Oleochemical raw materials and

N. B. Godrej and co-workers. Proceedingsfirom "Alpha Olefins from Oleochemical Raw Materials," The Third World Detergent Confierence, Montreux, Switzerland, Sept. 1993. 

Coconut oil and tallow have been traditional oleochemical raw materials for many years. However, the significant increase in the production of palm oil over recent decades has had a marked influence on the availability of such feedstocks. 

Another area of major indnstrial importance is the production of oleochemical raw materials such as fatty acids, fatty acid methyl esters, fatty alcohols, and glycerol. The company Henkel is the world s largest processor of renewable fats and oils, with a capacity of 10 t. Tailor-made catalysts are used in most oleochemical reactions. 

K. HiU, Fats and oils as oleochemical raw materials , Pure Appl Chem, 2000,72, 1255-64. 

The demand for inexpensive and renewable energy and chemical products will further spur the oleochemical industry. The metathesis of oleates offers new synthetic routes to valuable raw materials and feed stocks with high chemoselectivity. The reaction is catalytic and could be performed at ambient conditions. Moreover, solvents could be substituted with "green" ionic liquids that will further enhance the growth of production. 

Hill, K., 2000. Fats and oils as oleochemical raw material. Pure and Applied Chemistry 72,1255-1264. 

Presently, about 50% of the surfactants used in the surfactant industry are derived from petrochemical raw materials, and the other 50% are derived from oleochemical raw materials. The most important smfactants used in consumer detergents are anionic and nonionic materials. The alcohols used are linear or essentially linear, which results in a more rapid and complete biodegradation of both oleochemical- and petrochemical-derived detergent smfactants. 

Castor is the only renewable vegetable oil resource (see Chemurgy) having a hydroxyl group stmcture and functionaHty that leads to diverse oleochemicals. In 1988, approximately 35,000 t/yr of castor oil were used to prepare raw materials for the manufacture of nylon-11. It is estimated that 40,000—45,000 t of... 

Compared with the fatty alcohol sulfates, which are also oleochemically produced anionic surfactants, the ester sulfonates have the advantage that their raw materials are on a low and therefore cost-effective level of fat refinement. The ester sulfonates are produced directly from the fatty acid esters by sulfona-tion, whereas the fatty alcohols, which are the source materials of the fatty alcohol sulfates, have to be formed by the catalytic high-pressure hydrogenation of fatty acids esters [9]. The fatty acid esters are obtained directly from the fats and oils by transesterification of the triglycerides with alcohols [10]. 

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. 

Alcohols in the range C12—Ci8 are important raw materials for the production of a key group of surfactants ethoxylates, sulfates and ethoxysulfates among others. Alcohols used in the surfactant industry are primary, linear, or with different degrees of branching, and they can be produced from either petrochemical sources (ethylene or linear paraffins) or from oleochemical products (animal fats and vegetable oils). 

Despite the general move towards use of fossil hydrocarbon feedstocks, some plant-derived materials have continued to provide economic or technical benefits that ensure they remain the preferred source of raw materials for industry. For example, cotton still accounts for 38% of all textile production due to its airflow- and temperature-regulating capabilities, which are difficult or costly to replicate with man-made fibres. Linseed oil remains a key feedstock in surface coating and linoleum flooring applications. Plant oils are still widely used in the oleochemicals sector, where coconut and palm oils are widely used in detergent... 

Raw materials. The hydrophobe for SME is currently derived exclusively from oleochemical sources, rather than from petrochemicals, as in the case of LAS and AOS. While these two sources can often provide surfactants of equivalent performance, oleochemcials are frequently preferred (especially in personal care applications) because they are derived from natural ingredients. The use of renewable resources is also cited as an additional benefit of oleochemical-based surfactants and this is discussed more fully in Section 4.2.1. 

Raw materials. It is possible to use any fatty acid as a feed material for sulphonation but economic considerations dictate that oleochemical material be preferred. Fatty acids are readily obtained from vegetable and animal oils and fats which are fatty acid triglycerides. These are transesterified to generate glycerol and three moles of a fatty acid ester, normally a methyl ester. The methyl ester can be distilled to give a specific cut and the fatty acid finally isolated by hydrolysis or hydrogenation of the ester. It is common to use animal fats (tallow) in which case the dominant C chains are 16 and 18. 

Derivatives of fatty acid from coconut oil are feedstock for a number of diverse nonfood products. Coconut oU fatty acids and glycerol are released by hydrolysis or alcoholysis of the fat. The fatty acids or their methyl esters, which are subsequently fractionated, constimte the starting materials for the oleochemical industry. The byproduct, glycerol, is purified by vacuum distillation. The purified product is, among others, a component of pharmaceutical preparations, an important ingredient in toothpastes, a raw material in the manufacture of nitroglycerol, and the fluid in hydraulic jacks and shock absorbers. 

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... 

There is a strong competition between products derived from oleochemicals and those derived from petrochemicals. With the current awareness on environmental issues and preference for environmentally friendly products, the utilization of palm oil/palm oil products for nonfood applications via the oleochemicals route is also expected to increase. Due to the ready availability of raw materials, technology, capital, and market demand, the nonfood applications of palm oil/palm oil products are expected to have a bright future. 

The oleochemical industry is fairly well developed and its future secure because of a reliable supply of raw materials. The world s fats and oils output has been growing rapidly over the past few decades, far beyond the need for human nutrition. The world s production and consumption of natural oils and fats has grown from 79.2 million t in 1990 to 117 million t in 2001. Malaysia, Indonesia, and Argentina are notable excess-supply producers India, the European Union countries, and China are notable high-demand areas that supplement regional production through imports (1). 

The C12-C18 fatty acid fractions, approximately 85% of the coconut oil fatty acid composition, are the primary raw materials for detergent-grade fatty alcohols. Coconut oil is a primary source of basic oleochemicals and a host of other oleochemical derivatives. Figure 1 indicates some of the major processes by which... 

Coconut oil is one of the most important raw materials for the oleochemical industry. The whole range of its fatty acid composition is used as the starting material for a wide variety of oleochemical products. Fatty acids are the building blocks that, with proper selection and application of oleochemistry, are converted to higher valued products. 

As a result of the current demand for biodegradable and environmentally friendly sources of raw materials, these uses have a place in the marketing of marine oils well into the twenty-first century and will command premium prices if special niches for the oil can be developed. The competitiveness of the oleochemicals... 

Oleochemicals are derivatives of fats and oils that are used in the chemical industry to produce a wide variety of products that are then used in numerous applications. The chemical reactions that are used require clean, relatively high-quality raw materials in most, but not all, cases. Some of these markets purchase raw materials on price alone, so they usually get the lowest quality oils. The successful operation can take the cheapest waste oils and convert them into high-value end-products. A good example of this is the conversion of spent restaurant grease into bio-diesel fuel. 

Willing, A. Oleochemical esters—environmentally compatible raw materials for oils and lubricants from renewable resources. Fett/Lipid 1999, 101, 192—198. 

Fatty alcohols make up one of the major basic oleochemicals having an increasing growth rate. As a primary raw material for surfactants, growth in fatty alcohol production parallels increasing economic prosperity and improved standards of living. Fatty alcohols are the raw materials of choice for surfactant manufacture because of their biodegradability and availability from renewable resources. 

Animal edible tallow is normally obtained from beef but also from sheep and goats, processed from suet. Unlike suet, tallow can be stored for extended periods without the need for refrigeration to prevent decomposition, provided it is kept in an airtight container to prevent oxidation. It is used in animal feed, to make soap, for cooking, as bird feed, and was used for making candles. It can be used as a raw material for the production of biodiesel and other oleochemicals. ... 

Fats and Oils The Raw Materials of Oleochemistry. Fats and oils are triglycerides (i.e., fatty acid esters of glycerol). They are the starting materials for the production of fatty acid methyl esters, which are important intermediates in the production of fatty alcohols and surfactants [198] by the oleochemical route, which has great ecological benefits [199]. The fatty acid methyl esters are produced either by the esterification of fatty acids after hydrolysis of the triglycerides or by direct transesterification with methanol. The overall transesterification reaction is as follows ... 

Unsaturated fatty compounds are of interest as renewable raw materials (1). These compounds can be functionalized at the C,C-double bond by electrophilic addition reactions to give new oleochemicals with potentially new and interesting properties. The alkylaluminum chloride-induced Friedel-Crafts acylation of unsaturated fatty compounds (Fig. 1), such as oleic acid [la], 10-undecenoic acid [2a], petroselinic acid [3a], and erucic acid [4a], and the respective esters and alcohols yield the corresponding P,y-unsaturated ketones (2,3). 

Table 11.2 gives a survey about major use areas for adhesives based on renewable sources. The share of renewable raw materials in the sealants market is well below 5%. Numbers in Table 11.2 do not include polyurethanes containing oleochemical-based polyols, vegetable oil-based polyesters and polyamides based on dimer fatty acids in total estimated at 35 mto in 2006, 42 mto in 2010. Projection into 2010 shows that without disruptive innovations the share of natural-based adhesives will further decline to a mere 15% in total. 

Thus, the use of renewable materials declined significantly over time, mainly due to the extremely low prices for petrochemical resources. Currently, approximately 96% of aU organic chemical substances are based on fossil resources. Nevertheless, a substantial number of industries are still based on renewable raw materials (RRMs). StiU half of the fibers used in the textile industry are natural materials (cotton, wool, flax) and the oleochemical industry satisfies sodely s daily hygienic needs for soaps with detergents that are based on vegetable oils. The building industry continues to use natural fibers for construction insulation purposes. 

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