驱油用脂肪醇聚氧乙烯醚磺酸盐研究进展

介绍了卤化脂肪醇醚法、烯烃加成法、硫酸酯盐转化法和羟乙基磺酸钠法合成脂肪醇聚氧乙烯醚磺酸盐的路线、工艺特点及优缺点,剖析了其泡沫性能的影响因素,耐温、耐盐耐钙性能的研究现状。脂肪醇聚氧乙烯醚磺酸盐类阴-非离子表面活性剂适用于高温、高矿化度油藏条件的开采,具有常规表面活性剂的多种优良性能,在油田开采中具有广阔的发展空间。     

Analysis of surfactant mixtures. I

Summary Some data on the use of 93% phosphoric acid as a reagent for recovering the hydrophobic portion of surfactants are presented, and their application to the analysis of surfactant mixtures is discussed. Aromatic sulfonates, straight-chain alkyl sulfates, fatty acid amides, and fatty acid esters decomposed to give good yields of the starting hydrophobic materials. Dioctylsulfosuccinate gave a mixture of octyl alcohols and olefins while the ethylene oxide condensates of lauryl alcohol, tridecyl alcohol, and tertiary dodecyl mercaptan gave olefins derived from the starting hydrophobic materials. Diisobutylene phenol-ethylene oxide condensate decomposed to olefins, conjugated olefins, and alcohols formed by rupture of the aromatic ring. The products are characteristic of the hydrophobic oils, and in most cases products from mixtures of surfactants can be separated by known analytical methods.Alpha-sulfo fatty acids or alkane sulfonates do not give recoverable oils by this treatment.     

2018 年中国表面活性剂原料及产品统计分析

摘 要： 结合2018年国内规模以上企业表面活性剂原料及产品的产销数据，对脂肪醇、烷基苯、脂肪酸等主 要行业原料以及脂肪醇醚硫酸盐、烷基苯磺酸盐、脂肪醇醚、烷基季铵盐、甜菜碱等主要产品的生 产与市场进行详细分析。传统产品发展地位依然坚挺，新品种发展迅速，行业结构和整体市场保持 平稳，垄断和洗牌成为趋势。 关键词：表面活性剂；产品；原材料；生产与市场；行情走势 中图分类号：TQ423 文献标识码：A 文章编号：1006-7264（2019）04-0001-04 DOI：10.3969/j.issn.1006-7264.2019.04.001     

磺酸盐类表面活性剂的合成和应用现状

本文综述了磺酸盐类表面活性剂的合成路线及其研究现状,并对脂肪醇聚氧乙烯醚磺酸盐表面活性剂、芳基或脂肪醇醚磺酸盐表面活性剂的合成进行了重点介绍。我国应大力开发原料易得、活性高的脂肪醇醚磺酸盐、脂肪酸酯磺酸盐表面活性剂,注重具有新颖结构、独特性能的AOT型和Gemini型表面活性剂的研究以适应更广泛的需求。     

Challenges to a mature industry: Marketing and economics of oleochemicals in Western Europe

Basic oleochemicals are produced by splitting and further reactions of oils and fats: fatty acids, glycerine, fatty acid methyl esters, fatty alcohols and amines. The last two are included in the list of oleochemical raw materials, primarily because of their importance in the preparations of further derivatives. The wide range of derivatives of oleochemical raw materials such as fatty alcohol ethoxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, quaternary ammonium compounds and soaps are summarized. Oleochemicals such as fatty alcohols and glycerine from oils and fats have equivalents on the basis of petrochemicals. Using the customary terminology, petrochemical products are referred to as “synthetics.” The are included in the present discussion because in the application of oleochemical raw materials the origin of the material is often less important than the structure. Oleochemistry can be regarded as a mature branch of chemistry, with many applications for its products, but with few completely new fields. The challenge and the opportunities for oleochemistry today lie in the changing economic and ecological conditions. Availability and price development of oils and fats are discussed with particular reference to European conditions, for these are the prerequisites if oleochemicals are to be competitive and are to improve their chances in the marketplace. The importance and development of the oleochemical raw material fatty acids, fatty acid methyl esters, glycerine, fatty alcohols and amines are considered on the basis of historical data. In considering future developments of oleochemicals, the capacity, demand and the possible influence of petrochemistry or crude oil is discussed. The highly developed oleochemical raw materials industry is a flexible supplier of medium-to long-chain fatty alkyl groups. These facts, together with the well organized supply lines for raw materials and the considerable potential of these renewable raw materials, could provide the necessary conditions for the oleochemical raw materials industry to fulfil its future tasks on a larger scale. This could arise, for example, due to the partial substitution of petrochemical surfactants, if this should become necessary as a result of developments in the price and availability of crude oil, or on grounds of ecological factors.     

表面活性剂在家用洗涤剂中的应用进展

论述了表面活性剂在家用洗涤剂中的应用现状和发展趋势,分析了直链烷基苯磺酸钠、α-烯基磺酸钠、脂肪醇聚氧乙烯醚硫酸钠、脂肪酸甲酯磺酸钠、脂肪醇聚氧乙烯醚、脂肪酸甲酯乙氧基化物、烷基糖苷等几种重要的表面活性剂的应用和市场情况,阐明了脂肪酸甲酯磺酸钠有望成为新一代有影响力的阴离子表面活性剂。指出家用洗涤剂的发展趋势将是功能化、浓缩化和液体化,表面活性剂将向油脂基和特种表面活性剂发展,其安全性也将倍受关注。建议加强油脂化学工业建设,为油脂基表面活性剂的发展打下坚实基础。     

The workhorse surfactants: LAS,alcohol sulfates,and ether sulfates

Relative market volumes are discussed illustrating why LAS, alcohol sulfates, alcohol ether sulfates, and branched chain alkylene benzene sulfonates are called “workhorse” surfactants. Typical heavy duty powder, heavy duty liquid, and light duty liquid formulations from around the world are given for each material. Low mole ether sulfates for heavy duty powders are discussed as to chemical constituency and performance. Comparisions of LAS to paraffin sulfonates and olefin sulfonates are given for light duty liquid formulations. Shampoo performance advantages of alcohol sulfates over olefin sulfates are illustrated.     

Gas chromatographic analysis of ester-type surfactants by using mixed anhydride reagent

Polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene fatty acid ester-type surfactants have been analyzed by gas chromatography after chemical decomposition by using the mixed anhydride of acetic and p-toluene-sulfonic acids. In this way, the hydrophobic groups of the polyoxyethylene alkyl ether sulfates and polyoxyethylene alkyl ether phosphates can be identified in the form of alkyl acetates, and the alkyl compositions can be determined easily. On the other hand, the hydrophobic groups of the polyoxyethylene fatty acid ester-type surfactants, such as polyoxyethylene fatty acid ester, polyoxyethylene glycerol fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, have been identified after conversion into their corresponding fatty acids. At the same time, the base compounds of the hydrophilic groups have been converted into ethylene glycol diacetate, glycerol triacetate, and isosorbide diacetate, respectively, so these surfactants may be distinguished easily.     

“Acid” pyrolysis-capillary chromatographic analysis of anionic and nonionic surfactants

A tandem “acid” pyrolysis-capillary chromatographic method for analyzing surfactants has been developed, and its application to the more common anionic and nonionic surfactant types investigated. In this method a surfactant is mixed with an acid, such as P₂O₅ or H₃PO₄, and dropped into a pyrolyzer attached to a capillary gas chromatograph. The resulting volatile pyrolyzate is carried into the chromatograph for analysis. According to the chromatograms, the point of cleavage during “acid” pyrolysis is quite selective, usually at a C-S or C-O bond. For example, LAS and ABS give peaks corresponding to the alkylbenzene precursors; primary linear alkyl sulfates and sulfonates, peaks corresponding to olefins with the same number of carbon atoms as the alkyl group; and alcohol and alkylphenol ethoxylates and ethoxylate sulfates, peaks corresponding to olefins from the alkyl group and to acetaldehyde and a higher aldehyde from the polyethoxy group. Alkylphenol derivatives are probably cleaved to form an alkylphenoxy intermediate, which then dealkylates to give the olefins. This method is quantitative for carbon number or carbon number and isomer distribution of hydrophobes in linear surfactants, semiquantitative for ethoxy content and for hydrophobes in branched chain surfactants, and qualitative for hydrotropes and certain foam additives. Surfactants, as well as mixtures of certain surfactant types, in built detergent formulations can be analyzed without isolation. Winner, Bond Award Medal, Philadelphia, October 1966.     

腰果酚表面活性剂的合成研究进展

综述了腰果酚表面活性剂的合成研究进展,重点介绍了腰果酚磺酸盐、腰果酚硫酸盐、腰果酚羧酸盐及腰果酚聚氧乙烯醚等表面活性剂的合成方法,并分别对其性能进行了概述。腰果酚表面活性剂除了具有优良的性能,其绿色的原料来源也更符合发展潮流。     

Nonsolvent quantitation of anionic surfactants and other inorganic ingredients in laundry detergent products by X-ray fluorescence spectrometry

This paper reports the development of a method for measuring alkyl-benzene sulfonates, alkyl sulfates, and other inorganic ingredients in laundry detergent products without requiring the use of chlorinated organic solvents such as chloroform. Zeolite is first filtered as a residue on filter paper from an aqueous detergent solution. A calcium solution is then added to the filtrate. Alkyl-benzene sulfonates, alkyl sulfates, and phosphate are precipitated as calcium salts and recovered as residues via filtration. The filters are then subjected to X-ray fluorescence spectrometry (XRF) for measuring the levels of zeolite, phosphate, and total anionic surfactant. The remaining filtrate is also subjected to XRF by using the microdroplet preparation for measuring levels of sulfate and silicate. Separately, the level of alkyl-benzene sulfonates is measured following the same XRF procedure after alkyl sulfates are hydrolyzed using an autoclave. This sample preparation procedure was investigated using XRF and was confirmed to be applicable for simultaneous measurements of alkyl-benzene sulfonates, alkyl sulfates, zeolite, phosphate, silicate, and sulfate without using any organic solvents. In the method described in this paper, interelement effects between anionic surfactants and phosphate are not negligible. Fluorescent X-rays of sulfur or phosphorus are absorbed by calcium complexes of phosphate or anionic surfactants. The slope of calibration curves varies with the levels of coexistent elements; external calibration methods cannot be employed for unknown sample matrices. However, for quality assurance purposes, this method is ideal in terms of turnaround time and laboratory hygiene.     

Effect of surfactant structure on stability of enzymes formulated into laundry liquids

The effect of surfactant structure on enzyme stability in heavy duty laundry liquids was investigated. Surfactants studied were alcohol ethoxylates and anionic surfactants having varying hydrophobic and hydrophilic types and chain lengths. Enzymes used were proteases and amylases. The results showed these enzymes were considerably more stable when formulated into laundry liquids containing alcohol ethoxylates and ethoxysulfates than when formulated with alcohol sulfates and surfactants containing sulfonate groups such as linear alkylbenzene sulfonates and alpha olefin sulfonates. Enzyme stabilizer systems were only partially effective in reducing the enzymedeactivating influence of sulfonate-containing surfactants. Presented at the AOCS meeting in Dallas, May, 1984.     

Darstellung und Eigenschaften von Fettsäurepolyglykolestersulfaten

Production and Properties of Fatty Acid Polyglycol Ester Sulfates Fatty alcohol oxethylates, produced by reaction of fatty alcohols from hydrogenated fatty acid methyl esters with ethylene oxide, are the basic material for an important class of anionic tensides, the fatty alcohol ether sulfates. The fatty acid polyglycol ester sulfates are a very interesting alternative to the fatty alcohol ether sulfates. The former are available by saving hydrogenation, in principle directly by fatty acid oxethylation or interesterification of fatty acids with polyglycols, followed by sulfatation. We report about the production of fatty acid ester sulfates by sulfatation of the fatty acid polyglycol monoesters by sulfurtrioxide or chlorosulfonic acid. By means of the results of physicochemical measurements and process trials it is discussed how far fatty acid polyglycol monoester sulfates are suited as alternative tenside raw material fatty alcohol ether sulfates.     

Oleochemical products as building blocks for polymers

The use of oleochemical derivatives is dominated by applications in the field of surfactants and emulsifiers. There also is a remarkable amount of highly specialised uses, for example in lubricants and as additives to modify the characteristics of polymers. Besides this, some products have been developed on the basis of oleochemical building blocks in the polymer backbone. Starting with oleic acid, the difunctional azelaic acid (C-9) is produced by ozonolysis for application in high-value polyesters and polyamides. Pyrolysis of castor oil or ricinoleic acid is the commercial route to sebacic acid (C-10). Castor oil itself is used as a polyol for the production of polyurethanes. Similar polyols with modified viscosity and application characteristics are made by epoxidation and ring-opening reactions of unsaturated fatty acid derivatives. Dimer acid (C-36) is obtained by a double bond reaction of C₁₈ unsaturated fatty acids. By using hydrogenation technology, which is wellknown in the oleochemical industry to produce fatty alcohols, dimerdiols can be prepared from dimer acid. This dimerdiol is of great interest in polyurethane application fields in general, because it is a liquid, hydrophobic, long-chain raw material with two primary hydroxyl groups. By condensation of dimerdiol to building blocks with a molecular weight around 2,000 it is possible to prepare soft segments, that allow the production of thermoplastic polyurethanes (TPU) with modified application characteristics. Two different soft segments based on dimerdiol, ethers, and carbonates are discussed. The advantages for TPUs prepared from these building blocks are hydrolytic and oxidative stability and resistance to saponification and polar solvents.     

Analysis of mixtures of ionic and nonionic surface-active agents. Separation and recovery of components by batch ion exchange

Mixtures of anionic and nonionic surfactants or cationic and nonionic surfactants can be separated by stirting an aqueous solution of the mixture with a small amount of a strong anion exchange or strong cation exchange resin, respectively. The resin-ionic surfactant complex is removed by filtration and washed; the nonionics are recovered from the filtrate and washings. By suitable treatment the ionic surfactants can be removed selectively from the resin. In the case of anionic surfactants, soaps, alkyl sulfates, and alkylaryl sulfonates can successively be removed from the resin; with cationics, nonquaternary and quaternary surfactants can be selectively removed. Results obtained with various mixtures of surface active agents are discussed. Presented at the 51st fall meeting, American Oil Chemists’ Society, New York, October 17–19, 1960.     

Ein Beitrag zur Dünnschichtchromatographie von Aniontensiden

A Contribution to the Thin-Layer Chromatography of Anionic Surfactants Anionic surfactants and some nonionic surfactants are chromatographed on silica gel plates with tetrahydrofuran + acetone (1 + 9 v/v) as solvent, sprayed with a solution of pinacryptol yellow and examinated under ultraviolet light at 366 nm. The surfactants appear as coloured fluorescent spots on a pale blue background. The relative air humidity has a major influence, i. e. the water content of the silica gel layer, which can be fixed by preconditioning of the plate by the vapour of the solvent. A complete separation of alkane-/olefinesulfonate, cumene/xylene-/toluenesulfonate, alkylbenzenesulfonate, α-sulfofatty acid methylester, fatty alcohol sulfate, fatty alcohol ether sulfate, fatty acid diethanolamide, fatty acid monoethanolamide and soap can be attained. Thin-layer chromatograms of a range of mixtures fatty alcohol sulfate/fatty alcohol ether sulfate and several fatty alcohol ether sulfates with increasing content of ethylen oxide are discussed.     

A comparison of surfactants derived from alcohols based on petrochemical and oleochemical sources

Samples of lauryl-range alcohols derived from palm kernel oil, coconut oil and ethylene (Ziegler) were derivatized into alcohol sulfates and alcohol ether sulfates (2 moles of ethylene oxide adduct). Physical properties and performance characteristics for earch surfactant were evaluated both individually and in light-duty liquid (LDL) dish-washing formulations. The slight differences observed in the physical and performance properties of the surfactants and their formulations were assignable to slight differences the individual alcohol, alcohol sulfate and alcohol ether sulfate samples employed in this study. The magnitude and type of variation found in the samples resulted from normal production variation and not from any properties inherent to the nature of the alcohol source. We therefore conclude that alcohol sulfates, alcohol ether sulfates and LDLs formulated from them exhibit identical physical property and performance characteristics, regardless of whether the original alcohol was manufactured from petrochemical or eleochemical sources.     

Microaerophilic biodegradation of tallow-based anionic detergents in river water

Nine anionic detergents from five general classes (alcohol sulfates, ether alcohol sulfates, sulfated alkanolamides, α-sulfo esters and alkylbenzenesul-fonates) were rapidly screened for biodegradability under aerobic and microaerophilic conditions in river water at 25 and 35 C. In decreasing order, the ease of biodegradation under microaerophilic conditions at 35 C was as follows: alcohol sulfates, sulfated alkanolamides, α-sulfo fatty acid esters and ether alcohol sulfates. Linear alkylbenzenesulfonate did not degrade. Presented at the AOCS Meeting, New Orleans, April 1970.     

Ozonation of Anionic and Non-ionic Surfactants in Aqueous Solutions: Impact on Aquatic Toxicity

The objective of this study was to investigate the influence of ozonation of anionic and non-ionic surfactants on their aquatic toxicity. Toxicity values of various commercially important anionic and non-ionic surfactants have been determined using the luminescent bacterium Vibrio fischeri. Surface tension measurements were made to study the interfacial activity. The behavior depends on the chemical structure. Some intermediate ozonation products were found to be more toxic than the base surfactant and others were found to be less. Surfactants with aromatic rings such as linear alkyl benzene sulfonates, or surfactants with glycosidic groups such as alkylpolyglucosides, exhibit a lower toxicity after ozonation. On the other hand, ether groups present in the fatty-alcohol ethoxylates and ether carboxylic derivative surfactants, and carboxylic acid derivates present in the ether carboxylic derivative surfactants lead to increasing toxicity after ozonation. Surfactants with ether groups probably formed short-chain polyethoxylated compounds and carboxylic acids, which are possibly responsible for the surface-tension decrease that promotes the toxicity increase.     

Ethersulfonate auf Basis ungesättigter Fettalkohole – eine neue Tensidklasse

Ether Sulfonates Basing on Unsaturated Fatty Alcohols – A New Tenside Type Alkenylpolyglycolalkylethers of the general form R-O-(CH₂-CH₂-O)_n-R′ (R = unsaturated fatty alkyl residue; R′ = alkyl group C₁-C₁₀) lead after sulfonation with a SO₃ air mixture, subsequent neutralization and alkaline pressure hydrolysis to a mixture of ether sulfonates. Sulfonation was carried out in a laboratory fall film reactor and optimized with respect to the SO₃/ ether ratio. Basing on the thus obtained results this reaction could be carried out in a continuous pilot sulfonation plant (through put: 50 kg ether/h). The new ether sulfonates are a very variable tenside type where different properties of application can be chosen in dependence on the ratio of hydrophobic to hydrophilic molecule parts.