Castor oil, production

Ricin can be extracted from the waste mash generated by castor oil production or from whole castor beans by a relatively simple and inexpensive process. The resulting product is a soluble white powder which is stable under ambient conditions, but can be detoxified by heating for 10 min at 80°C or for 1 h at 50°C (Burrows and Renner, 1999). 

Castor oil plays a very important role, especially in the earlier stages of the PU industry, even before synthetic polyols were available. Worldwide production of castor oil is around 1,200,000-1,800,000 t/year [76], the world leader in castor oil production being India (750,000 t/year) [76] (India 64%, China 23%, and Brazil 7%). 

In 2010, the worldwide castor oilseed production was over 1 x 10 tons while the castor oil production amounted to around 600 000 tons [6, 12], Most of the oil is destined for motor lubrication and for use in the cosmetics area. After distribution to the other handful of application fields, only a mere 150 000 tons are allocated for the production of sebacic acid. This quantity leads to approx. 70 000 tons of sebacic acid, of which only roughly 20 000 tons are currently dedicated for polyamides. Even with the additional circa 50 000 tons of castor oil needed for PAl 1, polyamides only represent about 10% of the crop harvest. 

The castor bean is stable and stores well, which gives the option of transporting the oilseed for further processing. Nonetheless, most castor-oil production is decentralized and takes place closer to the cultivation areas. On the other hand, sebacic acid and undecenoic acid production is generally centralized by a few players operating in the vicinity of their distribution markets. The polymerization facilities, if not linked directly to the acid processing plants, are also centralized at key petrochemical hubs. 

In addition to seed meal, the husks of the fruit that bears castor seed is a significant coproduct of castor oil production. Castor meal is sold and used as fertilizer, as it is rich in nitrogen, 7.54% N, which is 10 times that of steer manure (Lima et al., 2011). The authors found that castor meal in excess of 4% prevented germination and caused plant growth inhibition or death, but a mixture of 4.5% meal and 5.5% husk promoted plant growth. While the meal is rich in N and P, the husk is rich in K, providing a balanced soil amendment that also adds organic material to the soil. 

Canoira, L., Galean, J.G., Alcantara, R., Lapuerta, M., Garcia-Contreras, R., 2010. Fatty acid methyl esters (FAMEs) from castor oil production process assessment and synergistic effects in its properties. Renewable Energy 35, 208-217. 

Undecylenic acid (or 10-undecenoic acid) (I), a comparatively inexpensive commercial product obtained from castor oil, reacts with bromine in dry carbon tetrachloride to give 10 11-dibromoundecoic acid (II), which upon heating with a concentrated solution of potassium hydroxide yields 10-niidecynoic acid (III) ... 

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for the manufacture of plasticizers. Sterling Chemicals linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derived from natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minor importance in the marketplace. 

In addition to DAA s use in the production of MIBK, DAA also finds use as a specialty reaction intermediate. Hydrogenation of DAA at 100°C and 30 MPa (83) yields hexylene glycol ( 1.43/kg, October 1994), widely used in castor oil-based hydrauhc brake fluids and as a solvent. Reaction of /)-phenetidine [156-43-4] with DAA synthesizes Monsanto s Santoquin (ethoxyquin) [91-53-2] (149), an antioxidant used in animal feeds and also as a mbber additive. Diacetone alcohol (acetone-free) was available at 1.32/kg as of October 1994. 

The by-product of this process, pelargonic acid [112-05-0] is also an item of commerce. The usual source of sebacic acid [111-20-6] for nylon-6,10 [9008-66-6] is also from a natural product, ticinoleic acid [141-22-0] (12-hydroxyoleic acid), isolated from castor oil [8001-79-4]. The acid reacts with excess sodium or potassium hydroxide at high temperatures (250—275°C) to produce sebacic acid and 2-octanol [123-96-6] (166) by cleavage at the 9,10-unsaturated position. The manufacture of dodecanedioic acid [693-23-2] for nylon-6,12 begins with the catalytic trimerization of butadiene to make cyclododecatriene [4904-61-4] followed by reduction to cyclododecane [294-62-2] (see Butadiene). The cyclododecane is oxidatively cleaved to dodecanedioic acid in a process similar to that used in adipic acid production. 

The starting amino acid for nylon-11 is produced from methyl ricinoleate [141 -24-2] which is obtained from castor oil (qv). The methyl ricinoleate is pyrolized to methyl 10-undecylenate [25339-67-7] and heptanal [111-71-7]. The unsaturated ester is hydroly2ed and then converted to the amino acid by hydrobromination, followed by ammoniation and acidification. The CO-amino acid product is a soft paste containing water, which is dried in the first step of the polymeri2ation process. 

Nylon-11. This nylon is produced from 11-aminoundecanoic acid, which is derived from castor oil. The acid is polymerized by heating to 200°C with continuous removal of water. Catalysts such as phosphoric acid are frequentiy used. There is no appreciable amount of unreacted monomer left in the product. 

Fats and Oils. Fats and oils (6) are traditionally sulfated using concentrated sulfuric acid. These are produced by the sulfation of hydroxyl groups and/or double bonds on the fatty acid portion of the triglyceride. Reactions across a double bond are very fast, whereas sulfation of the hydroxyl group is much slower. Yet 12-hydroxyoleic acid sulfates almost exclusively at the hydroxyl group. The product is generally a complex mixture of sulfated di-and monoglycerides, and even free fatty acids. Other feeds are castor oil, fish oil, tallow, and sperm oil. 

With the exception of tall oil and castor oil acids, and acids used for sodium and potassium soaps, Tables 3, 4, and 5 provide detailed production and disposition information on the U.S. triglyceride-based fatty acids. These data show a 2—3%/yr growth rate between 1985 and 1990, virtually in line with world projections, with the most significant growth occurring in the stearic and coconut acid segments. 

Whereas commercial production of castor oil existed ia the United States ia the 1800s, production shifted to tropical and subtropical countries ia the early 1900s. World War I, World War II, and the Korean conflict each iafluenced efforts to produce hybrid castor species and iacrease U.S. planting, and by the late 1960s, approximately 80,000 acres of castor were grown ia the United States produciag 29,500 metric tons of castor oil. U.S. production was competitive until 1972 when Federal price supports were withdrawn. U.S. production dropped almost to zero by 1974. 

Sulfonation of castor oil using anhydrous SO yields a product having better hydrolytic stabiUty than that from the sulfuric acid reaction. The organically combined SO is low compared to the amount of SO introduced to the reaction the final product contains only 8.0—8.5 wt % combined SO although 17 wt % SO is added. The product contains less inorganic salts and free fatty acids than the sulfuric acid product (36). 

Alkali Fusion. Tha alkaU fusion of castor oil using sodium or potassium hydroxide in the presence of catalysts to spHt the ricinoleate molecule, results in two different products depending on reaction conditions (37,38). At lower (180—200°C) reaction temperatures using one mole of alkah, methylhexyl ketone and 10-hydroxydecanoic acid are prepared. The 10-hydroxydecanoic acid is formed in good yield when either castor oil or methyl ricinoleate [141-24-2] is fused in the presence of a high boiling unhindered primary or secondary alcohol such as 1- or 2-octanol. An increase to two moles of alkali/mole ricinoleate and a temperature of 250—275°C produces capryl alcohol [123-96-6] CgH gO, and sebacic acid [111-20-6] C QH gO, (39—41). Sebacic acid is used in the manufacture of nylon-6,10. 

Oxidized castor oils are excellent nonmigrating, nonvolatile plasticizers (qv) for ceUulosic resins, poly(vinyl butyral), polyamides, shellac, and natural and synthetic mbber (see Rubber, natural). The high viscosity products are also used as tackifiers in gasket compounds and adhesives (qv) because of good oil and solvent resistance. They also serve as excellent pigment grinding media and as a base for inks (qv), lubricating oils, and hydrauHc oils (62). 

Other Lethal Agents. There are a number of substances, many found in nature, which are known to be more toxic than nerve agents (6). None has been weaponized. Examples of these toxic natural products include shellfish poison, isolated from toxic clams puffer fish poison, isolated from the viscera of the puffer fish the active principle of curare "heart poisons" of the digitaUs type the active principle of the sea cucumber active principles of snake venom and the protein ricin, obtained from castor beans (See Castor oil). 

LesquereUa is an oilseed crop that has been mentioned as a potential industrial crop but is not yet grown in significant quantities. Castor beans have been a crop in the United States and provide a weU-known lubricating product, castor oil [8001-79-4]. However, castor is grown only in small quantities and most of the castor used in the United States is imported from Bra2il (11). 

Guanine is obtained fiom various fish including menhaden, herring, and alewives. To prepare the colorant, scales are scraped from the fish, levigated, and washed with water, and then made into one or more commercial forms, depending on the intended use. Typically, guanine is suppHed as a paste or suspension in water, castor oil, or nitrocellulose. Guanine is not a colorant in the strict sense but instead is used to produce iridescence in a product. 

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