Propylene, chlorination

The process involving aHyl alcohol has not been iadustriaHy adopted because of the high production cost of this alcohol However, if the aHyl alcohol production cost can be markedly reduced, and also if the evaluated cost of hydrogen chloride, which is obtained as a by-product from the substitutive chlorination reaction, is cheap, then this process would have commercial potential. The high temperature propylene—chlorination process was started by SheH Chemical Corporation ia 1945 as an iadustrial process (1). The reaction conditions are a temperature of 500°C, residence time 2—3 s, pressure 1.5 MPa (218 psi), and an excess of propylene to chlorine. The yield of aHyl chloride is 75—80% and the main by-product is dichloropropane, which is obtained as a result of addition of chlorine. Other by-products iaclude monochioropropenes, dichloropropenes, 1,5-hexadiene. At low temperatures, the amount of... 

Materials of Construction. GeneraHy, carbon steel is satisfactory as a material of construction when handling propylene, chlorine, HCl, and chlorinated hydrocarbons at low temperatures (below 100°C) in the absence of water. Nickel-based aHoys are chiefly used in the reaction area where resistance to chlorine and HCl at elevated temperatures is required (39). Elastomer-lined equipment, usuaHy PTFE or Kynar, is typicaHy used when water and HCl or chlorine are present together, such as adsorption of HCl in water, since corrosion of most metals is excessive. Stainless steels are to be avoided in locations exposed to inorganic chlorides, as stainless steels can be subject to chloride stress-corrosion cracking. Contact with aluminum should be avoided under aH circumstances because of potential undesirable reactivity problems. 

The epoxidation of propylene to propylene oxide is a high-volume process, using about 10% of the propylene produced in the world via one of two processes [127]. The oldest technology is called the chlorohydrin process and uses propylene, chlorine and water as its feedstocks. Due to the environmental costs of chlorine and the development of the more-efficient direct epoxidation over Ti02/Si02 catalysts, new plants all use the hydroperoxide route. The disadvantage here is the co-production of stoichiometric amounts of styrene or butyl alcohol, which means that the process economics are dependent on finding markets not only for the product of interest, but also for the co-product The hydroperoxide route has been practiced commercially since 1979 to co-produce propylene oxide and styrene [128], so when TS-1 was developed, epoxidation was looked at extensively [129]. 

Propylene oxide in the amount of 5000 tons/yr will be made by the chlorohydrin process. The basic feed material is a hydrocarbon mixture containing 90% propylene and the balance propane which does not react. This material is diluted with spent gas from the process to provide a net feed to chlorination which contains 40 mol % propylene. Chlorine gas contains 3% each of air and carbon dioxide as contaminants. 

Allyl chloride by propylene chlorination Generic MMlb/y 80 250 7.581 0.6... 

In general, cyclopropane undergoes addition less readily than propylene chlorination, for example, requires a Lewis acid catalyst to polarize the chlorine molecule (compare Sec. 11.11). Yet the reaction with sulfuric acid and other aqueous protic acids takes place considerably faster for cyclopropane than for propylene. (Odder still, treatment with bromine and FeBrj yields a grand mixture of bromo propanes.)... 

Fig. 6-12, Propylene chlorination effect of reaction temperature on product compositions.

Propylene, chlorinated Single Tg I was Elvaloy 741 Allard and Prud homme (1982)... 

Propylene, chlorinated Neopentyl glycol adipate Single Tg transparency I had 67 wt% Cl Goh et al. (1985)... 

Type Chloroprene Polysulfide Ethylene Propylene Chlorinated Polyethylene Chlorosulfonated Polyethylene... 

Polyethylene-g-poly(styrene-alt-MA), 473, 474 Poly(ethylene-co-propylene) chlorinated and MA grafted, 466 MA grafting procedure, 465 MA vulcanized, 465 maleimide grafted, 466 poly(styrene-alt-MA) grafted, 473, 474 Poly(ethylene-co-propylene-co-acetylene), MA grafted, 472... 

Propylene Chlorine Allyl Chloride Hydrochloric Acid... 

Propylene, chlorinated 2,2-Dimethyl- 1,3-propylene adipate Single Tg, tr isparency I had 67 wt.% Cl 287... 

PolyCpropyleneX isotactic (Profax 6701, Hercules) Poly(propylene), chlorinated (Parlon PIO, Hercules) Poly(2-methyl propene) 63.09... 

---