Oleochemical

SDA Glycerin and Oleochemicals Statistics Keport, The Soap and Detergent Association, New York, 1992. 

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

Oleochemicals Fat Acids, Fat Alcohols, Fat Amines, Course sponsored by the Education Committee of the American Oil Chemists Society, Kings Island, Ohio, Sept. 13—16, 1987. 

Historically, these sulfonates have been difficult to produce in good quaUty and to formulate into laundry powders because of thermal and hydrolytic stabihty problems. Used basically as an anionic, oleochemically sourced replacement for LAS, FAE sulfonate benefits include good detergency at low concentration, low environmental load, and good supply of high quaUty material (71). To avoid possible thermal stabihty problems, these sulfonates have found apphcation in Hquid products. They are used in at least one U.S. dishwashing Hquid, and the cocoyl derivative, Alpha-Step MC48, is marketed by Stepan Chemical Company. 

A reexamination of so-called renewabdity has shown that advantages for oleochemicals are not sufftcientiy clear (115), especially because manufacture of surfactants ia the United States accounts for only 0.03% of aimual cmde 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 10 (110). Approximately one-half was anionic surfactant ( 1.8 x 10 ) and one-third nonionic surfactant ( 1.2 x 10 ). The balance was made up by cationics ( 1.2 X 10 ) and amphoterics ( 600 x 10 ). The U.S. International Trade Commission (116) provides a minutely detailed breakdown of surfactant production. 

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. 

A.. Kaufman and R.. Ruebusch, Oleochemicals A. World Overview presented at World Conference on Oleochemicals—Into the 21st Century Kuala Lumpur, Malaysia, Henkel Corp., Emery Group, Oct. 1990 adjusted by author estimates for worldwide tall oil and castor acids. 

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... 

H. K. Schwitzer iu T. H. Applewhite, ed.. World Conference on Oleochemicals into the 21st Century, American Oil Chemists Society, Champaign, IU., 1990. 

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

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]. 

The initial studies of LSDAs were carried out with oleochemicals because of their structural similarity to soap. However, since the molecular structure of an efficient LSDA is characterized by a bulky hydrophilic polar head attached to a long hydrophobic tail, it is also possible to prepare LSDAs from petrochemicals. Sulfated sulfonamide derivatives of alkylbenzenes, such as commercially available detergent alkylates, were synthesized as follows [17] ... 

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. 

Oleochemical-based alcohols are generally produced from either coconut or palm kernel oils. These lauric oils have carbon chain distributions in the C12-C14 range, where detergency performance is optimum. Figure 1 summarizes the... 

For at least the next 25 years enough lauril (natural C12-C14) oil will not be available to replace petrochemical-based surfactants even if this were desired. However, the oleochemical share of the surfactant intermediate market will grow because a large portion of excess lauric oil (coconut and palm kernel) will be designated for the surfactant market and used to supply the fatty alcohol capacity that has been announced for startup in the coming years. 

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 used as lubricants are added to polymer resins to improve the flow characteristics of the plastic during processing they also stabilise the cells of polyurethane foams during the foaming process. Surfactants are either nonionic (e.g. fatty amides and alcohols), cationic, anionic (dominating class e.g. alkylbenzene sulfonates), zwitterionic, hetero-element or polymeric (e.g. EO-PO block copolymers). Fluorinated anionic surfactants or super surfactants enable a variety of surfaces normally regarded as difficult to wet. These include PE and PP any product required to wet the surface of these polymers will benefit from inclusion of fluorosurfactants. Surfactants are frequently multicomponent formulations, based on petro- or oleochemicals. 

BAYER AG HUNTSMAN URETHANE SPECIALTIES EUROPEAN COMMISSION BAYER MATERIALSCIENCE AG ALBERDINGK BOLEY GMBH GERMANY,GOVERNMENT HOBUM OLEOCHEMICALS HESSE-LIGNAL... 

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 total world production of natural oils and fats in 1997 amounted to 100 X 106 t, of which 80 X 106 t were of vegetable and 20 X 1061 of animal origin [28]. From these oils and fats, 80% are suitable for human nutrition and 14% end up in so-called oleochemical uses, among them... 

A certain shift from petrochemically-based to oleochemically-based surfactants, namely on the alcohol derivatives field, has occurred in recent years in industrialised countries. Figure 1.2 represents the key derivatives and major intermediates used in the production of 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). 

Oleochemical alcohols are primary, even carbon-numbered structures with a high linearity (>95%), while the petrochemical derivatives can be even or odd numbered, and depending on the process, their linearity can be as high as the oleochemicals (Ziegler alcohols) or can exhibit variable branching (30% modified 0X0-60% standard OXO). 

Alcohols are also widely produced from fats and oils, and in some cases one of the oldest techniques utilised in the manufacture of soap, fat splitting, is also used as part of the process. Vegetable oils as well as animal fats are all triglycerides and consequently a key step of the various technologies used in the alcohol manufacture involves the separation of glycerine. Oleochemical alcohols are produced using two... 

Oleochemical alcohols, sometimes known as natural alcohols, are also identified by the carbon range C12-C14 lauric, Ci6-Ci8 tallow, regardless of the origin of the raw material. C1(-i-C18 alcohols were predominantly produced in the past from tallow, hence their name, although today they are also widely produced from palm oil. Lauric range alcohols are produced from either coconut oil or from palm kernel oil. 

The continued use of ABS in some small markets, for example the South East Asia region, despite the advantages offered by LAS in terms of performance characteristics such as foam generation and detergency [75,76], seems to be linked to political situations (oleochemical producer pressure) rather than to any other economical justification. 

European Oleochemicals Allied Products Group, http //www.apag.org/oleo. 

Fig. 2.3.8. Chromatogram of the NIC derivatives of oleochemical AEOs in a standard solution (a) AEOs and NPEOs in extracts of the influent (b) and final effluent (c) of a sewage treatment plant. Chromatogram of the NC derivatives of PEGs in a standard solution (d) and extracts of the influent (e) and final effluent (f). Stationary phase Cis column mobile-phase methanol-acetonitrile (a)-(c) and acetonitrile-water (d)-(f).

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-... 

In polymer applications derivatives of oils and fats, such as epoxides, polyols and dimerizations products based on unsaturated fatty acids, are used as plastic additives or components for composites or polymers like polyamides and polyurethanes. In the lubricant sector oleochemically-based fatty acid esters have proved to be powerful alternatives to conventional mineral oil products. For home and personal care applications a wide range of products, such as surfactants, emulsifiers, emollients and waxes, based on vegetable oil derivatives has provided extraordinary performance benefits to the end-customer. Selected products, such as the anionic surfactant fatty alcohol sulfate have been investigated thoroughly with regard to their environmental impact compared with petrochemical based products by life-cycle analysis. Other product examples include carbohydrate-based surfactants as well as oleochemical based emulsifiers, waxes and emollients. 

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

---