定量环法制备气体标准物质
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摘要
高精度气体标准物质是保证化学计量准确性的一项重要前提,目前的天然气气体标准物质制备步骤繁琐、费时,不确定度水平低,难以满足天然气成分量的高精度测定。为此,研发了定量环(Loop)法制备气体标准物质的方法,对其加入微量原料的不确定度、制备过程的不确定度进行了评定,与传统稀释法制备过程进行了对比分析,并采用气相色谱法对其重量法定值进行了验证。研究结果表明:(1)传统制备方法称量气瓶必须使用量程大、精度低的天平,多级稀释会重复地引入称量过程中的不确定度;(2)定量环法制备混合气体标准物质,制备步骤可以一步完成,制备过程中引入的不确定度降低了一个数量级;(3)定量环法减少了制备的步骤以及原料的使用量,提高了混合气体标准物质的制备效率;(4)定量环法已成功用于天然气及硫化物混合气体标准物质的制备中,有望得到更加广泛的应用,使得气体标准物质的制备更加高效、定值更加准确;(5)采用气相色谱法对该方法制备得到的混合气体标准物质的标称值进行方法验证,结论认为:该方法具有很好的可行性及准确性。
High-accuracy gas reference material is an important prerequisite to guaranteeing the accuracy of stoichiometry. At present, however, the existing procedures of preparing gas reference material are complicated and time-consuming with high degree of uncertainty, so it is difficult to realize the high-accuracy measurement of gas compositions. In this paper, a loop method of preparing the gas reference material was developed. Then, its uncertainty degree on trace materials and preparation process was assessed and compared with the preparation process of the traditional dilution method. Finally, its weighing value was verified by means of a gas chromatography. And the following research results were obtained. First, the weighing cylinder of traditional preparation methods need a balance of wide range and low precision, so the uncertainty degree in the weighing process is introduced many times by multi-stage dilution. Second, when the loop method is adopted to prepare mixed gas reference material, the preparation can be completed in one step, so the uncertainty degree introduced in the preparation process is decreased by one order of magnitude. Third, by virtue of the loop method, the previously-used preparation procedures are simplified, the consumption of raw material is reduced and the preparation efficiency of mixed gas reference material is increased. Fourth, the loop method has been successfully applied to the preparation of gas reference material of natural gas and sulfide mixtures, and it is promising in more extensive application to realize efficient preparation and accurate valuing of gas reference material. And fifth, a gas chromatography is used to verify the nominal value of mixed gas reference material prepared by the loop method. And it is indicated that the loop method is of strong feasibility and accuracy.
High-accuracy gas reference material is an important prerequisite to guaranteeing the accuracy of stoichiometry. At present, however, the existing procedures of preparing gas reference material are complicated and time-consuming with high degree of uncertainty, so it is difficult to realize the high-accuracy measurement of gas compositions. In this paper, a loop method of preparing the gas reference material was developed. Then, its uncertainty degree on trace materials and preparation process was assessed and compared with the preparation process of the traditional dilution method. Finally, its weighing value was verified by means of a gas chromatography. And the following research results were obtained. First, the weighing cylinder of traditional preparation methods need a balance of wide range and low precision, so the uncertainty degree in the weighing process is introduced many times by multi-stage dilution. Second, when the loop method is adopted to prepare mixed gas reference material, the preparation can be completed in one step, so the uncertainty degree introduced in the preparation process is decreased by one order of magnitude. Third, by virtue of the loop method, the previously-used preparation procedures are simplified, the consumption of raw material is reduced and the preparation efficiency of mixed gas reference material is increased. Fourth, the loop method has been successfully applied to the preparation of gas reference material of natural gas and sulfide mixtures, and it is promising in more extensive application to realize efficient preparation and accurate valuing of gas reference material. And fifth, a gas chromatography is used to verify the nominal value of mixed gas reference material prepared by the loop method. And it is indicated that the loop method is of strong feasibility and accuracy.
引文
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[5]周理,陈赓良,郭开华.对天然气推荐性国家标准GB/T 31253的讨论[J].天然气工业, 2017, 37(12):87-91.Zhou Li, Chen Gengliang&Guo Kaihua. A discussion on the Chinese national standard GB/T 31253:From Recommendatory(GB/T)to Guidance(GB/Z)[J]. Natural Gas Industry, 2017,37(12):87-91.
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[7]罗勤.天然气能量计量在我国应用的可行性与实践[J].天然气工业, 2014, 34(2):123-129.Luo Qin. Practicability and application of natural gas energy determination in China[J]. Natural Gas Industry, 2014, 34(2):123-129.
[8]徐孝轩,李奇,荆栋.多气源天然气输配管网的能量计量方法[J].天然气工业, 2018, 38(1):116-122.Xu Xiaoxuan, Li Qi&Jing Dong. An energy measurement method for multi-source natural gas distribution pipeline networks[J].Natural Gas Industry, 2018, 38(1):116-122.
[9]秦云松,张吉军,林媛媛.天然气流量计量标准装置的工艺流程优化[J].天然气工业, 2017, 37(8):102-107.Qin Yunsong, Zhang Jijun&Lin Yuanyuan. Process optimization of a natural gas flow measurement standard device[J]. Natural Gas Industry, 2017, 37(8):102-107.
[10]韩桥,吴海,李春瑛,盖良京.天然气标准物质与能量计量[J].计量技术, 2008(10):25-26.Han Qiao, Wu Hai, Li Chunying, Gai Liangjing. Natural gas reference material and energy metrology[J]. Measurement Technique,2008(10):25-26.
[11]周泽义,金美兰.标准气体溯源体系的建立及其量值传递规范化研究[C].杭州:中国工业气体工业协会年会, 2000.Zhou Zeyi&Jin Meilan. Establishment of standard gas traceability system and standardization research on its value transfer[C].Hangzhou:Annual meeting of China Industrial Gases Industry Association, 2000.
[12]国际标准化组织.气体分析校准用混合气体的制备第1部分:Ⅰ类混合气体称量法:ISO 6142-1:2015[S].日内瓦:ISO,2015.International Organization of Standardization. Gas analysis—preparation of calibration gas mixtures—part 1:Gravimetric method for Class I mixtures:ISO 6142-1:2015[S]. Geneva:ISO,2015.
[13]方正,周鑫,潘义.氮气中1μmol·mol-1硫化氢气体标准物质的研制[J].化学研究与应用, 2014, 26(11):1809-1912.Fang Zheng, Zhou Xin&Pan Yi. The development of hydrogen sulfide in nitrogen gas reference material at 1μmol·mol-1level[J]. Chemical Research and Application, 2014, 26(11):1809-1912.
[14]李红梅.标准物质质量控制及不确定度评定[M].北京:中国质检出版社, 2014.Li Hongmei. Quality control and uncertainty evaluation of standard materials[M]. Beijing:China Quality Inspection Press, 2014.
[15]国家质量监督检验检疫总局.测量不确定度评定与表示:JJF1059.1—2012[S].北京:中国计量出版社, 2012.General Administration of Quality Supervision, Inspection and Quarantine of the PRC. Evaluation and representation of measurement uncertainty:JJF 1059.1-2012[S]. Beijing:China Metrology Press, 2012.
[16]全国标准物质管理委员会.标准物质的研制管理与应用[M].北京:中国计量出版社, 2010.National Standard Materials Management Committee. Development,management and application of standard materials[M].Beijing:China Metrology Press, 2010.
[17]迟久春.天然气分析用标准气体系研究[J].天然气工业,1990, 10(6):73-78.Chi Jiuchun. Research of standard gas series used for natural gas analysis[J]. Natural Gas Industry, 1990, 10(6):73-78.
[18]陈赓良,赵榆.研制多元标准气混合物的相关问题讨论[J].天然气工业, 2011, 31(2):94-97.Chen Gengliang&Zhao Yu. A discussion on the related issues in the research and preparation of the multi-component reference gas mixture[J]. Natural Gas Industry, 2011, 31(2):94-97.
[19]中国国家标准化管理委员会.气体分析校准用混合气体的制备称量法:GB/T 5274—2008[S].北京:中国标准出版社,2008.Standardization Administration of the PRC. Gas analysis—Preparation of calibration gas mixtures—Gravimetric method:GB/T5274-2008[S]. Beijing:Standards Press of China, 2008.
[20]周鑫,李志昂,董了瑜,方正.注射称量法配气中的称量线性研究及不确定度评定[J].化学试剂, 2017(5):505-508.Zhou Xin, Li Zhi'ang, Dong Liaoyu&Fang Zheng. Weighing linearity study and uncertainty evaluation for gravimetric preparation of reference gas mixture using injection method[J]. Chemical Reagents, 2017(5):505-508.
[21]方正,周鑫,霍玉朋,董了瑜,李志昂.电子质量比较器在重量法配气中的称量不确定度评定[J].中国测试, 2016, 42(12):38-41.Fang Zheng, Zhou Xin, Huo Yupeng, Dong Liaoyu&Li Zhi'ang.Weighing uncertainty evaluation on electronic mass comparator for gravimetric preparation of reference gas mixture[J]. China Measurement&Test, 2016, 42(12):38-41.
[22]胡树国,王德发,王哲.微量气体转移技术在重量法制备气体标准物质中的应用[J].计量学报, 2013, 34(1):72-75.Hu Shuguo, Wang Defa&Wang Zhe. The application of trace gas transfer technique to preparing gas CRMs by gravimetric method[J]. Acta Metrologica sinica, 2013, 34(1):72-75.
[23]胡树国,李佳.利用气体微量转移技术制备低含量R12气体标准物质[J].化学分析计量, 2012, 21(5):4-7.Hu Shuguo&Li Jia. Preparation of low concentration gas standard mixture of R12 by a small amount of gas transfer technique[J]. Chemical Analysis and Meterage, 2012, 21(5):4-7.
[2]周理,陈赓良,潘春锋,许文晓.天然气发热量测定的溯源性[J].天然气工业, 2014, 34(11):122-127.Zhou Li, Chen Gengliang, Pan Chunfeng&Xu Wenxiao. Traceability of the calorific value measurement of natural gas[J]. Natural Gas Industry, 2014, 34(11):122-127.
[3]周理,陈赓良,郭开华,王伟杰,王晓琴.对国际标准ISO10723:2012的认识与讨论[J].天然气工业, 2018, 38(7):108-112.Zhou Li, Chen Gengliang, Guo Kaihua, Wang Weijie&Wang Xiaoqin. Understanding and discussion on the international standard ISO 10723:2012[J]. Natural Gas Industry, 2018, 38(7):108-112.
[4]段继芹,李长俊,周芳.对“用气体超声流量计测量天然气流量”国家标准的修改建议[J].天然气工业, 2018, 38(1):109-115.Duan Jiqin, Li Changjun&Zhou Fang. Recommended revision of the Measurement of Natural Gas Flow by Ultrasonic Gas Flow Meters(GB/T 18604-2014)[J]. Natural Gas Industry, 2018, 38(1):109-115.
[5]周理,陈赓良,郭开华.对天然气推荐性国家标准GB/T 31253的讨论[J].天然气工业, 2017, 37(12):87-91.Zhou Li, Chen Gengliang&Guo Kaihua. A discussion on the Chinese national standard GB/T 31253:From Recommendatory(GB/T)to Guidance(GB/Z)[J]. Natural Gas Industry, 2017,37(12):87-91.
[6]中国国家标准化管理委员会.天然气发热量、密度、相对密度和沃泊指数的计算方法:GB/T 11062—2014[S].北京:中国标准出版社, 2014.Standardization Administration of the PRC. Natural gas—Calculation of calorific values, density, relative density and Wobbe index from composition:GB/T 11062-2014[S]. Beijing:Standards Press of China, 2014.
[7]罗勤.天然气能量计量在我国应用的可行性与实践[J].天然气工业, 2014, 34(2):123-129.Luo Qin. Practicability and application of natural gas energy determination in China[J]. Natural Gas Industry, 2014, 34(2):123-129.
[8]徐孝轩,李奇,荆栋.多气源天然气输配管网的能量计量方法[J].天然气工业, 2018, 38(1):116-122.Xu Xiaoxuan, Li Qi&Jing Dong. An energy measurement method for multi-source natural gas distribution pipeline networks[J].Natural Gas Industry, 2018, 38(1):116-122.
[9]秦云松,张吉军,林媛媛.天然气流量计量标准装置的工艺流程优化[J].天然气工业, 2017, 37(8):102-107.Qin Yunsong, Zhang Jijun&Lin Yuanyuan. Process optimization of a natural gas flow measurement standard device[J]. Natural Gas Industry, 2017, 37(8):102-107.
[10]韩桥,吴海,李春瑛,盖良京.天然气标准物质与能量计量[J].计量技术, 2008(10):25-26.Han Qiao, Wu Hai, Li Chunying, Gai Liangjing. Natural gas reference material and energy metrology[J]. Measurement Technique,2008(10):25-26.
[11]周泽义,金美兰.标准气体溯源体系的建立及其量值传递规范化研究[C].杭州:中国工业气体工业协会年会, 2000.Zhou Zeyi&Jin Meilan. Establishment of standard gas traceability system and standardization research on its value transfer[C].Hangzhou:Annual meeting of China Industrial Gases Industry Association, 2000.
[12]国际标准化组织.气体分析校准用混合气体的制备第1部分:Ⅰ类混合气体称量法:ISO 6142-1:2015[S].日内瓦:ISO,2015.International Organization of Standardization. Gas analysis—preparation of calibration gas mixtures—part 1:Gravimetric method for Class I mixtures:ISO 6142-1:2015[S]. Geneva:ISO,2015.
[13]方正,周鑫,潘义.氮气中1μmol·mol-1硫化氢气体标准物质的研制[J].化学研究与应用, 2014, 26(11):1809-1912.Fang Zheng, Zhou Xin&Pan Yi. The development of hydrogen sulfide in nitrogen gas reference material at 1μmol·mol-1level[J]. Chemical Research and Application, 2014, 26(11):1809-1912.
[14]李红梅.标准物质质量控制及不确定度评定[M].北京:中国质检出版社, 2014.Li Hongmei. Quality control and uncertainty evaluation of standard materials[M]. Beijing:China Quality Inspection Press, 2014.
[15]国家质量监督检验检疫总局.测量不确定度评定与表示:JJF1059.1—2012[S].北京:中国计量出版社, 2012.General Administration of Quality Supervision, Inspection and Quarantine of the PRC. Evaluation and representation of measurement uncertainty:JJF 1059.1-2012[S]. Beijing:China Metrology Press, 2012.
[16]全国标准物质管理委员会.标准物质的研制管理与应用[M].北京:中国计量出版社, 2010.National Standard Materials Management Committee. Development,management and application of standard materials[M].Beijing:China Metrology Press, 2010.
[17]迟久春.天然气分析用标准气体系研究[J].天然气工业,1990, 10(6):73-78.Chi Jiuchun. Research of standard gas series used for natural gas analysis[J]. Natural Gas Industry, 1990, 10(6):73-78.
[18]陈赓良,赵榆.研制多元标准气混合物的相关问题讨论[J].天然气工业, 2011, 31(2):94-97.Chen Gengliang&Zhao Yu. A discussion on the related issues in the research and preparation of the multi-component reference gas mixture[J]. Natural Gas Industry, 2011, 31(2):94-97.
[19]中国国家标准化管理委员会.气体分析校准用混合气体的制备称量法:GB/T 5274—2008[S].北京:中国标准出版社,2008.Standardization Administration of the PRC. Gas analysis—Preparation of calibration gas mixtures—Gravimetric method:GB/T5274-2008[S]. Beijing:Standards Press of China, 2008.
[20]周鑫,李志昂,董了瑜,方正.注射称量法配气中的称量线性研究及不确定度评定[J].化学试剂, 2017(5):505-508.Zhou Xin, Li Zhi'ang, Dong Liaoyu&Fang Zheng. Weighing linearity study and uncertainty evaluation for gravimetric preparation of reference gas mixture using injection method[J]. Chemical Reagents, 2017(5):505-508.
[21]方正,周鑫,霍玉朋,董了瑜,李志昂.电子质量比较器在重量法配气中的称量不确定度评定[J].中国测试, 2016, 42(12):38-41.Fang Zheng, Zhou Xin, Huo Yupeng, Dong Liaoyu&Li Zhi'ang.Weighing uncertainty evaluation on electronic mass comparator for gravimetric preparation of reference gas mixture[J]. China Measurement&Test, 2016, 42(12):38-41.
[22]胡树国,王德发,王哲.微量气体转移技术在重量法制备气体标准物质中的应用[J].计量学报, 2013, 34(1):72-75.Hu Shuguo, Wang Defa&Wang Zhe. The application of trace gas transfer technique to preparing gas CRMs by gravimetric method[J]. Acta Metrologica sinica, 2013, 34(1):72-75.
[23]胡树国,李佳.利用气体微量转移技术制备低含量R12气体标准物质[J].化学分析计量, 2012, 21(5):4-7.Hu Shuguo&Li Jia. Preparation of low concentration gas standard mixture of R12 by a small amount of gas transfer technique[J]. Chemical Analysis and Meterage, 2012, 21(5):4-7.