Process intensification in gas/liquid/solid reaction in trickle bed reactors: A review

As an important form of reactors for gas/liquid/solid catalytic reaction,trickle bed reactors (TBRs) are widely applied in petroleum industry,biochemical,fine chemical and pharmaceutical industries because of their flexibility,simplicity of operation and high throughput.However,TBRs also show inefficient production and hot pots caused by non-uniform fluid distribution and incomplete wetting of the catalyst,which limit their further application in chemical industry.Also,process intensification in TBRs is necessary as the decrease in quality of processed crude oil,caused by increased exploitation depths,and more restrictive environmental regulations and emission standards for industry,caused by increased environment protection consciousness.In recent years,lots of strategies for process intensification in TBRs have been proposed to improve reaction performance to meet the current and future demands of chemical industry from the environmental and economic perspective.This article summarizes the recent progress in techniques for intensifying gas/liquid/solid reaction in TBRs and application of intensified TBRs in petroleum industry.

Suppressing secondary reactions of coal pyrolysis by reducing pressure and mounting internals in fixed-bed reactor

Pyrolysis of Shenmu coal was performed in fixed-bed reactors indirectly heated by reducing operating pressure and mounting internals in the reactor to explore their synergetic effects on coal pyrolysis. Mounting internals particularly designed greatly improved the heat transfer inside coal bed and raised the yield of tar production.Reducing pressure further facilitated the production of tar through its suppression of secondary reactions occurring in the reactor. The absolute increase in tar yield reached 3.33 wt% in comparison with the pyrolysis in the reactor without internals under atmospheric pressure. The obtained tar yield in the reactor with internals under reduced pressure was even higher than the yield of Gray–King assay. Through experiments in a laboratory fixed bed reactor, it was also clarified that the effect of reducing pressure is related to volatile release rate in pyrolysis. It did not obviously vary tar yield at pyrolysis temperatures below 600 ℃, while the effect was evident at 650 and 700 ℃ but became limited again above 800 ℃. Under reduced pressure the produced tar contained more aliphatics and phenols but less aromatics.

Approximate analytical solution of non-linear reaction diffusion equation in fluidized bed biofilm reactor

A mathematical model for the fluidized bed biofilm reactor (FBBR) is discussed. An approximate analytical solution of concentration of phenol is obtained using modified Adomian decomposition method (MADM). The main objective is to propose an analytical method of solution, which do not require small parameters and avoid linearization and physically unrealistic assumptions. Theoretical results obtained can be used to predict the biofilm density of a single bioparticle. Satisfactory agreement is obtained in the comparison of approximate analytical solution and numerical simulation.

Bifurcation characteristics of coal spontaneous combustion and analysis of critical state of gaseous reaction in a packed bed

The numerical model was presented for the coal combustion in the packed bed. The bifurcation characteristic of the ignition-extinction of solid-phase smoldering and tran- sition to flaming was studied for the packed bed of coal.One of the Frank-Kamenetskii parameter β_1 was selected as the control parameter.The computed results show that the bifurcation curve is obviously divided into two zones of solid-phase reaction and gas- phase reaction,and the total process of ignition-extinction presents twice bifurcation cha- racteristic.Moreover,the vanishing of critical state of ignition-extinction is studied.One of the transition points,ε_2=0.05,is numerically solved for the vanishing of critical state.The larger the value of ε_2 is,the easier the gas-phase can react.However,the combustion temperature will decrease with increasing ε_2.The other transition point α_2=0.53 is also ob- tained.With increasing the value of α_2,the combustion temperature of gas-phase reaction is close to the smoldering temperature of coal.When α_2 is infinite,the only reaction occur- ring is the smoldering combustion of solid-phase,and the gas-phase cannot react.

Oxide coating mechanism during fluidized bed reduction: solid-state reaction characteristics between iron ore particles and MgO

Experiments on the solid-state reaction between iron ore particles and MgO were performed to investigate the coating mechanism of MgO on the iron ore particles＇ surface during fluidized bed reduction. MgO powders and iron ore particles were mixed and compressed into briquettes and, subsequently, roasted at different temperatures and for different time periods. A Mg-containing layer was observed on the outer edge of the iron ore particles when the roasting temperature was greater than 1173 K. The concentration of Fe in the Mg-containing layer was evenly distributed and was approximately 10wt%, regardless of the temperature change. Boundary layers of Mg and Fe were observed outside of the iron ore particles. The change in concentration of Fe in the boundary layers was simulated using a gas–solid diffusion model, and the diffusion coefficients of Fe and Mg in these layers at different temperatures were calculated. The diffusion activation energies of Fe and Mg in the boundary layers in these experiments were evaluated to be approximately 176 and 172 k J/mol, respectively.

Synthesis of Silver Sulf ide Quantum Dots Via the Liquid–Liquid Interface Reaction in a Rotating Packed Bed Reactor

We developed the high-gravity coupled liquid-liquid interface reaction technique on the basis of the rotating packed bed(RPB)reactor for the continuous and ultrafast synthesis of silver sulfide(Ag2S)quantum dots(QDs)with near-infrared(NIR)luminescence.The formation of Ag2S QDs occurs at the interface of microdroplets,and the average size of Ag2S QDs was 4.5 nm with a narrow size distribution.Ag2S QDs can disperse well in various organic solvents and exhibit NIR luminescence with a peak wavelength at 1270 nm under 980-nm laser excitation.The mechanism of the process intensification was revealed by both the computational fluid dynamics simulation and fluorescence imaging,and the mechanism is attributed to the small and uniform droplet formation in the RPB reactor.This study provides a novel approach for the continuous and ultrafast synthesis of NIR Ag2S QDs for potential scale-up.

Effect of porosity on hydrogenation kinetics of Mg-3Ni-2MnO_2 nanocomposite powder reaction bed

Hydrided Mg-3Ni-2MnO2 composite powders were fabricated by reactive ball milling with hydrogen, and accumulative hydrogenation kinetics and temperature field of reaction bed with various porosities (0.37, 0.53 and 0.63) were measured. The results show that the accumulative hydrogenation kinetics of Mg-3Ni-2MnO2 powder reaction bed depends strongly on the effect of heat transfer, mass transfer and intrinsic reaction together. The reaction bed with the porosity of 0.53 exhibits the largest hydrogenation rate. During the hydrogenation process, the temperature of reaction bed rises quickly due to the fast release of heat, and the temperature difference between center and wall with 0.53 porosity can keep high even for a long time, which promotes fast heat transfer. The further analysis indicates that more emphases should be put on heat transfer rate rather than the only improvement of the effective thermal conductivity.

Fluidized-bed chlorination thermodynamics and kinetics of Kenya natural rutile ore

Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.

Technical Challenges and Progress in Fluidized Bed Chemical Vapor Deposition of Polysilicon

Various methods for production of polysilicon have been proposed for lowering the production cost andenergy consumption, and enhancing productivity, which are critical for industrial applications. The fluidized bed chemical vapor deposition （FBCVD） method is a most promising alternative to conventional ones, but the homogeneous reaction of silane in FBCVD results in unwanted formation of fines, which will affect the product qualityand output. There are some other problems, such as heating degeneration due to undesired polysilicon deposition on the walls of the reactor and the heater. This article mainly reviews the technological development on FBCVD of polycrystalline silicon and the research status for solving the above problems. It also identifies a number of challenges to tackle and principles should be followed in the design ofa FBCVD reactor.

Reduction of 1-3 mm iron ore by H_2 in a fluidized bed

The reduction of 1-3 mm fine powder of iron ore by H2 was conducted in a lab-fabricated kg class high temperature fluidized bed. The results show that the differential pressure in the fluidized bed, which has small fluctuation with time, increases with the increase of gas flowing velocity. The utilization ratio of gas decreases when the reaction lasts longer time indicating that the reaction is faster at the beginning of reduction and becomes slower in the latter process. The higher the reaction temperature is, the higher the utilization ratio of gas is, but the difference of utilization ratio among the different temperatures becomes smaller with time. The utilization ratio of gas and the metallization ratio can reach 9% and 84% respectively at 750℃ for 20 min, which shows the reduction reaction by H2 is very fast. The increase of metallization ratio with gas velocity performs quite good linearity, which shows that a higher velocity of reducing gas can be used to improve the productivity of the reactor when H2 is used as reducing gas. With the increase of charge height, the metallization ratio decreases, but the utilization ratio of gas increases. The reaction temperature can be reduced to 700-750℃ from 800-850℃ when H2 is used as reducing gas.

Mathematical Simulation on Oxidation of Ilmenite in Fluidized Bed

An unsteady-state mathematical model describing the behaviors of gas and solid during the oxidation of ilmenite in a fluidized bed was developed on the basis of the two-phase theory of a fluidized-bed reactor. The longitudinal distribution of the concentration of gaseous species and that of the unreacted ratio of solid material in both bubble phase and emulsion phase as well as their variation with reaction time were determined by means of mathematical simulation with kinetic parameters measured experimentally, furthermore, the reaction behavior of particles with different size in a multiparticle system was also analyzed, and finally, the potential way for increasing the reactor efficiency was put forward.

CO_2 –H_2O–coal interaction of CO_2 storage in coal beds

In order to study the physical and chemical reaction after CO2 injected into coal beds at different condition.The physical and chemistry reaction among CO2,H2O and coal was studied,and the influence on permeability and porosity of coal beds was carried out.The experimental method was used,so did the basic theory of mineralogy,coal petrology,geochemistry,analytical geochemistry and physical chemistry.In this experiment,the changes of mineral and permeability of coal and water quality were observed through CO2 solution reacting with different coal samples.The differences could be found out by comparing the properties and microcrystalline structure before and after the reaction.There are three results were carried out:First,the content of carbonate in coal beds decreases because of the dissolution reaction between carbonate minerals and CO2 solution,and precipitation is formed by reaction of chlorite and orthoclase.Second,the result that permeability and porosity of coal beds are improved after the reaction is proposed.Third,the initial permeability of different coal samples plays a great role on the reaction,and the improvement of permeability is not obvious in the samples which have too low or too high permeability,and the improvement is good in medium permeability(0.2–3 mD).

Determination of the intrinsic kinetics of iron oxide reduced by carbon monoxide in an isothermal differential micro-packed bed

The intrinsic kinetics of iron oxide reduced by carbon monoxide is evaluated by a method of online measuring concentration of off-gas in an isothermal differential micro-packed bed. Under the condition of getting away from the influence of gas diffusion and gas–solid heat transfer and mass transfer, the reaction of Fe2O3 to Fe3O4, Fe3O4 to Fe O and Fe O to Fe in the process of single reaction can be clearly distinguished from each other, and the relevant activation energy is characterized to be 75.4, 74.4, and 84.0 k J·mol-1, respectively. Therefore, the change of surface area in the reaction process due to losing oxygen could be easily calculated by combining it with pre-exponential parameters of Arrhenius equations. In conclusion, these kinetic parameters are verified by the experimental data for the process of ore reduced by carbon monoxide in a packed bed.

Oxidation Kinetics of Ilmenite Powder in Fluidized Bed

The oxidation kinetics of Panzhihua ilmenite was studied in a fluidized bed in the temperature range of 1053-1153 K. Within this temperature interval, the reaction can be expressed: From the experimental results, it was clarified that the intrinsic chemical reaction is the rate-controlling step.

Experiments and Modeling of the Preparation of Ultrafine Calcium Carbonate in Spouted Beds with Inert Particles

A novel reaction-drying process was carried out in a spouted bed reactor with inert particles and used to prepare ultrafine CaCO3 particles. Effects of concentrations of CO2 and Ca(OH)2, and reaction temperature on Ca(OH)2 conversion were experimentally investigated. The particle sizes and composition of CaCO3 produced were characterized with transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results indicated that ultrafine CaCO3 particles with mean size of 80 nm could be obtained with this novel process.By modifying the Arrhenius Equation and considering the Ca(OH)2 state, a kinetic model was established to describe the process in the spouted bed. The model parameters estimated from the reaction-drying experiments were found to fit well the experimental data, indicating the applicability of the proposed kinetic model.

Highly reactive and reusable heterogeneous activated carbons-based palladium catalysts for Suzuki-Miyaura reaction

Suzuki-Miyaura reaction of aryl halides with phenylboronic acid using a heterogeneous palladium catalyst based on activated carbons(AC) was systematically investigated in this work. Two different reaction modes(batch procedure and continuous-flow procedure) were used to study the variations of reaction processing. The heterogeneous catalysts presented excellent reactivity and recyclability for iodobenzene and bromobenzene substrates in batch mode, which can be attributed to stabilization of Pd nanoparticles by the thiol and amino groups on the AC supports. However, significant dehalogenation in the reaction mixture and Pd leaching from the heterogeneous catalysts were observed in continuous-flow mode.This unique phenomenon in continuous-flow mode resulted in a dramatic decline in reaction selectivity and durability of heterogeneous catalysts comparing with that of batch mode. In addition, the heterogeneous Pd catalysts with thiol-and amino-modified AC supports exhibited different reactivity and durability in batch and continuous-flow mode owing to the difference of interaction between Pd species and AC supports.

Kinetic Study of Sulfur Dioxide Elimination by Limestone through the Lab Scale Circulating Fluidized Bed Combustor

Characteristics of sulfur dioxide emission from coal and petroleum coke combustion were examined in a lab scale circulating fluidized bed (CFB) combustor. The rate constant of the first order rate expression for the absorption SO2 on the CaO surface was similar regardless of the origin of the limestone, the particle size and the initial SO2 concentration. However, the total SO2 absorption capacity was different depending on the origin of the limestone. The breakability of the particle which provides new surface for the reaction seems to play a major role in the absorption characteristics.

中国大规模盐穴储氢需求与挑战

氢能是来源广泛且低碳清洁的能源,大力发展氢能产业是实现双碳目标和应对全球能源转型的重要举措。在氢能“制备―储存―运输―应用”全产业链中,储氢难问题长期制约着氢能产业高质量发展。盐穴储氢具有成本低、规模大、安全性高和储氢纯度高等突出优势,是未来氢能大规模储备的重要发展方向,也是我国能源低碳转型的重大战略需求。综合调研了我国制氢产业和氢能消费现状,分析了我国盐穴储氢的需求。调研了国外利用盐穴储存天然气和氢气的技术及工程现状,总结了我国盐穴储气库发展和建设历程。对比了利用盐穴储存天然气、氦气、压缩空气和氢气的异同点,提出我国盐穴储氢面临三大科技挑战:层状盐岩氢气渗透与生化反应、盐穴储氢库井筒完整性管控、储氢库群灾变孕育与防控。研究成果明确了我国氢气储备需求的快速增长趋势和大规模盐穴储氢的重点攻关方向。

增强型生态浮床填料筛选及工况优化

生态浮床作为一种经济、环保的黑臭水体处理工艺得到广泛应用,但其处理能力受制于植物根系深度及表面积。通过悬浮球、生物绳、弹性和组合填料分别与间种的粉绿狐尾藻(Myriophyllum aquaticum)和西伯利亚鸢尾(Iris sibirica)植物构建生态浮床,探究不同填料对生态浮床效能的强化作用及微生物机制;并在优选填料的基础上进一步探究优选填料的最优添加工况及其强化下浮床对污染物去除的动力学模型。填料优选实验结果显示,生物绳填料对COD、氨氮和总磷的去除率最佳,分别为>99%、43.85%和14.03%;高通量测序分析显示,生物绳填料表面生物膜微生物丰富度最高、物种组成分布最均匀、微生物多样性最高,且生物绳填料可定向富集Flavobacterium、Exiguobacterium、Chryseobacterium、Microbacterium、Caulobacter等脱氮除磷相关功能菌。生物绳工况优化结果显示,修复轻度黑臭水体的最佳生物绳填料投加量为12.5 m/m^(3),其对COD、氨氮和总磷的去除率分别为96.4%、38.5%和56.6%;动力学模型拟合显示,一级动力学模型能更好地拟合生物绳强化生态浮床的氨氮及COD降解规律。

沸腾床渣油加氢裂化装置结焦情况分析与操作优化

分析了沸腾床渣油加氢裂化装置易结焦堵塞的原因,介绍了某炼化公司沸腾床渣油加氢裂化装置易结焦区域和结焦典型症状,从原料、催化剂、反应和分馏工况等方面进行了优化。通过将原料渣油引入脱固油浆减缓结焦,动态调整渣油转化率控制装置结焦:加工中东高硫低氮原油所产渣油时,转化率可控制在75%以上;加工低硫中东原油所产渣油时,转化率控制在不大于70%;加工低硫高氮原油所产渣油时,转化率控制在不大于65%。每吨渣油原料置换新鲜催化剂0.90~0.95 kg,低控减压塔塔底液位(25%~30%),提高塔底物料返混流量以减少沥青质在塔底器壁生焦。优化操作后,常压塔底油总沉积物质量分数稳定小于0.2%,确保了装置在渣油高转化率下的长周期稳定运行。