By STARCHES AND RELATED PRODUCTS Starch consists of a chain of p-glucopyranosyl units and has the general formula (CHyoO), with n = 250 to over 1000. Two major components are recognized as usual, a branched- chain form, amylopectin (75 to 80% in common starches), and a linear form, amylose HoH CHO ( is © Jt Jk \ ok , / ev \o OH OH Ca H HA 4 eH H OH Amlose segmeat of a linear chain eo | HOH ine | (m0. ¢ 0. Na a" NH . Ww \ / \oit u On ° H ou Amilapectin: segment af a Branched chain \ vA Som Starch is one of the most common substances existing in nature and is the major basic con- stituent of the average cliet. Industrially, its applications'S are numerous, and it is used in more than 300 modern industries, including the manufacture of textiles, paper, adhesives. insecticides, paints, soaps, explosives, and such derivatives as dextrins, nitrostarch, and corn sugar. In recent years such derivatives as heat-resistant adhesives, esters comparable with cellulose esters, carboxylic acids from the oxidation of dextrose, and wetting agents have been produced HISTORICAL? Iisa well-known fact that the ancients used starch in manufacturing paper jas an adhesive and stiffener) as carly as 8500 8c, The Egyptians of this period cemented papyrus together in this maimer Between ab. 700 and 1300, most paper was heavily coated with starch, but the practice wis abandoned toward the end of the fourteenth century and was not revived until the modern era, The use of starch in testiles began during the Middle The Corn Industries Research Foundation, Inc., 1001 Connecticut Ave., Washington D.C, publishes an important series of pamphlets on the corn wet-grinding industries, which are kept up to date. Titles are Corn in Industry, Corn Starch, Corn Gluten, Corn Act, Corn Syrups and Sugars Knight, The Starch Industry, Pergamon, Oxford, 19696u Ages, when it was a common stiffening agent. By 1744 the English.were using it in sizing and warp glazing. Textile demands soon brought about the introduction of potato starch to sup- plement the wheat starch solely available up to this time. In 1811 the discoveries of Kirchhoff with respect to glucose and the thinning of starches by enzymic action gave great impetus to starch manufacture through the increased fields of application created. The use of roasted starch (dextrins) did not begin until 1821, its usefulness being discovered as the result of a textile fire at Dublin, Ireland. It had, however, been prepared by LeGrange as early as 1804 The first starch produced in this country was white potato starch, made at Antrim, N.H., in 1831. In 1842, Kingsford began the production of cornstarch, which became increasingly popular until, by 1885, it had risen to the position of the leading textile starch in the Geld. It was in this period also that the manufacture of dextrins (roasted starches) began in the United States. USES AND ECONOMICS. In 1981 about 6.7 X 10° kg of starch was produced in the United States for all purposes, including conversion into syrup and sugar. Of this total about 98 per- cent was cornstarch. Imports are principally tapioca, sago, and arrowroot starches, and exports are principally cornstarch. The largest single use for cornstarch is as food, about 25 percent being thus consumed. Industrial uses account for the remaining 75 percent. The paper industry utilizes cornstarch as a filler and a sizing material. Textile, laundry, foundry, air flotation, oil-well drilling, and adhesives use much starch (Chap. 25). White potato starch can be employed for almost every one of the uses outlined for cornstarch; it has a more desir~ able phosphoric acid content but is more expensive Wheat, rice, arrowroot, and cassava (tapioca) starches also have many of the sare appli- cations as cornstarch. Rice starch is particularly preferred for laundry purposes. Tapioca starch is very common as a food. In addition to the starches themselves, many further reaction products are made. These include the following products: dextrin, which is available in more than 100 different blends and types varying from pure white to light yellow in color is used to make a great number of different pastes, gums, and adhesives. Corn syrups are a hydrolysis product of cornstarch, containing dextrose, maltose, higher saccharides, and water. Approx- imately 95 percent is used for food, and varying types are offered to the trade: conventional syrups, primarily dextrose made by acid or enzyme hydrolysis; syrup solids and crystalline dextrose made by drying conventional syrup; and three grades of high-fructose corn syrup (HFCS) made by conversion with a special enzyme and containing 42%, 55%, and 90% fruc- tose. Nonfood and industrial applications are important, as in the textile, leather-tanning, adhesive, pharmaceutical, paper, and tobacco industries. Corn sugar, or dextrose, is the sugar found in the blood and is our primary energy food. Its many food uses are dependent upon its lower rate of crystallization, lesser sweetness, and different crystal formation, Dextrose is consumed in baking and has additional uses in preserved foods, soft drinks, candy, and ice cream. It is widely employed by the medical profession for infant feeding and for prescrip- tions in syrup form, Industrially, it is important as a constituent of the viscose-rayon spinning bath, in leather tanning, in tobacco conditioning, and in fermentation. Important by-products of the starch industry are corn gluten, feed and meal, corn-oil meal, and corn oil. Virtually all gluten and meal are used as feed, but a specially prepared gluten, very high in protein, is employed as a raw material in manufacturing plastics and lacquers. Concentrated steep water is consumed in the growing of penicillin and streptomycin (Chap. 40). Inositol, or hexahy- droxycyclohexane, a sugar substance and a member of the vitamin B complex, is made from corn steep water.ol MANUFACTURE OF STARCH, DEXTRiN, AND DEXTROSE FROM CORN. Corn wet refining is a large industry, processing more than 12.8 X 10° kg of corn per year. Chemically, the corn kernel consists of from 11 to 20% water, with the following average constituents, expressed in percent.” Moisture 16 Oil 3.8 Starch 61 Fiber 2 Proteins 9 Sugars 1.6 Pentosans 5.8. Ash 13 On this basis, 100 kg of corn yields 51.3 kg of starch, 39.2 kg of by-products (ghaten meal, corn bran, germ-oil meal, and steep water), and 2.8 kg of corn oil. The refining process utilizes wet milling in a dilute sulfurous acid medium using shelled corn as the raw material,” as shown in Fig. 30.6. The sequences are as follows: The first operation consists of cleaning the corn by means of screens, compressed air, and electromagnets. The cleaned corn is soaked (steeped) for 2 days in circulating warm water (46 to 52°C) containing 0.10 to 0.30% sulfur dioxide to prevent fermentation during the soak- ing period. Large hopper-bottomed wood or stainless-steel steeping vats (holding 8200 kg of 2°Corn Industries Research Foundation, op. cit., 1958. *Forbath, Process Maze Yields Maize Products, Chem. Eng. 68 (5) 90 (1961) (owchart); Wet Milling of Corn, Chem. Eng. 69 (16) 117 (1962) copa 4 | a, wel a = cova = | _ nd om comeldad 3 | {we | [axe] 14 Fiber to feed Sarnes | ems | | com sree Fig. 30.6. Corn produets outline flowchart. (Com Products Refining Corp. and Dorr-Oliver.)corn) are employed for this operatic, which softens the gluten and loosens the hulls. The steep water dissolves salts, soluble carbohydrates, and protein The cleaned and softened kernels : re degerminated between two studded steel plates, one rotating and one stationary, which ter the kernels apart and extricate the corn gernts without crushing them. The corn germs are |:quid-separated from the hulls in so-called germ sepa- rators, formerly large, agitated tank Now stationary cone-shaped hydroclones® (Fig. 30.7} are more efficient, using continuous vravity separation of the germ by the centrifugal action of a tangentially injected suspension of germ-fiber starch, with the lighter germ in the over- flow (top center). This results in a cl-aner and more accurate process at less capital invest- ment. The germ is subjected to oil extraction as described in Chap. 28, using either expellers or solvent extraction The remainder of the corn kerne! contains starch, gluten, and cellulosic fiber. It is wet ground in impact fiber mills and p:ssed through high-capacity stationary sereens® called sieve bends, depicted in Fig. 30.8. In: he sieve bends the starch and gluten are washed coun- tercurrently with process water to remove them from the fiber, which is the oversized mate- rial, all of which was mechanically s-parated in the fiber-milling operation To separate the heavier starch from the gluten, the old, cumbersome, gravity starch tables ‘Dorr-Oliver, Hydrocyclones, Chem, Eng. 71 (1) 48 (1964). *£Elsken and Ehenger, Stationary Screens, Chem. Eng. Prog. 59 (1) 76 (1963) an-diameter hydroclones. All six hydroclones shown ope arallel with the lighter germ in the central overflows, (DorrFig. 30.8, Fiber-washing 120° sieve bend. Stationary screens of a 120° are. (Dorr-Oliver.) have been discarded, and this separation is now done in pressure-nozzle discharge centrifuges (Fig. 30.9) and purification by pumping through starch-washing hydroclones** (Figs. 30.10 and 30.11) from which the “middlings” are returned to the centrifuge for recycling. These centrifugal devices intensify the force of gravity, require less space. and are cleaner, since they are completely enclosed. The gluten, as shown in Fig. 30.6. is sent to be mixed with oil cake and fiber for animal feed. Some gluten is partially dehydrated and sold as an adhesive or alcohol-extracted to yield zein. The highly mechanically purified starch is dried and sold soluble dextrins and gums “cooked” to heat-convert it to Over 70 percent of the cornstarch produced by wet milling is now used in the manufacture of corn sweeteners, principally HFCS. A modest percentage of the syrup formed is converted to crystalline dextrose using crystallizers similar to the one shown in Fig. 30.12. If commercial starch is to be made, the starch is removed from suspension with a vacuum rotary string-discharge filter, The cake is broken and dried by flashing or in a continuous tunnel dryer traveling countercurrent to the air. The starch enters with a moisture content of 44% and exits at 10 to 14% This form is sol pearl starch. Powdered starch is ground and *James, Industrial Starches, Noyes, gamon, Oxford, 1965. ark Ridge, N.J., 1974; Bradley The Hydroclone, Per-‘venrLow & Fig. 30.9. Gluten sepuration joverlow) by Merco disk pressure-nozzle bow! cer trifuge The suspension enters into the cen*er feed well. at the bottom of impeller throws the slurry to the outer portion of the disk stack. Here centrifugal force throws the heavier starch toward the periphery of the rotor ad, as a result, the starch panicles settle on the underside of the individual disks and slide down hich the to the outer area of the bowl, where the voncentrated stireh shires as diseba through the nozzles (on the periphery) and through the underilow A somewhat glatensater fraction similar Mercu centrifuge is used te Uuicker. the septs screened pearl starch Lump, or gloss, starch is made from powdered starch containing 2 slightly higher percent of moisture. Precooking the starch yields gelatinized starches. For thick-boiling starch, alkali conversion is used; {or thin-boiling starch, mild acid conversion Oxidized starch, also known as dialdvhyde starch, is made by treating starch with hypochlo- rite or electrolytically produced periodic acid. Specialized food starches known as cross: inked starches result {rom treatment of starch with POC], epichlorohydrin, or sodium meta- phosphate. Starch esters such as starch acetate and ethers made with ethylene or propylene oxide enjoy considerable use as textil- sizes Another product of corn refining i: dextrin, ur roasted starch, Starch itself is not soluble in dily to give various commercial adhesives water, but its derivative, dextrin, dissolv 1 is carried on in round. steam-jacketed tanks equipped with its sticking during the heating period, which for certain gums, The temperature also pastes, and gums: Conver seraper and open at the top. The sersper preve may vary from 2h for sume white dextrins to 15, influences the kind of dextrin being prepared The average yi sugar froma hectare of cane is 13,400 kg, A hectare of beets usually produces about 8400 ky of sugar. Prese 1 13,600 kg of grain per hectare The 13,600 kg of corn grain will produce 9700 kg of starch which can be converted to 10,100 kg uf glucose. Sincr cane requires about 18 months to produce and corn less than half that ade from cornstarch, yields per hectare orn yields appro it is apparent that, if acceptable sweetene:s can be year are far greater and costs consequently less than for cane even if the value of corn oil,Fig. 30.10, Purification of starch through gravity accentuated by centrifugal washing in mo s. These hydroclones are much different than those of Fig. 80.7, being only 10 mm in diameter and made of nylon, with up to 450 arranged in a separate in parallel By employing a series of nine lone iuiits, both insoluble protein (ginten and solubles are removed from the starch slurry. (Dorr-Oliver.) housing, and operativ of these multiple hyd protein, and ensilage is ignored, This favorable economic situation has led to the conversion of over 70 percent of the cornstarch produced to sweetener for food use. A variety of other products and by-products from starch processing are commercially important. Superabsorbents are starch graft polymers using made by starch modification. The important. Many starch-containing adhesives have b capable of absorbing up to 1500 times their weight of w polyacrylonitrile as the cross-linking agent, Basic caramel BStarch as a Source of Sweeteners, Die Starke November 7, 1973, p. 1; Wieland. Enzy in Food Process ducts, Noyes, Park Ridye, N.J.. 1972; Rosenaweig. A Swe Fature Buoys High-Frnctose Corn Syrup, Chen, Eng. 83.20) 54 (1976); Valle Sweeteners Outlook, Sugar J. 43 (8) 13 (1981). \ Surrey of the Literature on Starch Adhesives, Washi sh. 1970. Worthy, Super-Shieper Gaining Commercial App (1979); Superabsorberts Seek Markets That Are Super, Che geand Pr mier, Corn pn State Ziegler and University, Pullman, V cation, Chem. Eng. News 57 (45) 23 1. Week 125 (3) 40 (1979).00 Fig. 30.11, The multiple hydroclones are shown with one honsine open. disclosing the stationars. sill, relatively short tnvtin vem trifugal devices fed through the side of the housing (not visible in the figure) Individually, the 480 hydrocknes are fed tangentially with the overflow, or lighter gluten, discharged from one housing and the underflow, or heavier starch, di-charged from the other housing. (Dorr-Oliver.; steep-liquor has proved to be a good culture medium for several microorganisms. The by- products, such as gluten fiom wheat starch manufacture, are used for cattle feed and hydro- cegetable jrrotein, a flavoring agent containing the favor enhan- lyzed to form hydrolyze cers. ghitamie acid and monosodium glutamate. Gasohol is being made in converted wet- milling plants in substantial quantity. By 1983, such plants in the United States are slated to produce 1.55 X 10° L of ethanol, a not inconsiderable quantity of motor fuel. Brazil has a very ambitious program to produce alcohol from sugar ca MISCELLANEOUS STARCHES Amylose. Atmylose occurs to the extent of 2 ncorustarch, the other 73% being ary lopectin Amplose is at linear chain of dextrose unis atl ssembles cellulose, which it can plant for many nse, such as in fils, adhesives, and paper. Waxy corn is almost all amy- lose and is being grown in increasing amounts However, there are a number of processes for separating the two st hes (Staley. Corn Products, ete.’ One process heats the cornstarch *Staley, Starch Carbohydrates, Chem. Eng. 68 (5) 80 (1961)junol oy410g —adid Avouoy 045slurry under pressure to prevent hoi! ng, whereupon the mixed starch dissolves. upon slow cooling to about 49°C the amylose c:stals form and are recovered, leaving the amylopectin to be precipitated upon further cooli: : White Potato Starch.” White potatoes contain 10 to 30% starch. Upon being received at the factory, the potatoes are wash and disintegrated to a water pulp, using a hammer mill. The pulp is treated with sulfur -lioxide gas, in the ratio 0.3 kg per kilogram of starch. and sent to a continuous horizontal centrifuge with an imperforate conical bow! and a con: tinuous-spiral-ribbon starch remover. The protein-water mixture is separated from the starch cellulose, and skins, and the latter three substances are resuspended in water The suspension is sieved, and the pulp from the sieves is reground and resieved. The liquor from the second sieving is again passed through a cratrifuge, suspended in water, and sent to separation devices. From this point on operations are similar to those used for the manufacture of corn- starch (Fig. 30.6), Two other processes are also used. In the batter process, which is similar to Martin's process, the dough formed is dispersed in water and the dispersed gluten collected on a sieve. Using alkali in a similar process disperses the gluten sufficiently that the starch settles out on standing Rice Starch, This is made from “cargo rice,” which still has the brown outer cuticle attached or from broken white grains rejected as foodstuff. The rice is steeped for 24 h with dilute caustic soda solution (1.005 specific gravity) in tanks with perforated false bottoms. At the end of the period the liquor is withdrawn, the rice washed, fresh liquor added, and steep- ing continued for another 36 to 48 h. ‘The resulting softened grains are ground with a caustic solution to a specific gravity of 1.24, and the mash is centrifuged. The solids obtained include all sorts of fibrous material, starch, and gluten. These are resuspended, a small amount of formaldehyde is added to inhibit fermentation, and they are recentrifuged and washed. & bleaching or bluing agent may be added at this point, The liquor is screened, adjusted toa specific gravity of 1.21, and sent to disk centrifuges. The resulting starch is dried for 2 days at 50 to 60°C. Cassava (Tapioca) Starch. This starch is obtained from the roots and tubers of the man- ioe plant. Imports are mainly from Thailand and Brazil. The average starch content varies from 20 to 30%. In general, the roots are pulped and washed on sieves to obtain the starch Separating and purifying operations are similar to those described for potato starch Sago Starch. This is obtained from the pith of the sago palm, and also from yams in the East Indies and Borneo. Pearl sago starch is made by drying the starch so us to form a plastic dough, which is then forced through sieves and dried in the air. Other Starch Sources. Sweet potutoes, sorghum, waxy sorghum, and waxy corn are all currently important sources of starch which is obtained from them by methods substantially similar to those described here. Knight, op. cit. p. 5869 SELECTED REFERENCES Arrington, L. J Beet Sugar in the West, Univ. of Washington Press, Seattle, Wash., 1966. Colbert, A. C.: Sugar Esters, Noyes, Park Ridge, N.J., 1974 Honig, P.: Principles of Sugar Technology, 3 vols., Elsevier, New York, 1962. James, R. W.: Industrial Starches, Noyes, Park Ridge, N.J., 1974 Johnson, J. C.: Immobiltzed Enzymes, Preparation and Engineering, Noyes, Park Ridge, N.J., 1971 Johnson, J. C.: Specialized Sugars for the Food Industry, Noves. Park Ridge, N.]., 1976. Knight, J. W.: The Starch Industry, Pergamon, Oxford, 1969 Lachmann, Starches and Corn Syrups, Noyes, Park Ridge. N.J., 1970. Murry, C. R. and J. E. Holt: The Mechanics of Crushing Sugar Cane, Elsevier, New York, 1967 Panacest, H. M. and W. R, Junk. Handbook of Sugars, 2d ed. Avi, Westport, Conn., 1980 Schalit, M. Guide to the Literature of the Sugar Industry, Elsevier, New York, 1970. Vukov, K.: Physics and Chemistry of Sugar-Beet in Sugar Manufacture, Elsevier, New York, 1977. Whistler, R. L,, et al, (eds,): Methods in Carbohydrate Chemistry, 5 vols., Academic, New York, 1965, 1964.0 Chapter 4 Plastic Industri€s The development of plastics from laboratory curiosities to products tailored to industry's needs has brought new and economical materials of construction to the engineer and the designer. Not only can plastics replace metals and other materials, but they can also be used with them. A plastic may be defined as a material that contains a polymerized organic sub- stance of large molecular weight as an essential ingredient, is solid in its finished state, and at some stage in its manufacture or its processing into finished articles can be shaped by flow The common basic raw materials are coal, petrochemicals, cotton, wood, gas, air, salt, and water. Plastics lend themselves to an exceedingly large number of applications because of their toughness, water resistance, excellent resistance to corrosion, ease of fabrication, and remarkable color range. ‘The use of a plastic material for a specific application is dependent upon its composition, its particular properties, and the design of the part. Synthetic resins are the largest source of plastics, with cellulose derivatives ranking next. All plastic materials of construction have lim- 'y can be used with the same degree of assurance as tations, but, when properly selected, metals and alloys nisToRICAL. The development of a commercial phenolic resin in 1909 by Baekland was the start of the synthetic plastic industry. His discovery stimulated the search for other plastics and resulted in an industry that has grown to become one of the nation’s top ten in size. The first plastic of industrial significance was cellulose nitrate (Celluloid) and was discovered about the middle of the nineteenth ce stury. It was first used in 1869 by Hyatt who was searching for an ivory substitute Cellulose acetate was developed in 1894 as a less flammable material and was used exten sively as a base for photographic film and as “dope” for airplane coverings during World War I From that time on, the introduction of new polymer materials was rapid. Table 34.1 shows the date of discovery and/or commercial introduction of the earlier plastics. CLASSIFICATION, Plastics are often divided into thermosetting, thermoplastic, oil soluble. and protein products as presented in Tables 84.2 and 34.3. On the basis of derivation, they may be grouped as natural resins, cellulose derivatives, protein products, and synthetic resins. In general, except where noted, synthetic resins formed by condensation polymerization are thermosetting (heat curing produces an infusible or insoluble product), and synthetic resins formed by addition polymerization are thermoplastic (heating softens and cooling hardens? indamentally different These twe_polymerization reactions are Addition polymerization involves a series of conversions which produce a polymer having a recurring structural unit identical with that of the monomer from which it is formed. Con- densation polymerization yields polymers whose recurring units lack certain atoms present in the original monomer. The reaction takes place by the combination of two or more units and the elimination of a small molecule such as water, methanol, or hydrogen chloride. During,i Table 34.1 Early History of Polymers: Poly mer Year Introduced Cellulose nitrate Ls68 Cellubise acetate Loyd Phenol formaldehyde 1909 Cellulose ethers 1912 Vinyl 1927 Urea-formaldehy de 1924 Acry lates 1931 Furans 1934 Polystyrene 1937 Polyamides 1938 Melamine-formaldehy de 1930 Polyesters 1942 Silicones 1942 Polyethylene 13, Fluorocarbons 1946 Epovy 1945 Crystalline poly propylene 1937 Phenony 1902 Table 34.2 ‘Types of Resins and Plastics, with Some Common Trade Names Thermosetting Resins Phenolic resins Bakelite, Durez, Catalin, Formica, Indur Amino resins. Plaskon, Beetle, Cymel, Miearta, Melinac Alkyd resins: Glypial, Rezyl, Becksol, Dulux Epoxy resins: Epon, Araldite, Ren, Epocast, Merblette Polyester (unsaturated) and allyl resins. Arapol, Atlas. Dapon Silicone resins Pyrotex, Dow Corning Polyimides: Vespel, Kapton Thermoplastic Resins Cellulose Derivatives Cellulose uitrate: Celluloid, Pyralin, Niteon Cellulose acetate: Kodapak, Tenite, Plastacele Cellulose propionates. Forticel, Reed Cellulose acetate-butvrates: Tenite HI, Kedapak 1 Ethy! cellulose: Ethoced, Soplasen, Camper Polyiner Resins Acrylate or polyacrylates: Plexiglas, Lucite, Acrylod Vinyls: Vinylite, Gelva, Butacite, Koraseal, Alvar, PVA Polysinylidenes Sean Styrenes: Styron, Lustres, Loalin Polvamides Nvlon Zvtel. Kevlar, Nomes Polvethers Penton, Gateon, Delrin Polyethylene Polyethylene, Poly-Eth, Tygothene, Pentothene Palypropylene: Poly-Pro, Pro-fax Fluorocarbons: Kel-F, Tellon, Fluorosint Polyesters. Mylar, Celanex, Ekonol Polycarbonates Levan, Merlon Polysulfones. Udel, Astrel 360, Vietrex, Radel