imp - From syngas to methanol and dimethylether Ferruccio...

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From syngas to methanol and dimethylether Ferruccio Trifiro` Summer School September 2009 Bologna
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Content of the lecture • 1) Synthesis of methanol from syngas • 2) Synthesis of dimethylether (DME) from methanol • 3) Synthesis of DME directly from syngas
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Global production of methanol • The global production of methanol is about 40 million ton per year, most of which is produced from natural gas. Today, the high price of oil and natural gas has spurred new interest in alternative feedstocks for the production of methanol. Various types of biomass have been considered, but on the shorter term coal appears to be the only viable alternative raw material for large scale methanol production. In fact, methanol has been produced from • coal for many years in specific geographical areas, notably in China.
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From methanol to fuels • 1) Methanol to DME (alternative to Diesel) • 2) Methanol for fuel cell • 3) Methanol for production of MTBE • 4) Methanol as fuel (altenatives to gasoline) • 5) Methanol for production of hydrogen • 6) Synthesis of gasoline (MTG process)
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From methanol to chemicals Methanol Acetic Acid Methyl methacrylate Methyl amines Methyl formiate Di-methylterephthalate Formaldehyde chloromethanes
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From methanol to to olefins • The different technologies for the future SYNGAS CH 3 OH DME OLEFINS PROPYLENE MTP MTO SDTO From Methane Coal Municipal wastes Recycled plastics Biomass Organic
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Synthesis of methanol •C O + 2 H 2 CH 3 OH Δ H 298k =-90.6kJmol -1 • Methanol synthesis is the second largest process after ammonia which use catalysts at high pressure • The mechanism is believed to be O + H 2 O-> CO 2 +H 2 Δ H 298k =-41.2kJmol -1 O 2 +2H 2 ->CH 3 OH+H 2 O Δ H 298k = -49kJmol -1
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Operative conditions for methanol synthesis Catalyst : CuO(60-70%)- ZnO(20-30%) –Al 2 O 3 (5- 15%)or Cr 2 O 3 (5-15%) Temp 220 o C-300 o C Pressure 50-100Atm (5-10MPa) Composition of the feed 59 -74%H 2 27- 15% CO 8% C0 2 3%CH 4 Conversion of CO to methanol per pass is normally 16– 40 %. H 2 : CO ratio of 2.17. The selectivity is around 99.8 %
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Commercial Technologies • Today there are four catalyst suppliers and six companies complete proprietary processes for methanol synthesis : ICI, Lurgi, Topsøe, Mitsubishi, M.W. Kellogg and Uhde. • Design figures for converters can be as high as 2,500-10,000 tonnes for day • A good catalyst in a natural gas-based plant may over its lifetime of about 4 years
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Ways to improve the yield in methanol 1) The reaction is exothermic and favored at low temperature, for this reason is necessary to remove the heat to keep the reaction temperature as low as possible in order to increase the conversion 2) To remove methanol during the synthesis in order to shift the equilibrium to higher CO to methanol conversion per pass (through the DME formation) 3) To develop more active catalysts which operate at lower temperature, increasing the thermodynamically allowed conversion
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Equilibrium CO conversion to methanol (H 2 /CO=2) 400 450 500 550 600 1 0,5 1 50bar 100 bar adiabatic I s o t h e r m a l Conversion Temperature CO K CO +2H 2 ->CH 3 OH
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This note was uploaded on 11/09/2011 for the course CHEMICAL E ech 401 taught by Professor Rammurti during the Spring '11 term at Punjab Engineering College.

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imp - From syngas to methanol and dimethylether Ferruccio...

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