常温高压下移动颗粒层除尘试验研究

介绍了用于整体煤气化联合循环（IGCC）热煤气和增压流化床燃烧联合循环（PFBC-CC）高温烟气除尘的移动颗粒层试验台。调试阶段进行了一系列的条件试验。改进后的常温下进行了试验,结果表明在高压下能够实现颗粒层过滤和气力循环清灰的一体化稳定运动。研究发现移动颗粒层过滤时,气流之间的压力平衡是一个关键因素,运行中必须严格控制过滤气体和输送气体的压力。移动颗粒层过滤器和循环清灰系统的结构对过滤性能有较大的影响。     

移动床除尘过程数学模型建立及机理讨论

在C.Tien固定床深层过滤数学模型基础上，通过引入移动床除尘比沉积率σ概念并考虑惯性碰撞、拦截、重力沉降、扩散机理的作用，建立了完整的颗粒移动床深层过滤过程数学模型，以此为基础结合工程应用中实测的粉尘数据范围计算了除尘效率，详细讨论了各种除尘机理及操作条件对除尘效率的影响。     

颗粒移动床过滤过程的数学模型

利用Ｃ．Ｔｉｅｎ等的固定床过滤净床模型及Ｔ．Ｔａｋａｈａｓｉ等的固定床过滤动态模型,通过合理定义移动床过滤对应于固定床过滤模型中的比沉积率σ参数以及对某些系数的修正,建立了模拟颗粒移动床过滤过程包含参数较为完整的数学模型并与试验结果进行了对照,结果表明此模型能够正确描述颗粒移动床过滤过程     

炉前煤低温干馏的工艺研究

为了模拟真实的循环流化床燃烧/煤热解多联产工艺中的移动床热解系统,同时验证静态挡板混合以及颗粒床除尘在该系统中应用的可行性,建立了处理煤量为10 kg/h的移动床固体热载体煤热解连续实验装置.结果表明,在混合段内没置挡板足一种有效的灰/煤混合方式,可以获得与机械混合接近的气、液产率;滤料性质、床层高度、过滤气速等均会对颗粒床除尘器的除尘效果产生影响,颗粒床的使用可将焦油中的含尘率控制在一定范围内.该研究可为炉前低温干馏工艺开发提供可靠的基础数据.     

炉前煤低温干馏工艺中的挥发分除尘

为了寻求优化的炉前煤低温干馏工艺中的挥发分除尘方案，在使用400目金属滤网对间歇式粉煤固体热载体热解装置挥发分除尘研究的基础上，将颗粒床过滤器用于该过程的除尘研究。热态除尘实验表明，颗粒床的使用有效地降低了滤网的过滤负荷。选用2mm石英砂和φ5mm×2mm瓷环作为滤料，通过对比实验发现，两种滤料除尘效率均在90％以上；随着过滤操作的进行，由于颗粒床内粉尘的沉积使其过滤效率有所提高，而对气、液收率的影响很小。结果表明，颗粒床与滤网结合可作为粉煤炉前低温干馏工艺中可供选择的挥发分除尘方案。     

单纳米颗粒在超微电极上的碰撞电化学分析：微电极和纳米管电极

纳米颗粒的功能与其尺寸、电荷密度和表面化学性质等密切相关,因此研究其内在关系至关重要。近年来,基于纳米颗粒碰撞的电化学方法可以实现对单个纳米颗粒的尺寸、浓度和聚集状态快速检测,进而有效区分纳米颗粒的个体差异和探索单个颗粒活性-结构之间的关系。鉴于电极的尺寸、形状对单颗粒碰撞结果存在显著影响,本文将重点介绍不同颗粒（金属、半导体和绝缘体）与传统超微电极和纳米管电极之间的碰撞行为,并基于目前纳米电化学碰撞技术的不足,展望未来纳米电化学碰撞技术的发展方向。     

水体微型颗粒的流式细胞术测定

应用流式细胞术（FCM）对水体中不同粒径级微型颗粒的数量、百分比及随时间变化进行了初步研究；仪器经流速校正，样品经过滤，外参法测定；结果表明FCM可快速、即时分析水体中的微型颗粒。     

镍/铁复合纳米微粒中与粒径相关的控制参数及磁性能分析

根据样品的TEM、EDX和VSM检测结果,分析制备纳米微粒工艺中与粒径相关的水/有机物(摩尔比R)比例对颗粒成核尺寸的影响,以及不同镍/铁比例(摩尔比)对粉末材料磁性能的影响.给出控制颗粒尺寸大小的R取值.     

Ni-Re/SiO2催化剂中Ni颗粒尺寸对乙醇胺催化胺化反应的影响

以醇和氨/胺为原料采用催化胺化法合成有机胺长期以来广受关注,该工艺反应副产物只有水,符合现代绿色化工理念.作为工业应用的成功案例,乙醇胺(MEA)催化胺化法目前已成为生产乙撑胺(包括乙二胺(EDA),哌嗪(PIP)等)的主要工艺.MEA催化胺化通常在过渡金属催化剂上进行,如Ni基催化剂,反应过程遵循"借氢机理",经历了"脱氢-缩合胺化-加氢"三个过程.目前,关于MEA胺化催化剂的研究主要以专利为主,据我们所知,对于催化剂金属颗粒尺寸和胺化性能之间的构效关系的研究极少,特别是对于金属粒径对胺化产物分布的影响,目前还未见报道.因此,本文的目的是合成具有不同Ni颗粒尺寸的Ni-Re/SiO_2催化剂,通过滴流床反应器评价,研究颗粒尺寸对MEA胺化活性和产物分布的影响.采用控制催化剂焙烧和还原条件的方法,制备了四种不同Ni粒径的Ni-Re/SiO_2催化剂;随后采用N_2物理吸附, H_2程序升温还原, X射线衍射, H_2化学吸附,光电子能谱,红外吸收光谱等对催化剂的孔结构、还原性、粒径分布、金属Ni活性比表面、分散度、表面Ni位点类型和电子性质进行研究.MEA催化胺化反应在滴流床反应器上进行,反应条件为170oC, 8.0 MPa, MEA液时空速0.5h~(–1), NH_3:MEA摩尔比10:1, H_2含量2.5 mol%.表征结果证明,成功制备了具有不同Ni粒径,且尺寸分布集中的Ni-Re/SiO_2催化剂, Ni粒径分别为4.5, 10.5, 14.6, 18.0nm.评价结果表明, Ni颗粒4.5 nm的Ni-Re/SiO_2催化剂具有最高的活性, MEA转化率高达85.7%, EDA和PIP收率为66.4%,优于以往专利文献所报道的值.结合表征结果分析,这是由于Ni-Re/SiO2 (4.5 nm)上的Ni粒径小,分散度高,因此Ni活性比表面积大,为胺化反应提供了充足的催化位点.进一步深入研究了Ni颗粒尺寸对MEA胺化反应的影响,发现随着Ni粒径增加,底物MEA的转换频率(TOF)从193 h~(–1)增加到253 h~(–1),表明大颗粒有利于胺化反应.此外,随着粒径增加,产物中伯胺和仲胺的摩尔比从1.0增加到2.0,产物EDA的TOFEDA值由63 h~(–1)增加到119 h~(~(–1)),表明Ni粒径变化影响了MEA胺化反应途径和产物分布,增大粒径有利于EDA的生成,从而提高了产物中的伯:仲胺之比.实验结果证明, Ni-Re/SiO2催化剂粒径影响了颗粒表面Ni的配位环境,从而改变了表面的电子结构.增大Ni粒径可提高面位点Ni的比例和表面电子云密度,导致中间产物容易从Ni表面脱附,从而有利于促进反应初始阶段MEA与NH_3的胺化,提高EDA选择性.     

非对称场流分离系统的构建及其在淀粉颗粒粒径表征中的应用

淀粉颗粒粒径与分子尺寸分别在1~100 μm和20~250 nm之间,是影响淀粉功能特性的重要因素之一。非对称场流分离(AF4)是一种基于样品与外力场相互作用机制的分离技术,已应用于表征淀粉分子尺寸分布。商品化的AF4系统的粒径检测范围为1 nm~10 μm,对于淀粉颗粒粒径表征具有一定的局限性。该文研制了AF4分离系统;考察了其在微米尺度下对红薯、莲子和大米淀粉颗粒粒径表征的性能;采用微米尺寸的聚苯乙烯乳化球(PS)标准样品验证了构建的AF4系统的分离性能。实验结果显示,构建的AF4系统对PS混合样品(粒径2、6、12、20 μm)实现了基线分离,同商品化AF4相比提高了检测上线,具有分离表征淀粉颗粒的潜力。此外,该文研究了载液组成对淀粉颗粒分离表征的影响;通过光学显微镜验证了构建的AF4系统在微米尺度上对淀粉颗粒粒径分布的表征能力。最后,采用商品化的AF4系统串联多角度激光光散射检测器和示差折光检测器对3种淀粉分子进行了分离表征,考察了淀粉的溶解温度对其表征结果的影响。在摩尔质量10 ⁶~10⁸ g/mol范围内,红薯和莲子淀粉的回转半径和水合半径的比值(R_g/R_h)在0.9~1.1之间,大米淀粉的R_g/R_h在1.2~1.4之间。实验结果证明构建的AF4系统是一种快速、准确的淀粉颗粒粒径表征方法,与商品化的AF4系统结合可为研究淀粉尺寸分布与其功能性质之间的关系提供技术支持。     

Particle-bubble collision models--a review

A critical review of the various models existing in the literature for the calculation of the collision efficiency between particles and single, rising gas bubbles is presented. Although all of these collision models predict that the collision efficiency increases with particle size, their dependence on the latter is different because of the various assumptions and hydrodynamic conditions used in each model. Collision efficiencies of quartz particles with single bubbles have been obtained from experimental flotation experiments under conditions where the attachment and stability efficiencies were at, or near, unity. These collision efficiencies were then used to test various collision models. Good agreement between the experimental and calculated collision efficiencies was only obtained with the Generalised Sutherland Equation. The differences in collision efficiencies obtained between the various models were mainly explained in terms of, firstly, the degree of mobility of the bubble surface and, secondly, a consideration of the inertial forces acting on the particles.     

Aggregate formation and collision efficiency in differential settling

A new method of application of Stokesian dynamics, which can efficiently simulate movements of up to 500 particles with interparticle interactions in reasonable computational times, has been developed for the purpose of investigating particle-cluster aggregation in aqueous systems. The method is applied to monodisperse non-Brownian spherical particles aggregating in differential settling, while repulsive colloidal interaction is presumed to be negligible, so that a minimum separation distance can represent the attractive van der Waals force. The final aggregates formed by this algorithm, composed of 300 primary particles, have a common fractal dimension of approximately 2.0. The computed collision efficiency, defined as the product of a global and a capture efficiency, is about 5.77x10(-3). This value is significantly larger than the collision efficiency of primary particles colliding with an impermeable solid sphere of the same size as the aggregate, illustrating the important interplay between the permeability and the formation of aggregates.     

Bubble particle heterocoagulation under turbulent conditions

An analytical model that enables the calculation of the flotation rate constant of particles as a function of particle size with, as input parameters, measurable particle, bubble, and hydrodynamic quantities has been derived. This model includes the frequency of collisions between particles and bubbles as well as their efficiencies of collision, attachment, and stability. The generalized Sutherland equation collision model and the modified Dobby-Finch attachment model developed previously for potential flow conditions were used to calculate the efficiencies of particle-bubble collision and attachment, respectively. The bubble-particle stability efficiency model includes the various forces acting between the bubble and the attached particle, and we demonstrate that it depends mainly on the relative magnitude of particle contact angle and turbulent dissipation energy. The flotation rate constants calculated with these models produced the characteristic shape of the flotation rate constant versus particle size curve, with a maximum appearing at intermediate particle size. The low flotation rate constants of fine and coarse particles result from their low efficiency of collision and low efficiencies of attachment and stability with gas bubbles, respectively. The flotation rate constants calculated with these models were compared with the experimental flotation rate constants of methylated quartz particles with diameters between 8 and 80 micro m interacting with gas bubbles under turbulent conditions in a Rushton flotation cell. Agreement between theory and experiment is satisfactory.     

The structure of small penta-twinned gold particles

The structural feathers of penta-twinned gold particles (size between 2 and 6 nm) generated by gas evaporation have been investigated by high resolution TEM. The structural characteristic of penta-twinned particles is different from that of quasi-crystals that the five coherent or incoherent twin boundaries separating the twin oriented segments do not join up along a common edge. The lattice parameter is reduced by 4–5% in comparison to that of bulk gold. The formation of the penta-twinned particles is proposed to occur by particle collision. The particles were observed to be crystalline at ambient temperature.     

An improved collision efficiency model for particle aggregation

A generalized geometric model is presented which describes the collision efficiency factor of aggregation (the probability of a binary particle or aggregate collision resulting in adhesion) for systems comprised of two oppositely charged species. Application of the general model to specific systems requires calculation of the area of each species available for collision with a second species. This is in contrast to previous models developed for polymer-particle flocculation that are based on the fractional surface coverage of adsorbed polymer. The difference between these approaches is suggested as an explanation for previously observed discrepancies between theory and observation. In the current work the specific case of oppositely charged nondeformable spherical particles (heteroaggregation) is quantitatively addressed. The optimum concentration of oppositely charged particles for rapid aggregation (maximum collision efficiency) as a function of relative particle size is calculated and an excellent correlation is found with data taken from literature.     

Bi-modal hetero-aggregation rate response to particle dosage

The rate of flocculation of cationic polystyrene latex (PSL) particles by smaller, anionic PSL particles has been measured using a low-angle static light scattering technique. The rate of aggregate growth has been investigated as a function of particle size ratio and relative concentration of each particle species (for a constant dose of cationic particles). Contrary to many previous reports, two peaks in the flocculation rate were observed as a function of dose. It is speculated that the peak observed at the lower particle concentration coincides with the dose yielding maximum constant collision efficiency in the steady-state regime, a condition which is attained only after complete adsorption of the smaller particles onto the larger particle species. The peak at the higher particle concentration is believed to be related to the maximum collision rate constant upon reaching the steady-state regime, the value of which corresponds to maximum degree of aggregation and therefore the maximum mean collision efficiency prior to reaching this condition. From classical collision kinetics, the rate of aggregate growth may be represented as being proportional to the product of the collision rate constant and collision efficiency at any given time. Given then that the maximum value of these two variables coincides with different particle concentrations, the product of the response of each to particle dosage can in some cases yield a net bi-modal aggregation rate response to particle dosage.     

Characterization of a high-pressure quadrupole collision cell for low-energy collision-indneed dissociation

A RF-only quadrupole collision cell of new design has been evaluated for use in tandem mass spectrometry experiments as a component of a triple quadrupole mass spectrometer. The new design permits operation at values of collision gas thickness higher by 1 order of magnitude than those used in most cells of this type. When operated at sufficiently high collision gas pressures, the transmission efficiency for precursor ions increases with increasing pressure, often to values greater than those observed in the absence of collision gas. Simultaneously, the attainable resolving power for fragment ions across the entire mass-to-charge ratio range, even for multiply charged precursors, also increases to the point where isomers of a quadruply charged fragment are resolved. The performance of the cell, judged in terms of yields and resolution of fragment ions, has been investigated as a function of the nature and pressure of collision gas, the kinetic energy of the precursor ions that enter the cell, and of the size and charge state of the precursors. The enhanced performance is explicable in terms of a marked deceleration of all ions that emerge from the cell to very low energies, probably a few tens of millielectronvolts, so that the cell effectively acts as an ion source for the second mass filter (fragment ion analyzer) to provide a spectrum of ions of fixed axial energy. The high transmission efficiency appears to arise from a collisional focusing effect analogous to that exploited in three-dimensional RF ion traps. The low axial energies imply that ion transit times through the cell are sufficiently long (several milliseconds) that, in precursor ion experiments where the first mass filter is scanned, a hysteresis effect is observed. This implies that in this operating mode compromises must be sought between scan speed and quality of peak shape. Examples are given of spectra obtained under realistic operating conditions that employ flow injection of samples.     

Controlling porosity within colloidal heteroaggregates

Heteroaggregates of cationic poly(2-vinylpyridine) microgels and anionic polystyrene latex particles have been made by mixing dilute, aqueous suspensions. The growth of the heteroaggregates was arrested by the addition of anionic silica particles that adsorbed to the free surface of the cationic microgel particles. The resulting heteroaggregates were then concentrated by vacuum filtration, freeze-dried, and characterized by mercury porosimetry and electron microscopy. The inclusion of soft, deformable microgels resulted in heteroaggregates with higher porosity than obtained with heteroaggregates of anionic and cationic latex particles. Control of the pore volumes within the freeze-dried filter cakes was demonstrated by two approaches. In the first approach, heteroaggregation at a constant KCl concentration of 0.01 mM was arrested at different times after mixing the latex and microgel particles, thereby limiting the size of the aggregates. The porosity of the resulting filter cake increased from 61 to 65 vol % as the aggregation time increased from 15 to 120 s. In the second technique, the aggregation time prior to arrest was maintained at 120 s while the KCl concentration was varied between 0.01 and 10 mM. The pore volume of the aggregates decreased from 65 to 57 vol % as the electrolyte concentration increased, a trend explained in terms of the effect of the Debye length on the aggregation process.     

The size of particle aggregates produced by flocculation with PNIPAM, as a function of temperature

This work investigates the effect of temperature on the size of alumina aggregates formed by flocculation with temperature responsive Poly(N-Isopropylacrylamide)(PNIPAM). The results are discussed in terms of the effects of temperature on particle collision, particle adhesion and aggregate breakage. It was found that the size of alumina aggregates increases with increasing solution temperature. Particle/particle collision and aggregate breakage are largely unaffected by increasing solution temperature and therefore could not account for the change in aggregate size. The dominant factor in aggregate growth with increasing temperature was found to be the increase in the force of adhesion between alumina particles. The appearance of the adhesive force is triggered by the increase in temperature above the lower critical solution temperature of PNIPAM.