基于非平衡级模型的低温甲醇洗流程模拟

对于多级分离过程的模拟通常都采用平衡级模型,而实际化工过程的非理想性使其应用受到了很大限制。本文引入非平衡级模型,采用修正的PSRK物性方法用Aspen plus软件对低温甲醇洗流程的吸收塔及CO2解吸塔进行模拟研究,并将其模拟结果与平衡级模型作对比。该模型下对吸收塔及CO2解吸塔的模拟结果都与设计值吻合很好。并将该流程吸收塔的非平衡级模型计算结果与本文作者教研组前期工作中研究的吸收塔的非平衡级模型结果作对比。研究结果表明,非平衡级模型可以应用于低温甲醇洗流程的模拟计算,为低温甲醇洗流程的设计计算提供了可靠的技术支持。     

A two-fluid model for non-equilibrium two-phase critical discharge

A general two-fluid model is developed to predict critical (choked) flow of initially saturated or subcooled flow from pipes and nozzles. The model contains improvements in the basic formulation, constitutive relations and solution technique over previously published models. It consists of six conservation equations as well as a seventh equation representing bubble growth in bubbly flow. It allows for hydrodynamic as well as thermal non-equilibrium. The model considers the development of three flow regimes, namely, bubbly, churn and annular flow regimes. The model predictions were compared with the limited available experimental data for which the axial pressure distributions were recorded. Excellent agreement was obtained.     

Homogeneous non-equilibrium two-phase critical flow model

An important aspect of nuclear and chemical reactor safety is the ability to predict the maximum or critical mass flow rate from a break or leak in a pipe system. At the beginning of such a blowdown, if the stagnation condition of the fluid is subcooled or slightly saturated thermodynamic non-equilibrium exists in the downstream, e.g. the fluid becomes superheated to a degree determined by the liquid pressure. A simplified non-equilibrium model, explained in this report, is valid for rapidly decreasing pressure along the flow path. It presumes that fluid has to be superheated by an amount governed by physical principles before it starts to flash into steam. The flow is assumed to be homogeneous, i.e. the steam and liquid velocities are equal. An adiabatic flow calculation mode (Fanno lines) is employed to evaluate the critical flow rate for long pipes. The model is found to satisfactorily describe critical flow tests. Good agreement is obtained with the large scale Marviken tests as well as with small scale experiments.     

A non-equilibrium model for fixed-bed multi-component adiabatic adsorption

A mathematical model for adiabatic adsorption of multiple components onto a fixed bed of adsorbent is developed. The model consists of a set of coupled, hyperbolic, parial-differential equations. Heat and mass transfer resistances evident in real systems are included in the model. Solutions of the equations are obtained by numerical application of the method of characteristics. Results show non-ideal mass and thermal wavefronts and complex wave-wave interactions in adiabatic adsorption of benzene and cyclohexane onto activated carbon. Phenomena of inversions in relative adsorptivity due to temperature changes are also shown. Column performance is indicated to be greatly affected by these phenomena. Cases considered demonstrate that time on stream before breakthrough may be doubled by increasing influent and initial bed temperatures. It is shown, in contrast to results obtained fron using the non-equilibrium model, that models based on assumptions of local equilibrium cannot quantitatively describe behavior of a typical industrial adsorption system.     

乙酸与正丁醇催化精馏过程模拟

用平衡级与拟均相非平衡级模型对乙酸和正丁醇催化精馏过程进行了数学模拟，结果表明，2种模型所得结果与实验值吻合较好，计算所得的汽液相浓度和汽液相流速沿塔高的分布规律与实验结果一致。     

液体中气泡上浮与传质过程的耦合模型

针对液体中气泡上浮与传质这一非稳态、强耦合过程,分析气泡的受力情况,考虑到非恒定Basset力的影响,得出了气泡瞬态加速度模型;利用绕球流动传质边界层模型,并引入非平衡传质理论,构建了气泡的瞬态非平衡传质模型;进而依据气泡质量变化率将两模型耦合,以此构建了完整描述这一过程的耦合模型。计算实例表明,Basset力对难溶性气泡的运动过程无明显影响,但对易溶性气泡影响显著;传质条件则对两类气泡都具有重要影响,且该模型中引入非平衡传质理论后,计算值与难溶性气泡的实验结果吻合更好。     

A three-phase nonequilibrium dynamic model for catalytic distillation

A detailed three-phase nonequilibrium (NEQ) dynamic model for simulating batch and continuous catalytic distillation (CD) processes has been developed. In this model, both molar and energy holdups in liquid and vapour phases are taken into account. Multicomponent mass transfer and heat transfer between vapour and liquid phases as well as between liquid and solid (catalyst) phases are described by the Maxwell-Stefan equations. The resulting differential and algebra equations in this model are implemented in gPROMS and C++. The simulation results are in good agreement with the experimental data obtained from the batch and continuous CD processes for the production of diacetone alcohol (DAA) using Amberlite IRA-900 as a catalyst. Sensitivity analysis on the mass transfer and kinetics using the three-phase NEQ dynamic model indicates that the formation of DAA is controlled by solid-liquid mass transfer, whereas the formation of mesityl oxide is kinetically controlled under the simulation conditions.     

Numerical approximation of nonlinear and non-equilibrium two-dimensional model of chromatography

This article is concerned with the numerical approximation of a nonlinear model describing the two-dimensional non-equilibrium transport of multi-component mixtures in a chromatographic column of cylindrical geometry. In contrast to previous studies, the work includes joint analysis of deviations from equilibrium and the possibility that radial concentration profiles can develop. The considered radial gradients are typically ignored, which can be problematic in the case of non perfect injections. The model consists of nonlinear convection-diffusion partial differential equations coupled with some differential and algebraic equations. A high resolution finite volume scheme is applied to solve the model equations numerically. The considered case studies include single-component, two-component and three-component elution on fixed (non-movable) beds of liquid chromatography. The developed numerical algorithm is an efficient tool to study the effects of mass transfer kinetics on the elution profiles.     

列管固定床反应器内CO氧化偶联制草酸二甲酯反应模拟及优化

针对列管式固定床反应器中的单根反应管,采用在接近工业条件下获得的CO氧化偶联制草酸二甲酯动力学方程,建立了一维、二维拟均相模型,并与单管实验结果进行了对比,结果表明一维拟均相反应器模型更能准确描述单管反应器内的CO偶联反应。进一步利用一维拟均相模型模拟计算了操作参数对床层热点温度、反应转化率、产物选择性及床层压降的影响,分析了反应器热点温度对操作参数的敏感性。计算结果表明：冷却介质温度对反应管热点温度、亚硝酸甲酯转化率有较大影响,是需要严格控制的工艺指标;较低的空速容易引起反应器飞温;反应器进口压力、原料气进料温度和反应物组成在计算范围内对反应器热点温度影响相对较小。为了提高偶联反应器的负荷和强化床层内的传热效果,可以将进料空速提高至4000 h^-1,同时,可以通过将反应器进口压力增大至500 kPa来降低压缩机能耗。研究结果可为现有列管式CO氧化偶联反应器的改进和工艺优化提供参考。     

Modeling a non-equilibrium distillation stage using irreversible thermodynamics

We compare transport equations derived from non-equilibrium thermodynamics to a classical rate model developed over the last 20 years, in terms of their ability to calculate the heat and mass fluxes by modeling a segment of a packed distillation column. We show, using water and ethanol separation as an example, that there is a significant coupling between heat and mass transfer. Neglect of this transport coefficient leads to variations in the magnitude, even the sign of the calculated heat flux, while the mass flux is less affected.     

湿蒸汽非平衡凝结流动的热力学特性

水蒸气凝结两相流动呈现高度的非平衡特性。目前,凝结参数都是利用半经验公式得出,很少考虑两相间传热温差以及耦合问题。在湿蒸汽两相流输运方程的基础上,建立了一种准确简单的凝结成核和水滴生长模型,采用具有较好激波捕获效果的高精度二阶TVD格式进行离散,计算了湿蒸汽非平衡凝结流动参数及凝结冲波分布。着重研究了湿蒸汽非平衡凝结流动的热力学特性,讨论了进口压力对凝结特性的影响,归纳了进口过冷度对成核率、水滴数、凝结冲波形态的变化规律。研究表明:进口压力增加,凝结位置逐渐向上游移动;进口过冷度降低,凝结位置向下游移动,达到较高的Mach数后,才会出现凝结成核;进口过冷度越高,非平衡凝结相变产生的湿度越高。凝结冲波出现后,湿蒸汽沿喷管继续高速流动,其流动规律与等熵流动相似。     

Modeling of an industrial fixed bed reactor based on lumped kinetic models for hydrogenation of pyrolysis gasoline

In this work, a mathematical model of an industrial fixed bed reactor for the catalytic hydrogenation of pyrolysis gasoline produced from olefin production plant is developed based on a lumped kinetic model. A pseudo-homogeneous system for liquid and solid phases and three pseudo-components: diolefins, olefins, and parraffins, are taken into account in the development of the reactor model. Temperature profile and product distribution from real plant data on a gasoline hydrogenation reactor are used to estimate reaction kinetic parameters. The developed model is validated by comparing the results of simulation with those collected from the plant data. From simulation results, it is found that the prediction of significant state variables agrees well with the actual plant data for a wide range of operating conditions; the developed model adequately represents the fixed-bed reactor.     

Kinetics measurement of ethylene-carbonate synthesis via a fast transesterification by microreactors

High-purity ethylene carbonate (EC) is widely used as battery electrolyte, polycarbonate monomer, organic intermediate, and so on. An economical and sustainable route to synthesize high-purity ethylene carbonate (EC) via the transesterification of dimethyl carbonate (DMC) with ethylene glycol (EG) is provided in this work. However, this reaction is so fast that the reaction kinetics, which is essential for the industrial design, is hard to get by the traditional measuring method. In this work, an easy-to-assemble microreactor was used to precisely determine the reaction kinetics for the fast transesterification of DMC with EG using sodium methoxide as catalyst. The effects of flow rate, microreactor diameter, catalyst concentration, reaction temperature, and reactant molar ratio were investigated. An activity-based pseudo-homogeneous kinetic model, which considered the non-ideal properties of reaction system, was established to describe the transesterification of DMC with EG. Detailed kinetics data were collected in the first 5 min. Using these data, the parameters of the kinetic model were correlated with the maximum average error of 11.19%. Using this kinetic model, the kinetic data at different catalyst concentrations and reactant molar ratios were predicted with the maximum average error of 13.68%, suggesting its satisfactory prediction performance.     

Runaway Criterion in Fixed Bed Catalytic Reactors with Radial Temperature Profile

The discrepancy between pseudo-homogeneous one-dimensional model and peeudo-homogeneous two-dimensional model is studied. It is found that there are great differences between two models. This paper compares the maximum and minimum values of the radial temperature in the hot spot in came that a single exothermic reaction is carried out, a correlation is obtlioed with peeudo-homogeneous one-dimensional model to describe the entire reactor behavier. A new runaway criterion, based on the occurrence of inflection in the hot spot locus, is developed for the case of pseudo-homogeneous two-dimensional model. This criterion predicts the maximum allowable temperature for safe operation and the regions of runaway, respectively. The calculated results show that, compared with the results based on pseudo-homogeneous one-dimensional model, runaway will easily occur when the radial temperature gradient has to be considered.     

Experimental study and process simulation of n-butyl acetate produced by transesterification in a catalytic distillation column

The production of n-butyl acetate by transesterification of methyl acetate with n-butanol, catalyzed by acidic ion-exchange resin NKC-9, was experimentally investigated in a homemade catalytic distillation column with a diameter of 80 mm. A non-equilibrium stage model for describing the catalytic distillation process was established and solved with Newton-Homotopy method. The effect of feeding mode, reflux ratio, material molar ratio and number of reactive sections on the conversion of methyl acetate was investigated. The experimental results agree well with those obtained by the theoretical simulation calculations, indicating the accuracy and reliability of the non-equilibrium model. It can be concluded that the non-equilibrium model established in this paper can provide theoretical guidance for the further process design and optimization.     

跨临界CO2快速膨胀过程中非平衡冷凝和闪蒸机理的数值研究

跨临界CO₂在高速膨胀时,压力和温度剧烈下降,会发生非平衡相变。其中在天然气超声速分离设备和超临界CO₂离心压缩机中CO₂会发生非平衡冷凝相变;在引射膨胀制冷系统中,跨临界CO₂在引射器主动喷嘴中发生非平衡闪蒸相变。为解决跨临界CO₂在膨胀过程中物性变化剧烈,非平衡相变模拟困难的问题,构建了新型非平衡相变CFD模型,以研究跨临界CO₂在超声速缩放喷嘴中的非平衡冷凝和非平衡闪蒸的相变过程和膨胀机理,模型耦合了温度驱动的蒸发-冷凝相变机制和压力驱动的空化-冷凝相变机制,并用文献中的试验结果验证了模型的准确性。研究结果表明,在冷凝相变过程中,由压力驱动的冷凝传质具有主要影响,压力驱动的冷凝传质主要存在于喷嘴喉部与内流区域,温度驱动的冷凝传质主要存在于喷嘴渐扩段壁面。冷凝传质速率随着进口压力的增加和进口温度的降低而增加,从而使冷凝的非平衡程度和喷嘴内的干度降低,喷嘴渐扩段内达到声速的位置也相应延后。在闪蒸相变过程中,由温度驱动的蒸发传质占据主导,蒸发相变主要发生在喷嘴喉部附近,空化相变主要发生在喷嘴渐扩段,两相CO₂在喷嘴的渐扩段达到声速。随着喷嘴进口压力的增加和进口温度的降低,闪蒸的非平衡程度增加,使喷嘴内的干度减小。本研究有助于厘清跨临界CO₂快速膨胀中的非平衡闪蒸和冷凝相变机理,并为跨临界CO₂膨胀设备的分析和优化设计提供参考。     

跨临界CO2快速膨胀过程中非平衡冷凝和闪蒸机理的数值研究

跨临界CO₂在高速膨胀时,压力和温度剧烈下降,会发生非平衡相变。其中在天然气超声速分离设备和超临界CO₂离心压缩机中CO₂会发生非平衡冷凝相变;在引射膨胀制冷系统中,跨临界CO₂在引射器主动喷嘴中发生非平衡闪蒸相变。为解决跨临界CO₂在膨胀过程中物性变化剧烈,非平衡相变模拟困难的问题,构建了新型非平衡相变CFD模型,以研究跨临界CO₂在超声速缩放喷嘴中的非平衡冷凝和非平衡闪蒸的相变过程和膨胀机理,模型耦合了温度驱动的蒸发-冷凝相变机制和压力驱动的空化-冷凝相变机制,并用文献中的试验结果验证了模型的准确性。研究结果表明,在冷凝相变过程中,由压力驱动的冷凝传质具有主要影响,压力驱动的冷凝传质主要存在于喷嘴喉部与内流区域,温度驱动的冷凝传质主要存在于喷嘴渐扩段壁面。冷凝传质速率随着进口压力的增加和进口温度的降低而增加,从而使冷凝的非平衡程度和喷嘴内的干度降低,喷嘴渐扩段内达到声速的位置也相应延后。在闪蒸相变过程中,由温度驱动的蒸发传质占据主导,蒸发相变主要发生在喷嘴喉部附近,空化相变主要发生在喷嘴渐扩段,两相CO₂在喷嘴的渐扩段达到声速。随着喷嘴进口压力的增加和进口温度的降低,闪蒸的非平衡程度增加,使喷嘴内的干度减小。本研究有助于厘清跨临界CO₂快速膨胀中的非平衡闪蒸和冷凝相变机理,并为跨临界CO₂膨胀设备的分析和优化设计提供参考。     

Experimental study and model of reaction kinetics of heterogeneously catalyzed methylal synthesis

Reaction kinetics of the heterogeneously catalyzed formation of methylal from aqueous methanolic formaldehyde solutions are studied in a plug flow reactor at 323, 333 and 343 K using the acidic ion exchange resin Amberlyst 15 (Rohm and Haas) as catalyst. Parameters of an activity-based pseudo-homogeneous reaction kinetic model are fitted to the experimental results. The model is based on the true speciation in the reacting solution and explicitly includes the oligomerization reactions of formaldehyde in aqueous methanolic solutions. The reaction kinetic model describes the experimental data well and is suited for process simulations in which both chemical reactions and phase equilibria have to be described simultaneously.     

考虑非平衡状态的裂缝性油藏周期注水分析

周期注水主要是利用毛管力的自吸作用，使低渗透层的油流入高渗透层，如此反复，低渗透层的油不断被采出，从而提高了油藏的采收率。在常规数值模拟中，相对渗透率是饱和度的函数，与时间无关。然而，实际周期注水的吸入过程是一种典型的非平衡过程，相对渗透率不但是饱和度的函数，还是时间的函数。而常规周期注水工艺和数值模拟研究中，却忽略了这个影响，导致周期注水效果与预期结果不符。基于Barenblatt的非平衡模型，本文研究了非平衡自吸过程对周期注水提高采收率的影响。结果表明考虑非平衡自吸过程后，周期注水提高采收率的程度比常规数值模拟周期注水所预期的要差，特别是在高含水期，非平衡自吸过程的影响会更加突出。这为我们选择和使用周期注水这一工艺提供了一定的指导意义。     

非平衡级法气体混合物吸收-水合双塔分离单元的模拟计算

水合物技术应用于低沸点气体混合物分离的优势在于其可在0℃左右操作,因此可极大地降低制冷所消耗的能量。由于此分离方法尚处在理论研究阶段,还不能实现工业化,因此对操作流程模拟计算的研究很有必要。采用非平衡级法(速率法)对水合塔-吸收塔串联操作流程进行了模拟计算,其中涉及水合物生成动力学模型、水合物分解动力学模型以及混合气体在乳液相的吸收传质动力学模型。探讨了两个串联分离塔操作参数,如温度、压力等,对分离效率的影响,所得结果对水合物技术分离低沸点气体混合物流程的设计有重要意义,同时也可为以后的工业化奠定一定的理论基础。