Reaction dichloroethane production

Dichloroethane is produced by the vapor- (28) or Hquid-phase chlorination of ethylene. Most Hquid-phase processes use small amounts of ferric chloride as the catalyst. Other catalysts claimed in the patent Hterature include aluminum chloride, antimony pentachloride, and cupric chloride and an ammonium, alkaU, or alkaline-earth tetrachloroferrate (29). The chlorination is carried out at 40—50°C with 5% air or other free-radical inhibitors (30) added to prevent substitution chlorination of the product. Selectivities under these conditions are nearly stoichiometric to the desired product. The exothermic heat of reaction vapori2es the 1,2-dichloroethane product, which is purified by distillation. 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

Carbon tetrachloride and 1,2-dichloroethane are very reactive with aluminum. These normally uninhibited feed stock solvents should not contact any aluminum metal. Carbon tetrachloride can be inhibited against aluminum attack with the same types of stabilizers used with 1,1,1-Tri. 1,2-Dichloroeth-ane will react with magnesium give a Grignard reaction-type product. 

PhaP was dissolved in dichloromethane or 1,2-dichloroethane (1 5 v/v) and a solution of triphosgene (0.33 equiv.) in the same solvent was added dropwise whilst cooling to maintain the temperature at 20 °C. After completion of the addition, the reaction mixture was stirred until gas evolution ceased. A solution of the substrate (Table 4.50), containing triethylamine where necessary, was then added (or inverse addition by means of syringe or cannula, if required). Tkfter the reaction, the products were isolated by standard techniques. 

Consider vinyl chloride production (see Example 2.1). In the oxychlorination reaction step of the process, ethylene, hydrogen chloride, and oxygen are reacted to form dichloroethane ... 

Methyl-5-aminothia2ole-4-carboxylic acid is diazotized with isoamyl nitrite in the presence of furan in 1.2-dichloroethane to give a mixture of products 163 (53%), 164 (33%). 165 (11%), and 166 (3%) (Scheme 104) (334). This reactivity experiment was carried out to examine the possibility of the occurrence of 4,5-dehydrothiazole (hetaryne). Hetaryne intermediates seem not to be involved as an intermediate in the reaction. The formation of 163 through 166 can be rationalized in terms of the intermediacy of 166a. 

Methane, chlorine, and recycled chloromethanes are fed to a tubular reactor at a reactor temperature of 490—530°C to yield all four chlorinated methane derivatives (14). Similarly, chlorination of ethane produces ethyl chloride and higher chlorinated ethanes. The process is employed commercially to produce l,l,l-trichloroethane. l,l,l-Trichloroethane is also produced via chlorination of 1,1-dichloroethane with l,l,2-trichloroethane as a coproduct (15). Hexachlorocyclopentadiene is formed by a complex series of chlorination, cyclization, and dechlorination reactions. First, substitutive chlorination of pentanes is carried out by either photochemical or thermal methods to give a product with 6—7 atoms of chlorine per mole of pentane. The polychloropentane product mixed with excess chlorine is then passed through a porous bed of Fuller s earth or silica at 350—500°C to give hexachlorocyclopentadiene. Cyclopentadiene is another possible feedstock for the production of hexachlorocyclopentadiene. 

Addition Chlorination. Chlorination of olefins such as ethylene, by the addition of chlorine, is a commercially important process and can be carried out either as a catalytic vapor- or Hquid-phase process (16). The reaction is influenced by light, the walls of the reactor vessel, and inhibitors such as oxygen, and proceeds by a radical-chain mechanism. Ionic addition mechanisms can be maximized and accelerated by the use of a Lewis acid such as ferric chloride, aluminum chloride, antimony pentachloride, or cupric chloride. A typical commercial process for the preparation of 1,2-dichloroethane is the chlorination of ethylene at 40—50°C in the presence of ferric chloride (17). The introduction of 5% air to the chlorine feed prevents unwanted substitution chlorination of the 1,2-dichloroethane to generate by-product l,l,2-trichloroethane. The addition of chlorine to tetrachloroethylene using photochemical conditions has been investigated (18). This chlorination, which is strongly inhibited by oxygen, probably proceeds by a radical-chain mechanism as shown in equations 9—13. 

Typical reactions using either 1,2-dichloroethane or 1,2-dichloropropane to produce carbon tetrachloride and tetrachloroethylene by the chlorinolysis reaction are shown in equations 21—23. Continued removal of tetrachloroethylene and recycling of carbon tetrachloride can result in a net zero production of carbon tetrachloride. Most chemical producers using chlorinolysis for the production of perchloroethylene in the future will take advantage of the per/tet equiUbrium to maximize perchloroethylene to avoid carbon tetrachloride ipiod.uction.From 1,2-dichloroethane ... 

Oxychlorination. This is an important process for the production of 1,2-dichloroethane which is mainly produced as an intermediate for the production of vinyl chloride. The reaction consists of combining hydrogen chloride, ethylene, and oxygen (air) in the presence of a cupric chloride catalyst to produce 1,2-dichloroethane (eq. 24). The hydrogen chloride produced from thermal dehydrochlorination of 1,2-dichloroethane to produce vinyl chloride (eq. 25) is usually recycled back to the oxychlorination reactor. The oxychlorination process has been reviewed (31). 

Dichloroethane is produced commercially from hydrogen chloride and vinyl chloride at 20—55°C ia the presence of an aluminum, ferric, or 2iac chloride catalyst (8,9). Selectivity is nearly stoichiometric to 1,1-dichloroethane. Small amounts of 1,1,3-tfichlorobutane may be produced. Unreacted vinyl chloride and HCl exit the top of the reactor, and can be recycled or sent to vent recovery systems. The reactor product contains the Lewis acid catalyst and must be separated before distillation. Spent catalyst may be removed from the reaction mixture by contacting with a hydrocarbon or paraffin oil, which precipitates the metal chloride catalyst iato the oil (10). Other iaert Hquids such as sdoxanes and perfluorohydrocarbons have also been used (11). 

Dichloroethane is also one of the iatermediate products of high temperature thermal chlorination of ethane or ethyl chloride. In ethane chlorination, the reaction proceeds through ethyl chloride as an iatermediate (12). 1,1-Dichloroethane itself is usually an iatermediate ia the productioa of viayl chloride and of 1,1,1-tfichloroethane by thermal chlorination or photochlofination (13). 

The photolysis of chlorodiazirine was investigated in several cases. From chloromethyl-diazirine (232) vinyl chloride was formed as the stable primary product of stabilization of chloromethylcarbene, with acetylene and hydrogen chloride as secondary products. Some 1,1-dichloroethane was assumed to have been formed through a linear diazo compound by reaction with HCl. Added HBr yielded 1-bromo-l-chloroethane (76MI5Q800). 

The chemistry of side reactions and by-products may also offer opportunities for increasing the inherent safety of a process. For example, a process involving a caustic hydrolysis step uses ethylene dichloride (EDC 1,2-dichloroethane) as a solvent. Under the reaction conditions a side reaction between sodium hydroxide and EDC produces small but hazardous quantities of vinyl chloride ... 

Homogeneous reactions are those in which the reactants, products, and any catalysts used form one continuous phase (gaseous or liquid). Homogeneous gas phase reactors are almost always operated continuously, whereas liquid phase reactors may be batch or continuous. Tubular (pipeline) reactors arc normally used for homogeneous gas phase reactions (e.g., in the thermal cracking of petroleum of dichloroethane lo vinyl chloride). Both tubular and stirred tank reactors are used for homogeneous liquid phase reactions. 

An example of the efficient formation of an electron-deficient double bond by RCM was disclosed by a Japanese group in a novel total synthesis of the macrosphelides A (209) and B (208) (Scheme 41) [100]. When the PMB-pro-tected compound 204 was examined as a metathesis substrate, the ring closure did not proceed at all in dichloromethane using catalysts A or C. When the reaction was carried out using equimolar amounts of catalyst C in refluxing 1,2-dichloroethane, the cyclized product 205 was obtained in 65% yield after 5 days. On the other hand, the free allylic alcohol 206 reacted smoothly at room temperature leading to the desired macrocycle 207 in improved yield. 

An interesting, halogen-exchange reaction takes place when [Ni(Et2dtc)2] is refluxed in 1,2-dichloroethane with an excess of a,a -di-bromo-o-xylene and a-bromo-a -chloro-o-xylene. The products, a,a -... 

Whereas cycHzation of the cu-keto-co -hydroxyamide 1466 in boihng toluene or xylene in the presence of camphorsulfonic acid (CSA) results in decomposition of the starting material 1466, heating of 1466 with excess TMSOTf 20 and N-methyl-morphoHne in 1,2-dichloroethane affords 46% of the desired cycHzation product 1467 [30] (Scheme 9.16). The close relationship of product 1467 to d -oxazolines suggests that reaction of carboxylic acids 11 with free (or C-substituted) ethanola-mines 1468 and HMDS 2/TCS 14 might lead analogously, via the silylated intermediates 1469, to d -oxazolines 1470 and HMDSO 7. As demonstrated in the somewhat related cyclization of 1466 to 1467, combination of TMSOTf 20 with N-... 

Iron-catalyzed C(sp )-C(sp ) bond-forming cross-coupling reactions of alcohols with alkenes has been reported by Tu and coworkers in 2009 [109]. Reactions of primary alcohols with various alkenes in the presence of a catalytic amount of FeCls in 1,2-dichloroethane afford the desired secondary alcohols as the crosscoupling products in moderate to good yields (Scheme 33). Iron sources such as... 

In the production of dichloroethane (EDC) by oxyhydrochlorination of ethylene, the products from the reaction are quenched by direct contact with dilute HC1 in a quench tower. The gaseous stream from this quench tower is fed to a condenser and the uncondensed vapours recycled to the reactor. A typical composition for this stream is shown in the diagram below operating pressure 4 bar. Calculate the outlet stream compositions leaving the condenser. 

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