13C qNMR结合DFSS方法测定油品芳碳率

doi:10.11938/cjmr20170102

波谱学杂志 ›› 2017, Vol. 34 ›› Issue (1): 8-15.doi: 10.11938/cjmr20170102

¹³C qNMR结合DFSS方法测定油品芳碳率

马琳鸽, 龙银花

北京低碳清洁能源研究所分析测试中心, 北京 102209

收稿日期:2015-12-25 修回日期:2017-01-04 出版日期:2017-03-05 发布日期:2017-03-05
通讯作者: 马琳鸽,Tel:010-57595628,E-mail:malinge@nicenergy.com E-mail:malinge@nicenergy.com
基金资助:
中澳能源联合研究（关键技术联合研究）资助项目（2013DFG61490）

Determination of Aromatic Carbon Mole Ratio in Oil Samples by Quantitative ¹³C NMR Spectroscopy with DFSS Methodology

MA Lin-ge, LONG Yin-hua

Analytical Center, National Institute of Clean-and-Low-Carbon Energy, Beijing 102209, China

Received:2015-12-25 Revised:2017-01-04 Online:2017-03-05 Published:2017-03-05

摘要/Abstract

摘要： 利用六西格玛设计（design for six Sigma，DFSS）方法，通过定量核磁共振碳谱（quantitative carbon nuclearmagnetic resonance spectroscopy，¹³C qNMR）对由11种已知烃类化合物组成的模型油品进行了芳香碳摩尔百分比C（ar）%，简称芳碳率]测定的系统研究，建立了C（ar）%与样品浓度Conc.、弛豫试剂浓度[Cr（acac）₃]和循环延迟D13个参数之间的数学模型，据此模型得到了优化的参数设置：Conc.为180 mg/mL，[Cr（acac）₃]为12 mg/mL，D1为10.5 s.按此设置进行了8组验证实验，其结果重现性较好，相对标准偏差（relative standard deviation，RSD）为0.61%；准确性较高，达到99.0%~100.6%.该方法也可用于其它分析测试方法的系统研究，且实验结果对现行油品芳碳率测定标准中相关参数，如[Cr（acac）₃]和D1的设置能够提出补充性建议.

关键词: 定量核磁共振碳谱(¹³C qNMR), 六西格玛设计(DFSS), 芳碳率, 模型油品

Abstract: Aromatic carbon mole ratios[C(ar)%] in model oil samples, which consisted of 11 saturated/unsaturated compounds with known contents, were determined by quantitative carbon nuclear magnetic resonance spectroscopy (¹³C qNMR) with the design for six Sigma (DFSS) methodology. An empirical model was established between C(ar)% and sample parameters, including sample concentration (Conc.), concentration of relaxation reagent Cr(acac)₃ and relaxation delay (D1). Based on the model, the optimal condition was determined to be at sample concentration 180 mg/mL, concentration of Cr(acac)₃ 12 mg/mL and D1 10.5 s. Eight verification experiments were performed under the optimal condition, and the results showed fairly good repeatability (RSD=0.61%) and accuracy (99.0%~100.6%). The work also gave some supplementary suggestions on parameter settings for the current GB method/ASTM method.

Key words: quantitative carbon nuclear magnetic resonance spectroscopy (¹³C qNMR), design for six Sigma (DFSS), aromatic carbon mole ratios, model oil samples

中图分类号:

O482.53

马琳鸽, 龙银花. ¹³C qNMR结合DFSS方法测定油品芳碳率[J]. 波谱学杂志, 2017, 34(1): 8-15.

MA Lin-ge, LONG Yin-hua. Determination of Aromatic Carbon Mole Ratio in Oil Samples by Quantitative ¹³C NMR Spectroscopy with DFSS Methodology[J]. Chinese Journal of Magnetic Resonance, 2017, 34(1): 8-15.

参考文献

[1] LA MAR G N. The problem with carbon-13 intensities in proton-decoupled nuclear magnetic resonance spectra. undermining the overhauser effect with free radicals[J]. J Am Chem Soc, 1971, 93(4):1040-1041.
[2] SCHOOLERY J N, BUDDE W L. Natural abundance carbon-13 nuclear magnetic resonance spectrometry for crude oil and petroleum product analyses[J]. Anal Chem, 1976, 48(11):1458-1461.
[3] 王京. 烃类油品中芳碳含量测定法-高分辨核磁共振法. 中华人民共和国石油化工行业标准SH/T 0793-2007[P]. 2007-08-01.
[4] Standard test method for aromatic carbon contents of hydrocarbon oils by high resolution nuclear magnetic resonance spectroscopy[S]. American Society for Testing and Materials. ASTM D5292-99.
[5] KANEMITSU T, WONG C H, KANIE O. Solid-phase synthesis of oligosaccharides and on-resin quantitative monitoring using gated decoupling ¹³C NMR[J]. J Am Chem Soc, 2002, 124(14):3591-3599.
[6] DICKINSON E M. Structural comparison of petroleum fractions using proton and ¹³C NMR spectroscopy[J]. Fuel, 1980, 59(5):290-294.
[7] SARPAL A S, KAPUR G S, MUKHERJEE S, et al. Estimation of oxygenates in gasoline by ¹³C NMR spectroscopy[J]. Energ Fuel, 1997, 11(3):662-667.
[8] TYNYS A, FONSECA I, PARKINSON M, et al. Quantitative ¹³C NMR analysis of isotactic ethylene-propylene copolymers prepared with metallocene catalyst:Effect of ethylene on polymerization mechanisms[J]. Macromolecules, 2012, 45(19):7704-7710.
[9] DÍAZ C, BLANCO C G. NMR:A powerful tool in the characterization of coal tar pitch[J]. Energ Fuel, 2003, 17(4):907-913.
[10] COOKSON D J, SMITH B E. Optimal conditions for obtaining quantitative ¹³C NMR data[J]. J Magn Reson, 1984, 57(3):355-368.
[11] SILVERSTIEN R M, WEBSTER F X, KIEMLE D J. Spectrometric identification of organic compounds (7th ed)[M]. Danvers:John Wiley & Sons, 2015.
[12] GUO G J, GU C C. Oil saturation in rock cuttings measured by nuclear magnetic resonance[J]. Chinese J Magn Reson, 2005, 22(1):67-72. 郭公建, 谷长春. 核磁共振岩屑含油饱和度分析技术的实验研究[J]. 波谱学杂志, 2005, 22(1):67-72.
[13] WANG Z Z, QIN L M, DU H F, et al. Effects of powdered fluorescent additives on NMR characteristics of drilling fluids[J]. Chinese J Magn Reson, 2014, 31(3):341-348. 王志战, 秦黎明, 杜焕福, 等. 钻井液粉末状荧光添加剂的核磁共振特性[J]. 波谱学杂志, 2014, 31(3):341-348.
[14] SHEN Y M, ZHENG W L, CHENG Y-C N, et al. USPIO high resolution neurovascular imaging in a rat stroke model of transient middle cerebral artery occlusion[J]. Chinese J Magn Reson, 2014, 31(1):20-31. 沈伊民, 郑伟丽, CHENG Y-C N, 等. 小鼠中风模型的超小氧化铁粒子神经血管成像[J]. 波谱学杂志, 2014, 31(1):20-31.

[1]	赵尚义王远军. 基于磁共振图像和改进的UNet++模型区分阿尔茨海默症患者和健康人群[J]. 波谱学杂志, 0, (): 0-0.
[2]	鲁晨董健健钟凯. 9.4T下TX模型鼠脑DTI成像研究[J]. 波谱学杂志, 0, (): 0-0.
[3]	王可张英华李雨晴邹定华. 固体核磁共振技术在水泥基材料研究中的应用[J]. 波谱学杂志, 0, (): 0-0.
[4]	刘可文刘紫龙汪香玉陈黎李钊吴光耀刘朝阳. 基于级联卷积神经网络的前列腺磁共振图像分类[J]. 波谱学杂志, 0, (): 0-0.
[5]	闫松屠小青彭梅. 光泵抽运³He极化程度监控系统的设计与实现[J]. 波谱学杂志, 0, (): 0-0.
[6]	张一鸣陈志雪杨晓云. 丁氟螨酯的波谱学数据解析与结构确证[J]. 波谱学杂志, 0, (): 0-0.
[7]	王强魏树峰王铮杨文晖. 基于粒子群与遗传算法的矩阵式梯度线圈优化设计[J]. 波谱学杂志, 0, (): 0-0.
[8]	王佳鑫冯继文陈俊飞王立英刘朝阳. 魔角旋转固体核磁共振探头中转子的研制[J]. 波谱学杂志, 0, (): 0-0.
[9]	赵智慧刘表兰闫小双武帅帅茹阁英毛诗珍冯继文. PSSS₅₀-b-PNIPAM₃₀₀嵌段共聚物在二元溶剂中自组装的NMR研究 [J]. 波谱学杂志, 0, (): 0-0.
[10]	刘慧霞, 辛家祥, 魏达秀. 核自旋单重态的制备及其转化效率和寿命的影响因素分析 [J]. 波谱学杂志, 0, (): 0-0.
[11]	雷振宇, 梁欣苗#, 雷友义, 杨丽, 冯继文. 固体核磁共振技术在锂/钠离子电池碳负极中的应用及研究进展 [J]. 波谱学杂志, 0, (): 0-0.
[12]	张之杰李端秀罗春仇汝臣邓宗武张海禄. 晶体学辅助的2-吡啶甲酸固体13C化学位移理论计算归属[J]. 波谱学杂志, 0, (): 0-0.
[13]	包婉静曾庆琦余钫秦蕾陈智勇. 一种非连续微波探询信号的实现[J]. 波谱学杂志, 0, (): 0-0.
[14]	张芬芬沈文斌徐开兵杨明. 基于定量核磁共振氢谱测定新药替格瑞洛[J]. 波谱学杂志, 0, (): 0-0.
[15]	徐广永董满园马建锋张利民. 固体核磁共振研究半晶聚-3-羟基丁酸酯和聚羟基丁酸戊酸酯的分子动力学（英文） [J]. 波谱学杂志, 0, (): 0-0.

¹³C qNMR结合DFSS方法测定油品芳碳率

Determination of Aromatic Carbon Mole Ratio in Oil Samples by Quantitative ¹³C NMR Spectroscopy with DFSS Methodology

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

PSSS₅₀-b-PNIPAM₃₀₀嵌段共聚物在二元溶剂中自组装的NMR研究

编辑推荐

Metrics

本文评价