Integrated FCC riser—regenerator dynamics studied in a fluid catalytic cracking pilot plant

In this paper a dynamic simulator of the fluid catalytic cracking (FCC) pilot plant, operating in the Chemical Process Engineering Research Institute (CPERI, Thessaloniki, Greece), is presented. The operation of the pilot plant permits the execution of case studies for monitoring of the dynamic responses of the unit, by imposing substantial step changes in a number of the manipulated variables. The comparison between the dynamic behavior of the unit and that predicted by the simulator arise useful conclusions on both the similarities of the pilot plant to commercial units, along with the ability of the simulator to depict the main dynamic characteristics of the integrated system. The simulator predicts the feed conversion, coke yield and heat of catalytic reactions in the FCC riser on the basis of semi-empirical models developed in CPERI and simulates the regenerator according to the two-phase theory of fluidization, with a dilute phase model taking account of postcombustion reactions. The riser and regenerator temperature, the stripper and regenerator pressure drop and the composition of the regenerator flue gas are measured on line and are used for verification of the ability of the simulator to predict the dynamic transients between steady states in both open- and closed-loop unit operation. All the available process variables such as the reaction conversion, the coke yield, the carbon on regenerated catalyst and the catalyst circulation rate are used for the validation of the steady-state performance of the simulator. The comparison between the dynamic responses of the model and those of the pilot plant to step changes in the feed rate and preheat temperature reveals the ability of the simulator to accurately depict the complex pilot process dynamics in both open- and closed-loop operation. The dynamic simulator can serve as the basis for the development of a model-based control structure for the pilot plant, alongside its use as a tool for off-line process optimization studies.     

Dynamic modelling of catalytic liquid-phase reactions in fixed beds—Kinetics and catalyst deactivation in the recovery of anthraquinones

Dynamic modelling of catalytic fixed-bed reactors with liquid-phase feed is of crucial importance, since catalyst deactivation often plays a central role in reaction engineering. General dynamic modelling of liquid-phase fixed beds was considered, including complex reaction kinetics and catalyst deactivation. The modelling concept was applied on a catalytic liquid-phase conversion reaction. The model was tested with pilot-plant data and showed a good predictivibility. The model can be used to optimize the production life cycles of fixed beds with catalyst deactivation.     

Heterogeneous Catalytic Reactor Design with Non‐Uniform Catalyst Considering Shell‐Progressive Poisoning Behavior

A novel methodology has been developed to design an optimum heterogeneous catalytic reactor, by considering non‐uniform catalyst pellet under shell‐progressive catalyst deactivation. Various types of non‐uniform catalyst pellets are modelled in combination with reactor design. For example, typical non‐uniform catalyst pellets such as egg‐yolk, egg‐shell and middle‐peak distribution are developed as well as step‐type distribution. A progressive poisoning behavior is included to the model to produce correct effectiveness factor from non‐uniform catalyst pellet. As opposed to numerical experiment with limited type of kinetic application to the model in the past, this paper shows a new methodology to include any types of kinetic reactions for the modeling of the reactor with non‐uniform catalyst pellet and shell‐progressive poisoning. For an optimum reactor design, reactor and catalyst variables are considered at the same time. For example, active layer thickness and location inside pellet are optimised together with reactor temperature for the maximisation of the reactor performance. Furthermore, the temperature control strategy over the reactor operation period is added to the optimization, which extends the model to three dimensions. A computational burden has been a major concern for the optimization, and innovative methodology is adopted. Application of profile based synthesis with the combination of SA (Simulated Annealing) and SQP (Successive Quadratic Programming) allows more efficient computation not only at steady state but also in dynamic status over the catalyst lifetime. A Benzene hydrogenation reaction in an industry scale fixed‐bed reactor is used as a case study for illustration.     

Modelling the kinetics of fast catalytic cracking reactions

Instantaneous kinetic constants and gasoline selectivities have been determined for catalytic cracking of n-hexadecane. The pulse technique was used in order to model the sequential build-up of coke which occurs on cracking catalyst within a riser transport-line reactor. The total amount of hydrocarbon injected per unit weight of catalyst was between 0 and 10. The mathematical model used to analyze the data was based on the unsteady state mass balance of the microcatalytic reactor with the assumption of plug flow. Results suggest a fast deactivation process during the run with fresh catalyst, while regenerated catalyst showed a slower deactivation. The catalyst regenerated three times evidenced a low apparent activation energy when temperature was increased from 500°C to 550°C.     

Modeling of naphtha reforming unit applying detailed description of kinetic in continuous catalytic regeneration process

Naphtha reforming is one of the most important processes in refineries in which high value-added reformate for gasoline pool and aromatics such as benzene, toluene, and xylene are produced. It is necessary to establish new naphtha reforming units and develop the traditional units to increase the efficiency of the processes. In this study, according to the recent progresses in the naphtha reforming technology, mathematical modeling of this process in continuous catalyst regeneration mode of operation is accomplished in two dimensions (radial and axial) by considering cross flow pattern. In addition, a new catalyst deactivation model has been proposed and a new reaction network model based on 32 pseudo-components with 84 reactions is investigated. Then, this model has been validated by comparing with industrial data, and its results have acceptable agreement.     

Optimal design of reactive distillation systems: Application to the production of ethyl tert-butyl ether (ETBE)

This work addresses the design of reactive distillation columns to produce ETBE, based on a detailed first-principles model that considers equilibrium and kinetic information, rigorous physical property data, and catalyst deactivation. An evolutionary algorithm is used to generate a sequence of feasible designs with improved characteristics in a sequential solution/optimisation strategy, by specifying the design variables (both integer and continuous) that characterise a particular column configuration. Two classes of optimisation algorithms are compared: genetic algorithms and particle swarm optimisation. The objective function considered is the gross annual profit.The results demonstrate that both algorithms are adequate to solve this design problem. The effect of catalyst deactivation included in the design stage played a determinant role in the optimal column specification. A post-design sensitivity analysis is developed to assess the quality of the solutions obtained, together with the individual effects of each design variable in the optimal configuration identified.     

Studies of carbonaceous species in alkali promoted iron catalysts during Fischer–Tropsch synthesis

The effects of La, Mg and Ca promoters on carbonaceous surface and bulk iron carbide species formed in the alkali promoted iron catalysts are studied under realistic Fischer–Tropsch synthesis (FTS) conditions. Compositions of bulk iron phase and phase transformations of carbonaceous species during pretreatment and FTS reaction were characterized using the temperature-programmed surface reaction with hydrogen (TPSR-H₂) and XRD techniques. Many carbonaceous species on surface and bulk were qualitatively and quantitatively identified by combined TPSR-H₂ and XRD spectra of the alkali promoted iron catalyst. These species, sorted by the their reactivity with H₂ from high to low, were recognized as (a) adsorbed, atomic carbon; (b) amorphous, lightly polymerized hydrocarbon or carbon surface species; (c) bulk carbides and (d) disordered and moderately ordered graphitic surface carbons. The results revealed that while the surface basicity of the iron catalyst increased the CO dissociation proceeds faster than carbon hydrogenation. This phenomenon leads to excessive carbon deposition and formation of inactive iron carbide phases and graphitic type carbonaceous surface species, and consequently leads to catalyst deactivation.     

Optimization of the n-hexane isomerization process using response surface methodology

Isomerization reactions on commercial zirconium sulfate catalyst are investigated in order to determine influence of hydrogen/feed ratio, space velocity and temperature on n-hexane conversion. Investigated range of inlet parameters includes values that are applied in the industrial practice of the isomerization process. Box–Behnken experimental design was carried out in order to optimize n-hexane isomerization process. Statistical analysis of experimental data was performed to obtain second order polynomial model and the optimum conditions were determined: hydrogen/feed ratio of 6, space velocity of 2 h⁻¹ and temperature of 170 °C. At optimum conditions conversion of n-hexane was 70 wt.%. In addition, temperature dependency of product composition was investigated at optimum values of hydrogen/feed ratio and space velocity. Obtained results show that methylpentanes greatly depend on temperature, unlike dimethylbutanes, in the studied range from 130 to 170 °C. Isomer that was produced in highest quantities was 2-methylpentane, while 3-methylpentane forms in somewhat smaller amounts. 2,2- and 2,3-dimethylbutanes, which contribute the most to the octane number value, are formed in relatively small quantities, amounting to less than 10 wt.% of the total amount of isomers formed.     

Effect of the diffusion phenomena in the catalyst grain on the selectivity of a system of parallel-consecutive reactions involved in the process of n-heptane dehydrocyclization

Analytical relations were derived for analyzing the selectivity of consecutive-parallel reactions occurring under conditions of the reforming process. With these relations it is also possible to determine how the shape of the catalyst grain, as well as the kinetic and diffusion phenomena that govern the process, affects the efficiency of the desired final products.     

热回收型太阳能分级溶液集热/再生系统模型及环境适用性分析

为了在极端气候条件下提高高浓度溶液的集热再生效率,提出一种带同级热回收和级间热回收的太阳能分级溶液集热再生方法。基于填料储液槽的热质平衡,建立预除湿溶液参数可动态调整的太阳能分级集热再生系统数学模型。数值模拟发现在不同室外环境条件下分级再生和单级再生效率对比存在临界点,室外环境温度和相对湿度高于临界点,太阳辐射辐射强度低于临界点,分级再生优于单级再生。文章最后综合给出分级集热再生的环境和溶液浓度适用范围,发现在低太阳辐射、高温高湿的气候环境下,其对高浓度溶液再生越有利。     

烯烃裂解增产丙烯催化剂再生性能

由于烯烃裂解技术反应自身的特点,催化剂容易积炭失活,需要进行多次再生,因此,催化剂的再生性能对烯烃裂解技术至关重要。在实验室对中国石化中原石油化工有限责任公司烯烃裂解工业装置的ZSM-5催化剂进行了多次反应和再生试验,考察其烯烃裂解反应性能,并运用TG、XRD、NH₃-TPD、氮气物理吸附以及SEM等对再生前后的催化剂样品进行表征。结果表明,开发的烯烃裂解催化剂经过13次的反应再生过程,新鲜催化剂与再生催化剂的比表面积和孔容基本相同,烯烃转化率、丙烯及乙烯收率无明显变化,烯烃转化率仍大于73%,丙烯和乙烯收率分别大于32%和10%。且催化剂骨架结构和酸中心稳定,在多次反应与再生过程中的酸量保持不变,具有良好的再生性能。     

Optimization of the active component distribution through the catalyst bed

A variational problem was formulated to determine the optimal axially non-uniform catalyst activity distribution along the fixed catalyst bed. It was observed that the mass transport limitations or non-isothermal temperature profile are necessary conditions for potential optimization of the catalyst distribution along the bed length. Under isothermal conditions with linear dependence of the reaction rate on concentration at a constant mass transfer coefficient, the uniform distribution is optimal. Analytical solution for the first-order reaction and numerical solutions for power-law kinetics were found.     

Kinetics of the catalytic deactivation by site coverage and pore blockage: Application of percolation theory

The kinetics of the catalyst deactivation by site coverage is analyzed using percolation theory. The pore space is treated as a lattice of voids interconnected by necks in a three-dimensional network. The deactivation is assumed to occur under kinetic control and to be primarily caused by blockage of necks. The effect of various factors (such as pore-size distribution, a mean coordination number, the rate constant of disappearance of active sites, and the kinetics of blockage of separate necks) on the deactivation process is demonstrated and discussed.     

Optimization of the active component distribution through the catalyst bed for the case of adiabatic reactor

This article is the next one in the previous series of publications concerning the optimal active component distribution. The aim of the present work is to extend the optimization problem taking into account the energy balance. The variational problem on searching for the optimal active component distribution profile along the catalyst bed was formulated for the case of an adiabatic reactor at an arbitrary form of reaction rate expression. The Euler differential equation was derived and the existence conditions for the solution of variational problem were obtained. A numerical algorithm was suggested and the optimal profiles of the active component distribution were calculated for the first-order reaction. Under isothermal conditions with linear dependence of the reaction rate on reactant concentration at a constant mass transfer coefficient, the uniform distribution is optimal. As opposed to the case of an isothermal reactor with a first-order catalytic reaction, in an adiabatic reactor considerable economy in the active component loading might be achieved due to optimization of its distribution. It was shown that the optimal active component distribution profiles were axially decreasing for the first-order exothermic reactions and increasing for endothermic reactions. The optimal active component distribution profile was calculated for the case of methane combustion on catalytic monoliths.     

Formation and reactions of isocyanic acid during the catalytic reduction of nitrogen oxides

Reactions which can produce and consume isocyanic acid (HNCO) over two types of catalysts active for the reduction of nitrogen oxides have been investigated. More than 1000 ppm HNCO can be produced by the reduction of 3000 ppm NO with H₂/CO mixtures over a Pt/SiO₂ catalyst. Complete hydrolysis of HNCO to ammonia and carbon dioxide occurs if even weakly catalytic materials, such as CeO₂/SiO₂ and BaO/SiO₂, are placed downstream. Isocyanic acid is also involved as an intermediate in the reaction of nitromethane over CoZSM5 and CuZSM5 under the conditions of hydrocarbon SCR. In the initial stages of reaction there is complete conversion through to N₂ with CuZSM5 but the process stops at ammonia with CoZSM5 at temperatures below 350°C. In both cases, but especially with CoZSM5, isocyanic acid becomes observable as the catalyst deactivates during continuous exposure at temperatures below about 290°C. In situ FTIR measurements indicate that deactivation is due to a reaction between isocyanic acid and ammonia which generates cyclic striazine compounds.     

Optimization of Petlyuk sequences using a multi objective genetic algorithm with constraints

In this work we use genetic algorithms to optimize Petlyuk sequences using a rigorous design model. A multi objective genetic algorithm (GA) with constraints was formulated and interconnected with the Aspen Plus process simulator to obtain each data point during the search process. In addition to providing more energy-efficient designs than some reported structures, two relevant trends were observed from the results of the case studies; one had to do with the feed location to the prefractionator as a function of the mixture properties, and the other one with optimal structures requiring four interconnecting stages instead of the two normally used for Petlyuk sequences. An application for the separation of azeotropic mixtures is also included. The optimal placement of vapor-liquid interconnections is again shown to be different for each interconnecting stream. The GA showed a robust performance, and was practically independent on the initial values for the search variables.     

Optimization of methane reforming in a microreactor—effects of catalyst loading and geometry

In this paper, the effect of the catalyst surface site density (catalyst amount) and reactor geometry on the reforming process of methane in a wall-coated, single-channel microreactor is investigated numerically. Such a reactor, consisting of a tubular flow channel and a thermal conductive channel wall, is a good representation of microfabricated channels and monoliths. It is found that the hydrogen selectivity changes significantly with varying catalyst loading, which is a noteworthy result. Thus, the reaction path leading to higher hydrogen production becomes more important by increasing the catalyst surface site density on the active surface. This is due to the splitting rate of methane and water, which is a function of catalyst density. Furthermore, this study shows the significance of scaling the inlet volume flow not only with the reactor volume (gas space velocity) but also with the catalyst amount (catalyst space velocity). Another unexpected result is the presence of an optimum channel geometry and an optimum catalyst amount if the gas space velocity and the catalyst space velocity are constant. This underlines the necessity of coordinating the channel diameter, the inlet volume flow rate, and the catalyst amount in order to obtain a maximum reformer performance. Furthermore, it is necessary to specify the catalyst amount, the inlet conditions and the geometry in order to characterize sufficiently a catalytic reactor.     

Chemical deactivation of V2O5/WO3–TiO2 SCR catalysts by additives and impurities from fuels, lubrication oils and urea solution: Part II. Characterization study of the effect of alkali and alkaline earth metals

A characterization study on a practice-oriented V₂O₅/WO₃–TiO₂ SCR catalyst deactivated by Ca and K, respectively, was carried out using NH₃-TPD, DRIFT spectroscopy, and XPS as well as theoretical DFT calculations. It was found from NH₃-TPD experiments that strongly basic elements like K or Ca drastically affect the acidity of the catalysts. Detailed DRIFT spectroscopy experiments revealed that these poisoning agents mostly interact with the Brønsted acid sites of the V₂O₅ active phase, thus affecting the NH₃ adsorption. Moreover, these experiments also indicated that the V⁵⁺ = O sites are much less reactive on the poisoned catalysts. XPS investigations of the O 1s binding energies showed that the oxygen atoms of the V⁵⁺ = O sites are affected by the presence of the poisoning agents. Based on these results and on DFT calculations with model clusters of the vanadia surface, the poisoning mechanism is explained by the stabilization of the non atomic holes of the (0 1 0) V₂O₅ phase as a result of the deactivation element. Consequently, V–OH Brønsted acid sites and V⁵⁺ = O sites are inhibited, which are both of crucial importance in the SCR process. The deactivation model also gives an explanation to the very low concentrations of potassium needed to deactivate the SCR catalyst, since one metal atom sitting on such a non-atomic hole site deactivates up to four active vanadium centers.     

A comparative study on the performance of a catalyst system for the desulfurization of two kinds of atmospheric residues, Kuwait Export and Eocene residual oils

Crude oil feedstock is becoming increasingly heavier with higher sulfur, conradson carbon residue (CCR) and asphaltenes contents. This trend will specifically impact residual oil processes aimed at converting the residual oil to distillate products and hydrotreating the residual oil to low sulfur fuel oils (LSFO). In this paper, the performance of a catalyst system typically used in industrial atmospheric residue desulfurization (ARDS) units was investigated using residual oils of Kuwait Export Crude (KEC) and Eocene Crude as feedstock. The catalyst system consists of a combination of five catalysts having different physico-chemical properties. The performance of the catalyst system was studied using a pilot plant equipped with two reactors in series for a complete life cycle. Sulfur content in the product for both tests was maintained at around 0.6%, by raising the temperature gradually to compensate for the catalyst deactivation. The tests were continued until the temperature of the back-end reactor (R2) reached 412 °C. The results showed that the life of the catalyst system using the atmospheric residues of KEC and Eocene was around 7500 and 3800 h, respectively. The results are discussed in terms of possible differences in the deactivation pattern caused by differences in the composition of the two types of crude oils used in the study.