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）.

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.

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.

Reduction of Precursors of Chlorination By-products in Drinking Water Using Fluidized-bed Biofilm Reactor at Low Temperature

Objective To investigate the reduction of chlorination by-products （CBPs） precursors using the fluidized-bed biofdm reactor （FBBR）. Methods Reduction of total organic carbon （TOC）, ultraviolet absorbance （UV254）, tfihalomethane （THM） formation potential （THMFP）, haloacetic acid （HAA） formation potential （HAAFP）, and ammonia in FBBR were evaluated in detail. Results The reduction of TOC or UV254 was low, on average 12.6% and 4.7%, respectively, while the reduction of THMFP and HAAFP was significant. The reduction of ammonia was 30%-40% even below 3℃, however, it could quickly rise to over 50% above 3℃. Conclusions The FBBR effectively reduces CBPs and ammonia in drinking water even at low temperature and seems to be a very promising and competitive drinking water reactor for polluted surface source waters, especially in China.

Extending homogeneous fluidization flow regime of Geldart-A particles by exerting axial uniform and steady magnetic field

The homogeneous/particulate fluidization flow regime is particularly suitable for handling the various gas–solid contact processes encountered in the chemical and energy industry.This work aimed to extend such a regime of Geldart-A particles by exerting the axial uniform and steady magnetic field.Under the action of the magnetic field,the overall homogeneous fluidization regime of Geldart-A magnetizable particles became composed of two parts:inherent homogeneous fluidization and newly-created magnetic stabilization.Since the former remained almost unchanged whereas the latter became broader as the magnetic field intensity increased,the overall homogeneous fluidization regime could be extended remarkably.As for Geldart-A nonmagnetizable particles,certain amount of magnetizable particles had to be premixed to transmit the magnetic stabilization.Among others,the mere addition of magnetizable particles could broaden the homogeneous fluidization regime.The added content of magnetizable particles had an optimal value with smaller/lighter ones working better.The added magnetizable particles might raise the ratio between the interparticle force and the particle gravity.After the magnetic field was exerted,the homogeneous fluidization regime was further expanded due to the formation of magnetic stabilization flow regime.The more the added magnetizable particles,the better the magnetic performance and the broader the overall homogeneous fluidization regime.Smaller/lighter magnetizable particles were preferred to maximize the magnetic performance and extend the overall homogeneous fluidization regime.This phenomenon could be ascribed to that the added magnetizable particles themselves became more Geldart-A than-B type as their density or size decreased.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

Experimental study on MSW gasification and melting technology

In order to develop municipal solid waste （MSW） gasification and melting technology, two preliminary experiments and a principle integrated experiment were fulfilled respectively. The gasification characteristics of MSW were studied at 500-750℃ when equivalence ratio （ER） was 0.2--0.5 using a fluidized-bed gasifier. When temperature was 550-700℃ and ER was 0.2--0.4, low heat value （LHV） of syngas reaches 4000-12000 kJ/Nm^3. The melting characteristics of fly ash were investigated at 1100-1460℃ using a fixed-bed furnace. It was proved that over 99.9% of dioxins could be decomposed and most heavy-metals could be solidified when temperature was 1100-1300℃. The principle integrated experiment was carried out in a fluidized-bed gasification and swirl-melting system. MSW was gasified etticiently at 550-650℃, swirl-melting furnace maintains at 1200-1300℃ stably and over 95% of fly ash could be caught by the swirl-melting furnace. The results provided much practical experience and basic data to develop MSW gasification and melting technology.

Effect of CaO on retention of S, Cl, Br, As, Mn, V, Cr, Ni, Cu, Zn,W and Pb in bottom ashes from fluidized-bed coal combustion power station

This work was conducted to evaluate whether Ca-bearing additives used during coal combustion can also help with the retention of some other elements. This work was focused on the evaluation of bottom ashes collected during four full-scale combustion tests at an operating thermal fluidized-bed power station. Bottom ashes were preferred to fly ashes for the study to avoid interference from condensation processes usually occurring in the post-combustion zone. This work focused on the behaviors of S, Cl, Br, As, Mn, V, Cr, Ni, Cu,Zn, W, and Pb. Strong positive correlations with CaO content in bottom ashes were observed（for all four combustion tests） for S, As, Cl and Br（R = 0.917-0.999）. Strong inverse proportionality was calculated between the contents of Pb, Zn, Ni, Cr and Mn and CaO, so these elements showed association to materials other than Ca-bearing compounds（e.g., to aluminosilicates, organic matter, etc.）. Somewhat unclear behaviors were observed for W, Cu, and V. Their correlation coefficients were evaluated as statistically ＂not significant＂, i.e., these elements were not thought to be significantly associated with CaO. It was also discovered that major enrichment of CaO in the finest bottom ash fractions could be advantageously used for simple separation of elements strongly associated with these fractions, mainly S and As, but also Cl or Br. Removal of5% of the finest ash particles brings about a decrease in As concentration down to 77%-80% of its original bulk ash content, which can be conveniently used e.g., when high As content complicates further ash utilization.

Preparation of nano-sized tungsten carbide via fluidized bed

Ultrafine or nano-sized of tungsten carbide(WC)is the key material to prepare ultrafine grained cemented carbides.In this paper,nano-sized WC powders were directly prepared by using industrial nano-needle violet tungsten oxide(WO2.72)as the raw material,a fluidized bed as the reactor,and CO as the carbonization gas.The relationship between particle sizes and reaction temperatures,residence times,atmospheres has been investigated systematically.In addition,the physical–chemical indexes(such as residual oxygen,total carbon and free carbon)of the products were measured.The results indicated that the particle size of WC increased with the increase of temperature from 800 to 950°C.As the residence time increased,the particle size decreased gradually,and then increased due to slight sintering.The introduction of hydrogen reduced the carbonization rate,and is not beneficial to obtaining nano-sized WC.Products that satisfy the standard were obtained when WO2.72 reacted with CO at 850°C,900°C and 950°C for 3.0 h,2.5 h and 2.0 h,respectively.The particle sizes of the three samples calculated from the specific surface area were 46.4 nm,53.2 nm and 52.1 nm,respectively.

Clustering behavior of solid particles in two-dimensional liquid-solid fluidized-beds

In this paper, the clustering behavior of solid particles in a two-dimensional （2D） liquid-solid fluidized-bed was studied by using the charge coupled devices （CCD） imaging measuring and processing technique and was characterized by fractal analysis. CCD images show that the distribution of solid particles in the 2D liquid-solid fluidised-bed is not uniform and self-organization behavior of solid particles was observed under the present experimental conditions. The solid particles move up in the 2D fluidized-bed in groups or clusters whose configurations are often in the form of horizontal strands. The box fractal dimension of the cluster images in the 2D liquid-solid fluidized-bed increases with the rising of solid holdup and reduces with the increment of solid particle diameter and superficial liquid velocity. At given solid holdup and solid particle size, the lighter particles show smaller fractal dimensions.

CFD simulation study of the effect of baffles on the fluidized bed for hydrogenation of silicon tetrachloride

In this study,the effect of channel baffles and louver baffles on the flow pattern in the large-scale industrial fluidized beds was studied by computational fluid dynamics(CFD)methods.Then,the effect of flow pattern on the chemical reaction performance was studied for the first time.Simulation results showed that the gas velocity distributed more uniformly,solid particles dispersed more homogeneously and aggregation scarcely occurred in the fluidized bed with louver baffles than that with channel baffles.The residence time distribution indicated that louver baffles remarkably suppressed gas back-mixing in comparison with channel baffles.The reasonable agreements of pressure distribution and reaction results between the simulation in the bed with channel baffles and the data on a large-scale industrial apparatus demonstrated the accuracy of the CFD model.The predicted conversion of SiCl_(4) in the bed with louver baffles(27.44%)was higher than that with channel baffles(22.69%),indicating that louver baffles markedly improved the performance of the fluidized bed.This study could provide useful information for future structural improvements of baffles in large-scale fluidized beds.

Experimental and numerical simulation of lignite chemical looping gasification with phosphogypsum as oxygen carrier in a fluidized bed

Phosphogypsum(PG)is a solid waste produced in the wet process of producing phosphoric acid.Lignite is a kind of promising chemical raw material.However,the high sulfur of lignite limits the utilization of lignite as a resource.Based on fluidized bed experiments,the optimal reaction conditions for the production syngas by lignite chemical looping gasification(CLG)with PG as oxygen carrier were studied.The study found that the optimal reaction temperature should not exceed 1123 K;the mole ratio of water vapor to lignite should be about 0.2;the mole ratio of PG oxygen carrier to lignite should be about 0.6.Meanwhile,commercial software Comsol was used to establish a fuel reaction kinetics model.Through computational fluid dynamics(CFD)numerical simulation,the process of reaction in fluidized bed were well captured.The model was based on a two-fluid model and coupled mass transfer,heat transfer and chemical reactions.This study showed that the fluidized bed presents a flow structure in which gas and solid coexist.There was a high temperature zone in the middle and lower parts of the fluidized bed.It could be seen from the results of the flow field simulated that the fluidized bed was beneficial to the progress of the gasification reaction.

Flue gas analysis for biomass and coal co‑fring in fuidized bed:process simulation and validation

Coal-conversion technologies,although used ubiquitously,are often discredited due to high pollutant emissions,thereby emphasizing a dire need to optimize the combustion process.The co-fring of coal/biomass in a fuidized bed reactor has been an efcient way to optimize the pollutants emission.Herein,a new model has been designed in Aspen Plus®to simultaneously include detailed reaction kinetics,volatile compositions,tar combustion,and hydrodynamics of the reactor.Validation of the process model was done with variations in the fuel including high-sulfur Spanish lignite,high-ash Ekibastuz coal,wood pellets,and locally collected municipal solid waste(MSW)and the temperature ranging from 1073 to 1223 K.The composition of the exhaust gases,namely,CO/CO_(2)/NO/SO_(2)were determined from the model to be within 2%of the experimental observations.Co-combustion of local MSW with Ekibastuz coal had fue gas composition ranging from 1000 to 5000 ppm of CO,16.2%–17.2%of CO_(2),200–550 ppm of NO,and 130–210 ppm of SO_(2).A sensitivity analysis on co-fring of local biomass and Ekibastuz coal demonstrated the optimal operating temperature for fuidized bed reactor at 1148 K with the recommended biomass-to-coal ratio is 1/4,leading to minimum emissions of CO,NO,and SO_(2).

Prediction of coating uniformity in batch fluidized-bed coating process

Coating of particulate materials in fluidized beds is a widely used technique to eliminate particle agglomeration,provide slow release of an active substance,or protect active ingredients.When thin polymer shells are applied on a particle surface,it is important to determine the process parameters that provide coating uniformity.In this study,the degree of coverage,defined as the fraction of the coated surface of the particles,is proposed as a quantitative criterion of coating uniformity.A new model for the batch fluidized-bed coating process is presented.The model allows prediction of the function of particle distribution according to the degree of coverage at a given process time and thereby enables assessment of coating uniformity.An algorithm for the numerical solution of model equations for a batch fluidized-bed coater is described.The influences of the main process parameters on the coating uniformity were shown.

Study on attrition of spherical-shaped Mo/HZSM-5 catalyst for methane dehydro-aromatization in a gas–solid fluidized bed

As a potential methane efficient conversion process,non-oxidative aromatization of methane in fluidized bed requires a catalyst with good attrition resistance,especially in the states of high temperature,longtime rapid movement and chemical reaction.Existing evaluation methods for attrition resistance,such as ASTM D5757 and Jet Cup test,are targeted for fresh catalysts at ambient temperature,which cannot well reflect the real process.In this study,spherical-shaped Mo/HZSM-5 catalyst prepared by dipping and spray drying was placed in a self-made apparatus for attrition testing,in which the catalyst attrition under different system temperatures,running time and process factors was investigated with percent mass loss(PML),particle size-mass distribution(PSMD)and scanning electron microscope(SEM).Carbon deposition on the catalyst before and after activation,aromatization and regeneration was analyzed by thermogravimetry(TG),and the attrited catalysts were evaluated for methane dehydro-aromatization(MDA).The results show that the surface abrasion and body breakage of catalyst particles occur continuously,with the increase of system temperature and running time,and make the PML rise gradually.The process factors of activation,aromatization and regeneration can cause the catalyst attrition and carbon deposits,which broaden the PSMD in varying degrees,and the carbon-substances on catalysts greatly improve their attrition resistance at high temperature.Catalyst attrition has a certain influence on its catalytic performance,and the main reasons point to particle breakage and fine powder escape.

A fluidized-bed model for NiMgW-catalyzed CO2 methanation

The reduction of carbon dioxide to methane by hydrogen("CO2 methanation")using renewable energy is a promising process for recycling CO2.Better catalysts and better reactors are both required for the practical application of CO2 methanation.This study examines how the operating parameters affect CO2 methanation in a highly efficient fluidized-bed reactor.We first measured the kinetics of the CO2 methanation reaction using an NiMgW catalyst,which has been reported to exhibit superior catalytic performance.We then developed a fluidized-bed reactor model based on an earlier model for CO2 methanation.The fluidized bed model indicated that the NiMgW was indeed superior to two other previously studied catalysts in terms of faster conversion of reactants and higher concentrations of product CH4 throughout the reactor.The overall rate of production of CH4 increased with temperature and H2/CO2 ratio and decreased as the inlet reactant flow rate,catalyst particle diameter,and catalyst particle sphericity increased.

The effect of the Ce content on the oxidative dehydrogenation of propane over CrOy-CeO2/γ-Al2O3 catalysts

A series of CrOy(17.5 wt%)-CeO2(X wt%)/γ-Al2O3 catalysts(X=0,0.5,2,5,8)with various Ce contentswere prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 550℃ and 0.1 MPa.The prepared catalysts were characterized by BET,H2-TPR,O2-TPD,XPS,XRD,SEM-EDS and Raman spectroscopy.Among the prepared catalysts,the 17.5Cr-2Ce/Al catalyst with the largest amount of lattice oxygen exhibited the best catalytic performance for the dehydrogenation of propane to propylene with lattice oxygen.The decreased presence of oxygen defects and reducibility were the factors responsible for the improved dehydrogenation activity of the catalysts.The CeO2 layer could inhibit the evolution of lattice oxygen(O2^−)to electrophilic oxygen species(O2^−),and the oxygen defects on the catalyst surfacewere reduced.The inhibited lattice oxygen evolution prevented the deep oxidation of propane or propylene,the average COx selectivity decreased from 24.41%(17.5Cr/Al)to 5.71%(17.5Cr-2Ce/Al),and the average propylene selectivity increased from 60.15%(17.5Cr/Al)to 85.05%(17.5Cr-2Ce/Al).

Evolution of deposited carbon during multi-stage fluidized-bed reduction of iron ore fines

The influence of reduction conditions on carbon deposition during fiuidized-bed pre-reduction of iron ore fines was investigated experimentally.The results showed that reduction temperature and the composition of reducing gases had a significant effect on the rate of carbon deposition and the type of carbon deposits (graphite and Fe3C).Low reduction temperature,high CO content,and addition of H2favored the deposition of carbon,especially graphite.The reduction conditions also significantly affected the surface morphology of the as-reduced iron ore fines.As the amount of deposited graphite increased,the formation of fibrous iron disappeared and graphite filaments were observed.The pre-reduced iron ore fines were further fiuidized in pure CO at 850℃ for final reduction.The results showed that graphite could suppress the formation of fibrous iron and decrease the surface viscosity,thereby inhibiting agglomeration during the final high-temperature reduction stage.Reactions that consume the deposited carbon during the final high-temperature reduction were identified and graphite was shown to be more reactive than Fe3C.To enhance the application of fluidization technology in producing sponge iron,a novel solid-state high-temperature reduction method via deposited carbon was proposed and demonstrated to be feasible.

Evaluation of oxygen uncoupling characteristics of oxygen carrier using micro-fluidized bed thermogravimetric analysis

Oxygen uncoupling characteristics of a natural manganese ore and a perovskitetype oxide CaMn_(0.5)Ti0_(37)5Fe_(0.125)O_(3)were studied by using a microfluidized bed thermogravimetric analysis(MFBTGA)technology which is based on a realtime mass measurement of fluidizing particles inside a bubbling bed reactor.The chemical stability,kinetics of the oxygen release and uptake reactions and fluidization property were investigated and the experimental data measured by MFBTGA were compared with the results in a regular TGA instrument(TGA Q500).The regular TGA Q500 results show the reactivity of both the manganese ore and perovskite oxide are stable for multi cycles,and the oxygen uncoupling capacity of the manganese ore is~1.2%(mass)which is~2 times higher than that of the perovskite oxide.However,the experimental results from the MFBTGA indicated that there is a serious agglomeration for the manganese ore.A very important finding is that the reaction rate of oxygen release and oxygen uptake of the perovskite oxide measured by the MFBTGA are~2 and~4 times faster than that of testedby the TGA Q500.We can conclude that MFBTGA is a very useful tool to measure the reactivity stability and kinetics of oxygen carriers in highthroughput analysis instead of the regular TGA.