Alcohol continued ethoxylates

HENKEL CX3RP. EMERY GROUP TRYCOL Ethoxylated Alcohols (Continued) ... 

Synonyms Ethoxylated tridecyl alcohol Isothdecanol ethoxylates Definition PEG ether of tridecyl alcohol commercial prods, contain 3-20 moles EO Formula (C2H40)xCi3H280, x = 3-20 Properties Liq. to paste HLB 8-16.3 (3-20 moles EO) nonionic HLB 8.0-16.3 Toxicology TDLo (oral, rat, 13 wk continuous)... 

Transfer the hydrolysed solution after extraction of the fatty alcohol or ethoxylate to a 500 ml volumetric flask, dilute to volume and mix. Use water for this dilution if the gravimetric procedure is to be followed, or acetone for the volumetric procedure. Continue as follows. The volumetric procedure is preferred if other surfactants are present. 

Table 10. Estimated Typical Operating Conditions and Rates of Commercial Continuous SO Falling Film Sulfonation Processes for Sulfonation of LAB and Lauryl Alcohol-3 Mol Ethoxylate Feedstocks ...

Summary of Characteristics of Falling Film Continuous SOj Sulfonation Processes. Both concentric and multitubular reactor systems suppHed by competing manufacturers have surprisingly similar operating characteristics organic feedstock loading of ca 0.4 kg/(h-mm) (circumference) for LAB, and ca 0.3 kg/(h-mm) for alcohol ethoxylates an SO concentration of 3.3—5.0 vol % SO for LAB sulfonation, and 2—3% SO ... 

Equation 20 is the rate-controlling step. The reaction rate of the hydrophobes decreases in the order primary alcohols > phenols > carboxylic acids (84). With alkylphenols and carboxylates, buildup of polyadducts begins after the starting material has been completely converted to the monoadduct, reflecting the increased acid strengths of these hydrophobes over the alcohols. Polymerization continues until all ethylene oxide has reacted. Beyond formation of the monoadduct, reactivity is essentially independent of chain length. The effectiveness of ethoxylation catalysts increases with base strength. In practice, ratios of 0.005—0.05 1 mol of NaOH, KOH, or NaOCH to alcohol are frequendy used. 

Because of the difficulty and dangers of using EO in a continuous process, ethoxylation is usually conducted in batch operations. The required amount of the EO and alcohols are measured and pumped into the reactor in order to complete the reaction. 

One kind of surface emulsion that is desirable is the Orinoco bitumen emulsion produced from in situ steam stimulation and recovery in the Orinoco River deposit in Venezuela. This emulsion is reformulated into Orimulsion , an O/W emulsion, containing about 30% fresh water and a stabilizing surfactant (typically about 0.1 percent each of monoethanolamine and an alcohol ethoxylate) [588,759,760], The O/W emulsion has a viscosity of about 450 mPa-s (30 °C, 100 s-1) compared with the original bitumen viscosity of about 10000 mPa-s [760,761], This emulsion can be used as an alternative fuel for power-generating plants. Being water-continuous the emulsion is easily handled and transported, but otherwise behaves similarly to fuel oil. 

In Nippon Shokubai s process(Figure 2), the 3 mole ethoxylate of a mixture of secondary alcohols can be produced from a mixture of normal paraffins through a fully integrated continuous process. The oxidation is carried out using ft-metaboric acid as a catalyst and an ammoniac base as an auxiliary catalyst to promote the reaction(4 ). The alcohol mixture obtained consists of all possible structural isomers of secondary alcohols having the same carbon numbers as the raw material used. 

Figure 1.1 presents the consumption of the major surfactants in the world market in 1996. Along with soap, linear alkylbenzene sulphonates (LAS) remain the most bulky and cost-effective anionic surfactants. LAS will continue to be the workhorse of the detergents industry on a global basis. However, the LAS share decreases gradually their recess is occupied by alcohol-derived surfactants, first of all alcohol sulphates (AS), alcohol ethoxylates (AE) and alcohol ether sulphates (AES). In West Europe alkylphenol ethoxylates (APE) have been removed over the last two decades from a large number of household applications in view of... 

Whatever the specific type, a valid question for all ordinary emulsions with or without surfactants is what is the maximum amount of the dispersed phase in the continuous phase when the former will still remain dispersed In other words, at what volume ratio does an inversion (i.e. OAV to W/O and the reverse) take place Emulsions for particle preparation are known to have been prepared where the volume ratio of the two phases can go up to near 1 1 [18]. In addition and contrast to this general idea about the relative contents of the two phases, one must also refer to the highly concentrated water-in-oil emulsions which can be prepared with a fluorinated surfactant and a fluorocarbon/hydrogenated surfactant (pronouncedly hydrophobic) and a hydrocarbon [19]. In these W/O emulsions, up to 98% w/w water is added, but inversion is never achieved. Highly concentrated W/O emulsions have also been described recently by Hakansson etal. [20] where the surfactant is of the alcohol ethoxylated type, the dispersed phase is aqueous in nature and the continuous phase, an aliphatic hydrocarbon. It has been indicated that such emulsions may contain more than 99% of the dispersed phase. These are, however, very special cases and do not demand further discussion here. Without going into specificities, let us look at the general factors that may influence inversion [3, 21, 22] ... 

Sodinm laureth sulfate or SLES (CAS no. 3088-31-1) is one of the most commonly used anionic surfactants in shampoo formulations. An aqueous concentrated SLES is derived from fatty alcohols, ethoxylated to an average of 2 moles (2EO), and sulfated via a continuous SO3 process. There are a large number of synonyms for SLES available in the literature. Those most frequently cited are provided in Table 8.2 along with strnctnral formula of the surfactant. 

Chlorosulfonic acid (CSA) sulfation of alcohols or alcohol ethoxylates is usually conducted in batch reaction mode, typically in glass-lined vessels, but requires little or no excess reagent to drive the reaction to completion and can be conducted in a continuous liquid-liquid contacting process. The reaction evolves a stoichiometric quantity of HCl gas, which can be captured either as an HCl solution or with caustic to yield sodium chloride. Product color, yield, and quality cau be very high, but throughput efficiency is modest in batch mode. 

Stepan was the first to develop and conunercialize a continuous falling film SO3 sulfonation process. The design is a multitubular unit. The company operates about 12 falling film SO3 sulfonation units in the United States, not only for the production of linear alkyl benzene sulfonates, but substantial amounts of fatty alcohol and fatty alcohol ethoxylates are also sulfated. Other key commercial reactor designs are by Chemithon, Ballestra SpA, Lion, Mazzoni SpA, and Meccaniche Modeme. Several features are common to all falling-film systems. Fatty alcohol and alcohol ethoxylates are reacted at a rate of about 0.3 kg/h/mm with SO3 concentration at about 2-3%. Liquid residence times are estimated at 10-30 s and most units operate with gas velocities in the range of hurricane wind velocities (121-322 km/h). ° Linear alcohols and linear alcohol ethoxylates are by far the easiest to sulfate. Caution is required with branched alcohols as color and conversion can suffer. 

Continuous sulfation of the ethoxylated fatty alcohols by a mixture of air/sulfur trioxide in a thin-film reactor (as for alkyl sulfonates), which is immediately (to avoid autohydrolysis) followed by neutralization typically with sodium hydroxide but also with ammonia or alkyl-amines to give the corresponding salts. The chemical reaction is as follows ... 

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