Naval stores rosin production

History of Naval Stores Production Statistics of Naval Stores Processes of Naval Stores Gum Naval Stores Wood Naval Stores Tall Oil Naval Stores Chemistry of Naval Stores Rosin Turpentine Fatty Acid... 

Rosin and associated products obtained from pine trees have been used for hundreds of years to caulk the bottoms of wooden sailing vessels and to lubricate the lines. These materials are known as naval stores because of this practice. 

Wood is the raw material of the naval stores iadustry (77). Naval stores, so named because of their importance to the wooden ships of past centuries, consist of rosin (diterpene resin acids), turpentine (monoterpene hydrocarbons), and associated chemicals derived from pine (see Terpenoids). These were obtained by wounding the tree to yield pine gum, but the high labor costs have substantially reduced this production in the United States. Another source of rosin and turpentine is through extraction of old pine stumps, but this is a nonrenewable resource and this iadustry is in decline. The most important source of naval stores is spent sulfate pulpiag Hquors from kraft pulpiag of pine. In 1995, U.S. production of rosin from all sources was estimated at under 300,000 metric tons and of turpentine at 70,000 metric tons. Distillation of tall oil provides, in addition to rosin, nearly 128,000 metric tons of tall oil fatty acids annually (78). 

The oleoresinous exudate or "pitch of many conifers, but mainly pines, is the raw material for the major products of the naval stores industry. The oleoresin is produced in the epithelial cells which surround the resin canals. When the tree is wounded the resin canals are cut. The pressure of the epithelial cells forces die oleoresin to the surface of die wound where it is collected. The oleoresin is separated into two fractions by steam distillation. The volatile fraction is called gum turpentine and contains chiefly a mixture of monoterpenes but a smaller amount of sesquiterpenes is present also. The nonvolatile gum rosin 5 consists mainly of llie dilerpenuid resin acids and smaller amounts of esters, alcohols and steroids. Wood turpentine, wood rosin and a fraction of intermediate volatility, pine oil are obtained together by gasoline extrachon of the chipped wood of old pine stumps. Pine oil is largely a mixture of the monoterpenoids terpineol. borneol and fenchyl alcohol. Sulfate turpentine and its nonvolatile counterpart, tall oil, 5 are isolated as by-products of the kraft pulping process. Tall oil consists of nearly equal amounts of saponified fatty acid esters and resin acids. 

Turpentine and Rosin The major naval stores products are turpentine, primarily composed of volatile terpenes, and rosin, mainly a mixture of resin acids. Principally the same products, but in different proportions, can be recovered by tapping resin-rich trees or by steam distillation or solvent extraction of wood residues and especially stumps. Today, however, the most important source for turpentine and rosin is the tall oil recovered after pulping of pine wood (see Section 10.3.1). 

Rosin, the other major naval stores product, is a brittle solid that softens at 80°C. Chemically it is composed of about 90 percent resin acids and 10 percent neutral matter. The resin acids are mainly /-abietic acid and its isomers, C2oH3002. These are tricyclic mono-carboxylic acids and are diterpenes. 

The Bureau of Agricultural Economics of the Department of Agriculture has several statistical services which are useful to the chemical industry. Of special interest is the quarterly Naval Stores Report, which contains figures on production, distribution, consumption, and stocks of turpentine, both wood and gum types. Industrial consumption of both rosin and turpentine are shown by 15 specific industries, including quantities consumed by chemicals and pharmaceuticals, ester gums and synthetic resins, and paint, varnish, and lacquer. In addition, this quarterly report covers miscellaneous naval stores production, including products such as pine oil and resin oil. 

In 1926 Hercules integrated backward by acquiring the Virginia Cellulose Company, the leading producer of cotton pulp, a major ingredient in nitrocellulose and related products. By the early 1930s, its lines had been expanded to include cellulose acetate, ethyl acetate, gum rosin, chlorinated rubber, and, with the acquisition of the Paper Makers Chemical Corporation in 1931, a line of products for paper production, which complemented the naval stores business. By then, in addition to the 60 percent of sales in explosives and propellants, 25 percent were in cellulose products and 15 percent in naval stores. 

Turpentine production from the three types of naval stores follows the same pattern as rosin (Figure 2). However, due probably to the simple method of recovery, sulfate turpentine dominated the other two sources as early as 1955. The near-term outlook is for a steady rate of turpentine production. A comprehensive review of turpentine production and use was given recently (11). 

Turpentine. Similar to rosins, turpentines differ in content of monoterpenes depending upon the type and sources. Typical southern pine derived turpentines have the analyses shown in Table II. Western U.S. woods contain an appreciable quantity of A3-carene. There is no gum and wood naval stores production in the west, only sulfate turpentine. 

For historical reasons, pine resin was known as Naval Stores , because of its use in the waterproofing of wooden ships. Depending on the way pine resin is isolated from wood, three products are distinguished, namely (i) gum naval stores, obtained by tapping living trees (ii) sulphate naval stores, also known as tall oil rosin, recovered during the kraft pulping of pine wood and (iii) wood naval stores, also known as wood rosin, obtained from the solvent extraction of harvested wood. 

Soltes J., Zinkel D.R, Chemistry of rosin, in Naval Stores. Production, Chemistry, Utilization (Eds. Zinkel D.R and Russel J.), Pulp Chemical Association, New York, 1989, pp. 261-345. 

Diterpenes usually are components of plant resins and sometimes are encountered as by-products from the isolation of essential oils (e.g., rosin or naval stores from turpentine production). The most commonly encountered diterpenes are nonvolatile acids from conifers and legumes (Croteau and Johnson, 1985 Langenheim, 1990). 

Tall oil fatty acids n. Class of products generally containing 90% or more fatty acid obtained by ffactionization of crude tall oil The fatty acids are a mixture of oleic and linoleic acids with lesser amounts of saturated and other unsaturated fatty acids. The remainder consists of rosin and neutral materials. Paint pigment, drying oils, polymers, resins, naval stores, cellulo-sics esters, and ink vehicles, vol 3. American Society for Testing and Material, 2001. 

Soltes EJ, Zinkel DF (1989) Chemistry of rosin. In Zinkel DF, Russel J (eds) Naval stores. Production-chemistry-utilization, 1st edn. Pulp Chemicals Association, New York, pp 261-345 Veien NK, Mattel T, Laurberg G (1992) Patch test results from a private dermatologic practice for two periods of 5 years with a 10-year interval. Am J Contact Dermat 3 189-192 Watsky KL (1997) Airborne allergic contact dermatitis from pine dust. Am J Contact Dermat 8 118-120 Widstrom L (1983) Contact allergy to colophony in soldering flux. Contact Dermatitis 9 205-207... 

Naval Stores Review 1986 Global rosin production lower in 1985. Naval Stores Review 96(2) 13... 

Whereas oleoresin-derived products of turpentine and rosin have been naval stores materials from antiquity, tall oil fatty acids are a 20th-century newcomer. Their inclusion in the naval stores arena is a result of the co-occurrence with rosin in crude tall oil and recovery by distillation as a product along with tall oil rosin. Successful commercial fractional distillation of crude tall oil was first achieved in 1949, although distilled tall oil products had been available for several decades. 

The previous sections of this chapter have considered the utilization of turpentine, rosin, and tall oil fatty acids, the primary commodity products of the naval stores industry. In the course of processing the raw materials (crude tall oil and crude sulfate turpentine, and stumpwood extractives), by-products are obtained in addition to turpentine, rosin, and tall oil fatty acids, the primary commodity products. 

The gum naval stores industry showed a similar pattern. During 1908, the peak year of production in the United States, more than 120000 tons of spirits of turpentine and 600000 tons of rosin were produced. Due to competition from wood naval stores after World War I and sulfate turpentine and tall oil after World War II, gum naval stores production declined to less than 4000 tons in 1985. The United States government, recognizing the inevitable demise of this product, completed the liquidation of its stocks in 1972, terminated the Naval Stores Conservation Program, and closed the Agricultural Research Service s Olustee (Florida) Research Laboratory in 1973 (44). 

Processes and products developed to produce industrial materials from renewable resources have been too numerous to record here. For competitive reasons — supply of raw materials and technical and economic considerations — some of the products have varied widely in industrial use. Major U.S. industrial consumption of renewable resources have recently included oils and fats (animal and vegetable) industrial alcohol (wheat, corn, grain sorghum) fibers (cotton lint, flax, hides and skins) paper (forest products) isolated proteins (milk casein, animal glues, soybean, corn) turpentine and rosin (naval stores) and other chemicals (monosodiiim glutamate--wheat starch and dextrin—corn lactose—milk molasses and pulp residues --sugarcane and beet tannin lecithin pectin furfural). 

NAVAL STORES. These include turpentine, rosin, copal, pentene, dipentene and pinene. In laboratoiy tests, alloy 3003 was resistant to products such as these. Naval stores have been processed and handled in aluminum alk equipment including rosin kettles. evaporators, condensers, storage tanks, transfer lines, distillation equipment, piping and shipping containers. See also Ref (3) p. 226. 

Turpentine and rosin are also produced by solvent extraction of heartwood chips of pine stumps, which are by-products of the lumber industry, and as by-products of the paper (sulfate or kraft pulping) industry. The last source is reported to account for the largest volumes of turpentine and rosin produced in the United States. These products derived from pines and other resinous conifers are commonly called naval stores. 

Rosin is graded and sold on the basis of color, the color grades ranging from pale yellow to dark red (almost black). The color is due almost entirely to iron contamination and oxidation products. Fresh oleoresin, as it exudes from the tree, will yield a rosin that is nearly colorless. Color-bodies are removed by selective solvents and selective absorption from a 10 to 15 percent gasoline solution passed through beds of diatomaceous earth. About 70 percent of the world s rosin is produced in the United States. Naval stores also include important fatty acids, as well as steroids and other products. 

---