Steam gasification of an australian bituminous coal in a fluidized bed

To produce low calorific value gas, Australian coal has been gasified with air and steam in a fluidized bed reactor (0.1 m-I.Dx1.6 m-high) at atmospheric pressure. The effects of fluidizing gas velocity (2–5 U_f/U_mf), reaction temperature (750–900 °C), air/coal ratio (1.6-3.2), and steam/coal ratio (0.63–1.26) on gas composition, gas yield, gas calorific value of the product gas and carbon conversion have been determined. The calorific value and yield of the product gas, cold gas efficiency, and carbon conversion increase with increasing fluidization gas velocity and reaction temperature. With increasing air/coal ratio, carbon conversion, cold gas efficiency and yield of the product gas increase, but the calorific value of the product gas decreases. When steam/coal ratio is increased, cold gas efficiency, yield and calorific value of the product gas increase, but carbon conversion is little changed. Unburned carbon fraction of cyclone fine decreases with increasing fluidization gas velocity, reaction temperature and air/coal ratio, but is nearly constant with increasing steam/coal ratio. Overall carbon conversion decreases with increasing fluidization velocity and air/ coal ratio, but increases with increasing reaction temperature. The particle entrainment rate increases with increasing fluidization velocity, but decreases with increasing reaction temperature. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Staging of the Fischer‐Tropsch Reactor with a Cobalt‐Based Catalyst

A method for systematic reactor design, described by Hillestad [1], is applied to the Fischer‐Tropsch synthesis. The reactor path is sectioned into stages and design functions are optimized to maximize an objective function. Two different objective functions are considered: the yield of wax and a measure of the profitability. With the chosen kinetic model [2] and the path temperature constrained by 240 °C, staging of the Fischer‐Tropsch synthesis based on the first criteria will increase the yield of wax. By introducing the cost of heat transfer area in the objective function, the total heat transfer area requirement of a two‐stage reactor is significantly less than of a single‐stage reactor.     

An Experimental Investigation of Hydrogen Production from Biomass

In gaseous products of biomass steam gasification, there exist a lot of CO, CH4 and other hydrocarbons that can be converted to hydrogen through steam reforming reactions. There exists potential hydrogen production from the raw gas of biomass steam gasification. In the present work, the characteristics of hydrogen production from biomass steam gasification were investigated in a small-scale fluidized bed. In these experiments, the gasifying agent (air) was supplied into the reactor from the bottom of the reactor and the steam was added into the reactor above biomass feeding location. The effects of reaction temperature, steam to biomass ratio, equivalence ratio (ER) and biomass particle size on hydrogen yield and hydrogen yield potential were investigated. The experimental results showed that higher reactor temperature, proper ER, proper steam to biomass ratio and smaller biomass particle size will contribute to more hydrogen and potential hydrogen yield.     

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.     

大型列管式催化氧化反应器研制的技术难点和解决方案

大型列管式催化氧化反应器是丙烯酸、顺酐、苯酐等装置中的关键核心设备,结构复杂、技术含量高、制造难度大。对丙烯酸反应器研制过程中出现的技术难点问题,通过大量分析、研究和试验,提出了有效的解决方案。     

A kinetic modelling study of ethane cracking for optimal ethylene yield

Current generation steam cracking plants are considered to be mature. As a consequence it is becoming more and more important to know whether the underlying mechanistic cracking process offers still scope for further improvements. The fundamental kinetic limits to cracking yields have recently been researched in detail for different feed stocks with a new synthesis reactor model, d-RMix, incorporating a large scale mechanistic reaction scheme, SPYRO^® [M.W.M. van Goethem, S. Barendregt, J. Grievink, J.A. Moulijn, P.T.J. Verheijen “Model-based, thermo-physical optimisation for high olefin yield in steam cracking reactors”, Chemical Research and Engineering Developments 88 (2010) 1305–1319]. Mathematical optimization revealed for ethane cracking a maximum ethylene yield of about 67 wt%. with a linear-concave optimal temperature profile along the reaction coordinate with a maximum temperature between 1200 and 1300 K. Further mechanistic analysis of these results showed that the linear-concave shape not only suppresses the successive dehydrogenation and condensation reactions of ethylene, but mainly reduces the role of the ethane initiation reaction to form two methyl radicals.     

Transient modeling of combined catalytic combustion/CH4 steam reforming

This paper presents an investigation into the complex interactions between catalytic combustion and CH₄ steam reforming in a co-flow heat exchanger where the surface combustion drives the endothermic steam reforming on opposite sides of separating plates in alternating channel flows. To this end, a simplified transient model was established to assess the stability of a system combining H₂ or CH₄ combustion over a supported Pd catalyst and CH₄ steam reforming over a supported Rh catalyst. The model uses previously reported detailed surface chemistry mechanisms, and results compared favorably with experiments using a flat-plate reactor with simultaneous H₂ combustion over a γ-Al₂O₃-supported Pd catalyst and CH₄ steam reforming over a γ-Al₂O₃-supported Rh catalyst. Results indicate that stable reactor operation is achievable at relatively low inlet temperatures (400 °C) with H₂ combustion. Model results for a reactor with CH₄ combustion indicated that stable reactor operation with reforming fuel conversion to H₂ requires higher inlet temperatures. The results indicate that slow transient decay of conversion, on the order of minutes, can arise due to loss of combustion activity from high-temperature reduction of the Pd catalyst near the reactor entrance. However, model results also show that under preferred conditions, the endothermic reforming can be sustained with adequate conversion to maintain combustion catalyst temperatures within the range where activity is high. A parametric study of combustion inlet stoichiometry, temperature, and velocity reveals that higher combustion fuel/air ratios are preferred with lower inlet temperatures (≤500 °C) while lower fuel/air ratios are necessary at higher inlet temperatures (600 °C).     

Enhancement of acetylene and ethylene yields in partially decoupled oxidation of ethane by changing the composition of heat carrier

In our previous work, a partially decoupled process(PDP) was proposed for efficient conversion of ethane to increase the ethylene yield and a new structural reactor called forward-impinging-back reactor(FIB)was proposed for scale-up. In this work, the influence of changing the composition and temperature of the heat carrier was investigated by simulations with detailed chemistry to further increase of the C₂(C₂ H₂+ C₂ H₄) yield in the PDP of...     

Model-based,thermo-physical optimisation for high olefin yield in steam cracking reactors

The steam cracking practice seems to have reached a stage of maturity which makes it increasingly difficult to improve ethylene yield. In order to determine if there is still scope for yield improvements it is helpful to know what the optimal reaction conditions for the steam cracking process are. This work presents a model-based synthesis approach that enables to determine the optimal thermal and physical reaction conditions for a particular feed, maximising olefin yield. A distributive reaction-mixing synthesis model has been combined with an industrially proven large kinetic scheme, SPYRO^®, which contains over 7000 reactions between 218 molecular and 27 radical species. The model combination allows optimising the following degrees of freedom with respect to olefin yield: feed distribution, product removal, macro-mixing, along a reaction volume coordinate. The reaction temperature upper limit is put at 1300 K, exceeding the current (metallurgical) bound by 100 K. For the cracking of ethane a linear-concave unconstrained temperature profile with a maximum temperature of ∼1260 K proves optimal which is lower than allowed while all ethane should be supplied at the entrance of the reaction volume. For propane and heavier feedstocks an isothermal profile at the upper temperature bound, with dips at the beginning and the middle of the reaction coordinate is optimal, while distribution of the hydrocarbon feed along the reactor coordinate results in higher yields. The theoretical maximum achievable ethylene yield for ethane cracking is found to be 66.8 wt% while in conventional cracking typically 55 wt% is considered to be the maximum value. This optimum is constrained by the pressure which is at its lower bound. The resulting residence time is in the same order as with current technology for ethane cracking. For the more heavy feedstocks these times are one order of magnitude smaller which will be a challenge for designing.     

对二甲苯氧化反应器连续全混流模型

在对二甲苯液相催化氧化动力学研究的基础上,比较了化学反应速率与气液传质速率的相对大小。结果表明,工业反应器中,该氧化过程受化学反应控制,动力学是影响反应速率的主要因素。从而不计传质,并将反应器考虑成CSTR模型,模拟计算结果与实际值比较吻合。用此模型对影响反应的各工艺条件的计算机试验表明,停留时间延长、催化剂浓度增加、温度升高、Br/Co(摩尔比)比增大有利于提高TA收率和降低4-CBA浓度,但燃烧消耗加剧;Co/Mn(摩尔比)配比对主反应影响不大,但燃烧副反应随Co/Mn配比增大而增大。     

A hybrid adsorbent-membrane reactor (HAMR) system for hydrogen production

Design characteristics and performance of a novel reactor system, termed a hybrid adsorbent-membrane reactor (HAMR), have been investigated for hydrogen production. The recently proposed HAMR concept couples reactions and membrane separation steps with adsorption on the membrane feed-side or permeate-side. Performance of conventional reactors has been significantly improved by this integrated system. In this paper, an HAMR system has been studied involving a hybrid-type packed-bed catalytic membrane reactor undergoing methane steam reforming through a porous ceramic membrane with a CO₂ adsorption system. This HAMR system is of potential interest to pure hydrogen production for fuel cells for various mobile and stationary applications. Reactor behaviors have been investigated for a range of temperature and pressure conditions. The HAMR system shows enhanced methane conversion, hydrogen yield, and product purity, and provides good promise for reducing the hostile operating conditions of conventional reformers, and for meeting the product purity requirements.     

丙烯催化氧化制丙烯酸的两段流化床工艺

分别在一段和两段流化床反应器中对丙烯催化氧化制备丙烯酸过程进行了研究. 主要考察了温度、丙烯空速和氧/烯比等操作条件对丙烯氧化制备丙烯醛的第一步反应中丙烯转化率和液相收率的影响. 结果表明,在两段流化床反应器中,由于能够有效抑制气体和固体的返混及催化剂床层中气泡的增长,第一步反应中丙烯转化率和液相收率可以分别大幅度提高到94.2%和74.4%. 得到第一步反应的优化条件为：丙烯空速20~21 L/(h·kg),操作温度360~365℃,氧/烯摩尔比1.6~1.8,在此条件下,考察了连续两步反应中的丙烯转化率和液相收率.     

Semibatch Production of Pharmaceutical Grade Magnesium Stearate: A Statistical Approach

Fractional factorial design was employed to investigate the effect of feed composition and the major operating variables on the production of pharmaceutical grade magnesium stearate in a double decomposition process. The studied variables were initial stearic acid concentration, initial sodium hydroxide concentration, initial magnesium sulfate concentration, as well as reactor temperature at the time of NaOH addition (the first reaction temperature) and reactor temperature during magnesium sulfate addition (the final reaction temperature), pH of the solution at the end of reaction (final pH). The moisture content of the cake produced after filtration and the yield of magnesium stearate in the dried cake (assay), were the most important responses investigated as a function of feed and operating variables and these were optimized through statistical analysis. The results of the study showed that both magnesium sulfate and NaOH had high positive effects on the final pH, with a nonsignificant effect of the other main factors being observed. Increasing the NaOH concentration and the first reaction temperature led to an increase in the assay production, whereas the binary interaction of stearic acid and NaOH revealed a negative effect. The acid as well as NaOH concentrations exhibited positive influence on the moisture content of the filtered cake. Finally, the simplex optimization method was used to obtain the optimal conditions. The results of the study were successfully adapted to the large scale production of pharmaceutical grade magnesium stearate and pharmaceutical grade product was produced meeting the standards required.     

A homogeneous chemical reactor analysis and design laboratory: The reaction kinetics of dye and bleach

An experimental module for senior-level reaction engineering/reactor design students is described. The module is used to characterize the kinetics of dye (food coloring) neutralization by household bleach, and the reactor system is configurable for use in either batch reactor or continuous-stirred tank reactor (CSTR) modes. The reactor temperature, volume, reactant feed rates, and reactant concentrations may be adjusted to enable students to obtain a wide range of kinetic data. Dye concentrations in the reactor are monitored by absorbance spectroscopy, and the kinetic rate law is determined directly from the batch reactor performance data. Students use the completed kinetic rate law to compare experimental steady-state CSTR performance data to the mathematical models derived from reactor design equations. Finally, the students use the kinetic behavior of the system to design a hypothetical plug-flow reactor for the same chemical reaction and a set of stated operational goals.     

10 kWth级串行流化床中木屑化学链燃烧试验

设计并建立了10 kW_th级串行流化床化学链燃烧反应器系统,以NiO/Al₂O₃为载氧体,在该系统上进行生物质（松木木屑）化学链燃烧分离CO₂的试验研究,探讨了燃料反应器温度T、水蒸气/生物质比率S/B对两个反应器（空气反应器和燃料反应器）气体产物组成以及燃烧效率的影响。试验结果表明,燃料反应器温度是影响生物质化学链燃烧过程的重要因素,随着温度的升高,燃料反应器气体产物中CO₂浓度不断上升,CH4浓度显著降低,CO浓度先升高而后迅速下降;较高的反应器温度有助于燃烧效率的提高。随着S/B的增加,燃料反应器气体产物中CO和CH₄浓度均会增大,CO₂浓度以及燃烧效率有所降低。在100 h的连续试验过程中,采用共沉淀法制备的NiO/Al₂O₃载氧体展现出良好的氧化-还原性能和较强的持续循环能力,是生物质化学链燃烧理想的载氧体。     

CO‐Free Hydrogen Production by Ethanol Steam Reforming in a Pd–Ag Membrane Reactor

In this work, the ethanol steam reforming (ESR) reaction has been studied by using a dense Pd–Ag membrane reactor (MR) by varying the water/ethanol molar ratio between 3:1 and 9:1 in a temperature range of 300–400 °C and at 1.3 bar as reaction pressure. The MR was packed with a commercial Ru‐based catalyst and a constant sweep gas flow rate in counter current mode was used. The influence of the temperature and the feed molar ratio on different parameters such as the ethanol conversion, the hydrogen production, the hydrogen yield and the CO‐free hydrogen recovery has been evaluated.     

丙烯酸的工业储存要点

文章通过对丙烯酸的理化性质、反应特性、危害性等特性的分析,介绍了丙烯酸在工业生产应用中的储存难点以及丙烯酸的聚合反应所带来的危害;并从储存设备的材质选型、储存环境的设计、防止泄漏及处理的措施、储存与输送过程中的温度控制、以及防止聚合反应等各方面,重点介绍了工业生产中丙烯酸原料储存的要点,供设计人员参考。     

MULTIVARIABLE CONTROL OF CATALYTIC CRACKING PROCESSES

Simple, explicit and physically intuitive Feedforward and Feedback control policies are designed for Fluidized Catalytic Cracking Processes. The Feedforward (FF) control algorithm compensates for changes in the feed rate and feed coking tendency by the use of the air flow and catalyst circulation rates as control variables to maintain the conversion and the reactor temperature at fixed levels. Through steady state and dynamic simulations the FF controller is shown to be very effective. To improve the dynamic response of the process and to account for the process/model mismatch a feedback (FB) controller is also designed to complement the FF action. The FB action is designed by use of the transformation related to the physical modes which correspond to the extensive variables of the process. It is shown that the required control structure consists of two loops. One uses the air flow rate to control the total sensible heat content of the reactor and regenerator solid phases. The other loop controls the regenerator enthalpy by changes in the catalyst circulation rate. The air flow rate controller includes an integral action to avoid reactor temperature offsets, while the catalyst circulation rate controller requires a nonlinear static observer to predict the coke concentration on the regenerated catalyst from dense bed and flue gas regenerator temperatures. The performance of the controller for changes on the oil feed rate, caking tendency of the feed, as well as for reactor temperature set point changes is faster and smoother than Kurihara's scheme.     

Comprehensive Fischer–Tropsch reactor model with non-ideal plug flow and detailed reaction kinetics

This paper presents a detailed first principle Fischer–Tropsch reactor model including detailed heat transfer calculations and detailed reaction kinetics. The model is based on a large number of components and chemical reactions. The model is tuned to a fixed bed nearplug flow reactor but can also be applied to slurry and micro-channel reactors.The presented model is based on a cascade of ideally stirred reactors. This modelling approach is novel for Fischer–Tropsch reactors and has the advantage of being able to represent none-ideal reactors. Using a large number of components and reactions makes it possible to better represent the product slate than with conventional modelling based on distribution models.The results of the simulations emphasise that temperature control is important. Global conversion and product yields are dependent on operating conditions especially the temperature. The model is used to calculate the dimensions of an industrial reactor from a laboratory scale reactor.     

OPTIMUM REACTOR DESIGN IN METHANATION PROCESSES WITH NONUNIFORM CATALYSTS

A generic methodology is developed to design a heterogeneous catalytic reactor for methanation processes. For the optimization of a heterogeneous catalytic reactor, nonuniform catalyst pellets such as a layered catalyst are considered with respect to reaction type, reactor performance, and component distribution inside the catalyst. Heterogeneous uniform and nonuniform catalyst models were developed to analyze the effect of mass and heat transfer between both bulk phase and catalyst surface and inside a catalyst pellet. Then, concentration profiles of hydrogen and carbon monoxide in the catalyst pellet and along the reactor axis were obtained by analyzing simulation results. It was shown that the application of different types of nonuniform catalyst pellets at a certain number of separate zones within a reactor could produce higher catalyst performance than a reactor with uniform catalyst. Furthermore, it proved a significant decrease of catalyst deactivation behavior such as coking and sintering. Layered catalysts were optimized to maximize an overall reactor performance over the catalyst lifetime, achieving capital cost reduction characterized by reactor size, catalyst amount, and degree of catalyst deactivation. Last, temperature control throughout the reactor operating periods was strategically planned for a reactor operation with distribution of nonuniform catalyst pellets. This methodology can also be usefully applied to the design of heterogeneous catalytic reactors for other processes such as hydro-treating process and cracking process.