螺旋内槽管内天然气-水-表面活性剂体系的水合物生成动力学计算

针对多组分气体（天然气）-水-表面活性剂体系在螺旋内槽管内的水合物生成过程,首先采用CFD方法结合群体平衡模型（PBM）,基于溶质渗透模型和Kolmogorov各向同性湍流理论对螺旋内槽管内气液传质系数进行了模拟;其次基于Kashchiev和Firoozabadi的经典水合物成核和生长理论,将其体系从单组分-水系统扩展到多组分气体（天然气-水-十二烷基硫酸钠）系统,同时结合经典结晶理论利用传质系数对水合物生长模型进行了修正,建立了适用于螺旋内槽管流动体系内天然气水合物生成动力学模型。通过模拟计算,获得不同水合物生产条件下天然气在水中的平均传质系数;进而利用Microsoft Visual C++编程计算得到不同条件下水合物生成动力学数据,在考察范围内,天然气水合物的成核速率随着反应体系有效表面能的增大而锐减,而水合物生成驱动力和生长速率未受影响,同时水合物生长速率随着流速和反应压力的增大及温度的降低而增大,成核速率随着压力的增大和温度的降低而增大。     

Modeling the ultrasonic cavitation‐enhanced removal of nitrogen oxide in a bubble column reactor

A model study of the sonochemical removal of nitric oxide (NO) in a bubble column reactor is presented. The detailed model is developed to investigate the actual cavitation phenomena taking place during the absorption of NO. The expansion and subsequent collapse of cavitation bubble according to the theory of cavity collapse—initially developed by Lord Rayleigh and then improved on by coupling the energy balance equation of the bubble and the chemical reactions taking place inside the cavity to calculate the composition of different species formed during the collapse—are modeled. The model takes into consideration (1) cavitation bubble dynamics, (2) generation and transfer of oxidizing species from bubble collapse through reaction kinetics, (3) transfer of NO from gas to liquid, and (4) chemical reactions of oxidizing species with dissolved NO. The results of the simulations surprisingly indicate that the chemistry induced by ultrasonic cavitation cannot explain the absorption of NO beyond about 30% of the inlet concentration if the mass transfer is assumed to be the same as that in the bubble column without ultrasound. When experimental values of mass‐transfer coefficients, calculated in the studies by other researchers (which are in the range of about five times the physical mass‐transfer coefficient in a bubble column), are used, absorption up to 80% are calculated in the simulations consistent with experimental results obtained from the sonochemical bubble column reactor. The present model provides a framework on which more robust and rigorous models can be developed for the complex gas‐liquid sonochemical systems and reactors. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2397–2411, 2012     

Estimation of mid‐distillates production rate in a low temperature Fischer–Tropsch process

BACKGROUND: The Fischer–Tropsch process is the most important path for converting natural gas to high quality liquid hydrocarbons. Low temperature Fischer–Tropsch synthesis in slurry bubble column reactors with cobalt‐based catalysts is used for mid‐distillates production. RESULTS: In this work the slurry bubble column reactor was simulated by applying the two‐bubble class mathematical model. In addition, the effect of operating parameters on synthesis gas conversion was studied. The distribution of products was also predicted from the simulation framework. CONCLUSIONS: The effect of synthesis gas inlet velocity on mid‐distillates production rate was studied in the present work. A maximum production rate for mid‐distillates of about 23 kg s^?1 was predicted from the simulation program. Copyright © 2011 Society of Chemical Industry     

多孔材料中甲烷水合物生成的传热数值模拟研究

水合物储运(NGH)是近几年发展起来的天然气储运技术,已具备实现工业化的潜力。但水合物的生长是传质传热控制的反应,因此在放大实验中存在诸多不确定因素。针对该问题,对水合物反应器中多孔材料内甲烷水合物生成传热过程建立了基于化学反应动力学和多孔材料内传质传热的甲烷水合物生成传热数学模型,可用于计算反应器内水合物生成分布和热量分布,指导水合反应器的设计和优化。通过模拟与实验数据对比验证了该模型的可靠性,并对使用了不同热导率填料的水合反应过程进行数值模拟。结果显示,模拟值与实验值的绝对平均相对误差小于6%,生成传热模型准确性高;在水合反应过程中,热量传递是影响水合物生成速率的关键因素之一。导热不良时,易在水合物生成中心部分形成局部过热,对水合物生长造成热抑制。在进行水合物生成放大实验时,应特别注意反应器内部的热量控制。     

An optimization method for enhancement of gas–liquid mass transfer in a bubble column reactor based on the entropy generation extremum principle

In this study, an optimization method is proposed to enhance the gas–liquid mass transfer in bubble column reactor based on the entropy generation extremum principle. The mass transfer–induced entropy generation can be maximized with the increase of mass transfer rate, based on which the velocity field can be optimized. The oxygen gas–liquid mass transfer is the major rate–limiting step of the toluene emissions biodegradation process in bubble column reactor, so the entropy generation due to oxy...     

多孔材料中甲烷水合物生成的传热数值模拟研究

水合物储运(NGH)是近几年发展起来的天然气储运技术,已具备实现工业化的潜力。但水合物的生长是传质传热控制的反应,因此在放大实验中存在诸多不确定因素。针对该问题,对水合物反应器中多孔材料内甲烷水合物生成传热过程建立了基于化学反应动力学和多孔材料内传质传热的甲烷水合物生成传热数学模型,可用于计算反应器内水合物生成分布和热量分布,指导水合反应器的设计和优化。通过模拟与实验数据对比验证了该模型的可靠性,并对使用了不同热导率填料的水合反应过程进行数值模拟。结果显示,模拟值与实验值的绝对平均相对误差小于6%,生成传热模型准确性高;在水合反应过程中,热量传递是影响水合物生成速率的关键因素之一。导热不良时,易在水合物生成中心部分形成局部过热,对水合物生长造成热抑制。在进行水合物生成放大实验时,应特别注意反应器内部的热量控制。     

Steady gas hydrate growth along vertical heat transfer tube without stirring

The hydration characteristics of a quiescent reactor with inner-placed vertical heat transfer tube were researched, the reaction materials were 300 ppm sodium dodecyl sulfate water solution and R141b. The growth morphology were described through the photos taken during the growth/decomposition processes. The temperatures of two points inside the reactor were also recorded and analyzed. The mass transfer mechanism was explained by surface free energy theory, the heat transfer process was also simulated. It was revealed that water can permeate into the guest phases along the surface of heat transfer tube, so massive gas hydrate can grow steadily along the vertical heat transfer tube in the guest phases without mechanic stirring, the reaction heat can be removed quickly by the coolant flowing inside the heat transfer tube. This finding will benefit gas hydrate application technologies such as natural gas storage and transportation with hydrate, or refrigerant cool storage with gas hydrate.     

Development of airlift bubble column dispersed with micro‐bubbles

Micro‐bubbles were dispersed in the bubble column with draft tube, and the length and diameter of draft tube were changed. The flow characteristics in air–water system were measured. Ozone gas and methylene‐blue aqueous solution were used, and the decomposition performance was examined. With increasing draft tube length, both the gas holdup and liquid velocity in the annular section increased. When the diameter ratio of draft tube to column was about 0.5, both the gas holdup and liquid circulation flow rate had maxima. For the decomposition by using ozone, the installation of draft tube enhanced the mass transfer and decomposition performance.     

On the bleaching kinetics of vegetable oils — experimental study and mass transfer‐based interpretation

This study focuses on the systematic investigation of the parameters involved in adsorptive vegetable oil bleaching. These parameters range from the quality of oil and bleaching conditions chosen (e.g. amount and activity of clay, initial water content, temperature, pressure) to the effects of the different reactor systems used (agitated vessel, bubble column) on the kinetics. The study of the latter aims to optimise the type and intensity of power input. The most efficient process was shown to take place in the bubble column reactor. The findings result in a kinetic model for the transport phenomena of the pigments from the oil phase into the clay. The model splits the effects in phenomena due to mass transfer resistances inside and outside of the clay particle. By doing so it is possible to describe the bleaching kinetics in dependence of the amount of clay added and on the size of the external mass transfer resistance, which is influenced by the power input into the reactor. Thus a on model‐based analysis of the effects as well as the optimisation of the bleaching reactor are made possible.     

Solid‐Liquid Mass Transfer at Gas Sparged Tube Bundles

The solid‐liquid mass transfer characteristics of an in‐line tube bank immersed in a gas‐liquid bubble column were investigated by measuring the rate of diffusion‐controlled dissolution of copper surface in acidified dichromate solution. Variables studied were the number of rows in the tube bank, physical properties of the solution, and nitrogen flow rate. The mass transfer coefficient was found to increase with increasing nitrogen flow rate. Increasing the number of rows in the tube bank was found to decrease the mass transfer coefficient. The data were correlated for the following conditions: 0.0021 < Fr.Re < 0.1603, 1 < N_r < 5 and 850 < Sc < 1370 by the equation J = 0.15 ( Fr.Re )^–0.15. Comparison was made between the present mass transfer data and previous heat and mass transfer studies conducted in packed and empty bubble columns.     

Carbon Dioxide Absorption in Triethanolamine Aqueous Solutions: Hydrodynamics and Mass Transfer

The carbon dioxide absorption process by triethanolamine aqueous solutions was analyzed in a bubble‐column reactor taking into account the chemical reaction mechanism, gas‐liquid interfacial area, and mass transfer rate. A speciation study of this gas‐liquid system was developed by ¹H and ¹³C NMR spectroscopy in order to obtain the reaction mechanism and stoichiometry. The gas‐liquid interfacial area was evaluated considering the variations of bubble size distribution and gas holdup during the operation time. The liquid‐phase mass transfer coefficient was calculated from the carbon dioxide absorption rate data by interfacial area evolution and reaction stoichiometry.     

Gas Holdup and Solid‐Liquid Mass Transfer in Newtonian and non‐Newtonian Fluids in Bubble Columns

Gas holdup and surface‐liquid mass transfer rate in a bubble column have been experimentally investigated. De‐mineralized water, 0.5 and 1.0% aqueous solutions of carboxy methyl cellulose (CMC), and 60% aqueous propylene glycol have been used as the test liquids. Effects of column diameter, liquid height to column diameter ratio, superficial gas velocity and liquid phase viscosity on gas holdup and mass transfer rate are studied. Generalized correlations for the average gas holdup and wall to liquid heat and mass transfer coefficients are proposed. These are valid for both Newtonian and pseudoplastic non‐Newtonian fluids.     

泡状流中水合物生成预测模型及实验

针对可燃冰钻采井筒内易发生水合物生成和堵塞的工程问题,本文开展了泡状流条件下甲烷水合物生成实验,发现流速增加会提高水合物生成速率,黄原胶质量分数的增加会降低水合物生成速率。基于传质理论,构建了适用于可燃冰钻采井筒内泡状流条件下水合物生成预测模型,模型考虑了连续相流体流变性、气泡破裂、聚并和形变等因素对泡状流中气液界面分布和气液间传质规律的影响,并耦合实验数据,提出了气泡群间的综合传质系数经验公式,用于描述气泡间相互作用对气液间传质速率的影响。对比实验结果,所建立模型对水合物生成量和水合物生成速率的预测误差分别在±5%和±15%以内,满足工程计算需求。该模型的构建有助于精准预测油气和可燃冰钻采井筒内水合物风险,为建立经济、高效的井筒水合物防治方案奠定理论基础。     

MASS TRANSFER AND REACTION IN BUBBLE COLUMN SLURRY REACTOR WITH DRAFT TUBE

Gas-liquid and liquid-solid mass transfer coefficients were obtained in a draft tube bubble column slurry reactor (abbreviated as DTBCSR) from the measurements of gas absorption and ion-exchange, respectively. Oxidation of sulfur dioxide on activated carbon was carried out in the same reactor. The effects of gas flowrates, diameters of draft tube and solid concentrations were investigated. These results were compared with those in a bubble column slurry reactor without draft tube (abbreviated as BCSR). Minimum gas velocities for complete suspension of solid particles in DTBCSR were lower than those in BCSR. Gas-liquid and liquid-solid mass transfer coefficients in DTBCSR were higher than those in BCSR. Both coefficients were almost independent of solid loadings. Reaction rates in DTBCSR were higher than those in BCSR and a stirred slurry reactor (abbreviated as SSR) except for lower gas flow rates and smaller particles.     

天然气水合物储运技术中水合物反应器的研究进展

可观的储气率与自保效应的存在使得天然气水合物能作为一种天然气储运的方式,并且在与其他如液化天然气、压缩天然气储运方式比较时有着自己独到的优势。但由于针对水合物储运的研究起步较晚,利用水合物储运天然气的技术尚未成熟。尤其是在水合物反应器的研究上,生成水合物的速率较低,无法达到工业生产所需要的水平。本文通过调研国内外文献与专利等资料,介绍了国内外天然气水合物储运技术发展状况,简述了水合物生成强化的物理化学手段与机械手段,详述了搅拌式等传统天然气水合物反应器与管式、超重力式等新型天然气水合物反应器的结构与工作原理。根据现有水合物反应器的特点与存在的问题,对水合物反应器的研究方向提出建议：未来应当加快对喷淋式、超重力式与流化床式反应器的放大研究,加快针对不同物理强化手段与机械强化手段的协同作用研究,建立起以天然气储运为目的的水合物反应器评价体系。     

机械扰动强化气体水合物快速生成研究进展

气体水合物技术在天然气固态储运、CO₂捕获与封存等领域具有广阔的应用前景。高效快速制备水合物是水合物应用技术产业化的关键技术之一。从成核机理、相平衡、传热和传质等角度简述了气体水合物快速生成机理,回顾了常见的搅拌、喷淋和鼓泡等机械扰动强化气体水合物快速生成方法的基本原理和特性。依据强化传质传热领域内的新进展,进一步阐述了新型机械扰动强化气体水合物快速生成方法的基本原理和特性,重点综述了流化床、超声波、超重力、撞击流等技术的研究进展。从耗气率、水合物生成速率、总能耗、气体转化率等角度分析评价了各种机械扰动强化气体水合物快速生成方法的优缺点。总体来说,目前各种机械扰动强化气体水合物生成技术仍处于实验室阶段,传统的搅拌、喷淋和鼓泡强化技术生成速率较低;新型的流化床、超声波、超重力和撞击流等技术也存在各种不同的缺点,有待进一步优化改进。同时指出探究微观成核机理、开发新型易固液分离的气体水合物生成系统以及构建水合物反应器评价体系等是未来气体水合物快速生成相关研究中需要进一步解决的问题。     

Reactor Modeling of Gas‐Phase Polymerization of Ethylene

A model is developed for evaluating the performance of industrial‐scale gas‐phase polyethylene production reactors. This model is able to predict the properties of the produced polymer for both linear low‐density and high‐density polyethylene grades. A pseudo‐homogeneous state was assumed in the fluidized bed reactor based on negligible heat and mass transfer resistances between the bubble and emulsion phases. The nonideal flow pattern in the fluidized bed reactor was described by the tanks‐in‐series model based on the information obtained in the literature. The kinetic model used in this work allows to predict the properties of the produced polymer. The presented model was compared with the actual data in terms of melt index and density and it was shown that there is a good agreement between the actual and calculated properties of the polymer. New correlations were developed to predict the melt index and density of polyethylene based on the operating conditions of the reactor and composition of the reactants in feed.     

Hydrodynamics and mass transfer of oscillating gas‐liquid flow in ultrasonic microreactors

Ultrasonic microreactors were used to intensify gas‐liquid mass‐transfer process and study the intensification mechanism. Fierce surface wave oscillation with different modes was excited on the bubble. It was found that for slug bubbles confined in smaller microchannel, surface wave oscillations require more ultrasound energy to excite due to the confinement effect. Cavitation microstreaming with two toroidal vortices was observed near the oscillating bubble by a streak photography experiment. Surface wave oscillation at the gas‐liquid interface increases the specific surface area, while cavitation microstreaming accelerates the interface renewal and thus improves the individual mass‐transfer coefficient. With these two reasons, the overall mass‐transfer coefficient was enhanced by 3–20 times under ultrasonication. As for gas‐liquid flow hydrodynamics, ultrasound oscillation disturbs the bubble formation process and changes the initial bubble length and pressure drop. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1294–1307, 2016     

Numerical Simulation of Absorbing CO2 with Ionic Liquids

Although separating CO₂ from flue gas with ionic liquids has been regarded as a new and effective method, the mass transfer properties of CO₂ absorption in these solvents have not been researched. In this paper, a coupled computational fluid dynamic (CFD) model and population balance model (PBM) was applied to study the mass transfer properties for capturing CO₂ with ionic liquids solvents. The numerical simulation was performed using the Fluent code. Considering the unique properties of ionic liquids, the Eulerian‐Eulerian two‐flow model with a new drag coefficient correlation was employed for the gas‐liquid fluid dynamic simulation. The gas holdup, interfacial area, and bubble size distribution in the bubble column reactor were predicted. The mass transfer coefficients were estimated with Higbie's penetration model. Furthermore, the velocity field and pressure field in the reactor were also predicted in this paper.