Preparation of fructone catalyzed by water-soluble Brφnsted acid ionic liquids

Fructone （2-methyl-2-ethylacetoacetate-1, 3-dioxolane）, a flavouring material, has been synthesized from ethyl acetoacetate and glycol using five water-soluble Brφnsted acid ionic liquids as catalysts for the first time. The used Brφnsted acid ionic liquids include [Hmim]Tfa, [Hmim]Tsa, [Hmim]BF4, [Bmim]HSO4, [Bmim]H2P04, and [Hmim]BF4 showed the highest catalytic activity for the preparation of fructone. After reaction, the product could be isolated from the reaction system automatically, and the ionic liquid could be directly reused without dehydration.

[bmim]Cl/[FeCl3] Ionic Liquid as Catalyst for Alkylation of Benzene with 1-Octadecene

Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB （linear alkylbenzenes） was performed. The results showed that the most important factor that governed the conversion of olefin and selectivity of LAB was reaction temperature. Moreover, the effects of different ionic liquids and molar ratio of benzene to 1-octadecene on the conversion and selectivity were obviously in different degrees. The reaction temperature, molar ratio of benzene to 1-octadecene and the amount of catalyst were lower, compared with the traditional reaction technologies. The experimental results demonstrated that the ionic liquid had higher activity at 30℃, with over 98% selectivity of monoalkylbenzene and 100% conversion of the olefin at the molar ratio 0.08 of FeCl3 in ionic liquid to 1-octadecene and 10 for benzene to 1-octadecene.

Removal of Nitride from Shale Diesel Fraction with FeCl3-Based Ionic Liquids

FeCl3-based ionic liquid [Bmim]Br/FeCl3 with lower viscosity was synthesized and its structure was character-ized with FT-IR spectroscopy. The denitrogenation performance of the ionic liquid was investigated using the Fushun shale diesel fraction with high nitrogen content. Experimental results showed that the ionic liquid presented good denitrogenation performance and the basic N and total N removal efficiency can reach 95.29% and 89.77% under conditions covering a tem-perature of 30 ℃, an IL/oil mass ratio of 1:1, an extraction time of 30 min, and a settling time of 2 h. Correspondingly, the basic N and total N contents in shale diesel fraction dropped from the original 5454 μg/g and 9832 μg/g to 257 μg/g and 1006 μg/g, respectively. In addition, the basic-N removal efficiency can still reach 60% at an IL/oil mass ratio of 1:7 during four recycles of the ionic liquid.

Transesterification of palm oil to biodiesel using Brφnsted acidic ionic liquid as high-efficient and eco-friendly catalyst

The transesterification of palm oil and methanol catalyzed by Br?nsted acidic ionic liquids was investigated. Four eco-friendly Br?nsted acidic ionic liquids were prepared and their structures were characterized by NMR, FT-IR and TG–DTG. The results demonstrated that [CyN_(1,1)PrSO_3H][p-TSA] was more efficient than the other ionic liquids and chosen as catalyst for further research. The influences of various reaction parameters on the conversion of palm oil to biodiesel were performed, and the orthogonal test was investigated to seek the optimum reaction conditions, which were illustrated as follows: methanol to oil mole ratio of 24:1, catalyst dosage of 3.0 wt% of oil, reaction temperature of 120 °C, reaction time of 150 min, and the biodiesel yield achieved 98.4%. In addition, kinetic study was established for the conversion process, with activation energy and preexponential factor of 122.93 k J·mol^(-1) and 1.83 × 10^(15), respectively. Meanwhile, seven-time recycling runs of ionic liquid were completed with ignorable loss of its catalyst activity. The refined biodiesel met the biodiesel standard EN 14214.

New Alkylation Route of Benzene with Ethylene Catalyzed by [bmim]Cl/FeCl_3 Ionic Liquid

Up to now the mechanism of Priedel-Crafts reactions catalyzed by ionic liquidhave not been fully understood, while carbocation mechanism was assumed. It was found that thesource of H^+ and the route of reaction initiated the alkylation of benzene with ethylene catalyzedby [bmim]Cl/FeCl_3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity forthe alkylation of benzene with ethylene suggests that there exists a new catalytic route. Thedistinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of[bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shiftsof proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl_3 content andshifted downfield when FeCl_3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to bedisengaged from imidazolium ring with formation of H^+ to initiate the reaction. Theisotope-substituted method was employed to prove this mechanism, through the GC-MS analysis ofalkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeCl_3ionic liquid was found to follow the carbocation mechanism, the resource of H^+ was presented andproved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found thatthe intensity of 2-H reduced 23% after reaction showing that the H^+ arising from alkylationreaction was supplied by 2-H on the imidazole ring.

7-Deazapurines:Synthesis of new pyrrolo[2,3d]pyrimidin-4-onescatalyzed by a Brφnsted-acidic ionic liquid as a green and reusable catalyst

Some new 2-aryl-3,7-dihydro-4H-pyrrolo[2,3-d]pyrimidin-4-ones have been prepared through cyclocondensation of 2-amino 1H-pyrrole-3-carboxamides with aromatic aldehydes followed by air oxidation in the presence of 3-methyl-1-（4-sulfonic acid）butylimidazolium hydrogen sulfate[（CH;）;SO;HMIM][HSO;],a Br（?）nsted-acidic ionic liquid,as a green and reusable catalyst in solvent-free conditions.

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

bmim]Cl/FeCl3 ionic liquids (where bmim = 1-butyl-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.

The alcoholysis of acetonitrile prompted by Brфnsted acidic ionic liquid [HSO_3-pmim]HSO_4

BrФnsted acidic ionic liquids based on imidazolium cation were employed as a series of environmentally benign catalysts and mediums in the alcoholysis of acetonitrile to synthesize ester. The results showed that BrФnsted acidic ionic liquid [HSO3- pmim]HSO4 was an efficient catalyst and medium for the alcoholysis of acetonitrile which could be recycled easily without obvious decline in catalytic activity, the highest yield could reach 85%.

Study on Desulfurization with Ionic Liquid [BMIM]PF_6

The removal of sulfur compounds(thiophene) from petroleum via extraction with ionic liquids was systematically studied.The ionic liquid[BMIM][PF_6]([BMIM]^+—1-butyl-3-methylimidazolium hexatiuorophosphate cation) was used to investigate its effect on thiophene removal.The test results showed that a higher temperature and a greater mass ratio of the ionic liquids versus the oil containing the sulfur compounds both helped to remove the thiophene from the feed oil.At a temperature of 60℃and an ionic liquid/feed oil mass ratio of 20%,the desulfurization rate could reach 52.39%, with the extraction time specified at 40 minutes.

Photocatalytic Oxidative Desulfurization of Gasoline by TiO_2 in[BMIm]Cu_2Cl_3 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.

Electrodeposition of aluminum on magnesium from ionic liquid(EMIM)Br-AlCl_3

An ionic liquid was prepared by mixing AlCl3 and 1-methyl-3-ethylimidazolum bromide(EMIM)Br under dry argon atmosphere.Electrodeposition of aluminum on magnesium was conducted at 298.15 K for 1 h by the ionic liquid and the electrochemical behavior was discussed.The results show that the aluminium deposition occurs at a potential about-0.1 V.Cathode surface was analyzed by SEM,XRD and EDS.Aluminum is successfully electrodeposited on magnesium from(EMIM)Br-AlC13 ionic liquid,and the crystal grain quality of the deposit at 15 mA/cm2is ideal with the perfect boundary of crystal grain.

Ionic liquid [bmim][BF_4] acts as solvent and promoter for synthesis of halo-containing N-arylphthalimides

A new synthetic process of N-arylphthalimide and halo-containing N-arylphthalimides through the reaction between phthalic anhydride and aromatic amines bearing halo groups in [bmim][BF4] was described, ionic liquid [bmim][BF4] acted as the dual role of solvent and promoter.

Novel Brфnsted Acidic Ionic Liquid Based on a Cyclic Guanidinium Cation:a Green,Efficient,and Recyclable Dual Slovent-catalyst System for Fisher Esterification

A novel BrФnsted acidic ionic liquid（IL） based on the cyclic guanidinium cation has been synthesized. This IL, as a strong BrФnsted acid catalyst or solvent, shows high catalytic activity and biphsaic behavor in the esterifications of carboxylic acids and alcohols. The produced esters as a separate phase can be conveniently decanted out from the IL and the IL is recyclable without any loss of catalytic activity.

铝基离子液体（BMIM）Br-AlCl3的制备与电沉积应用

在高纯氩气气氛下，将AlCl3与溴化1-丁基-3-甲基咪唑（BMIM）Br反应合成透明的铝基离子液体（BMIM）Br-AlCl3；采用红外光谱仪、扫描电镜及X射线能谱仪对其结构进行表征。在298．15K下进行16h铝电沉积实验，通过循环伏安曲线法测定其电化学窗口。研究结果表明：铝基离子液体（BMIM）Br-AlCl3的电化学窗口为3．40V；扫描电镜分析表明，阴极新生态的铝晶粒生长完整、晶界完善；X射线能谱分析阴极表面新生态铝的结果显示主元素为铝，微量元素为氧。

以TFE-[BMIm][Br]为工质对的吸收式制冷循环性能分析

本文选择含离子液体体系TFE-[BMIm][Br]作为吸收式制冷循环的工质体系,基于文献数据给出了计算TFE- [BMIm][Br]热物性模型,建立并联双效吸收式制冷循环的模拟程序,分别考察了四种双效并联制冷流程中溶液换热器的热交换效率、蒸发温度、吸收温度以及发生温度对系统性能、溶液循环倍率以及系统操作压力的影响.探索新工质对TFE- [BMIm][Br]的可行性,确定了TFE-[BMIm][Br]双效并联吸收式制冷循环的适宜的运行操作范围以及适宜的流程方案.

A Simple and Selective Procedure for α-Bromination of Alkanones with [Bmim]Br_3 as a Promoter under Solvent-free Conditions

Reaction of alkanones with 1-butyl-3-methylimidazolium tribromide （[Bmim]Br3） under solvent-free conditions, selectively gave the corresponding ct-bromoalkanones with excellent yields.

Recycling and Activity Recovery of Chloroaluminate Ionic Liquid as Catalyst for Alkylation of Benzene with 1-Dodecene

Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pilot plant with continuous mixingreactingseparatingrecycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquidliquid settling phase separator, was introduced as an alternative. The results showed that the continuous fast mixing and separation of ionic liquid catalyst from reactant mixture could be synchronously accomplished within a wider flow rate ratio range of the recycling reaction mixture to the ionic liquid catalyst. The recycling of chloroaluminate ionic liquid was realized. ICPAES detection results of Al content in the reactants proves that in-situ Al compensation to the reaction system may be an important choice to prolong the stable running time of moisture-sensitive ionic liquid BMIMClAlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.

Br离子液体中微波辐射加热促进稻草秸秆酸水解制备还原糖

为了探讨微波辐射及离子液体对酸催化植物纤维素水解的促进作用,以稻草秸秆为原料,在[Bmim]Br离子液体介质中,用微波辐射加热促进纤维素的酸水解,并对水解产物中的还原糖进行了测定。着重考察了微波辐射功率、微波辐射时间、硫酸浓度、反应温度等因素对还原糖收率的影响。结果表明,在[Bmim]Br离子液体介质中,用微波辐射加热促进稻草酸水解制备还原糖的最佳条件是:30.0mL质量分数为10.0%的硫酸、[Bmim]Br10.0mL、微波辐射温度85℃、微波辐射时间45min、微波辐射功率500W,在此条件下还原糖的收率达到了22.94%,而常规酸水解得到的还原糖收率为14.50%。显然,在[Bmim]Br离子液体介质中,微波辐射加热促进稻草酸水解所得还原糖收率大于常规酸水解的所得还原糖收率。由此可知,离子液体介质中,微波辐射加热能够促进植物纤维素的酸水解,并显著缩短糖化时间,使得还原糖的收率提高。

氯化胆碱添加剂对[Bmim]Cl-AlCl_3离子液体体系电解精炼铝的影响

研究了AlCl3摩尔分数为0.667的[Bmim]Cl-AlCl3离子液体体系中氯化胆碱(ChCl)添加剂对体系电导率及电解精炼铝的影响.结果表明,当ChCl浓度小于8mmol/L时,体系的电导率随ChCl浓度增加而显著提高,但ChCl浓度进一步增加体系的电导率逐渐降低.添加少量ChCl后,阴极还原峰电位正移,还原峰电流逐渐降低.在温度373K和电流密度50A/m2条件下添加5mmol/LChCl进行恒电流电解,电解过程的槽电压显著降低,阴极电流效率显著提高(接近100%),直流电耗仅为0.611kW·h/kg,只有纯离子液体体系电解铝的50%,且在低碳钢基体上得到的铝沉积层光滑致密、晶粒细化.