Pulp mills

Increases in U.S. demand for caustic soda have been unpredictably high in the last few years. Between 1987 and 1989, the annual increase in demand was about 3% (6). However, the caustic soda market is mature and new areas of significant growth have not surfaced in recent years. The unexpected recent demand is generally related to two factors the pick-up in the U.S. economy after the slump of 1986 and pulp mills operating at fiiU capacity, leading to less efficient caustic use. 

Industrial Wastewater Treatment. Industrial wastewaters require different treatments depending on their sources. Plating waste contains toxic metals that are precipitated and insolubiHzed with lime (see Electroplating). Iron and other heavy metals are also precipitated from waste-pidde Hquor, which requires acid neutralization. Akin to pickle Hquor is the concentrated sulfuric acid waste, high in iron, that accumulates in smokeless powder ordinance and chemical plants. Lime is also useful in clarifying wastes from textile dyeworks and paper pulp mills and a wide variety of other wastes. Effluents from active and abandoned coal mines also have a high sulfuric acid and iron oxide content because of the presence of pyrite in coal. 

As of 1995, the forest industry in the United States employed about 1.6 million people and produced products valued at over 200 biUion each year, approximately 20 biUion of which was in exports. There were 350 pulp mills, 600 paper and board mills, and ca 4500 converting plants in the United States producing ca 30% of the total world production. The United States and Western Europe, which represent ca 13% of the world population, consumed about 60% of production. 

Wood Residuals. Chips, sawdust, and other residuals such as planar shavings are used as a primary source of fiber for some pulp mills. Chips are screened and placed in a purchased chip pile. Sawdust and other residuals obtained from wood processing plants must be cooked separately and requite special digesters and handling equipment. These materials may also be burned as hog fuel. 

Closed-Mill Concept. The closed-mill concept, or water circuit closure, has been studied by the pulp and paper industry for many years. In some parts of the paper manufacturing process, up to 98% of the water is recycled within the process, eg, the wet end of the paper machine. However, in the pulp mill, especiaUy kraft mills, effluents are produced owing to the need to purge from the system various metals that come in with the wood, as weU as organic by-products from the pulping process, additives, and especially chloride ions that originate in the bleach plant. 

Economic Aspects and Uses. Production and sales values for high purity sodium hydrosulfide are Hsted ia Table 1. These figures exclude the low purity material produced by oil refiners, beHeved to be sold primarily to pulp mills. Estimates of uses of NaHS ia the United States for 1994 are as shown (3,4) ... 

Paper Products. Paper (qv) products account for about 2% of sulfur demand. The largest single segment of demand is in the manufacture of wood pulp by the sulfite process (see Pulp). In this process, the main sulfur intermediate is sulfur dioxide, which is generally produced at the plant site by burning elemental sulfur. Some sulfur dioxide, however, is produced as a by-product at smelter operations, purified andUquefied, and shipped to the pulp mills. The sulfur dioxide is converted to sulfurous acid, and the salt of this acid is a principal component of the cooking Hquor for the sulfite process. 

Pulp Manufacture. Sodium sulfite is utilized in neutral semichemical pulping, acid sulfite pulping, high yield sulfite cooling, and some kraft pulping processes (339). Many pulp mills prepare their own sulfite and recycle as much as possible, but use of merchant sodium sulfite by pulp mills is substantial. Much of the by-product sodium sulfite from resorcinol manufacture goes into pulp appHcations as well as a substantial fraction of the lower assay manufactured sodium sulfite. 

Economic Aspects. U.S. capacity for production of merchant sodium dithionite (soHds basis) was estimated at 93,000 metric tons in 1994. There are three North American producers of sodium dithionite. Hoechst Celanese is the largest producer (68,000 tons capacity) with two formate production locations and one zinc process location. Olin (25,000 t capacity) produces solution product only at two locations using both the amalgam and electrochemical processes. In 1994, Vulcan started a small solution plant in Wisconsin using the Olin electrochemical process. In addition, it is estimated that 13,000 t/yr is produced at U.S. pulp mills using the Borol process from sulfur dioxide and sodium borohydride. Growth is estimated at 2—3%/yr. The... 

Proper soap removal increases the pulp mill s evaporator capacity by 5%. Therefore, soap is often recovered as weU at other places in the pulp mill, such as the weak black Hquor storage tanks and the heavy black Hquor oxidation system (13,14). 

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]. 

When chlorine dioxide is used for pulp bleaching in conjunction with the Kraft (sulfide) process for chemical pulping, by-product sodium sulfate can be used as a source of makeup sulfur and sodium consumed in the chemical cycle. The demand for sodium and sulfur in pulp bleaching is related to the loss of these chemicals through carryover in unbleached pulp. As process improvements have sought to reduce pollution from pulp mills, less sodium sulfate makeup is required. The trends in pulp bleaching to increase substitution of chlorine with chlorine dioxide have caused an oversupply of sodium sulfate, so that this by-product is often regarded as waste (81). 

Pulp bleaching with chlorine dioxide is most often performed at an acidic pH, so that the final pH of the bleach Hquor is in the range of 2—5. Under these conditions, the residual concentration of chlorite and chlorate ions in the bleach Hquor are minimized and chloride ion is the predominant chlorine species in the spent bleach (77). In addition to direct addition to pulp in bleaching, chlorine dioxide also finds use in wastewater treatment from pulp mill operations as a means to remove effluent color (85). 

Adsorption. Adsorption (qv) is an effective means of lowering the concentration of dissolved organics in effluent. Activated carbon is the most widely used and effective adsorbent for dyes (4) and, it has been extensively studied in the waste treatment of the different classes of dyes, ie, acid, direct, basic, reactive, disperse, etc (5—22). Commercial activated carbon can be prepared from lignite and bituminous coal, wood, pulp mill residue, coconut shell, and blood and have a surface area ranging from 500—1400 m /g (23). The feasibiUty of adsorption on carbon for the removal of dissolved organic pollutants has been demonstrated by adsorption isotherms (24) (see Carbon, activated carbon). Several pilot-plant and commercial-scale systems using activated carbon adsorption columns have been developed (25—27). 

---