Carbonation brines

In the commercial electrolysis of brine, carbon anodes and iron cathodes are employed. The anode reaction is mainly the discharge of chlorine ions ... 

The corrosion problems caused by environment can be classified in to two categories (a) downhole environment and (b) surface environment. Whereas the surface environment is mainly the corrosion related to the absorption and atmospheric contaminants, the downhole environment is highly aggressive as it may contain brine, carbon dioxide, acids and hydrogen sulfide, all of which are highly corrosive. The downhole environment is also subjected to elevated temperatures. Corrosion protection of drilling equipment is a challenging job in the oil industry. 

The soda-ammonia process occurs in two main stages. First, brine is saturated with ammonia gas and this ammoniacal brine is then treated with carbon dioxide. The equilibrium... 

The reaction is initiated with nickel carbonyl. The feeds are adjusted to give the bulk of the carbonyl from carbon monoxide. The reaction takes place continuously in an agitated reactor with a Hquid recirculation loop. The reaction is mn at about atmospheric pressure and at about 40°C with an acetylene carbon monoxide mole ratio of 1.1 1 in the presence of 20% excess alcohol. The reactor effluent is washed with nickel chloride brine to remove excess alcohol and nickel salts and the brine—alcohol mixture is stripped to recover alcohol for recycle. The stripped brine is again used as extractant, but with a bleed stream returned to the nickel carbonyl conversion unit. The neutralized cmde monomer is purified by a series of continuous, low pressure distillations. 

Sodium hydroxide brine electrolysis lime-sodium carbonate reaction (not presently used)... 

Recovery of Ammonia. The filter Hquor contains unreacted sodium chloride and substantially all the ammonia with which the brine was originally saturated. The ammonia may be fixed or free. Fixed ammonia (ammonium chloride [12125-02-97]) corresponds stoichiometrically to the precipitated sodium bicarbonate. Free ammonia includes salts such as ammonium hydroxide, bicarbonate, and carbonate, and the several possible carbon—ammonia compounds that decompose at moderate temperatures. A sulfide solution may be added to the filter Hquor for corrosion protection. The sulfide is distilled for eventual absorption by the brine in the absorber. As the filter Hquor enters the distiller, it is preheated by indirect contact with departing gases. The warmed Hquor enters the main coke, tile, or bubble cap-fiUed sections of the distiller where heat decomposes the free ammonium compounds and steam strips the ammonia and carbon dioxide from the solution. 

Lake Texcoco. Lake Texcoco, a few miles northeast of Mexico City, is in the lowest part of the Valley of Mexico. The lake is mostly dry and alkaH is recovered from brine weUs that have been drilled into the underlying stmcture. The brine is concentrated first in a spiral flow solar evaporation pond and further in conventional evaporators. This strong brine is carbonated and then cooled to crystallize sodium bicarbonate which is subsequently filtered and calcined to soda ash. Purity of this product is similar to Magadi material (9,29). 

Magnesium sulfate heptahydrate may be prepared by neutralization of sulfuric acid with magnesium carbonate or oxide, or it can be obtained directly from natural sources. It occurs abundantly as a double salt and can also be obtained from the magnesium salts that occur in brines used for the extraction of bromine (qv). The brine is treated with calcium hydroxide to precipitate magnesium hydroxide. Sulfur dioxide and air are passed through the suspension to yield magnesium sulfate (see Chemicals frombrine). Magnesium sulfate is a saline cathartic. 

The copper-chelating abihty of sahcylaldoxime has been used to remove copper from brine in a seawater desalination plant effluent. A carbon—sorbate bed produced by sorption of the oxime on carbon proved to be extremely effective in the continuous process (99). In another apphcation, the chelating abihty of sahcylaldoxime with iron and copper was used to stabilize bleaching powders containing inorganic peroxide salts (100). 

For brines having very low iodide concentrations, ie, in some facilities in Japan and in the former USSR, the activated carbon method of recovery is used. This method consists of a process involving the treating of the acidified brine with sodium nitrite in large tanks, where the following reaction takes place ... 

The free iodine, which remains in solution, is recovered by adsorption on activated carbon. After this step is completed, the residual brine is neutralized with lime or ammonia. 

Among nonmetallic materials, glass, chemical stoneware, enameled steel, acid-proof brick, carbon, graphite, and wood are resistant to iodine and its solutions under suitable conditions, but carbon and graphite may be subject to attack. Polytetrafluoroethylene withstands Hquid iodine and its vapor up to 200°C although it discolors. Cloth fabrics made of Saran, a vinyHdene chloride polymer, have lasted for several years when used in the filtration of iodine recovered from oil-weU brines (64). 

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S0 3, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach Hquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH NO, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and cosdy ore particle/leach hquor separation step. 

Preparation and Manufacture. Magnesium chloride can be produced in large quantities from (/) camalhte or the end brines of the potash industry (see Potassium compounds) (2) magnesium hydroxide precipitated from seawater (7) by chlorination of magnesium oxide from various sources in the presence of carbon or carbonaceous materials and (4) as a by-product in the manufacture of titanium (see Titaniumand titanium alloys). 

The key difference between the brine process and seawater process is the precipitation step. In the latter process (Fig. 6) the seawater is first softened by a dding small amounts of lime to remove bicarbonate and sulfates, present as MgSO. Bicarbonate must be removed prior to the precipitation step to prevent formation of insoluble calcium carbonate. Removal of sulfates prevents formation of gypsum, CaS02 2H20. Once formed, calcium carbonate and gypsum cannot be separated from the product. 

The aqueous sodium naphthenate phase is decanted from the hydrocarbon phase and treated with acid to regenerate the cmde naphthenic acids. Sulfuric acid is used almost exclusively, for economic reasons. The wet cmde naphthenic acid phase separates and is decanted from the sodium sulfate brine. The volume of sodium sulfate brine produced from dilute sodium naphthenate solutions is significant, on the order of 10 L per L of cmde naphthenic acid. The brine contains some phenolic compounds and must be treated or disposed of in an environmentally sound manner. Sodium phenolates can be selectively neutralized using carbon dioxide and recovered before the sodium naphthenate is finally acidified with mineral acid (29). Recovery of naphthenic acid from aqueous sodium naphthenate solutions using ion-exchange resins has also been reported (30). 

Obtaining maximum performance from a seawater distillation unit requires minimising the detrimental effects of scale formation. The term scale describes deposits of calcium carbonate, magnesium hydroxide, or calcium sulfate that can form ia the brine heater and the heat-recovery condensers. The carbonates and the hydroxide are conventionally called alkaline scales, and the sulfate, nonalkaline scale. The presence of bicarbonate, carbonate, and hydroxide ions, the total concentration of which is referred to as the alkalinity of the seawater, leads to the alkaline scale formation. In seawater, the bicarbonate ions decompose to carbonate and hydroxide ions, giving most of the alkalinity. 

Sodium and potassium benzoate are substances that may be added direcdy to human food and are affirmed as GRAS (33—35). Benzoic acid and sodium and potassium benzoate are now used as preservatives in such foods as sauces, pickles, cider, fmit juices, wine coolers, symps and concentrates, mincemeat and other acidic pie fillings, margarine, egg powder, fish (as a brine dip component), bottled carbonated beverages, and fmit preserves, jams, and jellies. The popularity of diet soft drinks has led to increased demand for both benzoate salts. 

North American Chemical Co. produces borax pentahydrate and decahydrate from Seades Lake brines in both Trona and West End, California (see Chemicals frombrines). The 88 km dry lake consists of two brine layers, the analyses of which are given in Table 11. Two distinct procedures are used for the processing of upper and lower lake brines. Borax is produced in Trona from upper lake brines by an evaporative procedure involving the crystallization of potash and several other salts prior to borax crystallization as the pentahydrate (104). A carbonation process is used in West End, California to derive borate values from lower lake brines (105). Raw lower stmcture brine is carbonated to produce sodium bicarbonate, which is calcined and recrystallized as sodium carbonate monohydrate. The borate-rich filtrate is neutralized with lake brine and refrigerated to crystallize borax. 

Great Salt Lake, Utah, is the largest terminal lake in the United States. From its brine, salt, elemental magnesium, magnesium chloride, sodium sulfate, and potassium sulfate ate produced. Other well-known terminal lakes ate Qinghai Lake in China, Tu2 Golu in Turkey, the Caspian Sea and Atal skoje in the states of the former Soviet Union, and Urmia in Iran. There ate thousands of small terminal lakes spread across most countries of the world. Most of these lakes contain sodium chloride, but many contain ions of magnesium, calcium, potassium, boron, lithium, sulfates, carbonates, and nitrates. 

The main metals in brines throughout the world are sodium, magnesium, calcium, and potassium. Other metals, such as lithium and boron, are found in lesser amounts. The main nonmetals ate chloride, sulfate, and carbonate, with nitrate occurring in a few isolated areas. A significant fraction of sodium nitrate and potassium nitrate comes from these isolated deposits. Other nonmetals produced from brine ate bromine and iodine. 

Recovery Process. Boron values are recovered from brine of Seades Lake by North American Chemicals Corp. In one process the brine is heated to remove some water and burkeite. The remaining brine is cooled to remove potassium chloride. This cooled brine is then transferred to another crystallizer where borax pentahydrate, Na2B40y 5H20, precipitates (18). In a separate process, boron is removed by Hquid—Hquid extraction followed by stripping with dilute sulfuric acid (19). Evaporator-crystallizers are used to recover boric acid [10043-35-3] H BO. In a third process, borax is recovered by refrigerating a carbonated brine. 

Older methods of stripping used with concentrations below 1000 ppm utilize a stream of air flowing countercurrent to the brine stream. The bromine is then recovered from the air with wet scrap iron, ammonia, sodium carbonate, or sulfur dioxide (23—25). 

Japan was the lea ding producer of iodine in the 1980s, producing nearly 7000 metric tons per year. Elemental iodine was released into brine by treatment with sodium nitrate or chlorine. The free iodine was then adsorbed on activated carbon. It was stripped from the carbon with sodium hydroxide followed by acidification to form a slurry of elemental iodine ... 

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