Upgrading Siberian (Russia) crude oil by hydrodesulfurization: Kinetic parameter estimation in a trickle-bed reactor

Hydrodesulfurization(HDS) of sour crude oil is an effective way to address the corrosion problems in refineries and is an economic way to process sour crude oil in an existing refinery built for sweet oil.Siberian crude oil transported through the Russia-China pipeline could be greatly sweetened and could be refined directly in local refinery designed for Daqing crude oil after the effective HDS treatment.In this study,the HDS of Siberian crude oil was carried out in a continuous flow isothermal trickle-bed reactor over Ni-Mo/γ-Al_2 O_3.The effects of temperature,pressure and LHSV were investigated in the ranges of 320-360℃,3-5 MPa and 0.5-2 h~(-1),keeping constant hydrogen to oil ratio at 600 L·L~(-1).The HDS conversion could be up to 92.89% at the temperature of 360℃, pressure of 5 MPa,and LHSV of 0.5 h~(-1), which is sufficient for local refineries(84%).A three phase heterogeneous model was established to analyze the performance of the trickle-bed reactor based on the two-film theory using Langmuir-Hinshelwood mechanism.The order of sulfur component is estimated as 1.28,and the order of hydrogen is 0.39.By simulating the reactor using the established model,the concentration of H_2, H_2 S and sulfur along the catalyst bed is discussed.The model is significantly useful for industrial application with respect to reactor analysis,optimization and reactor design,and can provide further insight of the HDS of Siberian crude oil.     

Kinetic model development and simulation of simultaneous hydrodenitrogenation and hydrodemetallization of crude oil in trickle bed reactor

One of the more difficult tasks in the petroleum refining industries that have not been considered largely in the literature is hydrotreating (HDT) of crude oil. The accurate calculations of kinetic models of the relevant reaction scheme are required for obtaining helpful models for HDT reactions, which can be confidently used for reactor design, operating and control. In this work, an optimization technique is employed to evaluate the best kinetic models of a trickle bed reactor (TBR) process utilized for hydrodenitrogenation (HDN) and hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and hydrodenickelation (HDNi) of crude oil based on pilot plant experiments. The minimization of the sum of the squared errors (SSE) between the experimental and estimated concentrations of nitrogen (N), vanadium (V) and nickel (Ni) compounds in the products is used as an objective function in the optimization problem to determine the kinetic parameters.A series of experimental work was conducted in a continuous flow isothermal trickle bed reactor, using crude oil as a feedstock and the commercial cobalt-molybdenum on alumina (Co-Mo/γ-Al₂O₃) as a catalyst.A three-phase heterogeneous model based on two-film theory is developed to describe the behaviour of crude oil hydroprocessing in a pilot-plant trickle bed reactor (TBR) system. The hydroprocessing reactions have been modelled by power law kinetics with respect to nitrogen, vanadium and nickel compounds, and with respect to hydrogen. In this work, the gPROMS (general PROcess Modelling System) package has been used for modelling, simulation and parameter estimation via optimization. The model simulations results were found to agree well with the experiments carried out in a wide range of the studied operating conditions. The model is employed to predict the concentration profiles of hydrogen, nitrogen, vanadium and nickel along the catalyst bed length in three phases.     

Coupling non-isothermal trickle-bed reactor with catalyst pellet models to understand the reaction and diffusion in gas oil hydrodesulfurization

In this work, a trickle-bed reactor coupled with catalyst pellet model is employed to understand the effects of the temperature and catalyst pellet structures on the reaction–diffusion behaviors in gas oil hydrodesulfurization(HDS). The non-isothermal reactor model is determined to be reasonable due to non-negligible temperature variation caused by the reaction heat. The reaction rate along the reactor is mainly dominated by the temperature,and the sulfur concentration gradient in the catalyst pellet decreases gradually along the reactor, leading to the increased internal effectiveness factor. For the fixed catalyst bed volume, there exists a compromise between the catalyst reaction rate and effectiveness factor. Under commonly studied catalyst pellet size of 0.8–3 mm and porosity of 0.4–0.8, an optimization of the temperature and catalyst pellet structures is carried out, and the optimized outlet sulfur content decreases to 7.6 wppm better than the commercial level at 0.96 mm of the catalyst pellet size and 0.40 of the catalyst porosity.     

Unsteady-state operation of trickle-bed reactor for dicyclopentadiene hydrogenation

Unsteady-state operation of a trickle-bed reactor (TBR) was investigated using a multi-step exothermic reaction, hydrogenation of dicylcopentadiene (DCPD) in the presence of Pd/Al₂O₃ catalyst. The influences of five operation strategies on the reactor performance were symmetrically studied and compared with the steady-state operation, including ON-OFF and PEAK-BASE modulations of the liquid flow rate or concentrations, and a novel hybrid modulation of liquid flow rate and concentration. Attempts were also made to develop an unsteady-state operated TBR model based on a plug-flow model incorporating fluid flowing behaviors, three-zone partial wetting catalyst, vapor-liquid phase equilibrium and enthalpy balance, to predict the overall performance under unsteady-state operations. Compared with the experimental observations, it is indicated that the developed model is generally reliable to predict performance enhancement for different modulation strategies.     

Periodically operated trickle-bed reactor for EAQs hydrogenation: Experiments and modeling

The influence of periodic operation on a consecutive reaction, the hydrogenation of 2-ethylanthraquinones (EAQs) over Pd/Al₂O₃, on a laboratory-scale trickle-bed reactor (TBR) was studied. The effects of operating parameters including cycle period, split, pressure, temperature, and time-average flow rate on the performance were experimentally examined in comparison with the steady-state operation. The results showed that under the interested operating conditions the conversion and the selectivity improved by 3-21% and 1-12%, respectively. A dynamic model consisting of a set of partial differential equations (PDEs) was developed to simulate the periodic operation of TBR for EAQs hydrogenation. The PDEs were converted into a set of ordinary differential equations (ODEs) using the method of lines (MOL) and then numerically solved by the semi-implicit Runge-Kutta method. The developed model was verified by simulating the effect of cycle period and split on the conversion and the selectivity enhancement and compared with the experimental results. It was found that the model was reliable and satisfactory when the cycle period was less than 200 s.     

Pseudo-steady state method on study of xylose hydrogenation in a trickle-bed reactor

A new approach to assess the overall mass transfer coefficients in a partial wetting trickle-bed reactor was proposed and tested in hydrogenation of xylose. An effective data-acquiring procedure featured by recycling a large volume of liquid feed has been adopted after the steady state operation. Since the volume of the fresh feed taken for recycling was so large that the xylose feed concentration decreased slowly during the prolonged recycling period, the pseudo-steady state was therefore achieved. By relating outlet and inlet xylose contents in liquid flow of the reactor, the reaction results varied with xylose feed concentration were simulated. The coefficients of the two reactants, hydrogen and xylose, were correlated simultaneously with a steady state reaction model. The estimated coefficients fell in the range of trickle-bed reactors at low flow rates and manifested a partial wetting status.     

Experimental and theoretical study of membrane-aerated biofilm reactor behavior under different modes of oxygen supply for the treatment of synthetic wastewater

This study compares, experimentally and theoretically, five different modes of supplying oxygen to a membrane-aerated biofilm reactor (MABR), and search for the more efficient ways of treating wastewaters. A single-tube MABR was used to measure the decrease of an organic substrate (sodium acetate) in water by supplying oxygen in different modes, namely: (1) by feeding the membrane tube either with oxygen or air (or none of them); (2) in some cases by simultaneous sparging air to the residual water. The dynamics of the substrate and oxygen consumption were measured during the batch experiment, and two mathematical models are developed to predict their transient responses using a Monod kinetic with dual substrate limitation. The models predict biomass growth and the production of extracellular polymer substances (EPS), which in turn causes the biofilm to grow; they account for the counter-diffusion of substrate and oxygen within the EPS structure that contains the cells, and one of them incorporates the mass transport by convection and diffusion in the surrounding liquid contained inside the interconnected pores and channels within the biofilm. Transport and kinetic parameters are estimated from experiments, and both models successfully predict concentration measurements in some of the set of experiments. It was found that all of the modes of oxygen supplied in a MABR were more efficient than the traditional suspended cell process.     

Experimental investigation of fast-mode liquid modulation in a trickle-bed reactor

Unsteady-state operation of trickle-bed reactors (TBRs) is a promising technique to improve reactor performances especially when mass transfer phenomena are rate controlling. Among the different techniques, fast-mode modulation of the liquid flow rate seems to be one of the most successful. In fact cycling the liquid flow rate at very low frequencies can induce the reactor to work at the high-interaction regime where mass and heat transfer phenomena are strongly enhanced. Fast-mode periodic operation, then, can be considered an extension of the natural high-interaction regime at a mean range of gas and liquid flow rate normally associated with trickling regime in steady-state conditions.Experimental tests have been performed in a TBR employing α-methyl styrene hydrogenation on Pd/C catalyst in unsteady-state conditions by “on-off” fast-mode liquid modulation. Results have been compared with the steady-state experiments at the corresponding average liquid flow rate, revealing a conversion rate improvement up to 60%. All experiments have been performed in isothermal conditions, so conversion improvement can be ascribed only to mass transfer increase and not to thermal effects. The variation of gas and liquid flow rates and liquid cycle parameters presented several important implications about the optimal working conditions.     

Kinetic parameter estimation and modelling of sucrose esters synthesis without solvent

In this paper, a kinetic model for the synthesis of the sucrose esters without solvent is developed. This synthesis is a heterogeneous reaction between the sucrose (solid) and the methyl palmitate (liquid) in the presence of a solid catalyst. We have established the kinetic model by steps, by first considering a homogeneous model and then by taking into account the heterogeneity of the medium. Thus, we have assumed additional steps in the model corresponding to the activation of the solid sucrose by the catalyst and autocatalytic steps. This activation parameter is associated to the viscosity of the medium. As a consequence of these observations, the study of the sensibility and the accuracy of the parameters allowed us to simplify the model.     

Optimal hybrid modeling approach for polymerization reactors using parameter estimation techniques

The dynamics of polymerization catalytic reactors have been investigated by many researchers during the past five decades; however, the emphasis of these studies was directed towards correlating process model parameters using empirical investigation based on small scale experimental setup and not on real process conditions. The resulting correlations are of limited practical use for industrial scale operations. A statistical study for the relative correlation of each of the effective process parameters revealed the best combination of parameters that could be used for optimizing the process model performance. Parameter estimation techniques are then utilized to find the values of these parameters that minimize a predefined objective function. Published real industrial scale data for the process was used as a basis for validating the process model. To generalize the model, an artificial neural network approach is used to capture the functional relationship of the selected parameters with the process operating conditions. The developed ANN-based correlation was used in a conventional fluidized catalytic bed reactor (FCR) model and simulated under industrial operating conditions. The new hybrid model predictions of the melt-flow index and the emulsion temperature were compared to industrial measurements as well as published models. The predictive quality of the hybrid model was superior to other models. The suggested parameter estimation and modeling approach can be used for process analysis and possible control system design and optimization investigations.     

Transesterification of sunflower oil in a countercurrent trickle-bed reactor packed with a CaO catalyst

Transesterification of sunflower oil with methanol to form biodiesel was performed in a countercurrent trickle-bed reactor, using calcium oxide particles 1-2 mm in diameter as a packed, solid base catalyst. Although biodiesel production generally requires a reaction temperature below the boiling point of methanol to maintain a heterogeneous, liquid-liquid reaction, in the present study the reaction temperature was varied from 80 to 140 °C to confirm the progress of transesterification in a gas-liquid-solid phase reaction system. Oil droplets released from a thin tube flowed downward, while vaporized methanol flowed upward in the bed. The effects of the reaction temperature, methanol and oil flow rates, and the bed height on the FAME yield were investigated. The oil residence time in the reactor, which was controlled by changing both the oil flow rate and the bed height, had a significant effect on the FAME yield. In addition, the FAME yield increased with reaction temperature and was maximal at 373 K due to the change in residence time associated with reduced oil viscosity at higher temperatures. The FAME yield was 98% at a reaction temperature of 373 K when the methanol and oil flow rates were 3.8 and 4.1 mL/h, respectively.     

Challenges for the periodic operation of trickle-bed catalytic reactors

Since the earliest publications just over a decade ago, the literature on periodic operation of trickle beds has grown rapidly. There are now over 30 published papers. Two applications, flow and feed composition modulation, for control of hot spots in large-scale reactors are sufficiently advanced for full-scale implementation if that has not already taken place. Models are now available that are capable of representing the time-average performance of periodically operated trickle beds, but these are not detailed enough to reproduce all of the transient behavior observed. Much about performance under periodic operation remains to be discovered. Research challenges are discussed under separate types of periodic operation: flow interruption, flow augmentation for hot spot control, feed composition modulation for hot spot control and to improve rate and/or to modify selectivity, and flow variation for enlargement of the pulse flow regime.     

Hydrodeoxygenation of vegetable oil in batch reactor: Experimental considerations

The generation of reliable experimental data in any experimental scale requires proper procedures not only for the reaction step but also for the feed preparation, separation, and characterization of products as well as calculations of conversion and product yields. Batch reactor is the most used experimental setup for carrying out exploratory studies for catalyst screening and development. This work is focused on describing and discussing a step-by-step methodology for conducting experiments for catalytic hydrotreating of vegetable oils in batch reactor. The proposed methodology considers literature and own experiences on advantages and disadvantages of different feed types, catalysts, experimental setup and procedures, effect of reaction parameters, separation and characterization of products, and calculations.     

Kinetic parameter estimation for cooling crystallization process based on cell average technique and automatic differentiation

In this paper, a cell average technique(CAT) based parameter estimation method is proposed for cooling crystallization involved with particle growth, aggregation and breakage, by establishing a more efficient and accurate solution in terms of the automatic differentiation(AD) algorithm. To overcome the deficiency of CAT that demands high computation cost for implementation, a set of ordinary differential equations(ODEs) entailed from CAT based discretized population balance equation(PBE) are solved by using the AD based high-order Taylor expansion. Moreover, an AD based trust-region reflective(TRR) algorithm and another interior-point(IP) algorithm are established for estimating the kinetic parameters associated with particle growth, aggregation and breakage. As a result, the estimation accuracy can be further improved while the computation cost can be significantly reduced, compared to the existing algorithms. Benchmark examples from the literature are used to illustrate the accuracy and efficiency of the AD-based CAT, TRR and IP algorithms in comparison with the existing algorithms. Moreover, seeded batch cooling crystallization experiments of β form L-glutamic acid are performed to validate the proposed method.     

Modeling, simulation and control of dimethyl ether synthesis in an industrial fixed-bed reactor

Dimethyl ether (DME) as a clean fuel has attracted the interest of many researchers from both industrial communities and academia. The commercially proven process for large scale production of dimethyl ether consists of catalytic dehydration of methanol in an adiabatic fixed-bed reactor. In this study, the industrial reactor of DME synthesis with the accompanying feed preheater has been simulated and controlled in dynamic conditions. The proposed model, consisting of a set of algebraic and partial differential equations, is based on a heterogeneous one-dimensional unsteady state formulation. To verify the proposed model, the simulation results have been compared to available data from an industrial reactor at steady state conditions. A good agreement has been found between the simulation and plant data. A sensitivity analysis has been carried out to evaluate the influence of different possible disturbances on the process. Also, the controllability of the process has been investigated through dynamic simulation of the process under a conventional feedback PID controller. The responses of the system to disturbance and setpoint changes have shown that the control structure can maintain the process at the desired conditions with an appropriate dynamic behavior.     

Set-point optimization of an adiabatic trickle-bed reactor system

A combined system parameter estimation and deactivation model identification procedure is proposed to create a grey model of an adiabatic residue hydrodesulfurization (RDS) trickle-bed reactor. Using the resulting grey model, a precomputed set-point table is used to optimize the set-point of the RDS reactor unit. The objective function chosen is the predetermined reactor outlet sulfur content and the optimal set-point is the reactor inlet temperature. Five crucial case studies using a dynamic simulator of an adiabatic RDS trickle-bed reactor demonstrate the applicability of the proposed algorithm in developing optimal set-points for a commercial process.     

Effects of carbon on the sulfidation and hydrodesulfurization of CoMo hydrating catalysts

The effects of carbon addition on CoMo catalyst performance for sulfidation and hydrodesulfurization (HDS) were investigated. The carbon-containing catalyst was prepared by impregnation of γ-Al₂O₃ support with NH₃ aqueous solution containing Co(NO₃)₂·6H₂O, (NH₄)₆Mo₇O₂₄·4H₂O and ethylenediamine. The results indicated that the incorporation of proper carbon on CoMo catalyst can improve its HDS performance. The carbon species on the catalyst were characterized by temperature-programmed oxidation and reduction, temperature-programmed desorption of ammonia and ultraviolet-visible diffuse reflectance spectra. Two forms of carbon species were differentiated: one is spread over the catalyst surface, similar to coke formed from reaction; the other interacts with active phase as an intermediate support. The carbon species acting as intermediate support may decrease the interaction of active metals with support, which enhances the sulfidation and HDS activities of CoMo catalyst. This work was presented at the 7th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Modelling of pervaporation: Parameter estimation and model development

Pervaporation is proved to be a commercially viable membrane separation process by this time. However, to become a widely applied process in the industry it is of crucial importance to develop membrane properties, process and module design as well as proper modelling in professional software environment. In this work a pervaporation model improvement of the basic solution–diffusion model (Rautenbach et al., 1990) is recommended and tested on experimental data. The reason behind this improvement is that the transport coefficient cannot be considered as constant assumed in the basic model in a wide concentration range. The change of the transport coefficient is considered as an exponential function of the composition of permeating compound. This exponential dependency is assumed by the authors after investigating the shape of the flux curves measured in a wider feed concentration range. The accuracy of this improved model is experimentally tested with the pervaporation of isobutanol–water, n-butanol–water, and ethanol–water mixtures on commercial hydrophilic composite membranes. This model improvement gives accurate and reliable data for a wide range of feed concentration proving that the assumption of practically constant transport coefficient cannot be applied. Therefore the use of this improved model in professional flowsheeting software packages is more reliable and reasonable than the application of the basic model for the design and operation of pervaporation, or a more effective hybrid separation system including pervaporation.