烷基苯生产—新的固体床烷基化技术（英）

固体床洗涤剂烷基化技术的成功工业化标志着新一代的直链烷基苯加工技术。被称为ＤＥＴＡＬ工艺的新工艺，免除了使用具有潜在危险的液体ＨＦ酸作催化剂的必要性，除了在操作安全及环境上的优越性外，ＤＥＴＡＬ工艺与ＨＦ技术相比，还有产品成本代，质量高的特点。     

Formulating characteristics of high and low 2-phenyl linear alkylbenzene sulfonates in liquid detergents

Detergent range linear alkylbenzene (LAB) currently is manufactured by two different processes, using either aluminum chloride or hydrogen fluoride as the alkylation catalyst. The alkylates from the two processes are not exactly the same. Furthermore, the properties of the linear alkylbenzene sulfonate (LAS) surfactants made by sulfonation of the LABs also differ. Because LAS is used in most types of detergent products, it is important to known how the properties of each type of LAS differ. This paper compares the formulating characteristics (such as viscosity, solubility and foaming) of high and low 2-phenyl LAS in some typical household cleaning product formulations. It is concluded that the two types of LAS should not be used interchangeably without first checking carefully all the physical properties required in a product. Presented at the AOCS meeting in Honolulu, Hawaii in May 1986.     

Economic cost outlook for surfactant intermediates

Synthetic alcohol, natural alcohol and linear alkylbenzene (LAB) surfactant feedstocks will all be needed to meet market requirements in the coming decade. Of the synthetic alcohol processes, the Alfol® alcohol process, due to its strong byproduct credit, will be the most cost efficient. Moreover, LAB and natural alcohols will have the lowest production costs of all surfactant intermediates throughout the decade.     

Alkylaromatics in Detergents Manufacture: Modeling and Optimizing Linear Alkylbenzene Sulfonation

Linear alkylbenzene sulfonic acid (ASA) is the main ingredient of many commercial formulations for industrial and domestic synthetic detergents. The current industrial ASA production method includes sulfonation of linear alkylbenzene (LAB) with sulfur trioxide in tubular falling‐film reactors. The present study investigates the influence of light alkylaromatics on the efficiency of ASA production. After dealkylation and polymerization, these aromatic compounds form viscous components in the sulfonation reactor. This increases the organic liquid viscosity and disrupts the uniformity of sulfonation. We present the results of IR analysis of the LAB and ASA samples, which indicate that the viscous components are sulfones that are part of the unsulfonated matter. With due consideration of the sulfonation process reaction network, we developed a mathematical model for a sulfonation reactor considering the alkylaromatics content in the feed flow and its effect on the reaction rates. The results allowed the improvement of sulfonation process in terms of increasing the number of days between the reactor washings. The sulfur flow rate increased from 371.7 to 380.9 kg h^?1 at the end of this period for the aromatics content in LAB of 4 wt.% and from 372.1 to 380.1 kg h^?1 for aromatics content in LAB of 6 wt.%. The proposed modifications of the process modes can increase the SO₃ conversion up to 98%.     

Monitoring the linear alkylbenzene sulfonation process using high-temperature gas chromatography

Controlling the linear alkylbenzene sulfonate (LAS) sulfonation process is a critical part of the LAS manufacturing process; this process can be monitored by assaying for LAS content, unsulfonated linear alkylbenzene (LAB), and LAB sulfones. Traditionally, assaying the LAB and LAB sulfone contents has been time consuming and not straightforward. A simple and rapid procedure is described for the isolation and simultaneous capillary gas chromatographic (GC) quantification of LAB and LAB sulfones in LAS. The procedure involves extraction of the unsulfonated LAB and the LAB sulfones into n-heptane; sodium linear alkylbenzenesulfonate or linear alkylbenzenesulfonic acid (reacted to form sodium linear alkylbenzenesulfonate) remains in the aqueous extraction solvent layer. High-temperature capillary GC using a specialty metal capillary column enables both LAB and high molecular weight LAB sulfones to be quantified.     

Linear Alkylbenzenes Sulfonation: Design of Film Reactor and its Influence on the Formation of Deactivating components

Linear alkylbenzene sulfonic acid (ABSA) is a valuable product of inorganic chemistry that is used to obtain linear alkylbenzene sulfonates. The current method for industrial production of ABSA includes sulfonation of linear alkylbenzene (LAB) with sulfur trioxide in tubular falling film reactors. In this work, we analyze the dependence of the dynamics of the deactivating components formation (tetralines and sulfones) on the structural parameters for a multi-tube film sulfonation reactor. To achieve this, we used an unsteady-state mathematical model that considers the feedstock composition and the change in the reaction medium activity. We determined that the film sulfonation reactor of optimal construction has 40 tubes of diameter of 43 mm. It was revealed that with an increase of the LAB supply to the reactor tube, the mass transfer coefficient also increases. For LAB flows of (95∙10⁻⁵) and (2.86∙10⁻⁵) m³ s⁻¹ per tube, the mass transfer coefficient is (1.73∙10⁻²) m s⁻¹ and (2.08∙10⁻²) m s⁻¹, respectively.     

基于石化产品的表面活性剂原料——直链烷基苯的现状及前景

综述了直链烷基苯（LAB）产品的经济状况、供求状况、性价比以及符合法规方面的情况,并对其主要衍生物LAS对人体及环境的危害性作了详细的评价,最终得到了一系列的结论。     

Addition of aromatic compounds to oleic acid catalyzed by heterogeneous acid catalysts

The addition of aromatic compounds to the double bond of oleic acid was studied using solid acid catalysts. For example, in the presence of an acid clay catalyst (bentonite), phenol reacted with oleic acid to yield 96% of an alkylphenol addition product. When toluene was used as the aromatic reactant, however, the yield of alkylbenzene addition product was less than 2%. In this instance, the major reactions observed were elaidinization and migration of the double bond of oleic acid. The addition of phenol to oleic acid in greater than 95% yield also was accomplished with the use of a sulfonic acid ion-exchange resin catalyst. This same catalyst also catalyzed the addition of toluene and benzene to oleic acid to yield 82% and 22%, respectively, of alkylbenzene-type addition products. In the latter instances, the major side product formed was γ-stearolactone. Capillary gas chromatographic (GC) analyses of the alkylbenzene addition products obtained showed them to be mixtures of positional isomers. The isomer distributions were subsequently determined by GC-mass spectrometry (MS). Visiting Scientist, Nippon Oil and Fat Co., Japan.     

Evaluation of the rheological properties of sulfonic acids and sodium sulfonates

Sulfonic acids of linear alkylbenzene (LAB) are converted into the corresponding sodium salts to produce the most widely used anionic surfactant worldwide, linear alkylbenzene sulfonate (LAS). Used in many industrial applications and consumer products, the physical and mechanical properties of the sulfonates are strongly dependent on the LAB manufacturing process. Until recently, commercial alkylation of benzene has employed aluminum chloride or hydrogen fluoride catalysts, but a new fixed-bed alkylation process (DETAL) has been developed with improved 2-phenyl isomer selectivity and low tetralin concentration. In order to better understand the rheology of LAS in aqueous media, a comprehensive comparative evaluation of sulfonic acids and sodium sulfonates of the three LAB process derivatives has been done using dynamic mechanical rheometry, steady shear viscometry, and X-ray diffraction for phase identification. LAB sulfonic acids are Newtonian fluids in the temperature range of 20–60°C. The neat AlCl₃, HF, and DETAL sulfonic acids are Newtonian fluids within the temperature range of 20–60°C. At 30 wt%, all three sulfonates are Newtonian at 20–60°C, and the 40 wt% AlCl₃ sodium sulfonate remains in the Newtonian regime within this temperature range. Lamellar liquid crystalline phases have been identified for the sulfonates in the concentration range of 40–60 wt% in water at 20–60°C, and a hexagonal lattice phase also has been identified for DETAL sodium alkylbenzene sulfonate at 40 wt%, 60°C. The presence of anisotropic phases results in non-Newtonian pseudoplastic behavior with time-dependent viscosity functions.     

直链烷基苯工艺技术的发展

详细地叙述了国内外表面活性剂的主要原料——直链烷基苯生产的新工艺和新技术,着重介绍了固体酸催化剂生产工艺的最新进展。列举了大量的数据和资料,为从事直链烷基苯生产的设计人员提供参考。     

A contribution to understanding secondary reactions in linear alkylbenzene sulfonation

Modern industrial sulfonation of linear alkylbenzene (LAB) in falling film reactors produces p-alkylbenzene sulfonic acid (HLAS), which is usually neutralized with caustic soda (NaOH) and used in detergent formulations. During the sulfonation process, other products such as anhydrides and sulfones are also formed. Four reactions are proposed to occur during aging and hydrolysis. As a consequences, approximately 25% of sulfones and 75% of unreacted LAB are removed during aging and are transformed into additional active matter. Anhydrides are completely eliminated during hydrolysis. On the other hand, sulfones formed during the process are difficult to remove once formed. The goal of this work was to optimize the various operating conditions of the sulfonation process and to understand the various secondary reactions that occur therein so as to obtain a maximal active ingredient concentration in the final sulfonated product and a minimum of unsulfonated matter. Formation of sulfones can be minimized by using an SO₃/LAB molar ratio slightly lower than the theoretical optimum.     

直链烷基苯生产技术进展及发展趋势

对直链烷基苯生产技术路线进行分析比较，指出直链烷基苯技术发展趋势，并对国内外市场需求进行预测，指出今后新建装置应取慎重态度，现有企业要尽快提高产品质量，加快对自主知识产权的IAB技术的开发。     

微通道反应器中工业混合直链烷基苯磺酸盐的连续合成工艺研究

直链烷基苯磺酸是一种重要的阴离子表面活性剂,由其合成的直链烷基苯磺酸盐是价格低廉的表面活性剂之一,广泛应用于洗涤和三次采油等领域。以某煤制油企业的工业混合烯烃生产的直链烷基苯为原料,在微通道反应器中连续合成直链烷基苯磺酸,考察磺化温度、原料摩尔比以及磺化剂浓度等工艺条件对磺酸产物的影响规律,并与纯十六烷基苯磺化规律进行对比。研究发现混合直链烷基苯磺化过程中各个工艺条件对产品收率的影响较大。在反应温度为50℃,SO₃与LAB摩尔比为1.0∶1,停留时间为5.09 s条件下,最终产品中活性物含量可达到94.5%(质量)。同时,设计并搭建了微反应器小试平台,实现连续合成混合烷基苯磺酸盐,磺酸盐产品收率在90%以上,可为该工艺的工业应用提供技术支持。     

LB-16有机硅杂化分子筛催化剂的制备及其在长链烷基苯合成中的应用

长链烷基苯(LAB)是制备合成洗涤剂烷基苯磺酸钠的主要原料,传统上LAB采用无机液体酸(HF)为催化剂将苯和长链烯烃烷基化而制得。在LAB的诸多异构体中,2-LAB因其更高的溶解性和可降解性而更受欢迎。使用低温成胶的策略,以水热合成法合成LB-16有机硅杂化分子筛催化剂,并考察其在LAB合成中的催化性能。结果表明,在反应温度190℃、空速0.2 h-1、苯烯物质的量比15∶1条件下,经过1 000 h催化试验,1-十二烯转化率大于99%,2-LAB选择性51%。LB-16有机硅杂化分子筛催化剂对苯与1-十二烯合成反应具有较好的催化活性和稳定性,同时对2-LAB具有较高的选择性,具有工业化应用前景。     

环保型实验磺化装置的开发及应用

开发了以液体SO3为原料的环保型实验磺化装置,应用该装置对直链烷基苯和α-烯烃进行磺化,采用国标方法对磺化产物的中和值、色泽、有效物及未磺化物含量进行测定,并将测定结果分别与工业直链烷基苯磺酸(GB/T8447—2008)和α-烯基磺酸钠(GB/T20200—2006)产品的理化指标相比较,结果表明,除α-烯基磺酸钠产品色泽值略高外,其他各项指标均达到相应的国标要求,从而证明了该装置在合成磺化产品以及改进磺化工艺中的可行性。     

Recent findings and experiences with alpha olefin sulfonates

In the sulfonation and sulfation of alpha olefin (AO), linear alkylbenzene (LAB), and alcohol ethoxylate (AE), improved reaction yields and products’ color were obtained by using the TO-Reactor recently developed in Lion Fat & Oil Co., Ltd., compared with those obtained in a conventional falling-film type reactor. These improvements especially were remarkable in the case of AO, so that light-colored alpha olefin sulfonate (AOS), having improved performance properties, was obtained without bleaching. For the performance tests, AOS was evaluated in several systems, together with some other surfactants, alcohol sulfate (AS), alcohol ethoxy sulfate (AES), linear alkylbenzene sulfonate (LAS), and alpha-sulfo fatty acid methyl ester (a-SEMe). AOS was one of the most useful surfactants for heavy duty powder detergents of low phosphate formulation because of its good detergency and foaming power, rinsing property, and free flowing property. Thus, bright white heavy duty powder detergents, containing 8% of P₂O₅, were developed with AOS (nonbleached), AES, LAS, sodium pyrophosphate (TSPP), and some other ingredients, which have been marketed in the household cleaning products field in Japan since 1976.     

烷基苯SO3磺化工艺改进

在采用烷基苯SO3磺化工艺制造烷基苯磺酸过程中,许多装置会遇到含量、色泽不稳定的问题。通过对某合成洗涤剂厂烷基苯SO3磺化设备、工艺等因素的研究分析,对生产工艺进行了系统改进,烷基苯磺酸含量稳定在96%以上,色泽稳定在30klett以下。     

烷基苯市场分析

通过对烷基苯的产能、下游产品的市场情况及烷基苯的未来应用领域等几个方面进行综合分析,从而得出烷基苯的市场供需情况。     

Supported solid and heteropoly acid catalysts for production of biodiesel

Biodiesel has developed attraction of most researchers recently because of its renewable resources and environmental benefits. Transesterification process in the presence of catalysts is the most common way, which is used for biodiesel production. Heterogeneous acid catalysts are considered more reliable than any other catalysts to carry out most vital reactions related to green chemistry (biodiesel production), because the production of biodiesel from solid acid catalysts is considered economically favorable. Nowadays, biodiesel is preparing from low quality feedstock by using solid acids catalysts in many research laboratory throughout the world. This article discusses how much catalyst shapes affect the efficiency of catalyst during catalysis. Different types of supports (zinc oxide, alumina, zirconia, and silica) are used to increase the efficiency of catalysts. Supported Lewis acid, Brønsted acid, and heteropoly acid catalysts show good efficiency for the catalytic transesterification of oil with alcohol. Heteropoly acid catalysts are tremendous and environment friendly acid catalyst and have ability to tolerate contaminations of oil resources such as water contents and free fatty acids (FFAs) contents. Keggin-type heteropoly acids are easily available and having stable structure while Wells–Dawson-type heteropoly acids are included in super acid class, due to these reasons heteropoly acids are considered as best acidic catalysts for biodiesel production by catalytic transesterification process. Therefore, this review also focused on the deactivation, regeneration and advantages of supported solid acid catalysts used for the catalytic production of biodiesel through transesterification.     

Analysis of Minor Products in Linear Alkylbenzene Sulfonation. Comparison Between the Traditional Gravimetric Method and High Performance Liquid Chromatography (HPLC) Procedures Versus High Temperature Gas Chromatography (HT-GC)

During the sulfonation process of the linear alkylbenzene (LAB) other products like sulfones and anhydrides are also formed in addition to the linear alkylbenzene sulfonic acid (HLAS). Most of them are transformed in different degrees during the aging and hydrolysis steps of the overall sulfonation process [Moreno et al. (2003) J Surfactant Deterg 6(2):137–142]. The use of HPLC technique since 1988 and earlier the use of high temperature gas chromatography (HT-GC) enable the separation and quantification of all the components of the free oil (FO) of the sulfonic acids—anhydrides; LAB and sulfones. The purpose of this paper is to review the current knowledge about the free oil analysis and to discuss a new analytical procedure based on the HT-GC to quantify the free oil content. We will compare the results obtained using this new method with other analytical procedures (traditional gravimetry) and near infrared (NIR) spectroscopy.