α-烯基磺酸盐表面活性剂在柴油氧化脱硫中的作用

以α-烯基磺酸盐表面活性剂为表面活性剂,过氧化氢-乙酸为氧化体系,柴油为研究对象,DMF为萃取剂,考察了H2O2/CH3COOH/α-烯基磺酸盐体系催化氧化柴油脱硫的适宜反应条件及脱硫效果。结果表明,加入α-烯基磺酸钠表面活性剂后,柴油脱硫实验较适宜反应条件是:表面活性剂的加入量为0.10 g,反应温度为40℃,反应时间为80 min,VH2O2/VCH3COOH=0.5,V氧化体系/V柴油=1,脱硫率最高,可从不加表面活性剂时的30.93%提高到72.28%。     

α-烯基磺酸盐的合成、性能及应用研究进展

介绍了α-烯基磺酸盐表面活性剂的结构,综述了其合成工艺,并从反应温和度、副反应以及后处理等方面对合成工艺进行了分析比较,总结了各工艺路线的优缺点。最后介绍了α-烯基磺酸盐的性质以及在各个领域的应用。     

α-烯烃磺酸盐市场情况

介绍了α-烯烃磺酸盐国内外生产及应用情况,并对其生产工艺参数、原料及公用工程消耗、三废排放情况、投资及生产成本作了介绍。中国α-烯烃磺酸盐的主要生产厂家有安徽安庆南风日化有限公司、西安南风日化公司、山西运城日化公司和湖南丽辰日化公司等,总磺化能力12.2t/h。近几年中国α-烯烃磺酸盐的生产发展很快,1999年的产量约1000t,2000年约1900t,2003年约1.7万t,预计今后几年中国α-烯烃磺酸盐的年均增长速率将达到16%。     

α-烯烃磺酸盐在个人清洁品中的应用

要介绍了α-烯烃磺酸盐（AOS）的性能及其在个人清洁品中的应用,列举了相关参考配方,AOS有可能逐步替代LAS、AES成为主要的表面活性剂。     

石蜡裂解α-烯烃制备AOS表面活性剂

以蜡裂解α-烯烃(AO)为原料制备了α-烯基磺酸盐(AOS)。所涉及的主要技术问题是:原料蜡裂解α-烯烃的精制处理,采用发烟硫酸为磺化剂的磺化工艺的优化。实验数据表明,采用蜡裂解AO为原料是可以生产 AOS的;其产物与市售AOS(采用乙烯齐聚α-烯烃合成)相比,色泽深、未磺化物含量高,然而实验室产品具有与市售AOS相当的表面张力,且发泡性能优于市售AOS。     

α-烯基磺酸盐的应用发展及生产工艺控制

介绍了α-烯基磺酸盐(AOS)的特性及其应用发展历程,阐述了AOS的磺化反应机理。通过对AOS的生产工艺特点进行分析,阐明了其生产工艺控制关键点,并列举了典型的工艺数据。     

α-烯基磺酸盐中磺内酯的测定

采用气相色谱-质谱法对α-烯基磺酸盐(AOS)中磺内酯3对异构体进行定性分析,同时采用气相色谱外标法结合火焰离子化检测器进行α-烯基磺酸盐制备的中间过程(磺化、中和及水解)以及最终成品中磺内酯含量的测定.从4批AOS样品所得到的测定结果表明,当磺内酯质量浓度在20μg·mL-1～200μg·mL-1范围内时GC峰值与磺内酯质量浓度表现为良好的线性关系,相关系数为0.999 0,最低检出限为5μg/g.精密度测试所得标准偏差为1.1%～6.5%(n=6).回收率达到90.00%～97.96%.     

松香基磺酸盐表面活性剂的合成及性能研究

以脱氢枞胺为原料,与马来酸酐反应,经磺化合成松香基磺酸盐。对产品结构进行红外光谱鉴定,并对产品的性能进行研究。研究表明: DHAAMS 的临界胶束浓度(CMC)为 0.798 mmol/L,发泡能力为 145 mm,乳化能力强,分水时间可达 9 min,与 SDS 的复配增效作用强烈,两者的物质的量之比为1:3时,增效作用最显著。     

α-烯基聚醚磺酸盐的耐盐性能及应用

以不饱和醇作引发剂利用双金属氰化物(DMC)催化加成共聚环氧丙烷、环氧乙烷,然后磺化中和成盐,研制出一种耐盐活性剂.该活性剂的耐受矿化度范围为2000～150000 mg·L-1.该活性剂不仅能把高矿化度水的表面张力从80.5 mN·m-1(30℃)降到37.1 mN·m-1(30℃),而且即使水中的Ca2 、Mg2 浓度高达10000 mg·L-1时,其表面活性剂水溶液也是无色透明的,没有任何沉淀和絮状物.在某油田稠油水中矿化度高达150000 mg·L-1的稠油降黏实验中发现,该活性剂能使含水稠油黏度从85000 mPa·s(30℃)降到14 mPa·s(30℃),并且还能使脱水后的原油本体黏度降低一半以上.     

The mixed surfactant system of linear alkylbenzene sulfonate and alpha olefin sulfonate

Physicochemical and detergency studies on the mixed surfactant system of linear alkylbenzene sulfonate-sodium salt (LABS) and alpha olefin sulfonate-sodium salt (AOS) have been carried out. The binary surfactant system exhibits minima in the surface tension and in the critical micelle concentration when the two surfactants are present in the ratio 80:20, indicating synergism in the mixed monolayer and in mixed micelles at this proportion of the two surfactants. The mixed micelles improve hard-water tolerance of LABS and reduce the loss of LABSvia Ca(LABS)₂ precipitation. Addition of AOS to LABS improves its lime soap dispersion properties. The effect is highly significant when AOS is present at the 20% level in the mixed surfactant system. A synergistic mixture of the two surfactants, when used in phosphate-free, carbonate-built detergent product formulation, exhibits superior detergency, low ash deposit and better stainremoving ability when compared to products containing LABS as the sole active surfactant.     

加氢柴油超深度氧化脱硫研究

采用KMnO4/HCl体系氧化大庆炼化公司加氢柴油,考察了反应温度、氧化时间、HCl溶液的pH值、氧化剂用量等对氧化脱硫效果的影响,最佳反应条件下柴油的脱硫率可达92.3%。在氧化过程中,采用红外光照射可使反应时间由30 min缩短到20 min,直接水洗氧化产物即可使柴油的脱硫率达到90%以上。与未使用红外光照射的氧化-萃取过程相比,省去了萃取剂及其回收费用,简化了操作流程,降低了超低硫柴油的生产成本。     

柴油氧化脱硫技术新进展

柴油低硫化及其含硫标准的日趋严格,是世界各国柴油产品质量与标准的发展趋势。加氢脱硫技术生产低硫柴油,存在投资大、操作费用高和操作条件苛刻的缺点,导致柴油成本大幅攀升,柴油氧化脱硫技术已成为研究热点。综述了国内外柴油氧化脱硫技术的研究进展,认为柴油氧化脱硫技术将成为今后生产超低硫清洁柴油的主要工艺之一。     

柴油空气催化氧化脱硫的探索研究

为克服柴油加氢脱硫技术投资大、操作条件苛刻及污染严重等问题,提出一种空气催化氧化脱硫方法。考察了催化剂种类及其用量、催化氧化温度、时间、空气流速等因素对脱硫效果的影响。实验结果表明,选用粉状白土作脱硫催化剂,在空气流量为1600 ml/min和160 ℃下反应30 min,可将原料油中硫的质量分数从1033×10^－6降到381×10^－6,脱硫率达63.12%。     

Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil

Aiming at the deep desulfurization of the diesel oil, a comparison of the catalytic effects of several Keggin type POMs, including H₃PW_xMo_12?xO₄₀ (x = 1, 3, 6), Cs_2.5H_0.5PW₁₂O₄₀, and H₃PW₁₂O₄₀, was made, using the solution of DBT in normal octane as simulated diesel oil, H₂O₂ as oxidant, and acetonitrile as extractant. H₃PW₆Mo₆O₄₀ was found to be the best catalyst, with a desulfurization efficiency of 99.79% or higher. Hence, it is promising for the deep desulfurization of actual ODS process. The role of the main factors affecting the process including temperature, O/S molar ratio, initial sulfur concentration, and catalyst dosage, was investigated, whereby the favourable operating conditions were recommended as T = 60 °C, O/S = 15, and a catalyst dosage of 6.93 g (H₃PW₆Mo₆O₄₀)/L (simulated diesel). With the aid of GC–MS analysis, sulfone species was confirmed to be the only product after reaction for 150 min. Furthermore, macro-kinetics of the process catalyzed by H₃PW₆Mo₆O₄₀ was studied, from which the reaction orders were found to be 1.02 to DBT and 0.38 to H₂O₂, and the activation energy of the reaction was found to be 43.3 kJ/mol. Moreover, the catalyst recovered demonstrated almost the same activity as the fresh.     

AOS中氯代磺内酯、不饱和磺内酯的测定

烯烃磺酸盐（AOS）中的氯代磺内酯和不饱和磺内酯被公认为是一种皮肤致敏剂,但国内未见氯代磺内酯和不饱和磺内酯的测定方法。采用气相色谱-质谱法,对AOS中的氯代磺内酯和不饱和磺内酯进行分析,该方法的最低检出限为0.015 mg/kg,具有准确、快速和简单等特点。     

Deep desulfurization of diesel fuels by catalytic oxidation

Reaction feed was prepared by dissolving dibenzothiophene (DBT), which was selected as a model organosulfur compound in diesel fuels, in n-octane. The oxidant was a 30 wt-% aqueous solution of hydrogen peroxide. Catalytic performance of the activated carbons with saturation adsorption of DBT was investigated in the presence of formic acid. In addition, the effects of activated carbon dosage, formic acid concentration, initial concentration of hydrogen peroxide, initial concentration of DBT and reaction temperature on the oxidation of DBT were investigated. Experimental results indicated that performic acid and the hydroxyl radicals produced are coupled to oxidize DBT with a conversion ratio of 100%. Catalytic performance of the combination of activated carbon and formic acid is higher than that of only formic acid. The concentration of formic acid, activated carbon dosage, initial concentration of hydrogen peroxide and reaction temperature affect the oxidative removal of DBT. The higher the initial concentration of DBT in the n-octane solution, the more difficult the deep desulfurization by oxidation is. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(4): 616–621 [译自: 高校化学工程学报]     

High performance sorbents for diesel oil desulfurization

Sorbents with different Ni loading supported on silica–alumina (SiAl) and activated carbon (AC) were synthesized and tested for removal of sulfur compounds from a model diesel oil, containing nearly 250 ppmw S as benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). A state-of-art Commercial Ni-based sorbent and two Norit activated carbons were also tested for comparison. Moreover, the influence on sorbents uptake capacity of the presence of aromatics in amounts representative of real diesel oils was studied. Both commercial and home-made materials performed worse in presence of aromatic compounds. Probably, the latter competed with the refractory sulfur compounds (DBT and 4,6-DMDBT) in the adsorption on active sites. As a first important result of the investigation the sorbents carrying 45% and 30% of Ni on SiAl showed a breakthrough uptake capacity of nearly, respectively, 2 and 2.6 times higher than Commercial sorbent as a consequence of their higher Ni dispersion and surface area. Moreover, activated carbons and the sample with 28%Ni on AC showed an even higher breakthrough uptake capacities. In particular, the deposition of nickel on activated carbon is an innovative approach which takes advantage of the selectivity of Ni towards S-species and the high adsorptive capacity of AC support.