Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can descri...Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can describe the transesterification reaction well. The Antoine equation of biodiesel is regressed with the vapor-liquid data cited of literature. The non-random two liquid （NRTL） model is applied to describe the system of fatty acid methyl ester （FAME）, methanol and glycerol and parameters are obtained. The Ternary phase map is obtained from Aspen Plus via the liquid-liquid equilibrium （LLE） data. In order to describe the production in a fixed-bed performs in industrial scale after being magnified 1 000 times, the Aspen Plus simulation is employed, where two flowsheets are simulated to predict material and energy consumption. The simulation results prove that at least 350. 42 kW energy consumption can be reduced per hour to produce per ton biodiesel compared with data reported in previous references.展开更多
Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors： calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption...Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors： calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption capacity of those sorbents was investigated in a fixed-bed reactor in the temperature range of 350-650 ℃. It was found that all of those sorbents showed higher capacity for CO2 absorption when the operating temperature higher than 450 ℃. The CaAc2-CaO sorbent showed the highest CO2 absorption capacity of 299 mg.g-1. The mor- phology of those sorbents was examined by scanning electron microscope （SEM）, and the changes of composition before and after carbonation were also determined by X-ray diffraction （XRD）. Results indicated that those sorbents have the similar chemical compositions and crystalline phases before carbonation reaction [mainly Ca（OH）2], and CaCO3 is the main component after carbonation reaction. The SEM morphology shows clearly that the sorbent pores were filled with reaction products after carbonation reaction, and became much denser than before. The N2 adsorption-desorption isotherms indicated that the CaAc2-CaO and CaCO3-CaO sorbents have higher specific surface area. lar2er oore volume and anoropriate pore size distribution than that of CaO-CaO and Ca（OH）2-CaO.展开更多
An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diame...An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefln over V2O5/γ-Al203 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa- rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100% conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run- away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl- ene production in an industrial scale reactor.展开更多
This study presents the deep removal of copper (Ⅱ) from the simulated cobalt electrolyte using fabricated polystyrene-supported 2-aminomethylpyridine chelating resin (PS-AMP) in a fixed-bed.The effects of bed height ...This study presents the deep removal of copper (Ⅱ) from the simulated cobalt electrolyte using fabricated polystyrene-supported 2-aminomethylpyridine chelating resin (PS-AMP) in a fixed-bed.The effects of bed height (7.0–14.0 cm),feed flow rate (4.5–9.0 mL/min),initial copper (Ⅱ) concentration of the feed (250–1000 mg/L),feed temperature (25–40 ℃) and the value of pH (2.0–4.0) on the adsorption process of the PS-AMP resin were investigated.The experimental data showed that the PS-AMP resin can deeply eliminate copper (Ⅱ) from the simulated cobalt electrolyte.The bed height,feed flow rate,initial copper (Ⅱ) concentration of the feed,feed temperature and feed pH value which corresponded to the highest removal of copper (Ⅱ) were 7.0 cm with 35 mm of the column diameter,4.5 mL/min,40℃,1000 mg/L and 4.0,respectively.The breakthrough capacity,the saturated capacity of the column and the mass ratio of Cu/Co (g/g) in the saturated resin were correspondingly 16.51 mg/g dry resin,61.72 mg/g dry resin and 37.67 under the optimal experimental conditions.The copper (Ⅱ) breakthrough curves were fitted by the empirical models of Thomas,Yoon-Nelson and Adam-Bohart,respectively.The Thomas model was found to be the most suitable one for predicting how the concentration of copper (Ⅱ) in the effluent changes with the adsorption time.展开更多
The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction ...The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.展开更多
This study was to examine the influence of reactions of char–O2and char–steam on the char reactivity evolution.A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown co...This study was to examine the influence of reactions of char–O2and char–steam on the char reactivity evolution.A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown coal at800 °C. The chars prepared from the gasification experiments were then collected and subjected to reactivity characterisation(ex-situ reactivity) using TGA(thermogravimetric analyser) in air. The results indicate that the char reactivity from TGA was generally high when the char experienced intensive gasification reactions in 0.3%O2in the fixed-bed reactor. The addition of steam into the gasification not only enhanced the char conversion significantly but also reduced the char reactivity dramatically. The curve shapes of the char reactivity with involvement of steam were very different from that with O2 gasification, implying the importance of gasifying agents to char properties.展开更多
One-dimensional heterogeneous plug flow model was employed to model an adiabatic fixed-bed reactor for the catalytic dehydration of methanol to dimethyl ether.Longitudinal temperature and conversion profiles predicted...One-dimensional heterogeneous plug flow model was employed to model an adiabatic fixed-bed reactor for the catalytic dehydration of methanol to dimethyl ether.Longitudinal temperature and conversion profiles predicted by this model were compared to those experimentally measured in a bench scale reactor.The reactor was packed with 1.5mm γ-Al2O3 pellets as dehydration catalyst and operated in a temperature range of 543-603K at an atmospheric pressure.Also,the effects of weight hourly space velocity(WHSV)and temperature on methanol conversion were investigated.According to the results,the maximum conversion is obtained at 603.15K with WHSV of 72.87h-1.展开更多
Recently, Fischer-Tropsch synthesis （FTS） has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids （BTL） processes. In Fischer-Tropsch （FT） section, biomas...Recently, Fischer-Tropsch synthesis （FTS） has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids （BTL） processes. In Fischer-Tropsch （FT） section, biomass-derived syngas, mainly composed of a mixture of carbon monoxide （CO） and hydrogen （H2）, is converted into various forms of hydrocarbon products over a catalyst at specified temperature and pressure. Fixed-bed reactors are typically used for these processes as conventional FT reactors. The fixed-bed or packed-bed type reactor has its drawbacks, which are heat transfer limitation, i.e. a hot spot problem involved highly exothermic characteristics of FT reaction, and mass transfer limitation due to the condensation of liquid hydrocarbon products occurred on catalyst surface. This work is initiated to develop a new chemical reactor design in which a better distribution of gaseous reactants and hydrocarbon products could be achieved, and led to higher throughput and conversion. The main goal of the research is the enhancement of a fixed-bed reactor, focusing on the application of KenicsTM static mixer insertion in the tubular packed-bed reactor. Two FTS experiments were carried out using two reactors i.e., with and without static mixer insertion within catalytic beds. The modeled syngas used was a mixed gas composed of H2/CO in 2 ： 1 molar ratio that was fed at the rate of 30 mL（STP）·min^- 1 （GHSV ≈ 136 mL·gcat^-1 ·h^-1） into the fixed Ru supported aluminum catalyst bed of weight 13.3 g. The reaction was carried out at 180 ℃ and atmospheric pressure continuously for 36 h for both experiments. Both transient and steady-state conversions （in terms of time on stream） were reported. The results revealed that the steady-state CO conversion for the case using the static mixer was approximately 3.5 times higher than that of the case without static mixer. In both cases, the values of chain growth probability of hydrocarbon products （α） for Fischer-Tropsch synthesis were 0.92 and 0.89 for the case with and without static mixer, respectively.展开更多
The removal of lead from ginseng ethanol extracts by a fixed-bed column filled with an adsorbent bearing amine and carboxyl groups was investigated. The Pb2+ content was determined by inductively coupled plasma mass s...The removal of lead from ginseng ethanol extracts by a fixed-bed column filled with an adsorbent bearing amine and carboxyl groups was investigated. The Pb2+ content was determined by inductively coupled plasma mass spectrometry. When the flowrate increased from 0.12 to 0.34 ml·min-1 , the column exhibited a marked increase in percentage of lead removal from 54.9% to 92.3%. Further increase in the flowrate did not bring evident changes to the lead removal, whereas an increase in the temperature could reinforce adsorption further, suggesting that the adsorption process was controlled by external film diffusion below the flowrate of 0.34 ml·min-1 , and by the intraparticle pore diffusion of lead ions when the flowrate exceeded it. A low remaining lead amount in extracts such as 0.11 mg·kg-1 (extracts powder) was achieved. The adsorbents also adsorbed effective constituents to some extent. But 88% of constituents adsorbed were taken off using a 70% ethanol aqueous solution.展开更多
In this work,the efficiency of an adsorption process,in which Moroccan diatomite(ND)is used as a low-cost adsorbent to remove Congo red(CR)dye from contaminated waters in batch and column system,was examined.The influ...In this work,the efficiency of an adsorption process,in which Moroccan diatomite(ND)is used as a low-cost adsorbent to remove Congo red(CR)dye from contaminated waters in batch and column system,was examined.The influence of experimental conditions(pH,adsorbent dose and temperature)on the adsorption of CR onto the ND adsorbent was studied.A study of the adsorption kinetics for CR revealed that a pseudo-second-order model provided the best fit to the experimental kinetic data,and the equilibrium data were well described by the Langmuir isotherm model with an adsorption capacity of 6.07 mg/g using 15 g/L of ND,pH=6,contact time 3 h and 25℃.On the other hand,the ND regeneration tests were investigated and showed that the desorption reaches at least 50%when using ethanol as eluent.In addition,the adsorption process in a continuous mode was studied.Breakthrough curves were properly represented by the Yoon—Nelson model.Hence,the adsorption capacity of 5.71 mg/g was reached using 0.114 g of adsorbent,CR concentration of 6 mg/L and a flow of 1 mL/min under 25℃.展开更多
An on-line prediction scheme combining the Karhunen-Love expansion and a recurrent neural network for a wall-cooled fixed-bed reactor is presented.Benzene oxidation in a pilotscale,single tube fixed-bed reactor is cho...An on-line prediction scheme combining the Karhunen-Love expansion and a recurrent neural network for a wall-cooled fixed-bed reactor is presented.Benzene oxidation in a pilotscale,single tube fixed-bed reactor is chosen as a working system and a pseudo-homogeneous twodimensional model is used to generate simulation data to investigate the prediction scheme presentedunder randomly changing operating conditions.The scheme consisting of the K-L expansion andneural network performs satisfactorily for on-line prediction of reaction yield and bed temperatures.展开更多
A new method is proposed for the determination of the parameters in a two-dimensionalmodel which characterizes the properties of axial and radial mixing and mass transport in afixed-bed adsorber.Parameter estimation f...A new method is proposed for the determination of the parameters in a two-dimensionalmodel which characterizes the properties of axial and radial mixing and mass transport in afixed-bed adsorber.Parameter estimation for the model is carried out with methane-air-5A molecularsieve in a bed under the condition of step injection of tracer from a point on the main axis of thebed by the curve fitting method in the time domain.展开更多
Ethylene is one of the most important basic chemicals in the modern chemical industry.Thermal or catalytic cracking of hydrocarbons is the main industrial technologies nowadays,which suffer from equilibriumlimitation ...Ethylene is one of the most important basic chemicals in the modern chemical industry.Thermal or catalytic cracking of hydrocarbons is the main industrial technologies nowadays,which suffer from equilibriumlimitation and rapid coke formation.The oxidative dehydrogenation of ethane(ODHE)is considered to be a promising alternative process since it overcomes equilibrium-limitations,avoids catalyst deactivation by coke formation,and decreases the number of side reactions.In this study,particle-resolved 2 D CFD simulations of fixed-beds filled with eggshell catalysts coupled with micro-kinetics of Pt-catalyzed ODHE were performed to understand the effect of operation conditions and catalyst properties on ethylene selectivity.The catalyst bed was created by discrete element method(DEM)and the central longitudinal section of the reactor tube was defined as the 2 D simulation region.Both of the homogeneous and catalytic heterogeneous chemical reactions were described by detailed micro-kinetics within the particle-resolved CFD simulation.At first,the established model of monolith reactors was verified by comparing the simulated results with experimental results reported in literature.Then,the effects of operation conditions and catalyst concentration on the ethylene selectivity in randomly packed beds were explored.The specific variation of certain operation conditions including inlet flow rate,inlet temperature,pressure,inlet C2 H6/O2 ratio and N2 dilution ratio can effectively increase ethylene selectivity.And the reduction of ratio of catalytic active area to geometric area Fcat/georepresenting catalyst properties from 140 to 30 increases the selectivity from 42.2%to 59.3%.This research can provide reference for the industrialization of ODHE process in the future.展开更多
Sulphuric acid activated immature Gossypium hirsutum seed(AIGHS) was prepared to biosorbe basic violet 10(BV10) from aqueous solutions.Methylene blue number,iodine number and Brunauer-Emmett-Teller surface analysis in...Sulphuric acid activated immature Gossypium hirsutum seed(AIGHS) was prepared to biosorbe basic violet 10(BV10) from aqueous solutions.Methylene blue number,iodine number and Brunauer-Emmett-Teller surface analysis indicated that the AIGHS were hetero-porous.Boehm titrations and Fourier-transform infrared spectra demonstrated the chemical heterogeneity of the AIGHS surface.Batch biosorption studies were used to examine the effects of process parameters in the following range:pH 2-12,temperature 293-313 K,contact time 1-5 h and initial concentration 200-600 mg·L^(-1).The matching of equilibrium data with the Langmuir-Freundlich form of isotherms indicated that the BV10 was adsorbed via chemisorption and pore diffusion.Kinetic investigation indicated multiple order chemisorption through an Avrami kinetic model.Film diffusion controlled the rate of BV10 biosorption onto AIGHS.The spontaneous and endothermic nature of sorption was corroborated by thermodynamic study.Continuous biosorption experiments were performed using a fixed-bed column and the influence of operating parameters was explored for different ranges of initial concentration 100-300 mg·L^(-1),bed height 5-10 cm,and flow rate 2.5-4.5 ml·min^(-1).A dose response model accurately described the fixed-bed biosorption data.An external mass transfer correlation was formulated explaining BV10-AIGHS sorption.展开更多
The first in China pilot tests of fixed-bed methanol-topropylene unit were successfully implemented at the Yangzi Petrochemical Company(YPC).It is told that this technology has opened up a new process for production o...The first in China pilot tests of fixed-bed methanol-topropylene unit were successfully implemented at the Yangzi Petrochemical Company(YPC).It is told that this technology has opened up a new process for production of propylene through coal gasification,and China has possessed both the fluidized-bed methanolto-propylene process(F-MTP)and the展开更多
In this work a one-dimensional mathematical model was developed to simulate methane conversion and hydrogen yield in a fixed-bed reactor filled with catalyst particles. For the reason that reforming reactions are sore...In this work a one-dimensional mathematical model was developed to simulate methane conversion and hydrogen yield in a fixed-bed reactor filled with catalyst particles. For the reason that reforming reactions are sorely endothermic process, the heat is supplied to the reactor through electrical heating. The reforming reactions have been investigated from a modelling view point considering the effect of different temperatures ranging from 500℃ and 977℃ on the conversion of methane and hydrogen yield. Simulation results show that the steam reforming of methane in a fixed-bed reactor can efficiently store high temperature end thermal energy. When the operating temperature is increased to 977℃, the conversion of methane is 97.48% and the hydrogen yield is 2.2408. As a conclusion, the maximum thermochemical efficiency will be obtained under optimal operating temperature (977℃) and the steam/methane (3.86) ratio.展开更多
This work investigated the applicability of heterogeneous and pseudo-homogeneous models to predict the dynamic behavior of a fixed-bed catalytic reactor. Some issues concerning the dynamic behavior of the system were ...This work investigated the applicability of heterogeneous and pseudo-homogeneous models to predict the dynamic behavior of a fixed-bed catalytic reactor. Some issues concerning the dynamic behavior of the system were discussed, such as the prediction of the inverse response phenomenon. The proposed models (Het- erogeneous I and II and Pseudo-homogeneous) were able to predict with qualitative similarity the main characteristics of the dynamic behavior of a fixed-bed catalytic reactor, including the inverse response. The computational time demanded for the solution of the heterogeneous models was 10 to 50% longer than in the case of the pseudo-homogeneous model, making the use of the former suitable for applications where computational time is not the major restriction (off-line applications). On the other hand, when on-line applications are required, the simplified model (Pseudo-homogeneous model) showed to be a good alternative because this model was able to predict (qualitatively) the dynamics of the reactor using a faster and easier numerical solution.展开更多
Catalytic fixed-bed is an efficient and facile system for scalable organic synthesis due to its continuous and fast flow operation process.As a key unit in the fixed-bed system,catalytically active packing materials a...Catalytic fixed-bed is an efficient and facile system for scalable organic synthesis due to its continuous and fast flow operation process.As a key unit in the fixed-bed system,catalytically active packing materials are required to possess some properties,such as high activity,excellent stability,and porous packing structure.Herein,we prepare a fibrous fixed-bed catalyst by anchoring Pd nanoparticles on N-doped graphene fiber(NHG)(Pd/NGF).Due to the porous and loose packing structure,the resultant Pd/NGF catalyst can be easily filled into the continuous-flow reactor to construct a fixed-bed system with low flow resistance.The corresponding catalytic fixed-bed system exhibits a favourable flow rate(8 mL/min)and excellent durability toward reduction reactions of N-containing unsaturated compounds to produce aromatic amines.This work provides a new design concept of fibrous fixed-bed catalysts with dual-active components(i.e.,graphene-derived active materials and metal nanoparticles)and catalytic organic synthesis in a continuous-flow process.展开更多
The distribution of adsorbent particle sizes typically has a significant impact on adsorption performance.Most fixed-bed adsorption studies adopt the assumption of average particle size to simplify the adsorption mode...The distribution of adsorbent particle sizes typically has a significant impact on adsorption performance.Most fixed-bed adsorption studies adopt the assumption of average particle size to simplify the adsorption model,but this does not eliminate the deviation between experiments and simulations caused by particle size distribution in practice.In this study,the population balance equation(PBE)and fixed-bed adsorption kinetics model were combined to simulate the adsorption process in a fixed-bed reactor,modeling the distribution of adsorbate uptake over time on adsorbent particles of different sizes.We integrated and optimized the PBE and fixed-bed mass transfer model in the algorithm,and the resulting combined model adopts a variable time step size,which can achieve a balance between computational efficiency and error while ensuring computational convergence.By slicing the model in the spatial dimension,multiple sets of PBE can be calculated in parallel,improving computational efficiency.The adsorption process of single-component and multi-component CO_(2)/CH_(4)/N_(2)on 4A zeolite without binder was simulated,and the influence of adsorbent particle size distribution was analyzed.Simulation results show that the assumption of average adsorbent particle size,which was commonly made in published work,will underestimate the time required for adsorbates to break through the fixed bed compared with the assumption of uniform adsorbent particle size.This model helps to consider the impact of adsorbent particle size distribution on the adsorption process,thereby improving the prediction accuracy of adsorbent performance.展开更多
Separations of mixtures in fixed-bed adsorbers are influenced by factors such as(1)selectivity of adsorption,Sads,(2)diffusional time constants,Đi/rc 2,and(3)diffusion selectivity,Đ1/Đ2.In synergistic separations,intr...Separations of mixtures in fixed-bed adsorbers are influenced by factors such as(1)selectivity of adsorption,Sads,(2)diffusional time constants,Đi/rc 2,and(3)diffusion selectivity,Đ1/Đ2.In synergistic separations,intracrystalline diffusion of guest molecules serves to enhance the selectivities dictated by thermodynamics of mixture adsorption.In antisynergistic separations,intracrystalline diffusion serves to reverse the hierarchy of selectivities dictated by adsorption equilibrium.For both scenarios,the productivities of the desired product in fixed-bed operations are crucially dependent on diffusional time constants,Đi/rc 2;these need to be sufficiently low in order for diffusional influences to be effective.Also,the ratioĐ1/Đ2 should be large enough for manifestation of synergistic or antisynergistic influence.Both synergistic and antisynergistic separations have two common,distinguishing characteristics.Firstly,for transient uptake within crystals,the more mobile component attains supraequilibrium loadings during the initial stages of the transience.Such overshoots,signifying uphill diffusion,are engendered by the cross-coefficientsΓij(i≠j)of thermodynamic correction factors.Secondly,the component molar loadings,plotted in composition space,follow serpentine equilibration paths.If cross-coefficients are neglected,no overshoots in the loadings of the more mobile component are experienced,and the component loadings follow monotonous equilibration paths.The important takeaway message is that the modeling of mixture separations in fixed-bed adsorbers requires the use of the Maxwell−Stefan equations describing mixture diffusion employing chemical potential gradients as driving forces.展开更多
基金The National Basic Research Program of China(973Program)(No.2010CB732206)the National Natural Science Foundation of China(No.21076044,21276050)
文摘Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can describe the transesterification reaction well. The Antoine equation of biodiesel is regressed with the vapor-liquid data cited of literature. The non-random two liquid （NRTL） model is applied to describe the system of fatty acid methyl ester （FAME）, methanol and glycerol and parameters are obtained. The Ternary phase map is obtained from Aspen Plus via the liquid-liquid equilibrium （LLE） data. In order to describe the production in a fixed-bed performs in industrial scale after being magnified 1 000 times, the Aspen Plus simulation is employed, where two flowsheets are simulated to predict material and energy consumption. The simulation results prove that at least 350. 42 kW energy consumption can be reduced per hour to produce per ton biodiesel compared with data reported in previous references.
基金Supported by the National Natural Science Foundation of China （21006053）, the Fundamental Research Funds for the Central Universities （65010551） and Special Projects of Environmental Protection （2009ZX07208）.
文摘Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors： calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption capacity of those sorbents was investigated in a fixed-bed reactor in the temperature range of 350-650 ℃. It was found that all of those sorbents showed higher capacity for CO2 absorption when the operating temperature higher than 450 ℃. The CaAc2-CaO sorbent showed the highest CO2 absorption capacity of 299 mg.g-1. The mor- phology of those sorbents was examined by scanning electron microscope （SEM）, and the changes of composition before and after carbonation were also determined by X-ray diffraction （XRD）. Results indicated that those sorbents have the similar chemical compositions and crystalline phases before carbonation reaction [mainly Ca（OH）2], and CaCO3 is the main component after carbonation reaction. The SEM morphology shows clearly that the sorbent pores were filled with reaction products after carbonation reaction, and became much denser than before. The N2 adsorption-desorption isotherms indicated that the CaAc2-CaO and CaCO3-CaO sorbents have higher specific surface area. lar2er oore volume and anoropriate pore size distribution than that of CaO-CaO and Ca（OH）2-CaO.
文摘An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefln over V2O5/γ-Al203 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa- rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100% conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run- away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl- ene production in an industrial scale reactor.
基金Project(2014CB643401)supported by the National Basic Research Program of ChinaProjects(51134007,51474256)supported by the National Natural Science Foundation of ChinaProject(2017TP1001)supported by the Hunan Provincial Science and Technology Plan Project,China
文摘This study presents the deep removal of copper (Ⅱ) from the simulated cobalt electrolyte using fabricated polystyrene-supported 2-aminomethylpyridine chelating resin (PS-AMP) in a fixed-bed.The effects of bed height (7.0–14.0 cm),feed flow rate (4.5–9.0 mL/min),initial copper (Ⅱ) concentration of the feed (250–1000 mg/L),feed temperature (25–40 ℃) and the value of pH (2.0–4.0) on the adsorption process of the PS-AMP resin were investigated.The experimental data showed that the PS-AMP resin can deeply eliminate copper (Ⅱ) from the simulated cobalt electrolyte.The bed height,feed flow rate,initial copper (Ⅱ) concentration of the feed,feed temperature and feed pH value which corresponded to the highest removal of copper (Ⅱ) were 7.0 cm with 35 mm of the column diameter,4.5 mL/min,40℃,1000 mg/L and 4.0,respectively.The breakthrough capacity,the saturated capacity of the column and the mass ratio of Cu/Co (g/g) in the saturated resin were correspondingly 16.51 mg/g dry resin,61.72 mg/g dry resin and 37.67 under the optimal experimental conditions.The copper (Ⅱ) breakthrough curves were fitted by the empirical models of Thomas,Yoon-Nelson and Adam-Bohart,respectively.The Thomas model was found to be the most suitable one for predicting how the concentration of copper (Ⅱ) in the effluent changes with the adsorption time.
文摘The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.
基金Support by the Victorian State Government under its Energy Technology Innovation Strategy programme and the 12th Five-Year Plan of National Science and Technology of China(2012BAA04B02)
文摘This study was to examine the influence of reactions of char–O2and char–steam on the char reactivity evolution.A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown coal at800 °C. The chars prepared from the gasification experiments were then collected and subjected to reactivity characterisation(ex-situ reactivity) using TGA(thermogravimetric analyser) in air. The results indicate that the char reactivity from TGA was generally high when the char experienced intensive gasification reactions in 0.3%O2in the fixed-bed reactor. The addition of steam into the gasification not only enhanced the char conversion significantly but also reduced the char reactivity dramatically. The curve shapes of the char reactivity with involvement of steam were very different from that with O2 gasification, implying the importance of gasifying agents to char properties.
文摘One-dimensional heterogeneous plug flow model was employed to model an adiabatic fixed-bed reactor for the catalytic dehydration of methanol to dimethyl ether.Longitudinal temperature and conversion profiles predicted by this model were compared to those experimentally measured in a bench scale reactor.The reactor was packed with 1.5mm γ-Al2O3 pellets as dehydration catalyst and operated in a temperature range of 543-603K at an atmospheric pressure.Also,the effects of weight hourly space velocity(WHSV)and temperature on methanol conversion were investigated.According to the results,the maximum conversion is obtained at 603.15K with WHSV of 72.87h-1.
基金supported by the project of the National Science and Technology Development Agency (NSTDA),Thailand
文摘Recently, Fischer-Tropsch synthesis （FTS） has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids （BTL） processes. In Fischer-Tropsch （FT） section, biomass-derived syngas, mainly composed of a mixture of carbon monoxide （CO） and hydrogen （H2）, is converted into various forms of hydrocarbon products over a catalyst at specified temperature and pressure. Fixed-bed reactors are typically used for these processes as conventional FT reactors. The fixed-bed or packed-bed type reactor has its drawbacks, which are heat transfer limitation, i.e. a hot spot problem involved highly exothermic characteristics of FT reaction, and mass transfer limitation due to the condensation of liquid hydrocarbon products occurred on catalyst surface. This work is initiated to develop a new chemical reactor design in which a better distribution of gaseous reactants and hydrocarbon products could be achieved, and led to higher throughput and conversion. The main goal of the research is the enhancement of a fixed-bed reactor, focusing on the application of KenicsTM static mixer insertion in the tubular packed-bed reactor. Two FTS experiments were carried out using two reactors i.e., with and without static mixer insertion within catalytic beds. The modeled syngas used was a mixed gas composed of H2/CO in 2 ： 1 molar ratio that was fed at the rate of 30 mL（STP）·min^- 1 （GHSV ≈ 136 mL·gcat^-1 ·h^-1） into the fixed Ru supported aluminum catalyst bed of weight 13.3 g. The reaction was carried out at 180 ℃ and atmospheric pressure continuously for 36 h for both experiments. Both transient and steady-state conversions （in terms of time on stream） were reported. The results revealed that the steady-state CO conversion for the case using the static mixer was approximately 3.5 times higher than that of the case without static mixer. In both cases, the values of chain growth probability of hydrocarbon products （α） for Fischer-Tropsch synthesis were 0.92 and 0.89 for the case with and without static mixer, respectively.
基金Supported by the National＇Natural Science Foundation of China （20976012, 20806009）, and the Specialized Research Fund for the Doctoral Program of Higher Education （20070007055, 20091101110035）.
文摘The removal of lead from ginseng ethanol extracts by a fixed-bed column filled with an adsorbent bearing amine and carboxyl groups was investigated. The Pb2+ content was determined by inductively coupled plasma mass spectrometry. When the flowrate increased from 0.12 to 0.34 ml·min-1 , the column exhibited a marked increase in percentage of lead removal from 54.9% to 92.3%. Further increase in the flowrate did not bring evident changes to the lead removal, whereas an increase in the temperature could reinforce adsorption further, suggesting that the adsorption process was controlled by external film diffusion below the flowrate of 0.34 ml·min-1 , and by the intraparticle pore diffusion of lead ions when the flowrate exceeded it. A low remaining lead amount in extracts such as 0.11 mg·kg-1 (extracts powder) was achieved. The adsorbents also adsorbed effective constituents to some extent. But 88% of constituents adsorbed were taken off using a 70% ethanol aqueous solution.
文摘In this work,the efficiency of an adsorption process,in which Moroccan diatomite(ND)is used as a low-cost adsorbent to remove Congo red(CR)dye from contaminated waters in batch and column system,was examined.The influence of experimental conditions(pH,adsorbent dose and temperature)on the adsorption of CR onto the ND adsorbent was studied.A study of the adsorption kinetics for CR revealed that a pseudo-second-order model provided the best fit to the experimental kinetic data,and the equilibrium data were well described by the Langmuir isotherm model with an adsorption capacity of 6.07 mg/g using 15 g/L of ND,pH=6,contact time 3 h and 25℃.On the other hand,the ND regeneration tests were investigated and showed that the desorption reaches at least 50%when using ethanol as eluent.In addition,the adsorption process in a continuous mode was studied.Breakthrough curves were properly represented by the Yoon—Nelson model.Hence,the adsorption capacity of 5.71 mg/g was reached using 0.114 g of adsorbent,CR concentration of 6 mg/L and a flow of 1 mL/min under 25℃.
基金Supported by the National Natural Science Foundation of China(No.29676014)and others.
文摘An on-line prediction scheme combining the Karhunen-Love expansion and a recurrent neural network for a wall-cooled fixed-bed reactor is presented.Benzene oxidation in a pilotscale,single tube fixed-bed reactor is chosen as a working system and a pseudo-homogeneous twodimensional model is used to generate simulation data to investigate the prediction scheme presentedunder randomly changing operating conditions.The scheme consisting of the K-L expansion andneural network performs satisfactorily for on-line prediction of reaction yield and bed temperatures.
基金Supported by the National Natural Science Foundation of China.
文摘A new method is proposed for the determination of the parameters in a two-dimensionalmodel which characterizes the properties of axial and radial mixing and mass transport in afixed-bed adsorber.Parameter estimation for the model is carried out with methane-air-5A molecularsieve in a bed under the condition of step injection of tracer from a point on the main axis of thebed by the curve fitting method in the time domain.
文摘Ethylene is one of the most important basic chemicals in the modern chemical industry.Thermal or catalytic cracking of hydrocarbons is the main industrial technologies nowadays,which suffer from equilibriumlimitation and rapid coke formation.The oxidative dehydrogenation of ethane(ODHE)is considered to be a promising alternative process since it overcomes equilibrium-limitations,avoids catalyst deactivation by coke formation,and decreases the number of side reactions.In this study,particle-resolved 2 D CFD simulations of fixed-beds filled with eggshell catalysts coupled with micro-kinetics of Pt-catalyzed ODHE were performed to understand the effect of operation conditions and catalyst properties on ethylene selectivity.The catalyst bed was created by discrete element method(DEM)and the central longitudinal section of the reactor tube was defined as the 2 D simulation region.Both of the homogeneous and catalytic heterogeneous chemical reactions were described by detailed micro-kinetics within the particle-resolved CFD simulation.At first,the established model of monolith reactors was verified by comparing the simulated results with experimental results reported in literature.Then,the effects of operation conditions and catalyst concentration on the ethylene selectivity in randomly packed beds were explored.The specific variation of certain operation conditions including inlet flow rate,inlet temperature,pressure,inlet C2 H6/O2 ratio and N2 dilution ratio can effectively increase ethylene selectivity.And the reduction of ratio of catalytic active area to geometric area Fcat/georepresenting catalyst properties from 140 to 30 increases the selectivity from 42.2%to 59.3%.This research can provide reference for the industrialization of ODHE process in the future.
文摘Sulphuric acid activated immature Gossypium hirsutum seed(AIGHS) was prepared to biosorbe basic violet 10(BV10) from aqueous solutions.Methylene blue number,iodine number and Brunauer-Emmett-Teller surface analysis indicated that the AIGHS were hetero-porous.Boehm titrations and Fourier-transform infrared spectra demonstrated the chemical heterogeneity of the AIGHS surface.Batch biosorption studies were used to examine the effects of process parameters in the following range:pH 2-12,temperature 293-313 K,contact time 1-5 h and initial concentration 200-600 mg·L^(-1).The matching of equilibrium data with the Langmuir-Freundlich form of isotherms indicated that the BV10 was adsorbed via chemisorption and pore diffusion.Kinetic investigation indicated multiple order chemisorption through an Avrami kinetic model.Film diffusion controlled the rate of BV10 biosorption onto AIGHS.The spontaneous and endothermic nature of sorption was corroborated by thermodynamic study.Continuous biosorption experiments were performed using a fixed-bed column and the influence of operating parameters was explored for different ranges of initial concentration 100-300 mg·L^(-1),bed height 5-10 cm,and flow rate 2.5-4.5 ml·min^(-1).A dose response model accurately described the fixed-bed biosorption data.An external mass transfer correlation was formulated explaining BV10-AIGHS sorption.
文摘The first in China pilot tests of fixed-bed methanol-topropylene unit were successfully implemented at the Yangzi Petrochemical Company(YPC).It is told that this technology has opened up a new process for production of propylene through coal gasification,and China has possessed both the fluidized-bed methanolto-propylene process(F-MTP)and the
文摘In this work a one-dimensional mathematical model was developed to simulate methane conversion and hydrogen yield in a fixed-bed reactor filled with catalyst particles. For the reason that reforming reactions are sorely endothermic process, the heat is supplied to the reactor through electrical heating. The reforming reactions have been investigated from a modelling view point considering the effect of different temperatures ranging from 500℃ and 977℃ on the conversion of methane and hydrogen yield. Simulation results show that the steam reforming of methane in a fixed-bed reactor can efficiently store high temperature end thermal energy. When the operating temperature is increased to 977℃, the conversion of methane is 97.48% and the hydrogen yield is 2.2408. As a conclusion, the maximum thermochemical efficiency will be obtained under optimal operating temperature (977℃) and the steam/methane (3.86) ratio.
文摘This work investigated the applicability of heterogeneous and pseudo-homogeneous models to predict the dynamic behavior of a fixed-bed catalytic reactor. Some issues concerning the dynamic behavior of the system were discussed, such as the prediction of the inverse response phenomenon. The proposed models (Het- erogeneous I and II and Pseudo-homogeneous) were able to predict with qualitative similarity the main characteristics of the dynamic behavior of a fixed-bed catalytic reactor, including the inverse response. The computational time demanded for the solution of the heterogeneous models was 10 to 50% longer than in the case of the pseudo-homogeneous model, making the use of the former suitable for applications where computational time is not the major restriction (off-line applications). On the other hand, when on-line applications are required, the simplified model (Pseudo-homogeneous model) showed to be a good alternative because this model was able to predict (qualitatively) the dynamics of the reactor using a faster and easier numerical solution.
基金the Key Research and Development Program of Hubei Province(No.2022BAA026)the Open/Innovation Project of Key Laboratory of Novel Biomass-Based Environmental and Energy Materials in Petroleum and Chemical Industry(No.2022BEEA06)+3 种基金the Open Project of Hubei Key Laboratory of Novel Reactor and Green Chemical Technology(No.NRGC202203)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(No.GCP20220205)the Innovation and Entrepreneurship Training Program Funded by Wuhan Institute of Technology(No.202310490007)the Postgraduate Innovation Foundation from Wuhan Institute of Technology(No.CX2022459).
文摘Catalytic fixed-bed is an efficient and facile system for scalable organic synthesis due to its continuous and fast flow operation process.As a key unit in the fixed-bed system,catalytically active packing materials are required to possess some properties,such as high activity,excellent stability,and porous packing structure.Herein,we prepare a fibrous fixed-bed catalyst by anchoring Pd nanoparticles on N-doped graphene fiber(NHG)(Pd/NGF).Due to the porous and loose packing structure,the resultant Pd/NGF catalyst can be easily filled into the continuous-flow reactor to construct a fixed-bed system with low flow resistance.The corresponding catalytic fixed-bed system exhibits a favourable flow rate(8 mL/min)and excellent durability toward reduction reactions of N-containing unsaturated compounds to produce aromatic amines.This work provides a new design concept of fibrous fixed-bed catalysts with dual-active components(i.e.,graphene-derived active materials and metal nanoparticles)and catalytic organic synthesis in a continuous-flow process.
基金the National Natural Science Foundation of China (21706075)Guangzhou Municipal Science and Technology Project (202201011269)
文摘The distribution of adsorbent particle sizes typically has a significant impact on adsorption performance.Most fixed-bed adsorption studies adopt the assumption of average particle size to simplify the adsorption model,but this does not eliminate the deviation between experiments and simulations caused by particle size distribution in practice.In this study,the population balance equation(PBE)and fixed-bed adsorption kinetics model were combined to simulate the adsorption process in a fixed-bed reactor,modeling the distribution of adsorbate uptake over time on adsorbent particles of different sizes.We integrated and optimized the PBE and fixed-bed mass transfer model in the algorithm,and the resulting combined model adopts a variable time step size,which can achieve a balance between computational efficiency and error while ensuring computational convergence.By slicing the model in the spatial dimension,multiple sets of PBE can be calculated in parallel,improving computational efficiency.The adsorption process of single-component and multi-component CO_(2)/CH_(4)/N_(2)on 4A zeolite without binder was simulated,and the influence of adsorbent particle size distribution was analyzed.Simulation results show that the assumption of average adsorbent particle size,which was commonly made in published work,will underestimate the time required for adsorbates to break through the fixed bed compared with the assumption of uniform adsorbent particle size.This model helps to consider the impact of adsorbent particle size distribution on the adsorption process,thereby improving the prediction accuracy of adsorbent performance.
文摘Separations of mixtures in fixed-bed adsorbers are influenced by factors such as(1)selectivity of adsorption,Sads,(2)diffusional time constants,Đi/rc 2,and(3)diffusion selectivity,Đ1/Đ2.In synergistic separations,intracrystalline diffusion of guest molecules serves to enhance the selectivities dictated by thermodynamics of mixture adsorption.In antisynergistic separations,intracrystalline diffusion serves to reverse the hierarchy of selectivities dictated by adsorption equilibrium.For both scenarios,the productivities of the desired product in fixed-bed operations are crucially dependent on diffusional time constants,Đi/rc 2;these need to be sufficiently low in order for diffusional influences to be effective.Also,the ratioĐ1/Đ2 should be large enough for manifestation of synergistic or antisynergistic influence.Both synergistic and antisynergistic separations have two common,distinguishing characteristics.Firstly,for transient uptake within crystals,the more mobile component attains supraequilibrium loadings during the initial stages of the transience.Such overshoots,signifying uphill diffusion,are engendered by the cross-coefficientsΓij(i≠j)of thermodynamic correction factors.Secondly,the component molar loadings,plotted in composition space,follow serpentine equilibration paths.If cross-coefficients are neglected,no overshoots in the loadings of the more mobile component are experienced,and the component loadings follow monotonous equilibration paths.The important takeaway message is that the modeling of mixture separations in fixed-bed adsorbers requires the use of the Maxwell−Stefan equations describing mixture diffusion employing chemical potential gradients as driving forces.
