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    US8138380-Electrolysis of Carbon Dioxide in Aqueous Media to Carbon Monoxide and Hydrogen for Production of Methanol

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    US8138380-Electrolysis of Carbon Dioxide in Aqueous Media to Carbon Monoxide and Hydrogen for Production of Methanol

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    US8138380-Electrolysis of Carbon Dioxide in Aqueous Media To Carbon Monoxide and Hydrogen For Production of Methanol

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    US8138380-Electrolysis of Carbon Dioxide in Aqueous Media to Carbon Monoxide and Hydrogen for Production of Methanol

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    2) United States Patent 6a os) 03) ey @y ws) (@) (60) on) (2 68) Olah et al. ELECTROLYSIS OF CARBON DIOXIDE IN AQUEOUS MEDIA TO CARBON MONOXIDE, AND HYDROGEN FOR PRODUCTION OF METHANOL Inventors: George A. Ola, Bevery Hills, CA (US); GK. Surya Prakash, Hacienda Heights, CA (US) Assignee: University of Southern California, Los Angeles, CA (US) Notice: Subject to any disclaimer, the team ofthis patent is extended or adjusted under 38 USC. 154(b) by 24 days Appl. Now 127784982 Filed: Apr. 6,2010 Prior P US 201010193370 A1 ication Duta Aug. 5, 2010 Related Us Application Data Continuation-in-par of application No, 12/171,904, filed on Jul. 11, 2008, now Pat No. 7,704,368, Provisional application No. 60949,723, fled on Ju 13,2007, Int.Cl. core 2770 (2005.01) cn7e 2900 (2006.01) csp 1/00 (2006.01) Ose ve (2006.01) sp 00 (2005.01), esc ve (2006.01) USS. C1. sso S68840; 68/700; 205/850: 205/555: 205/633; 2051637 Field of Classification Search 205/855, 208/633, 637, 450, 568/700, 840 See pplication file for complete search history. ‘USO08138380B2 (10) Patent No. 4s) Date of Patent: US 8,138,380 B2 Mar. 20, 2012 66) References Cited US. PATENT DOCUMENTS 40267 A | ‘81977 Alves eal dosiaat AA@.SD A + S198 Couch etal. 204288 (Coutinved) POREIGN PATENT DOCUMENTS 08246177 A 911996 (Continsed) (OTHER PUBLICATIONS Hori eal, “SiverCoatad Ton Exchange Membrane Electrode Applied to Flecuochomical Reduction of Carbon Dioxide” "Hecuochimics Aca (a0 month 2003), vol. 4%, pp. 2681-2687 * (Coutinved) Primary Examiner — Edna Woug (74) Attornes, Agent, or Firm — Winston & Sten LLP on ABSTRACT An environmentally beneficial method of producing metha- tol from varied sources of carbon dioxide including flue ‘ses of fossil fuel hurning powerplants, industrial exhaust ‘ses or he atmosphere iisell, Converting carhon dioxide by fn electrochemical reduction of earbon dioxide ina divided ‘electrochemical cell that includes an anode ia one comput- ‘meat andametal eahode electrode in compartment that also cconiins an aqueous solution comprising methanol and an electrolyte, An anion-conducting membrane ean be provided between the anode and cathode to produce at the cathode therein a reaction mixture containing earbon monoxide and hydrogen, which ean be subsequently used to produce meth rol while also producing oxygen in the cel tthe anode, The ‘oxygen produced atthe anode can be recycled for elicent ‘combustion of fossil fuels in power plants to exclusively produce CO, exhausts forcaptureand reeycling as the source '5fC0, fo the cell 19 Claims, 2 Drawing Sheets ‘The Methanol Economy Process ZL | wore aah US 8,138,380 B2 Page 2 US. PATENT DOCUMENTS 5590638 A 21007 Swamp etal... 420404 Shoxsos A * 7/1999 Olahet a ‘foais O07 KI B2 92008 Tanaka et a Seam 200sb040809 AL_ 3/2003. Divisek 4200 aoosorTiows AL* 122008 Faroogus eta 2019 0060048817 06 Fradte ea door 0045125 aonvo1294so Al FOREIGN PATENT DOCUMENTS. ‘3007 Harvigsen ea (62007 amie ee sl Ru 2062750 C1 611996 Wo — wourK77 Al _ 12002 WO ——-WOO2088272 AL © 102002 OTHER PUBLICATIONS Shen tl, "Methanl Syathesi FromCashon Monoxide and 1 Catalyzo Over Pu1C<02 Prepare bythe Deposition- Precip tion Meth", Catalysis Later (00 month, 2000), v9. 64, pp. ase Hori otal, “lectroeattic Press of CO Selectivity in Hlsto- ‘chemical Reduction CO2 at Meal Electrodes inAgueos Masia Electrochimicn Acta (ao month. 1994) vol 39, Nou. (1/2, pp. ss3-1830." ‘Ogden tal, “Elst Hydrogen From Thin-Film Solar Celis Int J-Hydzogen Enorgy ao moat, 1990), vol 18, No.3. pp. 188° 15> Sscki et al, "Plectochemica! Reduction of CO2 with High Curent DensityingCO2 + Methanol Medium l-CO Formation Promoted by “Ttrabutlamsnosiun Cation, Journal of Fleeteoaalytical Chemis try (0 moth, 1998), vl. 39, pp 77-82." Bizzeo ot a, “NonHalolaminate Room-Temperatur fic Lige ids in Electochemisry—-A Revi”, ChemPhyschen (a moat 2004), vol, pp 11061120" Sancher-Sanchez tal, “Eetochemical Approaches to Alleviation ‘ofthe Problem of Catboa Dose Accumulation Pure Appl Chem, {Go month 2001), vol 73, No. 12.pp 1017-1927 ‘rua etal. “Ticetrockemical Redtion of Carbon Dioxide in ‘Various Metal Flecvodes in Low-Temperature Agucous KHCO, Media” J Hlstrochem. Co, 137(6)1772-1778 (1990) ‘or tal, "Plecroatatic Process of CO Selectivity in Eleto: ‘henial Reduction of CO, a Metal Electrodes in Aqueous Mein letrochimica Acta, 3411 12 1853-1859 (1994), Koya etal. "Novel CO, Plsrochemieal Retction to Mtha- fol fr HD Storage” Feray & Fs, 18 288-286 (200). allo et aly "Fletochemieal Reuetion of Carbon Dioxide in ‘Median at ow Temperate” Flectrchisiea Act S(18)2177- 21791993), (Ogden eal, “Hectic Hyogen from Thi IJ Hydeogen Enersy, 15G3).188-169 (1090. (Osea al, "Catalytic Conversion of CO and COs ito Methanol ‘wa x Solar Cell? Jounal of Molecular Catayaig 34:309-311 (986), Sickie a, “Blectrochemical reduction of CO, with high current ‘densi ina CO, + methanol mim Il-CO formation promoted by terabtylamnmeniam eaion” Journal of Elestonnayicl Chem te, 3942} 77-82 Can, 1995), Sickie al, “Electrochemical Reduction of CO, witht Density ina CO, Methanol Medium I. Phy. Chem 9:6440- 84461995). Sincher-Sinchez tl, "Elestochemical approsches to alleviation ofthe preblam of cabon dioxide accumulation” Pue Apel. Chem. 3312 :1917-1927 QOD Tipk etal “Hectrchemists Enlisted in War, the Carbon Dowie Reaction atl” The HletoshemealSosety Inerfice, pp. 32-35 (Spring 2001), International Seach Rept and he Writes Opinion ofthe Interna tional Searching Abort, application No. PCT/US2O08 063803, fat Fe, 2009, ln Solar Cll” * cited by examiner U.S. Patent Mar. 20,2012 Sheet 1 of 2 US 8,138,380 B2 Methanol derived chemical products and materials Formaldehyde rea resins Welty ter-buiy ether Prenol_resins {ute elaine resin Acetic acid Xylene resin Ethonol Paraformoldehyde Acetaldehyde Methane-di-isocyanate (MD)] Aoelic Anhydride Bulonedol Chloromethanes [Polyals Povyaceta Isoprene examine Others Welty methaoryate (NWA) Polymethyl methacrylate (PUMA) Methacrylates Methnol Coating resins Methyl formate] Formamide HN Formic acid Welty amines [Dimethyl formamide (ONF) Nethylethanolamine Dimethylacetomide (OMAC) Tetramelhy! ammonium hydroxide (TMA) (Corbamates Figher orrines toy {erephthoate Palyethyleneterephtholate (PEI) Dimethyl ether (OME) [oefins—}-—[Cosline Hydrogen Hp Lysate monoxide CO) ‘Single cell proteins = PRIOR ART Biochemicals [others FIG.1 U.S. Patent Mar. 20,2012 Sheet 2 of 2 US 8,138,380 B2 The Methanol Economy Process From industrial exhausts ‘and the atmosphere Selective lactrochemica! nication irocai and Their Products FIG. 2 US 8,138,380 B2 1 ELECTROLYSIS OF CARBON DIOXIDE IN AQUEOUS MEDIA TO CARBON MONOXIDE "AND HYDROGEN FOR PRODUCTION OF METHANOL ‘This application is # continuation-in-part of application Ser, No, 12/171,906 filed Jul, 11, 2008, now U.S. Pat No. 7,704,369, which claims the benefit of provisional appl tion no, 6(/949,723 filed Jul. 13, 2007, the entire conten of ‘each of which is expressly ineomporated herein by reference thereto. BACKGROUND Hydrocarbons ae essential in modern lite. Hydrocarbons ‘are use a il and aw material in various eds, including the chemical, petrochemical, plastics, anl rubber industries. Fossil fuels, suchas cal, il and gas, are composed of hydro- ‘carbons with varying ratios of earbon and hydrogen, and is non-renewably used when combusted, forming earbon diox- fide and water, Despite their wide application and. high demand, fossil fuels present a number of disadvantages, ‘inching the finite reserve, ireversible combustion and con tribution to air pollution and global warming. Considering these disadvantages, and the increasing demand for enersy. “ltemnative sources of enengy are needed ‘One such alternative frequently mentionad is hydrogen, and the so-called “Iydrogen economy” Hydrogen is bene a8 a clean fuel, producing only water svhen combusted ‘ree hydrogen, however, isnota natural energy source, ands generation from hydmearhons or water is highly energy= consuming process. Further, when hydrogen is produced from hydrocarbons, any claimed benefit of hydrogen a 2 ‘lean felis outweigled bythe fet that generation of hydo= en itself, mainly by reforming of natural gas, il or coal t© synthesis gas (*syn-gas”) a mixture of CO and Hs far rom ‘loan. Itconsumes fossil fuels, witha quater af the energy of the fuel being Tost a heat. Hyrogen is also nota convenient ‘energy storage medium hecatse it i difficult and costly to handle, store, anspor and distribute. As itis extremely volar tile and poteatialy explosive, hydrogen gas requires high- pressure equipment, costly and non-existent infastructure, special materials to minimize diffusion and leakage, and ‘extensive safety precautions to prevent explosions. was suggested that a more practical allematve is meth nol. Methanol, CHOH, is the simplest liquid oxygenated hydrocarbon, differing from methane (CH) by a single ad- tional oxygen atom, Methanol, also called methy! alcohol or ‘wood alcoho, isa colorless, water-soluble guid witha mild leoholic odor, an is easy fo store and transport. It freezes at =97.6°C., boils at 64.6" Cand has a density of 0.701 at 20° c ‘Methanol is not only a convenient and safe way to store ‘energy. Methanol ether can be Blended with gasoline oF ‘diesel and used a fuel, for example in internal combustion ‘engines or electricity generators. One ofthe most efficent use ‘of methanol isin fuel cells, particularly in direct methanol {uel cell (OMEC), ia which methanol isditecily oxidized with to carbon dioxide aad water while producing electri ‘Contrary to gasoline, which isa complex mixtureof many ‘differen iydrocarbons andl additives, methanol is single ‘chemical compound. It contains about half the energy density ‘of gasoline, meaning that two liters of methanol provides the same energy a8 a liter of gasoline. Even though methanol’s ‘eneray content is lower, ithas a higher octane rating of 100, (Gverage of the rescarch octane ntimber (RON) of 107 and ‘motor octane number (MON) of 92), which means that the 0 o 2 {ueVsie mixture can_be compressed to a smaller volun ‘before being ignited, This allows the engine to runat a higher compression ratio (10-11 to I against 8.9 t0 1 ofa gasoline cengine), more efficiently than @ gasoline-powered engine. Eliciency is also increased by methanol’ higher “ame spect which enables faster, more complete fuel combustion inthe engines. ‘These factors explain the high ellcieney of ‘methanol despite is lower energy density than gasoline. Fur- ther, to render methanol more ignitable even under the most {igi conditions, methaaol can be mixed with gasoline, With volatile compounds (dimethyl ether), with other compo- nents or with a device to vaporize or stomize methanol. For ‘example, an automotive fuel can be prepared by adding ‘methanol {o gasoline with the fuel having a minimum gaso- line eontent of at least 15% By volume (MSS fuel) so that it can readily start even in low temperature environments. Of course, any replacement of gasoline in such fuels will eon- servooil resources andthe amount of methanol to add ean be {determined depending upon the specific engine design, ‘Methanol has a latent heat of vaporization of about 3.7 times higher than gasoline, and can absorb a significantly larger amount of heat when passing from liquid to gas This helps remove heat away from the engine and enables the se ofan ait-eooled radiator instead of heavier water-cooled system, Thus, compared to gasoline-powered car, a metha- ‘ol-powered engine provides a smaller lighter engine block, reduced cooling requirements, and better acceleration and mileage capabilities. Methanol is also more environme {iendy than gasoline, and produces los overall emissions of air polutants sch as hydrocarbons, NO,, SO, and parien- Iates ‘Methanol is also one of the safest fiels available. Com- pared to gasoline, methanol's physical and chemical proper- tics significantly reduce the risk offre. Methacol has lower volatility, and methanol vapor must be four times more eon- centratad than gasoline for ignition to occur. Even when ‘gnited, methanol buens about four times slower than gaso- line, releases heat only t one-cighth the rate of gasoline fie, ands far less likely to spread to surounding ignitable mate- Fas because ofthe low radiant eat output. It has been est ‘mated by the EPA that switching from gasoline to methanol ‘would reduce incidence of ful-related ie by 90%. Methanol ‘bums with a colorless flame, but additives can solve this problea. ‘Methanol also provides an attractive and more environ: sment-friendly altemative to diesel fuel. Methanol does not produce smoke, soot, or particulates when combusted, in contrast to diesel fuel, which generally produces polluting particles during combustion. Methanol also produces very Jowemissions of NOx becauseit ume ata lower temperature than diesel. Furthermore, methanol has a significantly higher vapor pressure compared to diesel fuel, and the higher vola- tility allows easy start even in cold weather, without produc- ing white smoke typical of cold star with 2 conventional hese engine. Ifdesired, additives or ignition improvers, sich asoety nitrate tetrahydrofurfuryl nitrate, peroxides o higher alky| ethers, can be ade to bring methan’scetane rating to the level closer to diesel, Methanol ean also be used in the ‘manufacture of biodiesel fuels by esterification of fatty acids Closely related and derived from methanol, aad also 2 sirable alternative fuel is dimethyl ether, Dimethyl ether is ‘easily obtained by methanol dehydration. Dimethy] ether (DME, CH,OCH,), the simplest of all ethers, isa colorless, nontoxic, non-corosive, non-areinogenic and environmen- tally friendly chemical that is mainly used today as an aerosol propellant in spray cans, in place ofthe banned CFC pases US 8,138,380 B2 3 DME has a boiling point of -25° C,, and is a gas under ambient conditions. DME bas no propensity to form perox- ‘des unlike higher homologous ethers. DME is, however, sily handled iguid and stored in pressurized tanks, much Tike liquefied petroleum gas (CPG). The intrest in dimethy] clr as alternative fu! lies in its high cetane rating of 55 to 60, which is moch higher than that of methanol andl is also higher than the cetane rating of 40 to $5 of conventional diesel sels. The cetane rating indicates that DME can be effectively used in diese engines. Advantageously, DME, like methanol js clean burning, and produces no soot pacticultes, Black smoke or SO,, and only very low amounts of NO, and other ‘emissions even without aer-tratment of is exhaust e85 Somie ofthe physical snd chemical properties DME, in com. parison to diese fel, are shown in Table 1 TABLE] Suman oft nisl opis Doe ans asl DME Dic st igi deat 2 20° CU) ‘so Jing rane halts am" ‘tieion temper (°C) “he Renmatliy imwsinsisl%) SIT Currently, DME is exclusively produced by dehydration of methanol. A method for synthesizing DME directly from sythesis gas by combining the methanol synthesis and deby- dation steps ina single process has also been developed. ‘Another methanol derivative is dimethyl carbonate (DMO), which can be obiained by converting methanol with phosgene or by oxidative carbonation of the methanol DMC has a high cetane rating, and ean be blended into diesel fuel ina concentration up to 10%, reducing fuel viscosity and improving emissions. ‘Methanol and its derivatives,e.¢, DME, DMC, and biodie~ sel, have many existing and potential uses. They can be used, for example, as substitute for gasoline and diesel fuel ia ICE-powered ears with only minor modification tothe exist- Jing engines and fuel systems. Methanol can also be used in Jue cells, for fuel cell vehicles (FCVs), which are considered to be the best alternative to ICES in the transportation field. DME is also a potential substitute for LNG and LPG for heating homes and in industrial uses ‘Methanol is also nsefu in reforming to hydrogen. In an effort address the problems associated with hydrogen stor- age and distribution, suggestions have been made to use lige uids rich in hydrogen suchas gasoline or methanol as asource ‘of hydrogen in vehicles via an on-board reformer. It is also considered that methanol is the safest oF al materials avail. able for such hydrogen production. Furhor, because of the high hydrogen content of Fquid methanol, even compared 10 pure cryogenic hydrogen (98.8 g of hydrogen in a liter of ‘methanol at mom temperature compared 10 70.8 in liquid hydrogen at ~253° C.), methanol isan excellent carter of hydrogen fuel, The absence of C—C bonds in methanol, which are difficult to break, facilitates its transformation 1 pure hydrogen with 80 to 90% eficeney. In contrast to a pure hydrogen-basod storage system, 2 reformer system is compact, containing on a volume basis ‘more hydrogen than even liquid hydrogen, and iseasy to store ‘and handle. without pressurization. A methanol steam reformers alsa advantagenusinallwing oper lower temperate (250-350°C.) and for being 0 o 4 ‘oon-boant applications. Furthermore, methanol contains no sulfuracontaminant for fue ells, and no nitrogen oxides are ormed froma methanol reformer because ofthe low operat. ‘ng temperature, Particulate matter and NO, emissions are virally eliminated, and ether emissions ar minimal. More- cover, methanol allows refueling to be as quick and easy as ‘with gasoline oF diese fuel. Thus, an on-board! methanol reformer enables rapid and elficiea delivery of hydrogen ‘rom liquid vel that can be easily distributed and sored inthe vehicle. To date, methanol isthe only liquid fuel that has been processed and demonstrated on a practical seal as suitable Thr fel use i. fel cell for transportation applications ‘In alition to on-board refoming, methanol also enables convenient production of hydrogen in feeling stations for refieling hydrogen fue cell vehicles, A fuel cell, an electro~ chemical device that converts fre chemical energy of fel relly into electrical energy, provides highly eficent way of procing electricity vis catalytic electrochemical oxide ‘ion, Forexample, ydrogen and oxygen air) are combined in ‘anclevirachemical cell-like device o produce water and elec- ticity. The process is clean, with water boing. the only byproduct. However, because hydrogen iself must fist be pradced in an enemgy-consuming proces, by electrolysis oF rom a hydrocarbon source (fossil fuel) with a reformer, hydrogen fel eels are sill nocessarly limited in wily ‘A system for producing high purity hydrogen bis been developed by steam reforming of methanol with a highly active catalyst, which allows operation at a relatively low temperature (240-290° C.) and enables flexibility in oper ‘ion as wel as rapid star-up and stop. These methanol-to- hydrogen (MTH) units aging in production capacity from 50 to 4000 nH por hour, are already used in various indus- tes, including the electronic, glass, ceramic, and food pro- cessing industries, and provide excellent reliability, pro- longed life span, and minimal maintenance. Operating at a relatively low temperature, the MTH process has a clear advantage over reforming of natural gas and other hydrocar- ‘bons which must be conducted at above 600°C, because less energy is needed to heat methanol ta the appropriate reaction temperature "The usefulness of methanol has lel to development of other reforming processes, for example, a process known a oxida tive steam reforming, which combines team reforming, par ‘ial oxidation of methanol, and novel catalyst systems, Oxi- {tive steam reforming produces high purity hydrogen with ‘zero or trace amounts of CO, at high methanol eonversionand temperatures as low as 290° C Its the advantage oF being, contrary to steam reforming, an exothermic reaeton, there ‘ore minimizing energy consumption. There is also atotber- ‘malreformingof methanol, which combines steam reforming ‘and partial oxidation of methanol ina. spocifie ratio and Addresses any drawback of an exothermic reaction by pro- ‘ducing only enough energy’ to sustai itself. Autothermal reforming is nether exothermic nor endothermie, and does not require any extemal eating onee the rection temperature js reached, Despite the aforementioned possibilities, hydeo- gen fc ells must use highly volatile and flammable hydro- den or reformer systems. USS. Pat, No, 5,599,638 discloses a simple direet methanol fuel cell (DMEC) based on proton exchange membranes (PEMD toaddress te disadvantages of hydrogen fuel cells. In ‘contrast o a ydrogen fuel ell, the DMEC is not dependent ‘on generation of hydrogen by processes sueh as electrolysis fof water or reformation of natural gas or hydrocarbon. The DMFC is also more cost effective because methanol, as Jiguid fuel, does no require cooling at ambient temperatures fr costly high pressure infrastructure and can be used with US 8,138,380 B2 5 storage and dispensing units, unlike hydrogen fol, whose storage and distribution requir new infrastructure urther. methanol has relatively high theoretieal volumetric ‘encray density compared to other systems such as conven tional bateris and the H.-PEM fel cell. This is of great $ portance for small portable applications (cellular phones, laptop computers, et.) for which small size and weight of ‘energy unit is desired ‘The DMFC offers numerous benefits in varions area, ‘including the transportation sector. By eliminating the need for methanol steam reformer, the DMEC significantly reduces the cost, complexity and weight ofthe vehiele, and improves fuel economy. A DMPC system is also comparable Jn its simplicity to a direct hydrogen fuel cell, without the ‘cumbersome problems of on-hoard hydrogen stonige oF hydrogen producing reformers. Because only water and COs are emitted, emissions of ether pollutants (ex., NO,, PM. 505, ete, ate eliminated, Direct methanol fel cll vehicles ‘are expected to be virtually ze emission vehicles (ZEV), ‘ag! use of methanol fuel cel vehicles offers to neatly eli nate air pollutants from vehicles in the long term, Further, unlike ICE. vehicles, the emission profile is expected to remain nearly unchanged over time. New membranes based ‘onhydrocarbon or hydrofiuorocarbon materials with reduced, ‘cost and exossover characteristics have been developed that allow room temperature efficiency of 34%. Further, inadliton o such ation exchange-type fel cells, anion exchange-ype fuel cells using an anion-conducting membrane and an anion-conducting binder (the anions are 30 ‘usually hydroxide ins) are also studied for methanol xida- tion (US Patent Applicaton Publication, US 2003/00 9509 Al) It's known that in anion exchange-type fuel cells, over- voltage atthe oxy zen electrode is reduced and the improve- ment of energy elicieney is expected. Further, its said that when methanol is used as the fuel, methanol crossover ‘herein methanol passes through the electrolyte membrane betwoen the electrodes is reduced. Hlosever, the hydroxide ‘dia is not compatible with carbon dioxide, which readily produce bicarbonate and earbonate salts ‘Methanol as indicated provides & mumber of important advantages 6 transportation fuel. Contrary to hydrogen, methanol does not require any energy intensive procedures Jor pressurization or Iiguefeetion, Because itis a liquid at oom temperature ican beeasily handled, store, distributed ‘and carried in wehieles, ean act as an ideal hydrogen career {or fue cel vehicles through on-board methanol reformers and can be used directly in DMFC vehicles, ‘Methanol is also an attractive source of fuel for state applications. For example, methanol can be used directly as diel in gas turbines to generate electric power. Gas turbines ‘ypically use natural zs or light petroleum disiate rsetions as fuel. Compared to such fuels, methanol can achieve highes power output and lower NO, emissions because of ts lower flame temperature. Since methanol does not contain sulfur, SO, emissions are also eliminated, Operation on methanol ‘offers the same flexibility son natural gasand disilat fuels, and can be performed with existing turbines, originally ‘desjuned for natural gas or other fossil fuels, after relatively ‘easy modification. Methanol is also an attractive fuel since duel grade methanol, with lower produetion cost than higher purity chemieal-grade methanol, can be used in turbines Because the size and weight ofa fuel ellisof less importance jin static applications than mobile applications various fuel ‘ells ther than PEM fuel ells and DMPC, suchas phospho= Fic acid, molten carbonate and solid oxide fuel cells (PAFC, MCFC, and SOFC, respectively), can albo be used 0 o 6 Inadition o use as fuels, methanol and methanolerved chemicals have other siniicant applications nthe chemical industry Today, methanol is one ofthe most important eed stock inthe chemical industry. Most of the 40 lion ons oF dumualy produced methanol is wed to manufacture a large ‘arctyof chemical products and material, including basic chemicals such as formaldelyde, acetic acd MTBE (al though itis inereasingly phased out inthe US. for environ: ‘mental akon), as Well as varius polymers, pains, adhe- sives, construction materials, snd llr, Worldwide, almost 7oPo of methanol is used to produce formaldehyde (38%), smethytat-buty ether (MTBE, 20%) and oe acid (11%) Methanol iz also a feedsock for ehloromethines, methy~ lamines, methyl methoerylat, and dimethyl terephthalate, among others. These chemical iatermediates ae then pro- cessed manufeture products sch a ps, resis, i cones, adhesives, antifeeze, and plastics. Formldchyde, rived in large quantities from methanol, is mainly sed to repre phenol, ure and melamine-formaldehvde aad polyacea evinw as well sx butanol and mcblene bis hoo isocyanate) (MDI; MDI foam is sed es insula in relrigertors, doors, and in cur dashboanls and bumper) Tomaldehyde resins ae predominantly employed an auhesve ina wide variety Of uppications, ez, manufacture ‘fpaniele board, plywood and other wood panels. Examples ff methanolderived chemical products and matenals are shown in FIG. 1 a producing basic chemical, aw material fodstock cone stitutes typically up to 60-706 ofthe manufacturing costs ‘Thee of feedstock therefore plays a signifeant economic role. Because ofits lower cost, methanol is considered a Potctil feedstock for processes curly uilizing more expensive feedstocks sochas ethylene and propylene, pro- dice chemicals including acetic i, accede, ethan ethylene glyco, styrene, and ethyibenzene, and various syn- thet hydrocarbon products For example, direct conversion of methanol to ethanol can be achieved wing @ rhodium ‘ase catalyst, which hs beea found to promote the ductive carbonation of methanol to acetaldehyde with selectivity lose 10 90%, anda rulhnium caus, which fre reduces fcealdehye to ethanol. The possibilty of pricing ety ce plycol via methanol oxidative coupling instead ofthe ‘ual process wingethleneas feedstock salso paaucd td Signiflcamt advances for syatheszing etylene ale fe dimethy ether obtained by methanol deyation, have also boon made Conversion of methanol to olefins such as ethylene and propylene, also known ss methanol a oefin (TO) techn fay is pariclarly promising onsiering the high demand for olefin materials especially in polyol production. The TO tschnology is presently a two-step proces, in which satura gasis converted tomethanol via srgas metho] Jsthen transformed to lei. It is omsiderd thst methanol is {inst deiydate to damethy! ether (DME), which then ects toormathylene snd propylene. Small amounts ofbutencs, her olefin, alkanes, nd aromatics are also formed. 2eH0H ‘Various catalysts, e-. synthetic aluminosilicate catalyst, such as ZSMCS (a zeolite developed by Mobil), silico US 8,138,380 B2 7 nophosphate (SAPO) molecular sieves such ss SAPO-34 and SAPO-17 (UOP), as well as bi-functional supported acid- base catalysts such as tungsten oxide over alumina (WOs! AJ,0;), have been fonnd to be active in converting methanol to ethylene and propylene at a temperature between 250 and 350°C. Thetypeand amountar the end product dependlon the ‘ypeo the catalyst and the MTO process used. Depending on the operating conditions, the weight ratio of propylene to ‘ethylene can be modified between about 0.77 and 1.83, allow= ing considerable lexiilty. For example, when using SAPO- 34 according 10 an MTO process developed by UOP and Nonk Hydro, methanol is converted 1 ethylene and propy- ene at more than 80% seletvity, and also to buteno, a val- able starting material for numberof procts at about 10%, While using an MTO process developed by Lungi with ZSM-5 catalysts, mostly propylene is produced at yields Wve 70%. A process developed by ExxonMobil, with ZSM-S catalyst produces hydrocarbons inthe gasoline and! ‘or distillate range at solectivity greater than 95%, ‘There is also a methanol to gasoline (MTG) process, ia ‘which modium-pore zeolites with considerable aidity, 2. ZSM-5, are used as catalyst. In this process, methanol is frst dehydmated to an equilibriom mixture of dimethyl ether methanol and water over a catalyst, and this mixture thea ‘converted to light olefins, primarily ethylene and propylene. The light olefins ean undergo further transformations to higher olefins, C,-Ce alkanes, and CC aromatis such as toluene, xylenes, and tmeshylbenzene, ‘With deereasing oil and gas reserves, i is inevitable that synthetic hydrocarbons would play a major role. Thus, ‘icthanol-hased synthetic hydrocarbons and chemicals av able through MTG and MTO processes will assume increas ing importance in replacing ol and gas-hased materials. The Tisted uses of methanol is only usrative and no i ‘Methatol can also be used as a source of single cell pro- ‘eins. single cell protein (SCP) refers toa protein produced by a microorganism, which degrades hydrocarbon substrates ‘while gaining energy. The proteincontentdependsonthetype ‘of microorganism, eg. bacteria, yeast, mold, ete. The SCP has many uses, inelaing vses 2s food and animal feed. Considering the numerous uses of methanol, itis clearly

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