功能化活性炭固载离子液体催化剂

制备了活性炭固载溴化1-（2-胺乙基氢溴酸）-3-甲基咪唑翁盐离子液体催化剂,并用TG和XPS对催化剂进行了表征。将该催化剂首次用于Knoevenagel缩合反应,结果表明活性炭固载离子液体催化剂具有良好的催化活性和稳定性,同时克服了均相催化剂难以分离的不足。     

硅胶负载酸性离子液体催化剂的制备及性能

以硅胶为载体,采用键合接枝法制备负载化Bronsted酸性离子液体催化剂[（TESP）MIm]HSo4／silica gel,利用元素分析、傅立叶变换红外光谱（FT—IR）和热重一差示扫描量热法（TGA—DSC）等方法对催化剂结构进行了表征。结果表明,离子液体[（TESP）MIm]HSO4负载量为1．503mmol／g的负载催化剂具有良好的热稳定性和重复使用性能。将其应用于乙酸和正丁醇的酯化反应,较佳反应条件为96℃,正丁醇0．12mol,乙酸0．10mol,环己烷用量6mL,催化剂用量为反应物总质量的4％,反应3h时,酯化率可达99．4％,催化剂重复使用6次后,酯化率仍可达到74．7％。     

Amino-functionalized Ionic Liquid as an Efficient and Recyclable Catalyst for Knoevenagel Reactions in Water

The Knoevenagel condensation of aromatic aldehydes with malononitrile and ethyl cyanoacetate using amino-functionalized ionic liquid, 1-aminoethyl-3-methylimidazolium hexafluorophosphate as catalyst was successfully performed in aqueous media. The catalyst can be recycled and reused at least six times without apparently loss of activity.      

Copper Nanoparticles in Ionic Liquid: An Easy and Efficient Catalyst for Selective Carba-Michael Addition Reaction

In this paper, we wish to report a novel synthesized copper nanoparticles in an ionic liquid employed as a catalyst for Michael addition between active methylene compound and α, β-unsaturated compounds to give corresponding compounds in excellent yield and in shorter reaction times.      

An Efficient and Reusable Catalyst of Bismuth-Containing SBA-15 Mesoporous Materials for Solvent-free Liquid Phase Oxidation of Cyclohexane by Oxygen

Bismuth-containing SBA-15 mesoporous materials with different n_si/n_Bi ratio was synthesized for the first time through a direct hydrothermal method, and characterized by various physico-chemical techniques. XRD patterns indicate that the synthesized materials have an ordered two-dimensional p6mm hexagonal mesostructure. Transmission electron microscopy and scanning electron microscopy studies show that Bi-SBA-15 has well-ordered hexagonal arrays of mesoporous channels and the morphology of rod-like particles. Raman spectroscopy and UV–Vis DRS show that bismuth atoms in Bi-SBA-15 exist in a highly dispersed state, and locate mainly at tetrahedrally coordinated sites. Thermogravimetric analysis was used to observe the removal of the organic template P₁₂₃. In the catalytic test, Bi-SBA-15 is found to be a very efficient and reusable catalyst for the oxidation of cyclohexane, in a solvent-free system, with oxygen as oxidant. The influence of different parameters, such as reaction time, reaction temperature, oxygen pressure, and the dosage of catalyst on the oxidation of cyclohexane, is also investigated.     

酸性离子液体催化甲基环戊烷异构化反应

以三级胺、盐酸和AlCl_3为主要原料制备了氯铝酸盐型酸性离子液体催化剂,并优化了催化剂的配比。考察了催化剂用量、反应温度、反应时间以及原料杂质等对甲基环戊烷异构反应的影响。结果表明,提高催化剂用量和反应温度可加快反应速率,在反应温度70℃,油剂比3.0,反应4 h后,环己烷的产率达到70%以上,微量杂质(正己烷和苯)几乎不影响甲基环戊烷的异构化反应。离子液体催化剂在补充活性组分AlCl_3的情况下可以实现循环使用。     

SiO_2固化SO_3H-功能化离子液体催化合成油酸甲酯

以1,3-丙烷磺内酯和巯基改性纳米二氧化硅球为原料,采用化学键合接枝法获得固化SO_3H-功能化离子液体的酸催化材料(SiO_2-IL)。采用NMR、FTIR和热分析方法对SiO_2-IL的结构和热稳定性进行了表征。考察了SiO_2-IL在油酸与甲醇酯化反应中的催化活性,分析了影响其催化性能的关键因素及原因。结果表明,该离子液体自身所具有的酸性以及固化过程中化学键合接枝程度均对其催化性能有所影响。对反应工艺条件进行了优化。结果表明,在反应温度60℃、n(甲醇)∶n(油酸)=12∶1、m(SiO_2-IL)∶m(油酸)=0.09∶1.00、反应时间5 h条件下,油酸甲酯收率最高为94%,催化材料经重复使用5次后,油酸甲酯收率仍可达74%。     

酸性离子液体催化合成N-甲酰吗啉

合成了7种酸性离子液体,并将其应用于催化合成N-甲酰吗啉的反应中,筛选出了一种可以重复使用的离子液体[HSO3-pmim]HSO4,并对其进行了表征。以吗啉和甲酸为原料,离子液体[HSO3-pmim]HSO4为催化剂,以一种环保的工艺合成了N-甲酰吗啉。用红外光谱对产品结构进行了分析表征,和N-甲酰吗啉标准谱图一致,用气相色谱测定产品质量分数大于99.8%。考察了影响反应的主要因素,确定了较佳反应条件:n(甲酸)∶n(吗啉)=1.15∶1,反应温度85~95℃,反应时间8.0 h。在该条件下[HSO3-pmim]HSO4重复使用7次后,没有明显消耗,N-甲酰吗啉的收率大于81.3%。     

离子液体催化合成醋酸正丙酯的工业实验

在南京扬子石化精细化工有限责任公司年产1500t醋酸正丙酯工业装置上进行了BILE-3型离子液体催化合成醋酸正丙酯的工业实验。考察了BILE-3型离子液体催化合成醋酸正丙酯工艺中反应体系水、酸度等工艺条件对酯化反应的影响,并与传统硫酸催化酯化工艺进行了比较。工业实验结果表明,酯化反应体系中水小于反应物料质量分数5%,酸度在45～65gKOH/100g,酯化釜液位高度在反应釜容积的50%～70%,酯化反应转化率为95%以上,选择性为99%以上;与传统硫酸催化酯化相比,BILE-3型离子液体催化工艺具有生产成本低、过程清洁、不腐蚀设备、运行周期长等优点。     

Microwave-Assisted Esterification of Oleic Acid Using an Ionic Liquid Catalyst

The combination of 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO₄) ionic liquid (IL) and microwave heating was used to esterify oleic acid as a green approach in biodiesel synthesis. To compare the heating systems, conventional heating and the ultrasonic method were employed but the microwave method was found to be more effective. H₂SO₄ and 1-methyl imidazole hydrogen sulfate ([Hmim]HSO₄) were also used in the esterification of oleic acid and their catalytic activities were compared to that of [Bmim]HSO₄. ILs provided some advantages such as reusability, easy recyclability, and very stable activity. There was only a small decrease in the catalytic activity of [Bmim]HSO₄ after four successive applications, which means that ILs can be reused, contrary to homogeneous catalysts. The combination of IL catalysts and microwave irradiation proved to be a potential alternative method for biodiesel production.     

酸性离子液体催化合成乙酸苯乙酯

以酸性离子液体己基甲基咪唑硫酸氢盐[n-C6Im][HSO4]为催化剂催化合成乙酸苯乙酯(PEAC)。通过对影响转化率的各种因素考察,得到最佳合成条件:2-苯乙醇与乙酸乙烯酯物质的量比为1∶1.2,离子液体催化剂用量5%(质量分数),反应温度140℃,反应时间6 h,PEAC转化率为91.8%。离子液体催化剂重复使用4次后,转化率开始缓慢下降,但补充适量硫酸后离子液体即可恢复催化活性。与传统的强酸催化剂相比,[n-C6Im][HSO4]具有合成的PEAC色泽好、催化剂易回收与重复利用的优点。