Showing papers in "Chemical Engineering & Technology in 1997"

Removal of sulfur compounds from naphtha solutions using solid adsorbents

Abstract: Two types of solid adsorbents, activated carbon and zeolite 13X, were used at 80°C to remove sulfur compounds from naphtha solutions. Adsorption isotherms have been determined in a pressure vessel. This investigation indicated that activated carbon is superior to zeolite 13X at such high temperatures. A new formula based on the Langmuir model has been found to fit the experimental data satisfactorily. Comparison of the findings of this study with those of a previous one conducted at ambient temperatures in this department indicates that such treatment generally gives better results at low temperature where almost complete recovery of the sulfur compounds can be performed by using zeolite 13X.

Bioheat equation of the human thermal system

Abstract: As an alternative to the existing bioheat transfer models a new system of two energy equations is proposed by considering the human body as a deformable porous medium. One equation is developed for the blood and the other for the peripheral skeletal tissue. It includes such significant factors as the vascular geometry and size, the blood flow and direction, thermal diffusion and the local thermal nonequilibrium between the blood and peripheral tissue. Discussion and application of both equations are given.

Dynamic modeling and simulation of a riser‐type fluid catalytic cracking unit

Abstract: A dynamic model is developed for a fluid catalytic cracking (FCC) unit to describe the dynamic behavior of both the riser and the regenerator reactors and their interactions. The cracking reactions are simulated by the four-lumped kinetic model [1]. The reactions in the riser occur in a transported bed with the fluid and the solids in ideal plug flow. The two-phase nature of the regenerator-fluidized bed is considered and the kinetic model for the coke combustion on the cracking catalyst [2,3] is incorporated. The proposed model is validated using steady-state plant data from an industrial unit and the results are found to be in good agreement. One of the main advantages of the model is that it does not include any partial differential equations. This facilitates the solution of the equations and makes the model particularly suitable for control studies. Simulation studies are performed to investigate the effect of changing various process variables, such as catalyst circulation rate, gas oil feed rate, and oxygen feed concentration.

Reaction kinetics of the CO2 reforming of methane

Abstract: The kinetics of the CO 2 reforming of methane was investigated in the temperature range 700-850°C at normal pressure with a 1:1 mixture of CH 4 and CO 2 on Ir/Al 2 O 3 catalysts. The feed composition was kept constant to avoid a change in mechanism associated with composition changes. Various rate models were fitted to the experimental data by numerically integrating the rate equations. All rate models included the reverse water gas shift reaction as the most important side reaction at these reaction conditions. The best agreement was obtained with a rate model based on the stepwise mechanism, where in the rate-determining step methane is decomposed to hydrogen and active carbon followed by the direct and fast conversion of this active carbon with CO 2 to 2CO. This model is also the first and only one containing a complete subset of reactions necessary to describe the network of reactions known to occur at these reaction conditions. Comparable fit quality was obtained with a simple first order model and with a model based on a Langmuir-Hinshel-wood rate expression, where the latter provided physically meaningless parameters. Values of the reaction parameters are given for the 5 best rate models studied.

Absorption of NO in an alkaline solution of KMnO4

Abstract: A packed column has been used to study the absorption of nitrogen oxide in an alkaline solution of potassium permanganate. The reactions taking; place during the absorption have been examined and the rate constants have been estimated from experimental data. The experiments show that potassium permanganate is an excellent absorbent for nitrogen oxide. However, to avoid formation of MnO2, the hydroxide concentration has to be very high, i.e. >3 mol/l. It was found that the reaction could be expressed as first-order with respect to NO and with respect to KMnO4. The rate constant may be expressed in terms of the hydroxide concentration as follows: k(mn) = 6114.9 10(1.9208 10-4 CNaOH) m(3) mol(-1) s(-1).

Oxidation of aqueous sulfide solutions by dioxygen Part I: Autoxidation reaction

Abstract: The autoxidation of aqueous sulfide solutions by dioxygen is studied at pH 9 and 14 and at initial sulfide concentrations between 1 and 100 mM. Disulfide as a primarary intermediate is proposed to enhance the sulfide oxidation by autocatalytically forming polysulfies. The postulate is supported by the observed acceleration of the process at increasing pH favoring the presence of disulfide rather than that of sulfur. The final reaction products thiosulfate and sulfate are proposed to result from the hydrolysis of the highly instable intermediate polythiosulfite in parallel parallel reaction pathways, assuming probabilities for breaking the sulfur chain at the α (sulfate) and β (thiosulfate) positions to be responsible for the selectivity. A reaction scheme is proposed, considering all experimental observations.

Methanol steam‐reforming in a catalytic fixed bed reactor

Abstract: Designing an appropriate methanol steam reformer requires detailed knowledge about the processes within such a reactor. Thus, the axial temperature and concentration gradients and catalyst ageing were investigated. It was found that for a fresh catalyst load, the catalyst located in the reactor entrance was most active during the experiment. The activity of this part of the catalyst bed decreased after some time of operation due to ageing. With further operation, the most active zone moved through the catalyst bed. From the results concerning hydrogen production and catalyst degradation, the necessary amount of catalyst for a mobile PEMFC-system can be estimated.

Oxidation of aqueous sulfide solutions by dioxygen. Part II : Catalysis by soluble and immobilized cobalt(II) phthalocyanines

Abstract: The oxidation of sulfide in oxygen-saturated aqueous solutions is accelerated by dissolved or silica-bonded cobalt phthalocyanines. On the basis of thermodynamical considerations it is postulated that the catalyst enhances the formation of disulfide as the initial elementary reaction step. The following reaction steps are largely unaffected by the catalyst, as indicated by a product ratio sulfate/thiosulfate=0.86, comparable to that of the uncatalyzed autoxidation. A Langmuir-Hinshelwood formalism is developed for the catalytic reaction step and is demonstrated to fit best with the kinetics. In addition, from the kinetic data free enthalpies for the adsorption of HS - (1) at the dissolved phthalocyanine (ΔG=-17.6 kJ/mole) and (2) at the immobilized complex (ΔG=-20.0 kJ/mole) are calculated.

Ion-exchange membrane processes for clean industrial chemistry

Abstract: New uses of artificial selective membranes, particularly ion-exchange membranes, improve on traditional methods of treating liquid mixtures before, during or after chemical or biochemical reactions. With the correct choice of ion-exchange membrane in a membrane reactor, reactions can be performed in such a way that the main product is not contaminated by undesired byproducts. Recent examples, mainly in organic chemistry, are given for eight typical ion-exchange membrane reactors: electrodialysis (ED), electrometathesis (EMT), electro-ion substitution (EIS), electro-ion injection-extraction (EIIE), coupled counter-transport (CCT), electro-electrodialysis (EED), electrohydrolysis with bipolar membranes (EHBM), and catalysis with ion-exchange membrane (IEMC).

Analysis of reactive distillation using the esterification of acetic acid as an example

Abstract: The uncatalyzed esterification of acetic acid is described in the literature as a typical example of reactive distillation. Many rigorous models were validated using this esterification as an example. Process proposals for the production of pure ethyl acetate from ethanol and acetic acid have been determined using short-cut methods with the assumption of chemical equilibrium only. In this publication, the limitations of this esterification are clarified, using a rigorous model that was developed. The reasons why reactive distillation appears to be unfavorable for this esterification are explained. It is, however, theoretically possible to obtain ethyl acetate in high purity with different variants of the process. Different process variants are examined in this work. Construction variables that are important for the design of reactive columns, such as the number of reactive separation stages and the holdup in the column, are analyzed. Furthermore, the influence of variables dependent on the component system, such as the phase equilibrium of the reactive system and the reaction kinetics on the conversion in the column, are described. It can be shown that the short-cut methods published so far for reactive distillation, which assume chemical equilibrium, are inadequate.

Comparison of hydrodynamic parameters for countercurrent and cocurrent flow through packed beds

Abstract: Hydrodynamic parameters have been determined in common equipment, i.e., same column and liquid and gas distributors, for cocurrent and countercurrent two-phase flow through fixed beds. The piston/dispersion exchange model (PDE) with usual Danckwerts' boundary conditions (closed/closed system) has been used to describe the liquid flow. A new imperfect pulse method has been used to estimate the PDE model parameters directly from the experimentally nonideal input and output response. The transition between trickle flow and pulse flow, for two-phase downflow, and the occurrence of flooding, for countercurrent flow, has been investigated using a macroscopic model for the two-phase flow.

Design rules for the wallcooled hydrothermal burner (WHB)

Abstract: The results of a process analysis and an experimental exploratory study of supercritical water oxidation (SCWO) show that elements of combustion technology are suitable to overcome the technical problems of SCWO. The Film Cooled Hydrothermal Burner (FCHB) which operates at 25 MPa up to 2000 K in the reaction zone keeping wall temperature under stress at 300 to 400 K shows further development potential of the Wallcooled Hydrothermal Burner (WHB) concept for SCWO, a still promising waste treatment process.

Simultaneous oxidation of nitrogen oxides and sulfur dioxide with ozone and hydrogen peroxide

Abstract: The use of ozone and hydrogen peroxide for the simultaneous oxidation of nitrogen and sulfur oxides was studied in experiments carried out in a stirred cell. It was found that in a gas mixture, containing both nitrogen and sulfur oxides, only the nitrogen oxides are oxidized by ozone. Contrary to earlier results, sulfur dioxide does not disturb the oxidation of nitrogen oxides under dry conditions. The consumption of ozone in the oxidation of nitric oxide was slightly below the stoichiometric level because the ozone was introduced into the reactor in the oxygen flow. When the molar ratio between ozone and nitric oxide was more than 0.4, some of the nitric oxide was oxidized to higher oxides of nitrogen, the final product being a solid mixture of N2O5 and (NO)2S2O7. Some nitrosyl sulfuric acid was formed in the aqueous solution of hydrogen peroxide in addition to sulfuric acid under wet conditions. Some white solid was found on the walls of the reactor. This solid is said it the literature to consist of H2SO4, HNOSO4 and (NO)2S2O7.

High shear rheology of paper coating colors – more than just viscosity

Abstract: Capillary viscometry is used to characterize viscosity, entrance pressure loss and apparent wall slip of paper coating colors at high shear rates. Special emphasis is laid on the dependence of these phenomena on solids content in order to account for changes in the rheology due to the dewatering of the color during the coating process. Coating colors with substantially different runnability have been investigated. Differences in apparent wall slip and high shear viscoelasticity (manifesting itself in extremely high entrance pressure losses) are observed at increased concentration, even if these phenomena do not show up at the initial solids content. Poor runnability is observed when viscosity, entrance pressure loss and wall slip increase strongly with increasing solids content. But all rheological features change simultaneously with the coating color recipe and it is not possible to separate out the contribution of the particular rheological features on the runnability of the coating colors or to correlate the runnability to a single rheological prorameter. Future work will have to focus on a numerical analysis of the blade coating process taking into account all the rheological features described here. First simulations including slip at the color/blade interface indicate that wall slip may cause severe runnability problems, at least when the apparent slip velocity exceeds the web velocity.

Kinetics of xanthan gum production from whey by constructed strains of Xanthomonas campestris in batch fermentations

Abstract: Two new constructed strains of X. campestris XLM1521 and XMT1, either alone or in mixed cultures were used for the production of xanthan gum in batch fermentations from whey. Fermentations were carried out at three different pH levels of 6.0, 7.0 and 8.0 and the results were compared with those previously reported for fermentations in Erlenmeyer flasks without controlling the pH. The kinetics of cultures of the strain X. campestris XLM1521 were studied in a batch reactor at constant pH values. A mathematical model, based on the Luedeking-Piret equation, was used and experimental design was employed in order to correlate model's parameters with pH variation. The highest xanthan gum concentration, 17.3 g/l, was observed at pH 8.0. This is the largest amount of xanthan gum reported so far.

Modeling of multi-solid liquid fluidized bed

Abstract: A dynamic model of the liquid fluidized bed containing two or more solid particle species of different size and density is presented. The model incorporates the particle mass transport mechanisms of the convection and the dispersion. The movement of the upper interface of the bed subject to a change in the liquid velocity is specified using the mass balance constraint. The particle velocities and dispersion coefficients are evaluated using correlations. The model is capable of describing the bed expansion, concentration profiles of the individual particle species, the bulk density profile, and the occurrence of layer inversion.

Aerodynamic characteristics of FGD spray towers

Abstract: On the basis of the balance of forces acting on droplets falling down inside a co- or counter-current spray tower, a model of scrubber aerodynamic characteristics was developed. Relations between pressure drop caused by spray, droplet concentration and residence time distribution of the dispersed phase were found analytically for slurry droplet motion in the range of 400

Impact of accessibility and acidity on novel molecular sieves for catalytic cracking of hydrocarbons

Abstract: The catalytic properties of extra-large pore aluminosilicate MCM-41, silicon containing VPI-5 and aluminium containing ETS-10 were investigated by MAT (Micro Activity Test) using n-hexadecane and 1,3,5-triisopropylbenzene as the model feeds and were then compared with the results obtained from Y zeolite in the H-form and a commercial FCC (Fluid Catalytic Cracking) catalyst. It could be demonstrated that not only the acidic properties of the investigated materials, but also the accessibility to the internal active sites of the investigated materials have a significant influence on activity and selectivity. It can be assumed that, by optimising structural and chemical properties, the mesoporously organised MCM-41 and related materials are suitable as active components in cracking catalysts for “deeper” cracking of high boiling hydrocarbons.

The characteristics of wave propagation in a vibrating fluidized bed

Abstract: Based on experiments, this paper describes that the vibration energy imported to a packed bed is through the collision between the vibration plate and the bed, and the vibration energy imported to a fluidized bed is through continuous wave propagation. A new type sensor was used to measure the wave signals in VFB. The wave characteristics are affected by bed properties. By analyzing the wave frequency spectrum, the bubble's behavior in the bed can be followed.

Gas holdup and mass transfer in solid suspended bubble columns in presence of structured packings

Abstract: Electrochemical gas absorption or biotechnical purification processes using structured packing as electrode or as biological support, respectively, may operate in bubble columns in presence of suspended solids. In both systems the knowledge of mass transfer rates from the liquid to the packing is important for the design of equipment. In the present investigation, the fluid dynamic behavior of a simple bubble column and a bubble column containing small size particles, both in presence of structured packing, was studied. Furthermore, mass transfer coefficients between the liquid and the structured packing were obtained by the electrochemical method. The influence of physical properties of the liquid phase, gas flow rate, kind and concentration of the suspended particles on both gas holdup and mass transfer was investigated. Correlations of the experimental data of mass transfer using dimensionless groups were derived and compared to previous correlations. Similarity with a heat transfer expression already used in two-phase systems was found.

Gas‐liquid mass transfer in bubble columns with a T‐junction nozzle for gas dispersion

Abstract: Bubble break-up, gas holdup, and the gas-liquid volumetric mass transfer coefficient are studied in a bubble column reactor with simultaneous injection of a gas and liquid through a T-junction nozzle. The theoretical dependence of bubble break-up and the volumetric mass transfer coefficient on liquid velocity in the nozzle is developed on the basis of isotropic turbulence theory. It is shown that correlations which are developed based on liquid jet kinetic power per nozzle volume explain average gas holdup and the volumetric mass transfer coefficient within an error of 15% for all gas and liquid flow rates and nozzle diameters used. Experiments with a larger scale column, height 4.64 m and diameter 0.98 m, show a transition from homogeneous to heterogeneous flow at a certain liquid flow rate through the nozzle. Liquid composition was found to have a significant effect on gas-liquid mass transfer. A phenol concentration of 10–30 mg/l in water increases the volumetric mass transfer coefficient of oxygen by 100%. This phenomenon may have significance in the chemical oxidation of wastewater.

A study of gain scheduling control applied to an exothermic CSTR

Abstract: This paper describes how gain scheduling control is applied to a continuous stirred tank reactor model. The CSTR process, equipped with a cooling system, is modelled. Based on the resulting nonlinear model, a gain scheduling controller is designed. The gain scheduling follows a scheme denoted bias compensation. Compared to earlier reported gain scheduling schemes, the proposed scheme results in a controller that is less complex, which is advantageous in the controller implementation stage. Numerous simulations are performed, using the gain scheduling controller and two choices of control input to the reactor model. The simulation results indicate that a gain scheduling controller performs better than a linear controller. Simulations using different choices of control input to the reactor model indicate that proper process design is crucial for the controlled process performance.

Application of mathematical modelling in a two‐component layer crystallisation process

Abstract: An algorithm for the computation of design variables in layer crystallisation processes is presented, based on an algebraic solution of the moving boundary equation for heat transfer, as well as on an expression for the concentration profile. The algorithm was applied to the discontinuous crystallisation of a NaCl-H 2 O solution around the wall of an internally cooled cylindrical tube. Good agreement between simulation results and laboratory experiments was observed. After input of experimentally measurable values of the distribution coefficient, the algorithm enables the prediction of the following process variables along the crystallisation time: layer thickness, temperature, and composition profiles across the layer, as well as the end-values of solid and liquid mass and concentrations. Multistage processes can be studied by the series association of crystallisation cycles, enabling the determination of the optimal number of stages that meets a specific design criterion.

Bubble emissions from submerged orifices – a critical review

Abstract: A comparative study of reported theoretical and experimental investigations evaluating the numbers and sizes of bubbles emerging from submerged orifices reveals that the lack of consistency can be attributed largely to faulty experimental techniques. Errors are attributed to an inadequate knowledge of the influence of the surface properties of the solid and liquid media on the emission process and to the lack of standardization of the equipment geometries especially regarding the pressure chambers and orifice plates. The analyses provide guidance to designing standardized equipment to produce reproducible bubbles.

Modelling of the reversed flow fixed bed reactor for catalytic decontamination of waste gases

Abstract: Catalytic decontamination of waste gases in a fixed bed reactor, operating at non-steady state conditions achieved by periodic gas flow reversal, is simulated on the basis of a mathematical model. The opportunity to utilize a significant part of the reaction heat is discussed and the effect of catalyst inactivation upon reactor performance is analyzed. Stable temperature regime and conversion exceeding 99.5% could be ensured by a more than eightfold reduction of catalyst activity.

Mechanical foam breaking : A physical model for impact effects with high speed rotors

Abstract: During recent years in chemical engineering processes for instance with aerated stirred tanks containing surface-active components foams and their mechanical control have become very important. However, there are still no rules for calculating mechanical foam breakers. As a contribution to foam control the present paper discusses the fundamentals of foam breaking by means of foam densities and gives a physical model for the mechanisms of a mechanical foam breaker when the main breaking effect is based on impact. The mechanisms were proved by measuring pressures in a foam breaker box. Diameters of secondary foam bubbles produced by foam breakers are calculated and discussed. Experimental investigations were made with different surfactants in aqueous solutions. The paper points out their influence on the process of foam breaking.

Kinetics of 4‐tert‐butylphenol hydrogenation over rhodium

Abstract: The kinetics of the liquid phase hydrogenation of 4-tert-butylphenol to form cis- and trans- 4-tert-butylcyclohexanol at 1.0–10.0 MPa and 40°C in isopropanol over a Rh catalyst has been studied. The kinetic behavior of this parallel system is described by a proposed reaction network. Keto-enol tautomeric transformation of adsorbed 4-tert-butyltetrahydrophenol and 4-tert-butylcyclohexanone is thought to be a key step, which governs the stereoselectivity of the overall complex reaction of alkylphenol hydrogenation.

Investigating the stability of falling films at round vertical film carriers under high pressure

Abstract: The instability of a falling film under high pressure (droplet formation) was characterized by the dimensionless Reynolds, Weber, and fluid-film numbers and could be predicted in a characteristic diagram. Incipient droplet formation was achieved with the given material properties of the system, i.e., at a constant KF number, by increasing the volumetric flowrate of the liquid phase. The investigations were performed with the material systems α-tocopherol/CO2 and squalane/CO2 in the pressure ranges between 8 and 35 MPa and 6 and 12 MPa, respectively, at four different temperatures between 313 and 353 K. The volumetric flowrate of the liquid phase was varied between 10 and 300 ml/min, whereas the speed of the supercritical gas phase in counter-current flow to the falling film in the falling-film cell was kept constant at 7 mm/s. The high-pressure falling-film cell used for this purpose had an external diameter of 104 mm, an internal diameter of 34 mm, and a total length of 710 mm. The diameter and length of the cylindrical falling-film carrier were 10 and 500 mm, respectively.

Secondary nucleation of sodium chlorate studied with the aid of asymmetric crystallization

Abstract: The size-dependent breeding of sodium chlorate crystals can be determined by carrying out experiments with seed crystals of optical antipodes of different sizes that undergo absolutely identical experimental conditions. Small portions of right- and left-handed seed crystals of different sizes were used. The number density distributions of the two opposite forms led to the total numbers of D- and L-crystals. The nucleation from different seed sizes under identical experimental conditions was found to be proportional to L4 in agreement with Clontz et al. [1] and Bennett et al. [2]. A computer program for the modelling of batch crystallization was used to calculate the development of the nucleation process. The data for the supersaturation course and for the development of the population of the right- and left-handed crystals are in good agreement with the experimental results. Only few generations (one or two) of secondary nucleation are being built during the process because of the strong influence of the size of crystals on the nucleation rate. The formation of two generations of secondary nuclei could be observed during three-hour batch crystallization runs.

Calculation of equilibrium composition in combustion products

Abstract: For a specific combustion problem involving calculations of several species at equilibrium, it is much simpler to write a special computer program and calculate the concentrations, rather than to use a generalized computer program To calculate these concentrations, one must solve a set of non-linear algebraic equations This work describes a procedure in which the Newton-Raphson method and the successive substitution method are combined It is was found that for these types of problems the value of unknowns and the nature of the equations are such that by adopting the two procedures simultaneously a much faster and reliable convergence is achieved This study also shows what possible species should be considered for these calculations