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。     

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。     

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。     

Modelling and experimental study of hydrate formation kinetics of natural gas‐water‐surfactant system in a multi‐tube bubble column reactor

To promote the heat and mass transfer during the hydrate formation process, an internal spiral‐grooved tube (ISGT) was proposed as the reaction tube in a large‐scale multi‐tube bubble column reactor with external slurry circulation. In order to investigate such multi‐component gas (natural gas)‐water‐surfactant systems during the hydrate formation process in the ISGT, based on the solute permeation model and Kolmogorov isotropic turbulence theory, a CFD method combined with the population balance model (PBM) was utilized to simulate gas‐liquid mass transfer coefficient. Then, the hydrate formation kinetics model in ISGT was modelled based on the model proposed by Kashchiev and Firoozabadi. The hydrate formation experiments were carried out in the multi‐tube bubble column reactor at six different pressure‐temperature‐circulating flow velocities of piston pump regimes to investigate the actual formation process of natural gas hydrate. The experimental results were then used to finetune the optimized parameters to facilitate accurate model predictions.     

水合物形态学研究进展

水合物技术在气体分离、气体储存、海水淡化、蓄冷等领域有巨大的应用潜力。研究水合物的生长方式和形态特征在提高水合物储气量、降低水合物开采风险和防止水合物管道堵塞等方面有重要意义。本文从分子尺度的水合物晶格结构、毫米尺度的水合物晶体形态学和厘米尺度的水合物宏观生长形态学三个方面系统回顾了水合物形态学研究进展：总结了不同客体分子生成的不同类型水合物的不同晶格结构;从笼型水合物和半笼型水合物两个方面,阐述了过冷度、液相组成对水合物晶体形态学的影响;从金属表面传热、相界面传质、晶核加入以及促进剂的使用四个方面,介绍了水合物生长形态学的生长方式及其机理。本文总结了形态学研究对水合物技术工业化应用的积极作用并为水合物形态学研究的进一步发展提供参考。     

A water droplet size distribution dependent modeling of hydrate formation in water/oil emulsion

Experimental data on chord length distributions and growth rate during methane hydrate formation in water‐in‐oil emulsions were obtained in a high pressure stirring reactor using focused beam reflectance measurement and particle video microscope. The experiments were carried out at 274.2 K for 10–30% water cuts and agitation rates ranging from 200 to 500 rpm initially at 7.72 MPa. Rapid growth was accompanied by gradually decrease in rate. Free water was observed to become depleted during rapid growth while some water remained encapsulated inside hydrate layers constituting a mass transfer barrier. The apparent kinetic constants of methane hydrate formation and free‐water fractions were determined using a newly developed kinetic model independent of the dissolution rate at the gas–oil interface. It was illustrated that continued growth depends on distribution and transfer of water in oil‐dominated systems. This perception accords with observations of hydrate film growth on suspended water droplet in oil and clarifies transfer limits in kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1010–1023, 2017     

中心圆柱电极EHD强化垂直管内沸腾换热的实验研究

以R123为工质采用中心圆柱电极对垂直管内沸腾换热的EHD强化进行了实验,得出了沸腾传热系数与电场强度、热流密度等相关参数的关系.测试了外加电场的电流以及击穿电场强度.从外加电场影响气泡的成长、跃离和运动规律的角度对EHD强化垂直管内沸腾换热的机理进行了分析.     

CO2水合物浆在水平圆管中的传热特性

在CO₂水合物浆流动传热特性测试实验系统上,采用套管式电加热的方法对CO₂水合物浆进行了分解实验,并对CO₂水合物浆的流动传热特性进行了分析。对CO₂水合物浆的相变特性进行了研究,得到CO₂水合物浆的相变温度在8～12℃。研究了在固相体积分数为13.2%以及流速为0.45m/s的条件下CO₂水合物浆在内径为8mm的水平不锈钢管中的传热特性,计算得到CO₂水合物浆在不锈钢水平圆管中的对流传热系数为1500～1800 W/(m²·K),并且其在流动传热过程中呈现先增大随后趋向平稳的趋势,在水合物的相变区相应的对流传热系数表现最大。研究了分解加热功率对管壁温和对流传热系数的影响,发现加热功率对管壁温度的影响较强。在实际应用中可利用CO₂水合物浆的相变作用来增强传热,提高传热效率。     

汽-液-液三相垂直管内充分发展流传热性能

研究了垂直管内连续相水和分散相戊烷泡滴之间的流动和传热性能 .在全面考虑了汽体的膨胀、水蒸气的蒸发、界面张力的作用、汽液两相的相互作用和滑移、泡滴的破碎等影响因素的基础上 ,建立了与实验结果吻合较好的一维流体力学模型和传热模型     

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。     

Methane hydrate dissociation experiment in a middle-sized quiescent reactor using thermal method

Dissociation kinetic behavior of methane hydrate was studied at 268.15 K using thermal method in a closed quiescent middle-sized reactor of 10 L, which with a multi-deck cell-type vessel as the internals and coiled copper tubes placed inside assuring hydrate form or dissociate in all cells of the vessel simultaneously to reduce or eliminate the scale-up effect. A dramatically reduced dissociation rate phenomenon - “buffered dissociation” due to the ice melting was observed. The influences of the water temperature, the heating rate, the quantity of hydrate, and the dissociation pressure upon the dissociation rate and the extent of the buffering effect were investigated experimentally to reveal the gas production mechanism from hydrate below the ice point. The experimental results indicate that the rate of heat transfer and the thermodynamic driving force were the key rate-limiting factors for hydrate dissociation in the closed reactor. The buffering effect of gas production can be eliminated and the dissociation rate can be increased by increasing the temperature of the heating water and lowering the dissociation pressure. However, the temperature buffering behavior cannot be eliminated.     

EXPERIMENTAL INVESTIGATION OF HIGHLY EFFECTIVE COOLING WITH AN EVAPORATING ANNULAR FLOW IN A SMALL VERTICAL TUBE

An experimental study was performed to investigate the heat transfer characteristics of the non-boiling annular two-phase flow of nitrogen gas and subcooled water through a small vertical heated tube with uniform wall heat flux. The experimental results were compared with the numerical calculations based on the two-phase flow boundary layer model. The experimental data show that the annular two-phase flow of nitrogen gas and subcooled water in a small vertical tube can provide quite high heat transfer ability, while wall temperatures lie in a low range even if at quite high wall heat fluxes. In particular, the highest values of the wall temperatures are insensitive to the change of flowing and heating conditions. This characteristic is quite suitable for highly effective cooling of polymer electrolyte membrane fuel cells.     

EXPERIMENTAL INVESTIGATION OF HIGHLY EFFECTIVE COOLING WITH AN EVAPORATING ANNULAR FLOW IN A SMALL VERTICAL TUBE

An experimental study was performed to investigate the heat transfer characteristics of the non-boiling annular two-phase flow of nitrogen gas and subcooled water through a small vertical heated tube with uniform wall heat flux. The experimental results were compared with the numerical calculations based on the two-phase flow boundary layer model. The experimental data show that the annular two-phase flow of nitrogen gas and subcooled water in a small vertical tube can provide quite high heat transfer ability, while wall temperatures lie in a low range even if at quite high wall heat fluxes. In particular, the highest values of the wall temperatures are insensitive to the change of flowing and heating conditions. This characteristic is quite suitable for highly effective cooling of polymer electrolyte membrane fuel cells.     

超声波悬浮TBAB溶液液滴表面半笼型水合物生长过程研究

利用超声波悬浮技术将四丁基溴化铵(TBAB)溶液液滴悬浮，观测了不同TBAB质量分数(15%、20%、25%)时的水合物生长过程，并与悬挂液滴进行了对比。实验发现，超声波悬浮的液滴处于快速旋转状态，液滴呈扁球状，水合物生长速率较快，但当液滴中含有气泡时生成水合物的诱导时间延长。总结出超声波悬浮状态下TBAB水合物生长方式可以分为两大类：由内而外，由外而内。由外而内又可以分为单平顶式、双平顶式和包裹式。建立悬浮液滴和悬挂液滴的传热模型，通过对比发现，超声波可以加快悬浮液滴的传热效率，加速水合物的生成和生长。该实验为观测水合物生长提供了一种新的方法。     

波纹管管外冷凝特性的研究

以煤油蒸汽和水蒸气为工质研究了波纹管管外冷凝时的传热特性。试验中采用内管为波纹单管的套管换热器,分为水平和垂直2种布置方式。在不同流速下,根据试验测量的温度和流量等参数计算波纹管管外传热系数;并与相同参数(流速、温度)条件下光管管外传热系数的理论计算值进行比较。结果表明:随液相雷诺数的提高,传热系数随之提高,相对光管,波纹管管外传热系数有明显提高;波纹管有效地增强了管外冷凝传热;水作为单一工质相对于多组分的煤油,波纹管对其管外冷凝强化效果更好。     

纳米管阵列表面流动沸腾传热特性的实验研究

利用阳极氧化法在钛换热管内表面制备出了一层管阵列结构纳米薄膜。以该纳米管阵列表面管为传热元件,蒸馏水为工质,采用管外电加热竖管强制循环工艺,在恒质量流速下考察了纳米管阵列表面管的流动沸腾传热性能。在实验的基础上,得出了纳米管阵列表面管流动沸腾传热系数关联式。实验结果表明,与光滑表面管相比,流动沸腾传热温差降低了30%～55%,在没有增加阻力的情况下,沸腾传热系数提高了1.5～2.2倍。     

夹套式上升管内荒煤气对流辐射传热的计算

通过理论推导和数值计算,分析了荒煤气在上升管内流动的对流传热和辐射传热问题。基于热平衡方程推导得到上升管内荒煤气流动传热微分方程,考察荒煤气进口温度、内壁面发射率、对流传热系数和斯坦顿数对上升管内壁面温度变化和荒煤气出口温度的影响。采用Matlab软件编制四阶Runge-Kutta计算程序求解,得出上升管内壁温度沿轴线方向的变化曲线和荒煤气的平均传热系数,荒煤气在夹套式上升管中的平均传热系数为30 W/(m^2·K)~36 W/(m^2·K),将此计算结果与他人的成果进行对比,吻合较好,误差为10%左右。结果表明:辐射传热过程主要受内壁面发射率和荒煤气进口温度的影响,内壁面发射率越大,辐射传热量越大;流体速度对对流传热的影响很大,随着流速的增加,对流传热量增大;焦炉在一个炼焦周期内,应该合理控制荒煤气的流量,可避免上升管内壁焦油的凝结;在设计上升管时,增大内壁面的发射率,可以提高上升管的传热效率。     

热管式气液固三相固定床鼓泡反应器的传热性能

为了研究热管式气液固三相固定床鼓泡反应器的传热性能,在一内径为50 mm、高800 mm床内充以多孔填料,内插一根φ16 mm×2 mm的水-不锈钢热管的固定床反应器中,用并流向上的热水和氮气进行传热试验研究.研究结果表明：传热量随气相速度u_g增大而增多,在气相速度达到某一数值后,气相速度对传热的影响不显著;并采用最小二乘法拟合得到了试验条件下固定床鼓泡反应器床层与热管加热段管壁之间传热系数的经验计算式.所得到的方程得到了热模试验的验证.     

Study of Single Phase Flow Heat Transfer and Friction Pressure Drop in a Spiral Internally Ribbed Tube

The experimental results of single‐phase flow heat transfer and pressure drop experiments in the turbulent flow regime in a spirally ribbed tube and a smooth tube are presented in this paper. The ribbed tube has an outside diameter of 22 mm and an inside diameter of 11 mm (an equivalent inside diameter of 11.6 mm) and the smooth tube has an outside diameter of 19 mm and an inside diameter of 15 mm. Both tubes were uniformly heated by passing an electrical current along the tubes with a heated length of 2500 mm. The working fluids are water and kerosene, respectively. The experimental Reynolds number is in the range of 10⁴–5 · 10⁴ for water and is in the range of 10⁴–2.2 · 10⁴ for kerosene. The experimental results of the ribbed tube are compared with those of the smooth tube. The heat transfer coefficients of the ribbed tube are 1.2–1.6 fold greater than those in the smooth tube and the pressure drop in the ribbed tube is also increased by a factor of 1.4–1.7 as compared with those in the smooth tube for water. The corresponding values for kerosene are 2–2.7 and 1.5–2, respectively. The heat‐transfer enhancement characteristics of the ribbed tube are assessed. This tube is especially suitable for augmenting single‐phase flow heat transfer of kerosene. Correlations for the heat transfer and the pressure drop for the spirally ribbed tube are proposed, according to the experimental data.     

竖直管气固鼓泡流化床传热机理的CPFD模拟

针对细颗粒气固鼓泡流化床中床料与竖直传热管壁面间的传热行为,在前期实验的基础上,采用计算颗粒流体力学(CPFD)方法从颗粒在传热壁面更新的角度,深入分析了传热特性与壁面气固流动行为之间的关联性。结果表明,模拟得到的传热管壁面颗粒更新通量和基于颗粒团更新模型的颗粒团平均停留时间均能很好解释实验测得的传热系数变化规律,这证实颗粒团更新是影响传热过程的控制性因素。模拟还发现随加热管从床层中心向边壁的移动,加热管周向方向上颗粒更新通量和传热系数的不均匀性都呈增大趋势。随着表观气速的增大,气泡行为导致床层颗粒内循环流率增大,这是导致颗粒团在加热管壁面上的更新频率增大以及床层与壁面间传热系数增大的根源。