Industrial oleochemicals

All petrochemical-based substances have higher gross energy requirements (GER, indicates the total primary energy consumption of the manufacturing process of a chemical product from its raw material) than those 

The metathesis of triacylglycerols and unsaturated fatty acid derivatives has emerged as a powerful tool in synthetic organic chemistry. The metathesis approaches most commonly applied in oleochemistry are 

Fatty acid methyl ester R = hydrocarbon part of tatty acids 

10 Transformation of fatty acid methyl esters into useful chemicals. 

Fatty acid chloride Ethylene diamine derivative 

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The hydrolysis of vegetable oil (triglyceride) produces glycerol, which is utilised to produce a number of other important industrial oleochemicals such as 1,3-propane diol, 1,2- propane diol, epichlorohydrin and acrylic acid, (Fig. 3.14). 

Environmental regulation in the oleochemical industry addresses pollution of air, surface, and groundwater, along with land pollution and soHd waste disposal. This is adrninistered by the Environmental Protection Agency (EPA) on the national level, an equivalent agency on the state level, and sometimes local agencies also deal with various aspects of pollution abatement. 

Concentrated efforts to introduce immohi1i2ed Hpase technology in the fats and oleochemicals industry have been made since the mid-1980s (88). 

Figure 3.56 in Section 3.8 illustrates the mechanism of phase-transfer catalysis. Tables 4.4 and 4.5 give examples of industrial importance in agrochemicals, pharmaceuticals, fine chemicals, oleochemicals, etc. 

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). 

Industrial Development and Application of Biobased Oleochemicals Table 4.1 Evaluation of environmental compatibility of chemicals. 

Several years ago research was undertaken to use oleochemicals to build up matrices for natural fiber reinforced plastics [9]. The use of natural fibers, such as flax, hemp, sisal, and yucca is of increasing interest for various applications, among them the automotive and public transportation industries, where the com-... 

Most of the preceding sections in this chapter have emphasized the use of CM for the homologation of terminal olefins. The microscopic reverse of this reaction, however, is also of great synthetic interest, as it provides a mild method for the cleavage of olefins. When ethylene gas is used as the cross-partner, the resulting CM reaction is known as ethenolysis. Prior to 2000, ethenolysis was almost exclusively used within the oleochemical industry to process unsaturated fatty oils or triglycerides into compounds of lower molecular weight. With the advent... 

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... 

Saponification, hydrolysis and esterification of vegetable oils to release fatty acids for the oleochemical uses detailed above, results in production of glycerol as a by-product. Glycerol is an important platform molecule in its own right, with numerous industrial uses (see Chapter 6 for more information). 

The oldest surfactant is soap, which may be traced back to the ancient Egyptians and beyond. Synthetic surfactants had been produced in the first half of the 20th century but it was only after World War II, with the development of the modern petrochemical industry, that alternative feedstocks to oleochemicals became readily available. Hence chloroparaf-fins and/or alphaolefins and benzene were used to produce alkylbenzene (or alkylate ), processes were developed to produce a range of synthetic fatty alcohols and alkylene oxide chemistry resulted in ethylene oxide and propylene oxide building blocks becoming readily available. 

The reaction is reversible and favored by the presence of moisture and catalysts including lipases, alkalis, and alkaline metals. In the oleochemicals industry, TAG are split by high-pressure steam. Unassociated fatty acids are called free fatty acids or FFA. 

Rendering produced an estimated 4.18 million metric tons of animal fats was produced in the United States in 2000 by rendering.87 Of this amount, approximately 18 percent and 6 percent were edible tallow and lard, respectively, and 41 percent and 35 percent were inedible tallow and grease. Approximately 15 percent and 34 percent of the edible tallow and lard, respectively, and 37 percent of the inedible tallow and grease were exported. Of the inedible tallow and grease used in the United States, an estimated 75 percent was used as animal feed, 16 percent was converted to fatty acids by the oleochemicals industry, 4 percent was used in soaps, and 3 percent in lubricants. Inedible animal fats are the lowest cost domestic fat sources. Their market price per pound sometimes is less than fuel oil, and rendering plants have chosen to bum them as fuels. In 2001, animal fats were included with vegetable oils for federally supported trials of biodiesel fuel. 

Fig. 34.35. Oleochemical derivatization pathways. (Modified from Zoebelein, H "Renewable resources for the chemical industry," INFORM, 3, 721-725 (1992), and Johnson, L. A. and Meyers, D. J "Industrial uses for soybeans," in Practical Handbook of Soybean Processing and Utilization, D. R. Erickson (Ed.), pp. 380-427, AOCS Press, Champaign, IL, 1995.)...

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