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US 8,212,088B2 56 methanol is used to produce formaldehyde (38%), methyl tert-butylether(MTBE, 20%) andaceticacid(11%).Metha nol is also a feedstock for chloromethanes, methylamines, methylmethacrylate,anddimethylterephthalate,amongoth ers. These chemical intermediates are then processed to manufactureproductssuchaspaints,resins,silicones,adhe sives, antifreeze, and plastics. Formaldehyde, produced in large quantities from methanol, is mainly used to prepare phenol-, urea- and melamine-formaldehyde and polyacetal resins as Well as butanediol and methylene bis(4-phenyl iso cyanate)(MDI;MDI foamisusedasinsulationinrefrigera tors, doors, and in car dashboards and bumpers). Formalde hyde resins are predominantly employed as an adhesive in a Wide variety of applications, e.g., manufacture of particle boards,plyWoodandotherWoodpanels.Examplesofmetha nol-derived chemical products and materials are shoWn in FIG. 1. In producing basic chemicals, raW material feedstock con stitutestypicallyupto60-70%ofthemanufacturingcosts. 20 The cost of feedstock therefore plays a signi?cant economic role. Because of its loWer cost, methanol is considered a potential feedstock for processes currently utiliZing more expensivefeedstockssuchasethyleneandpropylene,topro ducechemicalsincludingaceticacid,acetaldehyde,ethanol,25 ethyleneglycol,styrene,andethylbenZene,andvarioussyn thetichydrocarbonproducts.Forexample,directconversion of methanol to ethanol can be achieved using a rhodium basedcatalyst,Whichhasbeenfoundtopromotethereductive carbonylationofmethanoltoacetaldehydeWithselectivity30 closeto90%, andarutheniumcatalyst,Whichfurtherreduces acetaldehydetoethanol.Thepossibilityofproducingethyl ene glycol via methanol oxidative coupling instead of the usualprocessusingethyleneasfeedstockisalsopursued,and signi?cantadvancesforsynthesiZingethyleneglycolfrom 35 dimethylether,obtainedbymethanoldehydration,havealso been made. Conversion of methanol to ole?ns such as ethylene and propylene, also knoWn as methanol to ole?n (MTO) technol ogy,isparticularlypromisingconsideringthehighdemand40 forole?nmaterials,especiallyinpolyole?nproduction.The MTO technologyispresentlyatWo-stepprocess,inWhich naturalgasisconvertedtomethanolviasyn-gasandmethanol isthentransformedtoole?n.Itisconsideredthatmethanolis ?rstdehydratedtodimethylether(DME),Whichthenreacts45 toformethyleneand/orpropylene.Smallamountsofbutenes, higherole?ns,alkanes,andaromaticsarealsoformed. 50 55 Various catalysts, e.g., synthetic aluminosilicate Zeolite catalysts, such as ZSM-5 (a Zeolite developed by Mobil), silicoaluminophosphate (SAPO) molecular sieves such as SAPO-34 and SAPO-17 (UOP), as Well as bi-functional sup portedacid-basecatalystssuchastungstenoxideoveralu 60 mina (WO3/Al2O3), have been found to be active in convert ing methanol to ethylene and propylene at a temperature betWeen 250 and 3500 C. The type and amount of the end product depend on the type of the catalyst and the MTO process used. Depending on the operating conditions, the 65 Weight ratio of propylene to ethylene can be modi?ed betWeen about 0.77 and 1.33, alloWing considerable ?exibil ity.Forexample,WhenusingSAPO-34 accordingtoanMTO processdevelopedbyUOP andNorskHydro,methanolis convertedtoethyleneandpropyleneatmorethan80% selec tivity, and also to butene (a valuable starting material for a number ofproducts) atabout 10%. When using an MTO process developed by Lurgi With ZSM-5 catalysts, mostly propyleneisproducedatyieldsabove70%.A processdevel opedbyExxonMobil,WithZSM-5 catalyst,produceshydro carbons in the gasoline and/or distillate range at selectivity greaterthan95%. 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 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 higher ole?ns, C3 -C6 alkanes, and C6-C 1O aromatics such as toluene,xylenes,andtrimethylbenZene. OlahhasdevelopedindependentlyMTO andMTG process usingsupportedbifunctionalacid-basenonZeoliticcatalysts. With decreasing oil and gas reserves, it is inevitable that synthetic hydrocarbons Would play a major role. Thus, methanol-basedsynthetichydrocarbonsandchemicalsavail ablethroughMTGandMTOprocessesWillassumeincreas ingimportanceinreplacingoilandgas-basedmaterials.The listed uses of methanol is only illustrative and not limiting. Methanol besides mentioned and other related uses can alsobeusedasasourceofsinglecellproteins.A singlecell protein(SCP)referstoaproteinproducedbyamicroorgan ism Which degrades hydrocarbon substrates While gaining energy. The protein content depends on the type of microor ganism, e.g., bacteria, yeast, mold, etc. The SCP has many uses, including uses as food and animal feed. Considering the numerous uses of methanol, it is clearly desirable to have improved and e?icient methods of produc ing methanol. Currently, methanol is almost exclusively made from synthesis gas obtained from incomplete combus tion(orcatalyticreforming)offossilfuel,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 animalmaterial,i.e.,materialsproducedbyalifeform, includingWoodandWoodWastes,agriculturalcropsandtheir 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 mentsinvolvingtheuseof“biocrude,”blackliquidobtained fromfastpyrolysisofbiomass,issomeWhatpromising,more development is needed for commercial application of biocrude. The presently existing method of producing methanol involvessyn-gas.Syn-gasisamixtureofhydrogen,carbon monoxide and carbon dioxide, and produces methanol over a heterogeneouscatalystaccordingtothefolloWingequations:PDF Image | CHEMICAL RECYCLING OF CO2 TO METHANOEDIMETHYL ETHER
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