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    United States Patent ‘US008957259B2 US 8,957,259 B2 Feb. 17, 2015 (10) Patent No. 4s) Date of Patent: (2) Dagle et al. (54) DIMETHYL ETHER PRODUCTION FROM METHANOL AND/OR SYNGAS. (75) Inventors: Robert A. Dagle, Richland, WA (US); ‘Yong Wang, Richiand, WA (US): Bddie G. Baker, Pasco, WA (US); Sanh Hu, Keanewick, WA (US) (73) Assignee: Battelle Memorial Institute, Richland, WA (US) (©) Notice: Subject to any disclaimer, the term ofthis patent is extended or adjusted under 35 USC. 1540) by Odays (21) Appl. Nos 11/241,324 (22) Filed: Sep. 30, 2005 (65) Prior Publication Data US 200710078285 A1_—_Apr. 5, 2007 G1) imc C7 4109 (2006.01) coe aia Covet) (2) US.Cl oe €07C 41/09 (2013.01); €07€ 41/01 01301) sre 568698 (58) Field of Classification Seureh sre 681698 See application file for complete search history. (66) References Cited US. PATENT DOCUMENTS 4011275 a > 31977 Zar sits dioosas A” g1986 Brake S218008 A + 61999 Lewmar etal s1¥700 SR2UIIL A + 101998 Gradyet al iasaes 65562306 B1* "2003. Shika ta: 22203 Sist6909 BL 92003 Tosovich ta Sa38.92 B12 102003 Weta sonsor 2002015 Al* 122002 Kibhy ta ‘3037 aonwotgne3 AL 112003 Wang etal 20040008725 AL 1/2008. Empedoctes ta Snusr7esi2 AL* 82005 Tombovich eal sisinas 3090249910 AL 102005 Jayush tal OTHER PUBLICATIONS Cao ot al, “Kinaie studios of metianol steam sefoamiag over PD/ZnOcatalystusing microchannel reactox” pled Cals General, ol. 262, pp. 19-29 (2004). Tet at, "The et of Sovent and Mixed Meth! to Dirst Sym thesis of DME from Biomass Symgns Vis Gasfeaton Bi-Funetionsl (Cini Preparation,” Pnterational Conference en ners Erion ‘mont and Disasters, Casts, North Carling. | py ul. 24°30, snus ia eal, “Conversion of Biomass Syngas to DME Using Microchanel Reon" Ind Bg. Chem Kes, vol pp. 1722-1727 (2008) Nakao et al, “Changes of Sufice Propet ad Wate Tolerant Catalytic Activity of Soli. Acid C5 Hy PW Oye in Water Langmar. vol 14,pp. 319-25 (1998). otbaer Hermann tal, “Biomass CHP Pant Gissing—A Success Sto” Exper Meeting on Pyobsisand Gasiaton of Biomass and fase, Strasbourg, France, Oct. 2002, 1¥ pages Folbauer and Ravch, “Hylgen-Rich Gas from Biomass Stcam- Gasfiation” Pulisabl Final Report, Institute of Chemical Eng foerng Fuel and Environmental Technology, Getridemak 9159, 1060 Wien, Mir. 31, 2001, 26 pages * cited by examiner Primary Examiner — Rosalynd Keys (74) Attornes, Agent, or Firm — Frank Rosenberg: Derek H. Mave: on ABSTRACT Disclosed are methods for producing dimethy ether (DME) rom methanol and for proiucing DME directly from syngas, suchas syngas rom biomass, Also disclosed are apparatus for [DME prociction. The disclosed processes generally function at higher temperatures wih lower contact mes and at lover pressures than conventional processes so as to produce higher [DME yields than do conventional processes. Certain embod- ‘ments ofthe processes are carried out in reactors providing areate surface to volume ratio tha the presently used DME reactors, Certain embodiments ofthe processes are carried ‘ut in systems comprising multiple microctinel reactors, 22 Claims, 9 Drawing Sheets U.S. Patent Feb. 17, 2015 Sheet 1 of 9 US 8,957,259 B2 +.) Ges vent Bypese te Tap US 8,957,259 B2 Sheet 2 of 9 Feb. 17, 2015 U.S, Patent TIE Leal gy \ heat exchange / reactant(s) fluid catalyst flow Fig. 2 U.S. Patent Feb. 17, 2015 Sheet 3 of 9 US 8,957,259 B2 (80% methanol feed, contact time =100ms) 8 saa DME Yield, % é 200 250 300 350 400 450 500 550 Temperature, C 100 DME yield % 30 40 50 60 contact time (ms) Fig. 3b U.S. Patent Feb. 17, 2015 Sheet 4 of 9 US 8,957,259 B2 (20% methanol feed, 300C) 100.00 ;~—____...______-~ 80.00 60.00 40.00 20.00 0.00 eo Catalyst 128) a Catalyst 304) DME Yield, % Contact Time, mili-second Fig. 4a | /# 20% MeOH) 30 40 50 60 8 contact time (ms) U.S, Patent CO Conversion,% Feb. 17,2015 Sheet 5 of 9 US 8,957,259 B2 5 MPa, HyCO-3:1 30 (23012! 235)821 2401 245 21290) 2255 Fig. 5 “Temperature, °C 260-265-270 100 CO Conversion, % 90 ms 0s Os Fig. 6 Temperature, °C 250 255 60S U.S, Patent Fig. 7 Fig. 8 Conversion Select DME Sletiviy, 6 Feb. 17, 2015 eee a Sheet 6 of 9 US 8,957,259 B2 80.00 Meine See enon CO Conese 60.00 40.00 20.00 +— mon -= 0.00 i —— 1000 3000 5000 7000 9000 11000 13000 15000 cusy, 100 95 85 80 | — 1s m0 U.S. Patent Feb. 17, 2015 Sheet 7 of 9 US 8,957,259 B2 z bo. doo 44 $cO Geaeie| ay DN AMO = sty ole |_ suv cain lle 2» — - 020s 06 08 1 4 dA te Ra ‘MeOH Cals: Deyn Cat Fig. 9 soso 1000 = * 7000 0.00 900 Convention 48 d pn (Selectivity © DME & MeOH Hoo sino Meine 3 cect xe Die soo 2n.00 | 10.00 oo ese ae) 3s) 00h 220 Fig. 10 U.S. Patent Feb. 17, 2015 Sheet 8 of 9 US 8,957,259 B2 3000 000 E 1000 7 aes 4 000 © sooo yo car 20 ep @ 30.00 Welw DME+MeOHG:1, 260 ) i m0 Be) G 7000 CO Cenversion(2:1, 285 Degree C) 1000 -— (OSel w MeOH¥DME(2:1, 285 Degree C) ee 1 2 3 4 Pressure, MPa Fig. 11 90.00 $0.00 7000 Foo $00 Ga E sooo Nw Stair DMEM ‘Sonneyoncnme sao | ees Cute Die j 000 2n00 a 00 ° store toon 0 GHSV,4" Fig. 12 U.S. Patent Feb. 17, 2015 Sheet 9 of 9 US 8,957,259 B2 OTe em eeeew se ceaey , apf wf} ————---- = === Wo 280380 at sat ‘Time on Steam, hours Fig. 13 ‘Products to Separation Units Fig 14 US 8,957,259 B2 1 DIMETHYL ETHER PRODUCTION FROM METHANOL ANDIOR SYNGAS ACKNOWLEDGMENT OF GOVERNMENT ‘SUPPORT This invention was mode with Government suppor under ‘Contract DE-ACOS76RLOI830 award by the US, Depaet- ment of Bnergy. The Government has certain rights in the invention, FIBLD Disclosed herein ae processes and systems for producing ‘dimethyl ether from syngas anor methanol. BACKGROUND Biomass feedstock, such as agriculture and forestry resi dues, plays an important role in developing alternatives to fossil fuels. Although there are several methods of generating ‘energy fom biomass gasification, in which a hydrogen-car- bon monoxide gas mixture (syngas) is produced, offers sev- ‘eral advantages. For example, syngas, like natural gas can Be bbumed in gas turbines, whieh are more efficient than steam boilers. Another key feature of syngs is lke petroleum prod- ues, it ean be converted to useful chemicals, including dim- ethyl ether (DME). Syngas is also an available “raw” fuel from sources other than biomass, such a fom coal gasifea- tion and natural gas stem reforming and other sources DME ean be used as building blocks for synthesizing ‘important chemicals, including dimethyl sulfate, high value ‘oxygenated compounds, and lower olefins. Because of is ‘environmentally benign properties, i can also be used es an aerosol propellant in products such as hairspray and shaving ‘ream, Resently, DME has heea suggested as a alternative sve for diesel engines, Fngine performance tests indicate that DME has thermal eficeneies equivalent to traditional diesel {vel Other advantages of using DME as a diesel replacement ‘include the reduced NO, easissions, near-rero stoke prode- tion, and less engine noise. However, there are obstacles 10 producing DME Irom biomass syngas at an economical sale For example, unlike petroleum, coal, and natural gas plans, Which are established for cenral, large-tale applications, biomass feedstock and gasification systems are widely dise tributed geographically. Teonventional DME process tech- nology is adopted, a sale of 2500 vel may be required for produetion economically comparable to conventional LPG Jue). Because itis dificult to deliver enough biomass 1 satisly this eiterion using conventional technology, 1 more ‘compact and efficient portable process for converting the biomass or other souree of syngas to DME is needed SUMMARY, Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DMF directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production, The disclosed processes nen ‘erally fntion a higher temperatures with lower contact times and at lower pressures than conventional processes so 18 to produce higher DMP. yields than do conventional pro- ‘cesses. For example, disclosed are processes for producing, ‘dimethyl ether comprising providing # source of methsnol, providing a catalyst, reacting the methanol and the catalyst at 5 temperature from about 200" C. to about 500° C. with @ ‘contact time of from about 15 milliseconds to about 250 0 o 2 liseconds, at shout 1 atm fo about less than 9 atm, aud ‘raducing greater than about 70% yield (mola percent yield) ‘of dimethyl ether. Cerin embodiments ofthe processes are carried out in a system comprising multiple microchannel ‘Also disclosed are processes for producing dimethyl ther comprising providing a souree of syngas, providing a hybrid catalyst, reacting the syngas aud the hybrid catalyst at & temperature from about 200° C, 10 about 400° C. with @ ‘gntaet time of om about 25 milliseconds to less than about 500 milliseconds, and producing greater than about 60% conversion of CO to dimethy ether. Certain embodiments of the processes are carried out in reactors providing greater surface to volume raios than the presently used DME reve- tors. Certain embodiments ofthe processes are carried ot in systems comprising multiple microchannel reactors. ‘Also disclosed are systems for producing DME from ‘methanol wherein the system includes module including a plurality of microchannel reactors, a source that feeds meth ‘ol toa methanol dehydration catalyst, ora plurality of mieeo- channel reactors and a source that feeds syngas to a hybrid catalyst, and wherein the microchannel reactors are operable at temperatures of greter than about 250° C. and with @ ‘conaet time of ess than shout 250 milliseconds to peoduce a DME yield of greater than about 70% (molar percent yield ‘whe referring fo DME production from methanol and per- ‘eat conversion of CO to DME when referring to DME from syngas). An alternative aplication includes on-demand! syn- thesis of DME from either syngas or methanol The foreyoing and other objects, features, and advantages, ‘ofthe invention will become more apparent from the Fallow ‘ng detsiled description, which proceeds with reference tothe ‘accompanying figures. BRIEF DESCRIPTION OF THE DRAWINGS. FIG. 1 isa schematic diagram of a reactor system and microchannel reactor assembly that may compase ceain embodiments of the disclosed invention FIG. 2illstrtes an embodiment ofa microchannel device FIG. 3 illustrates DME yields in certain embodiments of the disclosed process for producing DME frm methanol FIG, 3illusirates DME yields in eta embodiments of the disclosed process for producing DME from methanol FIG, 4a illustrates DME yields in certain embodiments of te disclosed process for producing DME from methanol FIG, 4 illustrates DME yields in certain embodiments of te disclosed process for producing DME from methanol IG. 8ilustrates an embodiment of syngas conversion © ‘methanol equiibeium CO conversion under different cond tions, equilibrium i ealeulated forthe reaction CO¥SH C0;-2CH,OHsH0. IG. 6ilustrates an embodiment of erect syngas conver sion to DME: CO equilibrium conversion under diferent conditions; equilibrium is ealeulstad for the reaction COsSHI,4CO,s5CH,OCH 21,0, IG. 7 ilstates the effet of GHISV on methanol synthe> sis in cen embodiments dislosed herein. IG. 8 ilsrates te fet of pressure on dehydration of ‘methanol in certain embodiments disclosed herein (H-2SMS éehyeration catalyst, 234" C, GHSV=10 600 r). FIG. 9 loses the effect of eatalyst ratio on CO eonver- sion neeriain embodiments disclose herein (MeOH syne- sis catalyst: dehydration catalyst: 1-260" C., P=38 MPa, HCO=3, GHSV=10 000 i) US 8,957,259 B2 3 FIG, 10 illuseates the eflect of reaction temperature oa syngas conversion to DME in certain embodiments disclosed herein (mixture of methanol synthesis catalyst and H-ZSM-S: P-3.8 MPa, GHSV-S000 i! H/CO-3), FIG. 1 illustrates the eect of pressure and H2/CO ratio ‘on DME formation in certain embodiments disclosed herein (inixture of methano! synthesis catalyst and H-ZSM-5; GHSV-S000 b>, FIG, 12 ilusteates the effect of GHSV on syngas conver sion fo DME in certain embodiments disclosed herein (mix- ‘ure of methanol synthesis catalyst and H-ZSM-5; P38 MPa, HJCO-2, T-286° C)). FIG. 13 ilusirates direct syngas conversion to DME in ‘ertiin embodiments diselosed herein (with a mixture of methanol synthesis catalyst and [1-7SM-S; P-38 MPa (GHSV-S000 8", H. FIG. 14 illustrates one possible embodiment of a modular ‘design of commercial DME production plant utilizing miero> ‘channel reaetors, DETAILED DESCRIPTION Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syrgas, such as syngas from biomass. Also disclosed are apparatus for DME production, .° “an” and “the” cleay indicates oth- ‘envise. The word “comprises” indicates “includes. It is fur- ther t be understood tht all molecular weight or molecular mass values given for compounds are approximate, and are provided for description. In addition, all physical parameters, suchas temperatures, pressuresand amountsare approximate unless otherwise indicated, whether the parameter is pre ‘ceded by the word “about” or is not. The materials, methods, fand examples are illustrative only and not intended to be Timiting, Unless otherwise indicated, description of compo- rents in chemsieal nomenclature refers tothe components st the time of addition to any combination specified in the ‘description, bu does not aevessarly preclude chemical nter- ‘actions among the components ofa mixture once mixed. AS ted herein percent (6) or percent yield refers to mole per ‘ent yield when referring to DME production from methanol Percent (96) values when referriag t© DME produced from sytgas refers to percent conversion of CO to DME. DME may be produced via a methanol debydration rac- tion, using acidic catalysts, such as phosphorie-acid modified amma AILO;, in a fixed-bed reactor. The cost of producing DME from methanol isin luenced by prceand availability, as ‘methanol itself is an expensive chemical feedstock. Prode- ing DME direct from syngas has many economic and teh- nical advantages over methanol dehydration, Thermody- ramically, DME production from syngas is more favorable than fom methanol, and the cost for DME production from syngas is lower with use of suitable catalyst. Direct DME synthesis involves many competing reaction pathways: eae een feel sskelina 0 o 4 DME fom Methanol Cerisn embodiments ofthe disclosed methods and appa rats comprise forming DME from methanol using a metha- ‘nol dehydration reaction, In particular embodiment, the pro- cess parameters of tempersture, contact time and catalyst produce a DME yield (molar percent yield) of greater abs “0 or about 80% oF even about 9%. In various embed ‘ments of the disclosed methods suitable catalysts ate used in conjunction with contact times as low as about 15 milli ‘nds and at temperatures as high as preater than about 500° CC. at pressures of from about 1 atm to about 40 atm or at pressutes of fess than abt 9 te, Catalysts for DME from Methanol Cerin embodiments ofthe disclosed methods include use ‘ofa zeolite catalyst with a SUAI ratio of 12,30, 60,08 80.8 particularly suitable catalyst comprises Ti-ZSM-5 zeolite ‘with a SVAL ratio of 30.4 suitable catalyst for producing DME from MeOH may include acidic eatalysts, y-aluminas, ‘and palladium-doped y-alumins. Pulladium-loped 7-alu- ‘mina eatalysts may be doped ata variety of concentrations, {orexample from about 0.1 to about 20% such as 0.5, 1,2, oF, 13%, by weight. Other suitable catalysts for producing DME rom MeOH may include, eg. 2olites with various Si/Al ratios (eg, H-ZSM-S available from Zeolyst Intemational) ‘orthe zeolite mordenite,phosphorie-acid mosifed aluminas, ‘itantes, tungsten oxide, supported heteropoy acid catalysts sreferabiy with conteolled eiditis, oe. tania oF Gana ‘olfed slumins or rironia, Heteropoly acid eatalysts may hhave controlled acidties by treatments known to those of ordinary skill in the art such as shown, for example, in Nak etal, “Changes of Surface Properties and Water- Activity Tolerant Catalytic of Solid Ackd 32.5110 SPW12040", 1: 14, 319.325 (1998), ‘which is incorporated herein by relerence Gas Hourly Space Velocity or Contact Time for DME from Methanol In particular embodiments the gas hourly space velo through the reaction zone mnges from about 240000 ft about 3600 i, preferably from about 240000 ho about 72,000 h-'. The gas hourly space velecty is defined as the volume of reactants per time per reaction zane volume. The volume of reactant gases iat standard conditions of pressure (1 atm or 10 KPa) and temperature (0° C. of 273.16 K), The reaction zone volume is defined by the postion of the reaction vessel volume where reaction takes place and which is ocew- pied by a pascous phase comprising reactants, prodets, and! ‘or inert; liquid phase comprising aqueous andor organic phases; and a solid phase comprising catalyst. Gas hourly ‘pace velocity isthe iverse of contact time, and thos, this process parameter may also be characterized in terms of ontet time rather than gas hourly space velocity. Suitable contact times maybe from about 1 Sto about 250 milliseconds ‘or fromabout [5 toabout $0 millisecond a from about 15 t0 shout 100 milliseconds or less than about 150 milliseconds, preferably less than about 50 millissconds. Conventions ‘methods use much longer contact times as compared to the short contact times used in the disclosed. embodiments; shorter contat times were likely not used to date for produ ing DME due to the relatively poor hest transfer in eonven- ‘ional reactors with Which steh short contact times Would have resulted in low DMP yields “Although contact times ae set forth above fora numberof cembodimients of the disclosed methods, preferred contact times will depead in part on the catalyst chosen and other process parancters (eg, the process tempemstre and the type bf reactor utilized forthe reaction), as would be understood US 8,957,259 B2 5 by one of ordinary skill in the at It isto be understood that ciher “short” contact times may be suitable fora pariclae ‘catalyst—any given catalyst requires sufficient “contact time" forthe reaction of methanol-lo-DME to oceur Hem= ‘ever iftoo much contacttime occurs ifthe contact times 190 high), undesired reactions occur resulting. in unwanted byproducts instead of DME. Certain embadiments of the ssclosed methods milize short contact times in part de 10 ‘operation ofthe disclosed methods in microchannel devices hich provide relatively high surface t0 volume ratios as ‘compated to conventional reactors. Process Temperstures for DME from Methatol The embodiments of the disclosed methods operate a tem peratures much higher than conventionally used to produce DME, The methods as disclosed herein beset rom carying ‘out the processes in microchannel devices $0 as to allow the process o operate at substantially oF near isothermal cond fons. Conventional reators for DME. production have not provided the henefit of isothermal or near isothermal reaction ‘environments. Fast kineties (high tanover rates achievable at relatively sbort contzet times) and isothermal conditions (lemperature contol) favor the DME proslction, In eertaia ‘embodiments of the diselosed methods the reaction zone temperature is typically in the range of Irom about 200° C.t0 500" C. Preferably, the reaction zone is operated a emper- tures f fom about 250° C. to 350" C.,orat temperatures oF about 300! "As ean be seen by reference 10 FIG. 3a, a DME yield of about 70% was obtained When using 0 y-alumina catalyst (3 ‘y-alumina catalyst with no additives, purchased feom Engel- hard) ata temperature of 450° C. with contact ime of about 100 milliseconds and about an 80% methanol foe. ‘As shown in FIG. 3b, a DME yield of about 90% was achieved at a contact time of about 25 milliseconds with zeolite catalyst having a SAI ratio of 30 was used and the process took place at about 300° C. with 20% methanol Teed. A DME yield of about 75% was achieved ata contact time of about 25 milliseconds when zeolite catalyst having 2 Si/Alratio of 30 was used and the process took place at about 250° C, with 2 20% methanol feed. Ata coataet time of 80 nillisconds, a DME yield of about 75% was achieved when zeolite catalyst having a SVAL ratio of 390 was used and the process took place at about 300° C. with a 20% methanol Tee. "As can be seen with reference to PIG. 4a, when using catalyst 12B or 308 (12B isa SUAI-12 zeolite and 308 isa SVAF-30 zeolite, both available from Zeolyst Intemational) atabout 300° C, with 20% methanol fed with contact times varying from about 15 to aboot 0 milliseconds, good DME Yields were generally achieved, expecially st contact times of about 25 milliseconds. As shown in FIG. 4b, a DME yield of bout 90% was achieved at a comtaet time of about 25 mili seconds when zeolite catalyst having a Sil ratio of 30 was used and the process tok place at about 300" C, with a 20% mthanol fecd, Although higher temperatures (ic, 275° ‘C-420° C.)have been reported as used in conventional DME. production methods, such higher temperatures had to be used ‘conjunction with relatively high pressures (Le om 1000 P1700 kPa (~10-15 atm). Process Pressures foe DME from Methanol Por particular embodiments ofthe disclosed methods for producing DME from methanol the reaction zone pressure is 'ypically at atmospheric pressure but the pressure could be varied fo be in the range of about I atm to about 10 atm, DMP from Syngas Another embodiment of the disclosed methods comprises Jorming DME from syngas using a hybrid catalyst sys o 6 The syngas useful for performing the disclosed methods includes any suitable syngas souree, such as syngas from biomass, coal, and/or natural gas. A hybrid eatalyst system including methanol synthesis from syngas and methanol ‘dehydration catalysts are used to directly produce DME, Suit able etalyst hybrids are used in conjunction with relatively short contact times and at relatively high temperatures Catalysts for DME from Syngas Crign embodiments ofthe disclosed methods include use ofthe following catalysts: combination of methanol syn- thesis catalysts (eg. eopper-based or palladium-based syn- thesis catalysts) such a PS1-SPPT (avaiable from Kataco Corp, formerly ICI India Ltd), and dehydration catalysts ZSM-5 zeolite witha Si/A rato 0f30 (availble from Zeolyst International) and acidic Al,O, (available from Fngchard Corp.) solid acid ALO, containing 4 wt % fluoride (@ ALO, available fom Engelhard). TABLE | elon Ast of Sali Ais Caer DME ieee ees = tai Certain usefil dehydration catalysts for performing par- sicular embodiments ofthe disclosed methods ae show in ‘Table 1. Although the acid strengths of these catalysts are Aiffereni, AL,O,, F —AlsOy and 7SM-S yield the same con- version and selectivity. The USY zeolite (alta stable Y-re0- lite) exhibits the lowest dehydration aetvity. A CO conver. sionofabout 40% is obtained which s the same as methano!- ‘nly synthesis. Low DME seectvity (10% further confinns thatthe loss of dehydration activity i esponsile for low CO conversion as discussed belo, Without being Ged 10 any particular theory, its belived that the unexpected phenom {enon might be associated withthe blocking of acid sites by water. Yeolite contains less acid sites but higher acid sirength than H-ZSMCS. I is plausible that water produced from the reaction strongly’ adsorbed on acid sits, therefore inhibiting the dehydration resetion rate. Thus, direet DME symthesis does not require strong solid acid and the acidity (oumber of atid sites) of the dehydration catalyst is more Smportant than the acid strength “The hybrid catalyst system use in certain embodiments disclosed hervin inelude DME synthesis performed under conditions of280°C.,38 MPaand GHSV of 3000-1. Ithas ‘een found that stability of the catalysts is affected by the presence of water. Oe particular embodiment comprises a Iybrid catalyst system combining commercial methanol syne thesis catalysts and a ZSM-S zeolite. As shown in FIG. 13, initial CO conversion of about 88% i obtained. As the pro” cess procoud a slows decrease in CO conversion i produced ‘Throghout the process in this embodiment, selectivity to CO, inreases slightly, but_methane scletvity remains ‘wachanged. From a earhon utilization pot of view the for ration of CO, fom the waters shift (WGS) reaction Appears to have negative effect on DME yield However, the US 8,957,259 B2 1 \WGS reaction is prefered in DME syatbesis to keep water ‘concentration low. sos enhance therateof the dehydration reaction. This is especially useful fora CO-rieh feedstock, as the WGS reaction ean also balance the ratio of CO and, by ‘depleting CO anal forming H Tt has boon reported thatthe presence of water inhibits ‘dehydration activity, However, as disclosed in certain meth- fds hercin, with the use of the disclosed hybrid catalyst ‘deactivation is not significant. Excess water, upon formation inthe reaction, may be removed via the WOS reaction. The WGS resetion proceeds at fester reetion rates than as con- ‘ventionaly believed and each equilibrium to yield 22% CO. ‘The WGS reaction depletes the water proiveed feom the dehydration reaction, which may reduce the interaction between water and methanol catalyst, and therefore retard ‘catalyst sintering. In certain embodiments, the catalysts are pre-teated in ‘manners known to those of ordinary skill inthe arto improve performance. For example, the dehydration eatalysts may be ‘calcined in ir thigh temperatures (eg, 00° C.) wo remove Physically absorbed! moistre for both the MeOH synthesis ‘and dehydration catalysts may be crushed and sieved (eg. sleved into 70-100 mesh). The hybrid catalyst may be prepared by mixing the syn- thesis and dehydration eatalysts in any suitable fashion, such > ‘as by mechanically mixing the catalysts ata desired ratio. It hha been discovered that an important parameter in the design ‘ofsuch a hybrid or dual eatalyst system is the catalyst loading rato, thats the methanol dehydration to methanol formation ‘aetvity, Too high of a methanol dehydeation activity com= pared with WGS activity leads toa high water prodction. Results shown in FIG. 9 indicate that CO conversion is alfected by the catalyst ratio, bt product selectivity is not sensitive tthe change of etalyst ratio. particularly useful catalyst ratio appears to be about 1:1 by weight but other ratios, such a 2:1 may be used, Conventionally, ratios of about 4:1 and higher are used although such ratios may be used in certain emboxtiments of the disclosed methods, lower ratios provide greater DME yields, ‘Gas Hourly Space Velocity or Contact Time for DME from, Symene In particular embodiments the gas hourly space velocity through the reection zane ranges fom about $00 to about 100,000", preferably from about 3,600)" to about 36,000 1, The gas hourly space velocity is defined as the volume of reactants pe time per reaction zone volume. The volume of reactant gases at standeed conditions of pressure (1 atm oF 101 kPa) and temperature (° C. of 273.16 K). The reaction ‘one volume is defined by the portion ofthe eacton vessel volume where esction takes place and whieh is occupied by gaseous phase comprising reactants, produets, andlor ners: 8 Tiguid phase comprising liquid products and/or other lige ids: and a solid phase comprising catalyst. ‘Pat another way suitable contact times for production of DME directly from syngas may be from about from about (0025 5 to about 7.2 , or from about from about 0.036 § 10 about 72 5 less than about 1s, or less than about 0.5, ‘Conventional methods use much longer contaet times than the short contact times used in the disclosed embodiments; shorter contact times were likely not used due tothe relatively poorer heat transfer in conventional reactors, which severely Fimitsymgas conversion and selectivity at short contact times. Asshown inFIG. 7, methanol synthesis is conducted under ‘constant temperate of about 250° C. and pressure of abort 38 MPa. When using deereasing GIISV, CO conversion increases first and begins to approach equilibrium conversion ‘of about 50%, This response may be in lange part occur 8 ‘because methanol syathesis is thermodynamical Timited. contrast. as shown in FIG. 12, in one particular embodiment of direst DME synthesis, conversion inereases significantly ‘with « decrease in GHSV. When GHSV is decreased from 20,000 to 5,000 h', conversion is increase from 319% t0 80%. Even when GHSV is changed, selectivity to CO, remains fairly stable. Process Temperatures for DME from Syngas The embodiment of the disclosed methods operateat em peratures much higher than conventionally sed to produce DME, The ability to extry out the process of these embodi- ‘mens a elatvely high temperatures is due at least in part 10 the use of micretech-sizod reactors as doscribod further below, and the ability to earry-out the reactions in a substan- silly isothermic environment. Incertain embodiments ofthe sisclosed methods the reaetion zone temperature is typically in the range of from about 200°C. to about 400° C. oF from shout 200" C, to about 350° C. Preferably, the reaction zone Js operated at temperatures of from about 240° C. to sbout 200°C. Tn one embodiment, a temperature range of from about 240° C. to about 260° C. is wed and the effect of the tem- perature on the catalytic activity of a methanol synthesis catalystand ZSM-S catalyst combined is depicted in FIG. 10. In ths particular embodiment a microchannel reactor sun as shown in FIG. 1 is operated in an isothermal mode. Two ‘thermal couples are installed in a catalyst bed and a furnace temperature is used (o control the catalyst bed temperature ‘The temperature difference between the top and bottom cata- Ist bod may bo controlled within about 2° C:, indicating excellent het removal eapabilityof the microchannel reactor Unlike methanol synthesis alone, where CO conversion decreases with an inerease in reaction temperature, FIG. 10 shows that temperature has positiveeffeeton CO couversion in direct syngas conversion to DME. The embodimeal uti Jizing microchanael reactors can be operated t higher reae- ‘ion temperatures (and lower presses) than are conventional actors to aehieve high space time yield but can sill operate fin the isothermal regime, Ata GEISV of 5000 b, CO con- version of about 890i achieved but isbelow the equlibrinm limitof DME synthesis (04), Thus the dehydration reaction ‘may proceed at slower rate than the methanol synthesis reac- tion and only a relatively low GHSV is needed to approach ‘equilibrium conversion "A large amount of CO, may be produced via the WGS reaction, Within the operating temperature range disclosed {or these embodiments seletivity to CO, remains substan- silly constant, Asa sult of isothermal operation in micro- channel reactors, hot spots on the catalyst surface and between catalyst panicles are eliminated therefore, negative side reactions are not favored Process Pressures for DME from Syngas “Thersaetion zone pressure is ypicllyiatherange of about (05 MPa to about 40 MPs, more preferably from about I MPa to about 12 MPa, and still more preferably from about 2 MPa to about 8 MPr, In certain embodiments, processes are utilized (with a GHISV of about $000 h"), using different Feed compositions (HYCO) 3:1 snd 2:1, Inreasing the pressure exhibited 9 positive effecton DME formation. As shown in FIG. 1, ata relatively low pressure of about 1:0 MDa, low CO conversion ‘eur. A sharp inerease in CO conversion is observed when pressure is increased from about 1.0 to about 3.8 MPa, This ‘counters conventional belie wheres indicated that in DME synthesis CO conversion ineresses with increased pressore but levels off at 2 MPs, beyond which the impact of pressure ‘on CO conversion was not significant Without being tied to US 8,957,259 B2 9 ‘any particular theory, itis proposed that using syngas asa raw Jue souree, and perhaps utilizing a microtech reactors con- figuration, and hecause the use of two Tunetionslly indepen- dent catalysts are closely interrelated, the performance of DME synthesis in, eg. a microchaanel rector is dierent fom conventional fixed-hed or slurry reactors allowing for treater DME yield at higher pressures. ‘One embodiment for producing DME includes conversion ‘of DME from methanol of DME from syngas in a microtech system, such as microchannel reactor. Suitable microteeh systemsare described in, e.g, U.S. Pat. No, 6,616,909, whieh is incorporated herein by reference. Microchannel reactors have the advantage of improved beat and mass transfer, hav- ing langer surface wo volume ratios than do conventional reae- tors, which allow for greater process intensification. AirProd- ucts commercial demonstration esults obtained froma slurry reactor were compared with thehybrid catalyst microchannel reactor system a8 dislosed herein, The performance results ‘are shown in Table 2 TABLE Peomuace Conpanson of Ss Comin ISDE i Diet Rasta Conan ctr contin Cy stey 2 ‘pes acti: xCO'E-A hae yl ater) on By way of example in FIG. 2, possible embodiment of a microchannel devive is shown, ‘The distance from the heat source to heatsink is about I centimeter or less. This distance js a function of the heat duty, the selection of eat transfer uid), and the effective thermal conductivity of a porous ‘catalyst inset. Thin shoes or tubes can he used to aban high hat duties and short contact times. The thickness ofthe web between the eaetion channel and the heat exchange chanel ‘can vary, but is preferably between about O01 inches and about 0.25 inches. The preferred thickness for the heat ‘exchange channel preferably ranges from 100 microas to 10, millimeters. The preferred thickness is 250 microns to mil- Jimeter Flow of the heat transfer fluid may be either eounter- ‘current, cross-curent, or co-current to the direction of the flow of reactants, ‘A microchannel reactor is preferably able to operate at relatively severe conditions to obtain high productivity. As shown in Table 2, DME synthesis may be conducted in @ microchannel reactor at GHSV=10 238 h', 2.2 times higher than in the commercial slurry reactors Side-by-side eompari- son reveals excolent performance of microchannel reactors. specific activity of3.52 ofCO(gh) anda spacetime yield ‘of 2.25 gi(gh) are obtained, respectively, Bven when the microchannel rector was operated under severe conditions selectivity to byproducts produced from methanation and pyrolysis were negligible, It is generally believed that back mixing occurs in the conventional shury reactor, which affects product selectivity, resulting in much lower DME. ‘yields than the presently disclosed methods, Back mixing was not present in the microchannel reactor. 0 o Enhancement yi Wed 10 improved mas transfer in a mierochannel reactor. Compared ‘with the conventional fixed-hed reactors, the (bulk) diffision length from gas phase to catalyst surice is significantly seduced. Furthermore unlike the slury reactors, there is no liquid holdup inside the microchannel reactor. Calelations show that in the microchannel reactor under reaction condi- ‘ions, the internal diffusion limitation is significany rednced, In adtion, 9 high linea velocity inthe microchan- el reactors facilitating the removal of water from thecstalyst surlace, leasing blocked acid sites and accelerating the

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