Sodium chloride production

FIGURE 6.1 Conditions used for evaporation for impurity removal, and the crystallization stage(s) for solar salt (sodium chloride) production from seawater. Operating details from Korovessis and Lekkas [II]. 

These features are likely to encourage further development of vacuum or solar evaporation salt recovery operations to work these brines in proximity to the desalination plants. In this way, various salts may be more profitably recovered from these artificially enriched seawaters for reasons similar to the present incentives to use the rich natural brine sources for sodium chloride production (Table 6.3). Similar energy savings should be obtained. 

Chlorosulfonic acid (CSA) sulfation of alcohols or alcohol ethoxylates is usually conducted in batch reaction mode, typically in glass-lined vessels, but requires little or no excess reagent to drive the reaction to completion and can be conducted in a continuous liquid-liquid contacting process. The reaction evolves a stoichiometric quantity of HCl gas, which can be captured either as an HCl solution or with caustic to yield sodium chloride. Product color, yield, and quality cau be very high, but throughput efficiency is modest in batch mode. 

During production sodium chloride can deposit in layers on tubing walls after partial vaporization of the water due to the pressure drop between bottomhole and wellhead when these deposits become important large enough, the diameter of the well tubing is reduced. 

Sodium hydroxide is manufactured by electrolysis of concentrated aqueous sodium chloride the other product of the electrolysis, chlorine, is equally important and hence separation of anode and cathode products is necessary. This is achieved either by a diaphragm (for example in the Hooker electrolytic cell) or by using a mercury cathode which takes up the sodium formed at the cathode as an amalgam (the Kellner-Solvay ceW). The amalgam, after removal from the electrolyte cell, is treated with water to give sodium hydroxide and mercury. The mercury cell is more costly to operate but gives a purer product. 

By the electrolysis of concentrated sodium chloride solution this process was initially used primarily for the production of sodium hydroxide but the demand for chlorine is now so great that the chlorine is a primary and not a by-product. 

The aqueous solution of sodium chlorate(I) is an important liquid bleach and disinfectant. It is produced commercially by the electrolysis of cold aqueous sodium chloride, the anode and cathode products being mixed. The sodium chloride remaining in the solution does not usually matter. There is evidence to suggest that iodic(I) acid has some basic character... 

The oxime is freely soluble in water and in most organic liquids. Recrystallise the crude dry product from a minimum of 60-80 petrol or (less suitably) cyclohexane for this purpose first determine approximately, by means of a small-scale test-tube experiment, the minimum proportion of the hot solvent required to dissolve the oxime from about 0-5 g. of the crude material. Then place the bulk of the crude product in a small (100 ml.) round-bottomed or conical flask fitted with a reflux water-condenser, add the required amount of the solvent and boil the mixture on a water-bath. Then turn out the gas, and quickly filter the hot mixture through a fluted filter-paper into a conical flask the sodium chloride remains on the filter, whilst the filtrate on cooling in ice-water deposits the acetoxime as colourless crystals. These, when filtered anddried (either by pressing between drying-paper or by placing in an atmospheric desiccator) have m.p. 60 . Acetoxime sublimes rather readily when exposed to the air, and rapidly when warmed or when placed in a vacuum. Hence the necessity for an atmospheric desiccator for drying purposes. 

The vanadium pentoxide catalyst Is prepared as follows Suspend 5 g. of pure ammonium vanadate in 50 ml. of water and add slowly 7 5 ml. of pure concentrated hydrochloric acid. Allow the reddish-brown, semi-colloidal precipitate to settle (preferably overnight), decant the supernatant solution, and wash the precipitate several times by decantation. Finally, suspend the precipitate in 76 ml. of water and allow it to stand for 3 days. This treatment renders the precipitate granular and easy to 6lter. Filter the precipitate with suction, wash it several times with cold 5 p>er cent, sodium chloride solution to remove hydrochloric acid. Dry the product at 120° for 12 hours, grind it in a mortar to a fine powder, and heat again at 120° for 12 hours. The yield of catalyst is about 3 - 5 g. 

The high sodium ion concentration results in facile crystallisation of the sodium salt. This process of salting out with common salt may be used for recrystallisation, but sodium benzenesulphonate (and salts of other acids of comparable molecular weight) is so very soluble in water that the solution must be almost saturated with sodium chloride and consequently the product is likely to be contaminated with it. In such a case a pure product may be obtained by crystallisation from, or Soxhlet extraction with, absolute alcohol the sul-phonate is slightly soluble but the inorganic salts are almost insoluble. Very small amounts of sulphones are formed as by-products, but since these are insoluble in water, they separate when the reaction mixture is poured into water ... 

The sulphonation of toluene at 100-120° results in the formation of p-toluene-sulphonic acid as the chief product, accompanied by small amounts of the ortho and meta isomers these are easily removed by crystallisation in the presence of sodium chloride. Sulphonation of naphthalene at about 160° 3uelds largely the p-sulphonic acid at lower temperatures (0-60°) the a-siil-phonic acid is produced almost exclusively. 

This product is sufficiently pure for the preparation of phenylacetic acid and its ethyl ester, but it contains some benzyl tso-cyanide and usually develops an appreciable colour on standing. The following procedure removes the iso-cyanide and gives a stable water-white compound. Shake the once-distilled benzyl cyanide vigorously for 5 minutes with an equal volume of warm (60°) 60 per cent, sulphuric acid (prepared by adding 55 ml. of concentrated sulphuric acid to 100 ml. of water). Separate the benzyl cyanide, wash it with an equal volume of sa+urated sodium bicarbonate solution and then with an equal volume of half-saturated sodium chloride solution- Dry with anhydrous magnesium sulphate and distil under reduced pressure. The loss in washing is very small (compare n-Butyl Cyanide, Section 111,113, in which concentrated hydrochloric acid is employed). 

Brine Preparation. Sodium chloride solutions are occasionally available naturally but they are more often obtained by solution mining of salt deposits. Raw, near-saturated brines containing low concentrations of impurities such as magnesium and calcium salts, are purified to prevent scaling of processing equipment and contamination of the product. Some brines also contain significant amounts of sulfates (see Chemicals FROMBRINe). Brine is usually purified by a lime—soda treatment where the magnesium is precipitated with milk of lime (Ca(OH)2) and the calcium precipitated with soda ash. After separation from the precipitated impurities, the brine is sent to the ammonia absorbers. 

The FCC is to food-additive chemicals what the USP—NF is to dmgs. In fact, many chemicals that are used in dmgs also are food additives (qv) and thus may have monographs in both the USP—NF and in the FCC. Examples of food-additive chemicals are ascorbic acid [50-81-7] (see Vitamins), butylated hydroxytoluene [128-37-0] (BHT) (see Antioxidants), calcium chloride [10043-52-4] (see Calcium compounds), ethyl vanillin [121-32-4] (see Vanillin), ferrous fumarate [7705-12-6] and ferrous sulfate [7720-78-7] (see Iron compounds), niacin [59-67-6] sodium chloride [7647-14-5] sodium hydroxide [1310-73-2] (see lkaliand cm ORiNE products), sodium phosphate dibasic [7558-79-4] (see Phosphoric acids and phosphates), spearmint oil [8008-79-5] (see Oils, essential), tartaric acid [133-37-9] (see Hydroxy dicarboxylic acids), tragacanth [9000-65-1] (see Gums), and vitamin A [11103-57-4]. 

Sodium bicarbonate may be prepared by the ammonia-salt (Solvay) process. Carbon dioxide is passed through a solution of sodium chloride in ammonia water. Sodium bicarbonate is precipitated and the ammonium chloride remains in solution. The ammonium chloride is heated with lime to regenerate ammonia (see Alkali AND CHLORINE PRODUCTS). 

Inorganic salts are also used to promote shampoo thickening. These should be used sparingly since an excess may have a deleterious effect on a product s physical stabiHty. Sodium chloride commonly is used in these cases. The additions of sodium stearate and stearic amides can be found in paste shampoos for thickening. 

Comparison to the Raschig Process. The economics of this peroxide process in comparison to the Raschig or hypochlorite—ketazine processes depend on the relative costs of chlorine, caustic, and hydrogen peroxide. An inexpensive source of peroxide would make this process attractive. Its energy consumption could be somewhat less, because the ketazine in the peroxide process is recovered by decantation rather than by distillation as in the hypcochlorite process. A big advantage of the peroxide process is the elimination of sodium chloride as a by-product this is important where salt discharge is an environmental concern. In addition to Elf Atochem, Mitsubishi Gas (Japan) uses a peroxide process. 

Included under other by-product column. The U.S. company producing HCl and coproduct sodium sulfate from sodium chloride and sulfuric acid shut down its plant in 1992. 

Although 4-hydroxybenzaldehyde can be made by the saligenin route, it has been made historically by the Reimer-Tiemann process, which also produces sahcylaldehyde (64). Treatment of phenol with chloroform and aqueous sodium hydroxide results in the formation of benzal chlorides, which are rapidly hydrolyzed by the alkaline medium into aldehydes. Acidification of the phenoxides results in the formation of the final products, sahcylaldehyde and 4-hydroxybenzaldehyde. The ratio of ortho and para isomers is flexible and can be controlled within certain limits. The overall reaction scheme is shown in Figure 1. Product separation is accomphshed by distillation, but this process leads to environmental problems because of the quantities of sodium chloride produced. 

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