甲基二乙醇胺水溶液在改进的湿壁塔上吸收二氧化碳的动力学模型

To get more accurate kinetic data of the absorption of CO2 into aqueous solution of N-methyldiethanolamine, a wetted wall column was modified to more uniformly distribute the liquid on the column surface and gas in the absorbing chamber and change the length of the column. The average liquid film thickness and the liquid-phase mass transfer coefficient were measured, and a correlation for the Sherwood number, Reynolds number and Schmidt number was obtained for the modified wetted wall column. The equilibrium concentrations in chemical reactions were calculated with a minor absolute error for calculating the rate constant more accurately. A mathematical model for the CO2 absorption was established based on the diffusional mass transfer accompanied with parallel reversible reactions, and the partial differential equation was solved by Laplace transform. An analytical expression for the concentration of carbon dioxide as a function of time and penetration depth in liquid film and the average interphase mass transfer rate was obtained. This model was also used to calculate the rate constant for a second-order reaction, which was in good agreement with reported data.     

MCM-36 zeolites tailored with acidic ionic liquid to regulate adsorption properties of isobutane and 1-butene☆

Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m~(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.     

Reaction kinetics and internal diffusion of Zhundong char gasification with CO2

Mass transfer usually affects the rate of chemical reactions in coal.The effect of internal diffusion on char gasification with CO₂ in the temperature range from 1123 K to 1273 K was investigated via thermo-gravimetric analysis and assessment of char morphology features.The results revealed that the effect of internal diffusion on the initial reaction rate was more significant with an increase of particle size,due to the concentration gradient of the gasification agent within the solid particles.In the early stage of gasification,the generation of new micropores and the opening of closed pores led to an increase in specific surface area.As the reaction proceeded,the openings were gradually expanded and the specific surface area continued to increase.However,with further reaction,disappearance of edge pores,melting and collapse of the pore structure led to a decrease in specific surface area.The intrinsic activation energy and reaction order based on the nth-order model were 157.67 kJ?mol^?1 and 0.36,respectively.Thus,temperature zones corresponding to chemical reaction and diffusion control were identified.Moreover,the calculated effectiveness factor provided a quantitative estimation of internal diffusion in the initial stage.     

甲烷的二氧化碳重整动力学研究

The kinetics of CO2 reforming of methane has been studied at 976-1033K on a commercial NiO/CaO/Al2O3 catalyst in a packed-bed continuous reactor. The reaction was carried out at atmospheric pressure and CO2/CH4 ratio > 2. The Hougen-Watson rate models were fitted to experimental data assuming the dissociative adsorption of methane as the rate-determining step. The reaction rate showed an effective reaction order of about unity for CH4. The apparent activity energy was found to be 104kJ·mol-1. Therefore the kinetic reaction parameters were determined and a possible reaction mechanism was proposed.     

Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22 zeolite

The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process.Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation.To regulate the isobutane/1-butene adsorption ratio,four types of ionic liquid (i.e.,IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite.The as-synthesized IL-immobilized MCM-22 (i.e.,MCM-22-IL) was characterized by FTIR,TGA,BET,XPS and XRD,and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume.But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly improved by the immobilization of ionic liquids.The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs.Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O,the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio.The results illustrated that immobilizing ionic liquids is an effective way to modify the textural,chemical and morphological properties of MCM-22.Accordingly,the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.     

Application of kinetics and computational fluid dynamics in pinene isomerization

A reliable kinetic model to describe the effects of various factors on the reaction rate and selectivity of pinene isomerization is developed. Furthermore, computational fluid dynamics(CFD) is applied to simulate the solid–liquid dispersion in reactor. The catalyst Ti M is obtained by improving the composition and structure of hydrated titanium dioxide. The kinetic equation of pinene isomerization is deduced based on reaction mechanism and catalyst deactivation model. The kinetic equation of pinene isomerization reaction is fitted, and the results show that the fitted equation is correlated with the experimental data. The rate and selectivity of pinene isomerization reaction are affected by the amount of catalyst, deactivation of catalyst, structure of catalyst, reaction temperature and water content of catalyst. The solid–liquid distribution of the reactor is calculated by computational fluid dynamics numerical simulation, and the solid–liquid dispersion in commercial scale reactor is more uniform than that in lab-scale reactor.     

KINETICS OF CATALYTIC DEHYDROGENATION

The dehydrogenation of tetralin over Ni-Mo/A1_2O_3,Fe_2O_3/Al_2O_3,Fe_2O_3 and FeS_2 has been shown inthis investigation to be a typical consecutive reversible reaction,with a small amount of 1,2-dihydronaph-thalene as an intermediate.On the less active catalyst Fe_2O_3,a few percent of 1,4-dihydronaphthalene(DHN)is also formed—the more active the catalyst,the lower the concentration of DHN.The rate of dehydrogena-tion rises with an increase of the partial pressure of tetralin,and declines with an increase of the partialpressure of hydrogen.It was observed that DHN is much more active than tetralin and naphthalene,andin the presence of a catalyst,it can be converted rapidly into naphthalene and tetralin.The fact that hydrogencan accelerate the hydrogenation of DHN is thought to be the main reason for its inhibiting the dehydroge-nation of tetralin.In the presence of a catalyst,1,4-DHN it unstable and can be isomerized into 1,2-DHNvery fast.These different catalysts have almost the same order of activities for dehydrogenation of tetralin,conversion of DHN and hydrogenation of naphthalene.On the hypothesis that the reaction is a consecutiveone on the catalyst surface and that the adsorbed DHN is a very active intermediate,a reaction model hasbeen deduced.The equilibrium constants of adsorption and the rate constants of the catalytic reaction werecalculated.The curves so calculated fit the experimental data very well,thus showing the validity of thismodel.Certain experimental results were explained in the light of this model and the related parameters.     

富镧稀土镍-苯浆液体系中液相苯加氢反应动力学研究

The kinetics of liquid-phase hydrogenation of benzene in misch metal nickel-five (MlNi5) and benzene slurry system was studied by investigating the influences of the reaction temperature, pressure, alloy concentration and stirring speed on the mass transfer-reaction processes inside the slurry. The results show that the whole process is controlled by the reaction at the surface of the catalyst. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particles are negligible. The apparent reaction rate is zero order for benzene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model obtained fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi5-C6H6 slurry system is 42.16 kJ.mol-1.     

Investigation of the liquid recycle in the reactor cascade of an industrial scale ebullated bed hydrocracking unit

One of the commercial means to convert heavy oil residue is hydrocracking in an ebullated bed. The ebullated bed reactor includes a complex gas–liquid–solid backmixed system which attracts the attention of many scientists and research groups. This work is aimed at the calculation of the internal recycle flow rate and understanding its effect on other parameters of the ebullated bed. Measured data were collected from an industrial scale residual hydrocracking unit consisting of a cascade of three ebullated bed reactors. A simplified block model of the ebullated bed reactors was created in Aspen Plus and fed with measured data. For reaction yield calculation, a lumped kinetic model was used. The model was verified by comparing experimental and calculated distillation curves as well as the calculated and measured reactor inlet temperature. Influence of the feed rate on the recycle ratio(recycle to feed flow rate) was estimated. A relation between the recycle flow rate, pump pressure difference and catalyst inventory has been identified. The recycle ratio also affects the temperature gradient along the reactor cascade. Influence of the recycle ratio on the temperature gradient decreased with the cascade member order.     

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.     

Determination of effectiveness factor of a partial internal wetting catalyst from adsorption measurement

The effect of partial internal wetting of catalyst pellets on apparent reaction kinetics at elevated temperatures and pressures is investigated experimentally and by modeling for benzene hydrogenation. A new method that combines adsorption and chemical reaction is introduced to study the kinetics influenced by capillary condensation of reagents at steady-state conditions. It is shown that the extent of liquid filling in the pellet interior has a critical effect on the global kinetics, and the current state of the catalyst depends on the history. Under certain conditions two steady states of the effectiveness factor exist. Moreover, either a decrease in temperature or increase in total pressure can increase the effectiveness factor. The model exhibits good agreement with experimental results.     

HYSTERESIS AND PHASE TRANSITIONS IN A SINGLE PARTIALLY INTERNALLY WETTED CATALYST PELLET: THERMOGRAVIMETRIC STUDIES

The hydrogenation of cyclohexene over palladium supported in a microporous γ-alumina pellet is studied thermogravimetrically with a view to measuring the extent of partial internal wetting associated with the different steady state branches. As many as three steady state branches having significantly different degrees of internal wetting and reaction rates, with transitions between them, are confirmed from observations of catalyst weight change. It is seen that with reduction in catalyst activity the middle branch, obtained by condensation from a vapor filled pellet, is much more prominent without showing an evaporative transition for the range of hydrogen partial pressures used here. The catalyst activity is therefore an important parameter affecting the structure of the steady state branches. Hysteresis effects are found to occur, and the thermogravimetric results also confirm the importance of history in determining the catalyst state. The measured degree of wetting is in accordance with that estimated from a mathematical model incorporating capillary condensation effects in addition to reaction-diffusion phenomena. The same model also satisfactorily interprets the reaction rate variations and transitions seen in the present work.     

Vapor-phase kinetics and its contribution to global three-phase reaction rate in hydrogenation of 1-methylnaphthalene

It has been considered that the contribution of the vapor-phase reaction (VPR) to the global three-phase reaction rate may become much lower as the catalyst effectiveness factor approaches unity. In this study, the hydrogenation of 1-methylnaphthalene was performed as an example of slow reactions using a laboratory-scale trickle-bed reactor (TBR) at 583 K, 8.0 MPa. It was qualitatively confirmed that VPR contributed to the product yields in TBR even in this slow reaction system when the liquid velocity was low and the volatility of the liquid was high. Langmuir–Hinshelwood type kinetic equations were established for the vapor-phase reaction. The product yields in TBR neither be explained by liquid- vapor-phase kinetics without external effects, nor the conventional partial wetting model. Therefore, a partial wetting model considering the contribution of VPR was proposed where the catalyst bed composed of externally partial and internally complete wet particles, and completely dry particles was assumed. Using this model, the product yields in TBR were suitably explained.     

1D and 2D simulations of partially wetted catalyst particles: A focus on heat transfer limitations

Hydrodynamics and transport phenomena inside Trickle Bed Reactors are strongly modified when superficial liquid velocity is not sufficient to insure a perfect wetting of catalyst particles. For this reason, the impact of partial wetting on catalyst effectiveness has been widely studied in past, in case of isothermal reactions. Heat transfer limitations, inside or outside catalyst particles, have also been investigated, but only in case of total wetting.In the present study, the effect of partial wetting is quantified numerically for various kinetics, mass and heat transfer limitations. When possible, an analogy is proposed between 1D and 2D models of particles. Robust rules are proposed to take into account for partial wetting in 1D-radial models of particles.The case of partial evaporation inside catalyst pores is also studied. Evaporation phenomena is approximated following a simple approach. Performed calculations show that the effect of partial wetting can affect very strongly catalyst effectiveness factors, especially in case of evaporation in the pores. The use of 1D approximations gives a good prediction of the global catalyst efficiency, as far as boundary conditions are symmetric between heat and mass transfer. Otherwise, 1D models are not relevant anymore.     

Catalytic wet oxidation of substituted phenols in the trickle bed reactor

Continual catalytic wet oxidation of phenol and its derivatives as a suitable chemical pretreatment before a biological treatment process was investigated. The evaluation of (i) the influence of amino-, carboxy- and sulfo- phenol substituents on the course of the oxidation of hydroxyl-aromatics, (ii) the catalytic ability of an active carbon, and (iii) the influence of reaction conditions, viz. temperature (120–160°C) and oxygen partial pressure (2–5 MPa) in the continuous trickle bed reactor, is presented. The active carbon type catalyst seems to be active enough for phenol oxidation, but it is not so effective for aromatic acids. The results of trickle bed operation were strongly influenced by hydrodynamics, viz. wetting efficiency. An insufficient catalyst wetting compensates for an effect of residence time in the bed and undesirable fluctuation of conversion appears at the low liquid velocities which are typical for waste water treatment processes. It is possible to achieve an optimal value of reactor productivity. © 1998 SCI     

MASS TRANSFER WITH CHEMICAL REACTION IN PARTIALLY WETTED FLAT PLATE CATALYST PELLETS: RIVULET FLOW ANALYSIS

Mass transfer with chemical reaction is analyzed in a system formed by a flat plate solid catalyst, partially wetted by a flowing rivulet of a liquid in contact with a stagnant pure gas. The paper solves the fluid dynamic problem of the liquid phase first, and afterwards incorporates the mass transfer and the chemical reaction. The system is assumed to be isothermal and at steady state, with a first order kinetics whose limiting reactant is in the gas phase. This work studies the influence of the gas-liquid surface tension, the liquid reactant flow rate, the liquid viscosity and the angle of inclination of the solid, upon the wetting factor. The model proposed also predicts the effect of these parameters and the Thiele modulus on the overall effectiveness factor and the molar flux of the limiting gaseous reactant at the catalytic solid-liquid interface in a direct way. This approach makes the wetting factor a non-manipulated variable.     

External and internal mass transfer effect on photocatalytic degradation

A rational approach is proposed in determining the effect of internal and external mass transfer, and catalyst layer thickness during photocatalytic degradation. The reaction occurs at the liquid–catalyst interface and therefore, when the catalyst is immobilized, both external and internal mass transfer plays significant roles in overall photocatalytic processes. Several model parameters, namely, external mass transfer coefficient, dynamic adsorption equilibrium constant, adsorption rate constant, internal mass transfer coefficient, and effective diffusivity were determined either experimentally or by fitting realistic models to experimental results using benzoic acid as a model component. The effect of the internal mass transfer on the photocatalytic degradation rate over different catalyst layer thickness under two different illuminating configurations was analyzed theoretically and later experimentally verified. It was observed that an optimal catalyst layer thickness exists for SC (substrate-to-catalyst) illumination.     

The effect of wetting liquid droplet size on the growth of agglomerates during wet drum granulation

Results of investigation of the effect of wetting liquid droplet size on the growth of agglomerates during wet drum granulation of dolomite flour of selected grain-size composition which guaranteed geometrical similarity were discussed.

The process of granulation was carried out batch-wise in a drum granulator 0.5 m in diameter and 0.4 m long at rotational speed 0.33 s⁻¹ and constant volumetric drum filling degree =0.1. On the bed tumbling in the drum, the wetting liquid (distilled water) was supplied at a constant flow rate Q_w=12×10⁻³ m³/h. The size of wetting droplets was changed using various air flow rates through pneumatic spray nozzles in the range Q_a=1.0 to 3.0 m³/h and applying a sprinkler which supplied (drop-wise) the liquid uniformly along the entire drum length. In the whole experimental cycle, constant mean saturation degree of the feed equal to S=0.293 was used. Relationships determining the effect of wetting droplet size and particle size distribution of the raw material on the rate of agglomerate growth during drum granulation were developed.     

在工业镍催化剂上苯气相加氢反应动力学

在常压下,应用内循环式无梯度反应器,研究了在国产工业镍催化剂上苯气相加氢的本征动力学.假设催化剂表面上存在两类不同的活性中心,氢及苯各自吸附在相邻的不同类型的活性中心上,设第一个氢原子加入苯环的步骤为反应速率控制步骤,据此以导出反应的动力学方程,与实验数据颇相符合,平均偏差6.1%.测得的本征反应活化能为13.1kcal/mol.苯的吸附热为9.84kcal/mol,与不存在化学反应时的测定结果相接近.     

THE EFFECT OF PARTICLE DILUTION ON WETTING EFFICIENCY AND LIQUID FILM THICKNESS IN SMALL TRICKLE BEDS

Partial wetting in small scale trickle bed reactors results in incorrect determination of intra-particle apparent kinetic parameters as well as in erroneous reactor scale-up. Although a dilution of catalyst particles with inert fines improves the catalyst wetting efficiency, it does not guarantee full external catalyst wetting at all superficial liquid mass velocities. In this work, a method is presented to relate the wetting efficiency obtained at different operating conditions and at different laboratories for diluted and non-diluted beds. Liquid film thickness in diluted and non-diluted beds is estimated. The effect of the operating conditions on partial wetting and liquid film thickness is discussed.