Turpentine, sulfate

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... 

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. 

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]. 

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. 

H)- and (+)-1imonenes are widely used ia the manufacture of terpene resias. Additionally, a (-)-limonene and (+)- P-pheUandrene mixture from sulfate turpentine has been used to produce terpene resias. (+)-Limoaeae from the citms iadustry coatiauaHy fiads aew uses as a solveat aot only for its solvency properties but also for its orange oil fragrance. 

Synthetic piae oil is produced by the acid-cataly2ed hydration of mainly a-piaene derived from sulfate turpentine, followed by distillation of the cmde mixture of hydrocarbons and alcohols. The predominant alcohol obtained is a-terpiueol, although under the usual conditions of the reaction, reversible and dehydration reactions lead to multiple hydrocarbon and alcohol components (Fig. 1). 

Chemical Designations - Synonyms D.D. turpentine. Gum turpentine. Spirits of turpentine. Sulfate turpentine. Turps, Wood turpentine Chemical Formula CioHi ... 

Fractional distillation of crude pine oil, 24 510 of crude sulfate turpentine, 24 476 Fractional extraction, 10 745, 759-760 Fractional factorial designs, 8 396 amount of coverage in experimental design texts compared, 8 395t commercial experimental design software compared, 8 398t Fractional velocity plots, 10 319-321 Fractionating towers, in plant layout,... 

The two pinenes are obtained from Crude Sulfate Turpentine (CST), which is a side product of the sulfate cellulose process from pine trees. Limonene is present in orange and lemon peels [which provide different enantiomers/ )], and is a cheap by-product of the citrus industry. 

A 45 kl tank of sulfate turpentine from a paper mill became dangerously heated, owing to oxidation arising from local high temperature and an air-purging procedure. 

Two other important side products of the kraft process are sulfate turpentine and tall oil. The turpentine is obtained from the gases formed in the digestion process. From 2-10 gal of turpentine can be obtained per ton of pulp. Tall oil soap is a black viscous liquid of rosin and fatty acids that can be separated from the black liquor by centrifuging. Acidification gives tall oil. These side products will be discussed later. 

Production. Anethole is isolated from anethole-rich essential oils as well as from sulfate turpentine oils. 

A fraction of American sulfate turpentine oil (0.5% of the total) consists mainly of an azeotropic mixture of anethole and caryophyllene. trans-Anethole can be isolated from this mixture by crystallization. 

Balsam turpentine oil is obtained from the resins of living trees of suitable Pinus species by distillation at atmospheric pressure and temperatures up to 180°C, or by other fractionation methods, which do not change the terpene composition of the resins. Wood turpentine oils, on the other hand, are generally obtained by steam distillation of chopped tree trunks, dead wood, or of resin extracted from this wood. Sulfate turpentine oil is produced as waste in the manufacture of cellulose by the sulfate process and is also a wood turpentine. Pine oil is another wood turpentine oil that is obtained by dry distillation of suitable pine and fir trees, followed by fractionation. However, the term pine oil is nowadays used for a product which is manufactured by hydration of turpentine oil (a-pinene). The resulting product is a mixture of monoterpenes containing o-terpineol as the main component. In addition to many other technical purposes, it is used to a large extent in cheap perfumes for technical applications. 

Worldwide production of turpentine oils was ca. 280000t in 1990, of which approximately one third was produced in the United States and Canada as sulfate turpentine oil. Other major producers are Russia, China, and Scandinavia. 

Pine Oil Manufacture. Synthetic pine oil manufacture is one of the principal uses of turpentine. U.S. production of synthetic pine oil in 1993 was 17,2441 at an average selling price of 1.10/kg (67). The amount of natural and sulfate pine oil was reported to be 17541. The world production of synthetic pine oil is estimated to be about twice the U.S. production figure. Natural pine oil is a product derived from the extraction of aged pine stumps, and sulfate pine oil is a product separated from crude sulfate turpentine in about 5% yield. The sulfate pine oil retains the sulfur odor of the sulfate turpentine, and its use is therefore limited to ore flotation and solvent applications. 

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 is produced from various species of pines and balsamiferous woods, and several different methods are applied to obtain the oils leading to different types of turpentine, such as (1) dry-distilled wood turpentine from dry distillation of chopped woods and roots of pine trees, (2) steam-distilled wood turpentine that is steam-distilled from pine wood or from solvent extracts of the wood, and (3) sulfate turpentine, which is a by-product of the production of cellulose sulfate. 

There were good intentions when a small chemical terminal in Savannah, Georgia, that supplied the paper and pulp industry decided to change their product mix. Their terminal was to be converted from handling all nonflammable chemicals to storing large quantities of flammable crude sulfate turpentine (CST). Crude sulfate turpentine is an impure form of turpentine produced as a byproduct of the Kraft pulping process. It is classified as a Class IC flammable liquid. 

Just before midnight on Sunday, April 10, 1995, fire erupted at the chain link and concertina wire-fenced terminal. The terminal was unmanned at 11 30 p.m. when the fire started. Several witnesses observed a flash, followed by an explosion and fireball. Other explosions and fireballs followed as the second and third tank containing crude sulfate turpentine exploded and burned. The firefighters had difficulty entering the area due to the intensity of the fire. [11]... 

For the first years of operation there were no flammables in the area. However, the company changed its strategy and started storing Class IC flammable liquids (crude sulfate turpentine) several months before the fire. Specific safety systems were requested by the permitting agencies. These safety requests were accepted by the owners. However, several safety systems were incompletely installed or not installed by the time of the incident. 

Foul-smelling fumes from the crude sulfate turpentine escaped the tanks both during tank fillings and during the daytime, when the sun increased the tank temperature. Malodorous tank vapors were routine. Company personnel planned to solve the problem by routing these offensive fumes to drums with activated carbon. [11,12]... 

Before the storage of the flammable liquid (crude sulfate turpentine, CST), there were no flammable materials in the terminals enclosure. Local fire protection agencies specified a fixed foam-piping, fire-suppressing system as a condition to store flammable liquids. The terminal s management agreed to the terms of the protection package. 

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