Mixers-settlers

The earliest large-scale continuous industrial extraction equipment consisted of mixer—settlers and open-spray columns. The vertical stacking of a series of mixer—settlers was a feature of a patented column in 1935 (96) in which countercurrent flow occurred because of density difference between the phases, avoiding the necessity for interstage pumping. This was a precursor of the agitated column contactors which have been developed and commercialized since the late 1940s. There are several texts (1,2,6,97—98) and reviews (99—100) available that describe the various types of extractors. 

Fig. 13. Mixer—settlers (a) IMI (b) General Mills (c) Davy-McKee and (d) CMS.

The simple box-type mixer—settler (113) has been used extensively in the UK for the separation and purification of uranium and plutonium (114). In this type of extractor, interstage flow is handled through a partitioned box constmction. Interstage pumping is not needed because the driving force is provided by the density difference between solutions in successive stages (see Plutoniumand plutonium compounds Uraniumand uranium compounds). 

A widely used type of pump—mixer—settler, developed by IsraeH Mining Industries (IMI) (115), is shown in Figure 13a. A unit having capacity 8.3 m /min (2000 gal /min) has been used in phosphoric acid plants (116). The unique feature of this design is that the pumping device is not required to act as the mixer, and the two phases are dispersed by a separate impeller mounted on a shaft miming coaxially with the drive to the pump. 

The General Mills mixer—settler (117), shown in Figure 13b, is a pump—mix unit designed for hydrometaHurgical extraction. It has a baffled cylindrical mixer fitted in the base and a turbine that mixes and pumps the incoming Hquids. The dispersion leaves from the top of the mixer and flows into a shallow rectangular settler designed for minimum holdup. 

The development of the novel Davy-McKee combined mixer—settler (CMS) has been described (121). It consists of a single vessel (Fig. 13d) in which three 2ones coexist under operating conditions. A detailed description of units used for uranium recovery has been reported (122), and the units have also been studied at the laboratory scale (123). AppHcation of the Davy combined mixer electrostatically assisted settler (CMAS) to copper stripping from an organic solvent extraction solution has been reported (124). 

Special safety constraints apply to equipment selection, design, and operation in nuclear reprocessing (269). Equipment should be reHable and capable of remote control and operation for long periods with minimal maintenance. Pulsed columns and remotely operated mixer—settlers are commonly used (270). The control of criticaHty and extensive monitoring of contamination levels must be included in the process design. 

Other Metals. Because of the large number of chemical extractants available, virtually any metal can be extracted from its aqueous solution. In many cases extraction has been developed to form part of a viable process (275). A review of more recent developments in metal extraction including those for precious metals and rare earths is also available (262). In China a complex extraction process employing a cascade of 600 mixer—settlers has been developed to treat leach Hquor containing a mixture of rare earths (131). 

However, such mixer—settler methods are continuous only by virtue of repeating a sequence of similar stages to achieve a given degree of extraction. More fully continuous methods of extraction were designed as tower systems and later as screw conveyor systems as effective methods of soHds transport became reHable. 

In addition, solvent extraction is appHed to the processing of other metals for the nuclear industry and to the reprocessing of spent fuels (see Nuclearreactors). It is commercially used for the cobalt—nickel separation prior to electrowinning in chloride electrolyte. Both extraction columns and mixer-settlers are in use. 

Modem commercial wet-acid purification processes (see Fig. 4) are based on solvents such as C to Cg alcohols, ethers, ketones, amines, and phosphate esters (10—12). Organic-phase extraction of phosphoric acid is accompHshed in one or more extraction columns or, less frequently, in a series of countercurrent mixer—settlers. Generally, 60—75% of the feed acid P2 s content is extracted into the organic phase as H PO. The residual phosphoric acid phase (raffinate), containing 25—40% of the original P2O5 value, is typically used for fertilizer manufacture such as triple superphosphate. For this reason, wet-acid purification units are almost always located within or next to fertilizer complexes. 

For solvent extraction of pentavalent vanadium as a decavanadate anion, the leach solution is acidified to ca pH 3 by addition of sulfuric acid. Vanadium is extracted in about four countercurrent mixer—settler stages by a 3—5 wt % solution of a tertiary alkyl amine in kerosene. The organic solvent is stripped by a soda-ash or ammonium hydroxide solution, and addition of ammoniacal salts to the rich vanadium strip Hquor yields ammonium metavanadate. A small part of the metavanadate is marketed in that form and some is decomposed at a carefully controlled low temperature to make air-dried or fine granular pentoxide, but most is converted to fused pentoxide by thermal decomposition at ca 450°C, melting at 900°C, then chilling and flaking. 

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

For vanadium solvent extraction, Hon powder can be added to reduce pentavalent vanadium to quadrivalent and trivalent Hon to divalent at a redox potential of —150 mV. The pH is adjusted to 2 by addition of NH, and an oxyvanadium cation is extracted in four countercurrent stages of mixer—settlers by a diesel oil solution of EHPA. Vanadium is stripped from the organic solvent with a 15 wt % sulfuric acid solution in four countercurrent stages. Addition of NH, steam, and sodium chlorate to the strip Hquor results in the precipitation of vanadium oxides, which are filtered, dried, fused, and flaked (22). Vanadium can also be extracted from oxidized uranium raffinate by solvent extraction with a tertiary amine, and ammonium metavanadate is produced from the soda-ash strip Hquor. Fused and flaked pentoxide is made from the ammonium metavanadate (23). 

Density. The difference in density between the two hquid phases in eqiiilibrium affects the countercurrent flow rates that can be achieved in extrac tion equipment as well as the coalescence rates. The density difference decreases to zero at a plait point, but in some systems it can become zero at an intermediate solute concentration (isopycnic, or twin-density tie line) and can invert the phases at higher concentrations. Differential types of extractors cannot cross such a solute concentration, but mixer-settlers can. 

FIG. 15-28 Pump-Mix mixer-settler. [Coplan, Davidson, and Xehroski, Chem. Eng. Prog., 50, 403 (1954), with permission.]... 

Overall Stage Efficiencies The mixer-settler extractors described have generally produced overall stage efficiencies in excess of 80 percent, usually nearly 90 to 95 percent. 

FIG. 15-29 Kerr-McGee multistage mixer-settler, a) and (h) For uranium, (c) For vanadium extraction. 

Treybal Tower Treybal [U.S. Patent 3,325,255, 1967) Chem. Eng. Prog., 60(5), 77 (1964)] adapted a mixer-settler cascade in tower form in which the liquids are setued between stages. 

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