糠醛气相催化加氢制糠醇工艺开发——固定床反应器数学模拟与分析

在糠醛气相催化加氢制糠醇单管实验基础上,提出了新的反应动力学模型,建立了该反应体系的拟均相二维平推流数学模型,用Powell优化方法对模型中参数进行估值。所建立模型能正确反映操作条件对反应器内温度分布和糠醇收率的影响,将它用于反应器模拟,计算结果与实测结果吻合较好。本文还应用该模型对糠醛加氢反应器进行模拟分析,得出了优化操作条件。     

Investigation of a fixed-bed pilot plant reactor by dynamic experimentation. Part 2. Simulation of reactor behaviour

Data collected with forced uncorrelated sinusoidal changes of the process variables are used to simulate the behaviour of a non-isothermal non-adiabatic pilot plant fixed-bed reactor. The test reaction applied is the hydrogenation of toluene to methylcyclohexane on an industrial nickel catalyst. A pseudo-homogeneous two-dimensional model as well as a one-dimensional model are applied to describe the reactor behaviour. The model parameters are estimated by defining an objective function based upon residuals of the discretized differential equations instead of upon deviation from the observed variables. This procedure leads to a drastic reduction of computer expenditure. Measured and simulated temperature and concentration profiles are compared on the basis of a number of plots and fitting quality criteria. The model parameters estimated from data collected during dynamic runs are comparable to those obtained from a series of stationary experiments (2₃ experimental design). However, with the dynamic experiments the data necessary for modelling can be collected much more efficiently.     

Exploring the Steady Operation of a Continuous Pilot Plant for the Di‐Nitration Reaction

Continuous‐flow synthesis of the selective herbicide pendimethalin was demonstrated in both a laboratory‐scale and a pilot‐scale reactor using only concentrated nitric acid as nitrating agent. The di‐nitration reaction follows second‐order kinetics where the reaction is first order with respect to both reactant and nitric acid. The pinched‐tube reactor was chosen for pilot‐scale reactor fabrication due to its excellent mixing and mass transfer characteristics compared to a straight‐tube reactor. The estimated mass transfer coefficient showed similar nature in the laboratory‐scale and the pilot‐scale pinched‐tube reactor, ensuring similar performance at the pilot scale. Di‐nitration in continuous flow, inline quenching, extraction, and phase separation are some of the salient features of the developed pilot plant. The importance of the start‐up time for achieving steady state in the flow system at the large scale is highlighted.     

Safety aspects in modelling and operating of batch and semibatch stirred tank chemical reactors

Safety aspects in modelling of batch and semibatch stirred tank reactors as well as a model based safety analysis have been considered. Applicability of two basic types of models – i.e. the perfectly mixed reactor model and the CFD model, both formulated for laboratory scale as well as pilot plant scale reactors – has been discussed. A formulation of the appropriate reactor model, which is adequate to the considered case study has been demonstrated and tested experimentally. Particular attention has been devoted to the formulation of robust CFD models employed to simulate a performance of the stirred tank reactors. It has been found that models for perfectly mixed reactors may have quite wide range of application, while the CFD models should be definitely used in case of fast reactions, high viscosity of the reacting mixture as well as of failure leading to stopping of the impeller. The CFD models are able to predict a dynamic behaviour of reactors at any circumstances, so they can play a significant role in safety analysis carried out for industrial scale reactors, for which experimental safety tests are expensive and dangerous.     

On the link between intrinsic catalytic reactions kinetics and the development of catalytic processes: Catalytic dehydrogenation of ethylbenzene to styrene

A procedure linking kinetic modeling of catalytic reactions to reactor modeling for different configurations is developed and applied to the catalytic dehydrogenation of ethylbenzene to styrene. The procedure is applied to four configurations, namely fixed bed with/without hydrogen selective membranes and bubbling fluidized beds with/without selective membranes. The kinetic data for the industrial catalyst are extracted from industrial fixed bed data using a rigorous heterogeneous model. The kinetic data for the three in-house prepared catalysts are obtained from the laboratory scale experiments using pseudo-homogeneous models.     

Supercritical water oxidation of flammable industrial wastewaters: economic perspectives of an industrial plant

BACKGROUND: Supercritical water oxidation (SCWO) is a promising technology that respects the environment, destroys wastes and allows energy recovery. This process has been applied to many model compounds and real wastewaters at laboratory scale. However, SCWO treatments at pilot plant scale of real wastewaters are scarce. The application of this technology to industrial wastewaters has drawbacks such as corrosion, salt deposition and high cost, so industrial scale‐up has been delayed. RESULTS: In a first stage, for safety reasons the feasibility of SCWO applied to flammable industrial wastewaters was evaluated at laboratory scale in an isothermal plug flow reactor with low concentrations (3–10 g COD L^?1), at a constant pressure of 250 bar and at different temperatures in the range 350–500 °C. In a second stage, experiments were conducted with much higher concentrations (20–90 g COD L^?1) in a SCWO reactor at pilot plant scale. Experiments at pilot plant scale demonstrated the possibility of working under autothermal conditions and the results were used to estimate the treatment costs for a SCWO plant with a capacity of 1 m³ h^?1. CONCLUSION: Results demonstrated the technical feasibility of using a SCWO process to treat flammable industrial wastewater at pilot plant scale due to the absence of operational drawbacks related to the flammability of this wastewater, such as plugging, pressurization or preheating problems and uncontrolled reactions (explosion, etc.). The economic feasibility was demonstrated, especially bearing in mind the energy recovery optimization. Copyright © 2011 Society of Chemical Industry     

Synthesis and Characterisation of In Situ Doped Silicon Nanoparticles

In situ boron, or phosphorous doped silicon nanoparticles were synthesised by pyrolysis of monosilane-diborane and monosilane-phosphane mixtures in free-space reactors. The studies were performed under atmospheric pressure in a laboratory reactor and a pilot plant for examination of scale-up effects. In the laboratory scale experiments, 1 vol % monosilane diluted in helium was used. The synthesis temperature varied between 600 and 800 ^°C. Pilot plant tests were run at 600 ^°C with 13.3 vol % silane diluted in hydrogen. The dopant content of the synthesised silicon powders was characterised by ETV-ICP-OES. Further investigations were carried out by using SEM, XRD, particle size analysis and FT-IR. An inhibition of the boron incorporation into the growing silicon lattice was found during the decomposition of the silane-diborane mixtures. This effect is a result of the low thermal stability of diborane. Silicon powders with higher boron contents and a wider particle size distribution leading to bigger particles, which showed no affinity to electrostatic charging, were obtained on the pilot plant scale. In phosphorus doping, reactor temperature was found crucial for the doping process.     

Acetaldehyde dimethylacetal synthesis with Smopex 101 fibres as catalyst/adsorbent

The synthesis of dimethylacetal using acetaldehyde and methanol as raw material in the presence of Smopex 101 fibres as catalyst and adsorbent in batch reactor and in a fixed bed adsorptive reactor, respectively, was studied. In the batch reactor the determination of thermodynamic and reaction kinetics data for acetalization reaction was presented. A kinetic model based on a pseudo-homogeneous rate expression using activities was proposed to describe the experimental kinetic results. The dynamic binary adsorption experiments were carried out in the absence of reaction at 293.15 K in a laboratory scale column. The experimental results of the adsorption of binary non-reactive mixtures are reported and used to obtain multi-component adsorption equilibrium isotherms of Langmuir type. The mathematical model was proposed to describe the adsorptive reactor dynamic behaviour. The experimental results obtained for the reaction and regeneration experiments were compared with the model proposed. Model equations were solved by orthogonal collocation on finite elements (OCFE) implemented by the PDECOL package, using the measured model parameters and was validated for both reaction and regeneration steps.     

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.     

Mass transfer in aerated fermentation broths in a stirred tank reactor

The volumetric mass transfer coefficients, k_La, measured in a pilot plant (0.1 m³) and an industrial (67.5 m³) fermentor during an actual fermentation process are presented. Problems related to the estimation of the phsyical properties as well as to the correlation of experimental data and to scale up procedures are discussed. Although the scale up factor was rather high, both sets of data could be represented by single correlation. Comparison of the experimental data with several available correlations demonstrated the need for pilot plant experiments and scale up procedures, since it is almost impossible to take into account all relevant system properties.     

A general simulation model of batch chemical reactors for thermal control investigations

This paper describes the development of a dynamic simulation model for stirred tank batch or semi-batch chemical reactors fitted with an alternative heating-cooling system. Heat and mass balances are established for the reactor and its jacket. Since the general purpose of our research is the thermal control of these reactors, special attention is devoted to the behaviour of the heating-cooling system. In this article, we are particularly concerned with an alternative system, i.e. different fluids at a constant temperature can be alternatively delivered to the jacket. The computer simulation programme is flexible, enabling simulation of a batch or semi-batch reaction vessel, ranging from a laboratory pilot plant to a full-scale production plant. A control algorithm is included which allows reactor operation with open or closed-loop temperature control. To demonstrate the good performance of the simulation model, experimental results are presented for both a pilot plant and an industrial reactor.     

Simulation von Extraktionskolonnen in der industriellen Praxis

The design of extraction columns is usually based on lab‐scale and pilot‐plant experiments. A new alternative design approach is based on lab‐scale experiments with single drops to quantify mass transfer and drop sedimentation. From these experiments, liquid‐liquid system specific parameters for the simulation of the extraction column are obtained. This approach has been successfully validated for standard‐test systems and shall now be established in industrial practice. As part of this, separation performance and flooding limits measured with pilot‐plant experiments are compared to simulation results that are obtained on the basis of single‐drop experiments. The challenges that come with the simulation of industrial systems are presented and discussed.     

Scale‐up of Mini‐Plant Extractors on Energy Dissipation‐Based Population Balances

The new scale‐up concept for extraction columns relies on three identities being kept idem, as is the total specific flow rate, energy dissipation, and mean droplet residence time in a compartment. The droplet population balance‐based model allows maintaining hydrodynamic similarity in different geometries, as is in a mini‐ or a pilot plant. This leads to similar breakage and coalescence probabilities giving comparable droplet size distributions, thus mass transfer area and extraction efficiency. A new breakage frequency term has been developed relying on the energy dissipation rate and is thus independent from geometric constraints. The traditional scale‐up rules are based either on a constant tip velocity (≈ N) or on a constant energy input (≈ N³), whereas here it follows a constant energy dissipation (≈ N²). A step‐by‐step approach to the new procedure proved by case samples is given. Data from literature pilot experiments could be verified by computer simulations, without using adaptable parameters. All parameters in the correlations where derived in a lab‐scale apparatus and the coalescence parameters were obtained in the mini‐plant experiments. Derivation between simulated and experimental pilot data for stage numbers was less than 14 %, operating parameters (rotational speed N, throughput) were underestimated by 4 % leading to a slightly smaller HETS (Height Equivalent of Transfer Stages) value as measured, affecting the column height with less than 1 %.     

Statistical identification of the dynamic behavior of a dual input heat exchanger network

Statistical modelling procedures proposed by Box and Jenkins are used to develop models for the transfer function and noise behaviour of a dual input pilot scale heat exchanger network. Data were collected under operating conditions closely resembling full scale industrial operation first with uncorrelated inputs and then with correlated inputs. Two modelling strategies, a superposition approach and a transformed input approach, are employed to analyze the data. Computational advantages of the transformed input procedure for correlated input situations is demonstrated and the effectiveness of both strategies in detecting nonstationarity in the system noise is also illustrated.     

Analysis of a solar-powered membrane distillation system

Nowadays, in dry and rural areas, solar-powered membrane distillation (SPMD) technology is considered a feasiblemeans for the production of pure water from brackish water. Prior to the design and construction of a SPMD pilot plant, there is a need to predict its performance theoretically by means of a computational simulation program. Unlike previous approaches followed by other investigators to develop a mathematical model that can describe the components of a SPMD pilot plant, the developed mathematical model in this study is based on the fact that the SPMD process by nature is unsteady. The performance of a proposed SPMD pilot plant is then obtained by means of a numerical solution of the model with the aid of a simulation computer program. The results reveal that the proposed SPMD pilot plant has some unique features, which differ from a similar MD process operated at steady-state conditions in a laboratory. The analysis of the system has shown that heat recovery via an external heat exchanger is not only possible, but even effective, and an economical way to intensify the SPMD process. The plant productivity can be improved by increasing the heat-exchanger capacity (KA), decreasing the flow rates of both feed and permeate or otherwise by increasing the effective surface area of the membrane. The achieved enhancements in the SPMD pilot plant productivity are directly related to an improved heat recovery rate in the heat exchanger. However, further analysis reported in this paper shows that the increase in KA and membrane area should be optimized for any planned capacity in the design of a SPMD pilot plant.     

Analysis of the elimination process of polymerisation inhibitors from styrene by means of adsorption

This work is focused on the analysis, modelling and scale‐up of a process of styrene purification. The first step in synthetic rubber production is to eliminate 4‐tert‐butylcatechol (TBC) which is added to styrene to prevent homopolymerisation during transport and storage. This process is carried out on an industrial scale by means of adsorption onto activated alumina. Equilibrium experiments at 10 °C correlated to the Langmuir–Freundlich equation: with a weighted standard deviation of 3.38%. Fixed bed column experiments were carried out on a laboratory scale to obtain breakthrough curves. A mathematical model that considers film and pore mass transfer resistances described satisfactorily the experimental results with a value of D_p = 3.96 × 10^?9 m² s^?1 which was obtained from correlation of experimental data to simulated curves. Finally, a pilot plant was built and operated in order to verify the validity of the mathematical model and parameters obtained previously. © 2002 Society of Chemical Industry     

Solvent extraction of meat offal

Summary Data are presented to show the effect of the various operating variables on the extraction of meat and bone scrap both in the laboratory and in a pilot plant model of the Iowa State College extractor. From the data presented it has been concluded that the extraction takes place mainly by a washing process with slight diffusion. A possible correlation is suggested for comparing laboratory and pilot plant data. formerly graduate assistant, Iowa Engineering Experiment Station, Iowa State College, Ames, Iowa     

Fine particle capture in biomass boilers with recirculating gas cyclones: Theory and practice

This paper addresses the theoretical development and experimental validation of optimized recirculating reverse-flow gas cyclones. The simulation of these systems is based on the predictive properties of a finite diffusivity model, modified to include partial recirculation of the cyclones' emissions.Experimental validation was obtained at laboratory and pilot scales at low temperatures (up to 350 K) and for cork waste biomass boilers at higher temperatures (up to 600 K). Under certain circumstances, with recirculation, the proposed system showed a better performance than an online pulse jet bag filter, and substantially better than with multicyclone systems. The generally observed unexpected high collection of submicron particles, which occurs with inlet concentrations as low as 100 μg/m³, is attributed to turbulent dispersion, either by promoting fine particle capture by larger ones, much like what occurs in recirculating fluidized beds, or by bringing fine particles near the cyclone wall.The extremely fine particle size distributions exiting from the recirculation system, as measured off-line at laboratory, pilot and industrial scales, were confirmed at pilot scale using online measurements through a laser monitor.     

Entwicklung petrochemischer Verfahren vom Laborversuch zur kommerziellen Anlage

Development of a petrochemical process from laboratory scale tests to a commercial plant. A plant producing TAME (tertiary amyl methyl ether) and isoamylene serves as an example illustrating the development of a petrochemical process from laboratory scale tests to a commercial size plant. TAME is an anti-knock compound used in unleaded gasoline, and isoamylene is a multi-purpose specialty chemical. In an introduction, the laboratory and pilot plants at EC Erdoelchemie GmbH in Cologne, Germany are presented. Subsequently the main process engineering developments made through experience gained with a semicommercial demonstration plant are discussed. These include optimization of the reactors, design of a methanol extraction unit, and the separation of TAME and high purity isoamylene in specially designed distillation towers. The high degree of coordination during the experimental testing phase to match the requirements of the basic and detail engineering allowed the commercial plant to be started up without expensive modifications within 4 years. The resulting savings overcompensate the costs of the semicommercial plant.     

Scale-up-Probleme bei der experimentellen Verfahrensentwicklung

Scale-up problems in experimental process development. The experimental process development of a new product can be performed in test facilities of varying dimensions. Small miniplants from a laboratory scale up to larger pilot plants, in which a few tons of product per day can be produced, are used. The scale-up factors, the risks involved in process and construction design, and a possible necessity of a limited production are important criteria for the size of the first technical realisation of the new process. The following examples highlight some special problems and their solutions in the experimental process development. Whereas a process, involving mainly fluids can be developed relatively well in a miniplant (laboratory scale), it is normally necessary to work on process development for a solid product involving difficult solid handling in a larger pilot plant. At the end of the paper some other scale-up criteria for process design are explained.