CO2及其碳同位素比值高精度检测研究

改进了一种基于傅里叶变换红外光谱法测量CO₂气体的装置, 改进后的装置能够提高CO₂检测精度, 并能同时测量CO₂碳同位素比值. 研究了温度和压力对CO₂浓度值和CO₂碳同位素比值测量的影响规律. 利用该装置连续测量了标准CO₂气体和环境大气, 对标准CO₂气体测量得到的CO₂浓度值及其碳同位素比值进行温度和压力影响修正, 获得了较好的精度和准确度. 关键词： 光谱学 同位素比值 傅里叶变换红外光谱 二氧化碳     

2μm波段高灵敏度离轴积分腔装置实际大气CO2测量

利用分布反馈式(DFB)二极管激光器为光源, 搭建了一套2 μm波段的离轴积分腔输出光谱装置. 利用高纯甲烷气体, 测量了腔镜反射率随腔内气体压力 变化的规律. 当腔内压力为3.59 kPa 时, 标定的镜面反射率为0.99865, 在此条件下, 基长55 cm 的离轴积分腔实现了407.4 m的吸收光程. 选取CO₂ 在4993.7431 cm^-1处的吸收谱线对实际大气中的CO₂浓度进行了测量, 探测限为0.53 ppmv (1σ), 利用小波去噪对光谱信号进行了去噪处理, 信噪比提高了80%, 探测限提高到0.29 ppmv(1σ). 利用搭建的装置在实验室内测量了从上午9时到中午12时实际大气中CO₂的浓度, 并与H₂O/CO₂分析仪进行了同时观测与对比分析, 初步验证了测量装置的可靠性.     

基于傅里叶变换红外光谱法CO2气体碳同位素比检测研究

介绍了基于傅里叶变换红外技术检测CO₂气体碳同位素比的新方法, 详细介绍了如何从HITRAN红外数据库中提取气体标准吸收截面; 介绍了基于非线性最小二乘法反演CO₂气体碳同位素比和整套实验装置的组成及实验步骤. 从理论和实验分析两方面讨论了温度和气压变化对δ¹³CO₂值的影响规律. 对于同一CO₂标准气体, 采用FTIR和同位素质谱法两种技术进行了δ¹³CO₂值对比检测, 两种测量技术的平均值差异仅为0.25%. 从实验结果可以看出, FTIR技术可以实现对CO₂气体碳同位素比的检测.     

V2CO2MXene从CO2/N2混合气体中选择性吸附CO2的第一性原理计算

二氧化碳作为温室气体中最重要的组成部分,其含量的变化将直接影响全球气候变化,在燃烧后气体中选择性捕获CO₂,对减缓因CO₂浓度过高引发的环境问题具有十分重要的意义.本文采用第一性原理计算的方法,研究了V₂CO₂ MXene材料对CO₂的选择性吸附性能.首先研究了不同官能团V₂CT_X MXene材料的结构和性质,发现V₂CO₂具有良好的稳定性.后研究了V₂CO₂对CO₂的吸附行为,结果表明,当CO₂被水平吸附时,V₂CO₂对CO₂气体分子的吸附能力较强且均满足在高性能吸附剂表面吸附CO₂的理想值(-0.42 eV-0.82 eV),可以适用于探测/捕获CO₂气体分子.此外,进一步研究了相同条件下V<...     

出口雷诺数对平面射流自保持性的影响

通过实验研究出口雷诺数对平面湍流射流自保持性的影响. 测量的射流来自相同的喷嘴但不同的雷诺数Re（≡U_jh/ν,其中U_j是出口平均速度、h是窄缝出口的厚度和ν是黏性系数）,其变化范围是Re=4582—57735.所得的数据包括沿轴线的平均速度、湍流强度、积分尺度、高阶矩和能谱. 实验发现,随着Re的增大,平面射流发展减慢,平均速度和湍流强 关键词： 平面射流 雷诺数 自保持性     

地基CO2廓线探测差分吸收激光雷达

研制了一台利用气溶胶散射信号的CO₂廓线探测差分吸收激光雷达. 系统利用染料激光器实现波长调制, 采用双光路气体吸收池, 结合Voigt拟合方法实现了脉冲红外激光的高精度定标. 针对输出激光带宽较宽的问题, 采取仿真实验评估了影响, 并设计了基于吸收池的订正因子获取方案. 进而, 开展了水平、垂直和连续观测实验, 通过与地面CO₂分析仪测量值的对比, 证明了系统具备优越的精密性和精确性. 实验表明, 该样机能够俘获CO₂浓度随高程和时间变化而产生的变化.     

黄绿色菱锌矿玉的谱学特征及颜色成因初探

菱锌矿颜色丰富,有黄色、蓝色、粉色、绿色等,矿物学特征及谱学特征的研究较少,对其不同颜色的成因认识亦不明确。选取黄绿色菱锌矿玉,利用X射线粉晶衍射仪、电子探针、激光剥蚀电感耦合等离子体质谱仪、傅里叶红外变换光谱仪、拉曼光谱仪、紫外-可见分光光度计、电子顺磁共振仪等分析显示,样品为纯净的菱锌矿,主要成分为ZnO,其平均含量为61.3%,次要成分有CaO,FeO,MnO,CdO及PbO。样品中含有微量过渡金属元素Fe和Mn,平均含量分别为7 363.5×10-6和3 558×10-6。样品在740,883和1 490 cm-1处出现菱锌矿的特征吸收带,740 cm-1归属于[CO₃]2-的面内弯曲振动单峰,883 cm-1属于[CO₃]2-的面外弯曲振动峰,1 490 cm-1处的强吸收谱带为[CO₃]2-反对称伸缩振动所致。拉曼谱有300,728和1 091 cm-1等方解石族特征峰,300 cm-1归属于ZnO对称伸缩振动,728 cm-1归属于[CO₃]2-面内弯曲振动,1 091 cm-1归属于[CO₃]2-对称伸缩振动。综合分析认为,Fe3+的6A₁→4E(D)跃迁、6A₁→4T₂(D)跃迁、Mn2+的d电子跃迁产生的紫外-可见光谱377,395和417 nm附近的吸收带是样品产生黄绿色的原因。EPR谱也显示出g=2.0左右的Mn2+的特征六重超精细共振谱线和g=1.98左右的Fe3+的特征谱线。结合样品成分和吸收光谱等特征,可以认为菱锌矿玉样品的黄绿色是由Fe3+和Mn2+的d—d轨道电子跃迁共同导致。     

基于频域吸收峰标定气体浓度的检测方法

传统的光学气体检测方法需要将时域信号转换为频域信号,从而获得气体的浓度。这种方法在转换过程中会引入误差,无法准确反映频率随时间的变化,造成气体浓度不能准确标定。提出一种基于频域吸收峰标定气体浓度的检测方法。以CO₂为例进行检测,利用基于BeerLambert定律的直接吸收法对CO₂和N₂的混合气体中CO₂的浓度进行测定。此方法通过采集激光束的光强和频率信息,并使用相邻平均法和Levenberg-Marquardt(LM)优化算法进行Lorentz拟合获得吸收光谱峰值强度。实验结果表明：激光峰值强度与气体浓度之间满足线性关系,Pearson相关系数可达0.999。因此,基于频域吸收峰标定气体浓度的检测方法可有效简化系统结构,避免时域到频域转换中频率漂移的影响,使得激光峰值强度与气体浓度之间线性度良好。     

长光程共振式二氧化碳气体光声传感器研究

二氧化碳(CO₂)是植物光合作用的原材料,也是一种温室气体,其过量地排放会影响动植物的生态环境。在碳达峰、碳中和的背景下,研制高灵敏度的CO₂检测装置具有重要意义。为了监测大气环境中CO₂含量的变化,设计了一种长光程共振式CO₂气体光声传感器,并以此搭建了光声检测装置。以中心波长为2 004 nm的分布式反馈激光器(DFB)作为激发光源,激光射入由漫反射材料制成的球型吸收腔,在腔内多次反射以增加气体的吸收路径。吸收腔外部被两个高热传导率的铝制半球包裹,降低由池体吸收光能后产生的热噪声。吸收腔上耦合一根声学管,当其工作在一阶纵向共振模态时,光声信号被放大,在管子末端达到极大值。为了进一步增大光声信号,通过饱和加湿样品的方式来加快CO₂气体的弛豫速率,加湿后的样品产生的光声信号是干燥样品的2.1倍左右。使用一系列浓度的湿润CO₂样品标定光声检测装置,结果表明,光声信号与浓度之间呈现良好的线性关系。在此基础上,通过对标准气体的检测实验,验证了装置的准确性与稳定性...     

基于TDLAS技术的海水中溶存CO2原位测量实验研究

海洋与大气交换的CO₂通量是研究海-气之间碳循环过程及海洋酸化问题的重要指标,其估算方法主要依赖于海水中CO₂的测量。可调谐半导体激光吸收光谱（TDLAS）作为一种常用的气体浓度检测技术,因其具有较好的环境适应性、选择性和较高的灵敏度,亦可发挥出水中溶存气体原位测量的潜力。为验证将TDLAS技术应用到海洋中溶存CO₂原位探测的可行性,将渗透膜脱气技术与实验室研发的TDLAS气体探测样机相结合,实现了海水中溶存CO₂的原位探测。为适应水下的复杂环境,样机整体被设计为铝合金密封舱结构,具有良好的密封性、耐压性与耐腐蚀性。激光光源采用中心波数位于4 990 cm-1的DFB激光器,其波数扫描范围为4 992～4 994.5 cm-1,可覆盖CO₂在4 992.51和4 993.74 cm-1的相邻两条吸收谱线。渗透膜采用具有优秀耐压性与透气性的Teflon AF-2400 X,可满足样机在深水区长期探测的目的。为兼顾较高探测灵敏度与较快响应速率双重指标要求,样机采用了一种小型化多次反射式气体吸收池,有效吸收光程可达8 m,内部仅需气体量24 mL,具有良好的吸收特性。在实验室对样机进行校正实验,使用样机对5种不同浓度(202.8×10-6,503×10-6,802×10-6,1 006×10-6和2 019×10-6)的标准CO₂气体进行测量,测量值与实际值的线性相关度R2高达99.94%,最大相对误差小于8%,减小了样机误差对测量值的影响。为评估样机长时间工作的稳定性,使用样机对浓度为802×10-6的标准CO₂气体进行了30 min的连续测量,平均测量浓度为802.6×10-6,其波动范围仅为10×10-6,样机精度约为0.5%,可满足水中溶存气体探测的要求。选取水深3米的近海码头进行试验,成功获得了24 h水中CO₂的典型吸收光谱及浓度时间序列测量结果,验证了样机水下工作的能力与稳定性。通过在东海海域五处不同深度的区域进行现场试验,成功获取溶存CO₂的典型吸收光谱,证明了结合渗透膜脱气技术的TDLAS探测样机在30 m以浅水域的工作适应性。     

CaO高温分离CO2过程的数值模拟

钙基吸收剂煅烧-碳酸化循环法(CCRs)是一种新兴的分离燃煤锅炉尾部烟气中CO2的方法.CaO与CO2碳酸化反应对于CCRs法的应用起着非常重要的作用.本文采用随机孔隙模型(RPM)对CaO与CO2碳酸化反应过程进行了研究,结果表明,适当提高CaO与CO2碳酸化反应的温度和系统压力,增加CaO吸收剂的初始孔隙率、优化CaO的初始比表面积等措施能够有效提高CaO碳酸化转化率和对CO2的吸收容量.     

The Ca-looping process for CO<Subscript>2</Subscript> capture and energy storage: role of nanoparticle technology

The calcium looping (CaL) process, based on the cyclic carbonation/calcination of CaO, has come into scene in the last years with a high potential to be used in large-scale technologies aimed at mitigating global warming. In the CaL process for CO₂ capture, the CO₂-loaded flue gas is used to fluidize a bed of CaO particles at temperatures around ~?650 °C. The carbonated particles are then circulated into a calciner reactor wherein the CaO solids are regenerated at temperatures near ~?950 °C under high CO₂ concentration. Calcination at such harsh conditions causes a marked sintering and loss of reactivity of the regenerated CaO. This main drawback could be however compensated from the very low cost of natural CaO precursors such as limestone or dolomite. Another emerging application of the CaL process is thermochemical energy storage (TCES) in concentrated solar power (CSP) plants. Importantly, carbonation/calcination conditions to maximize the global CaL-CSP plant efficiency could differ radically from those used for CO₂ capture. Thus, carbonation could be carried out at high temperatures under high CO₂ partial pressure for maximum efficiency, whereas the solids could be calcined at relatively low temperatures in the absence of CO₂ to promote calcination. Our work highlights the critical role of carbonation/calcination conditions on the performance of CaO derived from natural precursors. While conditions in the CaL process for CO₂ capture lead to a severe CaO deactivation with the number of cycles, the same material may exhibit a high and stable conversion at optimum CaL-CSP conditions. Moreover, the type of CaL conditions influences critically the reaction kinetics, which plays a main role on the optimization of relevant operation parameters such as the residence time in the reactors. This paper is devoted to a brief review on the latest research activity in our group concerning these issues as well as the possible role of nanoparticle technology to enhance the activity of Ca-based materials at CaL conditions for CO₂ capture and energy storage.     

Sintering mechanism of CaO during carbonation reaction in the presence of water vapor

In this paper, CaO sintering in the presence of water vapor for CO₂ capture were carried out by ReaxFF(Reactive Force Field) molecular dynamics. The CaO sintering model was simulated at different temperatures (873 K-1273 K) and atmospheres (CO₂, H₂O), respectively. The results showed that water vapor could significantly promote the sintering process of CO₂ capture by CaO. The Mean-square displacement (MSD) and Boltzmann–Arrhenius dependency were used to study the diffusion properties of CaO particles. The decreased diffusion activation Ea and increased pre-exponential factor D₀ indicate that CaO particles have a stronger initial diffusivity and a lower diffusion barrier in the presence of CO₂ and H₂O. The inner and outer regions of CaO atoms were analyzed and it was found that the activation energy is the main factor to enhance the diffusion in the presence of CO₂ for CaO sintering process, whereas the pre-exponential factor dominates with both CO₂ and H₂O. Water vapor enhanced the sintering pf CaO carbonation reaction is mainly achieved by promoting atoms in the inner layers of CaO particles. The types and numbers of sintering atoms during the sintering process were counted, and the distances between Ca and O atoms were calculated, which found that water vapor first dissociates into hydroxyl and H protons on the CaO surface, and the hydroxyl group will stay on the surface of CaO and combine with CO₂, while the H proton will combine with O inside CaO to promote the sintering of CaO further.     

新型CaO／MgO高温CO2吸收剂的循环反应特性

本文采用3种方法制备了新型复合CaO／MgO吸收剂，考察了不同制备方法对复合钙基吸收剂碳化／煅烧循环反应性能的影响。结果表明，不同制备方法能决定了钙基吸收剂中CaO颗粒与MgO颗粒在微观层面上的不同均匀混合程度，因此得到吸收剂的性能差异巨大。采用溶胶凝胶燃烧合成法制备的CaO／MgO吸收剂的性能明显优于其他两种常见方法...     

CaO脱硫化学反应速率与气体扩散速率对比

区分氧化钙脱硫反应中的化学反应动力学速率与二氧化硫、氧气分子的扩散速率是一个难题。通过系列样品的TGA实验,在简化假设的基础上找到了CaO颗粒脱硫反应中的化学反应动力学速率与二氧化硫、氧气分子的扩散速率的变化规律。实验结果表明:化学反应速率和二氧化硫、氧气分子的扩散速率随着反应温度的上升、脱硫剂颗粒粒径的降低和氧化钙纯度的提高而提高。适当提高脱硫反应温度、最大限度地降低颗粒粒径是提高氧化钙脱硫反应速率的主要措施。     

Aggregation modeling of calcium carbonate particles by Monte Carlo simulation

The mechanism on aggregation of spindle granular particles of calcite was investigated for the carbonation of calcium hydroxide in aqueous suspension for the purpose of controlling morphology of CaCO₃. The experimental carbonation process was carried out in a semi-batch bubble column reactor under different conditions. Although, fine rhombic nano-particles diameter ranged from 100 to 200 nm were obtained at 291 K, a higher temperature of 300 K provided spindle granular particles with a length of 1.0–1.5 μm and a width of 0.3–0.5 μm. The average crystallite size was 28 nm for the fine rhombic nano-particles and 43 nm for the spindle granules. Zeta potential measurement for the spindle granules indicated that the suspension tended to be aggregated during the carbonation process. The effect of the degree of particle aggregation on the shape of the obtained calcite particles was studied by Monte Carlo simulations. Our simulation results elucidated the dependence of aggregation on unit particles, i.e., primary particles, on the experiment carbonation condition where the spindle granules were formed out of the unit particles under the same condition as the experiments. In addition, the formation mechanism of the granules was investigated by applying classical nucleation theory to the present simulations.     

Cellular automaton model of precipitation/dissolution coupled with solute transport

Precipitation/dissolution reactions coupled with solute transport are modeled as a cellular automaton in which solute molecules perform a random walk on a regular lattice and react according to a local probabilistic rule. Stationary solid particles dissolve with a certain probability and, provided solid is already present or the solution is saturated, solute particles have a probability to precipitate. In our simulation of the dissolution of a solid block inside uniformly flowing water we obtain solid precipitation downstream from the original solid edge, in contrast to the standard reaction-transport equations. The observed effect is the result of fluctuations in solute density and diminishes when we average over a larger ensemble. The additional precipitation of solid is accompanied by a substantial reduction in the relatively small solute concentration. The model is appropriate for the study of the role of intrinsic fluctuations in the presence of reaction thresholds and can be employed to investigate porosity changes associated with the carbonation of cement.     

CaO表面CO对NO还原作用的实验与模型研究

循环流化床炉内石灰石脱硫对NOx排放产生影响,包括对挥发分氮氧化的催化作用以及对CO-NO还原的催化作用。利用固定床反应器对不同条件下CaO颗粒表面NO+CO的催化反应特性进行了探究。实验表明,无氧条件下,CaO能够显著催化CO还原NO,NO转化率与反应温度和CO浓度正相关,与NO浓度负相关.基于Langmuir-Hinshelwood机理建立了CaO催化NO+CO反应动力学模型,模型考虑了颗粒内、外扩散的影响.该模型适用于氧气浓度很低、CO浓度较高条件下。而在有氧气氛中,该反应受到明显抑制,且O2浓度越高,抑制作用越明显;当CaO周围氧气浓度远大于CO时,可忽略CaO对NO的催化还原作用。     

炉内喷钙脱硫过程数值模拟

建立了一套较为完整的对炉内喷钙脱硫过程进行模拟的方法，获得了炉内气固两相流动、温度分布、石灰石颗粒脱硫化学反应和SO2浓度分布的详细情况。石灰石颗粒的硫化反应主要发生在颗粒与烟气均匀混合之前。     

Nucleation of CaCO3 polymorphs from a colloidal alcoholic solution of Ca(OH)2 nanocrystals exposed to low humidity conditions

A study of the stability of calcium carbonate polymorphs formed as a result of the carbonation process from an alcoholic colloidal solution of nanocrystals of Ca(OH)₂ in low relative humidity (RH) conditions (33% and 54% RH) is presented in this research. The crystalline behavior, the time dependence of nucleation and the phases’ transformations as a result of exposure to low humidity conditions are evaluated. The carbonation process is slow, starting with the nucleation of amorphous calcium carbonate, associated to an amorphization process that affects both the portlandite (Ca(OH)₂) and the initial unstable CaCO₃ polymorphs. The excess of alcohol in the solution decreases the surface tension and the nucleation is accelerated by the fast evaporation of the solvent, which avoids the particles to diffuse to their lowest energy sites, giving smaller particles with lower crystallinity as RH decreases.