用于活性组分分布在颗粒表层的催化剂评价的等温积分反应器

设计了颗粒催化剂实验室筛选及考评装置 ,给出了活性组分分布在催化剂外表层的环柱状气相乙烯氧乙酰化合成醋酸乙烯催化剂的考评实例 .通过无梯度反应器研究了该催化剂的宏观反应动力学 ,采用反应 -传热模型对气相乙烯氧乙酰化合成醋酸乙烯多重反应进行了模拟计算 .实验和模拟计算结果吻合 ,表明所采用的装量 30ml微型积分反应器 ,当催化剂与惰性载体的稀释比为 1∶2时 ,可实现床层内等温操作 ,用于筛选活性组分分布在环柱状载体外表层催化剂 ,有良好的可比性     

流化床甲烷化基础与应用最新进展

由于CO甲烷化的快速表面反应、强放热特性,相比固定床,采用小颗粒催化剂的流化床甲烷化技术在反应活性和催化剂稳定性方面具有明显的技术优势。从高耐磨催化剂、流化床反应器及其创新、短流程两段甲烷化技术构建及其验证等方面总结了流化床甲烷化技术开发的最新进展。优化催化剂前体制备方法、调变催化剂组成可获得具有较高骨架强度和均匀性的催化剂一次微粒,进而通过优化的喷雾造粒工艺和填充黏结剂,制备出具有可调变粒度分布、高强度和高球形度的流化床用粉末催化剂,但其黏结剂的添加明显影响催化剂的低温活性。通过改性如Al₂O₃和FCC催化剂的球形颗粒,进而负载活性组分,开发了制备高活性、磨损指数小于1.5的流化床甲烷化Ni基催化剂的另一种技术方法。实验室研究证实了流化床甲烷化反应速率极快,在分布板上数毫米处即可实现可能的最高转化率,且在转化率和催化剂稳定性方面明显优于固定床,不仅由于流态化催化剂床层温度均匀,而且催化剂在床层内不停循环,加快了颗粒表面的更新。增大空速和表观气速,流化床的催化剂床层膨胀,反应气体与催化剂颗粒表面间的有效接触面积增加,使得流化床甲烷化对空速和表观气速的可调范围大。操作在更高气速条件的输送床甲烷化避免了操作气速的上限限制,可大幅降低反应器尺寸,有效提高单位截面的原料气负荷能力。输送床甲烷化可采用高热导率的催化剂颗粒传递反应热,相对于气体移热效率高、能力大。流化床甲烷化已在生物废弃物利用和焦炉煤气甲烷化方面开展了侧线示范,形成了相对多段绝热固定床工艺更简单的短流程两段甲烷化新工艺。     

Intensification of Deep Hydrodesulfurization Through a Two-stage Combination of Monolith and Trickle Bed Reactors

Deep hydrodesulfurization (HDS) is an important process to produce high quality liquid fuels with ultra-low sul-fur. Process intensification for deep HDS could be implemented by developing new active c...     

A301催化剂等压合成氨的可行性

原粒度A30 1催化剂在大型合成氨厂实际工况条件下的工业旁路试验结果表明 :在 7.0～ 7.5MPa等压合成氨工艺条件下 ,A30 1催化剂的氨净值为 10 %～ 12 % ,在 8.5MPa或 10MPa微加压合成氨工艺条件下 ,氨净值可达 12 %～ 15 % ,可以满足合成氨工业经济性对氨净值的要求 .因此采用A30 1催化剂实现等压或微加压合成氨是可行的 ,并可获得显著的经济效益     

A novel approach to the design and operation scheduling of heterogeneous catalytic reactors

A number of studies have been conducted to reduce the overall level of catalyst deactivation in heterogeneous catalytic reactors, and improve the performance of reactors, such as yield, conversion or selectivity. The methodology generally includes optimization of the following: (1) operating conditions of the reaction system, such as feed temperature, normal operating temperature, pressure, and composition of feed streams; (2) reactor design parameters, such as dimension of the reactor, side stream distribution along the axis of the reactor beds, the mixing ratio of inert catalyst at each bed; and (3) catalyst design parameters, such as the pore size distribution across the pellet, active material distribution, size and shape of the catalyst, etc. Few studies have examined optimization of the overall catalyst reactor performance throughout the catalyst lifetime, considering catalyst deactivation. Furthermore, little attention has been given to the impact of various configurations of reactor networks and scheduling of the reactor operation (i.e., online and offline-regeneration) on the overall reactor performance throughout the catalyst lifetime. Therefore, we developed a range of feasible sequences of reactors and scheduling of reactors for operation and regeneration, and compared the overall reactor performance of multiple cases. Furthermore, a superstructure of reactor networks was developed and optimized to determine the optimum reactor network that shows the maximum overall reactor performance. The operating schedule of each reactor in the network was considered further. Lastly, the methodology was illustrated using a case study of the MTO (methanol to olefin) process.     

The gas–liquid contacting effect on the operation of small scale upflow hydrotreaters

The effect of reactor geometry and bed dilution on the extent of gas oil hydrodesulfurization was tested by conducting hydrodesulfurization experiments in two laboratory reactors of different scale with non-diluted and diluted beds in ascending flow. The superficial gas and liquid velocities and the catalyst bed height were kept constant while the main difference between the two reactor scales was the reactor diameter. The diluted bed of the mini-reactor showed the best performance and its results were identical in upflow and downflow mode. The differences between the performance of the mini- and the bench-scale reactor operating in upflow mode have been investigated. Reactor performance simulation was attempted by a mathematical model that takes into account axial dispersion of the liquid phase and gas–liquid mass transfer. Bench-scale reactor operation was characterized by lower mass transfer rates than the corresponding mini-scale one. Combining model predictions and mock up operation it is concluded that the stronger mass transfer resistances calculated for the bench-scale reactor are associated with poorer gas distribution through the catalyst bed. Reduction of the bed diameter results in better gas–liquid contact by forcing the gas bubbles to distribute more effectively into the liquid phase.     

A recycle reactor for measuring hydrogen isotope exchange kinetics under vapour phase and trickle bed conditions

A recycle reactor system has been developed to measure the activities of catalysts for isotope exchange between hydrogen gas and water vapour. To allow testing of reasonably large quantities of catalysts, the reactor was operated with a high recirculating flow of hydrogen gas passing through a saturator to provide the water vapour required for the reaction. In this mode of operation, only a small spiking gas flow was required as feed compared to the very high feed flow that would be required for once-through operation. The reactor was also operated as a trickle bed by recirculating the saturator water. By testing catalysts under both vapour and trickle bed modes, it was possible to investigate the effect of trickling water over the catalyst on the catalytic activity. Kinetic exchange rates under vapour phase operation were calculated from both plug flow and well-mixed reactor models. The former model was found to be the appropriate one for the ranges of operating conditions investigated. However, for trickle bed operation, the well-mixed reactor model was found to be the suitable one. Vapour phase and trickle bed tests done with random bed and structured bed catalysts indicated that the gas phase isotope exchange reaction was not impaired by the presence of liquid water in the reactor.     

An NMR Imaging Study of Steady-State and Periodic Operation Modes of a Trickle Bed Reactor

NMR imaging has been applied to study the steady-state and the periodic operations of a functioning trickle bed reactor. It has been revealed that under conditions of the continuous supply of a liquid reagent to the catalyst bed, the bed was mostly filled with the liquid phase and was characterized by the uniform and stationary distribution of a liquid phase, whereas under conditions of the periodic supply of a liquid reagent to the catalyst bed with the same liquid flow velocity the bed was mostly dry and was characterized by a non-stationary distribution of the liquid phase. The oscillations of the liquid phase content within the bed, corresponding to the modulated liquid flow, have been observed. It has been shown that performing the hydrogenation reaction in a trickle bed reactor under conditions of the periodic supply of a liquid reagent to the catalyst bed leads to the intensification of the hydrogenation process. It becomes apparent in the significant increase of the temperature of the catalyst bed as well as in the increase of the conversion degree in the regimes under forced time-varying liquid flow rates in comparison to the steady-state regime of the reactor operation.     

Katalytische Abluftreinigung: Verfahrenstechnische Aufgaben und neue Lösungen

Catalytic air purification; Challenges and new solutions. The integration of regenerative heat exchange into the catalyst bed allows for the autothermal operation of catalytic air purification with a low content of combustible gas. Concentrations corresponding to an adiabatic temperature rise of less then 20 °C can be processed without an additional heat source; in case of higher concentratons a side stream withdrawal allows for the utilization of the total heat of combustion at the highest reactor temperature. The feedback of heat due to the integrated heat exchange gives rise to an unusual reactor behaviour. An analogy of fixed bed reactor operation with countercurrent heat exchange is used to derive simple equations for reactor design and operation. If conventional catalyst packings are replaced by monolithic catalysts, substantial reduction in pressure loss and/or packed bed volume can be obtained. The corresponding relations are briefly discussed.     

Pd/C催化剂失活原因探讨

从PTA加氢精制反应原理探讨了Pd C催化剂失活原因及解决方法。生产过程中的工艺参数控制 ,操作和原料质量是影响Pd C催化剂活性的主要因素 ,稳定反应器操作 ,更换腐蚀严重的管线及设备 ,提高保护床层高度 ,用强碱液冲洗反应器床层等可再生和延长Pd C的寿命     

Mass transfer‐limited wet oxidation of phenol

Catalytic wet oxidation carried out in a continual three‐phase trickle‐bed reactor contributes to the sustainability of chemical technology. It was found that the hydrodynamics and the mass‐transfer of reactants could have a significant impact on the performance of the trickle‐bed reactor. An aqueous phenol oxidation was tested at different temperatures and liquid feed rates and the activities of both the CuO‐supported catalyst and the extruded active carbon were compared. To avoid the impact of liquid maldistribution, a bed of catalyst particles diluted with fine glass spheres was also used. Rate‐limited conditions of both liquid‐ and gas‐phase presented reactants were determined. Under the conditions of gas component transfer limitation, a better wetting of the diluted catalyst bed can lead to a worsening in the reactor performance due to the lower overall reaction rates. © 2001 Society of Chemical Industry     

Experimental study of ignition and extinction waves and oscillatory behavior of a tubular nonadiabatic fixed bed reactor for the oxidation of carbon monoxide

An experimental study of axial temperature profiles in a nonadiabatic tubular fixed bed reactor has been made under the transient operation. The catalytic carbon monoxide oxidation occurring on a Pt/alumina catalyst has been used. Ignition and extinction waves have been studied both in a short and a long catalyst bed. It is shown that in a short bed ignition and extinction occur at the reactor outlet while for a long bed the ignition and extinction process takes place inside the reactor and is not influenced by the outlet part of the reactor. A systematic measurement indicates that in a narrow range of inlet parameters the integral nonadiabatic nonisothermal reactor may operate in an oscillatory state. These oscillations can be periodic or aperiodic.     

Cu/γ-Al2O3 catalyst for the combustion of methane in a fluidized bed reactor

The applicability of a catalyst based on copper dispersed on γ-Al₂O₃ spheres (1 mm diameter) for fluidized bed catalytic combustion of methane has been assessed. Catalyst properties have been determined by physico-chemical characterization techniques and fixed bed activity tests revealing the presence of a surface CuAl₂O₄ spinel phase, still active and stable in methane combustion after repeated thermal ageing treatments at 800 °C. Methane catalytic combustion experiments have been performed in a 100 mm premixed fluidized bed reactor under lean conditions (0.15–3% inlet methane concentration), showing that complete CH₄ conversion can be attained below 700 °C in a fluidized bed of 1 mm solids with a gas superficial velocity about twice the incipient fluidization velocity.     

Optimal temperature profiles in tubular reactors for several catalyst decay laws

Theoretical and experimental work on tubular reactors has shown that a high temperature reaction zone can be induced to move counter to the flow of reactants by conduction and/or radiation through the solid phase. This naturally occurring phenomenon represents a transient mode of operation that can be argued to be preferable to conventional modes of operation. In order to test this hypothesis the complete time and space dependent optimal temperature policy was generated for a tubular reactor subject to several catalyst decay laws. The solutions revealed that a critical parameter is the ratio of the activation energy for the main reaction to that for the catalyst decay reaction. For values of this ratio less than one, the optimum temperature profiles represent a low temperature reaction zone that occupies the entire active bed at all times, essentially a conventional mode of operation. However, for this ratio greater than one the profiles represent a short high temperature reaction zone that propagates with time along the length of the reactor. For a catalyst decay law independent of conversion, propagation in either axial direction was optimal, but for a decay law dependent upon conversion the optimization procedure only generated reverse propagating zones.     

Catalytic partial oxidation of methane to syngas in a fixed-bed reactor with an O2-distributor: The axial temperature profile and species profile study

Catalytic partial oxidation of methane (CPOM) to syngas has been investigated in a fixed-bed reactor with an O₂-distributor (FR-OD). The axial temperature profile and species profile along the Ni or Rh-based catalyst bed have been measured at different conditions. As the O₂ was distributed radially into the catalyst bed through several rows of holes arranged at the special zone of the OD, a microenvironment maintaining a low O₂/CH₄ ratio (0.10–0.22) was provided in the catalyst bed. The hotspot phenomena appeared at the entrance of the catalyst bed have been effectively controlled. A more uniform temperature profile along the catalyst bed has been given, which is beneficial to the stability of catalyst and the safety of reactor operation.     

一种CO优先氧化装置的实验研究

质子交换膜燃料电池需要CO含量低于10μL/L的富氢合成气作为燃料。CO优先氧化是一种深度脱除CO的有效方法。设计了一种CO优先氧化反应器,考察了催化剂装填方式、CO空速和氧碳比对反应器性能的影响。结果表明:对于所测试的操作条件,催化剂稀释之后分三段装填有利于反应器床层温度的均匀分布和出口CO浓度的降低;氧碳比越高出口CO浓度越低,当氧碳比为2.8时出口CO浓度为7μL/L。连续20 h的测试表明,反应器床层温度分布均匀,出口CO浓度保持在10μL/L以下。     

Deactivation of ICI low temperature methanol catalyst in an industrial reactor

The deactivation behavior of one of the ICI low temperature methanol catalysts (ICI-51-Z) in a typical ICI multibed quench reactor has been studied in relation to methanol production with respect to time of operation, using some representative sets of plant data collected over two years time span. A pseudo-homogeneous first order model of the methanol synthesis reactor was formulated for this purpose. The best set of catalyst deactivation parameters for different beds was found using a nonlinear parametric estimation technique. Catalyst in the entering bed was found to deactivate most with the time of operation, while subsequent beds deactivate progressively less quickly.     

流化床与固定床中甲烷裂解制氢过程的比较

本文对流化床与固定床操作模式下的甲烷催化裂解制氢进行了比较研究。以纯甲烷为原料，分别考察了75Ni10Cu15Al和2Co1Al（原子比）催化剂上流化床与固定床操作模式下甲烷裂解制氢反应，结果表明流化床中的甲烷裂解反应速率较高。流化床操作的高表观速率主要是因为此模式下有效消除了外扩散，同时极大减少了内扩散阻力。同时不同温度下催化剂上生长的碳的TEM表征发现，金属颗粒尺寸随反应温度增加而增加，表明催化剂烧结是失活原因之一。但相同温度下固定床中催化剂金属颗粒尺寸明显大于流化床中的金属颗粒尺寸，且金属颗粒尺寸分布变宽，这说明流化床反应器有利于阻止金属颗粒的烧结。通过对甲烷裂解催化剂失活原因的分析发现流化床中催化剂颗粒的流态化有利于延长催化剂活性寿命。     

新型惰性膜反应器中丁烷氧化脱氢制丁二烯和丁烯

The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (bntene and bntadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.     

Dynamic modelling of a gas phase catalytic fixed-bed reactor—I: Experimental apparatus and determination of reaction kinetics

A large scale fixed bed pilot reactor for performing dynamic experiments is described. The reactor system is especially designed to suppress secondary dispersion effects not characteristic for the packed bed itself.As a model reaction the reaction between oxygen (<1%) and hydrogen on a platinum catalyst supported by alumina has been used.Differential reactor experiments disclosed a hysteresis phenomenon in the catalyst activity. The catalyst is generally more active when going from high to low temperatures than vice versa.A global first order reaction rate expression with Arrhenius temperature dependency fits the fixed-bed reactor profiles well but the static gains badly. However by simultaneous estimation of frequency factor and activation energy in several axial segments a much better approximation to the static gains was obtained. This result indicates that the reaction kinetics is more complicated than first assumed. However for dynamic modelling the exact reaction mechanism is not needed.