用微反应器实现可见光驱动的不对称氧化连续化反应

将可见光催化、不对称合成、分子氧氧化和连续化集成,创新性地用玻璃微通道反应器实现可见光活化分子氧氧化的β-酮酸酯类化合物的不对称α-羟基化反应的连续工艺。用金鸡纳碱衍生的相转移有机催化剂在气-液-液多相体系内实现可见光催化,分子氧不对称氧化连续反应。在心形微通道反应器内,1-茚酮-2-甲酸金刚酯底物完全氧化为(S)-2-羟基-1-茚酮-2-甲酸金刚酯,产物收率95%,对映选择性87.0%。与间歇反应相比,采用微反应器的连续反应在保持产物高立体选择性基础上将30 min反应停留时间缩短至1.08 min。该方法具有快速、低能耗、连续、高效等优势,具有良好的工业化前景。     

Selective conversion of allyl alcohol to oxygenates and hydrocarbons using ion exchanged zeolite Y

The reaction of allyl alcohol using zeolite Y as catalyst has been investigated and it is shown that it can be converted into a range of products, including hydrocarbons, acrolein and diallyl ether. Control of product selectivity can be achieved by careful selection and manipulation of the charge balancing cation, a series of catalysts can be prepared which, for the conversion of allyl alcohol, lead almost exclusively to the initial formation of either (a) C₂-C₆ hydrocarbons and coke (H-NaY), (b) acrolein (H-CsY), (c) propene (Li-NaY) or (d) diallyl ether (Cs-NaY). The effects of addition of H₂ and H₂O to the reactant are described and discussed with respect to the reaction mechanism and the reaction of potential intermediates (2-propanol and propene oxide) is also described. Mechanisms of formation of the major products are proposed that involve the concerted action of Brønsted acid and basic sites within the zeolite. In particular, since the addition of H₂O does not affect the product distribution, it is considered that the mechanism of hydrocarbon formation does not involve the allyl cation as an intermediate.     

丙烯氧气氧化制环氧丙烷工艺开发进展

以分子氧为氧源的丙烯环氧化反应是近年来发展起来的一种清洁型环氧丙烷合成技术。综述了丙烯氧气氧化工艺的开发背景、开发进展及其经济性。丙烯与O₂氧化工艺以及丙烯与O₂、H₂氧化工艺因反应过程和反应机理不同而采用相异的催化剂和工艺条件,虽然丙烯氧气氧化工艺存在产率低、生产成本高的缺点,但作为具有最佳原子经济性和较低投资费用的新工艺路线,具有工业化应用前景。     

丙烯氧化制环氧丙烷研究进展

环氧丙烷 (PO)是重要的有机化工原料和中间体 ,目前工业采用氯醇法和间接氧化法生产。这两种方法均存在严重缺陷 ,有待于改进。本文主要介绍丙烯直接氧化法制取PO的近期进展 ,指出了丙烯直接氧化法研究的难点和今后研究的方向。     

Multiplicity in the partial oxidation of propylene over a copper-molybdena catalyst

Measurement of rates of formation of acrolein and acetaldehyde in the partial oxidation of propylene over a copper molybdate catalyst were made under steady-state and transient modes. These measurements disclosed a rate of product formation multiplicity apparently attributable to the oxidation state of the catalyst and not to surface phenomena usually thought to be the source of hysteresis in catalytic systems.     

Recent Developments in Selective Catalytic Epoxidations with H2O2

In this review the state-of-the-art of catalytic processes known today for selective epoxidations using aqueous H₂O₂ as the oxidant is presented. Recent achievements from our laboratories on the development of catalysts for epoxidations with H₂O₂ are given as well. For all systems their viability for application in green catalytic processes is evaluated, based on selectivity of the reaction, turnover frequency, substrate scope and solvent needed.     

Selective reduction of nitric oxide by methane on H-form zeolite catalysts in oxygen-rich atmosphere

Selective reduction of NO by CH₄ in the presence of excess oxygen was investigated using H-form zeolite catalysts. H-ZSM-5, H-ferrierite, and H-mordenite showed high catalytic activity and selectivity. On the contrary, H-USY and Al₂O₃ were not effective for this reaction. Both NO-CH4 and O₂-CH₄ reaction hardly proceeded on H-ZSM-5. Higher NO_x conversion was obtained in the NO₂-O₂-CH₄ and NO₂-CH₄ systems than in the NO-O₂-CH₄ system under high GHSV condition. It seemed that NO₂ plays an important role for selective reduction of NO by CH₄ on H-form zeolites.     

The kinetics of the oxidation of propylene over a bismuth molybdate catalyst

Using statistical design procedures an initial-rate study of the oxidation of propylene over a silica-supported bismuth molybdate catalyst was carried out using a differential-bed reactor over the following range of conditions: temperatures from 350 to 390°C, oxygen and propylene concentrations from 1.0 to 8.0 mmol/L. Among the models considered a Redox Steady-State Model (with half-order oxygen concentration) involving oxygen adsorption and reaction with propylene from the gas phase was found to provide the best fit to the data.     

萃取法测定氯丙烯氧化液油相中双氧水含量

建立了氯丙烯氧化液油相中双氧水含量的测定方法。考察了硫酸溶液的用量、碘化钾溶液的用量及萃取后静置时间等条件对双氧水含量分析的影响。结果表明,最佳分析条件为样品用水萃取后,依次加入硫酸溶液、碘化钾溶液、4滴钼酸铵溶液,用硫代硫酸钠标准溶液滴至近终点。该方法准确、快速、灵敏,测定的相对标准偏差为0.69%~1.58%,回收率为91.7%~102%。     

氧化钼改性催化剂制备及其丙烯氧化性能

氧化钼改性催化剂,研究了氧化钼的加入量和制备温度对催化剂性能的影响,考察了反应工艺条件对催化剂反应性能的影响。实验结果表明,掺杂4%氧化钼改性可以显著提高催化剂的选择性,尤其钼酸铵在400℃焙烧而制得的氧化钼效果最佳,氧化碳收率由原来的3.8%降至3.0%,同时对反应工艺条件的变化具有较强的适应性,尤其提高了对温度和负荷的适应能力,在近20℃的温度范围和±20%的负荷范围内表现出了良好的选择性。     

负载钌的HMS催化剂催化氧化醇

引言 在有机中间体的研究和制备中,均相催化剂应用最为广泛[1].虽然均相催化剂活性高,但由于存在反应体系复杂、稳定性较差、催化剂成本较高、难以与反应体系分离、回收反复使用困难等缺点,使得借助于固相材料为催化剂已成为绿色化学研究中追求资源节约、环境友好、条件温和和原子经济的一个重要研究方向,是实现清洁生产的重要技术基础[2].     

Sequential statistical design strategy in a kinetic study of propylene oxidation

A sequential design strategy was used to direct an experimental kinetic study of propylene oxidation over bismuth molybdate. Two statistical criteria were used to design experiments. The first is a joint criterion for the dual problem of model discrimination and parameter estimation which was proposed by Hill et al. (1968), but which to the best of our knowledge has not been tested in an experimental program. Using this joint criterion design, it was demonstrated that both the objectives of model discrimination and precise parameter estimation were effectively accomplished. After model discrimination had been achieved, a design strategy for further improvement in parameter precision was found, as expected, to be effective for that purpose.     

光照及需氧条件下Al2O3-AlBrx催化醇的选择性氧化反应

以脱脂棉为模板制备了多孔管状结构的Al2O3材料,用不同浓度的氢溴酸对多孔管状结构的Al2O3材料进行化学剪裁,制备了活性量可控,比表面积可调,不同形貌的负载型催化剂Al2O3-AlBr x。采用电场发射扫描电镜(SEM)和X射线衍射仪(XRD)对催化剂进行了表征。结果表明,该催化剂较好地复制了棉纤维的宏观和微观结构,呈现出明显的生物形貌特征。在光照条件下以空气为氧化剂的醇的选择性氧化反应中,发现催化剂Al2O3-AlBr x-3可以高选择性地将醇氧化为相应的醛、酮或酸,并对反应机理进行了探讨。该催化剂循环使用3次仍保持较高的催化活性。     

Selective liquid-phase oxidation of toluene with molecular oxygen catalyzed by Mn-TiO2 under solvent-free conditions

In this paper, we reported the preparation, characterization, and catalytic performance of TiO₂ doped with Mn for the selective oxidation of toluene to benzyl alcohol and benzaldehyde without any solvent. The structure of the catalyst was determined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption–desorption analysis (Brunauer–Emmet–Teller [BET]), scanning electron microscope (SEM), transmission electron microscope (TEM), and mapping. The results demonstrated that the catalytic properties of Mn-TiO₂ were higher than those of pure Mn₃O₄ and TiO₂. The effects of reaction temperature, reaction time, oxygen pressure, and the amount of catalyst were studied. Under the optimal conditions, Mn-TiO₂ could afford 6.4% toluene conversion at a combined benzyl alcohol/benzaldehyde selectivity of 58.6%. Moreover, the catalyst can be repeated in the experiment for five times without significant loss of activity.     

Alkane oxidation on isolated Cu2+ ions in zeolitic matrix: a relation between catalytic activity and Cu2+-site local topography

Catalytic ethane oxidation, with O₂, using H-ZSM-5 and H-mordenite containing different discrete types of isolated Cu(II) cations was studied. An ESR spectroscopic study was carried out on copper ion coordination in zeolites. It was shown that the intrinsic activity of Cu(II) ion depends strongly on the Cu²⁺-site local topography. Covalent-bonded Cu(II) cations in the most coordinatively unsaturated square-planar coordination in H-ZSM-5 demonstrated the highest activity in C₂H₆ complete oxidation.     

V-MCM-41催化环己烯环氧化性能

采用水热法合成了V-MCM-41,并用ICP-AES、FTIR、DRS-UV-Vis、XRD、BET等技术对其进行了表征,发现只有部分V进入分子筛,所合成的V-MCM-41具有较高的结晶度,并且其结晶度随晶化液中V/Si摩尔比的增大而升高。V-MCM-41催化环己烯/H₂O₂氧化反应结果表明,当V-MCM-41中V含量大于1.10%（摩尔分数）时,骨架V-O-V物种在催化环己烯氧化反应的同时,也可加速H₂O₂的分解;乙腈是该反应体系的最佳溶剂,最佳反应温度为70℃。最佳反应结果表明,环己烯的单程转化率和H₂O₂有效利用率可分别达到23.91%和95.4%。     

ZSM-5分子筛在MTP反应中的催化性能

合成了3种不同晶粒尺寸的ZSM-5分子筛,并制得MTP催化剂,对ZSM-5分子筛催化剂在MTP反应中的性能进行系统研究。采用XRD、SEM、N2物理吸附和TGA等对ZSM-5分子筛催化剂进行表征,发现小晶粒的ZSM-5分子筛具有良好的抗积炭性能,在MTP反应中具有较高的稳定性。采用小晶粒分子筛制成的催化剂,考察反应工艺条件对催化剂催化性能的影响,结果表明,丙烯选择性随反应温度和空速提高而增加,降低反应压力和提高水醇质量比也有利于提高丙烯选择性,为调整MTP工艺的产物分布和优化反应工艺条件提供了技术依据。     

Ultrafine tuning of the pore size in zeolite A for efficient propyne removal from propylene

The removal of trace propyne (C3H4) from propyne/propylene (C3H4/C3H6) mixtures is a technical and challenging task during the production of polymer-grade propylene in view of their very similar size and physical properties.While some progress has been made,it is still very challenging to use some highly stable and commercially available porous materials via an energy-efficient adsorptive separation process.Herein,we report the ultrafine tuning of the pore apertures in type-A zeolites for the highly effi-cient removal of trace amounts of C3H4 from C3H4/C3H6 mixtures.The resulting ion-exchanged zeolite 5A exhibits a large C3H4 adsorption capacity (2.3 mmol g-1 under 10-4 MPa) and high C3H4/C3H6 selectivity at room temperature,which were mainly attributed to the ultrafine-tuned pore size that selectively blocks C3H6 molecules,while maintaining the strong adsorption of C3H4 at low pressure region.High pur-ity of C3H6 (＞99.9999％) can be directly obtained on this material under ambient conditions,as demon-strated by the experimental breakthrough curves obtained for both 1/99 and 0.1/99.9 (V/V) C3H4/C3H6 mixtures.     

ZSM-35分子筛的酸改性及其用于丙烯水合制异丙醇反应的性能

采用水热合成法制备Na-ZSM-35分子筛。用不同浓度NH_4NO_3溶液对ZSM-35分子筛进行铵交换,不同焙烧温度下进行焙烧处理,制成H-ZSM-35分子筛。采用XRD、SEM、FT-IR和NH3-TPD对酸改性ZSM-35分子筛催化剂进行表征,并用于丙烯水合反应,考察其催化性能。结果表明,交换液浓度0.4 mol·L-1和450℃焙烧处理的ZSM-35分子筛催化剂的B酸中心最多,丙烯水合制异丙醇催化性能最佳。在丙烯水合制异丙醇反应中,反应产物异丙醇物质的量分数为15.96%,选择性为98.52%。