Chloride chlorinated hydrocarbons

Many chlorinated hydrocarbons react readily with aluminum in the so-caHed bleeding reaction. A red aluminum chloride—chlorinated hydrocarbon complex is formed. Storage of uninhibited chlorinated solvents in aluminum vessels results in corrosion in a short period of time. Proprietary organic inhibitors permit commercial use of reactive solvents such as 1,1,1-trichloroethane and trichloroethylene for cleaning of aluminum. 

Electrolytic chlorine from a steel bottle contains small amounts of oxygen, chlorine oxides, nitrogen, carbon monoxide, carbon dioxide, hydrogen chloride, chlorinated hydrocarbons, and moisture. For complete purification, chlorine washed with concentrated sulfuric acid is condensed into a receiver (preferably calibrated) cooled in ether/carbon dioxide, and a regular stream of chlorine is produced by placing the receiver in a bath of ice and water. A safety flask should be placed between the reaction flask and the chlorine supply. Chlorine bombs cool very considerably if chlorine is removed in a rapid stream they should, if that happens, never be warmed above 30°C (vapor pressure of Cl2 at 0° 3.76 atm, at +10° 5.14, at +20° 6.86, at +30° 8.97, and +40° 11.52 atm). 

The majority of the chlorine produced is used internally within the chemical industry for the manufacture of polyvinyl chloride, chlorinated hydrocarbons, propylene oxide, etc, (Table 3.1), Hence, it is common to find chlor-alkali plants as part of very large, integrated chemical complexes and the capacity of such plants may be 0,5 x 10 tons Ci2/yean On the other hand, concern about the transport and storage of liquid chlorine has led to a different trend towards smaller plants sited close to the user This is particularly attractive when there is an almost balanced requirement for both chlorine and sodium hydroxide, e.g. in pulp and paper mills (Table 3,1). A typical plant in this application may have a capacity of 10 ions Cl2/year, On an even smaller scale, the same concerns lead to a need for plants, for example, to provide Cl to prevent biological growth on... 

Hydrogen chloride - Inorganic acid gas Methanol - Primary alcohol Methyl chloride - Chlorinated hydrocarbon gas Nitrobenzene - Nitro-compound... 

In early designs, the reaction heat typically was removed by cooling water. Crude dichloroethane was withdrawn from the reactor as a liquid, acid-washed to remove ferric chloride, then neutralized with dilute caustic, and purified by distillation. The material used for separation of the ferric chloride can be recycled up to a point, but a purge must be done. This creates waste streams contaminated with chlorinated hydrocarbons which must be treated prior to disposal. 

Chlorine reacts with saturated hydrocarbons either by substitution or by addition to form chlorinated hydrocarbons and HCl. Thus methanol or methane is chlorinated to produce CH Cl, which can be further chlorinated to form methylene chloride, chloroform, and carbon tetrachloride. Reaction of CI2 with unsaturated hydrocarbons results in the destmction of the double or triple bond. This is a very important reaction during the production of ethylene dichloride, which is an intermediate in the manufacture of vinyl chloride ... 

CeUulose triacetate is insoluble in acetone, and other solvent systems are used for dry extmsion, such as chlorinated hydrocarbons (eg, methylene chloride), methyl acetate, acetic acid, dimethylformamide, and dimethyl sulfoxide. Methylene chloride containing 5—15% methanol or ethanol is most often employed. Concerns with the oral toxicity of methylene chloride have led to the recent termination of the only triacetate fiber preparation faciHty in the United States, although manufacture stiH exists elsewhere in the world (49). 

Hydrogen chloride is produced by the direct reaction of hydrogen and chlorine, by reaction of metal chlorides and acids, and as a by-product from many chemical manufacturing processes such as chlorinated hydrocarbons. 

Physical Properties. Thionyl chloride [7719-09-7], SOCI2, is a colorless fuming Hquid with a choking odor. Selected physical and thermodynamic properties are Hsted in Table 6. Thionyl chloride is miscible with many organic solvents including chlorinated hydrocarbons and aromatic hydrocarbons. It reacts quickly with water to form HCl and SO2. Thionyl chloride is stable at room temperature however, slight decomposition occurs just... 

In the chemical industry, titanium is used in heat-exchanger tubing for salt production, in the production of ethylene glycol, ethylene oxide, propylene oxide, and terephthaHc acid, and in industrial wastewater treatment. Titanium is used in environments of aqueous chloride salts, eg, ZnCl2, NH4CI, CaCl2, and MgCl2 chlorine gas chlorinated hydrocarbons and nitric acid. 

By-products from EDC pyrolysis typically include acetjiene, ethylene, methyl chloride, ethyl chloride, 1,3-butadiene, vinylacetylene, benzene, chloroprene, vinyUdene chloride, 1,1-dichloroethane, chloroform, carbon tetrachloride, 1,1,1-trichloroethane [71-55-6] and other chlorinated hydrocarbons (78). Most of these impurities remain with the unconverted EDC, and are subsequendy removed in EDC purification as light and heavy ends. The lightest compounds, ethylene and acetylene, are taken off with the HCl and end up in the oxychlorination reactor feed. The acetylene can be selectively hydrogenated to ethylene. The compounds that have boiling points near that of vinyl chloride, ie, methyl chloride and 1,3-butadiene, will codistiU with the vinyl chloride product. Chlorine or carbon tetrachloride addition to the pyrolysis reactor feed has been used to suppress methyl chloride formation, whereas 1,3-butadiene, which interferes with PVC polymerization, can be removed by treatment with chlorine or HCl, or by selective hydrogenation. 

Heated zirconium is readily chlorinated by ammonium chloride, molten stannous chloride, zinc chloride, and chlorinated hydrocarbons and the common chlorinating agents. It is slowly attacked by molten magnesium chloride in the absence of free magnesium, which is always present in the KroU process. 

Chlorination of various hydrocarbon feedstocks produces many usehil chlorinated solvents, intermediates, and chemical products. The chlorinated derivatives provide a primary method of upgrading the value of industrial chlorine. The principal chlorinated hydrocarbons produced industrially include chloromethane (methyl chloride), dichloromethane (methylene chloride), trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), chloroethene (vinyl chloride monomer, VCM), 1,1-dichloroethene (vinylidene chloride), 1,1,2-trichloroethene (trichloroethylene), 1,1,2,2-tetrachloroethene (perchloroethylene), mono- and dichloroben2enes, 1,1,1-trichloroethane (methyl chloroform), 1,1,2-trichloroethane, and 1,2-dichloroethane (ethylene dichloride [540-59-0], EDC). 

Acetjiene has found use as a feedstock for production of chlorinated solvents by reaction with hydrogen chloride or chlorine (6). However, because of safety concerns and the lower price of other feedstock hydrocarbons, very Htfle acetylene is used to produce chlorinated hydrocarbons in the United States (see Acetylene-derived chemicals). 

The most widely used method of analysis for methyl chloride is gas chromatography. A capillary column medium that does a very good job in separating most chlorinated hydrocarbons is methyl siUcone or methyl (5% phenyl) siUcone. The detector of choice is a flame ionisation detector. Typical molar response factors for the chlorinated methanes are methyl chloride, 2.05 methylene chloride, 2.2 chloroform, 2.8 carbon tetrachloride, 3.1, where methane is defined as having a molar response factor of 2.00. Most two-carbon chlorinated hydrocarbons have a molar response factor of about 1.0 on the same basis. 

Methylene chloride is one of the more stable of the chlorinated hydrocarbon solvents. Its initial thermal degradation temperature is 120°C in dry air (1). This temperature decreases as the moisture content increases. The reaction produces mainly HCl with trace amounts of phosgene. Decomposition under these conditions can be inhibited by the addition of small quantities (0.0001—1.0%) of phenoHc compounds, eg, phenol, hydroquinone, -cresol, resorcinol, thymol, and 1-naphthol (2). Stabilization may also be effected by the addition of small amounts of amines (3) or a mixture of nitromethane and 1,4-dioxane. The latter diminishes attack on aluminum and inhibits kon-catalyzed reactions of methylene chloride (4). The addition of small amounts of epoxides can also inhibit aluminum reactions catalyzed by iron (5). On prolonged contact with water, methylene chloride hydrolyzes very slowly, forming HCl as the primary product. On prolonged heating with water in a sealed vessel at 140—170°C, methylene chloride yields formaldehyde and hydrochloric acid as shown by the following equation (6). 

Hexachloroethane is formed in minor amounts in many industrial chlorination processes designed to produce lower chlorinated hydrocarbons, usually via a sequential chlorination step. Chlorination of tetrachloroethylene, in the presence of ferric chloride, at 100—140°C is one convenient method of preparing hexachloroethane (142). Oxychlorination of tetrachloroethylene, using a copper chloride catalyst (143) has also been used. Photochemical chlorination of tetrachloroethylene under pressure and below 60°C has been studied (144) and patented as a method of producing hexachloroethane (145), as has recovery of hexachloroethane from a mixture of other perchlorinated hydrocarbon derivatives via crystalH2ation in carbon tetrachloride. Chlorination of hexachlorobutadiene has also been used to produce hexachloroethane (146). 

Materials of Construction. GeneraHy, carbon steel is satisfactory as a material of construction when handling propylene, chlorine, HCl, and chlorinated hydrocarbons at low temperatures (below 100°C) in the absence of water. Nickel-based aHoys are chiefly used in the reaction area where resistance to chlorine and HCl at elevated temperatures is required (39). Elastomer-lined equipment, usuaHy PTFE or Kynar, is typicaHy used when water and HCl or chlorine are present together, such as adsorption of HCl in water, since corrosion of most metals is excessive. Stainless steels are to be avoided in locations exposed to inorganic chlorides, as stainless steels can be subject to chloride stress-corrosion cracking. Contact with aluminum should be avoided under aH circumstances because of potential undesirable reactivity problems. 

Chisso-Asahi Fertilizer Company, Ltd. This company utilizes thermoplastic resins, such as polyolefins, poly(vinyhdene chloride), and copolymers, as their coating materials. The coatings are dissolved in fast-drying chlorinated hydrocarbon solvents and are appHed to a variety of substrates including urea, diammonium phosphate [7783-28-0] potassium sulfate [7778-80-3], potassium chloride [7447-40-7], and ammonium nitrate/potassium sulfate-based N—P—K fertilizers. 

Catalyst Deactivation. Catalyst deactivation (45) by halogen degradation is a very difficult problem particularly for platinum (PGM) catalysts, which make up about 75% of the catalysts used for VOC destmction (10). The problem may weU He with the catalyst carrier or washcoat. Alumina, for example, a common washcoat, can react with a chlorinated hydrocarbon in a gas stream to form aluminum chloride which can then interact with the metal. Fluid-bed reactors have been used to offset catalyst deactivation but these are large and cosdy (45). 

Polyvinyl chloride Polyvinyl chloride (PVC) and chlorinated polyvinyl chloride (CPVC) pipe and tubing are available in sizes 12 in and smaller for PVC and 4 in and smaller for CPVC. They have excellent resistance at room temperature to salts, ammonium hydroxide, and sulfuric, nitric, acetic, and hydrochloric acid but may be damaged by ketones, aromatics, and some chlorinated hydrocarbons. 

Unplasticized polyvinyl chlorides (type I) have excellent resistance to oxidizing acids other than concentrated and to most nonoxidizing acids. Resistance is good to weak and strong alkahne materials. Resistance to chlorinated hydrocarbons is not good. Polyvinyhdene chloride, known as Saran, has good resistance to chlorinated hydrocarbons. 

Much later (Marcinkowsky and Berty 1973) it was proven that ethane did indeed have an effect. In the study of the inhibitor action of chlorinated hydrocarbons it was discovered that these compounds chlorinate the silver catalyst and ethane removes the chlorine from the catalyst by forming ethyl chloride. Since the inhibitor was in the 10 ppm range and similar quantities were used from the ethane present in about one volume percent, the small difference could not be calculated from material balance. The effect of ethane was only noticed as significant by the statistics, which justifies the statement made by Aris (1966) that, The need for sophistications should not be rejected unsophisticatedly. ... 

Absorption of pollutant gases is accomplished by using a selective liquid in a wet scrubber, packed tower, or bubble tower. Pollutant gases commonly controlled by absorption include sulfur dioxide, hydrogen sulfide, hydrogen chloride, chlorine, ammonia, oxides of nitrogen, and low-boiling hydrocarbons. 

Chlorine and chlorides G SPA Chlorinated hydrocarbons Chloralkali Paper and pulp processing Petrochemicals Metal extraction and refining... 

Chlorinated organics are hydrocarbons that have one or many chlorine atoms. Oxidation of chlorinated hydrocarbons yields COj, water vapor and hydrogen chloride (HCl) gas. Some typical chlorinated organics are TCE and PCE. These organics have calorific values as low as 5,000 BTU/lb. 

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