Calcium chloride, direct oxide

Ethylene oxide has been produced commercially by two basic routes the ethylene chlorohydrin and direct oxidation processes. The chlorohydrin process was first iatroduced dufing World War I ia Germany by Badische Anilin-und Soda-Eabfik (BASE) and others (95). The process iavolves the reaction of ethylene with hypochlorous acid followed by dehydrochlofination of the resulting chlorohydrin with lime to produce ethylene oxide and calcium chloride. Union Carbide Corp. was the first to commercialize this process ia the United States ia 1925. The chlorohydrin process is not economically competitive, and was quickly replaced by the direct oxidation process as the dominant technology. At the present time, all the ethylene oxide production ia the world is achieved by the direct oxidation process. 

Plutonium metal is prepared by two methods--direct reduction of the oxide by calcium (DOR)U,2J, and reduction of PuF by calcium in our metal preparation line (MPL)(3) (see Figure 1). In the DOR process, the plutonium contenF of the reduction slag is so low that the slag can be sent to retrievable storage without further processing. Metal buttons that are produced are no purer than the oxide feed and/or the calcium chloride salt. Los Alamos purifies the buttons by electrorefin-ing(4i,5 ), yielding metal rings that are > 99.96 percent plutonium. 

Direct Oxide Reduction. In DOR, calcium chloride is used as a solvent to dissolve the calcium oxide in the reaction ... 

The next major raw material for which we discuss the derived chemicals is calcium carbonate, common limestone. It is the source of some carbon dioxide, but, more importantly, it is used to make lime (calcium oxide) and slaked lime (calcium hydroxide). Limestone, together with salt and ammonia, are the ingredients for the Solvay manufacture of sodium carbonate, soda ash. Soda ash is also mined directly from trona ore. The Solvay process manufactures calcium chloride as an important by-product. Soda ash in turn is combined with sand to produce sodium silicates to complete the chemicals in the top 50 that are derived from limestone. Since lime is the highest-ranking derivative of limestone in terms of total amount produced, we discuss it first. Refer to Fig. 2.1, Chapter 2, Section 1, for a diagram of limestone derivatives. 

First prepare a pure solution of calcium chloride by following the directions for the preparation of calcium nitrate in Exercise 7 but substituting hydrochloric acid for nitric acid and using 100 g. of marble. Do not add the excess of acid at the end of the operation but leave the solution strongly alkaline. It is also well to add about 10 cc. of bromine water to the acid solution while boiling it and before the addition of the slaked lime. This is to oxidize any ferrous salts that may be present. 

In tonnage production, acetaldehyde may be manufactured by (1) the direct oxidation of ethylene, requiring a catalytic solution of copper chloride plus small quantities of palladium chloride, (2) the oxidation of ethyl alcohol with sodium dichromate, and (3) the dry distillation of calcium acetate with calcium formate. 

The same differential behavior can be observed with amine nucleophiles. For example, calcium triflate promotes the aminolysis of propene oxide 84 with benzylamine to give 1-(A -benzyl)amino-2-propanol 85, the result of attack at the less substituted site <03T2435>, and which is also seen in the solventless reaction of epoxides with heterocyclic amines under the catalysis of ytterbium(III) triflate <03SC2989>. Conversely, zinc chloride directs the attack of aniline on styrene oxide 34 at the more substituted carbon center <03TL6026>. A ruthenium catalyst in the presence of tin chloride also results in an SNl-type substitution behavior with aniline derivatives (e.g., 88), but further provides for subsequent cyclization of the intermediate amino alcohol, thus representing an interesting synthesis of 2-substituted indoles (e.g., 89) <03TL2975>. 

Chloro ketones have been prepared by direct chlorination " or by the action of sulfuryl chloride. Cyclohexanol suspended in water in the presence of calcium carbonate is oxidized and chlorinated in one step to 2-chlorocyclohexanone (57%). ... 

Calcinm glectrowinning in piutniiium production. A potential application of inorganic membranes in radioactive waste treatment is in the industrially practiced direct oxide reduction process. In this process plutonium oxide is calciothermit y reduced to plutonium in the presence of calcium chloride according to the following reaction ... 

The effluent salt is the radioactively contaminated calcium chloride saturated with calcium oxide which can not be discarded as-is. Thus it is desirable to cathodically reduce calcium oxide to calcium which can then be recycled back to the direct oxide reduction process. The primary difficulty in obtaining a cathodic calcium deposit is due to the evolution of carbonaceous anodic gases which encourage various reverse reactions in the cell leading to loss of deposited calcium. 

In other processes similar to the Solvay process (see Section 3.1.1.3.3), potassium carbonate is produced directly from potassium chloride with amines such as isopropylamine via a potassium hydrogen carbonate step, but contaminated calcium chloride brine is produced as a byproduct whose disposal poses environmental problems. In the former States of the USSR potassium carbonate is also produced from alkali aluminosilicate deposits (e.g. nepheline) together with aluminum oxide, cement and sodium carbonate. 

By reduction, it is possible to pass from nitrobenzene to aniline through the intermediate compounds nitrosobenzene and phenyl-hydroxylamine, and by oxidation in the reverse direction. It has been shown that nitrosobenzene and phenylhydroxylamine are formed in the electro-reduction of nitrobenzene, but it is impossible, at present, to effect some of the transformations indicated above in such a way that the reactions can be used as preparative methods. Some, however, can be used for this purpose. Phenylhydroxylamine, for example, is oxidized in the cold by potassium bichromate and sulphuric acid to nitrosobenzene, and is converted by reducng agents into aniline. In certain cases it is possible, by selecting the proper reagent, to effect the change indicated by two of the steps noted above. Phenylhydroxylamine is best prepared by treating with zinc dust a solution of nitrobenzene in dilute alcohol which contains a small amount of calcium chloride. 

The Chlorohydrin process involves the reaction of propylene with chlorine and water to produce propylene chlorohydrin. The propylene chlorohydrin is then dehydrochlorinated with lime or caustic to yield propylene oxide and a salt by-product. The chemistry is very similar to the chlorohydrin route from ethylene to ethylene oxide which was eventually replaced by the direct oxidation process. There are two major problems with the chlorohydrin route which provided the incentive for developing an improved process. There is a large water effluent stream containing about 5-6% calcium chloride or 5-10% sodium chloride (depending on whether lime or caustic is used for dehydrochlorination) and trace amounts of chlorinated hydrocarbon by-products that must be treated before disposal. Treatment of these by-products is expensive. The only practical way to handle it is to use caustic so that sodium chloride is produced and then integrate the effluent stream with a caustic-chlorine plant so that it can be recycled to the caustic plant. This, however, is also expensive because recovery of sodium chloride from this relatively dilute stream has a high energy cost. 

Chen, G. Z., D. J. Fray, and T. W. Farthing. Direct Electrochemical Reduction of Titanium Dioxide to Titanium in Molten Calcium Chloride. Nature 407 (2000) 361-364. First description of the FFG-Cambridge method—possibly game-changing procedure for reducing metal oxides. 

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