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.     

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.     

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.     

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.     

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%。     

Characterization of [bmim]Cl／FeCl3 Ionic Liquid with Spectra

[bmim]Cl/FeCl3 ionic liquids (where bmim = 1-buty1-3-methylimidazolium) were characterized by XPS (X-ray photoelectron spectroscopy), FT-IR (Fourier transform infrared spectroscopy), Raman and NMR (nuclear magnetic resonance) spectra. The results show that Fe2Cl7^- and FeCl4^- ions are the principal anions in acidic ionic liquids, whose concentrations change with the content of FeCl3 and an equilibrium exists between them. An isosbestic point existing in FT-IR spectra indicates that an interaction involving at least two species occurs and their concentrations vary with acidity.Chemical shifts of the hydrogen located in the cations of ionic liquids are sensitive to the composition of ionic liquids.The change in chemical shifts may be explained in terms of anion-cation interactions. The chemical shifts of 2-H are affected by metal halides, which shift downfield and the 2-H is more deshielded with the increase in metal halides.     

Characterization of [bmim]Cl/FeCl_3 Ionic Liquid with Spectra

1. Introduction As substitutes for traditional liquid acids such asH2SO4 and HF, the applications of room-temperatureacidic ionic liquids have been attracted significantattention (Davis and Fox, 2003; Gordon, 2001; Seddon,et al., 2003; Sheldon, 2001; W…     

Deep Desulfurization of Diesel Fuel by Extraction with Task-Specific Ionic Liquids

Abstract

Extraction of S-compounds from diesel oil by task-specific ionic liquids has been investigated. The influences of different ionic liquids, extraction time, extraction temperature, different S-compounds, the amount, and the recycling of ionic liquid were studied. This process is capable of removing up to 56% of dibenzothiophene in model diesel oil under optimum extraction conditions. At the same time, this process was applied to the real predesulfurized diesel oils. The results indicate that such a process could be an alternative to common hydrodesulfurization for deep desulfurization.     

于离子液体的高酸原油脱酸效果研究

利用咪唑和环烷酸反应生成与原油极性差异大、易于分离的离子液体，脱除原油中的环烷酸。考察了咪唑含量、剂油比、反应时间、反应温度和搅拌速率对高酸原油一级脱酸效果的影响，并在所选的一级脱酸反应条件下，进一步考察了三级逆流萃取的脱酸效果。结果表明，在咪唑质量分数为30%、剂油质量比为0.4、反应时间5 min、反应温度30 ℃、搅拌速率300 r/min的条件下，北疆原油的一级脱酸率可达61.5%，酸值较低的蓬莱原油的一级脱酸率可达68.6%，酸值更低的1号和2号调和油一级脱酸率分别达到了70.6%和72.2%。试验所用的四种原油在剂油质量比为0.4时，三级逆流萃取的脱酸率可以提高到75%左右；当剂油质量比增大到0.6时，三级逆流萃取的脱酸率可达到84%以上。     

Deep Desulfurization of Model Oil by Extraction with a Low-viscosity Ionic Liquid [BMIM]SCN

In this work, a low-viscosity ionic liquid 1-buthyl-3-methylimidazole thiocyanate ([BMIM]SCN) was utilized as extractant for the extractive desulfurization of thiophene in model oil. Several conditions were investigated respectively, including extraction time, temperature, and volume ratio of ionic liquid to model oil. Also the kinetics of extraction of thiophene were proposed. Under the optimal extractive conditions, the removal of thiophene in model oil was 55.6%. Other sulfur compounds and real oil were also investigated. Furthermore, the total desulfurization efficiency could reach 98.3%. In addition, the ionic liquid could be recycled seven times with negligible decrease in 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.     

离子液体中纤维素催化转化制5-羟甲基糠醛

 采用1-丁基-3-甲基咪唑离子液体(BmimCl)为溶剂,以磺酸功能化离子液体N-(4-磺酸基)丁基三甲胺硫酸氢盐和CrCl₃氯化为催化剂,开展了纤维素一锅法催化转化制5-羟甲基糠醛(HMF）的研究。采用高效液相色谱分析了液体产物。分别考察了催化剂种类、用量、反应温度和时间对纤维素转化的影响。结果表明,使用离子液体为溶剂,磺酸功能化离子液体和CrCl₃协同作用,将纤维素转化为HMF。当反应在130℃下,磺酸功能化离子液体、CrCl₃和纤维素的摩尔比为5∶4.5∶100时,HMF 收率和产物总收率分别为41%和51%。     

采用质子酸离子液体反应萃取精馏制备醋酸甲酯

以醋酸、甲醇为原料,以质子酸离子液体为催化剂和萃取剂,采用反应萃取精馏法制备了醋酸甲酯。考察了质子酸离子液体和配料比、回流比及反应时间对反应萃取精馏的影响。实验结果表明,质子酸离子液体是制备醋酸甲酯的良好催化剂和萃取剂,能消除醋酸甲酯与水或甲醇的共沸点,提高醋酸甲酯的纯度和收率;在3种质子酸离子液体[Hmim]CF3COO,[Hmim]BF4,[Hmim]HSO4中,[Hmim]HSO4(Hmim为N-甲基咪唑)的催化活性最高。反应萃取精馏的最佳工艺条件是:m(HOAc)∶m(CH3OH)∶m([Hmim]HSO4)=100∶50∶1,回流比2.5,反应时间30min。在此条件下,醋酸甲酯的纯度可达99.84%,收率可达98.65%。采用闪蒸的方法可回收醋酸、甲醇及质子酸离子液体,质子酸离子液体可重复使用8次。     

Removal of basic nitrogen compounds from fuel oil with [C4mim]Br/ZnCl2 ionic liquid

Metal-based ionic liquid [C₄mim]Br/ZnCl₂ was synthesized, and its structure was characterized using FTIR spectroscopy and a mass spectrometer. The denitrogenation performance of the ionic liquid was investigated using coker diesel oil as feedstock. Experiment results showed that [C₄mim]Br/ZnCl₂ presented a good denitrogenation performance, obtaining about 94.95% basic N-removal efficiency under the condition with a temperature of 50°C, 1:1 (w/w) IL:oil, extraction time of 30 min. In addition, the basic N-removal efficiency can still reach above 50% at 1:7 IL/oil (w/w) during four recycles of the ionic liquid.     

超声波辐照浸渍法制备MnO2/γ-A12O3催化剂及其柴油催化氧化脱硫性能

 分别采用超声波辐照浸渍法和普通浸渍法制备了MnO₂/γ-Al₂O₃催化剂,运用电感耦合等离子体原子发射光谱（ICP-AES）和X射线衍射（XRD）对催化剂进行表征,在空气-异丁醛-MnO₂/γ-Al₂O₃体系中评价其对加氢柴油的氧化脱硫催化性能,并考察了反应温度、异丁醛用量、空气流量、溶剂类型和剂/油体积比对柴油氧化脱硫反应的影响。结果表明,超声波辐照浸渍法制备的MnO₂/γ-Al₂O₃催化剂对柴油氧化脱硫的催化性能明显优于普通浸渍法制备的催化剂。最适宜的催化柴油氧化脱硫反应的条件为：乙腈为溶剂、加氢柴油30 mL、温度35℃、异丁醛20 mmol、空气流量0.06 L/min、超声波辐照浸渍法制备的MnO₂/γ-Al₂O₃催化剂0.08 g、剂/油体积比1/6和催化氧化时间10 min。在此条件下可将柴油硫质量分数从542μg/g 降至31μg/g,柴油脱硫率和回收率分别为94.3%和93.3%。     

The direct dimethyl ether (DME) synthesis process from syngas II. Intrinsic kinetics and catalyst deactivation in one-step LPDMEtm process

In Part I of this series, it was seen that the favorable thermodynamic and kinetic coupling in the one-step LPDME^tm process – of methanol dehydration reaction (very rapid kinetics and at/near thermodynamic equilibrium) with the methanol synthesis reaction (slower kinetics and under thermodynamic limitation) – leads the beneficial “chemical synergy”.

In this part II of Series, we briefly discern the intrinsic kinetics of the LPMeOH^tm and LPDME^tm systems, and also shed light of the catalyst deactivation phenomena in these processes. Among the many reports on intrinsic kinetics of the one-step LPMeOH^tm and LPDME^tm processes, two illustrative kinetic studies, from the groups of University of Akron and Air Products and Chemicals, Inc. are highlighted and discussed further. For development of intrinsic kinetic models of LPMeOH^tm and LPDME^tm systems, a detailed thermodynamic framework has been developed which allows one to compute the liquid phase concentrations of reactive species, at phase equilibria and at chemical reaction equilibria. The intrinsic kinetic models of the LPDME^tm system are mainly based on the independent, component kinetic models of methanol synthesis (van den Bussche and Froment, 1996) and methanol dehydration (Bercic & Levec, 1992). From an overarching analysis of the deactivation of supported copper catalysts for methanol synthesis and other reactions (methanol decomposition and methanol steam reforming), we propose that thermal sintering, i.e., increase in Cu particle size and loss of metal surface area, is the only cause of catalyst deactivation in methanol synthesis reactions over Cu/ZnO/Al₂O₃ industrial-type methanol catalysts.     

Production of olefins from syngas over Al2O3 supported Ni and Cu nano-catalysts

The most important products that can be produced from syngas are methanol, dimethyl ether and light olefins (ethylene and propylene). The light olefins are the most important syngas products, because many of the chemicals are produced from them. The aim of this work was to study the olefins production from syngas over Al₂O₃-supported Ni-Cu nano-catalysts. In addition, the effect of various factors such as catalyst on olefin production and CO conversion has been investigated. The concentration of heavier olefins (C5) was greater than the remaining olefins, since the rate of reactions must be increased to form C1 to C4. In the case of a Ni/Al₂O₃ catalyst, C1 and C4 was initially increased and then decreased with an increase in Ni loading from 0% to 15%.     

[Bmim]Br/FeCl3离子液体脱除页岩油柴油中的氮化物

合成了低粘度的离子液体[Bmim]Br/FeCl3,采用红外光谱对其结构进行表征,并考察其对高氮含量的抚顺页岩油柴油馏分中氮化物的脱除效果。结果表明：[Bmim]Br/FeCl3离子液体具有良好的脱氮性能,在萃取温度30 ℃、剂油质量比1:1、萃取时间30 min、静置时间2h的条件下,[Bmim]Br/FeCl3对柴油馏分中碱氮和总氮的脱除率分别为95.29%和89.76%,对应的柴油馏分中的碱氮和总氮含量分别由5454μg/g,9832μg/g降低到257μg/g,1006μg/g。且该离子液体经回收重复使用4次后,在剂油质量比1:7的条件下,碱氮脱除率仍能达到60%。     

CHEMICAL BASIS OF MIDDLE DISTILLATE FUEL INSTABILITY: Interactive Effects of Selected Nitrogen Heterocycles with Organic Bases in a Shale-Derived Diesel Fuel.

ABSTRACT

Fuel instability reactions are defined in terms of the formation of deleterious products such as filterable sediments and peroxides. Gravimetric stability tests have been carried out at 80^°C using two model nitrogen heterocycles: 2,5-dimethy1pyrrole, DMP, and 3-methylindole, 3-MI, in an otherwise stable shale derived middle distillate fuel. Potential interactive effects for these model nitrogen heterocycles have been described by the presence of organic base co-dopants. Organic bases employed included: tri-n-butylamine, N, N-dimethyl-aniline, and 4-dimethylaminopyridine. Simple organic amines exerted only minor interactive effects, usually an increase in filterable sediment in the range of 5–15%. However, the diamine species, 4-dimethylaminopyridine, interacted in a strong positive fashion to generate increased amounts, 22–44%, of sediment.