Allyl chloride, manufacture

MCA SD-99, 1973) HCS1980, 125 RSC Lab. Hazards Data Sheet No. 28, 1984 Piccinini, N. et al., Plant/Operations Progr., 1982, 1, 69-74 An operability analysis to identify potential risks in an allyl chloride manufacturing plant has been published. 

An operability analysis to identify potential risks in an allyl chloride manufacturing plant has been published. 

To illustrate the use of the algorithm, a case of allyl chloride manufacturing was used. Allyl chloride is manufactured by means of non-catalytic chlorination of propylene. Consider the following reaction system. 

Table 6-9. Calculated Heats of Reactions, Allyl Chloride Manufacture...

Fpichlorohydrin (chloromethyloxirane), which has a production capacity ia the United States of 291,000 t/yr, is manufactured by the chi orohydrin a tion of allyl chloride and subsequent dehydrochloriaation of the glycerol dichi orohydrin isomers (69). Dow and Shell Chemical are the two producers of epichlorohydrin ia the United States. 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

The chlorhydrin route is also used in the manufacture of epichlorohydrin from allyl chloride (187) ... 

According to the 1981-83 National Occupational Exposure Survey (NOES, 1997), approximately 3000 workers in the United States were potentially exposed to allyl chloride (see General Remarks). Occupational exposure to allyl chloride may occur in its manufacture and in the production of epichlorohydrin, glycerol and a wide range of other chemical products. 

Allyl Chloride. The manufacture of allyl chloride, commercialized in 1945, was the first of several modem high-temperature chlorination technologies applied for hydrocarbons. Preheated dry propylene mixed with dry chlorine in a ratio of 4 1 is reacted at 500-510°C to produce allyl chloride.193-195 Chlorine reacts quantitatively in a few seconds. The main byproducts are isomeric monochloropropenes and dichloropropenes. Allyl chloride is used mainly in the manufacture of allyl alcohol and glycerol via epichlorohydrin. 

There are four processes for industrial production of allyl alcohol. One is alkaline hydrolysis of allyl chloride. A second process has two steps. The first step is oxidation of propylene to acrolein and the second step is reduction of acrolein to allyl alcohol by a hydrogen transfer reaction, using isopropyl alcohol. At present, neither of these two processes is being used industrially. Another process is isomerization of propylene oxide. Until 1984. all allyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced allyl alcohol industrially by a new process which they developed- This process, which was developed partly for the purpose of producing epichlorohydrin via allyl alcohol as the intermediate, has the potential to be the main process for production of allyl alcohol. The reaction scheme is as follows ... 

Some radical reactions are used industrially on a large scale including radical-induced polymerisations but these are beyond the scope of this book. A few simple molecules are also made this way including the diene 29 needed for the manufacture of pyrethroid insecticides. As the molecule is symmetrical, disconnection in the middle gives two identical halves providing we make them radicals and not cations or anions. The reaction is carried out at ICI by mixing butene 31 and the allylic chloride 32 at very high temperature.7... 

The two chlorinated propene compounds shown are colorless liquids with pungent, irritating odors. Allyl chloride is an intermediate in the manufacture of allyl alcohol and other allyl compounds, including pharmaceuticals, insecticides, and thermosetting varnish and plastic resins. Dichloropropene compounds have been used as soil fumigants, as well as solvents for oil, fat, dry cleaning, and metal degreasing. 

Recently Ru3(CO)12 has been reported to be an effective catalyst for hydrosilylation of 1-octene [10] and of allyl chloride (Eq. 3) [11] by triethoxysilane.The latter process is of great importance for production of the main intermediate in manufacturing silane coupling agents. 

The key reaction in this manufacturing process is the hot chlorination of propylene, which fairly selectively gives substitution to methyl group rather than the addition to the double bond. In this chlorination step, fresh propylene is first mixed with recycle propylene. This mixture is dried over a desiccant, heated to 650-700°F, and then mixed with chlorine (C3H6 to Cl2 ratio is 4 1) and fed to a simple steel tube adiabatic reactor. The effluent gases (950°F) are cooled quickly to 120°F and fractionated. The yield of allyl chloride is 80-85 percent. 

Derivation (1) By-product of soap manufacture (2) from propylene and chlorine to form allyl chloride, which is converted to the dichlorohydrin with hypo-chlorous acid this is then saponified to glycerol with caustic solution (3) isomerization of propylene oxide to allyl alcohol, which is reacted with peracetic acid, (the resulting glycidol is hydrolyzed to glycerol) (4) hydrogenation of carbohydrates with nickel catalyst (5) from acrolein and hydrogen peroxide. 

Epichlorohydrin or chloromethyloxirane is manufactured from allyl chloride, and, in 2006, had a merchant price of US 1.66 kg [4]. It is used as a building block in the manufacture of plastics, epoxy resins, phenoxy resins, and other polymers, and as a solvent for cellulose, resins, and paints, and has also found use as an insect fumigant. Epoxy resins (aryl glycidyl ethers) are manufactured successfully in large scale (1.2 x 10 metric tons in 2000) [26] and are widely used in a variety of industrial and commercial applications [27]. These are made by addition reactions of epichlorohydrins or by epoxidation of allyl ethers or esters (Table 1.1). Epichlorohydrin can be reacted with an alkali nitrate to produce glycidyl nitrate, an energetic binder used in explosive and propellant compositions. 

Commercial Scale Manufacture of Allyl Chloride and Allyl Alcohol from Propylene. 

The use of organic halogen compounds as the starting products for the synthesis of other organic chemicals is too immense a field to do more than indicate some of the commercial applications. In his book I4S) on the chemistry of petroleum derivatives, Ellis includes a chapter on the production of alcohols and esters from alkyl halides, and also one on miscellaneous reactions of halo-paraffins and cycloparaffins. The manufacture of amyl alcohols and related products from the chlorides has been well covered 14 ) 1 )-A two-step process for the synthesis of cyclopropane by chlorinating propane from natural gas and dechlorinating with zinc dust was devised in 1936 152). A critical review of syntheses from l,3-dichloro-2-butene was published in Russia in 1950 (1-54). The products obtainable from the allylic chlorides are covered in a number of articles 14If 14 157). 

AUyl Chloride High-temperature Chlorination of Propylene Allyl chloride is manufactured by the noncatalytic chlorination of propylene... 

Thermochemistry of AUyl Chloride Manufacture. The calculated heats of reaction of allyl chloride and by-products of reaction are shown below in Table 6-9,... 

Epichlorohydrin (l-chloro-2,3-epoxy propane), is obtained by the chlorination of propylene, followed by the reaction of allyl chloride with hypochlo-rous acid. The resultant product is treated with Ca(OH)2 and is a colourless liquid with a density of 1.18 g cm mp -57°C and bp 115°C. It is a colorless liquid with a pungent garlic-like odour, moderately soluble in water but miscible with most polar organic solvents. Its principal use is as a reactant in the manufacture of diglycedyl ether-based epoxy resin. 

A common problem in the manufacture of fine chemicals is that a substrate may have more than one reactive site. A well known, but intractable, problem is the nitration of monosubstituted benzenes, which always leads to a mixture of isomers. Reactions which involve nucleophilic substitution are more amenable to control of regioselectivity by choice of solvent. An excellent review on the reactivity of ambident anions is available, in which this subject is treated [17]. An instructive example is the alkylation of phenol with allyl chloride [18] (equation 12.10). Table 12.13 shows how the properties of O- and C-alkylation are affected by solvent. 

Glycerol is the polyhydric alcohol most widely used for the preparation of alkyd resins and is obtained both synthetically and as a by-product in the manufacture of soap. The principal methods for the synthesis of glycerol are based on either the chlorination or oxidation of propylene. In the former methods, the first step is the hot chlorination of propylene to give allyl chloride ... 

A selected list of reactivity ratios for vinyl chloride with a number of comonomers are given in Table IV. The copolymerization ratios of 1-chloro-l-propene and 2-chloro-l-propene are of interest. These isomers of allyl chloride, strangely enough, seem to be impurities formed in the manufacture of vinyl chloride by some processes. These compounds could find application in the reduction of the cost of poly(vinyl chloride), if they were copolymerized with vinyl chloride. Also to be noted is that the... 

Mth this in mind, a new (grassroots) production facility to produce commercial-grade allyl chloride is being investigated. This facility would most likely be situated in La Nueva Cantina, Mexico, close to our petrochemical facility, which would be able to supply propylene. The supply of chlorine from local manufacturers will also be plentiful. Your group has been given the task of doing a process estimate for this new facility. 

Glycerin by the Epichlorohydrin Process. In the epichlorohydin process, synthetic glycerin is produced in three successive operations, the end products of which are allyl chloride, epichlorohydrin, and finished glycerin, respectively. A portion of the allyl chloride is used to manufacture allyl alcohol, and a portion of the epichlorohydrin is used in the manufacture of epoxy resins. 

Allyl Acetate. Industrial production of aHyl acetate started only rather recendy. Nevertheless, among the aHyl compounds, its production is second to that of aHyl chloride. It is produced mostiy for manufacturing aHyl alcohol and its manufacture by acetoxylation of propylene has been described previously. The aHyl acetate obtained may be separated and purified by distillation. 

From Allyl Alcohol. An alternative route to dichlorohydrias from aHyl chloride begias with the hydrolysis to aHyl alcohol. Significant yields of 2,3-dichloropropanol can be obtained from the reaction of chlorine with allyl alcohol if the reaction is performed ia the presence of concentrated hydrochloric acid (65). Several patents for the manufacture of 2,3-dichloropropanol by the chlorination of allyl alcohol at low temperature, —30° to +20° C, ia 25—40% HCl solution have appeared (66—68). Product yields as high as 98% are claimed. 

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