Solvent countercurrent

The partition of different lipids between two immiscible solvents (countercurrent distribution) is useful for crude fractionation of lipid classes with greatly differing polarities. Repeated extractions in a carefully chosen solvent pair increase the effectiveness of the separation but in practice mixtures of lipids are still found in each fraction. A petroleum ether-ethanol-water system can be used to remove polar contaminants (into the alcoholic phase) when interest lies in the subsequent analysis of neutral glycerides, which may be recovered from the ether phase. Carbon... 

If the solid matrix moves continuously towards the solvent, countercurrent extraction is performed. Depending on the techniques developed in percolation, three different types can be distinguished. 

The design of countercurrent contactors is considerably simplified when the solvents A and B are not significantly miscible. The mass flows of A and B then remain constant from one stage to the next, and the material balance at any stage can be written... 

Immersion-type extractors have been made continuous through the inclusion of screw conveyors to transport the soHds. The Hildebrandt immersion extractor (18) employs a sequence of separate screw conveyors to move soHds through three parts of a U-shaped extraction vessel. The helix surface is perforated so that solvent can pass through the unit in the direction countercurrent to the flow of soHds. The screw conveyors rotate at different speeds so that the soHds are compacted as they travel toward the discharge end of the unit. Alternative designs using fewer screws are also available. 

The De Danske Sukkerfabriker (DDS) diffuser extractor (Fig. 6) is a relatively simple version of this family of machines, employing a double screw rotating in a vessel mounted at about 10° to the horizontal. The double screw is used to transport the soHds up the gradient of the sheU, while solvent flows down the gradient. Equipment using a single screw in a horizontal sheU for countercurrent extraction of soHds under pressure has been described (19). 

The heated polymer solution emerges as filaments from the spinneret into a column of warm air. Instantaneous loss of solvent from the surface of the filament causes a soHd skin to form over the stiU-Hquid interior. As the filament is heated by the warm air, more solvent evaporates. More than 80% of the solvent can be removed during a brief residence time of less than 1 s in the hot air column. The air column or cabinet height is 2—8 m, depending on the extent of drying required and the extmsion speed. The air flow may be concurrent or countercurrent to the direction of fiber movement. The fiber properties are contingent on the solvent-removal rate, and precise air flow and temperature control are necessary. 

Chemistry. Chemical separation is achieved by countercurrent Hquid— Hquid extraction and involves the mass transfer of solutes between an aqueous phase and an immiscible organic phase. In the PUREX process, the organic phase is typically a mixture of 30% by volume tri- -butyl phosphate (solvent) and a normal paraffin hydrocarbon (diluent). The latter is typically dodecane or a high grade kerosene (20). A number of other solvent or diluent systems have been investigated, but none has proved to be a substantial improvement (21). 

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. 

The purified acid is recovered from the loaded organic stream by contacting with water in another countercurrent extraction step. In place of water, an aqueous alkafl can be used to recover a purified phosphate salt solution. A small portion of the purified acid is typically used in a backwashing operation to contact the loaded organic phase and to improve the purity of the extract phase prior to recovery of the purified acid. Depending on the miscibility of the solvent with the acid, the purified acid and the raffinate may be stripped of residual solvent which is recycled to the extraction loop. The purified acid can be treated for removal of residual organic impurities, stripped of fluoride to low (10 ppm) levels, and concentrated to the desired P2 s Many variations of this basic scheme have been developed to improve the extraction of phosphate and rejection of impurities to the raffinate stream, and numerous patents have been granted on solvent extraction processes. 

Sedimentation is also used for other purposes. For example, relative motion of particles and Hquid iacreases the mass-transfer coefficient. This motion is particularly useful ia solvent extraction ia immiscible Hquid—Hquid systems (see Extraction, liquid-liquid). An important commercial use of sedimentation is ia continuous countercurrent washing, where a series of continuous thickeners is used ia a countercurrent mode ia conjunction with reslurrying to remove mother liquor or to wash soluble substances from the soHds. Most appHcations of sedimentation are, however, ia straight sohd—Hquid separation. 

Solvent Extraction. Solvent extraction has widespread appHcation for uranium recovery from ores. In contrast to ion exchange, which is a batch process, solvent extraction can be operated in a continuous countercurrent-fiow manner. However, solvent extraction has a large disadvantage, owing to incomplete phase separation because of solubihty and the formation of emulsions. These effects, as well as solvent losses, result in financial losses and a potential pollution problem inherent in the disposal of spent leach solutions. For leach solutions with a concentration greater than 1 g U/L, solvent extraction is preferred. For low grade solutions with <1 g U/L and carbonate leach solutions, ion exchange is preferred (23). Solvent extraction has not proven economically useful for carbonate solutions. 

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). 

The process (Fig. 3) is a countercurrent Hquid-Hquid extraction. The feedstock is introduced near the top of an extraction tower and the Hquid propane near the bottom, using solvent-to-oil ratios from 4 1 to 10 1. The deasphalted oil—propane solution is withdrawn overhead and the asphalt from the bottom, and each is subsequently stripped of propane. 

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