Revealing the catalytic mechanism of an ionic liquid with an isotope exchange method

The alkylation mechanism catalyzed by an ionic liquid (as a Lewis acid) may be different from the traditional alkylation mechanism catalyzed by Br nsted acid,especially as their initiation steps are still not clear.In this paper,an isotope exchange method is used to investigate the catalytic mechanism of AlCl 3 /butyl-methyl-imidazolium chloride ionic liquid in the alkylation of benzene with 1-dodecene.The proposed catalytic mechanism was confirmed by analysis of ionic liquid before and after reaction and of the alkylation products of deuterated benzene (C 6 D 6) with 1-dodecene.The proposed mechanism consists of the equilibrium reaction between [Al 2 Cl 7 ] +H + and [AlHCl 3 ] + +[AlCl 4 ],in which the Br nsted acid [AlHCl 3 ] + is supplied by the reaction of 2-H on the imidazolium ring and [Al 2 Cl 7 ].The alkylation reaction is initiated by the Br nsted acid [AlHCl 3 ] + which reacts with 1-dodecene to form a carbonium ion,then the carbonium ion reacts with benzene to form an unstable σ complex,leading to the formation of 2-phenyldodecane.     

纳米MoS2在钢冷轧轧制液中的摩擦润滑性能研究

The nano-MoS2 particles were adopted to substitute for the extreme-pressure and anti-wear additives to the rolling fluid for steel strips.An optimal formulation and technical process for adding nano-MoS2 particles to the rolling fluid were obtained through orthogonal experiments with three factors at three levels.The tests have led to the following conclusions:(a) the nanoparticles should be added to a base oil with high saponification value;(b) the concentration of nanoparticles in rolling fluid should be equal to 0.6%;and (c) when the reaction time needed for surfactants (oleic acid,for example) to modify the nanoparticles was 40 min,the rolling fluid could have the best tribological properties.The lubricity of rolling fluid was verified by using a 4-high cold rolling test mill which showed that the rolling fluid with nano-MoS2 particles had the excellent lubricant performance to improve the surface quality of the steel strip remarkably.The mechanism of nano-MoS2 particles in the rolling process has been investigated by a series of characterization instruments,which have showed that,with its fullerene-like structure,the nano-MoS2 particles have self-lubricating properties and extra-low friction coefficient,and can easily form a protective film with low shear strength on the surface of friction pairs.     

A Study on Phase States of the Catalytic System of FeCl3-Al（i-Bu）3-pyridine

The catalyst FeCl3-Al(i-Bu)3-pyridine has a high catalytic activity for butadiene polymerization (Shen, et al., 1987; Xia, et al., 1991). However, the preparation mode of catalysts, including the ratio and the order of adding the components, and the aging time, has a considerable influence on the catalytic activity and on the relative molecular weight of polybutadiene. In the paper, the results of the electron microscope, super-filtration and Tyndall effect experiments show that the catalyst…     

ELUCIDATION OF HYDRODESULFURIZATION AND HYDROGENATION MECHANISMS USING RADIOISOTOPE TRACER METHODS

To meet the specification of sulfur and aromatic contents in diesel fuel, it is necessary for refiners to develop a new catalyst with high activity of hydrodesulfurization and hydrogenation. In the present study, the properties of noble metal catalysts for hydrodesulfurization and hydrogenation in the presence of sulfur compounds have been investigated. The hydrogenation activity of phenanthrene (PHE) on single noble metal and double noble metal catalysts-Pt/Al2O3, Pd/Al2O3 and Pd-Pt/Al2O3 in the presence of dibenzothiophene (DBT) was performed in a fixed bed flow reactor. The Pt based catalysts revealed the similar HDS activities and higher HYD activity compared with convertional Mo based catalysts. The maximum activity was obtained around 320℃ for both catalyst types. The Pt based catalysts produced perhydrophenanthrene as a major product at the maximum activity in the hydrogenation of PHE while the Mo based catalysts produced octahydrophenanthrene. A ^35S radioisotope pulse tracer method (^35S RPTM) was used to estimate the behavior of sulfur on the working catalysts and to clarity the differences between Pt and Mo based catalysts. Very little amount of labile sulfur was accumulated on the Pt and Pd catalysts in the HDS of [^35S]DBT (PtS0.25 or PdS0.25). This indicates that the mechanism of DBT HDS on noble metal catalysts is significantly different from that on conventional Mo based catalysts where Mo is present as MoS2 less than 60% of which can be labile in the case of Co-Mo/Al2O3. Another Ru-Cs/Al2O3 catalysts were also prepared and the behavior of sulfur on the working catalyst was compared with those of Mo based catalysts and Pt and Pd catalysts. The values of labile sulfur in the kIDS reaction for Ru-Cs catalysts approximately correspond to RS0.5-0.74. These amounts of labile sulfur are much higher than those for Pt and Pd catalysts. The result suggests that the oxidation state of Ru species is present between the oxidation states of Pt or Pd and Mo, and can change in the wide range during the HDS reaction, different from PtS0.25 (PdS0.25) and MoS2 which is unchangeable under the usual HDS conditions. From the approach of using [^35S]H2S it was found that the labile sulfur was hardly formed during the presulfiding procedure but was formed only during the actual HDS. This is also a unique character of Ru catalysts.     

ZSM-5/MAPO Composite Catalyst for Converting Methanol to Olefins in a Two-Stage Unit with a Dimethyl Ether Pre-Reactor

A ZSM-5/MAPO composite catalyst was prepared by adding ZSM-5 zeolite powder to a conventional molecular sieve synthesis system, followed by modification with NH_4H_2PO_4. The samples were characterized by XRD, SEM, IR, NH_3-TPD, and BET analyses. The catalytic property of the samples toward the methanol-to-olefin(MTO) reaction was evaluated in a connected in series two-stage unit equipped with a continuous flow(once-through) fixed-bed tubular reactor similar to an industrial reactor. The first reactor mainly converted methanol into dimethyl ether and water, followed by being subject to continuous reaction in the second reactor, in which DME was converted to hydrocarbons. The composites exhibited the typical framework topology of MFI, AEI and AFI, which represented the ZSM-5 zeolite, the molecular sieves AlPO-18 or SAPO-18, AlPO-5 or SAPO-5, respectively. The composites showed several advantages for optimizing the zeolite acidity, enhancing the mass transfer, and restraining the side reactions. Catalytic reaction results showed that the composites exhibited higher selectivity to light olefins(84.0%) and lower selectivity to C_2―C_4 alkanes and C_5~+ hydrocarbons than pure ZSM-5. Moreover, the composite zeolite loaded with 3% of P demonstrated improved catalytic activity and stability for the conversion of methanol to propylene, because the coking rate was obviously suppressed.     

Numerical Simulation of Particle Concentration in a Gas Cyclone Separator

The particle concentration inside a cyclone separator at different operation parameters was simulated with the FLUENT software. The Advanced Reynolds Stress Model (ARSM) was used in gas phase turbulence modeling. Stochastic Particle Tracking Model (SPTM) and the Particle-Source-In-Cell (PSIC) method were adopted for particles computing. The interaction between particles and the gas phase was also taken into account. The numerical simulation results were in agreement with the experimental data. The simulation revealed that an unsteady spiral dust strand appeared near the cyclone wall and a non-axi-symmetrical dust ring appeared in the annular space and under the cover plate of the cyclone. There were two regions in the radial particle concentration distribution, in which particle concentration was low in the inner region (r/R≤0.75) and increased greatly in the outer region (r/R>0.75). Large particles generally had higher concentration in the near-wall region and small particles had higher concentration in the inner swirling flow region. The axial distribution of particle concentration in the inner swirling flow (r/R≤0.3) region showed that there existed serious fine particle entrainment within the height of 0.5D above the dust discharge port and a short-cut flow at a distance of about 0.25D below the entrance of the vortex finder. The dimensionless concentration in the high-concentration region increased obviously in the upper part of the cyclone separation space when inlet particle loading was large. With increasing gas temperature, the particle separation ability of the cyclone was obviously weakened.     

Reactive Adsorption of Thiophene Using a NiZnO-Based Adsorbent

The thiophene removal ability of the synthesized NiZnO-based adsorbent was tested in a lab-scale fixed-bed system. The X-ray diffractometer (XRD) and the temperature-programmed reduction (H2-TPR) instrument were used to characterize the samples. The XRD and TPR results showed that there existed stronger synergetic effect between ZnO and NiO to form well-dispersed adsorbent particles when the Zn/Ni molar ratio in adsorbent was 0.4, and that the optimum temperature for reduction of the NiZnO-based adsorbent was approximately in the range of 350℃—400℃. In addition, the effects of reaction temperature, and reaction pressure on the reactive adsorption desulfurization tests were studied.     

Methanol and DME Co-production from CO2 hydrogenation over hybrid catalysts

Catalytic hydrogenation of CO2 into methanol and dimethyl ether was carried out over hybrid catalysts consisting of methanol-synthesis catalyst and zeolite. The methanol-synthesis catalyst, Cu/ZnO/Al2O3, was prepared by a co-precipitation method. Then it was physically mixed with HZSM-5 zeolite at weight ratios of 2：1, 1：1 and 1：2. The CO2 hydrogenation reaction was conducted in a fixed-bed microreactor at 250℃ and 40 bar in pre-mixed H2/CO2 feed with H2：CO2 molar ratios of 3：1 and 7：1. Products detected include methanol, dimethyl ether, carbon monoxide and water. Conversion of CO2 and yield of oxygenated products were influenced by the weight ratio of Cu/ZnO/Al2O3：HZSM-5 in the hybrid system and also the feed ratio. The Cu/ZnO/Al2O3： HZSM-5 hybrid at 1：1 resulted in methanol yield of 22.0% and was found to be an efficient hybrid catalyst for the CO2 hydrogenation reaction.     

Study on the Mechanisms for Baeyer-Villiger Oxidation of Cyclohexanone with Hydrogen Peroxide in Different Systems

The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing ε-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.: (1) the non-catalyzed reaction type, where the C=O of ketones is activated by H+, which is electrolytically dissociated from H2O2 and H2O, to improve the capability of C=O group for accepting the electron pairs; (2) the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with ·OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; (3) the Brnsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by Brnsted acid; (4) the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π*C=O orbital of cyclohexanone and HOMO of Sn-containing zeolites; and (5) the solid Lewis acid catalyzed H2O2 to form Me-OOH oxidative species by converting the highest occupied molecular orbital (HOMO) of Ti-OOH into a singly occupied molecular orbital (SOMO), making the O-O group highly electrophilic to attack the C=O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.     

Proximity of Problem-Based Learning(ABP)Methodology to Experimental Teaching in Organic Chemistry.IMINE Synthesis

Different imines were prepared.The reaction was carried out using different conditions,with aromatic aldehydes,aniline and with different energy sources.Yield,purity and experimental fusion point were calculated in each case,and they were compared to the ones found in literature.The importance of structural effects of aldehyde reacting with aniline was established as well as reaction conditions.The efficacy of the reaction can not be predicted,since each aldehyde has a different structure and therefore reacts differently.The main objective of this project is academic.A methodology to carry out a structured research(it is one of the levels of problem-based learning(ABP)),was implemented.Students work in pairs using Combinatorial Chemistry,and each pair does a different exercise on the same theoretical objective.Results from every team are discussed in a seminary where conclusions regarding which was the most efficient reaction are reached.     

FeCI3—AI（i—Bu）3—Phen催化剂的电导率

在25C加氢汽油介质中,将FeCI3-AI(i-Bu)3-Phen胶体催化剂的3组分分别以单、多组分按不同配比混合成非水体系,考察了它们的电导率与浓度的关系。结果表明,AI(i-Bu)3以缔合状态存在并解离成离子对,它与FeCI3的作用是胶粒的主要反应。Phen与Fe^2 络合有阻止Fe^2 被还原成更低价态（Fe^ ,Fe^0)的作用。适当过量的AI（i-Bu)3形成双电层,使催化剂胶粒稳定,同时将Fe^3 还原成Fe^2 。     

聚丁二烯基锂/三异丁基铝引发苯乙烯阻滞负离子聚合

以聚丁二烯基锂(PBLi)为引发剂、i-Bu3Al为调节剂、环己烷为溶剂,在70～120℃下引发苯乙烯聚合,研究了n(i-Bu3Al)∶n(PBLi)对阻滞苯乙烯聚合行为的影响;并用NMR方法对反应的聚合动力学进行了研究。实验结果表明,加入i-Bu3Al时体系的聚合反应速率降低,n(i-Bu3Al)∶n(PBLi)越大,聚合反应速率越慢,甚至反应完全停滞;当n(i-Bu3Al)∶n(PBLi)=1.0、反应温度由90℃升至120℃时,聚合反应速率大幅加快,1.5 h内苯乙烯转化率达到90%以上。当n(i-Bu3Al)∶n(PBLi)较小时,两者可能形成较高活性的1∶2络合体;当n(i-Bu3Al)∶n(PBLi)较大时可能形成低活性的1∶1络合体,且1∶2络合体自身及其与1∶1络合体之间均存在构型转换。     

稀土催化剂中混合烷基铝对丁二烯聚合的影响

研究了Al(i-Bu)2H和Al(i-Bu)2分别与Nd(naph)3,Al(i-Bu)2Cl组成烯土化剂，按不同配比组成混合烷基铝稀土催化体系引发丁二烯聚合的反应，结果表明混合铝中Al(i-Bu)2H,Al(i-Bu)3的配比对催化体系的聚合性及产物[η]值有重要影响，实验在5L三釜连续模式装置上进行了放大，制备的稀土顺丁橡胶与意大利Enichem公司生产的同门尼胶样结构及性能相当。     

磁化率和紫外-可见光谱法研究MoO_2Cl_2-Al(i-Bu)_2OPhCH_3体系合成1,2-聚丁二烯的催化性质

MoO_2Cl_2-Al(i-Bu)_2OPhCH_3体系的磁化率和紫外-可见光谱测定结果表明,Al-Mo两组份—接触立刻发生化学反应。Al/Mo(mol比)=0.23时,体系磁化率达到极大值,是Mo(V)存在的标志。其光谱吸收带分别是742nm和335nm。Al/Mo>1时,Mo(V)的光谱吸收带渐渐消失。Al/Mo≥2时,体系在室温下就显催化活性。     

Ni(naph)_2-Al(i-Bu)_3-BF_3·OEt_2-ROH体系催化丁二烯聚合的动力学研究

本文探讨了ROH增溶BF_3·OE_2的机理,研究了Ni(naph)_2—Al(i-Bu)_3-BF_3·OEt_2-ROH催化丁二烯聚合反应的动力学行为,考察了温度、催化剂浓度对聚合反应的影响:并且确立了聚合反应的动力学方程为: -d[Bd]/dt =kp·[C~*]·[Bd]=kpf[Ni]_0[Bd]并求得聚合反应的表观活化能Ea=20.6kcal/mol等其它动力学参数。     

硅桥联茂金属催化1-癸烯聚合的研究

用硅桥联茂金属催化体系rac-Me_2Si(1-Ind)_2ZrCl_2/Al(i-Bu)_3/[Me_2NHPh]~+[B(C_6F_5)_4]~-催化1-癸烯聚合,考察了茂金属浓度、Al/Zr摩尔比、B/Zr摩尔比、反应温度、反应时间对聚合产物性能的影响。结果表明:在Zr/1-癸烯摩尔比为4×10~(-5)、Al/Zr摩尔比为80、B/Zr摩尔比为1.2、反应温度为80℃、反应时间为1h的条件下,1-癸烯的转化率达到97.6%,运动黏度(100℃)为599.4mm~2/s,黏度指数为285,倾点为-26℃,数均相对分子质量为12 608,相对分子质量分布为1.86。同时结合聚合反应机理和催化剂微观构型,对比分析了硅桥联茂金属催化体系rac-Me_2Si(1-Ind)_2ZrCl_2/Al(i-Bu)_3/[Me_2NHPh]~+[B(C_6F_5)_4]~-与亚乙基桥联茂金属催化体系rac-Et(1-Ind)_2ZrCl_2/Al(i-Bu)_3/[Me_2NHPh]~+[B(C_6F_5)4]~-在催化1-癸烯聚合方面的不同表现,表明无论是从催化剂的活性还是从产物相对分子质量来看,硅桥联茂金属催化剂的性能明显优于亚乙基桥联催化剂。最后釆用全自动反应量热仪进行放大反应,得到此反应的聚合反应热为61.8kJ/mol。     

化学反应法MgCl_2载体高效钛催化剂的乙烯-丙烯共聚合

研制了化学反应法高效载体钛催化剂 ,主催化剂制备的加料顺序为MgCl2 、n -C4H9OH、i-Bu3Al、TiCl4,然后与i-Bu3Al组成高活性催化体系。用此催化剂进行乙丙共聚 ,常温常压下催化效率可达 190kg/g以上 ,聚合反应具有三个显著特征 :催化活性高 ,较钒体系提高 2 0倍以上 ;共聚反应催化效率大大高于乙烯、丙烯各自均聚的催化效率 ;丙烯在此催化体系下具有比其它催化体系更高的共聚活性。     

后过渡金属铁系催化剂与Et[Ind]_2ZrCl_2复配催化乙烯原位共聚中的“共单体效应”

研究了以{2-[2-MeC6H4N=C(Me)]2C5H3N}FeCl2为齐聚催化剂、以Et[Ind]2ZrCl2为共聚催化剂复配,在甲基铝氧烷作用下催化乙烯原位共聚的“共单体效应”。在n(Al)/n(Zr)、n(Al)/n(Fe)和n(Al)/n(Fe+Zr)分别为2000时,改变齐聚催化剂/共聚催化剂的配比,均观察到共单体效应。探讨了助催化剂用量、主催化剂用量和聚合温度对共单体效应的影响。助催化剂用量的增加使出现最佳活性点的n(Fe)/n(Zr)发生了前移,而主催化剂用量的增加使出现最佳活性点的n(Fe)/n(Zr)发生了后移。聚合温度的改变使共单体效应的变化规律发生了改变。     

NdCl_3·nTBP/MgCl_2-AlR_3催化体系合成丁二烯橡胶

探讨了以NdCl_3的磷酸三丁酯(TBP)溶液为主催化剂、烷基铝为助催化剂、MgCl_2为载体组成的Ziegler-Natta型催化体系引发丁二烯(Bd)聚合的某些规律。用AlEt_3作助催化剂,聚合物的顺1,4-结构含量仅为57％,反1,4-结构含量为42％;而以Al(i-Bu)_3作助催化剂,聚合物的顺1,4-结构含量为88％,反1,4-结构含量为11％。各种陈化体系中,以NdCl_3·nTBP/MgCl_2-Al(i-Bu)_3-Ip三元体系的催化活性最高,当Nd/Bd(摩尔比)为7×10~(-5)时,单体转化率达80％。低温聚合可获得高顺式、高分子量聚合物。