1 Chapter 1 Synthesis Gas and Methanol Synthesis Gas CO H 2 Methanol

2 Petrochemical Products 95% based upon oil or natural gas

3 Synthesis Gas (various mixtures of CO/H 2 ) Some ( about 16%) made from coal, but most from natural gas and oil in the presence of steam. -CH O 2  CO + H 2 –  H = -22 kcal/mol -CH H 2 O  CO + 2H 2 –  H = + 36 kcal/mol CO/H 2 ratio adjusted by varying the amount of O 2 and H 2 O

4 Syn Gas - Uses (various mixtures of CO/H 2 ) Chemical feedstock - source of CO and H 2 Production of methanol Synthesis of aldehydes/alcohols from olefins via hydroformylation Manufacture of hydrocarbons

5 CO separated from Syn Gas One of three ways –Low temperature separation –CuCl solution –Semipermeable membranes

6 Carbon Monoxide Separated from Syn Gas By low temperature separation –CO 2 removed to 50 ppm by scrubbing with ethanolamine –CO 2 and H 2 O removed by molecular sieve adsorbents –Condense to separate CH 4 and CO from mixture ( -180C, pressure) –Depressurize to distill the CO overhead

7 Carbon Monoxide Separated from Syn Gas By CO absorption in CuCl solution under pressure followed by desorption under reduced pressure. By semipermeable membranes

8 Uses of pure CO Carbonylation of methanol to acetic acid Carbonylaton of methyl acetate to acetic anhydride Reaction with Cl 2 to produce phosgene.

9 Uses of pure CO

10 H2H2 About 50 million tons manufactured worldwide

11 H2H2 About 50 million tons manufactured worldwide Think about this!!!

12 H2H2 About 50 million tons manufactured worldwide Think about this!!! At a U.S. population of 285 million, that is as if every man, woman and child in the U.S. each produced about 400 pounds each year.

13 H2H2 About 50 million tons manufactured worldwide From syn gas by any of: –Low temperature fractional condensation –Pressure swing absorption of impurities on zeolite –Separation with semipermeable membranes

14 Hydrogen is used in petroleum refining and in the following chemical processes:

15 C 1 units Methanol Formaldehyde Formic Acid Hydrocyanic Acid Methylamines Chloromethanes/ Chlorofluoromethanes

16 Methanol CO + 2 H 2 CH 3 OH Uses catalysis –ZnO – Cr 2 O 3 typical –CuO – ZnO – Al 2 O 3 used by BASF Celanese process involves oxidation of a propane – butane mixture followed by distillation to produce methanol, acetic acid, formaldehyde and acetaldehyde

17 Methanol 2.8 billion gallons per year produced in the U.S. group.com/chemprofile.htmhttp:// group.com/chemprofile.htm Check out this web site!

18 Methanol Uses MTBE, 37 % formaldehyde, 23 % acetic acid, 12 % chloromethanes, 6 % methyl methacrylate,3% methylamines, 2% dimethyl terephthalate, 2 % miscellaneous, including solvents, antifreeze and fuels, 15 %