Thiocyanate-extraction process

In the initial thiocyanate-complex Hquid—Hquid extraction process (42,43), the thiocyanate complexes of hafnium and zirconium were extracted with ether from a dilute sulfuric acid solution of zirconium and hafnium to obtain hafnium. This process was modified in 1949—1950 by an Oak Ridge team and is stiH used in the United States. A solution of thiocyanic acid in methyl isobutyl ketone (MIBK) is used to extract hafnium preferentially from a concentrated zirconium—hafnium oxide chloride solution which also contains thiocyanic acid. The separated metals are recovered by precipitation as basic zirconium sulfate and hydrous hafnium oxide, respectively, and calcined to the oxide (44,45). This process is used by Teledyne Wah Chang Albany Corporation and Western Zirconium Division of Westinghouse, and was used by Carbomndum Metals Company, Reactive Metals Inc., AMAX Specialty Metals, Toyo Zirconium in Japan, and Pechiney Ugine Kuhlmann in France. 

Solvent extraction has proved to be the most effective method for the separation of zirconium and hafnium, which invariably occur in nature in close association, owing to their almost identical chemical properties. These metals have found considerable use in the nuclear-power industry on account of their unusually high (hafnium) and low (zirconium) neutron-capture cross-sections. It is evident that the mutual separation of the two metals must be of a high degree to make them suitable for such applications. Two different solvent-extraction processes are known to be used on a commercial scale in one process, zirconium is selectively extracted from nitrate media into TBP in the second process, hafnium is selectively extracted from thiocyanate solutions into methyl isobutyl ketone (MIBK). 

The oxide Is dissolved in HN4OH, thiocyanate added to the soln. and the reduction-extraction process repeated after acidification. 

Another factor that affects the solute extraction is the temperature. This is significant in case of reaction-controlled processes such as thiocyanate extraction by trimethyl ammonium chloride [86]. Thiocyanate ions are rapidly transported into the membrane with increase in temperature. This is due to the strong influence of temperature on the reaction rate constants. 

Chlorination of zircon has been the process mainly used in the United States because it produces ZrCU, which is used in the Kroll process for making zirconium metal (Sec. 8.3), and because ZrCU was the feed material for the first process developed for separating hafnium from zirconium, using thiocyanate extraction (Sec. 7.3). 

A similar hexone-thiocyanate process has been operated in the U.S.A., firstly by the Northwest Electrodevelopment Laboratories at Albany since 1952 and the Carborundum Metals Corporation plant near Akron, New York, since 1953. They use packed and unpacked columns and the difficulties associated with polymerization of thiocyanic acid were alleviated by using a solvent consisting of 80 per cent hexone and 20 per cent butyl acetate instead of solely hexone. > The zirconium product is precipitated as the acid sulphate, phthalate or salicylate, and a certain additional degree of purification is obtained at this stage. A typical analysis of pure zirconium oxide after hexone-thiocyanate extraction and salicylate precipitation is as follows ... 

Most LWR fuel rod cladding is made of Zircaloy (and its derivatives), which is an alloy of primarily zirconium and tin. Other alloying elements include niobium, iron, chromium, and nickel. Zircaloy was chosen because it has a very low cross section for thermal neutrons. Naturally occurring zirconium contains about l%-5% hafnium. The hafnium must be removed because it has a very high thermal neutron cross section and is often used in making control rods for reactors. The separation process used in the United States is a liquid-liquid extraction process. It is based on the difference in solubility of the metal thiocyanates in methyl isobutyl ketone. In Europe, a process known as extractive distillation is used to purify zirconium. This method employs a separation solvent that interacts differently with the zirconium and hafnium, causing their relative volatilities to change. This enables them to be separated by a normal distillation process. The separated zirconium is then alloyed with the required constituents. 

In the zirconium extraction process, several corrosive chemicals are used, including methyl isobutyl ketone, HCl, ammonium thiocyanate, H2SO4, and zirconyl chloride. Zirconium has been foimd to withstand the rigors of this manufacturing process. Six examples are given, as follows ... 

Thiocyanates are present in water primarily because of discharges from coal processing, extraction of gold and silver, and mining industries. Thiocyanates in soil result from direct application of weed killers and disposal of by-products from industrial processes. Less important sources include release from damaged or decaying tissues of certain plants such as mustard, kale, and cabbage. 

If the ratio be unity, the concentrations of the solute in each solvent will be the same if the ratio be far removed from unity, a correspondingly large proportion of the solute will be found in the one solvent which can be utilized to extract the Soln. from the other solvent. E.g. ether will remove ferric chloride from its aq. soln., and since many other chlorides are almost insoluble in ether, the process is utilized in analysis for the separation of iron from the other elements the solubility of cobalt thiocyanate in ether is utilized for the separation of cobalt perchromic acid is similarly separated from its aq. soln. by ether molten zinc extracts silver and gold from molten lead the extraction of organic compounds from aq. soln. by shaking out with ether or other solvent is much used in organic laboratories. 

The principle Zr ore, zircon (Zr silicate) is processed by caustic fusion or by direct chlorination of milled coke and zircon mixts. Washing of the Na fusion cake leave an acid soluble hydrated Zr oxide, whereas chlorination yields mixed Si and Zr tetrachlorides which are separated by distillation. Removal of the Hf from the Zr takes place through counter current liq-liq extraction (Ref 33), For this purpose the oxide or the tetrachloride is dissolved in dil hydrochloric acid to which ammonium thiocyanate is added as a complexing agent. The organic extracting phase is methyl isobutylketone... 

The selective extraction of hafnium from thiocyanate media into diethyl ether was first reported in 1947.300.30i xhe technique was subsequently investigated extensively in the USA with a view to the development of a suitable industrial-scale process, it being found advantageous for MIBK to be used as the solvent in place of diethyl ether.302 The first commercial plant was completed in 1952,303 ancj the process has since been used widely in the USA, England, France, Germany and Japan. Several descriptions of the process have been given in the literature.287-289 303-305... 

The reasons for the selective extraction of hafnium over zirconium from thiocyanate solutions by solvating extractants are not well understood. Hence, a recent review of the chemistry of these metals described the separation process but offered no explanation for the observed selectivity.306 There is no evidence that differences in the stabilities of the thiocyanate complexes of hafnium(IV) and zirconium(IV) are responsible for the selective extraction of the former, since the formation constants of the respective complexes are essentially identical for both metals.307 However, there is some indication that the hafnium thiocyanates are more readily solvated by the extractant than are the corresponding complexes of zirconium. 

Membrane technology may become essential if zero-discharge mills become a requirement or legislation on water use becomes very restrictive. The type of membrane fractionation required varies according to the use that is to be made of the treated water. This issue is addressed in Chapter 35, which describes the apphcation of membrane processes in the pulp and paper industry for treatment of the effluent generated. Chapter 36 focuses on the apphcation of membrane bioreactors in wastewater treatment. Chapter 37 describes the apphcations of hollow fiber contactors in membrane-assisted solvent extraction for the recovery of metallic pollutants. The apphcations of membrane contactors in the treatment of gaseous waste streams are presented in Chapter 38. Chapter 39 deals with an important development in the strip dispersion technique for actinide recovery/metal separation. Chapter 40 focuses on electrically enhanced membrane separation and catalysis. Chapter 41 contains important case studies on the treatment of effluent in the leather industry. The case studies cover the work carried out at pilot plant level with membrane bioreactors and reverse osmosis. Development in nanofiltration and a case study on the recovery of impurity-free sodium thiocyanate in the acrylic industry are described in Chapter 42. 

The conventional techniques applied to recover thiocyanate are solvent extraction, distillation, and gel filtration. These processes suffer disadvantages. The process that resorts to solvent extraction needs a large amount of energy for cooling. The process that utilizes distillation under pressure also needs a huge quantity of energy and gives off toxic thiocyanate gas. 

Apart from ammonia, some other inorganic species extracted by hquid membranes are strong acids like nitric acid and thiocyanate ions from aqueous solutions using carrier-mediated coupled transport process. 

Lin and Long [41] applied ELM to effectively separate nitrate ions (94% efficiency) from water with tri-n-octyl amine as the extractant and sodium carbonate as the internal phase. H+ ions were also transported along with NOs from external to the internal phase (cotransport). Kobya et al. [86] studied the kinetics of thiocyanate ion removal from aqueous potassium thiocyanate solution by counter-transport process using quaternary ammonium salt of hexadecyl trimethyl ammonium chloride as the cander and sodium chloride solution as the stripping phase. 

Trivalent americium forms relatively unstable complexes with Cl and NOs and more stable complexes with the thiocyanate ion CNS. These americium complexes are more stable than those of the corresponding lanthanide compounds, so that americium can be separated from trivalent lanthanides by anion exchange with concentrated solutions of liQ, liNOs, or NH4CNS. Trivalent americium can be extracted with TBP from a concentrated nitrate solution. It can also be extracted with TBP from a molten LINO3 -KNOs eutectic at 150°C, with much higher distribution coefficients than in extraction from aqueous solutions. Americium is more readily extracted by this process than is trivalent curium [K2]. 

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