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一种近红外光谱定量分析软件预测性能评价方法

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光谱学与光谱分析 2025年第1期45卷 213-221页

作者：李蓉郝璐袁洪福何桂梅邓天龙杜彪龚丽岳欣天津科技大学海洋与环境学院天津300457 天津市滨海新区环境创新研究院天津300457 中国环境科学研究院北京100012 北京易兴元石化技有限公司北京101300 中国石油大学(北京) 北京102249

常用的多元分析模型评价指标尚缺乏评价近红外分析软件多项重要预测性能指标的能力,成为近红外光谱仪预测性能以及实际近红外应用中模型适用性评价的痛点。为此,旨在发展一种近红外定量分析软件预测性能的评价方法。以近红外测定汽油烯... 详细信息

常用的多元分析模型评价指标尚缺乏评价近红外分析软件多项重要预测性能指标的能力,成为近红外光谱仪预测性能以及实际近红外应用中模型适用性评价的痛点。为此,旨在发展一种近红外定量分析软件预测性能的评价方法。以近红外测定汽油烯烃浓度为研究对象,收集了192个国Ⅵ汽油样品,包括92#、95#和98#;采集其近红外光谱;按照GB/T 30519-2014测定其烯烃浓度作为参考值,分别使用两种不同的多元分析软件(1种是偏最小二乘(PLS)建模软件,另1种是非PLS的软件),建立了两个校正模型。研究发现,与参考值相比,PLS模型对低浓度样品预测值呈正偏差,高浓度的呈负偏差,即“均值化”现象。常用的模型预测性能评价指标尚不能评价模型预测值的均值化程度,也不能评价:(1)预测值与参考值偏差大于参考方法再现性的样本占比,(2)模型泛化能力。本文针对上述问题,提出了4项新评价指标包括均值化指数(AE)、预测偏差超限值样本占比(Ratio)、异常样本预测偏差(DAS)和孤立样品预测偏差(DIS)。综合常用的评价指标和新评价指标(共12项),对仪器选型的近红外光谱定量分析软件预测性能的评价、实际近红外分析应用中模型适用性的评价均具有实际意义,对近红外分析学术研究也具参考意义。

关键词：近红外光谱多元分析模型评价近红外分析软件评价汽油烯烃浓度

Isothermal Evaporating Phase Equilibria in the Quaternary System （LiCl+NaCl+Li2SO4+Na2SO4+H2O） at 348.15 K and 0.1 MPa: An Experimental and Theoretical Study

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盐湖研究 2019年第2期27卷 69-77页

作者： GUO Ya-fei YUAN Fei LI long WANG Shi-qiang deng tian-long College of Marine and Environmental Sciences Tianjin University of Science and Technology Tianjin 300457 China tianjin Key Laboratory of Marine Resources and Chemistry Tianjin 300457 China

The gradient solar pond technique is an economic separating process employed in the inorganic chemical industrial production of salt lake chemical engineering processes. In this paper, a novel isothermal evaporation experimental method was employed to simulate the evaporation phase equilibrium for the reciprocal quaternary system (LiCl+NaCl+Li2SO4+Na2SO 4+H2O) at 348.15 K to serve as a useful guide for lithium salt production via the depth solar *** isothermal evaporation equilibrium solubilities and physicochemical properties,including the densities and pH values, were experimentally investigated. The dry-salt phase diagram,water-phase diagram, and the diagram of the physicochemical properties versus composition were plotted with respect to the experimental data. The dry-salt phase diagram consists of three invariant points,seven univariant solubility curves, and five crystallization regions, specifically halite(NaCl,Ha),thenardite (Na2SO4,Th),double salt (Li2SO4 · Na2SO4 , Db2), lithium sulfate monohydrate (Li2SO4 ·H2O, Ls), and lithium chloride monohydrate(LiCl·H2O, Lc). Based on Pitzer and its extended HMW model, the Pitzer single salt parameters, mixing ion interaction parameters, and thermodynamic stable equilibrium constants for the quaternary system at 348.15 K were obtained. The calculated phase diagram and experimental isothermal phase diagram at 348.15 K exhibited a great difference. Based on these results, the isothermal evaporation phase diagram can truly reflect the salt sedimentary in salt lakes and can be applied as a useful guide for the solar pond process.

关键词： Phase diagram Solubility Lithium chloride Lithium sulfate Pitzer model

308.15K下MgB_4O_7-H_2O体系热力学性质研究

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高校化学工程学报 2016年第5期30卷 1007-1013页

作者：戈海文邓天龙姚燕中国科学院青海盐湖研究所青海西宁810008 天津市海洋资源与化学重点实验室(天津科技大学) 天津300457

采用等温溶解法对章氏硼镁石(MgB_4O_7-9H_2O)在纯水中溶解及转化进行研究,结果表明章氏硼镁石在308.15K下稳定存在12 h,溶解度为0.04813 mol×kg^(-1);12 h后,平衡固相向多水硼镁石(Mg_2B_6O_(11)·15H_2O)转化。根据文献的化学平衡常... 详细信息

采用等温溶解法对章氏硼镁石(MgB_4O_7-9H_2O)在纯水中溶解及转化进行研究,结果表明章氏硼镁石在308.15K下稳定存在12 h,溶解度为0.04813 mol×kg^(-1);12 h后,平衡固相向多水硼镁石(Mg_2B_6O_(11)·15H_2O)转化。根据文献的化学平衡常数以及实验pH值,计算液相中硼酸根离子摩尔分数在溶解转化过程中变化规律,并给出溶液中可能存在的反应及其相应的机理。采用等压法研究了308.15 K下MgB4O_7-H_2O体系离子强度为0.1066~0.2680 mol×kg^(-1)的等压平衡浓度和水活度,计算了渗透系数及饱和蒸汽压,获得了该体系渗透系数和饱和蒸汽压随离子强度的变化规律;应用Pitzer离子相互作用模型,对实验数据进行多元线性回归,得到308.15 K下MgB_4O_7-H_2O体系的纯盐参数β(0)、β(1)、β(2)和Cφ分别为39.3990、-61.5421、655.1369、-86.0430,标准偏差为0.00723。Pitzer离子相互作用模型计算的渗透系数值与实验结果一致,这对完善含镁、硼盐湖卤水体系的热力学模型具有重要意义。

关键词： MgB4O7-H2O体系相转变等压法渗透系数 Pitzer模型

抗坏血酸-磺胺增效氢化物发生-原子荧光光谱法测定土壤中镉

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分析化学 2010年第4期38卷 542-546页

作者：赖冬梅邓天龙成都理工大学材料与化学化工学院天津科技大学海洋科学与工程学院

建立了一种用抗坏血酸-磺胺双络合体系进行氢化物原子荧光光谱法测定土壤中镉的新方法。研究了抗坏血酸-磺胺双络合体系对方法的增效作用,以及Ni2+对测定的显著增感作用;探讨了氢化物发生的反应机理,并应用核磁共振仪对机理进行实验验... 详细信息

建立了一种用抗坏血酸-磺胺双络合体系进行氢化物原子荧光光谱法测定土壤中镉的新方法。研究了抗坏血酸-磺胺双络合体系对方法的增效作用,以及Ni2+对测定的显著增感作用;探讨了氢化物发生的反应机理,并应用核磁共振仪对机理进行实验验证。该方法测镉的最佳条件为:以3%HCl为载流,20g/LKBH4溶液为还原剂,在0.05%抗坏血酸+0.05%磺胺双络合试剂+0.1mg/LNi2+体系中,镉的线性范围为2～40μg/L,相关系数(r)0.9993,检出限为0.08μg/L,RSD<4.8%(n=14)。应用本方法测定了4种国家土壤标准物质中镉的含量,结果与标准值吻合。

关键词：镉增效剂氢化物发生原子荧光光谱土壤

Solid-Liquid Phase Equilibria in the Aqueous System Containing Potassium,Magnesium,and Borate at 308.15 K

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盐湖研究 2019年第2期27卷 78-84页

作者： SHI Chun-cheng YANG Juan WANG Shi-qiang ZHAO Dong GUO Ya-fei deng tian-long College of Marine and Environmental Sciences Tianjin University of Science and Technology Tianjin 300457 China tianjin Key Laboratory of Marine Resources and Chemistry Tianjin 300457 China

Experimental studies on the solubility, density, refractive index, and pH value in the aqueous system containing potassium, magnesium, and borate at 308.15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results, the diagrams of solubility, density, refractive index, and pH value in this system were plotted. We found that there were one eutectic point and two crystallization regions corresponding to the large area of inderite (L + Mg2B6O11·15H2O) and the relatively small area of potassium borate tetrahydrate (L + K2B4O7 ·4H2O), respectively. Neither double salt nor solid solution was found in this system. The physicochemical properties (density, refractive index, and pH value) in solution at 308.15 K changed regularly with increasing potassium borate concentration. The calculated values of density and refractive index using empirical equations of the aqueous system were in good agreement with the experimental values.

关键词： Stable phase equilibrium Phase diagram Solubility Physicochemical property

四元交互体系Li^+,K^+/Cl^-,CO_3^(2-)-H_2O在298K时相平衡及物理化学性质研究

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高等学校化学学报 2000年第10期21卷 1572-1574页

作者：邓天龙殷辉安唐明林成都理工学院应用化学系成都610059

Zabuye Saline Lake, Tibet, China, is unrivalled in the world for its very high salinity, in particular, for the very high concentration of ions of lithium, potassium, and boron in the brine. It belongs to alkaline and carbonate borate type salt lake. As a part of the study on phase equilibrium of the 6 component subsystem Li +, Na +, K +/Cl -, CO 2- 3, B 4O 2- 7 H 2O of the brine system, a study on the reciprocal quaternary system Li +, K +/Cl -, CO 2- 3 H 2O at 298 K was done with isothermal dissolution equilibrium method in the present work. The phase equilibrium of the reciprocal quaternary system Li +, K +/Cl -, CO 2- 3 H 2O at 298 K was studied with isothermal dissolution method in this work. The physico chemistry properties of the corresponding equilibrium solutions such as densities, viscosities, refractive index, conductivities and pH value were determined. The dried salt diagram of the system consists of four crystallization fields (KCl, Li 2CO 3, LiCl·H 2O, K 2CO 3·3/2H 2O) and five isothermal solubility curves. There are no double slat or solid solution found. Pitzers model of the electrolyte solution theory was used for parameterization from the results of solubility determination for subsystems and the prediction of solubilities for the reciprocal quaternary system was made. The solubility data of the experiment are in agreement with those calculated. [WT5HZ]

关键词：水盐体系溶解度相平衡 Pitzer模型

Determination of Lithium in High Salinity Samples by Inductively Coupled Plasma Optical Emission Spectrometry(ICP-OES)

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Determination of Lithium in High Salinity Samples by Inducti...

中国化学会第七届全国热分析动力学与热动力学学术会议

作者： HAN Tao YU Xiao-ping GUO Ya-fei LI Ming-li DUO Ji deng tian-long College of Chemical Engineering and Materials Science Tianjin University of Science and Technology Central Laboratory of Geological Mineral Exploration and Development Bureau of Tibet Autonomous Region

Lithium is an important strategic metal and new energy material,and its development and utilization attract extensive attention *** are huge amount of lithium resources in high salinity brines especially in salt lake and underground *** is necessary to accurately determine lithium content during the development of these ***,high concentrations of Na,K,Caand Mgin brines will result in serious interference with the determination of trace *** coupled plasma optical emission spectrometry (ICP-OES) has the ability of multi-element simultaneous analysis with wide linear *** order to realize swift and accurate determination of lithium in brines,the analysis of lithium in high salinity samples by ICP-OES was carried out in detail in this *** showed that lithium has a higher signal to noise ratio at 610.364 nm,where no obvious spectral line interferences of Na,K,Ca,Mgand argon were presented for the determination of ***,large amount of Na,Kand Mgcoexisting in the high salt brine samples would lead to positive matrix interferences,while the Cacaused negative *** internal standard method which is widely used to eliminate matrix interferences could not effectively solve this problem using whether yttrium or scandium as an internal standard *** the standard addition method involves complex operations and is not suitable for batch sample analysis,while the matrix matching method must match these interfering components with corresponding ions and thus is not suitable for the analysis of batch samples with different matrix compositions,the feasibility to match complex matrix with a single component was investigated in this *** Cl widely exists in brines and has obviously sensitizing effect on lithium determination,we found after a series of studies that when the total amounts of NaCl,KCl,MgCl in samples were no more than 40g/L,the interferences of these coexisting ions could be su

关键词： Lithium High salinity sample ICP-OES Interference

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砷污染土壤的蜈蚣草修复研究进展

土壤 2007年第3期39卷 341-346页

作者：潘志明邓天龙成都理工大学材料与生物工程学院成都610059

本文评述了As污染土壤的蜈蚣草植物修复及其对As的解毒机制的研究进展,内容着重包括蜈蚣草对As的富集特征,As在蜈蚣草中的赋存形态、迁移及其转化,土壤以及土壤中P、Ca和K等元素对蜈蚣草吸收、转运As的影响等方面。

关键词：蜈蚣草植物修复砷污染土壤

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含砷金矿的磁场强化生物预氧化

应用化学 2000年第4期17卷 362-365页

作者：汪模辉邓天龙廖梦霞成都理工学院应用化学系成都610059

对新疆沙尔布拉克含砷原生金矿 ,进行了磁场强化 -氧化亚铁硫杆菌预氧化研究 .着重研究了磁场对细菌生长和细菌浸矿的影响 .结果表明 ,磁化水配制 9K培养基能促进细菌的生长 ,提高细菌的活性 ,对细菌浸矿有明显的促进作用 ,缩短细菌预... 详细信息

对新疆沙尔布拉克含砷原生金矿 ,进行了磁场强化 -氧化亚铁硫杆菌预氧化研究 .着重研究了磁场对细菌生长和细菌浸矿的影响 .结果表明 ,磁化水配制 9K培养基能促进细菌的生长 ,提高细菌的活性 ,对细菌浸矿有明显的促进作用 ,缩短细菌预氧化周期 .此法无需引入化学试剂即可强化生物浸矿过程 ,改变水的结构 ,促进氧气在水中的溶解 ,提高矿石成分的溶解性 .

关键词：含砷金矿生物氧化磁场强化浸金工艺