behave as atypical two-component system. These features ‘contribute to the unpredictability and dificulty of the sepa ration of the unique crude product stream of the present invent The present invention, surprisingly and unexpectedly, achieves effective separation of alkylenating sen(s) trom the inventive erude product stream to yield a purified product ‘comprising acrylate product aad very low amounts of other impurities, In one embodiment, the alkylenating split is performed such that lower amount of acetic acids present in the resulting alkylenating stream. Preferably, the alkylenating agent steam comprises ite ornoacetc seid. Asan example, the alkylenating agent stream, in some embodiments co prises less than 50 wt % acetic acid, eles than 43 wt 9%, Jess than 25 wt 26, less than 10 wt, less than 5 w1%, less than 3 wt %, or les than 1 %, Surprisingly and unexpeet- ‘edly, the present invention provides forthe lower amounts of acetic acid in the alkylenating agent stream, which, benefi- ally educes or eliminates the need for further treatment of the alkylenating agent stream to remove actie sci In some ‘embodiments, thealkylenating agent stream may be treatedto remove water therefrom, eto purge Water In some embodiments, the alkylenating agent splits per- formed in atleast one column, ¢.,at last two columns or at Jeast three columns, Preferably, the alkyleating agent is per- ormed in a to column system. In other embodiments, the alkylenating agent spit is performed via contact with an. ‘extrction agent. In other embodiments, the alkylenating agent split is performed via precipitation methods, eg, Pionate is used, the mintare comprises less than 10 wt % ‘water, eg, ess than 5 wt % of less than 1 wt %. Tn some embodiments, the condensation reaction may achieve favorable conversion of acetic acid and favorable selectivity and productivity to acrylates. Por purposes of the present tention, the term “conversion” refers to the amount ‘facet acid the feed tha is converted to acompoundother than acetic acid, Conversion is expressed as percentage based on acetic acid in the Teed, The conversion of acti acid may be at least 10%, eat least 20%, a leas 40%, oFat least 50%, Selectivity, as itrefersto the formation of seryate product, isexpressed the ratio ofthe amount of carbon inthe desired product(s) and the amount of carbon in the total products ‘Thisratio may be multiplied by 1000 ariveat the selectivity. Preferably, the estalys selectivity to aerate products, ©. ‘erylic acid and methyl serylate, sat least 40 mol%, eg. at least 50 mol %, at lest 6D mol 9%, or atleast 70 ml %. In some embodiments, the selectivity to aryl acid ist least 390 mol %, al last 40 mol%, orat least 50 mol %; andor the selectivity to methylacrylate is at least 10 mol%, e.g. atleast 15 mol % ora least 20 mel %. ‘The terms “productivity” oF “space time yield” as used herein refers to thegrams ofa specified product, eg, aerylate products, formed per hour during the condensation based on the liter of catalyst used. productivity of at leat 20 grams ‘of aerylate pret per liter catalyst per hour, eg, a least 0 ‘grams of acrylates per liter catalyst per hour or atleast 100 trams of aerylates per liter catalyst per hour, is preerre. terms of ranges, the productivity preferably is fom 20 to 500 trams of sorylaes per liter catalyst per hour, ©. fom 20 10 200 grams of aerylates pr liter catalyst per hour or fram 4040 140 grams of aerylates per liter eatalyst per hour In one embodiment, the inventive process yilds atleast 1,800 kg/hr of finished serylc acid, eat Teast 3,500 kwh, least 18,000 kg, ora least 37,000 kr. Preferred embodiments of the inventive process demon- stratealow selectivity to undesirable preduets, suchas carbon ‘monoxide and carbon dioxide. The selectivity to these unde- sinsble products preferably is less than 29%, ex, less than 25% or less than 15%, More preferably, these undesirable products are not detectable. Formation of alkanes, ‘ethane, may be low, and ideally Tess than 2%, les than 1%, oF Jess than 0.5% ofthe acetic acid passed over the catalyst is ‘converted to alkanes, which have litle value other than as fc. ‘The alkanoie acid or ester thereof and slkylenating agent may be fed independently or aller prior mixing to a revetor ‘containing the eaalyst. The reactor may’be any’ suitable rac tor or combination of reactors, Preferbly, the reactor com- prises a fixed bed reactor ora series of fixed bed reactors. In ‘one embodiment, the reactor is a packed bed reactor or a series of packed bed reactors. In one embodiment, the reactor is a fixed bed reactor. OF course, other reactors such a8 @ ‘continuous stred tank reactor ora fuiized bed reactor, may be employed, In some embodiments, the alkanoic acid, og. acetic ac, ‘andthe alkylenating agent, eg. fommaldehyd, ate fed to the reactor ata molar ratio of at least 0.10:1, eg. a least 0.75:1 ‘ort least :1- In terms of ranges the molar ratio of alkanoic id to alkylenating agent may range from 0.10:1 to WO:t of from 0.75:1 to 5:1. Jn some embodiments, the reaction ofthe 0 o 10 alkanoie acid and the alkylenating ent is condted with a oichiometic excess of alkanoic acid, In these instances, acrylate selectivity may be improved. As an example the acrylate selectivity may be at least 10% higher than a selee- tivity achieved when the reaction iseonduieted with an excess ofalkylenating agent, .,at least 2% higher or atleast 30% higher. In other emboximents, the reaction of the alkanoie ‘cid and the alkylenating agents conducted with stoichio- metric excess of alkylenating agent. The condensation eaction may beconducted ata tempera ture ofa least 250° C., ea least 300° C., oF at east 350° C. In tems of ranges, the reaction tempersture may range rom 200°C, t0 500°C, e.g, ram 250°C. to 400°C, or rom 280° C. to 380° C. Residence time in the reactor may range from 1 second to 200 seconds, e.2, fom 1 second t0 100 seconds, Reaction pressure isnot particularly limited, ad the reaction is typically performed near atmospheric presse. In ‘one embodiment he reaction may be conducted ata pressure ranging from 0 kPa 10 4100 kPa, e, from 3 kPa to 345 KPa, for from 6 103 kPa. The aoelie aeid conversion, in some tembodiniens, may vary depending upon the reaction tem- perature Tn one embodiment, the reaction is conducted at a gas hourly space velocity ("GHSV") greater than 600 hr, ep ateater than 1000 hi or grester than 2000 hi-', In one ‘embodiment, the GFSV ranges from 600 iu to 10000 hr, 2, from 1000 hr" to 8000 he! or from 1500 he” to 7500 tir! As one particular example, when GHSV is atleast 2000 hr! the aerylate product STY may beat least 150 grhiliter ‘Water may be present inthe reactor in amounts up 60 6 by weight ofthe reaction mixture, c upto SOs %orup {0 40,w0 %. Water, however, i preferably reduced doe to its egative effect on procest rates and sepanition costs a one embodiment, aa inet or reactive gas is supplied to the reactant stream, Examples of inert gases include, but are not Timited to, nitrogen, helium, argon, and methane Examples of reactive gases or vapors include, but are not Timid to, oxygen, eatbon oxides, sulfur oxides, and alkyl halides. When reactive gases such as oxygen are added to the reactor, these gases, n some embodiments, may be added in stages throughout the catalyst hed a desired levels as well as feeding with the other feed components at the beginning of the reactors. The addition of these additional components may improve reaction elliciencies, Tnone embodimest, the unreacted componeas such asthe alkanoie cid and formaldehyde as well asthe inen orreetive gases that remain are reeycled to the reactor after sufiient ‘Separation from the desired prod. ‘When the desired product is an unsaturated ester made by reacting an ester of analkanoic aid ester with formaldehyde, the alcobol corresponding tothe ester may aso be fed to the reactor either with oe separately tothe other components. For ‘example, when methyl aerylate is desired, metnol may be {ed tothe reactor. The aleohol, amongst other effets, redoces the quantity of acids leaving the rector. Its not necessary thatthe alcohol is added ot the beginning ofthe reator and it ‘may for instance be added i the middle or neae the back, ia ‘order to eect the conversion of aids such as propionic acid, methacrylic acid to their respective esters without depressing catalyst activity: In one embodiment, the alcohol may be added] downstzeam of the reaetor Catalyst Composition ‘The catalyst may be any suitable catalyst composition As fone example, condensation catalyst consisting of mixed oxides of vanadium and phosphorus have been investigated land deseribed in M. Ai, J. Catal, 107, 201 (1987). M. AJ (Catal, 124, 283 (1990): M. Ai, Appl. Catal, 36,221 (1988): US 9,193,661 B2 ul ‘and M. Ai, Shohubai, 29,522 (1987), Other examples include binary vanadiuetitanium phosphates, vanadium-silc phosphates, and alkali metal-promoted silicas, eg. eesium- ‘or potassium. promoted silica, Ina proferred embodiment, the inventive process employs catalyst composition comprising vanadium, titanium, and ‘optionally atleast one oxide additive. The oxide aditives) if present, are preferably present in the active phase of the Catalyst. In one embodiment, the oxide additive(s) are selected from the group consisting of silica, alumina, zirco- nia, and mixtures thereof or any other metal oxide oer than ‘lal oxides of titanium or vanadium. Preferably, the molar ratio of oxide additive to titanium ia the ative phase of the ‘catalyst composition is greater than 0.05:1, eg, greater than 41:1, greater than 0.5: or greater than 1:1. In terms of ranges, the molar ratio of oxide additive to titanium in the inventive catalyst may range from 0.05:1 to 20:1, e,from (01:1 to 10:1, or rom 1:1 10:1 In these embodiments, the ‘catalyst comprises titanium, vanadium, and one or more ‘oxide additives and have relatively high molar ratios of oxide additive to titanium, In other embodiments, the catalyst may further comprise ‘other compounds clement etalsandioraon-metals) For ‘example, the catalyst may further comprise phosphorus and! ‘oroxygea, Inthese cases, the catalyst may comprise from 15 1% (045 w1% phosphorus, eae, from 20 wt % w 35 wt % ‘or from 23 wt % to 27 wt %6: andr rom 30 1 % 10 75 WI% ‘oxygen, eg, from 35 WL % 0 65 w1% or feom 48 wt 9% 0 ST wt In some embodiments, the catalyst further comprises adi- tional metals andlor oxide additives, These additional metals and/or oxide additives may function as promoters. If present, the additional metals andor oxide additives may be selected ‘rom the group consisting of copper, molybdenum, tungsten nickel, niobium, and combinations thereof. Other exemplary promoters that may be included inthecatalystof the invention Include lithium, sodium, magnesium, aluminum, chromium, ‘manganese, iron, cobalt, caleium, ytium, ruthenium, silver tin, barium, lanthanum, the rare earth metals, hafnium, tant Jum, rhenium, thorinm, bist, antimony, geemanivm,2it= ‘onium, wrasium, cesium, zine, and silicon and mixtures thereof Other modifiers include boron, gallium, arsenic, fur, halides, Lewis acids such as BE,, ZnB, and SaCl, Exemplary processes for incorporating promoters into cata- lyst are described in US, Pat, No. $.364,824, the early of ‘which is incorporated herein by reference Ifthe catalyst comprises additional metal(s) and/or metal ‘oxidex(s), the eatalyst optionally may comprise additional ‘metal andlor metal oxides in an amount from 0.001 w1 % 0 301%, eg, from 0.01 w% 105 wi Mor from 0.1 81% 1 5 wt %. Ifpresent, the promoters may enable the catalyst 10 hhavea weight/weight spacetime yield of atleast 25 grams of ‘serylic ueid/aram caalysth, eg, least $0 grim of acrylic /gram eatalyst-h, oF at least 100 grams of acrylic acid! ram catalyst, TInsomeemibodiments, the catalyst is unsupported, In these ‘cases, the catalyst may comprise a homogeneous mixture ora, heterogeneous mixture as described above. In one embod ‘ment, the homogeneous mixture isthe prot of an iatimate mixture of vanadium and titanium oxides, hydroxides, and phosphates resulting from preparative methods suet as con- trolled hydrolysis of metal alkoxides or metal complexes In ‘other embodiments, the heterogeneous mixture isthe product ‘of physical mixture ofthe vanadium and titanium phos- phates. These mixtures may include formulations prepared fiom phosphorylating physical mixture of preformed hydrous metal oxides. In other eases, the miture(s) mity 0 o 12 include amixtureof preformed vanadium pyrophosphate and ‘itanium pyrophosphate powders. Tn another embodiment, the catalysts supported catalyst comprising a catalyst support in addition to the vanadium, titanium, oxide additive, und optionally phosphorous and ‘oxygen, inthe amounts indicted shove (wherein the molar ranges indicated are without regard tothe moles of eaalyst suppor, including any vanadium, titanium, oxide additive, phosphorous or oxygen contained in the catalyst support. The total weight of the support (or modified support, based ‘on the total weight ofthe catalyst preferably from 75 wt. % 1099.9 wi. %, ex, from 78 wt. % to 97 WL % or from 80 Wt 61095 wi. Ye The support may vary widely. In one embed nen, the support materials selected from the group consi ing of silica, alumina, zirconia, titania, aluminosilcates, ‘zeolite materials, mixed metal oxides (including but not im ited to binary oxides such as SiO, —Al,O,, SiO;—TiO,, SiO,—Zn0, SiO;—MgO, Si0.— 7102, “Al,0,—Mg0, ALLO, TiO, Al,O,—Z00, TiO,—MyO, Ti0,—Z10., ‘THO,”Zn0, TiO, —SnO,) and mixtures thereof, with silica being one prefered suppor. Inembesdiments where the. lyst comprises a titania support the titania support may com- prise a major or minor amount of rutile andior anatase it nium dioxide. Other suitable suppor materials may inelude, Tor example, stable metal oxide-based supports of ceramie™ based suppomts. Prefered supports include siieaesous sup- ports, suchas sii, silewalumin, a Group TIA silicate such as calcium motasilicate, pyrogenic silica, high purty silica, silicon carbide, shet silicates or clay minerals such as mont- rorillosite, heidellite, saponite, pillared clays, other microporous and mesoporous materials, and mixtures thereol Other supports may inclide, bt are not limited to, ion oxide, magnesia, seatite, magnesium oxide, carbon, sraphite igh surface area graphitized carbon, netvated car bons, and mixtures there. These listings of supports are ‘merely exemplary and are not meant limit the seape ofthe present invention. Insome embodiments, a zeolitic suppor is employed. For ‘example, the zeolite suppor may’be selected from the group consisting of montmorillonite, NH, ferrite, H-morder PVOx, vermiculite-], H-ZSMS, NaY, IESDUSY, Y zeolite ‘ith high SAR, setivated bentonite, ILUSY, MONT:2, HY, ‘monleaite SAR 20, SAPO-34, Aluminosilicate (X), VUSY, Aluminosiieate (CaX), Re¥, and mixtures thereof H-SDUSY, VUSY, and H-USY are modified ¥ zeolites belonging to the fayjasite family. In one embodiment, the suppor is zeolite that does not contain any metal oxide snclifer(s). In some embodiments, the catalyst composition ‘comprises a zeolite support and the active phase comprises a ‘ictal selected from the group consisting of vanadium, ale ‘minum, nickel, molybdenum, cobalt, iron, tungsten, zinc, copper, titanium cesium bismuth, sodium, calcium, chro” ‘ium, cadmium, zirconium, and mixtures thereof-Insomeof these embodiments, the active phase may also comprise hydrogen, oxygen, andor phosphors. Tnother embodiments, i addition othe active phaseand a support, the inventive catalyst may further comprise a support ‘medifiet.A modified suppor, in one embodiment, relates to suppor tat includes support material and a support modi- ier, which, for example, may adjust the chemical or physical properties ofthe support material such as the aeity or basc- ity of te suppor material In embodiments that use a most fied support, the support modifier is present in an amonnt rom 0.1 wt. % 0 50-Wt. 9%, eg. from 0.2 wt. %t0 25 wt %, from 0.5 wi. %to 1S wi. %, oF from lw. %to St. %, based ‘on the total weight of the catalyst composition US 9,193,661 B2 13 In one embodiment, the support modifier is an acide sup port modifier. In some embodiments, the catalyst support is ‘modified with an adie support modifier. The support maxi fir similarly may be an acidic modifier that has low vol tility or lite volatility. The acidic moditiers may be selected fiom the group consisting of oxides of Group IVB metals, ‘oxides of Group VB metals, oxides of Group VIB metals ion ‘oxides, aluminum oxides, and mixtures thereof. In one ‘emboviiment, tho acidic moxitier may’ be soloted from the nroup consisting of WO,, MoOs, Fe,0s, Cr.0y, V.0s, MnO, CuO, C0,0s, Bi,0s, TiO,, 2:0, Nb.Os, Ta,0., Al,O5, B:Os. P,O,, and $b,0,, In another embodiment, the support modifi isa basic support modifier. The presence of chemical species such as alkali and alkaline earth metals, are normally considered basic and may conventionally be considered detrimental t0 ‘catalyst performance. The presence of these species, low= ‘eve, suprisingly and unexpectedly, may be beneficial to the ‘catalyst performance. In some embodiments, these species may aetas catalyst promoters ora necessary part of teaeiic ‘catalyst strcture such in layered or sheet silieates such as, ‘montmorillonite. Without being bound by theory it is posta- Jated that these cations eeate a strong dipole with species that create acidity. “Additional modifiers that may be inch in the catalyst include, for example, boron, aluminum, magnesium, zireo- nium, and hata, "As will be appreciated by those of ordinary skill in the at, the suppor materials, if included in the catalyst ofthe present ‘invention, preferably are selected such tht the catalyst sys- tem is suitably aetve, selective and robust under the process ‘conditions employed forthe formationat the desired proc, eg. aerlic aid or alkyl aerylate. Also, the active metals, andor pyrophosphates that are included inthe catalyst ofthe ‘invention may be dispersed throughout the suppor, costed on the outer surface ofthe support (egg shell) or decoratedon the surface of the support. In some embodiments in the ease of ‘acro- and meso-porous materials, the active sites may be ‘anchored or applied to the surfaces of the pores that are distributed thrghout the paticleand hence are surface sites available to the reactants bot are distributed throughout the support patil. “The inventive catalyst may’ furlher comprise otber add tives, examples of which may include: molding wsistats for ‘enhancing. moldabilty; reinforcements for enhancing the strength of the catalyst; pore-forming or pore modification agent for formation of appropriate pores in the catalyst and binders. Examples of these other additives include stearic acid, graphite, starch, cellulose, silica, alumina, glass fibers, silicon carbide and silicon nitride Preferably. these additives ‘donot have detrimental elfacison te catalytic performances, ‘eg. conversion and/or activity. These various additives may be added in such an amount thatthe physical strength ofthe catalyst does not readily deteriorate to such an extent that it becomes impossible to use the catalyst practically as an instil catalyst. Separation ‘As discussed above the erude product stream is separated 1o yield an intermediate serylate product stream. FIG. is @ ‘low diagram depicting the formation of the erude product stream and the separation thereof to obiain an intermediate ‘acrylate product stream, Acryate product system 100 com- Prises reaction zane 102 and allylenating agent split zone 132, Reaction zone 192 comprises reactor 106, alkanoie acid feed, eg. acetic acid feed, 108, alkylenating agent feed, eg Tormaldehyie feed 110, and vaporizer 12, 0 o 14 Acetic seid and formaldehyde are fed t vaporizer 112 via ines 108 and 110, respectively, o create a vapor feed stream, Which exits vaporizer 112 via Tine 114 and is directed 10 reactor 106. In one embodiment, lines 108 and 110 may be ‘combined snd jolly fed to the Vaporizer 112, The temper tore ofthe vapor feed steam inline 114 is preferably from 200° C.10600°C.,ea, from 250°C. to 500°C. or from 340° C. 10 425°C. Altermatively, vaporizer may not be employed and the reactants may be fed directly to reactor 106, Any feed that snot vaporized may be removed from vapor- iver 112 and may be reeled or discanded. In addition, although Fine 114i shown as being directed to the upper half fof reactor 106, line 114 may be directed to the middle oF bottom of fist reactor 106, Further modiieaions aod addi- tional components to reaction zane 102 and alkylensting agent split zane 132 ace described below ‘Reactor 106 contains the catalyst thats used inthe reaction to form erude prodiet stream, which is withdeawn, preferably continously, from reactor 106 via fine 116. Although FIG. 1 shows the crude produet steam being withdrassn from the bottom of reactor 106, the enude product stream may be ‘withdrawn from any portion of reactor 106. Exemplary com- position ranges forthe erude product stream are shown ia ‘Table 1 above, In one embodiment, one or more guant beds (not shown) may be used upstream of the reactor to protect the catalyst {rom poisons or undesirable impurities contained in the feed ‘orretum/reeyele streams. Such stard beds may be employed inthe vapor o liquid steams. Suitable guard bed materials ‘may inclide, forexample, carbon, silica, alumina, ceramic, oF resins. Inone aspect, the guard bed media is fhnetionalize eg, silver functionalized, to trap particular species such as sulfur o halogens. "The enide procict stream i ine 116s fed to alkylenating ‘agent split unit 132. Alkylenating agent split unit 132 may ‘comprise one or more separation units, e.g. {Wo OF More ar three or more. In one example, the alkylenating agent split ‘unit contains multiple columas, as shown in FIG. 3. Alky- Jenating agent split unit 132 separates the enue product stream into at least one intermediate acrylate product stream, whieh exits via Tine 18 and at least one alkylenating agent seam, which exis vi line 120. Exemplary compositional ranges forthe intermediate aerylate product steam are shown in Table 2. Components other than those iste in Table2 may also be present in the intermediate acrylate product stream. "Examples include methanol, methyl acetate, methyl aerylate

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