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CHM 585

Chapter 2. Petroleum CrackingC4Methanol derivativesMTBEFormaldehydeAcetic AcidEthylene, Chloroalkali and derivatives. . Major Petroleum Fractions. Thermal Cracking. Radical cleavage of hydrocarbons400

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CHM 585

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    1. CHM 585/490 Chapter 2

    2. Chapter 2 Petroleum Cracking C4 Methanol derivatives MTBE Formaldehyde Acetic Acid Ethylene, Chloroalkali and derivatives

    4. Major Petroleum Fractions

    5. Thermal Cracking Radical cleavage of hydrocarbons 400 500 C under pressure

    7. Example of Products from Naptha Cracking

    8. Typical C4 Composition

    9. MTBE Synthesis C4 raffinate is reacted with methanol at 30 - 100C with an acid ion exchange resin Isobutene selectively reacts Methanol and MTBE form a pressure dependent azeotrope. Methanol removed either by a pressurized distillation or by pervaporation (membrane)

    14. MTBE U.S.Production 282,000 barrels per day (2001) 42 gallons per barrel => 12 million gallons per day Density = 0.74 1 gallon of water = 8.3 lbs. 6.1 lb. MTBE per gallon 72 million pounds per day At 365 days => 26 billion pounds per year

    15. December 1998 underground storage tanks for gasoline were required to be double walled with a detection system between the inner and outer tanks. Cost penalty to the use of ethanol in place of MTBE about 5 cents per gallon even with government subsidies for ethanol.

    16. Formaldehyde 12.5 Billion Pounds per year U.S. capacity on a 37 percent basis. ( Demand about 10 billion pounds) Commercial production is from methanol either by silver catalyst or metal oxide catalyst processes. Seventy to 80 percent of formaldehyde output is used captively.

    17. Formaldehyde Producers Borden, Georgia Pacific and Hoechst Celanese are major U.S. producers Wright Chemical has capacity of 160 million pounds ( Chem Expo report)

    18. Formaldehyde HCHO 3 Commercial Forms Aqueous solution ( 35-55%) Cyclic trimer (trioxane) from the acid catalyzed reaction of formaldehyde Paraformaldehyde can be reversibly converted to the monomer by heat or acid

    19. Formaldehyde Uses 40%: urea- and phenol-formaldehyde resins used in particleboard and plywood, respectively 13%: polyacetal resins 11%: 1,4-butanediol

    20. Acetic Acid CH3OH + CO CH3CO2H Catalyst developed by Monsanto is Rhodium (Rh) in the presence of I2 The reaction involves CO insertion into a CH3-Rh bond Co and iridium based catalysts also known

    21. Acetic Acid 6 Billion pounds per year produced in the U.S. Celanese is the major producer 42% used to make vinyl acetate monomer

    22. Vinyl Acetate The dominant method of commercial production is by reaction of ethylene with acetic acid and oxygen in the presence of a palladium catalyst. About 2 billion pounds produced in North America Main use is for polymer manufacture

    23. Ethylene In terms of quantity produced, ethylene is the most important organic chemical Ranked # 4 among all chemicals after 1. Sulfuric acid 2. Nitrogen 3. Oxygen

    24. Ethylene U.S. Production About 60 billion pounds made per year (2002) Major U.S. manufacturers (capacity lb.) Equistar ( 10B) Exxon Mobil ( 9B) Dow (8B) Chevron Phillips (8B) Shell(7B)

    25. Ethylene Steam cracking of hydrocarbons accounts for virtually all of the ethylene produced throughout the world. Hydrocarbons used as feedstocks range from natural gas liquids (ethane, propane and butane) to petroleum liquids (gas oils and naphtha). Roughly 70 percent of the US ethylene industry's production is used captively for downstream derivatives.

    26. Ethylene Uses Polyethylene 54% Ethylene dichloride, 18% Ethylene oxide 12% Ethylbenzene, 6 %

    27. Chloralkali Chlorine / Caustic Cl2 / NaOH 13 million tons of chlorine 15 million tons of NaOH Coproduced by the electrolysis of NaCl

    28. U.S. Chlorine Producers Dow 4 billion tons per year OxyChem 3 billion tons per year PPG 2 billion tons per year These three are also the top caustic producers

    29. Manufacture The process of manufacture uses electricity and salt. In manufacture, for every 80 tonnes of caustic soda, 71 tonnes of chlorine and 2 tonnes of hydrogen are co-produced. Each tonne of caustic soda requires around 2200 kWh of electricity and 1.55 tonnes of salt.

    31. Chlorine / Caustic Three processes of manufacture. Mercury cell - the oldest technology employed which has been largely closed down around the world being less efficient and polluting. (HoltraChem) Diaphragm cell - the dominant technology. Membrane cell - preferred technology for new plants

    32. Diaphragm Cell

    33. Chlorine / Caustic Diaphragm acts to separate the anode and cathode to prevent mixing of chlorine with NaOH or hydrogen The effluent cell liquor contains about 14% NaCl and 12% NaOH. This is passed though an evaporation train where NaCl is removed by crystallization and returned as a feed material

    34. NaOH Use 54%: direct application (pulp and paper, soaps and detergents, alumina, petroleum, textiles, water treatment) 35% organic chemicals (propylene oxide, polycarbonate,ethyleneamines, epoxy resins, 11%: inorganic chemicals (sodium/calcium hypochlorite, sulfur-containing compounds, sodium cyanide).

    35. Chlorine Use 36% Polyvinyl chloride (ethylene dichloride and vinyl chloride monomer) 41% Other organic chemicals 15% inorganic chemicals 4% water treatment 1% pulp and paper 3% miscellaneous

    36. Ethylene Dichloride About 16 billion pounds produced in U.S. 94% goes to PVC manufacture OxyVinyls (JV between OxyChem and Geon) number 1 manufacturer Dow # 2 Formosa #3

    37. EDC Synthesis Direct Chlorination C2H4 + Cl2 C2H4Cl2 liquid phase; FeCl3 or CuCl2 catalysts Oxychlorination C2H4 + 2HCl + O2 C2H4Cl2 + H2O Gas phase; CuCl2 catalyst

    38. VCM Synthesis

    39. Balanced VCM Process Chlorination of ethylene C2H4 + Cl2 C2H4Cl2 Cracking to make vinyl chloride 2C2H4Cl2 2C2H3Cl + 2HCl OxyChlorination C2H4 + 2HCl + O2 C2H4Cl2 + H2O Overall 2C2H4 + Cl2 + O2 2C2H3Cl + H2O

    40. Ethylene Oxide

    41. Ethylene Oxide 9 Billion lbs in U.S. Dow/Union Carbide, Shell, Huntsman and Equistar are some of the major producers 57% used for ethylene glycol Source for various ethers and alcohols

    42. Ethylene glycol

    43. Ethylene Glycol Uses 58% for Polyester (PET) 26% for antifreeze

    44. Ethylbenzene

    45. Ethylbenzene U.S. Production 14 billion pounds annually Lyondell, Sterling, Cos-Mar (Ato-Fina & GE), Dow and Chevron are among the major producers Used for styrene production

    46. Styrene

    47. Styrene 12 Billion pounds Same producers as ethylbenzene Used for polystyrene production

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