Chlorohydrins propylene -chlorohydrin

Propylene Chlorohydrin. Propylene chlorohydrin is synthesized with the aim of producing propylene oxide. Although the latter is manufactured commercially mainly by the direct oxidation of propylene, the chlorohydrination process is still in limited use. 

I.2. Propylene Chlorohydrin. Propylene chlorohydrin is one of the most important intermediates used in the production of PO, which is a raw material for producing propylene glycols and urethane polyether polyols. The United States and Western Europe are the largest producers of propylene chlorohydrin, accounting for 74% of the world s production. The main environmental issues relate to the chlorinated waste generated in the process and the disposal of the byproduct calcium chloride sludge. The formation of... 

CH3 CH0H CH20H, a colourless, almost odourless liquid. It has a sweet taste, but is more acrid than ethylene glycol b.p. 187. Manufactured by heating propylene chlorohydrin with a solution of NaHCO under pressure. It closely resembles dihydroxyethane in its properties, but is less toxic. Forms mono-and di-esters and ethers. Used as an anti-freeze and in the preparation of perfumes and flavouring extracts, as a solvent and in... 

Propylene oxide [75-56-9] is manufactured by either the chlorohydrin process or the peroxidation (coproduct) process. In the chlorohydrin process, chlorine, propylene, and water are combined to make propylene chlorohydrin, which then reacts with inorganic base to yield the oxide. The peroxidation process converts either isobutane or ethylbenzene direcdy to an alkyl hydroperoxide which then reacts with propylene to make propylene oxide, and /-butyl alcohol or methylbenzyl alcohol, respectively. Table 1 Hsts producers of propylene glycols in the United States. 

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). 

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. 

The chlorohydrin process involves reaction of propylene and chlorine in the presence of water to produce the two isomers of propylene chlorohydrin. This is followed by dehydrochlorination using caustic or lime to propylene oxide and salt. The Dow Chemical Company is the only practitioner of the chlorohydrin process in North America. However, several companies practice the chlorohydrin process at more than 20 locations in Germany, Italy, Bra2il, Japan, Eastern Europe, and Asia. 

Process flow sheets and process descriptions given herein are estimates of the various commercial processes. There are also several potential commercial processes, including variations on the chlorohydrin process, variations on the hydroperoxide process, and direct oxidation of propylene. 

Chlorohydrination. The mechanism for the formation of propylene chlorohydrin is generally beheved to be through the chloronium ion intermediate (109,112). 

The chloronium ion intermediate can react with water to produce the desired propylene chlorohydrin, with chloride ion to produce 1,2-dichloropropane, or with propylene chlorohydrin to produce isomers of dichloro-dipropyl ether. 

The l-chloro-2-propanol isomer represents about 85% of the chlorohydrin produced. In order to minimise the formation of dichlotide coproduct and ether, the reactant compositions are chosen such that the effluent Hquid contains 4—5 wt % propylene chlorohydrin. Under these conditions, the yield of chlorohydrin, dichloride, and ether from the reactants is reported to be 87—90, 6—9, and 2%, respectively (109,110,112). 

In two proposed alternative processes, the chlorine is replaced in the hypochlorination reaction by hypochlorous acid [7790-92-3] HOCl, or tert-huty hypochlorite. In the first, a concentrated (>10% by weight) aqueous solution of hypochlorous acid, substantially free of chloride, chlorate, and alkah metal ions, is contacted with propylene to produce propylene chlorohydrin (113). The likely mechanism of reaction is the same as that for chlorine, as chlorine is generated in situ through the equiUbrium of chlorine and hypochlorous acid (109). 

In the second proposed alternative process, tert-huty hypochlorite, formed from the reaction of chlorine and tert-huty alcohol, reacts with propylene and water to produce the chlorohydrin. The alcohol is a coproduct and is recycled to generate the hypochlorite (114—116). No commercialisation of the hypochlorous acid and tert-huty hypochlorite processes for chlorohydrin production is known. 

Epoxid tion. Epoxidation, also referred to as saponification or dehydrochlorination, of propylene chlorohydrin (both isomers) to propylene oxide is accompHshed using a base, usually aqueous sodium hydroxide or calcium hydroxide. 

Production of propylene oxide in the United States in 1993 was estimated at 1,240,000 metric tons, and as having a 10-yr average aimual growth rate of 3.9% (229). Projections were for continued growth at about 4%/yr. Producers include Dow Chemical s chlorohydrin plants in Ereeport, Texas, and Plaquemine, Louisiana, and ARCO Chemical s hydroperoxide plants in Bayport and Chaimelview, Texas. Texaco started up a 180,000-t/yr plant in Port... 

Butylene Oxide. Butylene oxides are prepared on a small scale by Dow by chlorohydrin technology. There appears to be no technical reason why they could not be prepared by the propylene oxide Oxirane process (see Chlorohydrins). 

Hypochlorous acid undergoes a variety of reactions with organic substances including addition, oxidation, C- and iV-chlorination, and ester formation. On an industrial scale, hypochlorous acid, generated m situ via chlorine hydrolysis, reacts with propylene forming primarily the a-propjlene chlorohydrin isomer. 

Table 2 gives physical property data for propylene chlorohydrins. 2-Chloro-l-propanol [78-89-7] HOCH2CHCICH2, is also named 2-propylene chlorohydrin, 2-chloropropyl alcohol, or 2-chloro-l-hydroxypropane. l-Chloro-2-propanol [127-00-4] CICH2CHOHCH2, also known as j -propjlene chlorohydrin, 1-chloroisopropyl alcohol, and l-chloro-2-hydroxypropane, is a colorless Hquid, miscible in water, ethanol, and ethyl ether. 

Dehydrochlorination to Epoxides. The most useful chemical reaction of chlorohydrins is dehydrochlotination to form epoxides (oxkanes). This reaction was first described by Wurtz in 1859 (12) in which ethylene chlorohydria and propylene chlorohydria were treated with aqueous potassium hydroxide [1310-58-3] to form ethylene oxide and propylene oxide, respectively. For many years both of these epoxides were produced industrially by the dehydrochlotination reaction. In the past 40 years, the ethylene oxide process based on chlorohydria has been replaced by the dkect oxidation of ethylene over silver catalysts. However, such epoxides as propylene oxide (qv) and epichl orohydrin are stiU manufactured by processes that involve chlorohydria intermediates. 

Hydrolysis to Glycols. Ethylene chlorohydrin and propylene chlorohydrin may be hydrolyzed ia the presence of such bases as alkaU metal bicarbonates sodium hydroxide, and sodium carbonate (31—33). In water at 97°C, l-chloro-2-propanol forms acid, acetone, and propylene glycol [57-55-6] simultaneously the kinetics of production are first order ia each case, and the specific rate constants are nearly equal. The relative rates of solvolysis of... 

Formation of Cyclic Carbonates. In the absence of water, chlorohydrins such as 2-chloroethanol and l-chloro-2-propanol react with an alkah carbonate or bicarbonate to produce cycHc carbonates such as ethylene carbonate [96-49-1] and propylene carbonate [108-32-7] ia yields of up to 80%... 

For many years ethylene chlorohydrin was manufactured on a large iadustrial scale as a precursor to ethylene oxide, but this process has been almost completely displaced by the direct oxidation of ethylene to ethylene oxide over silver catalysts. However, siace other commercially important epoxides such as propylene oxide and epichlorohydrin cannot be made by direct oxidation of the parent olefin, chlorohydrin iatermediates are stiU important ia the manufacture of these products. 

Commercial chlorohydrin reactors are usually towers provided with a chlorine distributor plate at the bottom, an olefin distributor plate about half way up, a recirculation pipe to allow the chlorohydrin solution to be recycled from the top to the bottom of the tower, a water feed iato the recirculation pipe, an overflow pipe for the product solution, and an effluent gas takeoff (46). The propylene and chlorine feeds are controlled so that no free gaseous chlorine remains at the poiat where the propylene enters the tower. The gas lift effect of the feeds provides the energy for the recirculation of the reaction solution from the top of the tower. 

Fig. 2. Diagram of a typical chlorohydrin reactor for manufacture of propylene oxide. M.O.L. = milk of lime. To convert kPa to mm Hg, multiply by 7.5.

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. 

Ghlorohydrination with Nonaqueous Hypochlorous Acid. Because the presence of chloride ions has been shown to promote the formation of the dichloro by-product, it is desirable to perform the chlorohydrination in the absence of chloride ion. For this reason, methods have been reported to produce hypochlorous acid solutions free of chloride ions. A patented method (48) involves the extraction of hypochlorous acid with solvents such as methyl ethyl ketone [78-93-3J, acetonitrile, and ethyl acetate [141-78-6J. In one example hypochlorous acid was extracted from an aqueous brine with methyl ethyl ketone in a 98.9% yield based on the chlorine used. However, when propylene reacted with a 1 Af solution of hypochlorous acid in either methyl ethyl ketone or ethyl acetate, chlorohydrin yields of only 60—70% were obtained (10). 

Ghlorohydrination with er -All l Hypohalites. Olefins react with ethyl hypochlorite [624-85-1] to form the corresponding chlorohydrin (49). In 1938 both Shell Development Co. (50) and Arthur D. Litde, Inc. (51) patented the preparation of chlorohydrins by the reactions of olefins with tertiary alkyl hypochlorites. Examples with ethylene and propylene in the Shell patent reported chlorohydrin yields of greater than 95% with tert-huty hypochlorite [507-40-4]. 

Almost 40 years later the Lummus Co. patented an integrated process involving the addition of chlorine along with the sodium chloride and sodium hydroxide from the cathode side of an electrolytic cell to a tertiary alcohol such as tertiary butanol to produce the tertiary alkyl hypochlorite. The hypochlorite phase separates, and the aqueous brine solution is returned to the electrolytic cells. The alkyl hypochlorite reacts with an olefin in the presence of water to produce a chlorohydrin and the tertiary alcohol, which is returned to the chlorinator. With propylene, a selectivity to the chlorohydrin of better than 96% is reported (52). A series of other patents covering this technology appeared during the 1980s (53—56). 

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). 

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