基于激光光谱法的尿素水溶液液膜多参数测量

在选择性催化还原(SCR)系统中,对尿素水溶液液膜多个参数(厚度、浓度及温度)进行高精度的定量分析,对减少液膜形成、提高SCR系统的催化反应效率、降低NO_x对环境的污染至关重要。基于比尔-朗伯定律,通过结合1420 nm和1488 nm两个波长的半导体激光器,提出一种恒温度条件下尿素水溶液液膜厚度和浓度同步测量,以及恒浓度条件下尿素水溶液液膜厚度和温度同步测量的新方法。并在此基础上,利用标准具验证了该方法的测量精度。结果表明恒温度条件下,该方法同步测量尿素水溶液液膜厚度和浓度的平均测量误差分别为0.82%和3.93%;恒浓度条件下,同步测量尿素水溶液液膜厚度和温度的平均测量误差分别为0.79%和2.58%。     

激光光谱法同步测量尿素水溶液液膜厚度与浓度

对尿素水溶液液膜厚度和浓度进行定量分析在工业应用中至关重要,而传统的测量方法只能对液膜厚度和浓度分别进行测量。提出了一种用于尿素水溶液液膜厚度和浓度高精度同步在线测量的新方法。通过灵敏度分析和内部交叉验证,选取了测量精度及灵敏度最高的一对波长组合(7040.75 cm^-1 与 6761.00 cm^-1)。由内部交叉验证可知,该方法测量液膜厚度误差小于1.40%,浓度误差小于5.76%。     

超声脉冲反射法和激光吸收光谱法同步测量流动液膜厚度

液膜流动现象在工业过程中广泛存在,对流动液膜厚度测量方法的测量研究至关重要。首先利用已知液膜厚度的标准具（100～1000 μm）对超声脉冲反射法和激光吸收光谱法精度进行验证;结果表明,超声脉冲反射法测量液膜厚度的平均测量误差为1.07%,激光吸收光谱法测量液膜厚度的平均测量误差为1.29%。同时结合两种方法对流动液膜进行研究,结果表明,当液膜在低速/中速/高速流动时,两种方法测量流动液膜的平均厚度吻合良好,平均厚度差值分别为16.59、16.26、13.36 μm,流动液膜厚度的标准方差的相对偏差分别为0.29%、7.71%、25.37%,且在三种不同速度下两种方法测得在1s的周期内液膜波动次数一致。     

超声脉冲反射法和激光吸收光谱法同步测量流动液膜厚度

液膜流动现象在工业过程中广泛存在,对流动液膜厚度测量方法的测量研究至关重要。首先利用已知液膜厚度的标准具(100~1000μm)对超声脉冲反射法和激光吸收光谱法精度进行验证;结果表明,超声脉冲反射法测量液膜厚度的平均测量误差为1.07%,激光吸收光谱法测量液膜厚度的平均测量误差为1.29%。同时结合两种方法对流动液膜进行研究,结果表明,当液膜在低速/中速/高速流动时,两种方法测量流动液膜的平均厚度吻合良好,平均厚度差值分别为16.59、16.26、13.36μm,流动液膜厚度的标准方差的相对偏差分别为0.29%、7.71%、25.37%,且在三种不同速度下两种方法测得在1s的周期内液膜波动次数一致。     

反应沉淀法制备碳酸钡纳米粉体的研究

以工业精制氯化钡和碳酸氢铵为原料，在旋转填充床中采用液-液相反应沉淀法合成碳酸钡钠米粉体。其条件为：氯化钡水溶液质量浓度24%。碳酸氢铵水溶液质量浓度17%，氯化钡与碳酸氢铵溶液体积流量比为1.5:1，转速0-1600r/min，反应温度常温。得到平均粒度为80nm、比表面积为24m^2/g、粒度分布窄的产品。该法工艺及操作简单，易于工业化。     

减压膜蒸馏浓缩硫酸钠溶液的实验研究

采用减压膜蒸馏技术在较低真空度下浓缩Na2SO4水溶液，研究了真空度、料液温度、料液流速以及料液浓度对膜通量与截留率的影响。结果表明，随着膜下游真空度增加，膜通量增大；料液温度显著影响膜通量；随着料液浓度增加，膜通量严重衰减；实验条件下聚丙烯中空纤维膜表现出很好的疏水性，Na2SO4的截留率接近100%。     

尿素法SNCR对大型电站煤粉锅炉运行影响的工业试验

在660MW超临界W火焰锅炉上开展了工业试验,研究了尿素法选择性非催化还原脱硝（SNCR）投运对锅炉热效率、NOx排放、SCR入口烟道截面NOx分布及炉内烟气温度的影响。结果表明：SNCR系统喷入炉内的水汽化吸热是导致锅炉热效率降低的主要原因,喷入炉内水流量增加1.0t/h,锅炉热效率降低约0.05个百分点;稀释水流量影响尿素溶液在炉内的雾化和分配效果,在尿素用量相同条件下适当增加稀释水流量,SNCR脱硝效率会显著提高;相对于试验负荷下约2400t/h的烟气流量,SNCR喷入炉内的尿素溶液流量相对较少（占0.2%～0.5%）,因此,对炉内烟气温度影响并不明显。在一定范围内调整稀释水和尿素溶液流量对SCR入口烟道截面NOx分布的影响并不明显,但是过低的稀释水流量会影响炉内尿素混合效果,进而影响SCR入口NOx浓度在烟道截面深度方向上分布的均匀性。     

300MW CFB锅炉SNCR+SCR深度脱硝性能研究

随着环保压力不断提高,流化床锅炉需进行深度脱硝改造以实现超低排放,但目前SCR改造在流化床锅炉上的应用研究较少。某厂320 MW流化床机组改造增加了SCR脱硝系统,基于该工程改造项目,笔者使用网格法对烟气场温度、烟气成分等参数进行测定,进行了改造前后的锅炉性能试验,研究了改造后SCR的脱硝性能及其影响因素,并测试锅炉效率。结果表明,不同负荷下,SCR入口平均温度在268.11～309.53℃,基本满足拓展的SCR反应温度窗口(260～420℃)。机组满负荷320 MW下,实测反应器脱硝效率为72.48%,对应的氨逃逸浓度为0.7 mg/Nm3。40%～100%负荷下,NOx排放均低于25 mg/Nm3,氨逃逸浓度不大于1 mg/Nm3。由于烟气温度水平较煤粉炉低,因此本试验中SCR反应器的脱硝效率低于应用于煤粉炉的SCR反应器。40%～100%负荷下的尿素耗量均低于同等级的煤粉锅炉,其中满负荷下的尿素耗量为279.09 kg/h。在相同排放数值下尿素耗量降低50%以上,节能降耗效果显著。排放结果与尿素耗量统计结果表明,SNCR与SCR耦合良好,应用于CFB锅炉具有较大优势。SCR出口处NOx分布并不均匀,在烟道水平截面上呈NOx浓度右侧高、左侧低的趋势,与SCR入口温度分布一致,温度是影响脱硝效率和NOx分布的主要因素。改造后平均锅炉效率为90.07%,与改造前锅炉效率持平,表明SCR改造对锅炉效率影响较小。锅炉90%以上热损失由排烟和物理未完全燃烧热损失造成,控制排烟热损失q2和物理未完全燃烧热损失q4是锅炉热效率提升的关键。     

酶法测定超微量尿素酶法分析尿素（三）

应用酶促水解和电位测量相结合的方法，测定浓度在５×１０￣（－６）～１×１０￣（－４）ｍｏｌ／Ｌ范围内的尿素水溶液中的尿素含量。在该浓度范围内，尿素的浓度－电位关系不符合能斯特方程，而是直接呈现出浓度－电位的直线关系。     

真空膜蒸馏用于多元醇水溶液分离的研究

利用自制的聚丙烯中空纤维膜,采用真空膜蒸馏法对1,2-丙二醇水溶液的分离进行了研究.考察了料液入口温度、冷侧真空度、料液流量以及料液浓度对膜通量和截留率的影响.结果表明,膜通量随料液入口温度、冷侧真空度及料液流量的增加而增加,随料液浓度升高而下降.截留率随料液入口温度、冷侧真空度和料液浓度的增加而下降,料液流量的变化对截留率没有明显的影响.本试验条件下最佳截留率可达100%,表明利用真空膜蒸馏技术可有效实现多元醇水溶液分离.     

Determination of Kinetic and Energetic Parameters of Chemical Reactions in a Heterogeneous Liquid/Liquid System

A global method is proposed for estimating the kinetic and energetic parameters of chemical reactions taking place in the continuous phase of a heterogeneous liquid/liquid system. This method, based on energy and mass balances, uses the thermal power freed or absorbed by the reaction mass. It is only applicable to systems with sufficient thermal effects. Knowledge of the mass flow exchanged between the dispersed and continuous phases is needed to establish the mass balance. It is determined thanks to a model based on the double film theory. The model was applied to the saponification of pure ethyl acetate in an aqueous reaction mass. It was possible to determine simultaneously the velocity constant and the reaction enthalpy, as well as the apparent overall mass transfer constant.     

Evaluation of a Method to Measure Black Carbon Particles Suspended in Rainwater and Snow Samples

We conducted a detailed evaluation of a method for measuring the mass concentrations and size distributions of black carbon (BC) particles in rainwater and snow. The method uses an ultrasonic nebulizer (USN) and a single particle soot photometer (SP2). The USN disperses sample water into micron-size droplets at a constant rate and then dries them to release BC particles into the air. The masses of individual BC particles are measured by the SP2, using the laser-induced incandescence technique. The loss of BC particles during the extraction from liquid water to air depends on their sizes. We determined the size-dependent extraction efficiency using polystyrene latex (PSL) spheres with 12 different diameters between 107 and 1025 nm. The PSL concentrations in water were measured by the light extinction at 532 nm. The extraction efficiency of the USN showed a broad maximum of about 10% in the diameter range 200–500 nm and decreased substantially at larger sizes. The accuracy and reproducibility of the measured mass concentration of BC in sample water after long-term storage were about ±25% and ±35%, respectively. We tested the method by analyzing rainwater and surface snow samples collected in Okinawa and Sapporo, respectively. The measured number size distributions of BC in these samples showed negligible contributions of BC particles larger than 300 nm to the total number of BC particles. A dominant fraction of BC mass in these samples was observed in the diameter range 100–500 nm.

Copyright 2013 American Association for Aerosol Research     

Microscopic observations of clathrate-hydrate films formed at liquid/liquid interfaces. II. Film thickness in steady-water flow

A series of experiments were carried out to measure, with the aid of direct observations through a high-resolution optical microscope, the local thickness of a ring-shaped hydrate film formed over the surface of each discoid drop of HCFC-141b (CH₃CCl₂F) held stationary in a narrow liquid-water channel confined by two transparent, parallel plates, while the experimental system was controlled at a temperature below the hydrate/liquid-water/liquid-HCFC-141b equilibrium temperature, T_tri, at atmospheric pressure. It was revealed that the thickness may be significantly different from place to place over the same hydrate film and that the thickness at each location decreases with an increase in the water flow rate and with a temperature rise. To clarify the dependency of the local film thickness thus measured on the convective mass transfer of the hydrate-guest substance from the film surface to the water flow, we performed numerical simulations of the convective mass transfer and also chromatographic measurements of the solubility of HCFC-141b in liquid water so that we could predict the local mass transfer coefficient and the mass flux of the hydrate guest, HCFC-141b, at any location along the hydrate-film/liquid-water interface. Plotting the film-thickness data obtained at each temperature level against relevant predictions of the mass transfer coefficient or the mass flux, we found the film thickness to be nearly inversely proportional to the mass transfer coefficient or the mass flux. This finding supports the idea that the film thickness is determined by the balance between the rate of hydrate-crystal dissociation induced by the aforementioned convective mass transfer and the rate of hydrate-crystal formation depending on the liquid-water permeation into the hydrate film.     

Simultaneous heat and mass transfer for multicomponent distillation in a wetted-wall column

A simultaneous heat and mass transfer model was applied to multicomponent distillation in a wetted-wall column. Experiments were carried out, using the benzene-toluene-ethylbenzene ternary system, in a wetted-wall column of 2.2 cm i.d. and 100 cm long equipped with special probes designed for simultaneous liquid sampling and temperature measurements. The experimental results show that the bulk liquid phase was saturated, indicating no resistance to mass transfer in the liquid film. Confirmation of the liquid phase saturation was made through a comparison of the experimentally measured liquid temperature with the calculated bubble point temperature. The average deviation between the measured and calculated temperatures was found to be 0.26°C.Individual mass transfer rates were evaluated locally by measuring compositions and temperatures as functions of column height and were compared to theoretical predictions using the exact film model solution of the Maxwell-Stefan multicomponent equations developed by Krishna and Standart. The comparison shows good agreement with average deviations of 15.76% for benzene, 23.09% for toluene and 23.23% for ethylbenzene.     

酸浸渣综合回收浸铅工艺研究

针对氰化提金工艺酸浸渣中低品位金属铅的综合回收,采用盐浸法对金属铅进行了浸出实验研究,通过正交试验详细考察了浸出液固质量比、浸出温度、氯化钠浓度、浸出pH和浸出时间等因素对浸铅率的影响。结果表明,浸出液固质量比为5、浸出温度为333.15 K、氯化钠质量分数为30%、pH=0、浸出时间为4 h的实验条件下,最佳平均浸铅率为92.05%,相对标准偏差RSD=4.3‰;室温下最佳平均浸铅率为90.20%,RSD=4.1‰。因此,酸浸渣常温盐浸提铅是综合利用矿产资源回收铅及提高金、银回收率的有效途径。     

颗粒形状对全散射法测量颗粒物质量浓度的影响

燃煤电厂排放颗粒物作为大气颗粒物主要来源之一受到广泛关注,实现颗粒物质量浓度的精确在线监测意义重大。激光全散射法作为一种常用的颗粒物质量浓度在线监测方法,受颗粒特性影响较大,易造成较大的测量偏差。为探究颗粒形状对全散射法测量的影响,搭建了全散射法测试台架,并采用球形二氧化硅颗粒对测试系统进行标定,标定结果显示,球形二氧化硅颗粒质量浓度与消光程度高度线性相关,相关系数R2>0.99,测量浓度与真实浓度偏差仅为1.8%。进一步采用633 nm与532 nm波长激光分别对3种非球形(棱形、不规则和片状)二氧化硅颗粒进行测试试验。测试结果显示,3种形状颗粒物的质量浓度与消光程度均高度相关,R2均高于0.99;3种形状颗粒物质量浓度的测量值与真实值偏差与颗粒形状及激光波长相关,对比发现,入射波长为633 nm时,不规则、棱形和片状颗粒的质量浓度测量值与真实值的测量偏差分别为16.1%、27.4%和36.6%;入射波长为532nm时,3种颗粒质量浓度的测量偏差分别为4.8%、11.4%和17.4%;颗粒形状一致条件下,532 nm入射波长时的测量偏差明显较小,通过波长的选择可降低颗粒形状变化造成的测量偏差。     

STABILITY ANALYSIS FOR THE PREDICTION OF THE MINIMUM TEMPERATURE OF FILM BOILING

The stability of film boiling on a vertical, constant temperature wall is analyzed by a steady-state small perturbation method. It was found that large amplifications of the perturbations in the downstream direction are predicted when the vapor Reynolds number falls below a critical value, indicating a great tendency to collapse the vapor film. Using a relatively simple model for the film thickness, the minimum wall temperature required to sustain the vapor film is calculated. The results show a tendency which is in agreement with experimental observation. It is suggested, however, that using a more accurate model for the film thickness can lead to a good prediction of the minimum wall temperature and explain the large effect of liquid subcooling, system pressure, surface tension and other fluid properties.     

水/二甲基乙酰胺/聚砜体系双结点线的神经网络预测

基于实验数据,采用人工神经网络对水/二甲基乙酰胺/聚砜体系的双结点线进行了预测. 设计并验证了具有两个输入神经元(体系温度和聚砜的质量分数)和两个输出神经元(水和二甲基乙酰胺的质量分数)的BP(Back Propagation)网络, 选取50组训练样本和39组检验样本分别对网络进行了训练与检验. 结果表明,对水与二甲基乙酰胺质量分数的预测平均相对误差分别为1.86%和0.10%. 采用该网络能较好地预测常压下、20~60℃温度范围内水/二甲基乙酰胺/聚砜体系的双结点线.     

含FeCl_3光学戊醇和异戊醇蒸汽压的测定和关联

采用静态法,分别测定了质量分数在5.0%—9.6%范围中3种不同浓度FeCl3加入后光学戊醇和异戊醇在100—140℃范围内的饱和蒸汽压,发现随着盐质量分数的增大,2种戊醇的蒸汽压在相同温度下的降低有较明显差异。压力测量采用水银U型管压差计,误差为±0.07 kPa,温度测量采用精密温度计,误差为±0.01℃。实验结果进一步用Antoine方程进行了关联,得到Antoine方程的3个参数A,B,C,关联值与实验测定值吻合得很好(对于光学戊醇和异戊醇,其平均偏差均在1%以内)。这些数据的测得为今后进一步研究加盐精馏分离2种戊醇提供了基础物性数据。