基于紫外吸收的烟气中NO和NO2成分浓度的同时测量

利用高分辨率光栅单色仪测量到的不同浓度的NO和NO2混合气体综合紫外吸收光学厚度,将光学厚度中的快变离散吸收与NO浓度相关,将慢变连续吸收与NO2浓度相关,同时反演NO和NO2的摩尔浓度。研究结果表明:(1)当气体总压接近一个大气压时,NO2反映出很强的转换为N2O4的倾向,转化率R最大值约为22.5%,远大于低气压下的R值,导致NO2吸收截面主要取决于N2O4的吸收特性,表现为慢变的连续吸收特征;(2)离散吸收截面随NO分压增大产生谱线增宽现象,吸收截面在增宽区域的积分值和NO浓度的线性相关性优于吸收截面峰值。测量和反演结果表明:当NO2分压在17～100Pa范围变化时,NO2摩尔浓度反演的平均相对误差为11.7%。当NO分压在63.8～181.62Pa范围变化时,基于积分法的NO浓度反演的最大相对误差为16.9%,平均相对误差为9.6%,而基于峰值法的NO浓度反演的最大相对误差为38.2%,平均相对误差为14.4%。因此,积分法反演较峰值反演具有更好的线性度和更高的精确度。利用上述测量技术,采用相对简单的测试装备,实现了NO和NO2多种成分浓度的同时测量。     

北京边界层大气中HONO和NO2垂直廓线的测量与分析

基于扫描长程差分吸收光谱(DOAS)系统于2007年8月27日～9月4日期间对北京市郊区进行了大气污染物HONO和NO2等垂直廓线的连续监测,详细探讨了HONO,NO2和HONO/NO2比值的垂直分布特征,重点研究了HONO的形成途径.结果显示HONO和NO2浓度随着高度的增加而降低,而HONO浓度梯度下降的更加剧烈;...     

O2/CO2气氛下CO对煤焦异相还原NO影响的研究

为揭示O₂/CO₂燃烧过程中高浓度的CO对煤焦异相还原NO的影响,在1073 K温度下使用山西褐煤在卧式炉上进行了实验。分别对O₂/CO₂浓度比及CO浓度下NO的还原特性进行详细实验研究。研究结果表明:在O₂/CO₂气氛下,O₂浓度为30%时具有较高的还原率;相同O₂浓度下O₂/CO₂气氛较空气气氛NO还原率高,表明在CO存在的条件下,高浓度的CO₂会促进NO的还原;当CO浓度从1.5%逐渐升高时,NO的还原率逐渐降低,到CO浓度为5%时,NO还原率比没有加入CO时还要低,而在空气气氛下CO浓度的变化对NO的还原率影响较小。     

硝酸镍-硝酸镧基体改进剂石墨炉原子吸收测定硫磺中痕量砷

本文研究了以硝酸镍 硝酸镧为基体改进剂 ,石墨炉原子吸收法测定硫磺中痕量砷 ,还研究了硫磺的控温电热酸消解和高压坩埚酸消解。试验表明 ,硫磺试样经硝酸 高氯酸消解后测砷 ,用硝酸镍 硝酸镧基体改进剂 ,比只用硝酸镍基体改进剂 ,灵敏度明显提高。试样的分析结果与HG ICP AES相吻合 ,方法检出限为0 0 34 μg·mL- 1 ,RSD≤ 2 1% (n =4) ,回收率 97 5 %～ 110 %。     

Quantum Number Dependence of Lineshift Coefficients Induced by Collisions with Noble Gas Perturbers in the nu(3) Band of NO(2)

To complete our study concerning lineshift in the rovibrational spectrum of (14)N(16)O(2), a pulse-driven three-channel lead salt diode laser spectrometer was applied to record high-resolution spectra at room temperature in the 6.2-μm region corresponding to the nu(3) band at low NO(2) concentrations. The shift was studied for collisions with the noble gases He, Ne, Ar, Kr, and Xe. This paper extends our recently published data in order to analyze the quantum number dependence of the shift effect more precisely. Therefore, in this paper, additionally eight unresolved NO(2) doublets covering an enlarged quantum number range (10 相似文献   

14N chemical shifts and quadrupole coupling constants of inorganic nitrates

The isotropic chemical shift and the nuclear quadrupole coupling constant for (14)N were obtained for 14 inorganic nitrates by solid-state MAS NMR measurements at two different field strengths, 9.4 and 11.7 T. The compounds studied were polycrystalline powders of AgNO(3), Al(NO(3))(3), Ba(NO(3))(2), Ca(NO(3))(2), CsNO(3), KNO(3), LiNO(3), Mg(NO(3))(2), NaNO(3), Pb(NO(3))(2), RbNO(3), Sr(NO(3))(2), Th(NO(3))(4)center dot4H(2)O, and UO(2)(NO(3))(2)center dot3H(2)O. Even though the spectra show broadening due to (14)N quadrupole interactions, linewidths of a few hundred hertz and a good signal-to-noise ratio were achieved. From the position of the central peaks at the two fields, the chemical shifts and the nuclear quadrupole coupling constants were calculated. The chemical shifts for all compounds studied range from 282 to 342 ppm with respect to NH(4)Cl. The nuclear quadrupole coupling constants range from 429 kHz for AgNO(3) to 993 kHz for LiNO(3). These data are compared with those available in the literature.     

均相条件下NO与CO、NCO的反应机理研究

基于量子化学密度泛函理论研究了NO与CO、NCO在均相条件下的反应机理并进行了动力学和平衡常数的分析. CO与NO的均相反应存在两条反应路径：两者首先反应形成中间体CNO₂,CNO₂不易稳定存在,其继续与CO、NO反应分别生成NCO、N₂O. NCO的生成速率大于N₂O,但两条反应路径的反应速率常数都很小.与已发现的反应路径相比,反应中间体CNO₂可以降低均相条件下CO与NO的反应能垒,分析发现CNO₂中的N原子是易发生反应的活性位点. NCO与NO的反应同样存在两条路径,优势反应路径随温度升高而改变,但非优势路径对反应的贡献不能忽略,分析平衡常数可知N₂的存在对反应影响可以忽略,因此燃烧环境中NCO与NO的反应既生成N₂O和CO,也生成N₂和CO₂.     

Preliminary results on the effect of power ultrasound on nitrogen oxide and dioxide atmosphere in nitric acid solutions.

The effect of ultrasound (20 kHz, 3 W cm-2) on the kinetics of HNO2 and H2O2 formation was investigated in a 1 M HNO3 medium for NO2-Ar and NO-Ar gas mixtures in various volume fractions (f(NO2) < 1.7 vol% and f(NO) < 1.1 vol%, respectively). The H2O2 formation rate measured in 1 M HNO3 in the presence of N2H5NO3 was observed to be much lower than that of HNO2 without N2H5NO3, and was relatively independent of the NO2 or NO gas volume fractions in the argon atmosphere. The HNO2 formation rate increased under ultrasound, and was higher with NO than with NO2. The induction period observed without ultrasound disappeared when ultrasound was applied. The first step in the sonochemical mechanism of HNO2 formation in the presence of NO2 involves thermal decomposition of NO2 into NO within the cavitation bubble. In the second step of HNO2 formation, NO reacts either with HNO3 in the cavitation bubble, or with NO2 in the cavitation bubble or at the bubble/solution interface.     

Rg·NO(Rg=He、Ne、Ar和Kr)团簇的理论研究

利用从头计算方法研究Rg·NO团簇(Rg=He,Ne,Ar和Kr)．采用CCSD(T)计算方法和cc-PVDZ基组计算中性Rg·NO团簇的的结构和振动频率．计算结果显示，中性的Rg·NO团簇呈现歪斜的T型结构，Rg原子靠近NO分子中O原子的一侧，Rg-N-O键角随质量的增加而增加．利用G2方法和高精度能量模型计算中性Rg·NO团簇基态的离解能和电离能，以及Rg·NO+团簇的离解能．计算结果表明，随着Rg原子极化率的增加，Rg·NO的电离能呈线性降低，而Rg·NO+的解离能呈线性增加， 电荷/诱导的偶极子相互作用对Rg·NO+中的NO+和Rg之间的相互作用能有重要贡献．     

高浓度CO2气氛下燃煤氮、硫污染物的释放特性

采用污染物在线分析仪、气相便携红外分析仪研究了程序升温条件下改变氧化介质时煤中氮,硫的释放特性以及含硫物相的浓度变化规律,探讨了不同气氛,CO2浓度与O2浓度单独变化时对NO、SO2析出特性的影响机理.结果表明:O2/CO2燃烧气氛下NO、SO2排放峰值及总量均低于O2/N2气氛.CO2气氛下烟气中存在大量的CO,有利于NO的降解,同时也促进了烟气中其他含硫物相的形成,随着CO2浓度的增加,特别是在燃烧后期,NO、SO2的排放显著降低.O2浓度改变对NO和SO2的释放影响不同:O2浓度升高促进了SO2的析出;但是O2浓度在一定范围内增加对NO的排放并无明显影响,随着O2浓度进一步增加,NO的释放峰向低温区迁移,同时排放量降低.     

Effects of fly ash on NOx removal by pulsed streamers

NO_x removal methods using plasma chemical reactions in nonthermal plasmas have been widely studied. In this paper, the effects of the addition of fly ash on NO_x removal using short-pulsed discharge plasmas are described. Fly ash which had been collected from a coal-burning thermal electrical power plant was used. Experiments were performed using four different mixtures of gases which included NO. These were (N₂+NO), (N₂+NO+O₂), (N₂+NO+H₂O), and (N₂+NO+O₂+H ₂O). These gas mixtures were used either with or without the addition of fly ash. The initial concentration of NO was fixed at 200 ppm (NO parts per million of the gas mixture), The study of the NO_x (NO+NO₂) removal was performed with the fly ash, as it is relevant to real situations in coal power plants. The results show that the presence of fly ash decreased the NO_x removal rate slightly in the case of dry gas mixtures while it increased the NO_x removal rate substantially in the case of wet gas mixtures. These results suggest that the presence of fly ash in the flue gases, which also contain a few percentages of moisture, would be advantageous to the treatment of flue gases emitted from thermal power plants for the removal of nitrogen oxides     

NO（D^2∑）共振增强的多光子离化谱

利用皮秒Nd：YAG激光器泵浦的光学参量发生傲大器作激发源，获得了NO分子在460～570nm波长范围内的多光子离化谱，测量了离化信号随激光强度的关系，其近五次方关系表明在460～570nm波长范围内NO分子吸收5个光子而离化。通过对谱线的归属，确认在此波长范围内，NO分子的离化过程是通过高激发态D^2∑的共振增强的多光子离化过程。用最小二乘法拟合，获得了D^2∑态的基振动频率和相互作用的力常数。     

新型Schiff碱双核铜配合物与DNA相互作用的光谱研究

研究了在pH5.3的醋酸-醋酸钠缓冲体系中,四甘醇醛缩苯丙氨酸Schiff碱与铜的双核配合物([Cu2L(NO3)]NO3)与DNA作用的情况.结果表明[Cu2L(NO3)]NO3在此体系下具有较强的荧光,DNA加入后对其荧光有一定的敏化作用.探讨了造成此种现象的可能原因,并推导了该二元体系的结合常数.     

低温等离子体分解N2/O2/NO气氛中NO试验研究

利用自行设计的介质阻挡放电型低温等离子体反应器,研究了NO初始浓度、O₂初始浓度、放电功率、电源频率等因素对NTP转化N₂/O₂/NO气氛中NO的影响规律。研究发现,NO去除率随功率增大而升高,到达一最大值后随功率增大而降低;NO去除率随O₂初始浓度增加而降低,随NO初始浓度增大而减小。相同放电功率下,同一组分中NO去除率随电源频率的增加而降低,因此相同放电功率下降低电源频率可提高NO去除率。O₂初始浓度不高于5%时,NO_x大部分为NO,NO₂和O₃浓度均随放电功率增大而降低,NO₂、O₃生成量随O₂初始浓度升高而增多。     

脉冲电晕放电脱除NO化学反应动力学过程

采用非接触的色散荧光发射光谱和时间分辨光谱方法,在大气压条件下,对脉冲电晕放电脱除NO的化学反应动力学过程进行了实验研究。在该研究中,首先利用色散荧光发射光谱方法,得到纯NO气体脉冲电晕放电中各活性粒子的色散荧光谱,并对其进行归属,确定了各活性粒子的灵敏指纹跃迁谱线;在此基础上,通过测量NO气体放电过程中所产生的N+,O,N₂及NO分子的灵敏指纹跃迁谱线的时间行为特性,研究脉冲电晕放电脱除NO的化学反应机理。实验结果表明：在脉冲电晕放电过程中,NO分子首先与高能电子发生非弹性电离碰撞,变成NO+离子,随后NO+离子发生解离反应,形成N+离子和O原子;N+离子在向阴极运动过程中与电子碰撞结合成激发态N原子,继而和其他激发态N原子结合成为激发态N₂;而O原子则应与其它O原子结合成为O₂。由此建立了大气压条件下纯NO气体脉冲电晕放电脱除NO的化学反应动力学模型。     

NO2分子高灵敏度痕量探测技术研究

 搭建了一台基于蓝光LED的非相干宽带腔增强吸收光谱系统,并将其应用于NO2分子的高灵敏度痕量探测研究。在3 s采样时间下, 系统探测灵敏度为3.2×10-9 cm-1（1 σ）,对应NO2的探测极限约为187 pmol/mol。利用Allan方差对系统最佳采样时间及系统稳定性进行分析,当采样时间延长至30 s时,系统的探测极限可提高至44 pmol/mol。将该系统应用于实际大气中NO2的连续测量,其测量结果与商业化NOx分析仪（Thermo 42i）进行了比对测试。     

循环流化床煤燃烧中氮氧化物排放的研究

循环流化床煤燃烧中氮氧化物排放的研究冯波，袁建伟，刘皓，卢建欣，林志杰，刘德昌（华中理工大学动力系武汉４３００７４）关键词循环流化床，氮氧化物１前言近年来，ＮＺＯ由于对臭氧层的破坏作用和一定的温室效应而引起了较大的关注。特别地，在流化床煤燃烧中（包括...     

傅里叶红外光谱法研究AP的快速热分解

用T-Jump/FTIR联用技术研究了模拟燃烧条件下AP的快速热裂解。在不同压力的高纯氮气条件下,以1000K.s-1的升温速率达到设定的温度(874和1274K)快速分解,用快速扫描傅里叶变换红外光谱原位实时分析分解产物的种类和浓度变化。结果表明,AP热裂解主要气相产物为NO2,N2O,NO,HCl和NOCl等,实验温度和压力都使AP快速热裂解气相产物N2O/NO2,NO/NO2和NO/NOCl的比值提高,因此认为AP不但存在凝聚相和非均相的气相/凝聚相反应,而且还有主要气相产物之间的"后续反应"。     

Influences of water vapor and fly ash addition on NO and SO2 gas conversion efficiencies enhanced by pulsed corona discharge

The NO and SO₂ gas conversion processes in a pulsed corona discharge field have been studied. The experiments were conducted to investigate the influences of water vapor and fly ash addition on the conversion efficiencies of NO and SO₂. Experimental results show that positive pulsed corona discharge can facilitate NO and SO₂ conversion processes, and the conversion efficiencies of NO and SO₂ are primarily dependent on the radicals OH, O and the active species O₃, HO₂, H₂O₂, etc. With water vapor addition, SO₂ conversion efficiency is improved, but NO conversion process is restrained. Low fly ash concentration helps to enhance the conversion of NO and SO₂; however, the conversion efficiencies of NO and SO₂ are drastically degraded by high fly ash concentration addition. The synergistic effects of water vapor and fly ash addition strengthen the chemical adsorption ability of the fly ash surface, which results in a considerable improvement in the conversion of NO and SO₂. Furthermore, the specific input energy plays an important role in NO and SO₂ conversion efficiencies. Measured conversion efficiencies of NO and SO₂ reach about 60% and 90%, respectively, under the conditions tested.     

Measurement of nitric oxide concentrations in flames by using electronic-resonance-enhanced coherent anti-Stokes Raman scattering

We have measured nitric oxide (NO) concentrations in flames by using electronic-resonance-enhanced coherent anti-Stokes Raman spectroscopy (ERE-CARS). Visible pump and Stokes beams were tuned to a Q-branch vibrational Raman resonance of NO. A UV probe beam was tuned into resonance with specific rotational transitions in the (v"=1,v'=0) vibrational band in the A(2)Sigma(+)-X(2)Pi electronic transition, thus providing a substantial electronic-resonance enhancement of the resulting CARS signal. NO concentrations were measured at levels down to 50 parts in 10(6) in H(2)/air flames at atmospheric pressure. NO was also detected in heavily sooting C(2)H(2)/air flames at atmospheric pressure with minimal background interference.