金属络合类离子液体用于汽油萃取脱硫的研究

本文由原料[Et₃NH]Cl、无水FeCl₃和无水CuCl合成了离子液体[Et₃NH]Cl-FeCl₃/CuCl,考察了其萃取脱硫性能。结果表明：在对模拟汽油（噻吩溶于正辛烷）和FCC汽油脱硫时,离子液体[Et₃NH]Cl-FeCl₃/CuCl均表现出了较好的脱硫性能。当离子液体和模拟汽油的体积比V(IL):V(oil)=0.08,时间t=50min,温度T=50℃时,模拟汽油中噻吩的脱除率能够达到 93.9%。在相同的温度和时间条件下,当离子液体和FCC汽油的体积比V(IL):V(oil)=0.1时,经过三次萃取,能够获得低硫（硫含量小于10μg/g）FCC汽油,FCC汽油的收率为94.3%。离子液体具有较好的循环使用能力,循环使用5次后,汽油中噻吩的脱除率没有明显降低。     

Application of High Shear Agitation for Desulfurization of Gasoline Using Ionic Liquids

The high shear agitation device was first adopted for gasoline desulfurization by ionic liquids. The effect of benzylimidazol fluoborate in desulfurization of gasoline and the influence of moisture on deuslfurization rate were investigated. The experimental results showed that the ionic liquid could effectively decrease the sulfur content of gasoline and the optimal conditions were as follows: The reaction could be carried out at room temperature, a volumetric ratio between oil and the liquid of 2∶1, a volumetric ratio between water and ionic liquid of 0.04∶1, a rotational speed of 5 krad/s, and a reaction time of 1 minute. The desulfurization rate of gasoline reached 53.6%, and the gasoline yield was up to 97.3%. The ionic liquid could be recycled for repeated use, and the use of high shear agitation for gasoline would have good prospects.     

The Extractive Desulfurization of Fuels Using Ionic Liquids Based on FeCl3

Abstract

Six Lewis acid ionic liquids were synthesized and employed as extractants for desulfurization of the model oil containing dibenzothiophene (DBT). Very promising ionic liquid was 1-butyl-3-methylimidazolium chloride-FeCl3 ([bmim]Cl/FeCl3), which performed best in the studied ionic liquids under the same operating conditions. It can remove DBT from model oil after continuous extraction for four steps, and the desulfurization efficiency can reach 97.9% under mild reaction conditions. Other sulfur-containing compounds were also investigated. The used ionic liquid could be regenerated six times without a significant decrease in activity.     

Ionic Liquid-based Extraction of Sulfur Compounds From Gasoline as a Complementary Process to Oxidative Desulfurization

The extractive desulfurization of a model and several real gasoline samples was investigated using imidazolium-based ionic liquids (ILs). Factorial design of experiments indicated that, among several process variables, the number of extraction steps and the IL/gasoline volume ratio were statistically highly significant. The results showed a desulfurization efficiency of 95.2% under the optimal conditions. The following order was observed for the extraction of thiophenic compounds: benzothiophene>thiophene>3-methylthiophene>2-methylthiophene, with 96.1% removal efficiency for the first one. The IL extraction was applied as a complementary process for the oxidative desulfurization by hydrogen peroxide and formic acid, which provided high efficiency and selectivity for desulfurization of gasoline.     

离子液体用于燃料油深度脱硫的研究进展

首先介绍了加氢催化脱硫和其他脱硫技术的特点,综述了近年来国内外利用离子液体在萃取脱硫、萃取脱硫与氧化脱硫耦合、萃取脱硫与生物脱硫耦合等方面的研究。认为离子液体萃取脱硫具有操作简便、可循环使用、无需氢气、环境友好、能深度脱硫等特点,是一项具有广阔发展前景的技术。若要实现该技术的工业化应用,还需进一步加强离子液体在合成工艺、脱硫选择性及回收再生等方面的研究。     

Modeling of the FCC Gasoline Desulfurization Process by Liquid Extraction with Sulfolane

Abstract

Extractive desulfurization of fluid catalytic cracking (FCC) gasoline with sulfolane was studied in a batch apparatus. The influence of three inlet parameters (temperature, inlet sulfur content, and solvent ratio) on the process response, that is, desulfurization efficiency, was investigated with the use of a Box-Behnken experimental design by response surface methodology. A mathematical model that can be used for predicting sulfur content in raffinate after extractive batch processing with sulfolane was statistically developed and proven with analysis of variance. Statistical analysis showed that the largest influence on desulfurization efficiency was solvent ratio, the second most significant influence was inlet sulfur content, followed by temperature, and last the interaction between solvent ratio and inlet sulfur content. The obtained second-order polynomial model shows that maximum desulfurization efficiency of 65.34% can be achieved at temperature of 50°C and higher values of inlet sulfur content and solver ratio in the researched range of inlet parameter values.     

离子液体萃取脱硫的研究

合成了一系列离子液体用于模拟油的萃取脱硫实验,考察了不同离子液体及其与模拟油的质量比、反应温度和反应时间等因素对模拟油萃取脱硫效果的影响。实验结果表明,离子液体1-丁基-3-乙基咪唑氯盐([BEIM]Cl)的萃取脱硫效果明显优于其他离子液体。当以[BEIM]Cl为萃取剂时,萃取脱硫的最优条件为:[BEIM]Cl与模拟油的质量比1.0,萃取温度30℃,萃取时间30min。在此条件下,单级脱硫率可达52.02%;经5级脱硫后,总脱硫率高达96.56%。采用溶剂反萃取法对[BEIM]Cl进行了再生,再生后[BEIM]Cl的脱硫率可达新鲜[BEIM]Cl的95%。     

Optimization of Oxidative Desulfurization of Dibenzothiophene Using a Coordinated Ionic Liquid as Catalytic Solvent

Abstract

Oxidative desulfurization (ODS) of dibenzothiophene (DBT) in n-octane with hydrogen peroxide/acetic acid using a quaternary ammonium coordinated ionic liquid (IL) (C₄H₉)₄NBr · 2C₆H₁₁NO as catalytic solvent has been studied. The ODS mechanism by coordinated ionic liquid [(C₄H₉)₄NBr · 2C₆H₁₁NO] was also carried out. The sulfur-containing compounds in model oil were extracted into ionic liquid phase and oxidized to their corresponding sulfones by H₂O₂. The effect factors for desulfurization of model oil were investigated in detail by means of monofactorial and orthogonal experiments (L₁₆(4)⁴). The results showed that the desulfurization efficiency of model oil could reach 98.6% under the optimal conditions of oxidation time, oxidation temperature, molar ratio of H₂O₂/sulfur (O/S), and volume ratio of model oil to coordinated ionic liquid were 30 min, 50°C, 16, and 1, respectively. The influences to the desulfurization efficiency of DBT decreased in the following order: volume ratio of model oil to coordinated ionic liquid (C₄H₉)₄NBr · 2C₆H₁₁NO (V_{model oil}/V_IL) > molar ratio of O/S > oxidation temperature > oxidation time, according to extreme analysis of the orthogonal test. The coordinated ionic liquid (C₄H₉)₄NBr · 2C₆H₁₁NO can be recycled 5 times without a significant decrease in desulfurization.     

汽油络合萃取脱硫实验研究

采用自制的脱硫络合萃取剂（TS-1）,考察其对汽油中含硫化合物的脱除效果。在萃取温度20℃,萃取时间3min,相分离时间15min,剂油体积比为9%的条件下,FCC汽油A中的硫含量从619μg/g降到136μg/g,达到国Ⅲ车用汽油硫含量标准（〈150μg/g）,汽油收率99.5%。在最佳操作条件下,还考察了TS-1对FCC汽油B、直馏汽油C和凝析汽油D的脱硫效果,使用较小剂油比,汽油B、C和D都可达到较高脱硫率。因此,络合萃取剂TS-1应用于汽油脱硫,具有对含硫化合物选择性好、用量少、汽油收率高和对汽油适应性优良等特点,在车用汽油深度脱硫方面展现了良好的应用前景。     

离子液体中季铵型六聚钨酸盐相转移催化氧化脱硫性能

制备了亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸盐([Bmim]BF4)和4种季铵型六聚钨酸盐催化剂,通过FTIR,UV-Vis,TG等方法对它们的结构进行了表征;考察了以H2O2为氧化剂,季铵型六聚钨酸盐催化剂在离子液体[Bmim]BF4中相转移催化氧化模拟油中二苯并噻吩(DBT)的活性。实验结果表明,随H2O2和催化剂用量的增加、反应温度的升高和反应时间的延长,DBT脱除率单调增加;适宜的反应条件为:以季铵型六聚钨酸盐[C18H37(CH3)3N]2W6O19为催化剂,模拟油用量5mL、离子液体[Bmim]BF4用量1 mL、反应温度50℃、反应时间3.0 h、n(催化剂)∶n(DBT)=1∶10、n(H2O2)∶n(DBT)=4;在此条件下,该脱硫体系的DBT脱除率可达99.6%,其脱硫效果好于仅用离子液体萃取脱硫和无离子液体的催化氧化脱硫体系的脱硫效果。     

Improving Stability of Gasoline by Using Ionic Liquid Catalyst

The composition, characteristics and preparation of ionic liquids are presented. The factors influencing the stability of gasoline and the significance of improving gasoline stability are discussed. A novel way to improve the stability of gasoline by using ionic liquid catalyst is developed. The contents of olefin, basic nitrogen and sulfur in gasoline are determined and the optimal experimental conditions for improving gasoline stability are established.The ionic liquid catalyst, which is environmentally friendly, can reduce the olefin content in gasoline, and such process is noted for mild reaction conditions, simple operation, short reaction time, easy recycling of the ionic liquid catalyst and ready separation of products and catalyst.     

Photocatalytic Oxidative Desulfurization of Gasoline by TiO2 in [BMIm]Cu2Cl3 Ionic Liquid

Photocatalytic oxidative desulfurization of gasoline in [BMIm]Cu2Cl3 ionic liquid was studied. A 500-W high-pressure mercury lamp was used as the light source for irradiation, nano-TiO2 was used as the photocatalyst and air was introduced by a gas pump to supply O2 as the oxidant. Influence of the ratio of V（ionic liquid） to V（oil） and the TiO2 addition on the desulfurization rate of gasoline was investigated. An oxidative kinetics equation was founded. The results showed that the [BMIm]CUECl3 ionic liquid was an effective extractant for the desulfurization of gasoline. The appropriate TiO2 addition was 0.05 g in 50 mL of reaction mixture. The yield of desulfurized gasoline could reach 98.2% after being subjected to reaction for 2 h under the conditions of adopting a ratio of V（ionic liquid）： V（oil）=1：4, an air flow of 100 mL/min and a TiO2 addition dosage of 0.05 g. The kinetics reaction for photo-oxidation of gasoline was a first-order reaction with an apparent rate constant of 1.9664 h^-1 and a half-time of 0.3525 h.     

离子液体萃取燃料油深度脱硫的研究进展

综述了各种类型的离子液体(ILs)萃取燃料油深度脱硫的研究进展。介绍了ILs中阴阳离子的萃取脱硫机理;对用于萃取脱硫的ILs的阳离子和阴离子进行了分类,阳离子从其演变过程分为单环芳烃阳离子、烷基改性的单环芳烃阳离子和多环芳烃阳离子,阴离子按其性质主要分为低黏度二腈胺根类、酸酯类和多卤代金属类,并讨论了它们的优缺点和发展历程;对ILs的再生方法进行了比较。最后提出了ILs萃取脱硫技术发展的重点是提高ILs萃取芳烃硫化物的分配系数和ILs的再生利用率。     

Desulfurization of model FCC gasoline by extraction with ionic liquid and conventional extraction solvents

To compare the desulfurization performance of conventional extraction solvents and novel ionic liquid, desulfurization experiments by extraction were conducted on sulfolane, acetonitrile, N-formyl morpholine, and [BPy]BF₄ using model Fluid Catalytic Cracking gasoline (thiophene and n-octane) as feedstock. Results showed that the desulfurization rate of ionic liquid was worse than conventional extraction solvents, but its yield of sweet gasoline was higher, which could reach to 90.36%. Among the four solvents, N-formyl morpholine had the best desulfurization performance, while sulfolane was the most stable extraction agent.     

含硫凝析油脱硫技术研究

综述了国内外含硫凝析油脱硫的研究进展 ,包括吸附脱硫、抽提脱硫、氧化脱硫和氧化-抽提脱硫,分析了各种脱硫方法的优缺点, 指出了今后含硫凝析油脱硫的研究方向,即优化现有脱硫工艺,开发新型高效催化剂以及开发绿色脱硫工艺.     

磷酸酯类离子液体在燃油深度脱硫中的应用

研究了3种磷酸酯类离子液体,即1,3-二甲基咪唑磷酸二甲酯盐([MM im]DM P)、1-乙基-3-甲基咪唑磷酸二乙酯盐([EM im]DEP)和1-丁基-3-甲基咪唑磷酸二丁酯盐([BM im]DBP)的制备过程,考察了这3种磷酸酯类离子液体对模型油中3-甲基噻吩、苯并噻吩和二苯并噻吩的脱除效果及磷酸酯类离子液体的电化学再生方法。实验结果表明,这3种磷酸酯类离子液体的脱硫能力强弱顺序为:[EM im]DEP>[BM im]DBP[MM im]DM P;且对二苯并噻吩的脱除效果最好,对苯并噻吩的脱除效果次之,对3-甲基噻吩的脱除效果较差。以[EM im]DEP为萃取剂,油剂质量比为1∶1时,经5次萃取后,二苯并噻吩的脱除率可达到99.5%。利用电解法对[EM im]DEP进行了再生,在5~10V电压下电解10h,[EM im]DEP的脱硫率可以达到新鲜[EM im]DEP的90%以上。     

The Oxidation-Extraction Desulfurization of FCC Gasoline

Abstract

With increasing environmental concern and stricter regulations, sulfur content is restricted in a low range. So there are many studies on the desulfurization methods to light oils. The oxidation-extraction desulfurization method for light oils provided a prospective way to reduce the sulfur content. The effects of the oxidation-extraction system were studied in this article. The results showed that the best oxidation time is 25 min, the best proportion of oil, catalyst, and oxidant is 50:5:1, temperature nearly has no effect on the oxidation desulfurization. This research provided a good prospect for the industrial application of the oxidation-extraction desulfurization.     

离子液体在燃料油脱硫中的应用进展

离子液体用于燃料油脱硫是一种环境友好的新技术。综述了离子液体用于燃料油脱硫的几种方法,包括直接萃取法、氧化-萃取法、络合萃取法和烷基化法,介绍了离子液体的几种再生方法,并进行了对比。     

催化裂化汽油光化学氧化脱硫

以水为萃取剂、空气中的O2为氧化剂、500W高压汞灯为紫外光光源,研究了催化裂化(FCC)汽油光化学氧化反应的机理和氧化产物,考察了反应条件对FCC汽油脱硫率的影响。实验结果表明,FCC汽油中的极性含硫化合物首先部分溶于水相中,然后在水相中被氧化。在空气通入量为150mL/min、水与FCC汽油的体积比为1.0的条件下,反应5h后FCC汽油脱硫率达40.6%,加入0.45g4A分子筛作为O2的吸附剂后FCC汽油脱硫率提高到70.2%。FCC汽油的光化学氧化反应为一级动力学反应,加入4A分子筛时的反应速率常数为0.217 4h-1,半衰期为3.18h。FCC汽油光化学氧化反应的主要产物为亚砜和砜,并进一步生成CO2、草酸、SO24-等。     

离子液体萃取耦合过氧钒配合物催化氧化燃油脱硫

<正>燃油中的硫化物燃烧后产生的SOx严重威胁着人类的健康。目前,工业上的脱硫技术主要为加氢脱硫(HDS)技术,但对于二苯并噻吩(DBT)及其衍生物,HDS技术很难将它们除去。萃取耦合氧化脱硫法被认为是一种具有很好应用前景的深度脱