Brine dissolving processes

The bittern (spent brine) from solar salt production contains 300 00 g/L dissolved solids relatively enriched in the less concentrated salt impurities. This may be either discarded or further worked to recover other elements of value. Brine from the Great Salt Lake, for instance, is processed for magnesium chloride hexahydrate recovery [10], which occurs at a density of 1.26g/cm. This is later converted to metallic magnesium [12]. The Dead Sea brines are processed primarily for potassium chloride (potash), but are also worked for sodium and magnesium chlorides and derived products such as bromine and hydrochloric acid [16] (Sections 6.2.2 and 8.8). 

Normal processing, shown in Fig. 6.7, involves cooling, which may also serve to remove entrained caustic, and compression. Hydrogen friequently is cooled by direct contact with brine. This is a simple matter of heat economization. Entrained caustic is removed by this operation but may be replaced by salt or brine mist. Process design must take into account the water condensed into the brine. The condensate from mercury-cell hydrogen will also contain mercury, both as a separate phase and in a dissolved form. After decantation from the metallic mercury, the liquid phase requires treatment before it can be discharged. 

Removal of brine contaminants accounts for a significant portion of overall chlor—alkali production cost, especially for the membrane process. Moreover, part or all of the depleted brine from mercury and membrane cells must first be dechlorinated to recover the dissolved chlorine and to prevent corrosion during further processing. In a typical membrane plant, HCl is added to Hberate chlorine, then a vacuum is appHed to recover it. A reducing agent such as sodium sulfite is added to remove the final traces because chlorine would adversely react with the ion-exchange resins used later in the process. Dechlorinated brine is then resaturated with soHd salt for further use. 

At Great Salt Lake Minerals Corporation (Utah), solar-evaporated brines are winter-chilled to —3° C in solar ponds. At this low temperature, a relatively pure Glauber s salt precipitates. Ponds are drained and the salt is loaded into tmcks and hauled to a processing plant. At the plant, Glauber s salt is dissolved in hot water. The resulting Hquor is filtered to remove insolubles. The filtrate is then combined with soHd-phase sodium chloride, which precipitates anhydrous sodium sulfate of 99.5—99.7% purity. Great Salt Lake Minerals Corporation discontinued sodium sulfate production in 1993 when it transferred production and sales to North American Chemical Corporation (Trona, California). 

Electrodialysis. Electro dialysis processes transfer ions of dissolved salts across membranes, leaving purified water behind. Ion movement is induced by direct current electrical fields. A negative electrode (cathode) attracts cations, and a positive electrode (anode) attracts anions. Systems are compartmentalized in stacks by alternating cation and anion transfer membranes. Alternating compartments carry concentrated brine and purified permeate. Typically, 40—60% of dissolved ions are removed or rejected. Further improvement in water quaUty is obtained by staging (operation of stacks in series). ED processes do not remove particulate contaminants or weakly ionized contaminants, such as siUca. 

Recovery Process. Commercial processes depend on the oxidation of bromide to bromine. Most of the Hberated bromine remains dissolved in the brine. The brine is then stripped of bromine followed by recovery of bromine from the stripping agent. Subsequent purification by distillation is often a final step. 

Concentration of Seawater by ED. In terms of membrane area, concentration of seawater is the second largest use. Warm seawater is concentrated by ED to 18 to 20% dissolved soHds using membranes with monovalent-ion-selective skins. The EDR process is not used. The osmotic pressure difference between about 19% NaCl solution and partially depleted seawater is about 20,000 kPa (200 atm) at 25°C, which is well beyond the range of reverse osmosis. Salt is produced from the brine by evaporation and crystallisa tion at seven plants in Japan and one each in South Korea, Taiwan, and Kuwait. A second plant is soon to be built in South Korea. None of the plants are justified on economic grounds compared to imported solar or mined salt. 

The terminal R groups can be aromatic or aliphatic. Typically, they are derivatives of monohydric phenoHc compounds including phenol and alkylated phenols, eg, /-butylphenol. In iaterfacial polymerization, bisphenol A and a monofunctional terminator are dissolved in aqueous caustic. Methylene chloride containing a phase-transfer catalyst is added. The two-phase system is stirred and phosgene is added. The bisphenol A salt reacts with the phosgene at the interface of the two solutions and the polymer "grows" into the methylene chloride. The sodium chloride by-product enters the aqueous phase. Chain length is controlled by the amount of monohydric terminator. The methylene chloride—polymer solution is separated from the aqueous brine-laden by-products. The facile separation of a pure polymer solution is the key to the interfacial process. The methylene chloride solvent is removed, and the polymer is isolated in the form of pellets, powder, or slurries. 

Electrical conductivity is of interest in corrosion processes in cell formation (see Section 2.2.4.2), in stray currents, and in electrochemical protection methods. Conductivity is increased by dissolved salts even though they do not take part in the corrosion process. Similarly, the corrosion rate of carbon steels in brine, which is influenced by oxygen content according to Eq. (2-9), is not affected by the salt concentration [4]. Nevertheless, dissolved salts have a strong indirect influence on many local corrosion processes. For instance, chloride ions that accumulate at local anodes can stimulate dissolution of iron and prevent the formation of a film. Alkali ions are usually regarded as completely harmless, but as counterions to OH ions in cathodic regions, they result in very high pH values and aid formation of films (see Section 2.2.4.2 and Chapter 4). 

Recrystallizer A process for reciystallizing sodium chloride from brine. Rock salt is dissolved in brine heated with direct steam. The solution is then partially evaporated under reduced pressure. Invented in 1945 by C. M. Hopper and R. B. Richards at the International Salt Company, Scranton, PA. See also Alberger. 

Salex A process for purifying sodium chloride. Continuous counter-current extraction with brine removes the impurities without dissolving the salt. There are three variants SALEX-B, SALEX-C, AND SALEX-M. Developed by Krebs Swiss. First operated in 1982. 

Kvaerner Chemetics have developed a novel, patented process [1] for the removal of multivalent anions from concentrated brine solutions. The prime market for this process is the removal of sodium sulphate from chlor-alkali and sodium chlorate brine systems. The sulphate ion in a brine solution can have a detrimental effect on ion-exchange membranes used in the production of chlorine and sodium hydroxide consequently tight limits are imposed on the concentration of sulphate ions in brine. As brine is continuously recycled from the electrolysers back to the saturation area, progressively more and more sulphate ions are dissolved and build up quickly in concentration to exceed the allowable process limits. A number of processes have been designed to remove sulphate ions from brine. Most of these methods are either high in capital or operating cost [2] or have large effluent flows. 

Properties and extraction processes Aquifer gas, also referred to as geo-pressured gas or brine gas, is natural gas found dissolved in aquifers, primarily in the form of methane. The solubility of natural gas, and thus the methane content of the water, can vary significantly, and depend on factors, such as the total pressure, temperature, salt content of the water and amount of other gases dissolved. The amount of gas dissolved in underground liquids increases substantially with depth. A general rule is that the deeper the aquifers and the higher the pressure, the higher the gas content. At depths down to 5 km, up to 5 m3 of methane can be dissolved per m3 of water in aquifers under normal hydrostatic pressure (load of water) under lithostatic pressure (load of water and rocks), this factor may increase to more than... 

Reverse osmosis is a process used by some plants to remove dissolved salts. The waste stream from this process consists of reverse osmosis brine. In water treatment schemes reported by the industry, reverse osmosis was always used in conjunction with demineralizers, and sometimes with clarification, filtration, and ion exchange softening. 

In the United States and most parts of the world, iodine is obtained com-merciaUy from brine wells. Many subsurface brines have iodine concentrations in the range of 10 to 100 mg/L. Various extraction processes are known including (i) precipitation with silver nitrate, (ii) oxidation with chlorine, and (hi) ion exchange. In the chlorine oxidation process, natural subsurface brine first is acidified with sulfuric acid and then treated with chlorine. Chlorine hberates iodine from the brine solution. Iodine is blown out into a counter-current stream of air. It is dissolved in a solution of hydriodic acid and sulfu-... 

Salt caverns are developed by solution mining, a process (leaching) in which water is injected to dissolve the salt. Approximately 7 to 10 units of fresh water are required to leach 1 unit of cavern volume. Figure 10-190 illustrates the leaching process for two caverns. Modern salt dome caverns are shaped as relatively tall, slender cylinders. The leaching process produces nearly saturated brine from the cavern. Brine may be disposed into nearby disposal wells or offshore disposal fields, or it may be supplied to nearby plants as a feedstock for manufacturing of caustic (NaOH) and chlorine (CI2). The final portion of the produced brine is retained and stored in artificial surface ponds or tanks to be used to displace the stored liquid from the cavern. 

Freeze concentration processes are based on the difference in component concentrations between solid and liquid phases that are in equihbrium. Most minerals and many organics grow less soluble in water as the temperature decreases. When an aqueous solution is cooled, ice usually crystallizes as a pure material, and dissolved components in the aqueous waste stream are concentrated in the remaining brine, thereby reducing the volume of waste. 

---