CO_2 capture using dry TiO_2-doped Na_2CO_3/Al_2O_3 sorbents in a fluidized-bed reactor

Abstract： In order to improve the reactivity of Na2CO3/Al2O3 sorbent with CO2, a new sorbent showing high reactivity was developed by doping Na2CO3/Al2O3 with TiO2 using impregnation. Fourteen multi-cycle carbonation/regeneration tests of the sorbent were carried out in a fluidized-bed reactor and the sorbent was characterized by X-ray diffraction and nitrogen adsorption. It is confirmed that TiO2 shows a positive effect on the adsorption process of Na2CO3 and the reaction rate is observed to increase significantly, especially in the first 10 min. Moreover, TiO2 is stable within the temperature range of the process and no other Ti-compounds are detected. The carbonation products are NaHCO3 and Na5H3 （CO3 ）4. The surface area and the pore volume of the sorbent keep stable after 14 cycles. The Fourier transform infrared spectroscopy and the X-ray photoelectron spectroscopy are used to analyze the effect mechanism of TiO2 on CO2 adsorption process of Na2CO3/Al2O3.

Fluidized-Bed Bioreactor Applications for Biological Wastewater Treatment： A Review of Research and Developments

Wastewater treatment is a process that is vital to protecting both the environment and human health. At present, the most cost-effective way of treating wastewater is with biological treatment processes such as the activated sludge process, despite their long operating times. However, population increases have created a demand for more efficient means of wastewater treatment, Fluidization has been demonstrated to in- crease the efficiency of many processes in chemical and biochemical engineering, but it has not been widely used in large-scale wastewater treatment. At the University of Western Ontario, the circulating fluidized-bed bioreactor （CFBBR） was developed for treating wastewater. In this process, carrier particles develop a biofilm composed of bacteria and other microbes. The excellent mixing and mass transfer characteristics inherent to fluidization make this process very effective at treating both municipal and industrial wastewater. Studies of lab- and pilot-scale systems showed that the CFBBR can remove over 90% of the influent organic matter and 80% of the nitrogen, and produces less than one-third as much biological sludge as the activated sludge process. Due to its high efficiency, the CFBBR can also be used to treat wastewaters with high organic solid concentrations, which are more difficult to treat with conventional methods because they require longer residence times; the CFBBR can also be used to reduce the system size and footprint. In addition, it is much better at handling and recovering from dynamic loadings （i.e., varying influent volume and concentrations） than current systems. Overall, the CFBBR has been shown to be a very effective means of treating wastewa- ter, and to be capable of treating larger volumes of wastewater using a smaller reactor volume and a shorter residence time. In addition, its compact design holds potential for more geographically localized and isolat- ed wastewater treatment systems.

Simulation of biodiesel industrial production via solid base catalyst in a fixed-bed reactor

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.

Carbon Dioxide Captured from Flue Gas by Modified Ca-based Sorbents in Fixed-bed Reactor at High Temperature

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.

Mathematical Model and Advanced Control for Gas-phase Olefin Polymerization in Fluidized-bed Catalytic Reactors

In this study, the developments in modeling gas-phase catalyzed olefin polymerization fluidized-bed reactors （FBR） using Ziegler-Natta catalyst is presented. The modified mathematical model to account for mass and heat transfer between the solid particles and the surrounding gas in the emulsion phase is developed in this work to include site activation reaction. This model developed in the present study is subsequently compared with well-known models, namely, the bubble-growth, well-mixed and the constant bubble size models for porous and non porous catalyst. The results we obtained from the model was very close to the constant bubble size model, well-mixed model and bubble growth model at the beginning of the reaction but its overall behavior changed and is closer to the well-mixed model compared with the bubble growth model and constant bubble size model after half an hour of operation. Neural-network based predictive controller are implemented to control the system and compared with the conventional PID controller, giving acceptable results.

Experimental Study and Modeling of an Adiabatic Fixed-bed Reactor for Methanol Dehydration to Dimethyl Ether

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.

Changes in char reactivity due to char-oxygen and char-steam reactions using Victorian brown coal in a fixed-bed reactor

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.

Reaction behavior of oil sand in fluidized-bed pyrolysis

The reaction behavior of oil sand from Inner Mongolia（China） were studied in a fluidizedbed pyrolysis process,and a comparative study was conducted on the properties of the liquid products obtained through fluidized-bed pyrolysis of oil sand and the native bitumen obtained by solvent extraction.The results indicated that the fluidized-bed pyrolysis,a feasible carbon rejection process,can be used to upgrade oil sand.The reaction temperature and time were found to be the key operating parameters affecting the product distribution and yields in fluidized-bed pyrolysis of oil sand.The optimal temperature was 490℃ and the most suitable reaction time was 5 min.Under these operation conditions,the maximum yield of liquid product was 80wt%.In addition,the pyrolysis kinetics of oil sand at different heating rates of 5,10,20 and 30℃/min was investigated using a thermogravimetric analyzer（TGA）.

Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane

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.

Scale up and stability test for oxidative coupling of methane over Na_2WO_4-Mn/SiO_2 catalyst in a 200 ml fixed-bed reactor

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.

Conversion enhancement of tubular fixed-bed reactor for Fischer-Tropsch synthesis using static mixer

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.

Highly selective synthesis of single-walled carbon nanotubes from methane in a coupled Downer-turbulent fluidized-bed reactor

For the synthesis of single-walled carbon nanotubes （SWCNTs） from CH4 over a Fe/MgO catalyst, we proposed a coupled Downer-turbulent fluidized-bed （TFB） reactor to enhance the selectivity and yield （or production rate） of SWCNTs. By controlling a very short catalyst residence time （1-3 s） in the Downer, only part of Fe oxides can be reduced to form Fe nano particles （NPs） available for the growth of SWCNTs. The percentage of unreduced Fe oxides increased and the yield of SWCNTs decreased accordingly with the increase of catalyst feeding rate in Downer. SWCNTs were preferentially grown on the catalyst surface and inhibited the sintering of the Fe crystallites which would be formed thereafter in the downstream TFB, evidenced by TEM, Raman and TGA. The coupled Downer-turbulent fluidized-bed reactor technology allowed higher selectivity and higher production rate of SWCNTs as compared to TFB alone.

Valorization of natural diatomite mineral:Application to removal of anionic dye from aqueous solution in a batch and fixed-bed reactor

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℃.

Experimental investigation of fluidized-bed reactor performance for oxidative coupling of methane

Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane （C2） yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.

Removal of Lead Ions from Ginseng Ethanol Extracts by Dynamic Adsorption in a Fixed-bed Column

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.

Fixed-bed column study for deep removal of copper(Ⅱ) from simulated cobalt electrolyte using polystyrene-supported 2-aminomethylpyridine chelating resin

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.

DETERMINATION OF PARAMETERS IN A TWO-DIMENSIONAL MODEL FOR FIXED-BED ADSORBERS

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.

On-Line Prediction of a Fixed-Bed Reactor Using K-L Expansion and Neural Networks

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.

Numerical investigation of complex chemistry performing in Ptcatalyzed oxidative dehydrogenation of ethane fixed-bed reactors

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.

Biosorption of basic violet 10 onto activated Gossypium hirsutum seeds:Batch and fixed-bed column studies

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.