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US 7,906,559B2 78 involves conversion of ethylene folloW by hydration, the overallreactionbeing2CH3aOH C2H5OH+H2O.Producing ethyleneglycolviamethanoloxidativecouplinginsteadof using ethylene as feedstock is also pursued, and signi?cant advances for synthesiZing ethylene glycol from dimethyl ether, obtained by methanol dehydration, have also been made. of microorganism, e.g., bacteria, yeast, mold, etc. The SCP has many uses, including uses as food and animal feed. ConsideringthenumeroususesofmethanolandDME, itis clearly desirable to have improved and ef?cient methods for their production. Currently, methanol is almost exclusively made from synthesis gas obtained from incomplete combus tion(orcatalyticreforming)offossilfuel,mainlynaturalgas (methane) and coal. Conversion of methanol to ole?ns such as ethylene and propylene, also knoWn as methanol to ole?n (MTO) technol ogy,isparticularlypromisingconsideringthehighdemand 10 suchmethanolproductionalsoinvolvessyn-gasandmaynot for ole?ns, especially in polyole?n and synthetic hydrocar- bonproductsproduction.TheMTO technologyispresentlya tWo-stepprocess,inWhichnaturalgasisconvertedtometha- nol via syn-gas and methanol isthen transformed to ole?n. It isconsideredthatintheprocess,methanolis?rstdehydrated 15 Waste byproducts, municipal solid Waste, animal Waste, to dimethyl ether (DME), Which then reacts to form ethylene and/or propylene. Small amounts of butenes, higher ole?ns, alkanes, and aromatics are also formed. aquatic plants, and algae. The method oftransforming biom ass to methanol is similar to the method of producing metha nol from coal, and requires gasi?cation ofbiomass to syn-gas, —H2O .HZO Ethylene& Propylene 2CH3OH +H2O CH3OCH3 _> H2C=CH2&H2C=CH_CH3 Variouscatalysts,e.g.,syntheticaluminosilicateZeolite25 catalysts, such as ZSM-5 (a Zeolite developed by Mobil), silicoaluminophosphate (SAPO) molecular sieves such as SAPO-34 and SAPO-l7 (UOP), as Well as bi-functional sup ported acid-base catalysts such as tungsten oxide over alu mina WO3/Al2O3 (Olah), have been found to be active in convertingmethanoltoethyleneandpropyleneatatempera ture betWeen 250 and 4000 C. The nature and amount of the end product depend on the type of the catalyst, contact time andotherfactorsoftheMTO processused.Dependingonthe 35 operatingconditions,theWeightratioofpropylenetoethyl ene can be modi?ed betWeen about 0.77 and 1.33, alloWing considerable ?exibility. For example, When using SAPO-34 catalystaccordingtoanMTO processdevelopedbyUOP and NorskHydro,methanolisconvertedtoethyleneandpropy 40 leneatmorethan80% selectivity,andalsotobutene,avalu able startingmaterial foranumber ofproducts, atabout 10%. WhenusinganMTO processdevelopedbyLurgiWithZSM-5 catalysts,mostlypropyleneisproducedatyieldsabove70%. AprocessdevelopedbyExxonMobil,WithZSM-5catalyst,45 produceshydrocarbonsinthegasolineand/ordistillaterange 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 50 dehydrated to an equilibrium mixture of dimethyl ether, 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-Cl0aromaticssuchas55 toluene,xylenes,andtrimethylbenZene. Withdecreasingoilandnaturalgasreserves,itisinevitable thatsynthetichydrocarbonsWouldplayamajorrole.Thus, methanol-basedsynthetichydrocarbonsandchemicalsavail ablethroughMTGandMTOprocessesareassumingincreas 60 ingimportanceinreplacingoilandgas-basedmaterials.The listed uses of methanol in FIG. 1 is only illustrative and not limiting. Methanol can also be used as a source of single cell pro teins.A singlecellprotein(SCP)referstoaproteinproduced byamicroorganismWhichdegradeshydrocarbonsubstrates Whilegainingenergy.Theproteincontentdependsonthetype folloWedbymethanolsynthesisbythesameprocessesused 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 involve syn-gas. Syn-gas is a mixture of hydrogen, carbon monoxideandcarbondioxide,andproducesmethanolovera heterogeneouscatalystaccordingtothefolloWingequations: The ?rsttWo reactions are exothermic With heat ofreaction equalto—2l.7kcal.mol_land—9.8kcal.mol_l,respectively, andresultinadecreaseinvolume.Conversiontomethanolis favored by increasing the pressure and decreasing the tem perature according to Le Chatelier’s principle. The third equation describes the endothermic reverse Water gas shift reaction(RWGSR). Carbonmonoxideproducedinthethird reactioncanfurtherreactWithhydrogentoproducemethanol. The secondreactionissimplythesum ofthe?rstandthethird reactions. Each of these reactions is reversible, and is there fore limited by thermodynamic equilibrium under the reac tionconditions,e.g.,temperature,pressureandcomposition ofthesyn-gas. Synthesisgasformethanolproductioncanbeobtainedby reformingorpartialoxidationofanycarbonaceousmaterial, such as coal, coke, natural gas, petroleum, heavy oil, and asphalt. The composition of syn-gas is generally character iZedbythestoichiometricnumberS,correspondingtothe equationshoWnbeloW. _ (moles H2 —moles CO2) _ (molesCO +moles CO2) 30 Methanol can also be made from reneWable biomass, but 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 Wastes, agricultural crops and theirPDF Image | CONVERSION OF CARBON DIOXIDE TO METHANOL
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