ARCO Chemical propylene oxide process

Synthesis. The total aimual production of PO in the United States in 1993 was 1.77 biUion kg (57) and is expected to climb to 1.95 biUion kg with the addition of the Texaco plant (Table 1). There are two principal processes for producing PO, the chlorohydrin process favored by The Dow Chemical Company and indirect oxidation used by Arco and soon Texaco. Molybdenum catalysts are used commercially in indirect oxidation (58—61). Capacity data for PO production are shown in Table 1 (see Propylene oxide). 

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. 

The most important chemical reaction of chi orohydrin s is dehydrochloriaation to produce epoxides. In the case of propylene oxide. The Dow Chemical Company is the only manufacturer ia the United States that still uses the chlorohydrin technology. In 1990 the U.S. propylene oxide production capacity was hsted as 1.43 x 10 t/yr, shared almost equally by Dow and Arco Chemical Co., which uses a process based on hydroperoxide iatermediates (69,70). More recentiy, Dow Europe SA, aimounced a decision to expand its propylene oxide capacity by 160,000 metric tons per year at the Stade, Germany site. This represents about a 40% iacrease over the current capacity (71). 

Standard Oil of California added the petrochemicals of Gulf Oil, purchased in 1984, to its subsidiary Chevron Chemical. Other United States petrochemical producers took advantage of special circumstances. Amoco was served by a strong terephthalic (TPA) base and its good performance in polypropylene Arco, by its Lyondell subsidiary in Channelview, Texas, and by its development of the Oxirane process through which propylene oxide could be produced by direct oxidation with styrene as a coproduct. The process also led to MTBE (methyl tertiary-butyl ether), the antiknock agent used as a substitute for tetraethyl lead. 

Fig. 6.11. Manufacture of styrene and propylene oxide from ethylbenzene and propylene. ARCO Chemical (Oxirane) process.

This process was originally developed and commercialized by Oxirane (a joint venture company between ARCO Chemical, now Lyondell, and Halcon) and independently by Shell Petrochemical Company. At present, this is one of the main processes for the commercial manufacture of propylene oxide (the other is a variant of the same that starts with isobutane instead of ethylbenzene, and produces propylene oxide together with tert-butyl alcohol, isobutylene, and... 

W. S. Dubner, R. N. Cochran, Propylene oxide-styrene monomer process, U.S. Patent No. 5,210,354,1993, Assigned to ARCO Chemical Technology. 

ARGO (ATLANTIC RICHFIELD) Landau s entrepreneurial inventiveness further yielded Arco Chemical, Atlantic Richfield s chemical subsidiary, another highly profitable new process. In this case, however, the innovation was developed not through licensing, but through a joint venture to commercialize Landau s process for the production of propylene oxide, the principal ingredient in urethane foams and other polyurethane polymers (as reviewed in Chapter 4). 

FI, 7.4. Propylene oxide production by oxidation with peroxide compounds. ARCO Chemical (Oxirunc) process, isobutane version. 1 - I... 

This ratio may vary from 2.1 to 25 according to the operating conditions. ARCO Chemical (formerly Oxirane) has developed a process derived from the propylene oxide r-butyl alcohol technology for the direct oxidation of iso butane to raise the proportion of alcohol... 

The only industrial method for producing tertiary butyl alcohol is based on a variant of the Oxirane /ARCO Chemical) process for manufacturing propylene oxide,in which isobutane is used as a co-reactant and the alcohol is a co-product The technological analysis of this scheme and the related economic data are given in Section 724, which discusses the manufacture of propylene oxide. 

Allyl alcohol can be made by the isomerization of propylene oxide. ARCO Chemical has obtained an exclusive worldwide license from Kuraray in Osaka, Japan for their hydroformulation technology to produce 1,4-butanediol from allyl alcohol. In 1990, ARCO commissioned both the alcohol and the 1,4-butanediol process at their Channelview, Texas propylene oxide plant [91. 1,4-Butanediol is a versatile chemical intermediate that can be used to produce tetrahydrofuran, polybutylene teraphthalate resins, polyurethanes, and pyrrolidone. At this time only a relatively small quantity of propylene oxide is used for this purpose. However, it is growing... 

ARCO Chemical has commercialized a process in their Channelview, Texas propylene oxide complex to produce 1,4 butanediol from allyl alcohol. The technology is licensed from Kuraray of Japan. It fits well with ARCO... 

Propylene oxide is manufactured in the United States principally by Dow Chemical Company (chlorohydrin process) and ARCO Chemical Company, a Division of Atlantic Richfield (the peroxidation process based on both isobutane and ethylbenzene). In Western Europe, major producers include Dow Chemical Company, ARCO Chemical, Shell, BASF, and Bayer, through a subsidiary. For a time, a peracetic acid process for propylene oxide was operated in Japan however, competitive sources of by-product acetic acid forced discontinuation of this process. 

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