Oleochemical feedstocks

Surfactant alcohols are linear, primary alcohols with carbon chain lengths in the C12-C14 and the C16-C18 range. Surfactant alcohols can be derived from either petrochemical or oleochemical feedstocks, and thus are referred to either as synthetic alcohols or as natural (oleochemical) alcohols. Petrochemical feedstocks used for surfactant alcohol production are ethylene and, to a lesser degree, paraffins. 

Surfactants can be produced from both petrochemical resources and/or renewable, mostly oleochemical, feedstocks. Crude oil and natural gas make up the first class while palm oil (+kernel oil), tallow and coconut oil are the most relevant representatives of the group of renewable resources. Though the worldwide supplies of crude oil and natural gas are limited—estimated in 1996 at 131 X 1091 and 77 X 109 m3, respectively [28]—it is not expected that this will cause concern in the coming decades or even until the next century. In this respect it should be stressed that surfactant products only represent 1.5% of all petrochemical uses. Regarding the petrochemically derived raw materials, the main starting products comprise ethylene, n-paraffins and benzene obtained from crude oil by industrial processes such as distillation, cracking and adsorption/desorption. The primary products are subsequently converted to a series of intermediates like a-olefins, oxo-alcohols, primary alcohols, ethylene oxide and alkyl benzenes, which are then further modified to yield the desired surfactants. 

As a class of surfactant, sulphonated methyl esters (SMEs) have been known since the 1980s, but have not been widely commercialised. Through the late 1990s into 2000, there were signs of increased use in Asia and the United States across a variety of applications. They share many similarities with olefin sulphonates but, importantly, they are made from renewable oleochemical feedstocks. This is preferred by many formulators, particularly in cosmetic and personal care applications. 

The carbon atom number for fabric softener structures usually follows the distribution of common oleochemical feedstocks. The average number is 17.5 for animal-based products such as tallow [32] and this carbon atom number also appears to be optimal for many... 

Physical Refining. The by-product in the physical refining of crude palm oil is the pahn fatty acid distillate (PFAD). It is obtained as a condensate of the volatile matters carried over from the deodorizer by the action of the stripping steam. It consists of 80-90% of free fatty acid. It has often been used as a raw material for soap making, feed compounding, and oleochemical feedstock. An important and valuable constituent of PFAD is vitamin E in the form of tocopherols and... 

C and fatty alcohols when working at 180 °C. Starting from oleic acid methyl ester, yields of up to 84% were obtained. Conversions of oleochemical feedstocks with Rh catalysts were possible, too [45]. 

Oleochemical feedstock sourcing for natural surfactants has been changing in recent years. Animal fats have lost ground in favor of vegetable oils, including the growing utilization of soybean oil [27]. 

The most common hydrophobe used to produce nonionic surfactants is alcohol. Alcohol can be produced by using both petrochemical and oleochemical feedstocks. 

A variety of oleochemical feedstocks (fats and oils) can be employed to make alcohols. Coconut and palm kernel oils, however, are most often used because they produce alcohols predominantly in the lauryl (C12 and C14) range, which is considered most desirable from a performance point of view, and because they produce highly saturated alcohols which helps to minimize the degree of hydrogenation required during alcohol manufacture. 

Oleochemical feedstocks and Ziegler alcohols are linear. Shell s SHOP process produces alcohols with approximately 20% predominantly methyl-branching, while other OXO-type alcohols contain approximately 40-50% predominantly methyl-branching. Alkylphe-nols and alcohols based on oligomerized alkylenes are generally highly branched. 

Alkylpolyglycosides (APGs ) are formulated into dishwashing liquids (along with anionic surfactants) and in various specialty applications. They were the first major surfactant to utilize an oleochemical feedstock for the hydrophilic portion of the surfactant molecule. 

Due to the fact that the conversion of oleochemical feedstocks into more valuable chemicals appears especially attractive, an economical metathesis of fats and oils and their derivatives should be considered seriously by the oleochemical industry. It has perspectives especially for production of products with a high added value. As an example, Figure 1 presents a process scheme for the (batch-wise) production of dimethyl octadecene-l,18-dioate from methyl oleate via metathesis in the presence of a supported Re207 catalyst [68]. 

The evolntion of the sophisticated prodncts and chemical-process technologies that are used today trace their origins back to the nineteenth centnry and the nascent chemical industry that relied on renewable oleochemical feedstocks. Synthetic snrfactants prepared by the reaction of olive oil with sulfnric acid, performed by Fremy in 1831, was among the first." ... 

American Oil Chemists Society. Cuphea Diverse fatty acid composition may yield oleochemical feedstock. JAOCS 62-1 6-12, 1985. 

Both the hydrophile and lipophile of surfactants can be derived from bio-based feedstocks. Figure 10.1 depicts the utilization of oleochemical feedstocks to manufacture food products, biofuels, chemicals, and materials as one would envision occurring within an oleochemical biorefmery. The latter term refers to the concept where an oleochemical (bio-based) feedstock is utilized in a chemical facility, which through various processing and separations schemes produces energy or fuel, chemical intermediates, materials, and other co-products. 

Of the enzymes listed in Table 10.1, Upases are the woikhorses. The employment of Upases in non-aqueous media is an estabUshed art, with over 25 years of research serving as a foundation. Lipases are abundant and relatively inexpensive enzymes that require no co-factors and are easily immobilized. Lipases from several thermophiUc organisms have been isolated, cloned, and mass produced via recombinant DNA technology in common vectors such as Escherichia coli. Some of the examples in Table 10.1 are surfactants formed from enzymatic hydrolysis of oleochemical feedstocks, such as MAG formed from lipase-catalyzed hydrolysis of TAG, and lysophospholipids via hydrolysis by Upases or phosphoUpase A. Ui the foUowing sections some specific examples from the literature are given of enzyme-catalyzed synthesis of bio-based surfactants. Other examples not described, such as the oxidation of fatty alcohols to aldehydes (OrUch et al., 2000) and the covalent attachment of fatty alcohols and bio-based diethyl carbonate (Banno et al., 2007, 2010 Matsumura 2002 Lee et al., 2010) are covered in the references provided. 

EA is a well-established, highly functional and essential component of many nonfood consumer products, most notably as an oleochemical feedstock... 

Oil palm (Elaeis guineensis Jacq.) is believed to be indigenous to West Africa. More than 80% of the world s palm oil comes from Southeast Asia, mainly Malaysia (50%) and Indonesia. Another species, such as American oil palm (Elaeis oleifera), are also cultivated for vegetable oil. One hectare of oil palm plantation produces 4.51 of oil per year which is three times the yield of coconut and more than 10 times that of soybean. Oil palms accumulate 90% of their oil in the mesocarp of fruits (pahn oil contains mostly palmitic and oleic acid, together 80% 10% LA), and the remaining comes from seed kernels (they contain >60% of medium-chain FAs, mainly, lauric acid). Pahn oil is mostly used in food products, as well as an oleochemical feedstock and a feedstock for biodiesel production. Pahn kernel oil is a most important feedstock used in the production of detergents and other applications of medium-chain FAs. 

The meat is used for nutrition and the tallow (mutton), obtained as a by-product, is used as an oleochemical feedstock. S. are not only bred for meat but also for - wool, leather and fur production. By-product is wool wax or grease (- lanolin). 

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