填料型预碳化塔的数学模型与模拟 ‘

硕酸化反应为一典型的连串、可逆放热反应,液膜内的快反应与液相本体的慢反应相互耦合,共同决定着ＣＯ２的化学吸收速率。本文在以往工作的基础上,通过对碳化机理和动力学的全面分析,建立了填料型预碳化塔的数学模型。对有关工业过程进行了模拟,指出了影响填料行为的关键因素并提出了相应的改进措施。     

Experimental investigation and mathematical modelling of wood combustion in a moving grate boiler

The use of biomass to generate energy offers significant environmental advantages for the reduction in emissions of greenhouse gases. The main objective of this study was to investigate the performance of a small scale biomass heating plant: i.e. combustion characteristics and emissions. An extensive series of experimental tests was carried out at a small scale residential biomass heating plant i.e. wood chip fired boiler. The concentrations of CO, NO_x, particulate matter in the flue gas were measured. In addition, mathematical modelling work using FLIC and FLUENT codes was carried out in order to simulate the overall performance of the wood fired heating system. Results showed that pollutant emissions from the boiler were within the relative emission limits. Mass concentration of CO emission was 550-1600 mg/m³ (10% O₂). NO_x concentration in the flue gas from the wood chips combustion varied slightly between 28 and 60 ppmv. Mass concentration of PM₁₀ in the flue gas was 205 mg/m³ (10% O₂) The modelling results showed that most of the fuel was burnt inside the furnace and little CO was released from the system due to the high flue gas temperature in the furnace. The injection of the secondary air provided adequate mixing and favourable combustion conditions in the over-bed chamber in the wood chips fired boiler. This study has shown that the use of wood heating system result in much lower CO₂ emissions than from a fossil fuel e.g. coal fired heating system.     

Non-isothermal lipase-catalyzed kinetic resolution in a packed bed reactor: Modeling, simulation and miniplant studies

A rigorous model is developed for the exothermic kinetic resolution of 1-methoxy-2-propanol with vinyl acetate catalyzed by immobilized Candida antarctica lipase B in a packed bed reactor. The non-isothermal two-dimensional heterogeneous model takes into account the coupled mass and energy balances, the uneven flow distribution and irreversible ping-pong bi-bi kinetics with competitive substrate inhibition by both enantiomers. This model is based on kinetic parameters, which were estimated in earlier work. The model simulation is validated with experimental results obtained in a fully automated modular miniplant and is shown to be capable of predicting the key parameters needed for process design of a kinetic resolution, the enantiomeric excess and the extent of conversion at a given superficial velocity.     

Tracer investigation of a packed column under variable flow

Tracer techniques are well-established methods in investigations of a flow process dynamics. The concept of experimental evaluation of residence time distribution (RTD) is widely utilized. There exist advanced methods of RTD function analysis. The methods generally assume the constant flow rate in the system. In this work, we aim to determine the flow parameters for a process under variable flow rate using ordinary tracer data. The experimental study analyzed as an illustration of the method is the tracer experiment carried out on a pilot scale system—packed bed reactor.     

Simulations of chemical absorption in pilot-scale and industrial-scale packed columns by computational mass transfer

A complex computational mass transfer model (CMT) is proposed for modeling the chemical absorption process with heat effect in packed columns. The feature of the proposed model is able to predict the concentration and temperature as well as the velocity distributions at once along the column without assuming the turbulent Schmidt number, or using the experimentally measured turbulent mass transfer diffusivity. The present model consists of the differential mass transfer equation with its auxiliary closing equations and the accompanied formulations of computational fluid dynamics (CFD) and computational heat transfer (CHT). In the mathematical expression for the accompanied CFD and CHT, the conventional methods of k-ε and are used for closing the momentum and heat transfer equations. While for the mass transfer equation, the recently developed concentration variance and its dissipation rate ε_c equations (Liu, 2003) are adopted for its closure. To test the validity of the present model, simulations were made for a pilot-scale randomly packed chemical absorption column of 0.1 m ID and 7 m high, packed with 1/2^″ ceramic Berl saddles for CO₂ removal from gas mixture by aqueous monoethanolamine (MEA) solutions (Tontiwachwuthikul et al., 1992 ) and an industrial-scale randomly packed chemical absorption column of 1.9 m ID and 26.6 m high, packed with 2^″ stainless steel Pall rings for CO₂ removal from natural gas by aqueous MEA solutions (Pintola et al., 1993). The simulated results were compared with the published experimental data and satisfactory agreement was found between them in both concentration and temperature distributions. Furthermore, the result of computation also reveals that the turbulent mass transfer diffusivity D_tvaries along axial and radial directions. Thus the common viewpoint of assuming constant D_t throughout the whole column is questionable, even for the small size packed column. Finally, the analogy between mass transfer and heat transfer in chemical absorption is demonstrated by the similarity of their diffusivity profiles.     

Simulation of activity loss of fixed bed catalytic reactor of MTO conversion using percolation theory

In this investigation, a reactor model for prediction of the deactivation behavior of MTO's porous catalyst in a fixed bed reactor is developed. Effect of coking on molecular transport in the porous structure of SAPO-34 has been simulated using the percolation theory. Thermal effects of the reaction were considered in the model and the temperature profile of the gas stream in the reactor was predicted. The predicted loss in catalyst activity with time-on-stream was in very good agreement with the experimental data. The resulting coke deposition and gas temperature profiles along the length of reactor suggested a reaction front moving toward the outlet of the fixed bed reactor at the operating experimental conditions of 1 h⁻¹ and 723 K for methanol space velocity and inlet temperature, respectively. Effects of space time, coordination of Bethe network, and effective diffusivity of component in reaction mixture on the reactor performance are presented.     

硫化氢在 Primene JM-T 中溶解度的测定与模型建立简

The primary aliphatic amine Primene JM-T was investigated as a potential absorbent for H2S removal. The solubility of HzS in JM-T was measured at 298, 313,333,353, and 368 K with H2S partial pressures from 20 to 760 kPa and HzS loading from 0.02 to 0.8 mol H2S per mol JM-T. Relevant physical properties, such as density, viscoslty and dielectric constant, ot the matenal were measured. ＇The thermodynamlc model with two-suttlX Margules equation was used to correlate the experimental vapor-liquid equilibrium data. Furthermore, the absorption mechanism in non-aqueous system is suggested and the difference between non-aqueous and aqueous absorption system is pointed out.     

Approximate design of loop reactors

A loop reactor (LR) is an N-unit system composed of a loop with gradually shifted inlet/outlet ports. This system was shown in our previous study [Sheintuch M., Nekhamkina O., 2005. The asymptotes of loop reactors. A.I.Ch.E. Journal 51, 224-234] to admit an asymptotic model for a loop of a fixed length with N→∞. Both the finite-unit and the asymptotic model exhibit a quasi-frozen or a frozen rotating pulse (FP) solution, respectively, within a certain domain of parameters that becomes narrower as feed concentration declines.In the present paper we derive approximate solutions of the ignited pulse properties in an LR as a function of the external forcing (switching) rate. Analysis of these solutions enable us to determine the maximal temperature in the system, as well as the boundaries of the FP domain. For the optimal solution we determine the maximal temperature and conversion dependencies on the reactor length and on N. The approximate solutions are verified by comparison with direct simulations of the asymptotic model and a good agreement was found. The obtained results can be successfully used for prediction of the finite unit LR.     

Study of gas cavity size hysteresis in a packed bed using DEM

When a high velocity gas jet is introduced into a packed bed a cavity is formed. The size of the cavity shows hysteresis on increasing and decreasing gas flow rates. This hysteresis leads to different cavity sizes at same gas flow rate depending on the bed history. The size of cavity affects the gas flow profiles in the packed bed. In this study the cavity size hysteresis phenomenon has been modeled using discrete element method along with turbulent gas flow. A reasonable agreement has been found between computed and experimental results on cavity size hysteresis. The effect of various parameters, such as nozzle height from the bed bottom and packing height, on the cavity size hysteresis has been studied. It is found that inter-particle interaction forces along with gas drag and bed porosity play an important role in describing the cavity size hysteresis. The injection of gas flow allows the particles to go to an unconstrained state than they were previously in, and their ability to remain in that state, even under decreased gas drag force, leads to the phenomenon of cavity size hysteresis.     

Transversal moving-front patterns: Criteria and simulations for two-bed and cylindrical shell packed-bed reactors

We show that a moving-front solution in a cylindrical shell packed-bed catalyzing a first-order activated reaction may bifurcate into transversal patterns when Pe_C/Pe_T<ΔT_ad/ΔT_m, i.e. when the ratio of the mass to heat Pe numbers is smaller than the ratio of the adiabatic to maximal temperature rises. This coincides with the previous condition of transversal patterns to emerge in stationary fronts [Pe_C/Pe_T<1 [Viswanathan, G., Bindal, A., Khinast, J., Luss, D., 2005. Stationary transversal hot zones in adiabatic packed-bed reactors. A.I.Ch.E. Journal 51, 3028-3038]] and extends the bifurcations condition to the case of moving fronts. The novel condition cannot be satisfied in a downstream propagating front (ΔT_m/ΔT_ad>1), but for an upstream propagating front (toward the cold reactor inlet) ΔT_m/ΔT_ad<1 and the symmetry breaking can be obtained within a feasible domain of operating conditions (Pe_C/Pe_T>1). It was also assumed that the axial and the transversal Pe numbers vary consistently, i.e. κ_C=Pe_C⊥/Pe_C=κ_T=Pe_T⊥/Pe_T. A similar condition was also obtained using a simplified model composed of two 1-D beds with heat and mass exchange between them.Bifurcation diagram showing domains of transversal patterns is constructed using a learning two-bed model. These predictions are verified by direct numerical simulations of the continuous 2-D cylindrical shell model showing various types of moving transversal patterns within a feasible domain of the state parameters with Pe_C>Pe_T. In the case of varying ratio (κ_C≠κ_T) the pattern domain can be significantly extended toward larger Pe_C/Pe_T.     

粗合成气净化系统脱硫塔的结构改进及应用

介绍中石油吉林石化公司化肥厂合成气装置脱硫系统生产工艺,由于原料渣油含硫量大幅度提高,装置投运时间长设备存在腐蚀与老化问题,粗合成气脱硫塔无法满足合成气中H2S含量低于5 mg/m3的要求,经改造,脱硫塔出口H2S含量降到2 mg/m3以下,延长了后部氧化锌精脱硫催化剂的使用周期.     

Modeling of a packed-bed electrochemical reactor for producing glyoxylic acid from oxalic acid

A two-dimensional reactor model was established for a packed-bed electrochemical reactor with cooled cathode (PERCC) for producing glyoxylic acid from oxalic acid based on the system's reaction kinetics, mass conservation equation, and the equation of charge conservation in terms of solution-cathode potential to describe the distributions of glyoxylic acid concentration and electrolyte potential in the cathode compartment of the PERCC. The equation for a circulating mixer was also presented to account for the accumulation of glyoxylic acid in the catholyte of a batch electroreduction process. Using the orthogonal collocation approach, the partial differential equations of the model could be converted into sets of algebraic equations and be numerically solved. The effects of operating temperature, conductivity of catholyte, operating cathode potential, and volumetric flow rate of the catholyte on the current efficiency and concentration of glyoxylic acid were simulated and discussed, with emphasis on the current densities generated from main and side reactions. The model was used in a batch operation process and a continuous operation process, with the predicted results being generally in good agreement with the experimental data for both the cases.     

Closed-form solution to the problem of reaction with fixed bed adsorption using delay-differential equations

Delay-differential equations (DDEs) can describe many chemical engineering models. However, the formalism of DDEs appears to be underutilized in chemical engineering. We have recast the canonical chemical engineering problem of batch reaction with fixed bed sorption into the form of a delay-differential equation, obtaining a more intuitive model and a simpler closed form solution than those previously reported. Considerable model reduction is possible through the use of DDE formalism when one considers that chemical processes can be partially represented by networks of transportation and state delays. Analytical and numerical methods for solution, as well as controllability and stability theory for systems of DDEs, are nearly as rich and developed as those for ordinary differential equations. Significant progress thus may be possible in areas such as the modeling, synthesis, and control of chemical processes, if the governing equations can be expressed in the form of delay-differential equations.     

气－固－固循环流化床填料层中压降及细颗粒含率的轴向分布

在气－固－固循环流化床中，尺寸较大的固相（通常作为催化剂）被固定在床中形成一段填料层，较小的固相一般为细颗粒（通常用作吸附剂或热载体）被气流携带穿过填料层。本文从讨论此类流化床中气－固两相并流流过填料层时压降的数学模型入手，应用实验测得的填料段的压降，细颗粒的平均动含率及细颗粒的循环流率等实验结果，回归了数学模型中的有关参数。在此基础上，应用这一数学模型对细粉的截面平均动含率在填料层轴向的分布行为进行了研究     

Modelling of gas interstitial velocity radial distribution over cross-section of a tube packed with granular catalyst bed; effects of granule shape and of lateral gas mixing

The previously presented [Zió?kowska, I., Zió?kowski, D., 1993. Modelling of gas interstitial velocity radial distribution over a cross-section of a tube packed with granular catalyst bed. Chemical Engineering Science 48, 3283-3292] mathematical model of gas flow field within a tube packed with a bed of spherical elements has been modernised. The modernisation consists in more rigorous treating of the radial gas dispersion within the bed voids in the fluid dynamic equations and in involving the formulae correlating the flow resistance in beds packed with various non-spherical elements (Raschig rings, cylinders) with their characteristics. The model solution relates the gas interstitial and superficial radial distributions with an empirical parameter—the local effective viscosity or corresponding Reynolds number, dependent on the geometric, aerodynamic and physical properties of the system which are usually known. The effective viscosity is associated with the kinetic energy dissipation due to the interface friction, the shear stresses in molecular and turbulent motion and the radial dispersion in the gas stream. Its knowledge makes possible the evaluation of the radial profiles of the gas interstitial velocity, as well as the dispersion coefficient, or corresponding Péclet number and the drag coefficient for individual element within the bed. The effective viscosity has been determined experimentally for beds of Raschig rings and cylinders by the method presented previously [Zió?kowska, I., Zió?kowski, D., 2001. Experimental analysis of isothermal gas flow field in tubes packed with spheres. Chemical Engineering and Processing 40, 221-233] and the results have been correlated with the system characteristics. Then the correlations have been used, according to the model, in evaluation of the radial distributions of the gas interstitial velocity, the radial dispersion coefficient and the drag coefficient for individual element within the bed.     

Comparison between simulated moving bed and reverse flow chromatographic reactors for equilibrium limited reactions

A staged linear model, containing five parameters, is developed to compare equivalent simulated moving bed chromatographic reactors (SMBCR) and reverse flow chromatographic reactors (RFCR). A first order reversible reaction and linear adsorption equilibrium, with preferential adsorption of the reactant is assumed. The analysis uses simple, easily computable analytical solutions that rigorously represents the transients in the cyclic steady state for both the RFCR and the SMBR. A comparison between the two types of reactors is carried out to determine the maximum conversion attainable and the range of operation where these systems have advantages over conventional steady state reactors. It is found that the maximum conversion of both reactors is similar. The range of operation in terms of amount of catalyst and range of switching times favors the RFCR, while the conversion at low separation factors favors the SMBCR.