Complex Extraction of Thiophenes Using Room Temperature Ionic Liquids

Two kinds of room temperature ionic liquids (RTILs) 1-butyl-3-methyl limidazolium chloroaluminate (III) ([bmim]Cl+AlCl₃) and 1-butyl-3-methyl limidazolium hexfluorophosphate ([bmim]PF6) were synthesized, respectively, and the removal of thiophenes from refined diesel was studied by the method of complex extraction. The results showed that under the best operational conditions, the content of thiophenes went down 46 wt% in chloroaluminate RTIL and 69 wt% in hexfluorophosphate RTIL, and other properties of diesel were improved at the same time. Both of the two kinds of RTILs can be used for several times through regenerating.     

Synthesis of Chloroaluminate Ionic Liquids and Use for Olefin Reduction in FCC Gasoline

Abstract

Room temperature ionic liquids (RTILs) are mainly referred to melting salt systems composed by organic cations and organic or inorganic anions that exhibit liquid-like behavior at or around room temperature. Chloroaluminate room temperature ionic liquid (chloroaluminate RTILs) is one kind of RTIL synthesized by chloride quaternary ammonium salts and anhydrous AlCl₃. Three kinds of chloroaluminate RTILs were synthesized using trimethylamine hydrochloride (TA), 1-butylpyrinium chloride (BPyC), or 1-methyl-3-alkylimidazolium (BMIC), respectively, with anhydrous AlCl₃ and their application in reducing the content of olefin in FCC gasoline from the Jinzhou Petrochemical Corporation was studied. The effects of chloroaluminate RTIL component and operation conditions on olefin reduction were investigated as well as the repeatability of chloroaluminate RTILs. The results show that at room temperature, when the ratio of anhydrous AlCl₃ to quaternary ammonium (mole/mole), the solvent-oil ratio (g/g), and the reaction time were 2/1, 20/100, and 1/2 h, respectively, the content of olefin in FCC gasoline was deduced more than 30%. The chloroaluminate RTILs could be used at least four times on the basis of keeping their activity.     

Extraction of Basic Nitrides from FCC Diesel Using Ionic Liquids at Room Temperature

1-Butyl-3-methylimidazolium chloroaluminate (III) room temperature ionic liquids (RTILs) were synthesized, and basic nitrides' removal from FCC diesel was studied by the method of complex extraction. The experiment results showed that the best operational conditions of the technology were that molar ratio of AlCl₃ to BmimCl (1-butyl-3-methylimidazolium chloride) was 3, weight ratio of RTIL to diesel was 0.03, reaction time was 3 min, and reaction temperature was 50°C under nitrogen protection. The content of basic nitrides went down from 68.6 μg/g to 0.7 μg/g under the conditions and other properties of FCC diesel were improved at the same time. RTILs could be used for several times as extract agent.     

Remove Olefin from Diesel Oil with Chloroaluminate(III) Ionic Liquids

Abstract

Ionic liquids are low-melting-point salts that represent an exciting new class of reaction solvents. In this article, the author mainly refers to the effects of the olefin removal in the diesel oil using [bmim]Br-AlCl₃ (where [bmim] is 1-butyl-3-methylimidazolium cation) ionic liquid. The result shows the better performance in the olefin removal. Therefore, an environmental friendly approach for olefin removal from diesel is provided.     

Synthesis of Chloroaluminate Ionic Liquids and Use for Olefin Reduction in FCC Gasoline

Room temperature ionic liquids (RTILs) are mainly referred to melting salt systems composed by organic cations and organic or inorganic anions that exhibit liquid-like behavior at or around room temperature. Chloroaluminate room temperature ionic liquid (chloroaluminate RTILs) is one kind of RTIL synthesized by chloride quaternary ammonium salts and anhydrous AlCl₃. Three kinds of chloroaluminate RTILs were synthesized using trimethylamine hydrochloride (TA), 1-butylpyrinium chloride (BPyC), or 1-methyl-3-alkylimidazolium (BMIC), respectively, with anhydrous AlCl₃ and their application in reducing the content of olefin in FCC gasoline from the Jinzhou Petrochemical Corporation was studied. The effects of chloroaluminate RTIL component and operation conditions on olefin reduction were investigated as well as the repeatability of chloroaluminate RTILs. The results show that at room temperature, when the ratio of anhydrous AlCl₃ to quaternary ammonium (mole/mole), the solvent-oil ratio (g/g), and the reaction time were 2/1, 20/100, and 1/2 h, respectively, the content of olefin in FCC gasoline was deduced more than 30%. The chloroaluminate RTILs could be used at least four times on the basis of keeping their activity.     

Deep Oxidative Desulfurization of Dibenzothiophene in Simulated Diesel with Tungstate and H2O2 in Ionic Liquids

Abstract

A green extraction and catalytic oxidative desulfurization (ECODS) system composed of simple tungsten-containing catalyst, 30 wt% H₂O₂, and ionic liquids was discovered suitable for the deep removal of dibenzothiophene (DBT) in simulated diesel. In the case of the system comprising Na₂WO₄ · 2H₂O, 30 wt% H₂O₂ and 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄), the removal of DBT could reach 99.7% at 60°C for 3 hr, which was superior to mere solvent extraction with ionic liquid or catalytic oxidation without ionic liquid. This desulfurization system could be recycled five times with a small decrease in activity.     

Effect of temperature on gas transport properties of supported ionic liquid membranes

The separations of the CO₂/N₂ and CO₂/CH₄ gas pairs using supported ionic liquid membranes (SILMs) with the immobilized ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate (bmim[BF₄]) and 1-butyl-3-methylimidazolium bis(2-ethylhexyl)sulfosuccinate (bmim[doc]) have been compared. The temperature dependences of the gas permeability, diffusion, and solubility coefficients have been obtained experimentally, and the temperature dependence of selectivity has been calculated. It has been found that the selectivity of membranes based on bmim[BF4] slightly decreases with temperature and the separation selectivity of CO₂/N₂ and CO₂/CH₄ systems on the membranes impregnated with bmim[doc] is almost independent of temperature.     

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.     

Study on Preparation Process of Lubrication from 1-Decene with Acidic Ionic Liquid Catalyst

Abstract

Poly-alpha-olefin (PAO) was researched over acidic ionic liquid catalyzed the oligomerization of 1-decene. Ionic liquid used was 1-butyl-3-methyl imidazolium as a cation and aluminum chloride as an anion, which could effectively catalyze oligomerization and had a higher selectivity. The optimum process conditions for the synthesis of PAO were that the reaction temperature was 160°C, the reaction time was 3 h, the mole ratio between AlCl₃ and [Bmim]Cl was 2.5:1, and the count of catalyst was 3 wt%. The components of product were analyzed with gas chromatograph, and the test results showed that the conversion of 1-decene was 74%. The product was the mixture of dimer, trimer, tetramer, and pentamer.     

Oxidative Desulfurization of Fuel Oil with Hydrogen Peroxide Catalyzed by Keggin-type Polyoxotungstate in a DC Magnetic Field

Abstract

The oxidation of sulfur-containing compounds was conducted in a DC magnetic field-assisted system, composed of model compound or diesel, 30 wt% hydrogen peroxide, and an iron mono-substituted Keggin-type heteropolytungstate [(C₄H₉)₄N]₄ [PW₁₁Fe(H₂O)O₃₉] catalyst. By combining oxidative desulfurization (ODS) in a magnetic field and acetonitrile extraction, when magnetic field intensity was at 17.3 mT, the removal efficiency of the model compound dibenzothiophene (DBT) in petroleum ether with 1,000 ppm S can reach 98% at 70°C within 30 min with O/S ratio = 3 and catalyst dosage 5%, with 2% increase over that without magnetic field assistance. Under the same reaction conditions, the sulfur level of diesel oil was reduced from 5,647 to 508 ppm. This shows that the DC magnetic field facilitates the oxidation of sulfur-bearing compounds, which allowed greater sulfur removal efficiency under milder reaction conditions.     

四甲基胍与离子液体协同催化合成苯氨基甲酸甲酯

将一系列咪唑类离子液体分别与四甲基胍(TMG)进行预混合制得一系列催化剂,于相同条件下考察了催化剂在苯胺(AN)与碳酸二甲酯(DMC)合成苯氨基甲酸甲酯(MPC)反应中的催化性能。结果表明,[bmim]BF_4([bmim]为1-丁基-3-甲基咪唑)与 TMG 混合制得的催化剂的活性最好。同时考察了催化剂制备条件对催化性能的影响,结果表明,在 m([bmim]BF_4):m(TMG)=2、20℃、60 min 的条件下制得的催化剂的性能最佳。优化了该催化剂合成 MPC 的反应条件,优化合成条件为n(DMC):n(AN)=3、170℃、3 h、催化剂用量为反应物总质量的15%,在此条件下,MPC 收率为46.0%,选择性为59.8%。将TMG 和[bmim]BF_4分别回收后,再制成催化剂循环使用,循环使用5次后,MPC 收率没有明显降低。     

[bmim]OH和[A336][FeCl_4]混合离子液体氧化吸收硫化氢

为了降低非水相催化氧化硫化氢体系的运行成本,将碱性的氢氧化1-丁基-3-甲基咪唑([bmim]OH)离子液体与价格较低的酸性三辛基甲基铵四氯铁酸盐([A336][FeCl_4])离子液体分别按照0.2∶1、0.5∶1、0.8∶1、1∶1和2∶1的比例混合,用所得到的混合离子液体进行硫化氢氧化吸收实验,系统研究了混合离子液体的水溶性、密度、红外光谱、黏度和酸性强度等性能,并对其硫容和反应产物进行了分析。研究结果表明:(1)[A336]FeCl_4季铵盐离子液体的酸性强度和价格均低于[bmim]Fe Cl4离子液体,可以降低离子液体非水相催化氧化硫化氢体系的成本;(2)混合离子液体不仅同时具有[bmim]OH和[A336][FeCl_4]的骨架结构,且其p H值、黏度和硫容均随[bmim]OH量的增加而增加;(3)混合离子液体明显弱于[A336][FeCl_4]离子液体的酸性强度,有利于硫化氢的吸收,其黏度随温度上升而剧烈下降的性质有利于中、高温脱硫。结论认为,当[bmim]OH/[A336][FeCl_4]的物质的量之比在0.5∶1~1∶1时,可以构建成本较低、酸性适中、黏度较低、硫容较高的中、高温脱硫体系。     

DEEP DESULPHURISATION OF A DIESEL BLEND IN A PILOT PLANT TRICKLE BED REACTOR

ABSTRACT

A pilot plant investigation was conducted to study the influence of hydrotreating conditions on conversion and characteristics of diesel blend and to determine the severity of operating conditions required to meet the proposed product specifications for diesel fuel in India. A typical diesel blend derived from various refinery streams with sulphur content of 2·06 wt% was hydrodesulphurised over a commercial NiO-MoO₃/Al₂O₃ catalyst in a pilot plant trickle bed reactor. The experiments were conducted at 300–370°C, 30–50 kg/cm², 2·0 3·0 hr^-1 liquid hourly space velocity and constant H₂/oil ratio of 185 m³/m³. The data showed that the diesel blend could be hydrotreated to meet revised product specifications of 0·25 wt% sulphur, 46 cetane number by increasing the severity of operation. The cetane number and aromatic saturation were limited by thermodynamic equilibrium at temperatures above 360°C. The influence of temperature was found to be more pronounced than that of pressure in the range of operating conditions studied.     

吡咯烷酮酸性离子液体高效催化纤维素水解制葡萄糖

合成并表征了一系列咪唑类和吡咯烷酮类酸性离子液体,并以这些离子液体作催化剂,采用1-丁基-3-甲基咪唑氯化盐([Bmim]Cl)为溶剂,开展了纤维素催化水解制葡萄糖的研究。先以纤维二糖为模型化合物,考察了纤维二糖-葡萄糖体系的稳定性,后续又分别考察了加水量、加水时间、催化剂种类及用量、反应温度和时间等因素对纤维素水解制葡萄糖反应的影响。结果表明,与咪唑类酸性离子液体相比较,吡咯烷酮类酸性离子液体是更优良的促进纤维素水解的催化剂。采用1-甲基-2-吡咯烷酮甲基磺酸盐(［Hnmp］CH₃SO₃)酸性离子液体为催化剂时,在110℃下,当催化剂、纤维素中包含的葡萄糖单元、水三者的摩尔比为1∶3∶210,加水方式为40 min内每隔10 min加1次,分5次加完时,反应2 h,葡萄糖的收率为68%。     

离子液体中正丁基苯基醚的绿色合成方法

制备了1-甲基-3-正丁基咪唑氟硼酸盐([bmim]BF_4)和N-正丁基吡啶氟硼酸盐([bpy]BF_4)两种离子液体,并作为溶剂和催化剂用于正丁基苯基醚的合成。考察了反应条件对正丁基苯基醚产率的影响,探讨了正丁基苯基醚的合成反应机理。在反应条件为65℃、2 h、氯代正丁烷与苯酚钠摩尔比为1∶1.2、离子液体与反应物的质量比为2∶1时,分别以[bmim]BF_4、[bpy]BF_4和混合离子液体([bmim]BF_4和[bpy]BF_4的摩尔比为1∶1)为溶剂和催化剂时,正丁基苯基醚的产率分别为80.2%、85.1%和96.9%。结果表明,混合离子液体因提高了与极性相异反应物的相溶性而明显提高了正丁基苯基醚的产率,并且具有良好的重复使用性能。     

离子液体中杂质对1-己烯氢甲酰化反应的影响

利用无卤化物路线合成了离子液体1-丁基-3-甲基咪唑对甲苯磺酸盐([bmim][p-CH3C6H4SO3]),并作为水溶性铑膦络合物Rh-TPPTS(TPPTS为三(间-磺酸钠盐苯基)膦)催化1-己烯氢甲酰化反应的溶剂,通过添加一定量的杂质来模拟反应,研究了离子液体中可能存在的杂质对1-己烯氢甲酰化反应的影响。研究结果表明,离子液体中存在的杂质对1-己烯氢甲酰化反应均有不同程度的影响,其中卤化物杂质引起催化体系的反应活性和总醛(包括庚醛和2-甲基己醛)的选择性大幅度下降;对甲苯磺酸杂质对反应活性的影响不大,能很好地抑制1-己烯的加氢副反应,但加剧了1-己烯的异构化副反应,导致总醛的选择性降低;当溶剂中水的体积分数小于35%时,水对反应没有明显影响,只有当水的体积分数超过35%时,催化活性才明显降低。     

碱性离子液体催化合成α-呋喃丙烯酸

实验以糠醛和丙二酸为原料,采用Knoevenagel法,以碱性离子液体为催化剂和溶剂,高效率合成α-呋喃丙烯酸。讨论了糠醛与丙二酸的用量、反应时间和温度等对缩合反应的影响。实验结果表明,最佳反应条件为:n([bmim]_2CO_3):n(糠醛):n(丙二酸)=1.3:1:1,反应温度30℃,反应时间20 min,收率大于98%。产物后处理简单,离子液体可多次循环使用。经核磁共振、红外光谱、质谱和元素分析对产物的结构进行了表征。     

Desulfurization of FCC Gasoline Over Mordenite Modified with Al2O3

Abstract

Mordenite modified with Al₂O₃ (Al₂O₃/mordenite) was synthesized and used for the desulfurization of FCC gasoline. The influences of operating parameters on the results were studied for the model solution composed of dibenzothiophene (DBT) and isooctane. Al₂O₃/mordenite exhibits higher sulfur capacity than other kinds of chemisorbents. The suitable composition of the chemisorbent is 30 wt% Al₂O₃ to 70 wt% mordenite. The optimal operating parameters are: temperature 160°C; velocity 3 h^?1 (WHSV). Under the stated conditions, desulfurization was carried out for the FCC gasoline with sulfur content of 220.4 μg/g. The chemisorbent can maintain the sulfur content under 50 μg/g for 40 h and has good regeneration ability after desorption using benzene.     

Oxidative Desulfurization of Dibenzothiophene Catalyzed by VO(acac)2 in Ionic Liquids at Room Temperature

A simple extraction and catalytic oxidative desulfurization (ECODS) system composed of VO(acac)₂, 30% H₂O₂, and 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) has been found to be suitable for the deep removal of dibenzothiophene (DBT) in model oil at room temperature. The optimal conditions were as follows: [n(H₂O₂)/n(DBT)/n(catalyst) = 100:20:1], model oil = 5 mL, ionic liquid [IL] = 1 mL, T = 30°C, t = 2 hr. With the ECODS system, the sulfur removal of DBT could reach 99.6%, which was superior to that of the simple extraction with IL (15.6%) or oxidation without catalyst (17.1%). The IL could be recycled five times without a significant decrease in activity.     

溶剂体系对壬二酸合成的影响

在两类离子液体([bmim]BF_4与[bmim]PF_6)及异丙醇或无溶剂等条件下考察了壬二酸合成中的溶剂效应,并采用过氧化氢氧化油酸经二步反应合成了壬二酸。结果表明,[bmim]PF_6是合成壬二酸的最好溶剂。第一步较佳反应条件为:反应温度60℃,n(油酸)∶n(过氧化氢)∶n(钨酸)∶n(溶剂)=1.0∶3.0∶0.04∶1.24,反应时间1 h;第二步较佳反应条件为:m(中间产物):m(过氧乙酸)=1∶4,反应温度90℃,反应时间3 h。壬二酸收率为39%,熔点104～105.3℃,纯度达98%。