气相法聚乙烯工艺冷凝态操作模式的稳定性和动态行为

气相法聚乙烯工艺冷凝态操作模式由于显著提高了循环气移热能力和反应器时空产率,已成为流化床乙烯聚合工艺的主流操作模式。建立了气相法聚乙烯工艺冷凝态操作模式的数学模型,包括流化床反应器模型,多级换热器模型和反应温度、压力以及循环气组成的控制模型。基于此,采用流程模拟方法,计算了系统在反应器温度采用闭环控制时的稳态解;根据系统对小扰动的动态响应特点,定性判断了反应器温度采用开环控制和闭环控制时聚合反应系统的稳定性;考察了系统对1-己烯分压和催化剂进料速率的阶跃响应特性。结果表明,反应器温度采用闭环控制时,聚合反应系统在所考察操作条件下均是稳定的,而采用开环控制时,解曲线被分叉点分割为稳定区域和不稳定区域。反应器温度对1-己烯分压阶跃变化的动态响应表明聚合反应系统存在长、短周期两类振荡,表明冷凝态操作模式下乙烯聚合反应过程是一个多控制回路耦合的复杂过程。     

Bifurcation Analysis of the Fluidized Bed Polyethylene Reactor with Internal Cooler

A mathematical model has been developed to simulate a gas‐phase ethylene polymerization reactor with internal cooler. The model was analyzed to determine the effects of reactor operating conditions on dynamics and stability. The reactor model employed assumed that both the gas and polymer phase in the reactor are well mixed. Comparing the present model to one with external heat exchanger confirms that, in either form, gas‐phase polyethylene reactors are prone to show unstable steady states, limit cycles and excursions toward unacceptably high temperature steady states. It was also observed that, with internal cooler, minor design changes in the cooler area available for heat transfer and in the inlet temperature of the coolant have a significant effect on the low stable steady state range of catalyst feed rates. With internal cooler, the suitable operating range increased with the increase in the area available for heat transfer. This effect is insignificant in the case of a reactor with external heat exchanger. Manipulating the reactor coolant inlet temperature and/or gas velocity can increase the stability range in the reactor with internal cooler as against one with external heat exchanger.     

稳态反应模型在气相聚乙烯反应器中的应用

通过对气相流化床聚乙烯工艺稳态反应模型的应用进行分析，讨论了中间控制参数温度、氢气乙烯摩尔比、共聚单体乙烯摩尔比、催化剂产率等输入变量对反应器输出变量树脂性能－熔体流动指数（MI）的影响。选择工业实例，对系统出现波动后人工调控MI与利用稳态反应模型的计算机调控MI的过程分别进行了计算，并对2种调控过程进行了比较，证明了稳态反应模型在工业质量控制中的优越性。     

单颗粒催化剂多定态特性的理论分析

借助于奇异理论和突变理论,本文对单颗粒催化剂的多定态特性进行了分析。得到了反应为一级不可逆放热反应时系统定态模型方程解的结构以及可能具有的歧化图型式;对非一级反应系统,利用区域搜索算法得到了其系统定态模型方程突变集合在操作参数平面上的投影图,分析了反应动力学表达式及动力学参数的变化对体系多定态特性的影响。     

ETHYLENE OXIDATION ON SILVER CATALYSTS: EFFECT OF ETHYLENE OXIDE AND OF EXTERNAL TRANSFER LIMITATIONS

Ethylene oxidation to ethylene oxide and to carbon dioxide over silver catalysts was studied in a CSTR. The effects of two factors on the catalyst performance were examined. The first was the presence of excess ethylene oxide in the feed. A kinetic model was introduced which assumed that ethylene and ethylene oxide compete for the same sites on the catalyst surface. This model provided reasonable quantitative agreement with kinetic and potentiometric measurements. The second factor that was studied was the presence of external heat and mass transfer limitations. It was found that such limitations cause a significant decrease of the selectivity to ethylene oxide. This decrease is a result of the temperature difference between the catalyst surface and the bulk of the gas phase and of the fact that the activation energy of ethylene combustion is greater than that of ethylene epoxidation. The contribution of other factors such as inhibition by CO₂ or possible incomplete mixing in the reactor is shown to be insignificant.     

Modelling of fluidized bed reactors—II: Uniform catalyst temperature and concentration

A model based on the simple two phase theory of fluidization including the catalyst particles as a third phase has been developed for a nonisothermal fluidized bed catalytic reactor with continuous circulation of catalyst particles. The dilute phase is assumed to be in plug flow, the emulsion phase gas is considered to be perfectly mixed and the particles are assumed to be perfectly mixed and uniform.Exact criteria for uniqueness and multiplicity of the steady state solutions are presented and some conclusions derived therefrom. Several examples illustrating the influence of some parameters on the steady state multiplicity are reported. The steady states are analyzed for local asymptatic stability using Liapunov's direct method, but the sufficient conditions for stability are found to be rather conservative.Numerical examples illustrating the transient behavior of the system are presented, and it has been found that the initial temperature of the catalyst particles is a predominant factor in determining which steady state will be approached.     

环柱状催化剂内强放热复合反应──传质──传热耦合过程研究(Ⅰ)催化剂曲折因子、有效导热系数的测定

采用经典定态法和改进的单颗粒线反应器法（SPSRM)测定了环柱状环氧乙烷银催化剂的曲折因子,两种方法测定结果十分吻合。提出一种测定固体催化剂颗粒有效导热系数的新方法。该方法简单、方便且不改变催化剂原有的形状及物理结构,可以在催化剂允许使用的任何温度下进行测定,准确度较高。用本方法测定了环氧乙烷合成银催化剂颗粒的有效导热系数,并用于催化剂内部浓度、温度、选择性计算,计算与实验结果吻合良好。     

环柱状催化剂内强放热复合反应──传质──传热耦合过程研究(Ⅰ)催化剂曲折因子、有效导热系数的测定

采用经典定态法和改进的单颗粒线反应器法（SPSRM)测定了环柱状环氧乙烷银催化剂的曲折因子,两种方法测定结果十分吻合。提出一种测定固体催化剂颗粒有效导热系数的新方法。该方法简单、方便且不改变催化剂原有的形状及物理结构,可以在催化剂允许使用的任何温度下进行测定,准确度较高。用本方法测定了环氧乙烷合成银催化剂颗粒的有效导热系数,并用于催化剂内部浓度、温度、选择性计算,计算与实验结果吻合良好。     

Dynamic mathematical modeling of a novel dual-type industrial ethylene oxide (EO) reactor

In this paper, the dynamic behavior of a novel dual-type industrial ethylene oxide reactor has been proposed with taking catalyst deactivation into account. The configuration of two catalyst beds instead of one single catalyst bed is developed for conversion of ethylene to ethylene oxide. In the first reactor which is an industrial fixed-bed water-cooled reactor, the feed gas is partly converted to ethylene oxide. This reactor functions at very high yield and at a higher than normal operating temperature. In the second converter, the reaction heat is used to preheat the feed gas to the first reactor and a milder temperature profile is observed. The potential possibilities of a two-stage catalyst bed system are analyzed using a 1D heterogeneous dynamic model to obtain necessary comparative estimates. A differential evolution (DE) algorithm is applied as an effective and robust method to optimize the reactors length ratio. The results obtained from the simulation demonstrate that there is a desirable catalyst temperature profile along the dual-type reactor (DR) compared with the conventional single-type reactor (SR). In this way, the catalysts are exposed to less extreme temperatures and thus, diminishing the catalyst deactivation via sintering. Results from this study provided beneficial information about the effects of reactors configuration on catalyst lifetime and ethylene oxide production rate simultaneously.     

Steady-state modeling and bifurcation behavior of circulating fluidized bed membrane reformer-regenerator for the production of hydrogen for fuel cells from heptane

The production of hydrogen for fuel cells by steam reforming of heptane is investigated in a Circulating Fluidized Bed Membrane Reformer-Regenerator (CFBMRR) system (A.I.Ch.E. Journal 49(5) (2003) 1250). Palladium based hydrogen permselective membranes are used for hydrogen removal and dense perovskite oxygen permselective membranes are used for oxygen introduction. A series of pseudo-steady-state simulations show that when the catalyst is not regenerated, the circulating nickel reforming catalyst deactivates quickly and the “half catalyst activity life” for efficient production of hydrogen is quite short, especially at high temperatures. Efficient continuous catalyst regeneration can keep the catalyst activity high (∼1.0). With continuous catalyst regeneration, autothermal operation for the entire adiabatic reformer-regenerator system is achievable when the exothermic heat generated from the catalyst regenerator is sufficient to compensate for the endothermic heat consumed in the riser reformer. This type of autothermal operation becomes less likely at high steam to carbon feed ratios. This is due to the fact that carbon deposition rate decreases leading to the decrease of autothermal circulating feed temperature and energy-based hydrogen yield (adiabatic hydrogen yield in autothermal reformer-regenerator system). Multiplicity of the steady states for the reformer is possible for this configuration. With the steam to carbon feed ratio as the bifurcation parameter, multiplicity occurs between the two bifurcation points 1.444 and 2.251 mol/mol. In this multiplicity region, the energy-based hydrogen yield at the upper steady state with high regenerator output temperature is surprisingly the lowest one. While it is the highest one at the lower steady state with low regenerator output temperature. The maximum energy-based hydrogen yield is about 15.58 moles of hydrogen per mole of heptane fed at the lower steady-state when steam to carbon feed ratio is very close to the bifurcation value of 1.444 mol/mol. After removing the sweep gas steam by downstream cooling and de-humidification, the product hydrogen from steam reforming of hydrocarbons can be used for fuel cells with high purity (∼100%).     

Effect of Polymer Particle Size and Inlet Gas Temperature on Industrial Fluidized Bed Polyethylene Reactors

Static and dynamic bifurcation behaviors dominate the operation of fluidized bed catalytic reactors for the production of polyethylene (UNIPOL Process) and have important implications on the safe operating temperature and polyethylene production rate. The investigations show that the multiplicity of the steady state phenomenon covers a wide range of parameters together with the phenomenon of periodic oscillations with sharply changing amplitudes with a change of the chosen bifurcation parameter. In some cases, the periodic branches terminate through periodic limit point (PLPs), while in other cases it terminates homoclinically. A detailed parameteric investigation using two-parameter continuation diagrams for the loci of static and Hopf bifurcation points as well as one parameter bifurcation diagrams shows that it is possible to increase the productivity of the unit considerably without exceeding the constraints of the polymer melting point. Gas feed temperature, catalyst feed rate, and polymer particle size distribution are important operating parameters in polyethylene fluidized bed reactors. Gas velocity plays a significant role in keeping the fluidized bed bubbling in addition to the fact that it acts as a cooling media by removing excess heat generated from the polymerization reaction. The kinetic behavior of the catalyst and effect of reactor temperature on product properties require, in some cases, operating just below the softening point of the polymer which requires a suitable controller to avoid polymer melting.     

铂催化剂上乙烯和一氧化碳同时氧化反应多定态特性的实验研究

对铂催化剂上乙烯和一氧化碳同时氧化反应多定态特性的实验研究结果表明：在实验条件下体系最多存在有两个稳定的定态,随乙烯和／或一氧化碳浓度的增加,系统的点火温度升高,熄火温度下降,存在多定态的操作参数区域增大;在较高的乙烯和／或一氧化碳浓度条件下,系统将出现自持,实验观测不到熄火现象。通过对体系多定态特性的分析可知,同时氧化反应体系的多定态特性并不等于两个单独氧化反应体系多定态特性的简单迭加,在两个反应之间,除了热量的相互作用外,还存在着动力学抑制作用。     

Selective hydrogenation of acetylene over Pd/CeO2

Five hundred ppm Pd/CeO₂ catalyst was prepared and evaluated in selective hydrogenation of acetylene in large excess of ethylene since ceria has been recently found to be a reasonable stand-alone catalyst for this reaction. Pd/CeO₂ catalyst could be activated in situ by the feed gas during reactions and the catalyst without reduction showed much better ethylene selectivity than the reduced one in the high temperature range due to the formation of oxygen vacancies by reduction. Excellent ethylene selectivity of ~100% was obtained in the whole reaction temperature range of 50°C–200°C for samples calcined at temperatures of 600°C and 800°C. This could be ascribed to the formation of Pd_xCe_1−xO_2−y or Pd-O-Ce surface species based on the X-ray diffraction and X-ray photoelectron spectroscopy results, indicating the strong interaction between palladium and ceria.     

Modeling and simulation of an integrated multi-shell fixed bed membrane reactor with well-mixed catalyst pattern for production of styrene and cyclohexane

A rigorous two-dimensional steady state mathematical model based on the dusty gas model is implemented to investigate the performance of a bench-scale integrated multi-shell fixed bed membrane reactor with well-mixed catalyst pattern for simultaneous production of styrene and cyclohexane. Since the styrene producing reaction is equilibrium limited, significant displacement of the thermodynamic equilibrium is achieved by three simultaneous actions of an auxiliary hydrogenation reaction of benzene using a well-mixed catalyst pattern, the membrane and the multi-shell reactor configuration. The simulation results show that the complete conversion of ethylbenzene is possible at relatively low temperature and shorter reactor length. Effective operating regions with optimal conditions are observed and explanations offered. An effective length criterion for the optimal conditions is presented. The effective operating regions are found to be sensitive to changes of catalyst bed composition, feed temperature, feed pressure and shells ratio. It is also found that the multi-shell configuration is superior to the single shell configuration. Although this investigation is restricted to two catalysts and two shells, some of the rich characteristics of this system have been uncovered.     

液相合成甲醇催化剂活性的研究

The effects of reduction procedure, reaction temperature and composition of feed gas on the activity of a CuO-ZnO-Al2O3 catalyst for liquid phase methanol synthesis were studied. An optimized procedure different from conventional ones was developed to obtain higher activity and better stability of the catalyst. Both CO and CO2 in the feed gas were found to be necessary to maintain the activity of catalyst in the synthesis process. Reaction temperature was limited up to 523K, otherwise the catalyst will be deactivated rapidly. Experimental results show that the catalyst deactivation is caused by sintering and fouling, and the effects of CO and CO2 on the catalyst activity are also investigated. The experimental results indicate that the formation of water in the methanol synthesis is negligible when the feed gas contains both CO and CO2. The mechanism for liquid-phase methanol synthesis was discussed and it differed slightly from that for gas-phase synthesis.     

The partial oxidation of some cyclohexenes and branched chain olefins over a silver catalyst

The oxidation of some cyclic and branched chain olefins over a silver catalyst effective for the conversion of ethylene to ethylene oxide has been investigated in a steady state flow system. The reaction of cyclohexene produces benzene and that of both 1-methylcyclohexene and 4-methylcyclohexene yields toluene. The selectivity to aromatics exceeds 20% for fractional conversions below 0.2, but it can be improved to almost 50% by inclusion of an optimum quantity of dichloroethane in the feed. Styrene is oxidised more slowly than the cyclohexenes and only carbon dioxide and water are produced. The oxidation of 3,3-dimethyl-1-butene and 3-methyl-1-butene occurs much faster than that of the cyclic molecules and some of the corresponding epoxides are produced. The selectivity with the dimethyl-butene is 9–13% for conversions to 0.2. The methylbutene requires a higher temperature for reaction and the epoxide yield is lower. Factors influencing reactivity and product distribution are discussed.     

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.     

三相鼓泡淤浆床环氧乙烷合成反应器数学模拟及工程分析

建立了加压三相鼓泡淤浆床环氧乙烷合成反应器的数学模型 ,计入了催化剂颗粒在床层中沉降形成沿床高浓度分布对反应的影响以及由于惰性液相载体部分返混对传递的影响 ,进一步利用经实验验证的上述数学模型模拟不同表观气速、床高、反应器直径 (扣除传热元件截面积 )、进口乙烯摩尔分数等参数对床层中催化剂浓度随床高的分布、出口环氧乙烷摩尔分数、环氧乙烷选择率以及单位质量催化剂环氧乙烷年产量的影响 .通过模拟分析预示了工业三相床环氧乙烷反应器的合理尺寸、表观气速、环氧乙烷选择率以及时空产率 ,为工业化提供必要的设计依据     

Oxidation of ethylene to ethylene oxide: catalyst deactivation in an industrial run

The deactivation of a silver catalyst for the selective oxidation of ethylene to ethylene oxide was investigated after six years of industrial use. Some tubes of the reactor were unloaded and the catalyst was divided into five parts: sample U1 at the gas inlet (top of the reactor) to sample U5 at the gas outlet were compared with fresh catalyst (F). This permitted the determination of a deactivation profile along the reactor. The performances of the fresh and discharged catalysts were examined in an internal recycle reactor in the range 503 – 543 K. The rate of ethylene oxidation (at a constant feed composition and reaction temperature) and the selectivity to ethylene oxide (at a constant ethylene conversion) varied according to the sequence F ≫ U5 ≅ U4 ≅ U3 > U2 > U1. At the same temperature, U1 and U2 were not only the least active, but also the least selective catalysts. The specific rate of ethylene oxidation (based on O₂ chemisorption data) followed a reverse sequence: U1 ≅ U2 > U4 > F. The apparent activation energies for the formation of ethylene oxide and of carbon dioxide were lower for U1 than for the other samples. Catalyst U1 was peculiar also for the temperature oscillations occurring in the reactor. The physico-chemical characterization of the samples has shown that (i) contamination by sulphur decreases from U1 to U5, (ii) oxygen uptake varies according to the sequence F > U4 > U2 ≅ U1, (iii) silver sintering occurred in the discharged catalysts and seems to be more pronounced for the top levels of the reactor tube and (1v) for some silver particles, changes of morphology accompany the metal sintering. Based on the previous literature, these findings were examined as possible explanations of the modified performances of the discharged catalyst.     

Oxidative coupling of methane over K/Ni/Ca oxide and K/Ni/Mg oxide catalysts

The oxidative coupling behaviour of a series of K/Ni/Ca oxide catalysts with low nickel-to-calcium ratios has been examined and the results are compared with those for a magnesium-based catalyst. The effect of gas composition and the stability of ethylene under reaction conditions have also been studied. The catalysts were calcined at 1200°C unless otherwise stated. Potassium was added after the calcination stage. It is found that a high calcination temperature of 1200°C is necessary to give a Ca-based catalyst with high activity and selectivity. The catalysts based on MgO were less selective. Substitution of K for Li in the MgO based catalyst gave a slight improvement in the selectivity. A series of experiments was carried out with the K_0.1Ni_0.012 Ca material with the aim of optimising the yield. It was found that the selectivity could be improved by increasing the concentration of CH₄ or by adding CO₂ to the feed. However the addition of CO₂ decreased the activity of the catalyst. The activity could be increased by increasing the H₂O concentration. An increase of the O₂ concentration in the feed from 10.85 to 13% with 31% of CH₄ and 21% H₂O increased the C₂ yield from 15.1% to 17.8%. In a series of experiments in which different concentrations of C₂H₄ were added to the feed, it was found that the main oxidation product of ethylene was CO₂. The formation of ethane was unaffected by the addition of ethylene. It is therefore proposed that two different sites are required for the oxidation of ethylene and the activation of methane to form ethane.