Oleochemicals renewables

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... 

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. 

The biorefinery scheme was developed initially for carbohydrate-containing feedstocks. Large biorefineries are currently operating in the USA (e.g., Cargill at Blair, Nebraska) and in Europe (e.g., Roquette Frs. at Lestrem, France). The concept can be extended to produce chemicals from other renewable feedstocks. An integrated production of oleochemicals and biofuels can be achieved in biorefineries using vegetables oils as main feedstock to produce versatile platform mole-... 

The shift to oleochemicals has been supported by increasing environmental concerns and a preference by some consumers, especially in Europe, for materials based on natural or renewable resources. Although linear alkylbenzenesulfonates (LASs) are petrochemically based, alcohol ethoxylates, alcohol ethoxysulfates, and primary alcohol sulfates are derived from long-chain alcohols that can be either petrochemically or oleochemically sourced. There has been debate over the relative advantages of natural (oleochemical) vs synthetic (petrochemical) based surfactants. However, detailed analyses have shown there is litde objective benefit for one over the other. 

A reexamination of so-called renewability has shown that advantages for oleochemicals are not sufficiently dear (115), especially because manufacture of surfactants in the United States accounts for only 0.03% of annual crude oil consumption (62). On these bases, the primary determinants of surfactant choice will continue to be cost effectiveness and availability. The 1993 U.S. market has been estimated to be worth 3.7 x 109 (110). Approximatdy one-half was anionic surfactant ( 1.8 x 109) and one-third nonionic surfactant ( 1.2 x 109). The balance was made up by cationics ( 1.2 x 106) and amphoterics ( 600 x 106). The U.S. International Trade Commission (116) provides a minutdy detailed breakdown of surfactant production. 

Justin Stege (Diversa Corporation) discussed the molecular evolution of enzymes for particular pathways, with a focus on the modification of oil composition. Oleochemical applications for such enzymes include applications as biocatalysts for fatty acid modifications. In a program to integrate production and processing, such enzymes can be used to modify the fatty acid content of vegetable oils in planta. Results show that expressing such new enzymes in oilseed crops has resulted in altered oil composition, and that the features may be used to better design plant-based oils for use as biofuels and as improved renewable feedstocks. 

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. 

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. 

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.)...

Production of Oleochemicals Fatty acid esters, which have traditionally been used as flavors, plasticizers, food preservatives, emulsifiers, and lubricants, are receiving renewed interest as an alternative energy source as biodiesel. They can be produced by the esterification of fatty acids and alcohols or by the alcoholysis of vegetable oils/triacylglycerols. 

Fats and oils are renewable products of nature. One can aptly call them oil from the sun where the sun s energy is biochemically converted to valuable oleochemicals via oleochemistry. Natural oleochemicals derived from natural fats and oils by splitting or tran -esterification, such as fatty acids, methyl esters, and glycerine are termed basic oleochemicals. Fatty alcohols and fatty amines may also be counted as basic oleochemicals, because of their importance in the manufacture of derivatives (8). Further processing of the basic oleochemicals by different routes, such as esterification, ethoxylation, sulfation, and amidation (Figure 1), produces other oleochemical products, which are termed oleochemical derivatives. 

The use of renewable resources as substrates in chemical processes has recently been reviewed [1]. There are two major topics of current research (1) oleochem-ical reactions, and (2) chemical transformation of carbohydrates. Nevertheless, the chemical possibilities of renewable resources as substrates - using homogeneous catalysis - are still very far from being fully exploited. 

Hill, K. (2007) Industrial development and application of biobased oleochemicals, in Catalysis for Renewables (eds G. Centi and R. van Santen), Wiley-VCH Verlag, Weinheim, Ch. 4, p. 75. 

Polyols from Renewable Resources -Oleochemical Polyols... 

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. 

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. 

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). 

Schematic pathways to oleochemical polyols. (Source T. Roloff, U. Erkens and R. Hofer, Polyols based on renewable feedstocks A significant alternative, Urethanes Technology, August/September 2005, 29.)...

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