Solid—Liquid Extraction Solid-liquid extraction is the process of separation of soluble constituents of a solid material using. a suitable solvent. Usually the soluble material is the target product, and the “inert” solid residue is a by-product or just a solid waste (for example, in extraction of oil from oil seeds, the oil the product, and the solid residue or cake is a by-product). In some cases, the undesirable soluble ‘materials are removed from the solid by using a solvent and the extracted solid is the product, (for example, extraction of de-fatted soy flour using aqueous ethanol as the solvent for removing, sugars and some non-protein solids; the solid residue called ‘soy protein concentrate’ is the product; the solutes extracted may be recovered as by-products). The overall process of liquid— solid extraction basically involves four steps: (i) intimate contact between the solid feed with the solvent; (ii) separation of the solution (or extract) from the exhausted solid; (ii) separation of the solvent (and the entrained solid, if any) from the extract followed by purification of the product; (iv) recovery of the solvent from the moist solid (by squeezing/pressing and drying to get a dry cake). Solid-liquid extraction is also called ‘leaching’, although here we shall use the term leaching in a slightly restrictive sense. This operation is different from “dissolution” in the sense that in dissolution almost the entire solid gets into solution leaving very little or no ‘inerts’ behind. But in solid—tiquid extraction or in ‘leaching’, a substantial part of the solid does not dissolve and. the soluble matters diffuse out through the solid during solid—liquid contact. ‘There are many examples of solid-liquid extraction in chemical and allied industries. Veg- cable oils are frequently extracted from oil seeds by a suitable solvent. Sometimes a part of the oil is removed from the seeds by pressing, and the residual oil in the ‘cake’ is recovered by extraction. Hexane is the most popular solvent for oil extraction because (i) it can be easily removed from the extract by ‘flashing’, (fi) it is non-toxic, (iii) it is reasonably cheap, and. (iy) itis miscible with vegetable oils in all proportions. Use of chlorinated solvents (e.g. trichlo- rocthylene) has been discontinued mainly because these are toxic and carcinogenic. The solvent hexane is separated from the extract and the oil is subjected to the refining process. The process. of ‘solvent extraction’ of oil seeds is schematically shown in Figure 9.1. Solid-liquid extraction is widely used in the food industries and a detailed account of it has been given by Schwartzberg, (1980). wn478 Chapter'9 Solid-Liquid Extraction Steaming (optional, necessary for low-oi hard kernels Direct extraction Exraction Gitmeal] (continuous horizontal |, [Peicizatiol], Cake [Pressing 35%) paket, Hildebrand or Boliman|™| flaking (A sere a ctor is commonly used) ‘eommon) [Desotvenier oi [Seam Oil for | ea stripping | refining Sal ‘Solvent ‘Solvent sean Meal (for Solent imal feed) revyeled Figure 9.1 Solventextractonofolseeds, 9.1 CLASSIFICATION OF SOLID-LIQUID EXTRACTION SYSTEMS Solid-Liquid extraction may involve different physico-chemical mechanisms depending upon the characteristics of the solid (particle size, porosity or compactness, reactivity, solute content, etc.) and of the solvent. Ifthe particle size of the solid is not small, there may be substantial diffusional resistance to transport of the solute within the solid. Whenever possible, the solid is broken down or disintegrated into particles or flakes (in the case of oil seeds, for example) to enhance the rate of extraction. Sometimes an acidic, alkaline or a complexing solution may be used for solubilization. of the target substances. Rickles (1965) classified commercial solid-liquid extraction systems into the following categories. Diffusional extraction Almost the entire mass transfer resistance lies in the solid phase in such a case and hence the name diffusional extraction. An example of a system of this category is extraction of sugar from sugar beet. Sugar beets are cut into small pieces called “cossettes’ which are treated with warm water (70-75°C). Diffusion within the solid occurs through denatured cell walls and through the Interstical liquid. The solvent (water) also diffuses in the opposite direction, thus diluting the solute within the cells. The rate and time of extraction depend mainly upon the thickness of the pieces, the ‘effective diffusivity’ of the solute in the solid, and the concentration of sugar in the extracting liquor. Many other solid-liquid extraction systems in which the extraction rate is controlled by solid-phase diffusion of the solute, are encountered in food processing industries (Schwartzberg, 1980).Classification of Solid-Liguid Extraction Systems 479 Washing extraction If the solid particle size is pretty small, the solid-phase diffusional resistance becomes negligibly small. In such a case, extraction virtually becomes a process of washing the solid with the solvent. ‘An example is extraction of oil from ‘flakes’ of oil seeds. Flakes are pretty thin (fraction of a millimetre), Further, during the flaking process much of the cells are ruptured and the diffusional resistance for transport of the solute within the solid becomes small. In washing extraction, a substantial amount of solvent is retained in the slurry after washing. The solute concentration in the liquid retained in the slurry is nearly the same as that in the bulk liquid. Leaching This involves dissolution of one or more substances from solid particles accompanied by chemical reaction(s). An acid, alkali or the solution of a complexing chemical is commonly used. for solubilizing the target materials. Leaching of ores (oxides, carbonates, sulphides, etc.)is a major step in hydrometallurgy. Leaching of copper minerals by sulphuric acid or an ammoniacal solution, leaching of gold from its ores by sodium cyanide solution are typical examples (use of cyanides is less common nowadays because its a severe pollutant). Low-grade ores are sometimes. leached under drastic conditions. For example, a recently developed method of leaching low- grade nickel ore, called nickel laterite, uses sulphuric acid at 250°C and 650 psi pressure 10 dissolve the nickel (Hairston, 1999); cobalt is the by-product. An extraction vessel with acid resistant bricks or with titanium cladding may be used under such an extreme condition. “Bioleaching" is a novel technique (Ciminelli et al., 2001) of dissolving ores, particularly the low-grade ones, cartied out at near ambient condition without the use of chemical agents. Bacterial species like Thiobacillus Ferrooxidans and thermiphilic species such as Sulphobacillum, Acidianus, and Sulpholobus convert ores, particularly sulphide ores, to soluble sulphates. The process, though slow, is non-polluting since no sulphur dioxide is emitted unlike the conventional roasting process, Bioleaching is in commercial use for extraction of copper (about one-fifth of global extraction of copper is done by bioleaching), gold, zinc, nickel, etc. Chemical extraction This is functionally similar to the leaching operation but usually refers to recovering solutes from. solids of organic nature. Recovery of gelatin from animal bones using an alkaline solution is an example of chemical extraction, A few more commercially important solid-tiquid extraction systems of the above categories are described in Table 9.1 Tablo 9.1 Commecialy important iqud-soié extraction systems (fickle, 1965; Schwartzberg, 1980) ‘Solita Foedsold ‘SoweniProduct (@)_Ditusionalexraction Sole coer Colle beane Water Fshols Fish meal, whole fsh ‘ooh, hexane, ecto produce fish protein cencerale Sugar Sugar beets Water, to produce sugar Water Frats ‘Sugar souion—for osmate dehydrator’ offs Conta.)