Establishment and Verification of Analytical Models Applied to NIRS Determination of Moisture and Sulfur in Crude Oil
摘 要
取原油样品120个,分别按照GB/T 11133-2015和GB/T 17040-2008中所述方法测定了上述原油样品中的水分和硫的含量。通过优化的近红外光谱(NIRS)条件采集了上述原油样品的NIR光谱图。采用杠杆值算法剔除4个异常样品。在建立水分含量分析模型时,采用的条件为:用Savitzky-Golay法对光谱进行滤波预处理,建模光谱区间为6 200~8 200 cm-1,主成分数为6,用偏最小二乘回归法(PLS)交叉验证建立分析模型。硫含量分析模型的建立条件为:采用二阶导数-Norris Derivative对光谱进行预处理,建模光谱区间为4 400~4 700 cm-1,主成分数为6,用PLS交叉验证建立分析模型。水分和硫含量模型的预测值与测定值的相关性较好。水分模型的决定系数(Rc2)为0.989 9,校正标准偏差(RMSEC)为0.084 2,说明其预测效果较好,可用于原油中水分含量的预测。硫含量模型的Rc2为0.996 3,RESEC为0.069 6,说明此模型的预测效果也较好,可用原油中硫含量的预测。应用所建立的两个模型对10个未知原油样品中水分和硫含量进行了预测,并与其测定值比较,结果表明两者之间的相对偏差均小于10%。
Abstract
Moisture and sulfur in 120 samples of crude oil were determined by the standard methods given in GB/T 11133-2015 and GB/T 17040-2008, respectively. And the transmission NIR spectra of the 120 samples were collected under the optimized condition. 4 abnormal samples were rejected by the algorithm of Leverage. Analytical model for prediction of moisture contents was established under the following conditions:① method of Savitzky-Golay was applied for wave-filtering pretreatment of the NIR spectra; ② spectal section in the range of 6 200 to 8 200 cm-1 was selected for the model establishing; ③ number of principle components was 6; and ④ the algorithms of PLS and alternate verification were used in the final model-establishment. Conditions for establishing the analytical model for prediction of sulfur contents were as follows:① method of 2nd derivative-Norris Derivative was applied to the pretreatment of the NIR spectra; ② spectral section between 4 400 to 4 700 cm-1 was selected for model establishing; ③ number of principle components was 6; and ④ the algorithms of PLS and alternate verification were adopted in the final model-establishment. Good correlationships between values of prediction and of determination of both the moisture and sulfur contents were obtained. And values of Rc2 and RMSEC found were 0.989 9 and 0.084 2 respectively (for the model of moisture prediction), and 0.996 3 and 0.069 6 respectively (for the model of sulfur prediction), showing that those two models can be used effectively for the prediction of moisture and sulfur contents in the crude oil. Ten unknown samples of crude oil were analyzed by NIRS under the prescribed condition and contents of moisture and sulfur were predicted by the 2 models. It was found that the predicted values of the 2 components in the 10 sample were in consistent with the values of the 2 components in these samples obtained by the standard analytical methods, giving relative deviations less than 10%.
中图分类号 O657.33 DOI 10.11973/lhjy-hx202006001
所属栏目 试验与研究
基金项目 国家重点研发计划(2016YFF0203704)
收稿日期 2019/12/27
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备注程欲晓,高级工程师,博士,主要从事进出口商品检验鉴定工作,chengyuxiao2006@aliyun.com
引用该论文: CHENG Yuxiao,ZHANG Jidong,SHAO Min,JIN Yinhua,GU Zhongyi,GUO Zhengyun. Establishment and Verification of Analytical Models Applied to NIRS Determination of Moisture and Sulfur in Crude Oil[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2020, 56(6): 621~626
程欲晓,张继东,邵敏,金樱华,顾中怡,郭争云. 近红外光谱分析原油中水分和硫含量模型的建立及验证[J]. 理化检验-化学分册, 2020, 56(6): 621~626
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【4】贾仕强,郭婷婷,刘哲,等.基于近红外光谱的带种衣剂玉米种子真实性鉴定方法研究[J].光谱学与光谱分析, 2014,34(11):2984-2988.
【5】胡芸,刘娜,姬厚伟,等.近红外光谱技术在线快速检测复烤片烟化学成分应用研究[J].安徽农业科学, 2017,45(19):78-80.
【6】苏婷,姜文月,李亚东,等.声光可调-近红外光谱法快速判断精芪双参胶囊的混合终点及测定黄芪甲苷的含量[J].中国药房, 2018,29(12):1616-1620.
【7】刘翔,李键,陈艳玲.NIRS测定水性树脂预聚体中NCO的方法研究[J].广州化工, 2016,44(13):128-130.
【8】程欲晓,咸洋,马腾洲,等.动植物油脂种类鉴别及其碘值测定的近红外光谱方法[J].理化检验-化学分册, 2013,49(12):1405-1409.
【9】BONA M, ANDRES J. Coal analysis by diffuse reflectance near-infrared spectroscopy:Hierarchical cluster and linear discriminant analysis[J]. Talanta, 2007,72(4):1423-1431.
【10】HE C, CHEN L J, YANG Z L, et al. A rapid and accurate method for on-line measurement of straw-coal blends using near infrared spectroscopy[J]. Bioresource Technology, 2012,110:314-320.
【11】樊瑞君,王煊军,刘祥萱,等.近红外光谱法测定喷气燃料的总硫含量[J].化学分析计量, 2006,15(3):16-18.
【12】徐广通,陆婉珍,袁洪福.近红外光谱法测定柴油中的芳烃含量[J].石油化工, 1999,28(4):263-265.
【13】王艳斌,袁洪福,陆婉珍,等.人工神经网络用于近红外光谱测定柴油闪点[J].分析化学, 2000,28(9):1070-1073.
【14】邢志娜,王菊香,刘洁,等.在用润滑油闪点的近红外光谱快速测定方法研究[J].石油与天然气化工, 2013,42(5):524-527.
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