Turpentine production

Egen employed a distiller, potter, two coopers, a chemist to manufacture castor oil, and a supervisor of turpentine production he also impressed twenty-nine blacks into service.93... 

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). 

Most terpenes show low acute oral toxicity and low dermal toxicity. Contact dermatitis is the most common symptom described as a result of exposure to terpenes. Other allergic reactions occur more rarely e.g. allergic rhinitis or allergic bronchial asthma. The most common products with an allergic potential (contact dermatitis) are oils of turpentine. Older turpentine products show higher allergic potential than freshly distilled products. Turpentines have now been replaced by other less toxic petrochemical products. 

Turpentine is by far the most widely produced essential oil in the world and consequently the privileged source for applications requiring large-scale supplies. The total world turpentine production showed a tendency to decline between the 1960s and the 1980s. However, statistics covering the next decade [9, 10] show that the turpentine production stabilized around 330 000 tons per year, with 70 per cent of the world production as sulphate turpentine, and the rest almost exclusively as gum turpentine [10, 11]. 

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). 

Wansbrough H,Turpentine production and processing, http //nzic.org.nz/ChemProcesses/forestry/4F. pdf [accessed 26.05.14]. 

Others— Single-component Turpentine products. Some blended... 

The primary use of a-pinene, and therefore of turpentine, involves the hydration by aqueous mineral acids to synthetic pine oil, the primary constituent of which is a-terpineol (Fig. 10.1.7). Between 40% and 50% of the world turpentine production is so used. Good emulsifiers are needed in the hydration reaction because the hydration takes place at the a-pinene-aqueous acid interface. Variations in reaction conditions, fractionation, and blending give pine oils with different compositions and properties. Over 90% of the US. pine oil is used in cleaner and disinfectant formulations because the piney odor is pleasant and because pine oil is a good emulsifier, an excellent solvent, and an effective germicide of low toxicity. 

The pulp and paper industry in Europe and North America has been producing chemicals from the extractives for almost a century, primarily as tall oil and turpentine products. 

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). 

Turpentine Oil. The world s largest-volume essential oil, turpentine [8006-64-2] is produced ia many parts of the world. Various species of piaes and balsamiferous woods are used, and several different methods are appHed to obtain the oils. Types of turpentines include dry-distiUed wood turpentine from dry distillation of the chopped woods and roots of pines steam-distilled wood turpentine which is steam-distilled from pine wood or from solvent extracts of the wood and sulfate turpentine, which is a by-product of the production of sulfate ceUulose. From a perfumery standpoint, steam-distilled wood turpentine is the only important turpentine oil. It is rectified to yield pine oil, yellow or white as well as wood spirits of turpentine. Steam-distilled turpentine oil is a water-white mobile Hquid with a refreshing warm-balsamic odor. American turpentine oil contains 25—35% P-pinene (22) and about 50% a-pinene (44). European and East Indian turpentines are rich in a-pinene (44) withHtfle P-pinene (22), and thus are exceUent raw materials... 

In several important cases, new synthetic strategies have been developed into new production schemes. An outstanding example of this is the production of an entire family of terpene derivatives from a-pinene (29), the major component of most turpentines, via linalool (3) (12). Many of these materials had been produced from P-pinene, a lesser component of turpentine, via pyrolysis to myrcene and further chemical processing. The newer method offers greater manufacturing dexibiUty and better economics, and is environmentally friendly in that catalytic air oxidation is used to introduce functionality. 

By-Products. There are three stages within the pulping operation at which wood-derived chemicals can be recovered as by-products. Turpentine is obtained from the reHef of gases after an initial steaming of chips in the digester. Better yields of turpentine are obtained from batch digesters than from continuous systems. Pines and firs give the best yields. Turpentine is composed principally of unsaturated bicycHc hydrocarbons, of which ca 90% are a- and P-pinenes and 5—12% other terpenes. 

In the gum rosin process, pine trees are wounded to stimulate the flow of gum. V-shaped slashes are cut through the bark, and the exudate is collected in a bucket below the slash. Production is stimulated by painting sulfuric acid on the slashes. The oleoresin (exudate) is separated by distillation into gum spidts of turpentine and gum rosin. The gum turpentine industry has decreased in importance in the 1990s because it is labor-intensive. The process is carried out in Russia, the People s Repubflc of China, Indonesia, Portugal, Brazil, and Mexico. 

The pyrolysis or carbonization of hardwoods, eg, beech, birch, or ash, in the manufacture of charcoal yields, in addition to gaseous and lighter Hquid products, a by-product tar in ca 10 wt % yield. Dry distillation of softwoods, eg, pine species, for the production of the so-called DD (destmctively distilled) turpentine yields pine tar as a by-product in about the same amount. Pine tar, also called Stockholm tar or Archangel tar, was at one time imported from the Baltic by European maritime countries for the treatment of cordage and ship hulls it was an important article of commerce from the seventeenth to the nineteenth century. The small amount produced in the late twentieth century is burned as a cmde fuel. Charcoal production from hardwoods, on the other hand, has increased in the 1990s years. 

Production of Hydrocarbons from Turpentine. In 1993, U.S. production of cmde turpentine was over 128 million liters at an average price of 0.21 /kg and includes cmde sulfate turpentine and turpentine from thermomechanical processes (5). In the same year, over 5.9 million Hters of gum, wood, or sulfate turpentine was imported into the United States, with the majority coming from Canada exports from the United States amounted to 6.16 million liters. 

OC-Pinene Manufacture. Industrially, a-pinene produced from the fractionation of sulfate turpentine can be used directly for most of its apphcations. The bulk price of technical-grade a-pinene, min 92%, was 1.32/kg in 1995 (45). The commercial product is shipped in tank cars, tank tmcks, or deck tanks. 

Principal terpene alcohol components of piae oils are a-terpiueol, y-terpiueol, P-terpiueol, a-fenchol, bomeol, terpiuen-l-ol, and terpiaen-4-ol. The ethers, 1,4- and 1,8-ciaeole, are also formed by cycli2ation of the p-v( enthane-1,4- and 1,8-diols. The bicycHc alcohols, a-fenchol [512-13-0] (61) and bomeol (62), are also formed by the Wagner-Meerweiu rearrangement of the piaanyl carbonium ion and subsequent hydration. Bomeol is i7(9-l,7,7-trimethylbicyclo[2.2.1]heptan-2-ol [507-70-0]. Many other components of piae oils are also found, depending on the source of the turpentine used and the method of production. 

Garyophyllene. (-)-CaryophyUene can be isolated from Indian turpentine and has been used to prepare a number of woody aroma products. The epoxides are produced by reaction with peracids. Acetylation of caryophyUene also gives a usehil methyl ketone (180) (Fig. 8). Acid-catalyzed rearrangement of caryophyUene in the presence of acetic acid gives a mixture of esters, which are related to caryolan-l-ol and clovan-2-ol (181). 

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). 

A rather impressive Hst of materials and products are made from renewable resources. For example, per capita consumption of wood is twice that of all metals combined. The ceUulosic fibers, rayon and cellulose acetate, are among the oldest and stiU relatively popular textile fibers and plastics. Soy and other oilseeds, including the cereals, are refined into important commodities such as starch, protein, oil, and their derivatives. The naval stores, turpentine, pine oil, and resin, are stiU important although their sources are changing from the traditional gum and pine stumps to tall oil recovered from pulping. 

Terpin hydrate [2451-01-6] (10), one of the most weU-known expectorants, is isolated from cmde pine rosin left after the distillation of volatile terpene hydrocarbons and alcohols. It is also manufactured from turpentine (a-pinene) by acid-cataly2ed hydration. Terpin hydrate may exist as cis and trans isomers, but only the cis isomer forms a stable, crystalline monohydrate. Terpin hydrate is available in the United States only in prescription products. 

Camphor was originally obtained from the camphor tree Lauras eamphora in which it appeared in the optically active dextro-rotary form. Since about 1920 the racemic ( ) mixture derived from oil of turpentine has been more generally used. By fractional distillation of oil of turpentine the product pinene is obtained. By treating this with hydrochloric acid, pinene hydrochloride (also known as bomyl chloride) may be produced. This is then boiled with acetic acid to hydrolyse the material to the racemic bomeol, which on oxidation yields camphor. Camphor is a white crystalline solid (m.p. 175°C) with the structure shown in Figure 22.3. 

I.4. Polyterpene resins. Terpene resins are obtained from natural terpene monomers obtained from naval stores, paper pulp production, and citrus juice production. Terpenes are found in almost all living plants, and the turpentine oil from pine trees is the most important source. 

Crude turpentine is distilled to obtain refined products used in the fragrance and flavour industry. Only the unsaturated mono- and bicyclic terpenes are of interest for resin production. These are mainly a-pinene, p-pinene and dipentcne (D,L-limonene) (Fig. 17). D-Limonene is obtained by extraction of orange peel in citrus fruits. 

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