液体连续相撞击流强化过程特性及相关技术装备的研发和应用

液体连续相撞击流（LIS）具有高效微观混合、强烈压力波动和促进过程动力学等对分子尺度过程极有价值的性质。本文在浸没循环撞击流反应器（SCISR）中深入研究了这些性质及其规律,进行了反应-沉淀法制取多种“超细”和纳米材料的实验,制得粒径更细小、分布更窄、形貌可控的超细粉体;研发了“无旋立式循环撞击流反应器”等多种基于应用LIS的反应、结晶技术装备并已付诸应用;描述了这些装备的流动结构、工作原理和工业应用情况。     

撞击流反应器中反应动力学研究

浸没循环撞击流反应器(SCISR)的主要特点是撞击区能显著强化微观混合且存在压力波动.对于若干反应体系例如正丁醇与浓硫酸反应等,SCISR显示出明显优于搅拌反应釜(STR)的反应动力学性能,在相同条件下,浸没循环撞击流反应器中所测的正丁醇与浓硫酸反应速率常数k比搅拌槽反应器高约10%.     

液体连续相撞击流特性及其在超细粉体制备中的应用

20世纪90年代以来撞击流领域研究重点转向以液体为连续相。液体连续相撞击流(US)具有有效促进微观混合和存在压力波动的特性,从而有利于超细粉体的制备。实验结果表明,浸没循环撞击流反应器(SCISR)是反应一沉淀法制取超细粉体的一种优越的反应技术装备。     

撞击流-沉淀法制取超细白炭黑中试研究

介绍了以工业级硫酸和工业级水玻璃为原料,利用撞击流反应-沉淀法制取超细白炭黑的中试试验。其反应过程在无旋立式循环撞击流反应器中进行。反应后物料经过陈化、过滤、洗涤,最后通过再浆进行喷雾干燥制得了超细白炭黑。用激光颗粒分析仪和比表面积-孔隙分析仪测定粒径及比表面积,结果表明:产品的平均粒径为2—3μm、比表面积高达822 m2/g,进一步证明了无旋立式循环撞击流反应器性能优越,操作稳定可靠,有利于制备超细粉体材料。     

撞击流法制备纳米无机粉体新技术

<正>成果简介撞击流(Impinging streams, IS)是一种较新颖的技术方法。其基本原理:两股等量两相流沿同轴相向流动,并在中点处撞击。其结果:在两根加速管之间造成一个高度湍动的撞击区,大大地强化了传质过程。撞击流原理见图1。研发的撞击流反应器可用于反应-沉淀法制取多种超细无机粉体产品,均获得非常好的结果。例如,利用撞击流反应器制备白炭黑的平均粒径为1～2μm,且粒径分布很窄;利用撞击流反应器制备了     

撞击流反应器中反应动力学研究

实验已经表明，浸没循环撞击流反应器（SCISR）的主要特点是撞击区能显著强化微观混合且存在压力波动，对于若干反应体未例如正丁璃与浓硫酸反应等．SCISR显示出明显优于搅拌反应釜的反应动力学性能．在相同条件下，浸没循环撞击流反应器中所测的正丁醇与浓硫酸反应速照常数K比搅拌槽反应器高约20％。     

撞击流反应器制取纳米钛酸钡

在浸没循环撞击流反应器中，以四氯化钛、氯化钡和草酸为原料，采用沉淀法制取纳米钛酸钡，并对产品进行了透射电子显微镜（TEM）表征。通过均匀实验设计，研究了反应温度、加料时间、反应后陈化时间及钡钛物质的量比等因素对产品粒径的影响；初步确定了制备纳米钛酸钡适宜的工艺条件为：反应温度75℃，陈化时间200min，加料时间20min，反应物中钡与钛的物质的量比1．01。制取的钛酸钡产品经TEM表征，其形状皆为球状，具有沉淀法制取的钛酸钡的典型粉体特征，在适宜工艺条件下制取的产品平均粒径为60nm。     

浸没循环撞击流反应器制备牙膏用磷酸氢钙

采用浸没循环撞击流反应器（SCISR），以焦磷酸钠和磷酸三镁为稳定剂，以磷钙液和石灰乳为原料，通过中和反应法制备出了平均粒度10μm的牙膏用微细磷酸氢钙；探讨了反应温度、熟化时间、反应器装填系数、反应终点pH、磷钙液质量浓度等对产品质量的影响。确定了最优操作条件：磷钙液质量浓度1．17～1．19kg／m^3，反应温度42℃，熟化时间2h，反应终点pH6．3，反应器装填系数0．75。得到产品符合HG3257—2001标准。     

撞击流-旋转填料床合成超细平台燃烧催化剂β-Cu

平台燃烧催化剂2,4-二羟基苯甲酸铜粉体的超细化是基于微观混合对沉淀反应影响原理的分析以及撞击流-旋转填料床的微观混合机理提出的。通过对撞击流-旋转填料床的微观混合时间理论计算表明,撞击流-旋转填料床的微观混合时间为0.04~5 ms,可以满足合成反应(特征时间3.8 s)对反应器的要求。利用IS-RPB反应器合成了体积平均粒径610 nm的超细2,4-二羟基苯甲酸铜,且粒度分布范围窄。     

平衡双注乳化反应器的开发（一）：双注乳化反应器的混和特性研究

混合影响液相沉淀反应的所有过程，使反应物分子接触，影响反应的发生和过饱和度的形成；使过饱和度和产物表面在反应器内重新分布，影响成核和生长的相对速率。因此对快速沉淀反应来说，混合在决定最终颗粒尺寸分布中起着极其重要的作用。本文分别研究了乳化反应器内宏观和微观混合特性以及各种混合方式对沉淀颗粒尺寸分布的影响。     

MICROMIXING EFFECTS ON BARIUM SULFATE PRECIPITATION IN A DOUBLE-JET SEMI BATCH REACTOR

The effects of turbulent mixing on barium sulfate precipitation in an imperfectly mixed double jet semi batch reactor were investigated experimentally and theoretically. When two feed solutions in separate streams were fed into the semi batch reactor, the precipitation was significantly altered by the impeller speed and the feeding time. Generally, in the range of low impeller speed (below 400 rpm), the suspension was segregated vertically in the reactor and the average particle size increased with increasing impeller speed. However, in the range of high impeller speed (above 400 rpm) the suspension was homogeneously dispersed in the reactor, but the trend of the turbulent mixing effect on the precipitation was opposite to that in range of the low impeller speed. The precipitation in the semi batch reactor was controlled by particle mass transfer and micromixing of the feed streams, both of which were promoted by increasing the impeller speed. At low impeller speed the influence of the mass transfer was dominant so that the particle size increased with increasing impeller speed, but at high impeller speed it was surpassed by the influence of micromixing so that the trend was reversed because enhanced micromixing generates a large number of small particles in the reactor.

To model our hypothesis for the effects of imperfect mixing on the reaction precipitation in the semi batch reactor, a micromixing-limited plug flow-ideal semi batch series reactor model was developed. The model predicts that enhanced micromixing created high supersaturation levels in the premixing region (plug flow reactor) which reduces the average particle size. The model also predicts the effect of feeding time on the precipitation in the semi batch reactor. These predictions are in excellent agreement with the experimental data. An interesting prediction of our model is that micromixing in the premixing region plays an important role in the overall reaction precipitation and its effect is greatly intensified as the turbulent mixing intensity is increased, which is opposite to our common sense.     

撞击流反应器流场数值模拟及其混合性能优化

利用数值模拟方法分析多喷嘴对称撞击流反应器内部流场以优化反应器结构。研究不同喷嘴数和进料条件对撞击流反应器内速度场、湍流特性及混合效果的影响。结果表明,不同喷嘴数撞击流反应器内流速分布为双峰型,等流速工况下速度梯度随喷嘴数增加而减小,高剪切力分布范围随喷嘴数增加先增大后减小。通过分析湍流尺度分布发现小尺度涡旋主要集中在撞击区,而大尺度涡旋主要集中在发展区,且四喷嘴撞击流反应器平均剪切应力及涡旋尺寸梯度最大,四喷嘴结构更有利于增强流体湍动强度并强化混合。撞击流反应器内平均湍动能随喷嘴数增加先增大后减小,其中四喷嘴撞击流反应器内平均湍动能最大。当撞击流反应器为四喷嘴结构时,其混合效果最好,完全混合时间最短为22 s。在本研究工况内四喷嘴结构为撞击流反应器混合的最优结构。     

双组分层撞击流反应器浓度场混沌分析

采用平面激光诱导荧光技术测量双组分层式撞击流反应器撞击区浓度分布,利用混沌理论分析不同喷嘴间距、喷嘴直径和射流雷诺数下撞击流反应器浓度场混沌特征参数(关联维、Kolmogorov熵和最大Lyapunov指数)的变化规律。结果表明,撞击流反应器内浓度场混沌特征参数随喷嘴间距的增大呈上下波动的变化趋势,Kolmogorov熵在L=2d时达到最大。浓度场混沌特征参数随喷嘴直径增大呈上下波动的变化趋势,Kolmogorov熵在d=8 mm时整体上最大;射流雷诺数为Re=22 000时整体上混沌特征参数最佳。受二次撞击区的影响,撞击面上靠近二次撞击区各点的混沌特征参数有明显提高。     

基于制备超细复合含能材料的对置受限式撞击流反应器微观混合性能

由于对置受限式撞击流反应器较高的传热及混合效率,能够制备出粒径小、均匀且分布范围窄的超细颗粒。本文采用碘化物-碘酸盐平行竞争反应体系研究入射速度、结构尺寸对对置受限式撞击流反应器微观混合效果的影响规律,并将混合腔尺寸同等比例放大一倍进行对比研究。结果表明,随着入射速度的增大,离集指数减小,微观混合效果提高。喷嘴间距与喷嘴直径比的增大使得离集指数增大,微观混合效果降低。离集指数随着混合腔高度、混合腔出口尺寸的增大呈现先增大后减小的趋势,且混合腔高度对混合效果的影响较混合腔出口尺寸显著。将对置受限式撞击流反应器混合腔尺寸扩大一倍,离集指数增加到原来的2.4倍,微观混合效果显著下降,但是在较大入射速度下,两种结构的混合效果差距减小。研究结果可为纳米复合含能材料的制备提供高效、安全的技术支持。     

Influence of the Metal Particle Size on the Ignition of Energetic Materials

A theoretical study of multi‐particle ignition uses a hot spot model which calculates the temperature evolution of individual hot spots in an energetic material. It indicated that ultra‐fine hot particles would be very effective in igniting energetic materials if impinging and penetrating the solid propellant. Igniting mixtures were prepared containing ultra‐fine Ti particles which react fastest compared with coarse particle mixtures, standard B/KNO₃ and black powder. The ultra‐fine particles, however, are obviously oxidized or gasified too fast as to reach the energetic material to be initiated and longer ignition delays are found mainly compared with coarse particle mixtures. An optimized mixture of coarse and ultra‐fine particles would give an improvement of ignition delay times.     

浸没循环撞击流反应器的压力脉动特性

The characteristics of pressure fluctuation in a submerged circulative impinging stream reactor (SCISR) were experimentally studied. The instantaneous signals of pressure fluctuation resulting from the turbulence in the SCISR were measured by sensors and recorded by a computer. The pressure signals at some special positions were sampled at different rotary speeds of propeller. After analyzing the signals with the Power Spectrum method, it was found that there was an inherent frequency in the dynamic pressure signals. The inherent frequencies of the point on the impinging plane were greater than 1000 Hz, so the pressure fluctuation was called high-frequency fluctuation. The fluctuation velocities with high inherent frequency resulted in a strong shear force field, which enabled the fluid to mix quickly on the micro-scale and the agglomerates of solid particles to disperse effectively.     

Impinging zone reactor and its mathematical model for ozonation of waste water

The impinging zone reactor combines the high shear associated with gas‐liquid co‐injection and the impingement of two jet streams to bring about high intensity mixing in a power efficient manner. The reactor has been field tested and proven to be effective and economical for ozonation of wastewater to reduce COD (Chemical Oxygen Demand) and color. A reactor mathematical model has been developed based on fundamental principles where ozone self‐decomposition in water and mass transfer enhancement due to fast reactions are explicitly considered. The model is especially useful for reactor scale‐up design and optimization.     

Analysis of gas-particle flow characteristics in impinging streams

A three dimensional Euler–Lagrange model for the gas-particle two-phase impinging streams (GPIS) is developed based on the direct simulation Monte Carlo (DSMC) method with consideration of particle rotation and collision. The gas-particle flow characteristics involved in GPIS as well as the effects of inlet gas velocity and particle rotation are analyzed. The results indicate that two pairs of counter-rotating gas vortices are developed at two sides of the opposite jet flows, which is able to entrain the particles and thus greatly weaken the deposition of particles. Interparticle collisions in the impingement zone produce two effects on the particle behaviors: the direct escaping of particles from impingement zone and the progressive accumulation of particles in impingement zone. Under the same inlet particle mass flow rate, the particle concentration in the impingement zone decreases with increasing inlet velocity of gas due to the increasing impinging reaction of interparticle collisions and growing entrainment of gas vortices. In addition, the rotation of particle provides an additional driving force to push the particles away from the impingement zone, leading to the higher speed of escaping particles and smaller maximum particle concentration at the center of impingement zone than those without particle rotation.     

撞击流强化混合特性及用于制备超细粉体研究进展

撞击流以其强化微观混合的优异特性在化学反应、结晶、制备超细粉体等方面有广泛应用。本文在撞击流技术强化混合特性的基础上对近年来几种撞击流反应器制备超细粉体研究进行了综述。简述了流体流动、受限空间、喷嘴形式及结构、外部激励等因素对浸没循环撞击流反应器、受限撞击流反应器、T形撞击流反应器、微小型撞击流反应器、撞击流-旋转填料床反应器混合性能的影响。从结晶、微观混合时间等角度分析了撞击流微观混合特性对化学反应及制备超细粉体的影响。并与常规反应器及方法对比,从超细粉体的粒度大小、形貌、表面、能量、分散性、电性能及稳定性等方面进行评估。提出一种双层对置撞击流反应器用于工业上大规模制取超细粉体的中试研究,并展望了撞击流技术用于制备超细粉体的前景。     

双层撞击流混合器浓度时间序列的多重分形分析

利用平面激光诱导荧光技术(PLIF)对双层撞击流混合器的浓度场进行了实验测量,获得了不同径向位置处的浓度时间序列,通过多重分形去趋势波动方法(MF-DFA)研究了浓度时间序列中的多重分形特性,得到不同喷嘴间距和射流雷诺数下的多重分形谱,实现了流场特性的定量表征。结果表明,随着喷嘴间距增大,浓度时间序列的奇异性减弱,随着射流雷诺数增大,浓度时间序列的奇异性增强,喷嘴间距对浓度时间序列奇异性的影响比射流雷诺数更为显著。浓度信号的奇异性越强,流体粒子脉动越剧烈,混合效果越强,喷嘴间距对混合的促进作用大于射流雷诺数。通过分析多重分形谱参数(Δα, αmin, α0)随径向位置的变化规律得出了流型的转变区域,并将双层撞击流混合器由撞击中心处向下分为二次撞击区、涡旋区、一次撞击区。浓度信号的奇异性二次撞击区>一次撞击区>涡旋区,对混合的促进作用二次撞击区>一次撞击区>涡旋区。研究结果为更深入地揭示撞击流混合器内部流动模式和撞击流复杂无序的流动机理提供了理论依据。