Organic propylene oxide

PROPENE The major use of propene is in the produc tion of polypropylene Two other propene derived organic chemicals acrylonitrile and propylene oxide are also starting materials for polymer synthesis Acrylonitrile is used to make acrylic fibers (see Table 6 5) and propylene oxide is one component in the preparation of polyurethane polymers Cumene itself has no direct uses but rather serves as the starting material in a process that yields two valuable indus trial chemicals acetone and phenol... 

Chemical Manufacturing. Chemical manufacturing accounts for over 50% of all U.S. caustic soda demand. It is used primarily for pH control, neutralization, off-gas scmbbing, and as a catalyst. About 50% of the total demand in this category, or approximately 25% of overall U.S. consumption, is used in the manufacture of organic intermediates, polymers, and end products. The majority of caustic soda required here is for the production of propylene oxide, polycarbonate resin, epoxies, synthetic fibers, and surface-active agents (6). 

The changeover from ROO radicals to HOO radicals and the switch from organic peroxides to HOOH has been shown as temperature is increased in propane VPO (87,141). Tracer experiments have been used to explore product sequences in propane VPO (142—145). Propylene oxide comes exclusively from propylene. Ethylene, acetaldehyde, formaldehyde, methanol, carbon monoxide, and carbon dioxide come from both propane and propylene. Ethanol comes exclusively from propane. 

As of this writing, the process has not been commercialized, but apparendy the alcohol can be separated from its propylene oxide coproduct process to maintain an economically competitive position. The formation of organic hydroperoxides is a concern, as it was in the Shell process. 

Polyethers prepared from propylene oxide are soluble in most organic solvents. The products with the highest hydroxyl number (lowest molecular weight) are soluble in water, not in nonpolar solvents such as hexane. The solubihty of 3000 molecular weight triols is high enough in solvents such as toluene, hexane, and methylene chloride that the triols can be purified by a solvent extraction process. 

Propylene oxide is highly reactive. It reacts exothermically with any substance that has labile hydrogen such as water, alcohols, amines, and organic acids acids, alkahes, and some salts act as catalysts. 

Propylene oxide [75-56-9] (methyloxirane, 1,2-epoxypropane) is a significant organic chemical used primarily as a reaction intermediate for production of polyether polyols, propylene glycol, alkanolamines (qv), glycol ethers, and many other useful products (see Glycols). Propylene oxide was first prepared in 1861 by Oser and first polymerized by Levene and Walti in 1927 (1). Propylene oxide is manufactured by two basic processes the traditional chlorohydrin process (see Chlorohydrins) and the hydroperoxide process, where either / fZ-butanol (see Butyl alcohols) or styrene (qv) is a co-product. Research continues in an effort to develop a direct oxidation process to be used commercially. 

Molecular weights of poly(propylene oxide) polymers of greater than 100,000 are prepared from catalysts containing FeCl (40,41). The molecular weight of these polymers is gready increased by the addition of small amounts of organic isocyanates (42). Homopolymers of propylene oxide are also prepared by catalysis using diethylzinc—water (43), diphenylzinc—water (44), and trialkyl aluminum (45,46) systems. 

The hydroperoxide process involves oxidation of propjiene (qv) to propylene oxide by an organic hydroperoxide. An alcohol is produced as a coproduct. Two different hydroperoxides are used commercially that result in / fZ-butanol or 1-phenylethanol as the coproduct. The / fZ-butanol (TBA) has been used as a gasoline additive, dehydrated to isobutjiene, and used as feedstock to produce methyl tert-huty ether (MTBE), a gasoline additive. The 1-phenyl ethanol is dehydrated to styrene. ARCO Chemical has plants producing the TBA coproduct in the United States, Erance, and the Netherlands. Texaco has a TBA coproduct plant in the United States. Styrene coproduct plants are operated by ARCO Chemical in the United States and Japan, Shell in the Netherlands, Repsol in Spain, and Yukong in South Korea. 

Hydroperoxide Process. The hydroperoxide process to propylene oxide involves the basic steps of oxidation of an organic to its hydroperoxide, epoxidation of propylene with the hydroperoxide, purification of the propylene oxide, and conversion of the coproduct alcohol to a useful product for sale. Incorporated into the process are various purification, concentration, and recycle methods to maximize product yields and minimize operating expenses. Commercially, two processes are used. The coproducts are / fZ-butanol, which is converted to methyl tert-huty ether [1634-04-4] (MTBE), and 1-phenyl ethanol, converted to styrene [100-42-5]. The coproducts are produced in a weight ratio of 3—4 1 / fZ-butanol/propylene oxide and 2.4 1 styrene/propylene oxide, respectively. These processes use isobutane (see Hydrocarbons) and ethylbenzene (qv), respectively, to produce the hydroperoxide. Other processes have been proposed based on cyclohexane where aniline is the final coproduct, or on cumene (qv) where a-methyl styrene is the final coproduct. 

After epoxidation a distillation is performed to remove the propylene, propylene oxide, and a portion of the TBHP and TBA overhead. The bottoms of the distillation contains TBA, TBHP, some impurities such as formic and acetic acid, and the catalyst residue. Concentration of this catalyst residue for recycle or disposal is accompHshed by evaporation of the majority of the TBA and other organics (141,143,144), addition of various compounds to yield a metal precipitate that is filtered from the organics (145—148), or Hquid extraction with water (149). Low (<500 ppm) levels of soluble catalyst can be removed by adsorption on soHd magnesium siUcate (150). The recovered catalyst can be treated for recycle to the epoxidation reaction (151). 

Ethylbenzene Hydroperoxide Process. Figure 4 shows the process flow sheet for production of propylene oxide and styrene via the use of ethylbenzene hydroperoxide (EBHP). Liquid-phase oxidation of ethylbenzene with air or oxygen occurs at 206—275 kPa (30—40 psia) and 140—150°C, and 2—2.5 h are required for a 10—15% conversion to the hydroperoxide. Recycle of an inert gas, such as nitrogen, is used to control reactor temperature. Impurities ia the ethylbenzene, such as water, are controlled to minimize decomposition of the hydroperoxide product and are sometimes added to enhance product formation. Selectivity to by-products include 8—10% acetophenone, 5—7% 1-phenylethanol, and <1% organic acids. EBHP is concentrated to 30—35% by distillation. The overhead ethylbenzene is recycled back to the oxidation reactor (170—172). 

EBHP is mixed with a catalyst solution and fed to a horizontal compartmentalized reactor where propylene is introduced into each compartment. The reactor operates at 95—130°C and 2500—4000 kPa (360—580 psi) for 1—2 h, and 5—7 mol propylene/1 mol EBHP are used for a 95—99% conversion of EBHP and a 92—96% selectivity to propylene oxide. The homogeneous catalyst is made from molybdenum, tungsten, or titanium and an organic acid, such as acetate, naphthenate, stearate, etc (170,173). Heterogeneous catalysts consist of titanium oxides on a siUca support (174—176). 

After epoxidation, propylene oxide, excess propylene, and propane are distilled overhead. Propane is purged from the process propylene is recycled to the epoxidation reactor. The bottoms Hquid is treated with a base, such as sodium hydroxide, to neutralize the acids. Acids in this stream cause dehydration of the 1-phenylethanol to styrene. The styrene readily polymerizes under these conditions (177—179). Neutralization, along with water washing, allows phase separation such that the salts and molybdenum catalyst remain in the aqueous phase (179). Dissolved organics in the aqueous phase ate further recovered by treatment with sulfuric acid and phase separation. The organic phase is then distilled to recover 1-phenylethanol overhead. The heavy bottoms are burned for fuel (180,181). 

Peracid Processes. Peracids, derived from hydrogen peroxide reaction with the corresponding carboxyUc acids in the presence of sulfuric acid and water, react with propylene in the presence of a chlorinated organic solvent to yield propylene oxide and carboxyUc acid (194—196). 

Propylene oxide is a useful chemical intermediate. Additionally, it has found use for etherification of wood (qv) to provide dimensional stabiUty (255,256), for purification of mixtures of organosiUcon compounds (257), for disinfection of cmde oil and petroleum products (258), for steriliza tion of medical equipment and disinfection of foods (259,260), and for stabilization of halogenated organics (261—263). 

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). 

The glycol ethers obtained from /-butyl alcohol and propylene oxide, eg, l-/-butoxy-2-propanol, have lower toxicities than the widely employed 2-butoxyethanol and are used in industrial coatings and to solubiHze organic components in aqueous formulations (28). 

Esterification is one of the most important reactions of fatty acids (25). Several types of esters are produced including those resulting from reaction with monohydric alcohols, polyhydric alcohols, ethylene or propylene oxide, and acetjiene or vinyl acetate. The principal monohydric alcohols used are methyl, ethyl, propyl, isopropyl, butyl, and isobutyl alcohols (26) (see Esterification Esters, organic). 

Yields of propylene chlorohydrin range from 87—90% with dichloropropane yields of 6—9%. The dichloropropane is not only a yield loss but also represents a disposal problem as few uses are known for this material. Since almost all the propylene chlorohydrin is dehydrochlorinated to propylene oxide with lime or sodium hydroxide, none of the chlorine appears in the final product. Instead, it ends up as dilute calcium or sodium chloride solutions, which usually contain small amounts of propylene glycol and other organic compounds that can present significant disposal problems. 

Because the epoxidation with Tl(III) is stoichiometric to produce Tl(I), reoxidation is needed. Halcon has patented processes based on such epoxidation to yield ethylene oxide (200—203). The primary benefits of such a process are claimed to be high yields of ethylene oxide, fiexibihty to produce either propylene oxide or ethylene oxide, and the potential of a useful by-product (acetaldehyde). Advances usiag organic hydroperoxides ia place of oxygen for reoxidation offer considerable promise, siace reaction rates are rapid and low pressures can be used. 

Cosolvents ana Surfactants Many nonvolatile polar substances cannot be dissolved at moderate temperatures in nonpolar fluids such as CO9. Cosolvents (also called entrainers, modifiers, moderators) such as alcohols and acetone have been added to fluids to raise the solvent strength. The addition of only 2 mol % of the complexing agent tri-/i-butyl phosphate (TBP) to CO9 increases the solubility ofnydro-quinone by a factor of 250 due to Lewis acid-base interactions. Veiy recently, surfac tants have been used to form reverse micelles, microemulsions, and polymeric latexes in SCFs including CO9. These organized molecular assemblies can dissolve hydrophilic solutes and ionic species such as amino acids and even proteins. Examples of surfactant tails which interact favorably with CO9 include fluoroethers, fluoroacrylates, fluoroalkanes, propylene oxides, and siloxanes. 

In the organic chemicals industry, H2O2 is used in the production of epoxides, propylene oxide, and caprolactones for PVC stabilizers and polyurethanes, in the manufacture of organic peroxy compounds for use as polymerization initiators and curing agents, and in the synthesis of fine chemicals such as hydroquinone, pharmaceuticals (e.g. cephalosporin) and food products (e.g. tartaric acid). 

The preferred catalysts are salts of inorganic and organic acids as well as tertiary amines. Phthalic anhydride, succinic anhydride and maleic anhydride are typical acid anhydrides, while ethylene oxide, propylene oxide, epichlorohydrin and phenyl glycidyl ether are typical epoxides. The synthesis of a ladder polymer was carried out by using bisanhydrides264. ... 

In reactor 1 2,6-xylenol is condensed with propylene oxide in the presence of NaOH at elevated temperature and pressure. The reaction is reasonably selective. However, some isomers are also formed in minor proportions. Therefore, the crude DMFP is dissolved in the organic solvent / and crystallized in tank 2, separated from the mother liquor in centrifuge 3, and dried in drier 4. 

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