Sulfate pulps

Schoettler has studied the alkali resistance of the xylan in pulps made from aspen wood. Verifying and extending previous work by March, he" observed a higher content of xylan resistant to 17.5% sodium hydroxide in aspen alkaline pulps (sulfate or soda process) than in aspen, chlorite holo-cellulose. Further chlorite treatment of an alkaline pulp did not reduce its xylan or resistant-xylan content. Alkaline (sulfate) cooking of the holo-cellulose did not increase the resistant-xylan content. These results are summarized in Table X. 

Wood can be disintegrated or digested by four methods sweetening the wood, or producing sodium hydroxide pulp, sulfate pulp, or sulfite pulp. 

Scheme 5.1.4 shows the conversion of wood by chemical pulping (sulfate or sulfite process) into cellulose and cellulose derivatives. The lignin and hemicellulose... 

Terpenes, specifically monoterpenes, are naturally occurring monomers that are usually obtained as by-products of the paper and citms industries. Monoterpenes that are typically employed in hydrocarbon resins are shown in Figure 2. Optically active tf-limonene is obtained from various natural oils, particularly citms oils (81). a and P-pinenes are obtained from sulfate turpentine produced in the kraft (sulfate) pulping process. Southeastern U.S. sulfate turpentine contains approximately 60—70 wt % a-pinene and 20—25 wt % P-pinene (see Terpenoids). Dipentene, which is a complex mixture of if,/-Hmonene, a- and P-pheUandrene, a- and y-terpinene, and terpinolene, is also obtained from the processing of sulfate Hquor (82). 

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S0 3, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach Hquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH NO, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and cosdy ore particle/leach hquor separation step. 

The most commonly used reinforcement for high pressure decorative and industrial laminates is paper (qv). The strong substrate layers, or filler, are kraft paper. Kraft is a brown paper made from a sulfate pulp process (8). It consists of both short cellulose fibers from hardwoods and long fibers from conifers. The long fibers impart most of the wet strength required for resin saturation processes. 

Rotary kilns and, to a lesser extent, Fluo-SoHds kilns are used to calcine a wet precipitated calcium carbonate filter cake in the kraft or sulfate paper-pulp process (15). Lime is regenerated for use as a causticization reagent in recovering caustic soda for pulp digestion. Losses in lime recovery are replaced by purchased lime (see Paper Pulp). 

Uses. The principal use of magnesium hydroxide is in the pulp (qv) and paper (qv) industries (52). The main captive use is in the production of magnesium oxide, chloride, and sulfate. Other uses include ceramics, chemicals, pharmaceuticals, plastics, flame retardants/smoke suppressants, and the expanding environmental markets for wastewater treatment and SO removal from waste gases (87). 

The pulp and paper industry and potable and wastewater treatment industry are the principal markets for aluminum sulfate. Over half of the U.S. aluminum sulfate produced is employed by the pulp and paper industry. About 37% is used to precipitate and fix rosin size on paper fibers, set dyes, and control slurry pH. Another 16% is utilized to clarify process waters. The alum sold for these purposes is usually Hquid alum. It is frequendy acidic as a result of a slight excess of H2SO4. Aluminum sulfate consumption by the pulp and paper industry is projected to remain constant or decline slightly in the near term because of more efficient use of the alum and an increased use of alkaline sizing processes (13). 

Kraft Process. The dominant chemical wood pulping process is the kraft or sulfate process. The alkaline pulping Hquor or digesting solution contains about a three-to-one ratio of sodium hydroxide, NaOH, and sodium sulfide, Na2S. The name kraft, which means strength in German,... 

ChemicalRecope . There are advantages and disadvantages to each of the base systems employed in sulfite pulping (see Table 4). Each has its own potential recovery systems except the calcium system, which is obsolete. Calcium-based Hquors can be burned, but scaling problems are severe, and conversion of the calcium sulfate to CaO is not economical. 

Sulfates of sodium are iadustriaUy important materials commonly sold ia three forms (Table 1). In the period from 1970 to 1981, > 1 million metric tons were consumed aimuaHy ia the United States. Siace then, demand has declined. In 1988 consumption dropped to 890,000 t, and ia 1994 to 610,000 t (1,2). Sodium sulfate is used principally (40%) ia the soap (qv) and detergent iadustries. Pulp and paper manufacturers consume 25%, textiles 19%, glass 5%, and miscellaneous iadustries consume 11% (3). About half of all sodium sulfate produced is a synthetic by-product of rayon, dichromate, phenol (qv), or potash (see Chromium compounds Fibers, regenerated cellulosics Potassium compounds). Sodium sulfate made as a by-product is referred to as synthetic. Sodium sulfate made from mirabilite, thenardite, or naturally occurring brine is called natural sodium sulfate. In 1994, about 300,000 t of sodium sulfate were produced as a by-product another 300,000 t were produced from natural sodium sulfate deposits (4). 

The principle uses of Na2S04 are in the manufacture of paper, soaps, and detergents. These accounted for 65% of U.S. consumption from 1990 to 1995, representing a significant shift from 1980 when paper production alone consumed 67%. Pulp (qv) and paper consume only 25% (2). The kraft paper process uses a mixture of sodium sulfide and sodium hydroxide to digest wood chips. Both the sulfide and hydroxide are generated, starting with sodium sulfate as the raw material. 

Manufacture. The oldest method for producing Na2S is by the reduction of sodium sulfate with carbon in a refractory oven at 900—1000°C. Whereas this method is no longer used commercially in the United States, a variation is used to produce sodium sulfide captively during kraft pulp processing to replace lost sodium and sulfur values that were initiated into the system by merchant-suppHed sodium sulfide. In this method, sodium sulfate is added to the system in the recovery furnace, where it is reduced by carbon from the wood pulp to produce sodium sulfide. 

The majority of the turpentine comes from the southeastern United States, which consists of 60—70% a-pinene, 20—25% P-pinene, and 6—12% other components. Because there is variation in components from different species of the pine tree as well as variation from the many paper pulp mills, there is obviously variation in the analysis of sulfate turpentines. Some of the other components consist of -menthadienes, alcohols, ethers such as anethole [104-46-1] and methylchavicol [104-67-0] and the sesquiterpene hydrocarbon, P-caryophyUene [87-44-5]. 

E. E. McSweeny, "Sulfate Naval Stores," in D. E. Zinkel and J. Russell, eds., Naval Stores, Pulp Chemical Assoc., New York, 1989, pp. 160—186. 

---