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 ([BMIM]Cl-AlCl3) 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 mixing-reacting-separating-recycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquid-liquid 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. ICP-AES 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 [BMIM]Cl-AlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.     

离子液体催化丁醇与盐酸反应制备丁基氯

The catalytic performance of some quaternary ammonium salts for the liquid phase reaction of butanol and hydrochloric acid at different conditions was studied experimentally and compared with the traditional catalyst （ZnCl2）. The organic ammonium catalysts investigated include ionic liquids N-butyl-N-methyl imidazolium fluoborate （[BMIM][BF4]） and N-butyl-N-methylimidazolium chloride （[BMIM]Cl） as well as hydrochloric salts of N-methylimidazol （[HMIM]Cl）, pyridine （[HPy]Cl） and triethylamine （[HEt3N]Cl）. It is shown that the intrinsic catalytic performance of all organic ammonium salts except [HEt3N]Cl is slightly superior to ZnCl2, while the selectivity of butyl chloride is nearly at the same level around 96%. The conversion of butanol increases slightly with temperature and the catalyst amount added while the variation of selectivity is not obvious. Based on the recycle experiments, the ionic liquids as catalyst for the reaction of butanol and hydrochloric acid can be used more than 5 times, which suggests great potential of using ionic liquids as novel catalyst for such reactions.     

化学修饰Novozym-435酶催化合成维生素E琥珀酸酯的研究

Vitamin E succinate was synthesized in organic solvents using a modified Novozym-435 as catalyst.In order to improve the catalytic performance of Novozym-435,the enzyme was modified using acetic anhydride, propionic anhydride and succinic anhydride separately.We found that both the hydrolytic activity and the thermal stability of the modified Novozym-435 were enhanced compared with the unmodified enzyme.The modified Novozym-435 catalysts were used to synthesize the succinate derivative of vitamin E.Compared with the native Novozym-435,the catalytic activity of the modified novozym-435 in promoting the synthesis of vitamin E succinate was dramatically increased,with the novozym-435 modified with succinic anhydride(N435-S)as the most active catalyst.Conditions for the synthesis of vitamin E succinate were also optimized.A mixture of tert-butanol and DMSO(volume ratio of 2︰3)was the most suitable medium for the reaction,whereas the appropriate molar ratio of vitamin E to succinic anhydride and reaction temperature were 1︰5 and 40°C,respectively.Under these reaction conditions,the yield of vitamin E succinate reached 94.4%.N435-S could be reused for five batches.     

A solvent-free,selective liquid phase hydrogenation of nitroarenes to aniline in slurry bubble mode on porous NiMo bimetallic catalyst

Ni Mo bimetallic catalysts were prepared by a solid reaction method. On the Ni Mo catalyst, the selective liquid phase hydrogenation of nitrobenzene to aniline was achieved in slurry bubble mode. And the high yields(98.9%) were obtained under the conditions of 80 °C, solvent-free and atmospheric pressure. The effect of Mo on the catalytic behavior of Ni based catalyst was investigated. The characterization displayed that the inclusion of Mo could improve the specific surface area and pore volume, and the solid reaction method made metal Mo enrichment on the surface of catalyst. These two aspects should be responsible for excellent catalytic performance of Ni Mo catalyst. In sum, we described a simple and efficient Ni Mo catalyst and provided a facile and green procedure for liquid phase hydrogenation of nitrobenzene to aniline.     

侧光光纤引导的内源可见光催化降解亚甲基蓝(英文)

The side-glowing optical fibers (SOFs) were chosen as the conducting medium of endogenous light; and 20 mg·L-1 methylene blue was chosen as the target to be degraded. The SOF is made up of quartz core with a silicon cladding, which can emit light through side surface more uniformly and transmit light for longer distance to avoid attenuation of light by liquid medium. The filament lamp was chosen as visible light source. Different reaction conditions, such as the presence of optical fiber or not, the quantity of SOF, light irradiation intensity were tested by measuring the methylene blue degradation of methylene blue. The results show that suitable reaction conditions were 1.167 g·L-1 Ag + /TiO 2 with 7% (by mass) of Ag + doped in TiO 2 , and 500 roots of SOF (30 cm length in solution). The photocatalytic degradation efficiency under 300W lamp irradiation for 8h was about 97%. And the photocatalytic degradation efficiency of methylene blue degradation was proportional to SOF quantity, light irradiation intensity and catalytic dosage within a certain range. Compared with general UV and visible light SOFs could save a huge amount of energy and cost, in the potential applications in dealing with organic pollutants on a large scale.     

离子液体催化的芳烃氯甲基化反应

Ionic liquids have been used as catalysts for Blanc reaction of toluene. The effects of reaction temperature, reaction time and dosage of the ionic liquid catalyst have been investigated, and the catalytic performance of different ionic liquid catalysts for toluene chloromethylation was also studied. The reaction was found to proceed under mild conditions with excellent conversion （up to 90%） in the absence of Lewis acids. The ionic liquids could be recycled and reused without loss of their catalytic activities.     

固体超强酸催化剂SO2-4/TiO2-MoO3的制备及其催化合成缩醛（酮）

SO4^2-/TiO2-MoO3, a novel solid superacid, has been prepared and its catalytic activity at different synthetic conditions was examined with esterification of n-butanoic acid and n-butyl alcohol as probing reaction.The optimum conditions were also found, that is, the mass ratio of MoO3 used in the compound is 25%, the calcination temperature 450℃, and the soaked consistency of H2SO4 is 0.5mol.L^-1. Then it was applied in the catalytic synthesis of six similar important ketals and acetals as catalyst and revealed high catalytic activity. Under the condition that the molar ratio of aldehyde/ketone to glycol was 1:1.5, the mass ratio of the catalyst to the reactants was 0.5% and the reaction time 1.0 h, the yield of ketals and acetals reached up to 63.2%. The catalyst can be easily recovered and reused.     

Heterogeneous Photooxidation of Phenol by Catalytic Membranes

In this work the heterogenization in polymeric membranes of decatungstate, a photocatalyst for oxidation reactions, was reported. Solid state characterization techniques confirmed that the catalyst structure was preserved within the polymeric membranes. The catalytic membranes were successfully applied in the aerobic photo-oxidation of phenol, one of the main organic pollutants in wastewater, providing stable and recyclable photocatalytic systems. The dependence of the phenol degradation rate by the catalyst loading and transmembrane pressure was shown. By comparison with homogeneous reaction, the catalyst heterogenised in membrane appears to be more efficient concerning the rate of phenol photodegradation and mineralization.     

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

Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR     

琥珀酸酯为内给电子体的新型MgCl2载体催化剂用于丙烯聚合

A novel MgCl2-supported Ziegler-Natta catalyst containing diethyl diisopropylsuccinate donor was prepared and propylene polymerizations with the combination of such catalyst and four external donors were investigated in detail. The catalyst was compared with a commercial one with phthalate as internal donor in terms of catalytic activity, hydrogen sensitivity and stereospecificity in propylene polymerization. The molecular weight, molecular weight distribution and microstructure of the produced polypropylenes were compared also. It was found that the novel catalyst containing succinate internal donor showed higher activity and higher stereospecificity than those with phthalate as internal donor. Consequently, polypropylenes obtained by the succinate-based catalyst showed high molecular weight, high melting temperature, high isotactic index and broad molecular weight distribution than those obtained with the commercial catalyst.     

［(MoO2)(acac)2］/t-BuOOH/H3PO4催化氧化体系对稠油中重组分的降解作用

针对稠油的重组分，探讨了催化氧化稠油降解反应体系中稠油黏度、平均分子量随反应时间、催化剂及氧化降解体系的变化规律.研究了各种条件下油层矿物在反应中的作用.实验结果表明，［(MoO₂)(acac)₂］催化剂对稠油的氧化降黏是非常有效的，其催化降解反应与氧化剂、氢质子供体以及油层矿物有关.在［(MoO₂)(acac)₂］/t-BuOOH/H₃PO₄/油层矿物体系中，稠油沥青质降解率达到81%，稠油黏度由原始的117.2 Pa·s下降到55.8 Pa·s，下降率为52.4%，平均相对分子质量下降了100.TLC-FID分析证明，稠油中的沥青质减少主要生成胶质、芳烃和饱和烃，这种理化性质的改变促进了稠油体系的稳定，对稠油开采、运输以及后处理工艺将起到推动作用.     

四苯硼二烷基咪唑盐离子液体的合成及其电导性能

近十几年来,离子液体由于其显著的化学、物理特性以及作为一种环境友好的高效催化剂、良好的有机反应溶剂以及在分离及电化学等方面的应用,成为国内外学者研究的热点．在已报道的离子液体的组成中,阳离子主要是含有取代基团的咪唑、吡啶、喹啉、异喹啉等含氮有机杂环,     

固定化Bronsted酸性离子液体催化酯化反应

设计合成了1-甲基-3-丁烷磺酸咪唑硫酸氢盐（［（n-Bu-SO₃H）MIm］［HSO₄］）、1-甲基-3-丁烷磺酸咪唑对甲苯磺酸盐（［（n-Bu-SO₃H）MIm］［p-CH₃C₆H₄SO₃］）和硫酸三乙胺（［Et₃NH］［HSO₄］）3种Bronsted酸性离子液体,考察了其催化正己酸与乙醇酯化反应的活性,分别采用浸渍法和溶胶-凝胶法将活性最佳的离子液体［（n-Bu-SO₃H）MIm］［HSO₄］固定在硅胶上,对固定化离子液体催化正己酸与乙醇酯化反应的性能及重复使用性能进行了比较,并采用¹H NMR、元素分析和FTIR等方法对其进行了表征。研究结果表明：采用浸渍法A、浸渍法B和溶胶-凝胶法固定的离子液体的负载量（质量分数）分别为15.5 %、20.5 %和40.5 %,催化正己酸与乙醇酯化反应所得正己酸乙酯的产率分别为75.3%、92.6%和92.6%。但浸渍法制备的固定化离子液体不稳定,重复使用4次（浸渍法A）和8次（浸渍法B）后离子液体负载量分别下降到3.0 %和7.0 %,正己酸乙酯产率分别降为24.2%和64.5%;而采用溶胶-凝胶法制备的固定化离子液体重复使用10次后,离子液体的负载量为39.0%,流失很少,正己酸乙酯产率依然高达92.7%。将溶胶-凝胶法制备的固定化离子液体进一步应用于其他脂肪酸与乙醇的酯化反应,乙酯产率均在90.0%左右,表明采用溶胶-凝胶法是制备固定化离子液体催化剂的有效方法。     

Fenton试剂对垃圾渗滤液中腐殖质的氧化/混凝作用

采用Fenton试剂处理反渗透浓缩垃圾渗滤液,通过COD,TOC,UV254以及COD/TOC等表征手段考察氧化/混凝作用对COD和腐殖质去除效果的影响。结果表明,Fenton试剂对浓缩渗滤液中腐殖质去除（11.9 % ~ 89.5 %）高于总COD去除（9.6 % ~ 75.2 %）;渗滤液中腐殖质降解和COD去除具有较好的相关性。混凝作用（CODcoag,HScoag）受氧化作用（CODoxid,HSoxid）的影响并与之相反,氧化作用越大,混凝作用越小。(COD/TOC)oxid变化表明,在[H₂O₂]>80 mmol.L^-1,pH=2.0~4.0, [Fe ²⁺ ]=40~160 mmol.L^-1,反应时间2 h的实验条件下,渗滤液中有完全氧化过程发生,同时(COD/TOC)coag的变化说明经混凝作用去除的有机物氧化态高于其它实验区间。     

蒽的电化学加氢

在隔离式电解槽中,以制备的泡沫Pb为阴极,Pt丝为对电极,饱和甘汞电极（SCE）为参比电极,研究了不同电解体系的伏安曲线和蒽的阴极电化学加氢行为.实验发现：在已研究的体系中,蒽阴极电解加氢为二氢蒽,其中CH₃CN+EtOH+H₂O+Bu₄NBr是加氢效果较好的电解体系.进一步研究CH₃CN+EtOH+H₂O+Bu4NBr电解体系中H₂O浓度、溶剂组成和支持电解质Bu₄NBr的浓度以及温度等因素对蒽电解催化加氢效果的影响,结果表明较理想的电解体系组成为：［H₂O］＝5.5mol•L^-1,［CH₃CN］/［EtOH］＝2/1(v/v),［Bu₄NBr］＝0.50mol•L^-1,温度为35℃,在该条件下,电解反应6 h,二氢蒽的产率可达91.37％.     

用NRTL方程计算含离子液体体系的汽液平衡

离子液体作为环境友好溶剂在反应和分离过程中具有良好的应用前景,含离子液体体系汽液平衡的计算及模型化研究具有重要的理论和实际意义.采用非电解质溶液NRTL方程表示溶液的非理想性,关联了［bmim］［PF₆］H₂O及［C₈mim］［PF₆］H₂O二元体系的等温汽液平衡,关联误差在2%之内;预测了这些体系在其他温度下的汽液平衡,预测的总平均误差均在5%之内.通过关联不同温度下有机物在离子液体C₈H₁₄S₂O₄F₆N₃和C₉H₁₆S₂O₄F₆N₃中的无限稀释活度因子的实验数据,得到了有关NRTL方程的二元作用参数,在此基础上预测了离子液体对二元共沸体系汽液平衡的影响.结果表明,含离子液体体系的汽液平衡可以采用传统的非电解质溶液模型如NRTL方程来描述,离子液体的“盐效应”可以显著改善组分的相对挥发度甚至消除共沸现象.     

氨基酸离子液体-MDEA混合水溶液的CO2吸收性能

为改善N-甲基二乙醇胺(MDEA)水溶液对CO₂气体的吸收性能,选择了四甲基铵甘氨酸(［N₁₁₁₁］［Gly］)、四乙基铵甘氨酸(［N₂₂₂₂］［Gly］)、四甲基铵赖氨酸(［N₁₁₁₁］［Lys］)、四乙基铵赖氨酸(［N₂₂₂₂］［Lys］)4种功能性离子液体作为活化剂与其复配组成新型CO₂吸收剂。用恒定容积法考察了总质量分数为30%的混合溶液吸收CO₂的性能,分析了离子液体在水溶液中与MDEA通过质子传递相互促进吸收CO₂的机理。实验结果显示离子液体能够显著提高MDEA水溶液吸收CO₂的速率,且吸收速率随着添加量的增加而提高。在本文所用的几种混合吸收剂中,阴离子为赖氨酸的离子液体混合吸收剂具有较高的吸收负荷;而［N₁₁₁₁］［Gly］-MDEA混合溶液对CO₂的初期吸收速率最快,同时［N_1111^］［Gly］-MDEA混合吸收剂的再生效率高于其他离子液体混合吸收剂,达到98%。     

酸性离子液体作催化剂的硝基苯加氢合成对氨基苯酚

针对硝基苯催化加氢合成对氨基苯酚(PAP)的过程,提出了Pt/SiO2和新型季铵型Brφnsted酸性离子液体N,N,N-三甲基-N-磺丁基硫酸氢铵(［HSO₃-b-N(CH₃)₃］HSO₄)构成的双功能催化体系。考察了离子液体浓度、Pt/SiO₂用量及操作条件对对氨基苯酚收率和选择性的影响。并与硫酸体系进行了对比。在85℃、4 h、0.4 MPa条件下,硝基苯转化率96.6%,对氨基苯酚的选择性为81.4%,优于Pt/SiO₂和硫酸溶液体系。可能的原因是,离子液体增加了硝基苯溶解度,并且抑制了中间产物苯基羟胺的深度加氢。反应后用减压过滤可分离出Pt/SiO₂催化剂;滤液经由萃取、减压蒸馏和结晶析出PAP。结果证明,该双功能催化体系重复使用3次,PAP收率没有明显的下降。     

酸性离子液体［HSO3-bpy］CF3SO3催化合成MDC

制备了一系列磺酸吡啶功能化酸性离子液体(ILs),采用Hammett指示剂与紫外联用法测定了其酸强度。考察了各酸性离子液体在苯氨基甲酸甲酯(MPC)与甲醛缩合制备二苯甲烷二氨基甲酸甲酯(MDC)反应中的催化活性。结果表明,离子液体的酸强度与其催化活性关联较好;［HSO₃-bpy］CF₃SO₃酸强度最高,催化活性也最好。以［HSO₃-bpy］CF₃SO₃为催化剂兼溶剂,优化了MDC合成反应条件。在反应温度70℃,反应时间60 min,MPC与甲醛的摩尔比为12,离子液体与MPC的质量比为4的条件下,MDC产率最高可达91.5％。用水处理反应液,通过减压蒸馏后的离子液体可以循环使用5次以上。     

离子液体催化合成丙交酯

丙交酯是合成可降解材料聚乳酸的重要中间体。以D、L-乳酸为原料,在离子液体催化剂存在下脱水环化合成丙交酯,研究了反应过程中离子液体的种类及用量等因素对丙交酯产率的影响,粗产品经重结晶纯化得到高纯度D、L-丙交酯,通过熔点、红外光谱和紫外光谱对产品进行了表征;实验表明,以离子液体为催化剂制备丙交酯具有可行性,体系粘度降低,反应条件温和,有利于丙交酯的生成;确定了[NH(C₂H₅)₃][HSO₄]为催化剂时的适宜工艺条件为催化剂用量5 wt%,缩聚温度110～140℃,解聚温度190～250℃。