Chlorine processing

Shell Chlorine Process. The Shell process produces CI2 from the HCl usiag air or O2 ia the preseace of cupric and other chlorides on a siUcate carrier (71). The reaction proceeds at an optimal rate ia the temperature range of 430—475°C at an efficiency of 60—70%. A manufactuting unit was built by Shell ia the Netherlands (41,000 t/yr) and another ia ladia (27,000 t/yr). Both plants have been closed down. 

Treatment of impure gold is largely via the Miller process (30) in which chlorine is bubbled through the molten metal and converts the base metals to chlorides, which volatilise. Silver is converted to the chloride, which is molten and can be poured. The remaining gold is less pure (99.6%) than that produced by the WohlwiU process and may require additional treatment such as electrolysis. If platinum-group metals (qv) are present, the chlorine process is unsuitable. 

Over 90% of the HCl produced ia the United States origiaates as a coproduct from various chlorination processes direct generation of HCl from and CI2 accounts for only about 8% of the total production. Table 11 describes the production contribution of HCl from significant sources through the period 1980 to 1992 (72). Figure 6 illustrates the historical production growth of HCl ia the United States (73). The growth rate, about 5—6% from 1955 to 1975, slowed to - 1% because of disparity between supply and demand (see Table 12). The production capacity ia 1993 was about 2.92 million metric tons, down 9.6% from the 1992 production of 3.24 million metric tons (74). 

Another solvent extraction scheme uses the mixed anhydrous chlorides from a chlorination process as the feed (28). The chlorides, which are mostly of niobium, tantalum, and iron, are dissolved in an organic phase and are extracted with 12 Ai hydrochloric acid. The best separation occurs from a mixture of MIBK and diisobutyl ketone (DIBK). The tantalum transfers to the hydrochloric acid leaving the niobium and iron, the DIBK enhancing the separation factor in the organic phase. Niobium and iron are stripped with hot 14—20 wt % H2SO4 which is boiled to precipitate niobic acid, leaving the iron in solution. 

The process involving aHyl alcohol has not been iadustriaHy adopted because of the high production cost of this alcohol However, if the aHyl alcohol production cost can be markedly reduced, and also if the evaluated cost of hydrogen chloride, which is obtained as a by-product from the substitutive chlorination reaction, is cheap, then this process would have commercial potential. The high temperature propylene—chlorination process was started by SheH Chemical Corporation ia 1945 as an iadustrial process (1). The reaction conditions are a temperature of 500°C, residence time 2—3 s, pressure 1.5 MPa (218 psi), and an excess of propylene to chlorine. The yield of aHyl chloride is 75—80% and the main by-product is dichloropropane, which is obtained as a result of addition of chlorine. Other by-products iaclude monochioropropenes, dichloropropenes, 1,5-hexadiene. At low temperatures, the amount of... 

The chlorination process, introduced in Europe in 1843, roasted ore with chlorides, followed by a hot brine leach and subsequent precipitation of the silver on copper. In 1887 it was discovered that gold and silver can be recovered by sodium cyanide, and this process displaced the dangerous chlorination process. By 1907 the cyanide process, where a cyanide solution is mixed with 2inc dust to precipitate the silver, was universally in use. 

A chlorination process (20,21,44—46) converts sucrose into sucralose [56038-13-2] (4,l, 6 -trichloro-4,l, 6 -trideoxy-galactosucrose), a heat-stable, noncariogenic, noncaloric, high intensity sweetener. Sucralose is approved for food use in Canada, Australia, and Russia. It is not yet approved for use in the United States. 

Manufacture. Titanium chloride is manufactured by the chlorination of titanium compounds (1,134—138). The feedstocks usually used are mineral or synthetic mtile, beneficiated ilmenite, and leucoxenes. Because these are all oxygen-containing, it is necessary to add carbon as well as coke from either coal or fuel oil during chlorination to act as a reducing agent. The reaction is normally carried out as a continuous process in a fluid-bed reactor (139). The bed consists of a mixture of the feedstock and coke. These are fluidized by a stream of chlorine iatroduced at the base (see Fluidization). The amount of heat generated in the chlorination process depends on the relative proportions of CO2 or CO that are formed (eqs. 1 and 2), and the mechanism that... 

Fabric preparation is often considered to be the most important stage to obtain good color yields, levelness, and brightness on wool fabric (104). This is done almost exclusively by an oxidative chlorination process, the most popular commercial methods using either a batch treatment with dichloroisocyanuric acid (DCCA), or a continuous fabric treatment with gaseous chlorine, called the Kroy process. 

Removal of metal chlorides from the bottoms of the Hquid-phase ethylene chlorination process has been studied (43). A detailed summary of production methods, emissions, emission controls, costs, and impacts of the control measures has been made (44). Residues from this process can also be recovered by evaporation, decomposition at high temperatures, and distillation (45). A review of the by-products produced in the different manufacturing processes has also been performed (46). Several processes have been developed to limit ethylene losses in the inerts purge from an oxychlorination reactor (47,48). 

Hexachloroethane [67-72-17, perchloroethane, CCl CCl, is a white crystalline soHd with a camphorlike odor. Hexachloroethane is nonflammable and has a number of minor industrial uses which are limited because of its toxic nature. Crystalline hexachloroethane is a minor product in many industrial chlorination processes of saturated and unsaturated hydrocarbons. 

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). 

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. 

Refining and Isomerization. Whatever chlorination process is used, the cmde product is separated by distillation. In successive steps, residual butadiene is stripped for recycle, impurities boiling between butadiene (—5° C) and 3,4-dichloto-l-butene [760-23-6] (123°C) are separated and discarded, the 3,4 isomer is produced, and 1,4 isomers (140—150°C) are separated from higher boiling by-products. Distillation is typically carried out continuously at reduced pressure in corrosion-resistant columns. Ferrous materials are avoided because of catalytic effects of dissolved metal as well as unacceptable corrosion rates. Nickel is satisfactory as long as the process streams are kept extremely dry. 

The first patent on the chlorination of polyethylene was taken out by ICI in 1938. In the 1940s scientists of that company carried out extensive studies on the chlorination process. The introduction of chlorine atoms onto the polyethylene backbone reduces the ability of the polymer to crystallise and the material becomes rubbery at a chlorine level of about 20%, providing the distribution of the chlorine is random. An increase in the chlorine level beyond this point, and indeed from zero chlorination, causes an increase in the Tg so that at a chlorine level of about 45% the polymer becomes stiff at room temperature. With a further increase still, the polymer becomes brittle. 

There are three basic terms used in the chlorination process chlorine demand, chlorine dosage and chlorine residual. Chlorine demand is the amount of chlorine which will reduced or consumed in the process of oxidizing impurities in the water. Chlorine dosage is the amount of chlorine fed into the water. Chlorine residual is the amount of chlorine still remaining in water after oxidation takes place. For example, if a water has 2.0 ppm chlorine demand and is fed into the water in a chlorine dosage of 5.0 ppm, the chlorine residual would be 3.0 ppm. 

THMs are a byproduct of the chlorination process that most public drinking water systems use for disinfection. Chloroform is the primary THM of concern. EPA does not allow public systems to have more than 100 parts per billion (ppb) of THMs in their treated water. Some municipal systems have had difficulty in meeting this standard. 

The composition of this alloy (54% nickel, 15% molybdenum, 15% chromium, 5% tungsten and 5% iron) is less susceptible to intergranular corrosion at welds. The presence of chromium in this alloy gives it better resistance to oxidizing conditions than the nickel/molybdenum alloy, particularly for durability in wet chlorine and concentrated hypochlorite solutions, and has many applications in chlorination processes. In cases in which hydrochloric and sulfuric acid solutions contain oxidizing agents such as ferric and cupric ions, it is better to use the nickel/molybdenum/ chromium alloy than the nickel/molybdenum alloy. 

Continuous chlorination processes permit the removal of mono-chlorohenzene as it is formed, resulting in lower yields of higher chlorinated benzene. 

Ni-Cr-Mo Ni-Mo Ni-Cu Chlorination processes Processes involving HCl and nonoxidising acidic chlorides Production and Distillation columns containing acidic chlorides HF alkylation Fluorination Applications where no pitting and no loss of reflectivity are necessary Valves, Bleaching operations Handling Pickling of... 

Two types of chlorination processes are used for the different kinds of raw material. The first process is a reductive process by which oxide-type raw materials in the form of ores or concentrates are chlorinated. The essence of this process is the interaction with chlorine gas in the presence of coal or other related material. 

The performance of different types of chlorination processes is discussed comprehensively in overview [31]. It should be mentioned that carbon tetrachloride can also be applied successfully in the chlorination of rare refractory metal oxides, including tantalum oxide. 

Phenanthridine (74) was converted by NBS into the 2-bromo derivative (40%) (55JA6379), but the bromine-sulfuric acid-silver sulfate reagent gave low yields of 1-, 4-, and 10-bromophenanthridines in the ratio (1 6.4 9.5), a reactivity order which contrasts with that found in nitration (1 > 10 > 4 > 2) (69AJC1105). Phosphoryl chloride converted phenanthridine 5-oxide into the 6-chloro derivative, but when that position was blocked by a phenyl substituent, the reductive chlorination process gave a 2-chloro compound (84MI2). 

The bleaching process, in contrast, poses major difficulties. Traditional paper bleaching uses chlorine gas, which is reduced to chloride anions, cr, as it oxidizes the colored pigments in wood pulp. The chloride anion is not a pollutant, as it is a major species in the oceans. Unfortunately, chlorine processing also generates small quantities of chlorine-containing dioxins such as 2,3,7,8-tetrachloro-dibenzo-p-dioxin, whose stmcture (below) appears less formidable than its name ... 

Trichloroethylene is currently produced in the United States using ethylene dichloride (a produet of ethylene and chlorine feedstocks) (EPA 1985e). PPG Industries uses a single-step oxychlorination proeess, which yields triehloroethylene and tetraehloroethylene. In the PPG proeess, ethylene dichloride is reaeted with chlorine and/or hydrogen chloride and oxygen to form the triehloroethylene and tetraehloroethylene. DOW Chemical produces trichloroethylene by a direct chlorination process, in which ethylene dichloride is reacted with chlorine to form trichloroethylene and tetraehloroethylene. 

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