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.     

Anodic behaviour of carbon materials in NaCl saturated NaAlCl4 fused electrolyte at low temperatures: A cyclic voltammetric study

The anodic behaviour of compacted graphite, graphite powder, glassy carbon and reticulated vitreous carbon electrodes in basic sodium chloroaluminate melt in the temperature range 428–573 K was studied using cyclic voltammetry. Chlorine evolution (> + 2.1 V vs Al) alone was the predominant reaction on the compact glassy carbon and fresh RVC electrodes. On compacted graphite, chlorine-assisted chloroaluminate intercalation was found to be a competitive process to the chlorine evolution. At high sweep rates, intercalation/deintercalation near the graphite lattice edges occur faster than chlorine evolution. Subsequent intercalation, however, is a slow process. Chlorine evolution predominates at higher temperatures and at higher anodic potentials. On graphite powders, a more reversible free radical chlorine adsorption/desorption process also occurs in the potential region below chlorine evolution. The process occurs at the grain boundaries, edges and defects of the graphite powder material. Intercalation/deintercalation processes are mainly responsible for the disintegration of graphitic materials in low-temperature chloroaluminate melts. Repeated intercalation/deintercalation cycles result in the irreversible transformation of the electrode surface and electrode characteristics. The surface area of the electrode is increased substantially on cycling. Electrode materials and operating conditions suitable for chlorine generation, intercalation/deintercalation and chlorine adsorption/desorption and power sources based on these processes are identified in this work.     

室温离子液体催化苯与环己烯的烷基化反应

室温离子液体是由特定的阳离子和阴离子构成、在室温或近于室温下呈液态的熔盐体系，具有独特的性质和功能。用制备的氯铝酸盐室温离子液体作催化剂，催化苯和环己烯进行烷基化反应，考察了苯与环己烯摩尔比、反应温度、反应时间对烷基化反应产物收率的影响，研究了离子液体的催化活性和稳定性。结果表明：以制备的氯铝酸盐离子液体为催化剂，在反应温度30℃、反应时间4h、苯烯摩尔比16：1的条件下，所得环己基苯的产物收率最高，为70．5％。制备的离子液体重复使用3次，产物收率仍达53．6％，说明该离子液体具有一定的稳定性。     

CO_2-氯铝酸离子液体-苯三组分物系气液平衡数据的测定

在40℃、3.00～11.80MPa的条件下,测定了CO2-溴代-1-叔丁基-3-甲基咪唑-氯铝酸([Bmim]Br-AlCl3)-苯三组分物系的气液相平衡数据,获得了三组分物系的相图,分析了平衡压力对相态及平衡组成的影响。实验结果表明,在恒定的温度、压力下,由于平衡组成的不同,CO2-[Bmim]Br-AlCl3-苯三组分物系存在一相到三相的多种相态;当压力从3.00MPa升至11.80MPa时,富苯相中CO2的质量分数从0.114增至0.640,苯的质量分数由0.703降至0.196;当压力达到CO2的临界压力范围时,有新相生成,物系发生相态的改变,三相区变为四相区,两相区变为三相区。     

Synthesis of phosphinic acid resin using acidic 1-butyl-3-methylimidazolium chloroaluminate ionic liquid as catalyst

The resin is functionalized by the introduction of phosphinic acid moieties by Friedel–Crafts phosphination reaction using acidic 1-butyl-3-methylimidazolium chloroaluminate ionic liquid as catalyst. The phosphorous and hydroxyl capacities of the resin are compared with those obtained by using conventional aluminium chloride catalysis. Extraction of uranium(VI) from nitric acid medium by the resins has been studied, and it was found that the distribution coefficient (K_d, mL/g) of uranium(VI) initially decreases with the increase in the concentration of nitric acid, and reaches a minimum value at 1.5 M in nitric acid followed by the increase in K_d values. A maximum distribution coefficient has been obtained when the concentration of nitric acid was 4.0–5.0 M. The extraction data have been fitted in to a Langmuir adsorption model for obtaining the apparent experimental capacity.     

Benzene alkylation with long chain olefins catalyzed by ionic liquids: a review

The introduction of ionic liquids to alkylation process gives a choice for “green production” in the petrochemical and detergent industry. A lot of papers and patents have been published using chloroaluminate ionic liquid as a novel catalyst for alkylation with high reactivity and easy separation from reactants. These included the acidity, characterization, determination and catalysis technologies in batch and continuous operation mode for different scales. According to published data and several results of pilot alkylation,including the authors’ experience,the prospect of chloroaluminate ionic liquids for commercials was also discussed. It has been pointed out that there still are many difficulties and challenges to be overcome for commercial application of the ionic liquid catalyst.     

HR-2不锈钢表面渗Al涂层的制备

为避免制备温度过高引起基体性能退化,采用了室温熔盐电镀与热处理复合技术在HR-2不锈钢卜进行了渗Al涂层制备研究,并对涂层的形貌、结构和成分进行了表征.结果表明,利用该技术制备渗Al涂层是可行的;经500℃和700℃两种温度下热处理,成功制得成分渐变,冶金结合且无缝隙和裂纹的10-15 μm厚渗Al涂层.经700℃下2 h热处理后,渗Al涂层与基体无明显界面,依次由(Fe,Cr,Mn,Ni)2Al5,(Fe,Cr,Mn,Ni)Al和(Fe,Cr,Mn,Ni)3Al3层组成;与700℃热处理后不同,经500℃下10 h热处理后,渗Al涂层与基体间界面明显,由内外两层组成.     

C_(11)A_7·CaCl_2的形成及其动力学

利用DTA、XRD等手段对C11A7·CaCl2 的形成进行了研究 ,发现C11A7·CaCl2 在 85 0℃左右开始形成 ,随着煅烧温度的升高 ,C11A7·CaCl2 的形成化合程度逐渐提高 ,但其形成反应速率增加不显著。对C11A7·CaCl2 的形成动力学研究表明 ,C11A7·CaCl2 的形成反应可用Ginstling动力学模型很好地描述 ,其反应活化能为 5 0 5kJ·mol 1,处于一般化学反应活化能数值的下限 ,因此其形成反应速率随煅烧温度的升高增加不显著     

氯铝酸盐双阳离子液体催化合成乙氧基亚甲基丙二酸二乙酯

以N-烷基咪唑和二氯烷烃为原料,经过取代反应合成氯化咪唑鎓盐,添加Al Cl3络合制备了7种氯铝酸盐双阳离子液体。以制备的离子液体为催化剂,通过原甲酸三乙酯和丙二酸二乙酯之间的缩合反应合成乙氧基亚甲基丙二酸二乙酯。采用IR对离子液体的酸度进行测定,通过27Al NMR检测离子液体中铝的形态来分析提出的反应机理。考察了催化剂种类、催化剂用量、反应物物质的量比、反应温度、反应时间及催化剂循环次数对反应的影响。得到的最佳工艺条件为:以1,6-双(N-甲基咪唑基)己烷氯铝酸盐离子液体[C6(Mim)2]Cl2-4Al Cl3作为催化剂,用量为0.8%(以丙二酸二乙酯物质的量计),原甲酸三乙酯、丙二酸二乙酯和乙酸酐物质的量比为1.75∶1.00∶2.50,反应温度100℃反应2 h后140℃反应6 h。该条件下,丙二酸二乙酯的转化率高达98%,目标产物的选择性和收率分别为98%和97%。     

HR-2钢表面在AlCl_3-EMIC熔盐中电沉积铝镀层的织构和形貌

12～28mA/cm2范围内,采用AlCl3-EMIC(氯化1-甲基-3-乙基咪唑)熔盐电沉积法在18～40℃获得铝镀层,用X射线衍射(XRD)仪和扫描电子显微镜(SEM)研究其织构与形貌。结果表明,铝镀层呈(200)晶面择优取向,其相对衍射峰强度随电流密度和沉积温度升高而减弱,随镀层厚度增加而增强。厚度为8μm时镀层择优取向最明显,其表面颗粒呈棱锥状均匀紧密排列。电流密度为12mA/cm2时,随温度升高镀层由(200)晶面择优取向转变为(200)和(222)晶面择优取向,其表面颗粒随之由较均匀的棱锥状转变为不规则的核桃仁状。讨论镀层织构形成的可能机制。