醇还原胺化反应催化剂研究进展

醇还原胺化反应是胺合成最有效、最有应用潜力的方法之一,而催化剂是还原胺化反应的关键。本文详细阐述了Ru、Ir、Pd、Cu、非金属等均相催化剂和Co、Ni、Ru、Pd等非均相催化剂在醇还原胺化反应中的研究进展,介绍了不同催化体系的催化性能和反应规律、应用特点和局限性。指出了均相催化体系的回收使用仍然是阻碍其应用的难题,研究重点应集中在高效、廉价催化体系开发、拓展应用范围和分离回收研究;非均相反应催化剂的专用性强,性能难以满足工业应用需求,加强微观结构及反应机理、高性能催化剂、高压体系中流场状态与过程研究以及提高活性、选择性和稳定性是未来的研究重点。     

A DUAL-CATALYST BED CONCEPT FOR INDUSTRIAL METHANOL SYNTHESIS

The present work investigates a dual-catalyst bed concept for industrial methanol synthesis. A system with two catalyst beds instead of a single catalyst bed is developed for methanol synthesis. In the first catalyst bed, the synthesis gas is partly converted to methanol in a conventional water-cooled Lurgi type reactor. This bed functions at a higher than normal operating temperature and at high yield. In the second bed, the reaction heat is used to preheat the feed gas to the first bed. The continuously reduced temperature in this bed provides increasing thermodynamic equilibrium potential. In this bed, the reaction rate is much lower and, consequently, so is the amount of reaction heat. This feature results in milder temperature profiles in the second bed because less heat is liberated than in the first bed. In this way the catalysts are exposed to less extreme temperatures and catalyst deactivation via sintering is circumvented. This system results in outstanding technical features due to the extremely favorable temperature profiles over the catalyst beds. In this work, a one-dimensional quasi-steady plug flow model is used to analyze and compare the performance of dual-bed and conventional single-bed reactors. The results of this work show that the dual-catalyst bed system can be operated with higher conversion and longer catalyst life time.     

A DUAL-CATALYST BED CONCEPT FOR INDUSTRIAL METHANOL SYNTHESIS

The present work investigates a dual-catalyst bed concept for industrial methanol synthesis. A system with two catalyst beds instead of a single catalyst bed is developed for methanol synthesis. In the first catalyst bed, the synthesis gas is partly converted to methanol in a conventional water-cooled Lurgi type reactor. This bed functions at a higher than normal operating temperature and at high yield. In the second bed, the reaction heat is used to preheat the feed gas to the first bed. The continuously reduced temperature in this bed provides increasing thermodynamic equilibrium potential. In this bed, the reaction rate is much lower and, consequently, so is the amount of reaction heat. This feature results in milder temperature profiles in the second bed because less heat is liberated than in the first bed. In this way the catalysts are exposed to less extreme temperatures and catalyst deactivation via sintering is circumvented. This system results in outstanding technical features due to the extremely favorable temperature profiles over the catalyst beds. In this work, a one-dimensional quasi-steady plug flow model is used to analyze and compare the performance of dual-bed and conventional single-bed reactors. The results of this work show that the dual-catalyst bed system can be operated with higher conversion and longer catalyst life time.     

苯加氢催化剂研究进展

介绍了苯加氢催化剂的分类,综述了均相催化剂、多相催化剂和离子液体催化剂的研究进展和生产工艺情况,其中多相催化剂可以对苯进行液相加氢和气相加氢。对苯加氢催化剂的评价和分析方法做了综述,讨论了苯加氢催化剂的加氢机理,对催化剂表面的吸附方式、反应速率的控制、苯和氢吸附的形式和分类问题做了说明。     

Temperature excursions in packed bed reactors with an axial variation of catalyst activity

Research appears to be growing on a type of structured reactor in which catalyst activity varies or in which different catalysts are arranged in the reactant flow direction. These reactors offer improved selectivity for some classes of complex reactions under non-isothermal conditions or when composition modulation is employed. Our examination of the rather extreme case of alternating layers of inert and active catalyst indicate that this reactor structure accentuates wrong-way temperature excursions after a step-change in temperature and amplifies periodic input temperature disturbances. Experiments used a near adiabatic 2.5 cm diameter reactor packed with 3 mm particles of 0.2 wt.% Pt/Al₂O₃. Inert layers were just the 3 mm alumina particles. Step and triangular wave inputs of constant amplitude were used. Temperature response in the bed was measured by an axial array of computer-monitored thermocouples. Measurements were compared to those made on a homogeneous mixture of catalyst and support under identical input conditions. Simulation studies show that accentuation of the temperature excursions depends on layer thickness. Even first-order reaction kinetics show accentuated temperature excursions when layered beds are used.     

工业有机废水深度处理：非均相Fenton催化剂研究进展

在众多水处理技术中,Fenton法能产生具有强氧化性的羟基自由基（·OH）,被认为是处理水中难生物降解有机污染物的有效方法。但是,传统的均相Fenton技术存在响应pH范围窄、催化剂活性组分不易回收分离、产生的铁泥会造成二次污染等问题,而非均相Fenton技术则可有效克服上述缺陷并具有良好工业应用前景。本文评述了Fenton反应,尤其是非均相Fenton技术近年来的发展情况,主要综述了其反应机理、反应活性的影响因素以及非均相Fenton催化剂研究现状。重点结合构-效关系、合成方法与反应机制探讨了国内外铁基与非铁基金属催化剂与碳基催化剂的发展进程以及其对于难降解有机物的处理效果。并总结了双氧水利用率、催化剂稳定性、反应的控速环节对非均相Fenton催化剂体系应用的影响与限制,为进一步改进催化剂的设计与制备方法提供了思路。     

Ce助剂对Ni/SiO2催化剂CO甲烷化活性的促进作用

采用等体积浸渍法制备了Ni/SiO2和Ni - Ce/SiO2催化剂,在连续流动微反装置上考察了催化剂的CO甲烷化催化活性.通过N2物理吸附、XRD、H2 - TPR、H2 - TPD、CO - TPD和H2 -TPSR手段对催化剂进行表征.结果表明,少量Ce助剂的添加促进了镍物种的分散和还原,使催化剂活性比表面积增加...     

High temperature stable magnesium oxide catalyst for catalytic combustion of methane: A comparison with manganesesubstituted barium hexaaluminate

The activity of magnesium oxide for catalytic combustion of methane was examined and the results were compared with experimental results for manganese-substituted barium hexaaluminate. The catalysts were calcined at temperatures up to 1 500°C and the effects of temperature, space velocity and calcination temperature were examined. The catalysts were also characterized with BET and XRD. For magnesium oxide calcined at 1 100°C the ignition temperature T_10% was decreased by 270°C compared to the non-catalyzed reaction. For the same catalyst T_50% was measured to be 795°C. The corresponding temperature for the hexaaluminate was 640°C. The difference between the two catalysts decreased after calcination at 1 500°C. For the magnesium oxide the influence of catalytically initiated homogeneous gas phase reactions was studied by varying the post catalytic volume of the reactor (and hence the residence time in the heated zone after the catalyst). It was shown that these catalytically initiated homogeneous gas phase reactions are significant for the methane conversion.     

颗粒尺度下混合催化剂床层中CO2加氢反应体系数值模拟

CO2的有效转化对于实现“双碳”目标具有重要意义。柱形颗粒比异形颗粒具有更优良的热导性和更小的颗粒表面积,因此,为获得更优异的床层性能,采用离散元方法(DEM)对异形颗粒混合堆积床内的CO2加氢反应体系进行颗粒尺度CFD模拟计算,探究不同堆积方式对床层多物理场分布、CO2转化率及CH4产率的影响。结果表明,催化剂内部存在扩散阻力,随着反应进行,颗粒内物质由分层分布渐变为均匀分布。随机混合床与常规床相比,随机混合床稳态前热点不易波动、稳态产率更高,而柱形床径向热场更均匀且热点更高。在四种规则混合床中,底部为4孔的两种催化剂床相较于底部为柱形的两种催化剂床,整体流场更均匀、高速区少、压降大、高温区占比大、稳态前热点不易波动;2层-底4孔催化剂床的稳态出口CO2转化率和CH4产率均最大;4层-底4孔催化剂床高温区占比较高,随着反应进行,高温区占比呈上升趋势,CO2转化率和CH4产率大幅下降。     

A two-stage catalyst bed concept for conversion of carbon dioxide into methanol

Conversion of CO₂ into methanol by catalytic hydrogenation has been recognized as one of the most promising processes for stabilizing the atmospheric CO₂ level, and furthermore the methanol produced could be used as fuel or basic chemical for satisfying the large demand world-wide. The present work investigates a two-stage catalyst bed concept for conversion of CO₂ to methanol. A system with two catalyst beds instead of one single catalyst bed is developed for conversion of CO₂ to methanol. In the first catalyst bed, the synthesis gas is partly converted to methanol in a conventional water-cooled reactor. This bed operates at higher than normal operating temperature and at high yield. In the second bed, the reaction heat is used to pre-heat the feed gas to the first bed. The continuously reduced temperature in this bed provides increasing thermodynamic equilibrium potential. In this bed, the reaction rate is much lower and, consequently, so is the amount of the reaction heat. This feature results in milder temperature profiles in the second bed because less heat is liberated compared to the first bed. In this way the catalysts are exposed to less extreme temperatures and, catalyst deactivation via sintering is circumvented. In this work, a one-dimensional dynamic plug flow dynamic is used to analyze and compare the performance of two-stage bed and conventional single bed reactors. The results of this work show that the two-stage catalyst bed system can be operated with higher conversion and longer catalyst life time.     

铜系低温选择性催化还原脱硝催化剂的研究进展

选择性催化还原（SCR）技术已广泛应用在燃煤电站烟气脱硝技术中,开发低温高活性、高抗中毒性能的催化剂体系已经成为国内外学者的研究重点。Cu系催化剂由于具有良好的脱硝性能及水热稳定性,得到了广泛的研究和关注。本文综述了近年来活性组分Cu负载在TiO₂、Al₂O₃、碳基材料和分子筛等材料上的研究进展;重点分析了Cu系催化剂低温SCR反应机理,主要包括Eley-Rideal （E-R）机理和Langmuir-Hinshelwood （L-H）机理,同时分析了SCR反应的两个必然过程：吸附（NH₃吸附和NO_x吸附）和反应;简要地介绍了Cu系催化剂的抗水抗硫中毒性能研究现状以及反应机理,同时介绍了碱金属中毒、飞灰和催化剂烧结对催化剂失活的影响,结合生命周期分析SCR脱硝系统还原剂氨和尿素对NO排放的影响。在此基础上展望了未来铜系催化剂的研究方向：采用新型方式对催化剂进行改性、进一步采用表征和模拟技术研究催化体系的反应机理、优化锅炉和催化剂设计减轻催化剂失活以及研究适用于其他还原剂条件的高选择性催化剂。     

低浓度甲烷流向变换催化燃烧反应研究

将制备的整体式催化剂应用于小型流向变换催化燃烧反应系统上,在甲烷初始浓度为0.2%,气量为30 L·min-1,换向半周期为10 min的工况条件下考察了不同预热温度对甲烷催化燃烧活性的影响以及反应系统床层轴向温度分布情况。结果表明,随着预热温度升高,甲烷催化燃烧活性呈现升高的趋势,同时,在催化剂中添加助剂元素Pt可以提高催化剂催化活性;催化剂的预热温度对反应器床层温度分布影响较大,特别是反应系统的催化段。     

Activity of solid catalysts for biodiesel production: A review

Heterogeneous catalysts are promising for the transesterification reaction of vegetable oils to produce biodiesel. Unlike homogeneous, heterogeneous catalysts are environmentally benign and could be operated in continuous processes. Moreover they can be reused and regenerated. However a high molar ratio of alcohol to oil, large amount of catalyst and high temperature and pressure are required when utilizing heterogeneous catalyst to produce biodiesel. In this paper, the catalytic activity of several solid base and acid catalysts, particularly metal oxides and supported metal oxides, was reviewed. Solid acid catalysts were able to do transesterification and esterification reactions simultaneously and convert oils with high amount of FFA (Free Fatty Acids). However, the reaction rate in the presence of solid base catalysts was faster. The catalyst efficiency depended on several factors such as specific surface area, pore size, pore volume and active site concentration.     

Asymmetric Homogeneous Hydrogenation in Flow using a Tube‐in‐Tube Reactor

In this update, the asymmetric homogeneous hydrogenation of a number of trisubstituted olefins utilizing the recently developed tube‐in‐tube gas‐liquid flow reactor is described. A number of chiral iridium‐ and rhodium‐based catalysts and other parameters such as pressure, solvent, temperature and catalyst loading were screened. The advantage of the flow set‐up for rapid screening and optimization of reaction parameters is illustrated. Furthermore, a comparative study using batch conditions aided in the optimization of the flow reaction set‐up. The set‐up was further modified to recycle the catalyst which prolonged catalytic activity.     

适用于丙烯二聚反应非均相催化剂的研究进展

丙烯二聚反应是生产4-甲基-1-戊烯、1-己烯等端碳烯烃的重要手段,其产物可作为特种高分子材料单体、汽油添加剂和化工有机中间体,关键技术在于高效催化剂的开发。非均相催化剂相比于均相催化剂因易回收、对环境污染小等优点受到了学者们的广泛关注。本文综述了丙烯二聚非均相催化剂的研究进展,依据固体碱催化剂与固体酸催化剂在丙烯二聚反应中不同的反应机理,比较了两者各自的优缺点。回顾了固体碱催化剂的发展历程及工业化应用,并以碱金属钾为例总结了反应机理。详细介绍了固体酸催化剂中的固体磷酸催化剂、分子筛催化剂和负载型过渡金属催化剂。针对固体碱催化剂制备条件苛刻等问题,提出了改善催化装置的新思路;针对固体酸催化剂选择性不足的劣势,指出了应该进一步完善机理,并合理设计酸性载体与过渡金属相结合的催化剂。     

Catalyst retention in continuous flow with supercritical carbon dioxide

This review discusses the retention of organometallic catalysts in continuous flow processes utilizing supercritical carbon dioxide. Due to its innovative properties, supercritical carbon dioxide offers interesting possibilities for process intensification. As a result of safety and cost considerations, processes that use supercritical carbon dioxide are preferably done in continuous flow, as they require a pressure upwards of 74 bar. Many of the reactions that benefit from the application of supercritical carbon dioxide also involve the use of a homogeneous catalyst however, requiring efforts to recycle the catalyst when these are applied in continuous flow. Alternatively, the catalyst may be retained in the reactor by modifying the process or catalyst, such as by catalyst immobilization, membrane separation, or biphasic processing exploiting the properties of supercritical carbon dioxide. Each of these methods is discussed, including their advantages and drawbacks. Also discussed are milli- and micro-flow processes and their possibilities for integrated catalyst retention and handling supercritical carbon dioxide.     

ZSM-5@t-ZrO2制备及其对甲硫醇催化合成影响机制

采用水热包覆法和物理共混法分别制备了ZSM-5@t-ZrO₂和ZSM-5/t-ZrO₂复合催化剂,并以ZSM-5和t-ZrO₂为对比参考,研究了不同结构催化剂的物化性质和催化性能。在此基础上,借助漫反射傅里叶变换红外光谱,考察了反应温度和预硫化操作对ZSM-5@t-ZrO₂复合催化剂上甲醇和硫化氢反应分子吸附转化的影响。结果表明,水热包覆环境修饰了ZSM-5@t-ZrO₂复合催化剂的物化性质,提升了甲醇硫醇化反应的催化性能和抗积碳积硫失活能力。在反应压力1 MPa、反应温度380 ℃、预硫化1 h、N₂流量100 mL/min的条件下,甲醇转化率、甲硫醇选择性及甲硫醇收率分别达到92.02%、90.56%和82.76%。硫化氢分子在ZSM-5@t-ZrO₂催化剂的碱位上吸附解离为巯基,进而攻击甲氧基,这是甲硫醇合成反应的速率控制步骤。380 ℃的反应温度和预硫化操作有助于构建形成匹配的甲氧基和巯基生成速率,在提高催化性能的同时还可有效降低积碳积硫形成速率。     

A novel reverse flow reactor coupling endothermic and exothermic reactions. Part I: comparison of reactor configurations for irreversible endothermic reactions

A new reactor concept is studied for highly endothermic heterogeneously catalysed gas phase reactions at high temperatures with rapid but reversible catalyst deactivation. The reactor concept aims to achieve an indirect coupling of energy necessary for endothermic reactions and energy released by exothermic reactions, without mixing of the endothermic and exothermic reactants, in closed-loop reverse flow operation. Periodic gas flow reversal incorporates regenerative heat exchange inside the reactor. The reactor concept is studied for the coupling between the non-oxidative propane dehydrogenation and methane combustion over a monolithic catalyst.Two different reactor configurations are considered: the sequential reactor configuration, where the endothermic and exothermic reactants are fed sequentially to the same catalyst bed acting as an energy repository and the simultaneous reactor configuration, where the endothermic and exothermic reactants are fed continuously to two different compartments directly exchanging energy. The dynamic reactor behaviour is studied by detailed simulation for both reactor configurations. Energy constraints, relating the endothermic and exothermic operating conditions, to achieve a cyclic steady state are discussed. Furthermore, it is indicated how the operating conditions should be matched in order to control the maximum temperature. Also, it is shown that for a single first order exothermic reaction the maximum dimensionless temperature in reverse flow reactors depends on a single dimensionless number. Finally, both reactor configurations are compared based on their operating conditions. It is shown that only in the sequential reactor configuration the endothermic inlet concentration can be optimised independently of the gas velocities at high throughput and maximum reaction coupling energy efficiency, by the choice of a proper switching scheme with inherently zero differential creep velocity and using the ratio of the cycle times.In this first part, both the propane dehydrogenation and the methane combustion have been considered as first order irreversible reactions. However, the propane dehydrogenation is an equilibrium reaction and the low exit temperatures resulting from the reverse flow concept entail considerable propane conversion losses. How this ‘back-conversion’ can be counteracted is discussed in part II Chemical Engineering Science, 57, (2002), 855-872.     

Development of a continuous process for the hydroformylation of long-chain olefins in aqueous multiphase systems

The challenging task of homogeneous catalysis is the efficient combination of reaction and catalyst recycling. In the hydroformylation of long-chain olefins generally cobalt-based catalysts are used, but in our investigation we used rhodium-based catalysts, because of their higher activity in comparison to cobalt catalysts. In hydroformylation reactions, the recycling of the expensive rhodium catalyst as well as the selectivity to linear aldehydes are very challenging. Multiphase systems offer the possibility to increase the interfacial area during reaction on the one hand and to separate the metal–ligand complexes easily from the organic product phase after reaction, to recycle the expensive catalyst for further reactions, on the other hand. Solubilisers such as surfactants or polar solvents can be used to formulate such a tuneable solvent system. Upon cooling of the reaction mixture, phase separation is achieved. Based on that combination of reaction and phase separation for catalyst recycling, a novel process concept was developed for the hydroformylation of long-chain olefins. In order to show the applicability of that concept in a continuous process a fully automated miniplant was designed.     

Iron oxide-based honeycomb catalysts for the dehydrogenation of ethylbenzene to styrene

Corning has recently developed a novel extrusion method to make bulk transition metal oxide honeycomb catalysts. One area of effort has been iron oxide-based catalysts for the dehydrogenation of ethylbenzene to styrene, a major chemical process that yields worldwide 20 MM tons/yr. In industry, the monomer is synthesized mostly in radial-flow fixed-bed reactors. Because of the high cross-sectional area for flow and shallow depth of the catalyst bed in these reactors, low reactor pressure gradients are maintained that favors the yield and selectivity for styrene formation. However, the radial-flow design has inherent detractions, including inefficient use of reactor volume and large temperature gradients that decrease catalyst service life. The overall economics of the process can be improved with parallel-channel honeycomb catalysts and axial flow reactors. The simple axial flow design of honeycomb catalysts provides low-pressure drop, while making more efficient use of reactor volume, with better heat and mass transfer characteristics compared to a conventional radial packed bed. An important part of this concept is the ability to fabricate a wide family of dehydrogenation catalyst compositions into honeycombs with the requisite chemical, physical, mechanical, and catalytic properties for industrial use. The ethylbenzene dehydrogenation (EBD) honeycomb catalysts developed by Corning have compositions similar to those commonly used in industry and are prepared with the same catalyst and promoter precursors and with similar treatments.

However, to enable extrusion of catalyst precursors into honeycomb shapes, especially at cell densities above 100 cell/in.², Corning’s process compensates for the high salt concentrations and the high pH of the batch material that would otherwise prevent or impede honeycomb extrusion. The improved rheological characteristics provide the necessary plasticity, lubricity, and resiliency for honeycomb extrusion with sufficient binder strength needed before calcination to the final product. Iron oxide-based honeycombs after calcination are strong and possess macroporosity and high surface area. In bench-scale testing, particular honeycomb catalyst compositions exhibited 60–76% ethylbenzene conversion with styrene selectivity of 95–91%, respectively, under conventional reaction conditions without apparent deactivation or loss of mechanical integrity.