正丁烷选择氧化中吸附氧与晶格氧的作用

引　言丁烷选择氧化制顺酐是以廉价低碳烷烃作为原料的直接选择氧化反应 ,近年来已引起广泛关注并进行了较多的研究[1] .普遍认为 ,这是一个以复合氧化物VPO作为催化剂 ,晶格氧参与催化循环、按氧化还原机理进行的反应[2 ] .为了提高这一反应的选择性 ,杜邦公司按照序贯氧化 还原原理重新组织催化循环的思想 ,率先提出了双反应器循环流化床 (CFB)的专利 ,并进行了晶格氧正丁烷选择氧化制顺酐的技术开发 ,建立了大规模工业示范装置 ,显示了改善性能的潜力[3] .鉴于在空间上和在时间域内使催化循环各步骤分离进行这两类非定态操作在实质上…     

环氧乙烷合成银催化剂宏观动力学及失活分析

在工业生产的条件下用无梯度反应器研究了工业颗粒银催化剂上乙烯氧化合成环氧乙烷宏观动力学 ,得到了能反映该系统主副反应特性的双速率方程 .建立了二维非均相反应器模型 ,模拟并比较了工业生产操作数据 ,获得了该种催化剂的活性校正因子随使用时间变化的经验关联式和主副反应失活速率方程     

ACTIVITY AND SELECTIVITY VARIATIONS IN THE OXIDATIVE DEHYDROGENATION OF ETHANE OVER A MOLYBDENUM - VANADIUM - NIOBIUM MIXED OXIDE CATALYST

A single pellet reactor was used to investigate the activity and selectivity variations with time in the oxidative dehydrogenation of ethane with a mixed oxide catalyst having a composition of Mo_0.71V_0.2Nb_0.09. Experiments conducted at 450°C in the absence of oxygen showed rapid deactivation. In these experiments very high selectivities, reaching to unity, were observed at fractional conversions of 0.1 or less. An increase in conversion and a decrease in selectivity was observed with a decrease in catalyst porosity and also with an increase in pellet length, indicating the significance of diffusion time. This effect is found to be especially significant at the initial stages of reaction (fresh catalyst). In the absence of oxygen a large amount of CO was produced during the first couple of minutes of the reaction. On the other hand, in the presence of oxygen, the major side product is CO₂. It was also concluded that gas phase oxidation of ethane to CO₂ is not significant.     

EFFECTS OF PORE DIFFUSION ON THE SYNTHESIS OF METHANOL

The hierarchical model concept is applied for solving of the test-problem. Three levels of hierarchy are defined. On the first one the reaction rate at an inner point of a pore in the catalyst pellet is examined. On the 2-nd level, taking pore diffusion into account and introducing the so-called distortion factor, the mean reaction rate concerning a pellet is calculated. On the 3-rd level, the rate of reaction at an inner point of the reactor is given, and the parametric study of industrial reactor is carried out.     

Oxidative dehydrogenation of n-butane on V/MgO catalysts—kinetic study in anaerobic conditions

The kinetics of the oxidative dehydrogenation of butane on a V/MgO catalyst has been studied under anaerobic conditions. In these conditions the oxygen from the catalyst lattice is consumed by the reaction, and the oxidation degree of the catalyst changes during the experiment. A kinetic model is proposed in which each reaction rate is related with the oxidation degree of the catalyst. The whole kinetic model is useful for the modelling of reactors where the catalyst operates in non-steady state, i.e. where the oxidation degree of the catalyst changes with time. It has also been found that whereas the main contribution to the oxidative dehydrogenation reaction comes from the lattice oxygen, there is also a non-selective contribution from weakly adsorbed oxygen.     

Oxidative dehydrogenation of propane to propene, 1: Kinetic study on V/MgO

The reaction kinetics of the oxidative dehydrogenation of propane to propene over a V/MgO catalyst were studied. Both propane and propene oxidation kinetics were measured independently to quantify the rates of the parallel and consecutive reactions to propene and carbon oxides. Specific experiments to evaluate reaction products effects showed that water inhibited reaction rates but co‐feeding CO₂ or propene had no measurable effect on selectivity or conversion. Kinetic data generated under integral reactor conditions and over an inert membrane reactor have also been used to estimate the kinetic parameters. Selectivity decreased as the oxygen partial pressure increased; however, propene yield was relatively insensitive to oxygen concentration. A dual site Mars‐van Krevelen model characterizes the reaction kinetics well. The role of lattice oxygen was established by alternating pulses of propane and oxygen. This redox model is able to predict the experimental tendencies observed in the three types of reactor studied.     

A sequential approach to modeling catalytic reactions in packed-bed reactors

A sequential modeling approach is proposed to simulate catalytic reactions in packed-bed reactors. The hydrogenation of alpha-methylstyrene and wet oxidation of phenol are selected as studied cases. The modeling scheme combines a reactor scale axial dispersion model with a pellet scale model. Without involving any fitting parameters, such an approach accounts for the non-linear reaction kinetics expression and different types of pellet-liquid wetting contact. To validate the developed modeling scheme and the parallel approach reported in the literature, the experimental observations for hydrogenation of alpha-methylstyrene to cumene have been employed. The predicted results by both approaches agree reasonably with the experimental data for both gas- and liquid-limited reaction. The proposed sequential approach was also used to simulate the dynamic performance of the reactor and pellets for the catalytic wet oxidation of aqueous phenol over a newly developed but rapidly deactivated catalyst (MnO₂/CeO₂). The simulation results for the catalytic wet oxidation process by both approaches were compared. The simulation describes the time evolution of the catalyst stability at different pellet points along the reactor axis. The performance of trickle beds and packed bubble columns over a range of operating conditions were also investigated, and packed bubble columns were found to achieve higher phenol conversion at the cost of more rapid catalyst deactivation.     

STEADY STATE AND DYNAMIC MODELLING OF A PACKED BED REACTOR FOR THE PARTIAL OXIDATION OF METHANOL TO FORMALDEHYDE II. EXPERIMENTAL RESULTS COMPARED WITH MODEL PREDICTIONS

Heterogeneous and pseudohomogeneous two-dimensional models are compared to steady state and dynamic experimental data from a packed bed reactor for the partial oxidation of methanol to formaldehyde over an iron oxide-molybdenum oxide catalyst. Highly effective parameter estimation software was used to fit selected model parameters to large sets of experimental data so as to obtain small residuals. Heat transfer parameters which were successful in matching data from experiments without reaction were not capable of fitting data from experiments with reaction, and it was necessary to increase the radial heat transfer for higher temperatures or reaction rates. Axial composition profile data was represented by estimating the preexponential factors and activation energy in a half-order redox rate expression for methanol oxidation. After some decline in catalyst activity, a time-varying axial catalyst activity profile was determined from the data. A redox-type rate expression for the oxidation of formaldehyde to carbon monoxide was proposed to fit the data. The dynamics of the reactor temperature profile were accurately represented by the model. The heterogeneous and pseudohomogeneous models gave similar results in fitting experimental data, although the parameters determined for the two models were somewhat different.     

CO and ethanol oxidation over LaCoO3 planar model catalysts: Effect of the thickness

The catalytic performance of the LaCoO₃ thin films toward CO and ethanol oxidation was studied in a reactor designed for the investigation of model planar catalysts. The effect of the thickness on the catalytic efficiency and the surface oxygen vacancies offers a straightforward method to identify or discriminate the oxygen species involved in the catalytic reaction. The weight-normalized reaction rate is demonstrated to be an intrinsic parameter and thus confirms the participation of the bulk lattice-oxygen in the studied catalytic reactions. Compared to other perovskite oxide powder catalysts, thin film catalysts show a remarkably higher activity toward ethanol and CO oxidation.     

Vapour phase oxidation of ethylene glycol to glyoxal on supported cupric oxide

The vapour phase oxidation of ethylene glycol to glyoxal by air was studied in a stainless steel tube reactor using cupric oxide as a catalyst on carriers such as active alumina, pumice stone, silicon carbide, ceramics and fused alumina. A catalyst containing 3 to 5% cupric oxide on pumice stone was found to be satisfactory for the process. The effects of temperature, period of reaction and concentration of ethylene glycol and oxygen on the yield and conversion to glyoxal were studied, and the most suitable conditions were determined for the process. Carbon dioxide and formaldehyde were the major by-products in the reaction. Formaldehyde was formed mainly due to the homogeneous reactions of ethylene glycol with oxygen in the void space of the reactor. The formation of glyoxal and carbon dioxide were correlated by suitable empirical rate expressions.     

瞬变应答法研究苯催化氧化的反应机理

采用瞬变应答法研究了苯在钒催化剂上催化氧化的反应机理。通过对应答曲线的分析,证明氧首先被催化剂表面吸附,然后以较慢的速率转化为晶格氧,这一步是苯催化氧反应速率的控制步骤。吸附氧是生成 CO 和 CO_2的氧源;晶格氧是生成顺酐的氧源。气相苯不直接参与反应,但以较快的速率可逆吸附于催化剂上,吸附的苯与晶格氧反应生成中间物 IN,IN 进一步氧化生成顺酐。顺酐可逆吸附于催化剂上,其介吸速率较慢。中间物和吸附的顺酐对反应起阻滞作用。     

Heterogeneous Catalytic Reactor Design with Non‐Uniform Catalyst Considering Shell‐Progressive Poisoning Behavior

A novel methodology has been developed to design an optimum heterogeneous catalytic reactor, by considering non‐uniform catalyst pellet under shell‐progressive catalyst deactivation. Various types of non‐uniform catalyst pellets are modelled in combination with reactor design. For example, typical non‐uniform catalyst pellets such as egg‐yolk, egg‐shell and middle‐peak distribution are developed as well as step‐type distribution. A progressive poisoning behavior is included to the model to produce correct effectiveness factor from non‐uniform catalyst pellet. As opposed to numerical experiment with limited type of kinetic application to the model in the past, this paper shows a new methodology to include any types of kinetic reactions for the modeling of the reactor with non‐uniform catalyst pellet and shell‐progressive poisoning. For an optimum reactor design, reactor and catalyst variables are considered at the same time. For example, active layer thickness and location inside pellet are optimised together with reactor temperature for the maximisation of the reactor performance. Furthermore, the temperature control strategy over the reactor operation period is added to the optimization, which extends the model to three dimensions. A computational burden has been a major concern for the optimization, and innovative methodology is adopted. Application of profile based synthesis with the combination of SA (Simulated Annealing) and SQP (Successive Quadratic Programming) allows more efficient computation not only at steady state but also in dynamic status over the catalyst lifetime. A Benzene hydrogenation reaction in an industry scale fixed‐bed reactor is used as a case study for illustration.     

DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW FIBER MEMBRANE REACTOR†

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the tube side while the reaction takes place in the catalyst solution which fills the shell side. The separation load of product from the catalyst solution can be reduced by using a hollow fiber membrane reactor instead of a conventional bubble column reactor. The reactor operates in a plug-flow pattern with a large mass transfer area per unit volume of catalyst solution

This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde reaction in an aqueous solution of palladium (H) chloride-cupric chloride with a silicone rubber membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that membrane reactors could achieve higher production rates per unit volume of catalyst than the conventional sparged reactor. The experimental data were in good agreement with the predictions by the mathematical model. The conditions under which the membrane reactor will be more advantageous than the conventional sparged reactors can be readily ascertained with the analytical solution of the simplified membrane reactor model.     

Electrochemical promotion of catalysis controlled by chemical potential difference across a mixed ionic-electronic conducting ceramic membrane – an example of wireless NEMCA

A La_0.6Sr_0.4Co_0.2F_0.8O₃ mixed ionic electronic conducting (MIEC) membrane was used in a dual chamber reactor for the promotion of the catalytic activity of a platinum catalyst for ethylene oxidation. By controlling the oxygen chemical potential difference across the membrane, a driving force for oxygen ions to migrate across the membrane and backspillover onto the catalyst surface is established. The reaction is then promoted by the formation of a double layer of oxide anions on the catalyst surface. The electronic conductivity of the membrane material eliminates the need for an external circuit to pump the promoting oxide ion species through the membrane and onto the catalyst surface. This renders this “wireless” system simpler and more amenable for large-scale practical application. Preliminary experiments show that the reaction rate of ethylene oxidation can indeed be promoted by almost one order of magnitude upon exposure to an oxygen atmosphere on the sweep side of the membrane reactor, and thus inducing an oxygen chemical potential difference across the membrane, as compared to the rate under an inert sweep gas. Moreover, the rate does not return to its initial unpromoted value upon cessation of the oxygen flow on the sweep side, but remains permanently promoted. A number of comparisons are drawn between the classical electrochemical promotion that utilises an external circuit and the “wireless” system that utilises chemical potential differences. In addition a ‚surface oxygen capture’ model is proposed to explain the permanent promotion of the catalyst activity.     

Modeling of partial oxidation in gas–solids downer reactors

Selective partial oxidations represent an important class of reactions in the process industry. Of particular interest is the partial oxidation of n‐butane to maleic anhydride (MAN), which is arguably the largest commercialized alkane partial oxidation process. Partial oxidation of n‐butane, which uses vanadium phosphorous oxide (VPO) as a heterogeneous catalyst, is believed to operate through a unique mechanism in which lattice oxygen oxidizes n‐butane selectively to MAN. Past work has shown that performing partial oxidation reactions in gas–solids riser configuration is realizable and commercially viable, which has lead to commercialization of this technology in the last decade. Though the riser configuration allows optimal and independent control of the oxidation and reduction steps, the riser unit suffers from solid backmixing at walls, which in turn result into lower conversion, nonoptimal selectivity and diminished overall yield of desired product. In recent years, there has been growing interest in downers involving cocurrent downflow of both solids and gas phases, hence offering relatively uniform flow characteristics. In this contribution, we explore through modeling the implications of effecting partial oxidation reactions in a downer (gas–solids cocurrent downflow) compared to that in a conventional riser reactor (gas–solids cocurrent up flow) operated under equivalent operating conditions. Further, we explore the operational space of downers for these reactions, suggesting ways for improving the productivity of downer for partial oxidation applications. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Catalytic oxidation of solid carbon and carbon monoxide over cerium‐zirconium mixed oxides

A series of cerium‐zirconium mixed oxides was prepared and evaluated in the catalytic oxidation of solid coke with 10 vol % O₂ in He at 673 K using a thermogravimetric analyzer. The measured first order rate constant for coke oxidation was proportional to the catalyst loading when the mass ratio of catalyst to coke was low, which enabled the calculation of a surface area specific reaction rate. The validity of the normalization method was confirmed by performing CO oxidation over the cerium‐zirconium mixed oxides in a fixed bed reactor at 573 K. Although there was no correlation between the coke oxidation rate and the oxygen storage capacity or the reducibility of the catalysts, there was an excellent correlation to the CO oxidation rate. Kinetic studies of both coke and CO oxidation suggested an important role of surface lattice oxygen from the catalyst in the two reactions. © 2016 American Institute of Chemical Engineers AIChE J, 63: 725–738, 2017     

Heterogeneous catalytic reactor design with optimum temperature profile II: application of non-uniform catalyst

A new methodology has been developed to design non-isothermal, non-adiabatic heterogeneous catalytic fixed bed and tubular reactors with optimal temperature profiles inside a reactor. Catalyst characteristics such as pellet diameter, shape and activity distributions inside a pellet are considered simultaneously for reactor design. Various types of non-uniform activity distributions inside a pellet are modelled and optimised for the maximisation of an objective such as yield or selectivity. Dirac-δ, layered and general non-uniform distribution profiles such as egg-shell, egg-yolk and middle peak distributions are applied for the reactor design. The research demonstrates that different catalyst distribution profiles can approach the optimum performance. Whilst it is known that the Dirac-δ profile (and its step-function equivalent) always gives the best performance for clean catalyst, other profiles can approach this performance and might offer advantages in catalyst manufacture and under degraded conditions. A profile-based synthesis approach is applied to generate various shapes of activity profiles for multiple sections along the reactor during the optimisation of non-uniform catalyst pellets. A case study with the ethylene oxidation process illustrates that the catalyst characteristics, such as activity distribution profiles inside a pellet, sizes and shapes can be manipulated to control the temperature through the reactor very effectively, leading to significant improvements in selectivity or yield. The non-uniform catalyst pellet is further applied to various reactor configurations such as inert mixing and side stream distributions. This work is the first to consider all of these effects simultaneously.     

Catalytic Membrane Reactors – Lab Curiosity or Key Enabling Technology?

Two industrially interesting partial oxidations have been performed in catalytic membrane reactors with oxygen‐transporting membrane: aromatization of natural gas and oxidation of ammonia to nitric oxide. In both reactions, the oxygen used has been separated from air through a perovskite membrane, which also is the catalyst for the ammonia oxidation. When conducting the methane aromatization in an oxygen‐transporting membrane reactor, coke deposition is reduced and the aromatics yield is higher than that of a reference non‐oxidative fixed‐bed reactor.     

含乙醇废水的超临界水氧化反应动力学及反应机理

研究了等温平推流反应器中乙醇的超临界水氧化反应（SCWO）,反应温度475～550 ℃、压力22～30 MPa、停留时间0.6～63.7 s、氧气与乙醇摩尔浓度比4.56～9.09.一氧化碳和二氧化碳分别是反应中间产物和最终产物.随停留时间增大、温度升高,乙醇去除率增大,压力和氧气浓度变化对过程无显著影响.以幂指数方程描述乙醇SCWO动力学,乙醇和氧气的反应级数分别为1和0,计算值和实验值相差基本在10%以内.超临界条件下分别以过氧化氢和氧气为氧化剂时乙醇的氧化反应无明显差别,亚临界条件下过氧化氢氧化速率大于氧气.基于对此现象的分析,作者推测：无论以过氧化氢或氧气作为氧化剂,在超临界水中,它们之间可以通过一系列自由基反应迅速达到平衡,且各物种的平衡分布与初始分布无关,体系的主要氧化过程在平衡分布下进行.     

OSCILLATIONS IN THE OXIDATION OF CARBON MONOXIDE ON A PLATINUM FOIL

Reported here are experimental observations of self-sustained oscillations in the rate of oxidation of carbon monoxide on a platinum foil in a gradientless reactor. The results particularly show the effects of catalyst activity and illustrate some unusual and complex dynamic behavior under nearly isothermal conditions.