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US 8,440,729B2 78 Another feasible Way to produce ethanol from methanol involvesconversionofethylenefolloWbyhydrationaccord ingtotheoverallreaction: Producing ethylene glycol via methanol oxidative cou plinginsteadofusingethyleneasfeedstockisalsopursued, and signi?cant advances for synthesiZing ethylene glycol fromdimethylether,obtainedbymethanoldehydration,have also been made. Conversion of methanol to ole?ns such as ethylene and propylene, also knoWn as methanol to ole?n (MTO) technol ogy,isparticularlypromisingconsideringthehighdemand forole?ns,especiallyinpolyole?nandsynthetichydrocar bonproductsproduction.TheMTO technologyispresentlya tWo-stepprocess,inWhichnaturalgasisconvertedtometha nol via syn-gas and methanol isthen transformed to ole?n. It is considered that in the process, methanol is ?rst dehydrated to dimethyl ether (DME), Which then reacts to form ethylene and/orpropylene.Smallamountsofbutenes,higherole?ns, 20 alkanes, and aromatics are also formed. Methanol can also be used as a source of single cell pro teins.A singlecellprotein(SCP)referstoaproteinproduced byamicroorganismWhichdegradeshydrocarbonsubstrates Whilegainingenergy.Theproteincontentdependsonthetype of microorganism, e.g., bacteria, yeast, mold, etc. The SCP has many uses, including uses as food and animal feed. Considering the numerous uses of methanol and dimethyl ether, it is clearly desirable to have improved and ef?cient methods for their production. Currently, methanol is almost exclusively made from synthesis gas obtained from incom plete combustion (or catalytic reforming) of fosil fuel, mainlynaturalgas(methane)andcoal. Methanol can also be made from reneWable biomass, but such methanol production also involves syn-gas and may not be energetically favorable and limited in terms of scale. As usedherein,theterm“biomass”includesanytypeofplantor animal material, i.e., materials produced by a life form, including Wood and Wood Waste, agricultural crops and their Waste byproducts, municipal solid Waste, animal Waste, aquaticplants,andalgae.Themethodoftransformingbiom ass to methanol is similar to the method of producing metha nolfromcoal,andrequiresgasi?cationofbiomasstosyn-gas, folloWed by methanol synthesis by the same processes used Withfossilfuel.Use ofbiomass alsopresentsotherdisadvan tages,suchasloWenergydensityandhighcostofcollecting andtransportingbulkybiomass.Althoughrecentimprove ments involving the use of “biocrude,” black liquid obtained fromfastpyrolysisofbiomass,issomeWhatpromising,more development is needed for commercial application of biocrude. The presently existing methods of producing methanol involvesyn-gas.Syn-gasisamixtureofhydrogen,carbon monoxide and carbon dioxide, and produces methanol over a heterogeneouscatalystaccordingtothefolloWingreactions: The ?rsttWo reactions are exothermic With heat ofreaction equal to about 21.7 kcal~mol/l and about 9.8 kcal~mol/l, respectively,andresultinadecreaseinvolume.Conversionto methanolisfavoredbyincreasingthepressureanddecreasing thetemperatureaccordingtoLeChatelier’sprinciple.The third equation describes the endothermic reverse Water gas shiftreaction(RWGSR). Carbonmonoxideproducedinthe third reaction can further react With hydrogen to produce methanol. The second reaction is simply the sum of the ?rst andthethirdreactions.Eachofthesereactionsisreversible, andisthereforelimitedbythermodynamicequilibriumunder the reaction conditions, e.g., temperature, pressure and com positionofthesyn-gas. Synthesisgasformethanolproductioncanbeobtainedby reformingorpartialoxidationofanycarbonaceousmaterial, such as coal, coke, natural gas, petroleum, heavy oil, and asphalt. The composition of syn-gas is generally character iZed by the stoichiometric number S, corresponding to the reaction shoWn beloW. (moles H2 —moles CO2) _ (moles CO +moles CO2) Ideally,Sshouldbeequaltoorslightlyabove2.Avalueabove 2 indicates excess hydrogen, While a value beloW 2 indicates relativehydrogende?ciency.Reformingoffeedstockhaving -H2O -H2O 2CH3OH CH3OCH3—> +H2O Ethylene& Propylene H2C=CH2 & H2C=CH—CH3 Variouscatalysts,includeWithoutlimitation,syntheticalu 30 minosilicateZeolitecatalysts,suchasZSM-5 (aZeolitedevel opedbyMobil),silicoaluminophosphate(SAPO)molecular sieves such as SAPO34 and SAPO-l7 (UOP), as Well as bi-functional supported acid-base catalysts such as tungsten oxideoveraluminaWO3/Al2O3,havebeenfoundtobeactive 35 in converting methanol to ethylene and propylene at a tem perature between 2500 C. and 4000 C. The nature and amount oftheendproductdependonthetypeofthecatalyst,contact time and other factors of the process used. Depending on the operatingconditions,theWeightratioofpropylenetoethyl 40 ene can be modi?ed betWeen about 0.77 and 1.33, alloWing considerable ?exibility. For example, When using SAPO-34 catalystaccordingtoanMTO processdevelopedbyUOP and Norsk Hydro, methanol is converted to ethylene and propy leneatmorethan80%selectivity,andalsotobutene,avalu 45 able startingmaterial foranumber ofproducts, atabout 10%. WhenusinganMTO processdevelopedbyLurgiWithZSM-5 catalysts,mostlypropyleneisproducedatyieldsabove70%. A process developed by ExxonMobil, With ZSM-5 catalyst, produceshydrocarbonsinthegasolineand/ordistillaterange50 atselectivitygreaterthan95%. There is also a methanol to gasoline (MTG) process, in Which medium-pore Zeolites With considerable acidity, e.g., ZSM-5, areusedascatalysts.Inthisprocess,methanolis?rst dehydratedtoanequilibriummixtureofdimethylether,55 methanol and Water over a catalyst, and this mixture is then convertedtolightole?ns,primarilyethyleneandpropylene. The light ole?ns can undergo further transformations to higherole?ns,C3-C6alkanes,andC6-Cl0aromaticssuchas toluene,xylenes,andtrimethylbenZene. 60 Withdecreasingoilandnaturalgasreserves,itisinevitable thatsynthetichydrocarbonsWouldplayamajorrole.Thus, methanol-basedsynthetichydrocarbonsandchemicalsavail ablethroughMTG andMTO processesareassumingincreas ingimportanceinreplacingoilandgas-basedmaterials.The65 listed uses of methanol in FIG. 1 are only illustrative and not limiting. 25PDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL BIOREFORMING
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