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HISTORY OF PAPER
Mechanical or groundwood pulp is made by subjecting wood to an abrading action, either by pressing the wood against a revolving grinding stone or by passing chips through a mill. The wood fibres are separated and, to a considerable degree, fragmented.
Chemical wood pulp is made by cooking wood chips with chemical solutions in digesters operated at elevated temperature and pressure. The chemicals used are (1) sulfite salts with an excess of sulfur dioxide and (2) caustic soda and sodium sulfide (the kraft process). The lignin of the wood is made soluble, and the fibres separate as whole fibres. Further purification can be accomplished by bleaching. Chemical wood pulp that is purified both by bleaching and by alkaline extraction is called alpha or dissolving pulp. It is used for specialty papers, for rayon and cellulose film production, and for cellulose derivatives, such as nitrate and acetate.
Semichemical pulp is made by treating wood chips with sulfite or alkali in amounts and under conditions that soften the lignin but dissolve only part of it. The softened chips are then defibred.
Pulpwood may arrive at the mill as bolts 1.2 metres (4 feet) in length or as full-length logs. The logs are sawn to shorter length, and the bolts are tumbled in large revolving drums to remove the bark. The debarked wood is next sent to grinders , where its moisture content is important for ease of grinding and quality of pulp. Moisture content should be at least 30 percent and preferably 45 to 50 percent. Wood of low moisture content is presoaked in a pond or sprayed with water.
Early grinders employed round slabs of natural sandstone 69 centimetres (27 inches) wide and 137 centimetres (54 inches) in diameter, often directly connected to water wheels, to produce five or six tons of pulp per day. The wood was hand-loaded into the grinders.
Today's much larger pulp grinders are usually powered by electric motors and automatically loaded. In a recently built mill, each grinder is gear-connected to a 10,000-horsepower motor; the pulpstone, at 360 revolutions per minute, can handle wood 1.5 to 1.6 metres (60 to 64 inches) long. Hydraulic cylinders produce a pressure of 14 kilograms per square centimetre (200 pounds per square inch) against the stone face. Pulp production from each stone is 130 to 150 tons every 24 hours.
The first artificial grinding stone was produced in 1924; since that time, artificial stones have replaced natural sandstone. Silicon carbide and aluminum oxide are the abrasives used in the manufacture of pulpstones. The abrasive material is broken down into a mixture of sizes that are screened to give fractions of uniform grain size. The abrasive grains are mixed with binder and fired at high temperature (2,300º C or 4,200º F) in the form of segments that are assembled to form the abrasive surface of the pulpstone.
The pulp stock flows from the grinder pit to a series of rifflers and screens, which separate the heavy foreign material and pieces of unfibred wood (shives), knots, bark, and the like.
Most groundwood pulp flows directly to an adjacent paper mill for use as stock. When shipped, it is formed into a sheet on a cylindrical vacuum filter. The sheets are pressed in a hydraulic press to a moisture content of about 50 percent, and the pressed sheets are formed into bales.
An important test to control the quality of groundwood pulp is freeness: the readiness with which water drains from and through a wet pad of pulp. Groundwood pulps are much less "free" than chemical wood pulps.
In groundwood pulp, the fibres are fragmented, and there is considerable debris (fines). Also, groundwood contains all the chemical constituents of wood, including lignin, hemicellulose, resin, and various colouring materials. This means that papers containing groundwood are subject to discoloration (yellowing) upon exposure to light and heat and after aging. The yellowing of newspaper and much book paper is an example of this. Because groundwood fibres are relatively short and have only a moderate ability to bond to each other, papers containing them do not have high strength. On the other hand, papers containing groundwood have good opacity; they are bulky and have good printing qualities.
Groundwood pulp does not have a high whiteness, being limited in this quality by the colour of the wood from which it is made. Although often bleached with peroxide or hydrosulfite to improve whiteness, it does not equal pure cellulose.
The effect of sulfurous acid (H2SO3) in softening and defibring wood was observed by B.C. Tilghman, a U.S. chemist, as early as 1857. Several years later he renewed his experiments and, in 1867, was granted a patent for making paper pulp from vegetable material. He used high temperature and pressure and observed that the presence of a base such as calcium was important in preventing burned or discoloured batches of pulp. His work, however, did not result in commercial use of the process.
During the 1870s the sulfite process for pulping wood was the subject of experimental work in Sweden, England, Germany, and Austria. Within a few years the process was in commercial operation both in Europe and in North America. For many decades the sulfite process was the leading process for the pulping of wood. Since 1940, however, the kraft process has taken a predominant position, and sulfite mills are no longer being constructed.
Sulfite cooking liquor, as it is pumped to the digester at the start of a "cook," consists of free sulfur dioxide dissolved in water at a concentration of 4 to 8 percent, together with from 2 to 3 percent in the form of bisulfite. Sulfite digestion is normally carried out as a batch process in a pressure vessel, a steel shell with an acid-resistant lining of ceramic tile set in acid-proof cement or stainless steel. A common digester measures five metres (16 feet) in diameter and 15 metres (50 feet) in height, with a domed top and a conical bottom. It has a capacity of 12 to 15 tons of pulp per batch. Digesters with a capacity of up to 35 tons have been constructed. Pulp mills normally have a series of digesters arranged in a digester building.
After the blow valve is closed at the bottom, the wood chips are allowed to flow into the top opening and are distributed to fill the digester completely. Hot acid from the accumulator is pumped into the digester unit, completely filling it and replacing the air. Steam provides the heat.
At the end of the cook, the contents of the digester are blown to a blowpit by rapid opening of the bottom valve. The violence of the blow defibres the cooked chips.
From 1 to 6 percent of the digester charge is undesirable material such as knots, uncooked chips, dirt, bark, fibre bundles, and shives. The screen room separates the unwanted particles from accepted fibre, normally on the basis of particle size; there is an increasing use of the centrifugal principle, which separates particles on the basis of density.
The sulfite cooking liquor does not "cook out" or disintegrate bark and other foreign material to the same degree as kraft liquor (described below), and hence more care must be used in selecting and cleaning wood chips for sulfite.
In the conventional sulfite cook using softwood, the typical yield is 44 to 46 percent, based on wood and with a lignin content of 2 to 5 percent. At that point, a relatively light-coloured pulp with good strength properties is obtained, suitable for use in the unbleached state, especially in mixture with groundwood for a variety of printing papers. For pulps in which high brightness (whiteness) is desired, the residual lignin is removed by bleaching.
In 1851 paper pulp was experimentally produced from wood by cooking it with caustic soda at elevated temperature and pressure. Although this soda process attained commercial importance, soda pulp was of relatively low strength; and use of the process was limited to manufacturing filler pulps from hardwood, which were then mixed with a stronger fibre for printing papers. Because this process consumed relatively large quantities of soda, papermakers devised methods for recovering soda from the spent cooking liquor; recovery has remained an integral part of alkaline pulping ever since.
In 1884 a German chemist, Carl F. Dahl , employed sodium sulfate in place of soda ash in a soda pulping recovery system. This substitution produced a cooking liquor that contained sodium sulfide along with caustic soda. Pulp so produced was stronger than soda pulp and was called "kraft" pulp, so named from the German and Swedish word for "strong." The process has also been termed the sulfate process because of the use of sodium sulfate (salt cake) in the chemical makeup. Sulfate, however, is not an active ingredient of the cooking liquor.
Many soda mills were converted to kraft because of the greater strength of the pulp. Kraft pulp, however, was dark in colour and difficult to bleach; for many years the growth of the process was slow because of its limitation to papers in which colour and brightness were unimportant. In the 1930s, bleached kraft became commercially important with the discovery of new bleaching techniques. The availability of pulp of high whiteness and the expanding demand for unbleached kraft in packaging resulted in rapid growth of the process, making kraft the predominant wood-pulping method.
Paper produced by the kraft process is particularly strong and durable. Acceptable pulp can be produced in the kraft process from many species of wood not suitable for sulfite. The various pines, for example, especially southern yellow pine, contain large amounts of wood resin or pitch. Chemically altered and dissolved in the kraft process, this material is removed from the pulp and becomes a valuable by-product. The wood pitch is not removed to the same degree in the sulfite process, and hence high-resin woods, such as pine, are not suitable.
In the cooking operation, wood chips are prepared and fed to the digesting equipment by methods previously described. The cooking vessels are still widely used as batch digesters. In the past 25 years, however, continuous digesters have been developed and are being widely adopted by the kraft industry. These huge cylindrical towers, more than 60 metres (200 feet) in height, have a number of zones or compartments. Wood chips and cooking liquor are fed into the top and injected into successive zones of high pressure and temperature, where impregnation and cooking takes place as the chips progress downward. Additional zones wash the spent liquor from the chips. Continuous digesters are capable of producing 600 tons of pulp per day.
In batch cooking, after the digester is charged with chips, a mixture of "black liquor," the spent liquor from a previous cook, and "white liquor," a solution of sodium hydroxide and sodium sulfide from the chemical recovery plant, is pumped in. The digester is heated either by direct injection of steam or by the circulation of the cooking liquor through a heat exchanger.
After completion of the cook, the spent cooking liquor is washed from the pulp; the latter is then screened and sent to the bleach plant or directly to the paper mill if it is to be used unbleached. Some of the spent liquor (black liquor) is used for an admixture with white liquor to charge new cooks; the remainder is sent to the recovery plant to reconstitute cooking chemicals.
All the sodium used for digestion is contained in the spent liquor, mostly in the form of sodium salts and sodium organic derivatives. The amount of sodium present is such that its reuse is economically necessary.
For semichemical pulping, wood preparation and chipping are essentially the same as that for other wood-pulping processes. The chips are steeped and impregnated with inorganic chemical solutions similar to those used for full chemical pulping, but in smaller amounts and with less severe conditions. Probably the most common is the solution of sodium sulfite in the neutral range, between acidity and alkalinity. Other agents used in some cases are acid sulfite, caustic soda, and kraft cooking liquor.
After the impregnation operation, the chips are fed into one or more disk refiners (described below) in series. The attrition action of refiners reduces the softened chips to pulp. The yield of semichemical pulp based on wood is 66 to 90 percent. The higher fibre yield pulps are usually termed chemimechanical pulps.
The semichemical pulps have chemical and strength properties intermediate between softwood, groundwood, and full chemical pulps. These are used in a wide range of papers and boards. The major tonnage of semichemical pulps goes into the light board, termed corrugating medium, which is fluted to serve as the interior layer of corrugated boxboard in heavy-duty containers. Stiffness and adequate strength are the important properties. Semichemical pulp is used in many low-cost printing papers.
The use of calcium and sodium hypochlorites to bleach paper stock dates from the beginning of the 19th century. In the early days of sulfite pulp manufacture, a single-stage treatment of pulp at low consistency, using calcium hypochlorite (chlorinated lime), satisfied most requirements.
This simple bleaching treatment, however, is not practical for kraft that is difficult to bleach, nor can it retain maximum pulp strength. Accordingly, multistage bleaching systems have evolved in which various sequences of chemical treatment are employed, depending upon the type of unbleached pulp and special requirements.
During the normal first stage in a modern bleach plant, the unbleached pulp is chlorinated. Three to four percent of gaseous chlorine is rapidly mixed with pulp at a temperature of 21º to 27º C (70º to 80º F); the mixture is quite acid due to the acidity of the chlorine. Chlorine is absorbed largely by reaction with the noncarbohydrate components of pulp, with no brightening effect and with only slight dissolution of lignin.
In the following stage an alkaline extraction with dilute caustic soda dissolves chlorinated compounds, which are then washed out.
In its simplest sequence the final stage consists of a treatment with a very alkaline hypochlorite to neutralize the solution, followed by a final wash.
In recent years the compound chlorine dioxide (ClO2) has become available for on-site preparation; it is too unstable to be shipped for wood pulp bleaching. By the use of small amounts of ClO2 in later bleaching stages, it is possible to achieve high degrees of purification and brightness without the degradation of cellulose.
The brightness of paper and other materials is determined by special reflection meters containing photoelectric cells that measure the amount of light of selected wavelength reflected by the surface. Freshly prepared pure magnesium oxide is considered to be 100 on the brightness scale. On this scale unbleached sulfite and groundwood cover the range from about 50 to about 62; peroxide bleached groundwood, 66 to 72; single-stage hypochlorite sulfite, 80 to 85; multistage bleached pulp, 85 to 88; and multistage with chlorine dioxide, 90 to 94.