质子交换膜燃料电池汽车用氢气 氦、氩、氮和烃类的测定 气相色谱法 编制说明

1质子交换膜燃料电池汽车用氢气氦、氩、氮和烃类的测定气相色谱法编制说明对环境造成的污染亦越来越严重，因此迫切需要寻找一种作为替代品的清洁燃料。氢能作为一种高效、清洁、低碳环保、可持续发展的二次能源，被视为最具发展潜力的清洁能源。氢燃料电池车是氢能的重要应用载体，燃料电池器件的构成及工作原理从本质上要求作为反应原料的氢气要满足特定的质量指标，以保障燃料电池的长周期、可靠运行。氢气中的惰性杂质（如氦气、氩气、氮气）的稀释作用和扩散作用会降低电池的电势，导致功率损耗，增加燃料消耗以及燃料电池效率的损失；一些碳氢化合物会吸附在催化剂层上，减少催化剂表面积，从而降低了电子交换膜燃料电池汽车用燃料氢气》产品标准规定燃料氢气中氦气含量本标准制定任务来源于国家标准化管理委员会国标委[2022]51号文2GB/T37244推荐采用GB/T2相色谱法测定组分第3部分：用两根填充柱测定氢、氦、氧、氮、二氧《气体中一氧气化碳、二氧气化碳和碳氢化合物的测定气相色谱法》测定总烃。GB/T27894.3采用氩气作载气测定天然气中的氦气组分，而当测定氢气中的氦气组分时，大量的氢气会导致其和氦气无法分离，因此方法不适用与FCV用氢气中氦气的测定。GB/T3634.2是对纯氢、高纯和氩气<100μmol/mol，前者分析方法采用气含量的方法面临无法实现氩气和氧气分离的问题，需要在系统中增加本方法基于双阀和双柱气相色谱系统，结合热导和氢火焰离子化检测器测定质子交换膜燃料电池汽车用氢气中氦气、氩气、氮气和烃类的333本文件适用于质子交换膜燃料电池汽车用氢气中氦气、氮气、氩气和烃类含量的测定。同时也适用于各类用途氢气中氦气、氩气、氮气和为分析氢气中的氦气、氩气、氮气和烃类化合物，确定了分析流程检测器，GC-TCD-FID使用氢气做载气，串接双定量环进样，可以同时直接测定氢气中十万分之一级含量的氦气、氩气、氮气和烃类。该设计选用特殊规格的分子筛柱实现了室温下氧气和氩气的分离，氦气、氩气、氮气通过热导检测器（TCD）通道阀切换进样进行分离和检测，烃753849261314为实现氧气和氩气能在一根色谱柱分离，本方法选用不同规格分子筛柱对于氧气氩气分离情况进行了考察，图2为采用不同规格分子筛柱5图2不同规格分子筛柱分析色谱图(a)30mRESTEK分子筛柱分析氦气、氩气、氧气、氮气混合组分色谱图；(b)60mRESTEK分子筛柱分析氦气、氩气、氧气、氮气混合组分色谱图；(c)50m5A分子筛柱分析空气色谱图结果表明，采用30mRESTEK分子筛柱时，氩气和氧气不能分离，而采用60mRESTEK分子筛柱可基线分离氩气和氧气组分，分离度达2.6;采用50m5A分子筛柱直接分析空气，氩气和氧气组分仍能基线分离，分离度达2.3。由于60mRESTEK分子筛柱实际需要采用2根30mRESTEK分子筛柱连接实现，为减少柱连接死体积，及操作简便性，本标准采用50m5A分子筛色谱柱。6使用氢气作载气，通过优化色谱操作条件，得到的典型色谱条件及阀事件表如表1所示：氢气中氦气、氩气、氮气和烃类典型色谱图如图3和图4所示，其中氦气摩尔分数为300μmol/mol,氩气摩尔分数为100μmol/mol,氮气摩设定值定量环色谱柱升温程序30℃,保持4min,25℃/min至190℃保持2min。运行时间12.4min色谱柱1、色谱柱2压力控制模式，压力16ps色谱柱3进样口(分流/不分流进样口)检测器(TCD)温度150℃参比气流速25mL/min,柱流量+尾吹检测器(FID)温度200℃~250℃,氢气流量30mL/min～35mL/min,空气流量350mL/min～400mL/min,氮气流量20阀事件阀10.01min开启阀20.05min开启载气氢气71-甲烷；2-乙烷；3-丙烷；4-正丁烷；5-正戊烷；6-正已烷；7-苯；8-甲苯共有来自国内不同区域、不同性质的9家实验室，采用不同厂家气相色谱仪开展了方法测定范围线性考察、准确度试验，根据试验结果，确定了方法定量方式、确定了方法测量范围内精密度和正确度。参与单位及仪器设备配置见表2。各实验室所用气体标准物质均由四川中测标物科技有限公司配制，摩尔分数范围分别为10μmol/mol~600μmol/mol、5μmol/mol~300氮气和甲烷混合标准物质，摩尔分数0.1μmol/mol~2μmol/mol范围内5个不同浓度点的乙烷、丙烷、正丁烷、正戊烷、正己烷、苯、甲苯混合标准物质共计42瓶，详见表3。8实验室编号实验室名称色谱仪型号L1L2L3L4L5L6L7L8L9中石化石油化工科学研究院有限浙江福立仪器股份有限公司中国测试技术研究院四川中测标物科技有限公司安捷伦科技（中国）有限公司大连大特气体有限公司广州能源检测研究院中石化（大连）石油化工研究院有限公司丰田汽车研发中心（中国）有限安捷伦7890B气相色谱仪，配热导检测器、火焰离子化检测器福立GC9720Plus气相色谱仪，配热导检测器、火焰离子化检测器安捷伦8890气相色谱仪，配热导检测器、火焰离子化检测器安捷伦8890气相色谱仪，配热导检测器、火焰离子化检测器安捷伦8890气相色谱仪，配热导检测器、火焰离子化检测器安捷伦8890气相色谱仪，配热导检测器、火焰离子化检测器岛津GC2030气相色谱仪，配热导检测器、火焰离子化检测器9实验室编号组分名称及摩尔分数S1299µmol/mol氦气、100µmol/mol氩气、101µmol/mol氮气、1.99µmol/mol甲烷、2.03µmol/mol乙烷、1.93µmol/mol丙烷、1.97µmol/mol正丁烷、1.92µmol/mol正戊烷、1.91µmol/mol正己烷、1.91µmol/mol苯、1.92µmol/molS2603µmol/mol氦气、303µmol/mol氩气、306µmol/mol氮气、203µmol/mol甲0.982µmol/mol甲苯混合气体，平衡气L1/L2/L7/S399.5µmol/mol氦气、49.4µmol/mol氩气、50.0µmol/mol氮气、99.9µmol/mol甲烷、0.523µmol/mol乙烷、0.497µmol/mol丙烷、0.507µmol/mol正丁烷、L1/L2/L7/0.493µmol/mol甲苯混合气体，平衡气S451.9µmol/mol氦气、20.2µmol/mol氩气、20.5µmol/mol氮气、1.00µmol/mol甲烷、0.206µmol/mol乙烷、0.196µmol/mol丙烷、0.200µmol/mol正丁烷、甲烷、0.105µmol/mol乙烷、0.0995µmol/mol丙烷、0.101µmol/mol正丁烷、0.0985µmol/mol甲苯混合气体，平衡气氢气S610.2µmol/mol氦气、5.12µmol/mol氩气、5.18µmol/mol氮气、10.0µmol/mol实验室编号组分名称及摩尔分数S1300µmol/mol氦气、99.1µmol/mol氩气、100µmol/mol氮气、1.9平衡气氢气体，平衡气氢气L3S399.4µmol/mL3S451.6µmol/mol氦气、20.2µmol/mol氩气、20.S530.1µmol/mol氦气、10.0µmol/mol氩气、10.0µmol/mol氮气、0.101µmol/mol甲烷、0.103µmol/mol乙烷、0.0980µmol/mol丙烷、0.100µmol/mol正丁烷、0.0970µmol/mol甲苯混合气体，平S610.1µmo烷混合气体，平衡气氢气实验室编号组分名称及摩尔分数S1298µmol/mol氦气、99.7µmol/mol氩气、101µmol/mol氮气、193µmol/mol甲S2604µmol/mol氦气、302µmol/mol氩气、306µmol/mol氮气、2.01µmol/mol甲平衡气氢气L4L4S451.4µmol/mol氦气、20.0µmol/mol氩气、20.3µmol/mol氮气、0.998µmol/mol甲烷、0.205µmol/mol乙烷、0.195µmol/mol丙烷、0.199µmol/mol正丁烷、S530.1µmol/mol氦气、9.96µmol/mol氩气、10.1µmol/mol氮气、0.100µmol/mol甲烷、0.104µmol/mol乙烷、0.0991µmol/mol丙烷、0.101µmol/mol正丁烷、0.0982µmol/mol甲苯混合气体，平衡气氢气S610.2µmol/mol氦气、5.09µm烷混合气体，平衡气氢气实验室编号组分名称及摩尔分数S1299µmol/mol氦气、99.2µmol/mol氩气、100µmol/mol氮气、2.00µmol/mol甲平衡气氢气体，平衡气氢气L5/L6S398.9µmol/mol氦气、49.2µmol/mol氩气、49.7L5/L6S452.0µmol/mol氦气、20.2µmol/mol氩气、2S530.4µmol/mol氦气、10.0µmol/mol氩气、10.2µmol/mol氮气、0.101µmol/mol甲烷、0.105µmol/mol乙烷、0.100µmol/mol丙烷、0.100µmol/mol正丁0.0992µmol/mol甲苯混合气体，平衡气氢气烷混合气体，平衡气氢气实验室编号组分名称及摩尔分数S1299µmol/mol氦气、98.9µmol/mol氩气、100µmol/mol氮气、2.01µmol/mol甲平衡气氢气体，平衡气氢气L8S398.3µmol/mol氦气、48.9µmol/mol氩气、49.4L8S452.2µmol/mol氦气、20.3µmol/mol氩气、2烷、0.207µmol/mol乙烷、0.1967µmol/mol丙烷、0.201µmol/mol正丁烷、S530.0µmol/mol氦气、9.93µmol/mol氩气、10.1µmol/mol氮气、0.100µmol/mol甲烷、0.104µmol/mol乙烷、0.0988µmol/mol丙烷、0.101µmol/mol正丁烷、0.0979µmol/mol甲苯混合气体，平衡气氢气S610.2µmol/mol氦气、5.09µm烷混合气体，平衡气氢气实验室编号组分名称及摩尔分数S1302µmol/mol氦气、98.7µmol/mol氩气、9平衡气氢气体，平衡气氢气L9S399.5µmol/mol氦气、49.4µmol/mol氩气、50.0L9S451.9µmol/mol氦气、20.2µmol/mol氩气、2S530.1µmol/mol氦气、9.95µmol/mol氩气、10.1µmol/mol氮气、0.100µmol/mol甲烷、0.104µmol/mol乙烷、0.0990µmol/mol丙烷、0.101µmol/mol正丁烷、0.0980µmol/mol甲苯混合气体，平衡气氢气烷混合气体，平衡气氢气烷、丙烷、正丁烷、正戊烷、正己烷、苯、甲苯进行色谱分析，以组分的摩尔分数标称值为横坐标，峰面积为纵坐标，斜率和截距依据最小二乘法并强制过原点计算，验证系统线性相关性。参与实验室氦气、氩气结果显示，各实验室校准曲线均成线性，相关系数R2大于0.995，于0.999，7个实验室对烃类组分组分所建校准曲线的相关系数R2大于0.999，表明使用不同分析仪器和分析室/(mol/μmol)/(mol/μmol)/(mol/μmol)实验室正丁烷斜率斜率斜率斜率R2R2R2R2/(mol/μmol)/(mol/μmol)/(mol/μmol)/(mol/μmol)L12.35640.99994.52980.99986.76210.99999.04180.9999L2569.330.99991016.160.99951504.210.99972027.590.9999L30.73010.99991.41390.99972.15950.99972.88610.9992L40.72050.99991.35790.99912.06670.99912.88570.9996L51.47760.99992.92910.99994.35770.99995.77880.9999L61.79220.99993.25880.99994.99100.99996.58310.9999L72.53900.99994.87070.99997.24180.99999.67650.9999L85203.90.99998904.40.99870.9998178660.9989实验室正戊烷正己烷苯斜率R2斜率R2斜率R2斜率R2/(mol/μmol)/(mol/μmol)/(mol/μmol)/(mol/μmol)L10.999913.4760.999913.5770.999915.7280.9999L22495.990.99993021.620.99992940.430.99962912.520.9993L33.34050.99984.05160.99994.06940.99984.80260.9999L43.37780.99984.08800.99994.13510.99994.79330.9999L57.10430.99998.68810.99998.64180.999910.06330.9999L67.97170.99999.38860.99999.39890.999810.77030.9999L712.0020.999914.7490.999514.7310.999917.0740.9990L8224830.9997279280.9989272460.9999303080.9997分别采用校准曲线法和单点校准法进行定量分析。对摩尔分数10µmol/mol~600µmol/mol范围内6个不同浓度点的氦气、摩尔分数5烷、正戊烷、正己烷、苯、甲苯进行色谱分析。校准曲线法以组分的摩尔分数标称值为横坐标，峰面积为纵坐标，斜率和截距依据最小二乘法100µmol/mol氮气、2µmol/mol烃类气体标准物质为校准样品计算。以1结果表明，两种定量方式得到的分析结果一致性良好，均可以作为定量分析用。在日常分析中，由于实验室不方便且较难获得准确度高的多个浓度水平的标准物质，使得校准曲线定量方式不宜使用，因此，本方法确定将单点校准法作为定量模式。按照表1分析条件，实验室L1对方法测定范围下限浓度值的氦气、氩气、氮气和C₁-C₆烃类、苯、甲苯气体标准物质进行检测，对应信噪比结果见表17,所得色谱图见图5和图6。表17组分在方法测定下限时信噪比含量/μmol/mol信噪比氦气氩气5氮气5甲烷乙烷丙烷正丁烷正戊烷正己烷苯甲苯图510μmol/mol氦气、5μmol/mol氩气和5μmol/mol氮气色谱图图60.1μmol/mol烃类色谱图5μmol/mol、各烃类摩尔分数在0.1μmol/mol时，各组分信噪比均不小于3,满足可信定量的要求。对氦气在测量范围(10μmol/mol~600μmol/mol)、氮气、氩气在测内进行实验室间研究。氦气、氩气和氮气组分方法精密度数据来自8个实验室间试验结果，参与实验室数量L=8,样品数S=6,重复数为2,由8个实验室、对6个样品进行的实验室间研究得到的数据列于表18~表20。甲烷组分方法精密度来自8个实验室间试验结果，参与实验室数量L=8,样品数S=6,重复数为2,由8个实验室、对6个样品进行的实验室间研究得到的数据列于表21。C₂-C₆烃类、苯、甲苯组分方法精密度来自8个实验室间试验结果，参与实验室数量L=8,样品数S=5,重复数为2,由8个实验室、对5个样品进行的实验室间研究得到的数据列于表22~表28。根据GB/T6683-2021对测试结果统计检验。氦气、氩气、氮气和各烃类精密度统计报告分别见附录一至附录十一。12121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212121212 氩气5~3000.2468x0.5811 苯0.02305x0.86250.05425x0.5580.03539x0.43080.02748x0.43150.03175x0.44170.01982(x-0.0001)0.3120.0486x0.67540.06726x0.5580.5645x0.43080.03414x0.43150.06486x0.44170.02222(x-0.0001)0.3120.05701x0.6754按照单点校准法定量，对两个实际样品进行方法重复性考察，验证rr参考ISO21087-2019对方法正确度确定的规定，方法的正确度根据各组分的实测值与标准物质标准值的的相对误差确定。采用单点校准定氮气组分在5μmol/mol～300μmol/mol测定范围内、甲烷组分在0.1μmol/mol～200μmol/mol测定范围内、C2-C6烃类、苯和甲苯组分在0.1测量范围内时，各浓度点测量值与标准值相对偏差计算值不大于L2L5L7L2L5L7标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L16036070.64%6036050.31%2992990.00%2992990.00%99.599.1-0.42%99.594.451.951.90.01%51.947.6-8.23%30.231.23.24%30.227.9-7.56%406%-667%L46046121.32%6106150.75%2982980.00%2992990.00%97.693.2-4.55%98.997.551.452.92.91%52.049.8-4.31%30.132.06.38%30.431.43.31%8.32-18.45%10.45%L66106026036091.01%2992990.00%2992990.00%98.999.40.54%99.598.052.051.451.953.02.08%30.428.3-6.80%30.231.393.94%8.30-18.64%10.80%L95825723023020.00%99.597.951.952.20.61%30.130.92.69%10.70%L2L5L7L2L5L7标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L13033060.99%3033102.39%0.00%0.00%49.449.91.05%49.444.5-9.91%20.220.220.2-2.56%9.66-3.37%8.68566%441L4302302-0.03%30030399.799.70.00%99.299.20.00%48.549.21.52%49.249.820.020.020.218.86%3.06%5.095.04-0.89%5.293.46%L63003020.71%3033040.26%99.2990.00%0.00%49.248.0-2.41%49.449.4-0.04%20.2-2.63%20.221.04.08%9.69.93-0.75%5.527.97%5.385.03%L9290283-2.53%98.798.70.00%49.450.82.81%20.220.00.94%5.154.86-5.56%L2L5L7L2L5L7标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L13063101.40%3063173.50%0.00%0.00%50.049.8-0.32%50.050.81.55%20.520.120.520.50.04%9.8-2.60%0.85%-996%542630%L43063090.82%3043122.78%0.00%0.00%49.148.7-0.80%49.749.5-0.48%20.322.820.5-3.21%19.33%9.89-3.02%5.155.9816.20%5.174.73-8.55%L6304297306304-0.52%0.00%0.00%49.748.150.049.8-0.35%20.520.120.521.49.6-5.93%17.39%5.174.79-7.37%5.106.0819.27%L9294286-2.82%99.999.90.00%50.048.6-2.74%20.421.13.58%16.60%5.214.72-9.42%L2L4L6L8L2L4L6L8标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L1203201-0.94%2032124.33%99.997.799.92.96%-0.29%1.57%0.00%0.00%0.22%0.977-2.32%0.1010.1020.78%0.1010.1042.57%L31.65%-2.04%99.71.86%99.297.2-2.02%9.989.7-2.71%9.70.00%2.012.010.00%3.64%1.34%0.1010.11715.84%0.1000.11615.82%L5200202200-0.42%99.31.97%99.397.66.01%6.02%2.002.000.00%2.002.000.00%3.63%0.976-2.38%0.1010.11816.42%0.1010.1098.39%L72032082.38%2063.50%99.998.74.55%2.81%9.970.82%0.00%2.012.010.00%2.92%2.08%0.1010.0973-3.68%0.10.0858-14.23%标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L12.032.030.00%2.032.030.00%2.26%-2.54%0.5230.5331.98%L20.5230.5340.2060.204-0.82%0.2060.2300.1050.1071.85%0.1050.1060.76%L32.042.040.00%2.052.050.00%1.25%0.9930.5240.5331.78%L40.5190.494-4.76%0.2070.2258.76%0.2050.176-14.33%0.1030.11713.77%0.1040.12519.65%L52.052.050.00%2.052.050.00%0.38%0.81%0.5200.5291.78%L60.5200.5220.37%0.2060.2110.2060.205-0.70%0.1050.1093.42%0.1050.102-2.96%L72.032.030.00%2.052.050.00%1.22%6.03%0.5230.5291.24%L80.5170.5282.05%0.2060.2143.85%0.2070.185-10.67%0.1050.1104.98%0.1040.11914.81%标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L10.00%0.00%0.9910.982-0.96%0.990.969-2.26%0.4970.5051.51%L20.4970.4900.1960.1981.07%0.1960.178-9.03%0.09950.09780.09950.0960-3.57%L30.00%0.00%0.9630.939-2.48%0.960.9953.91%0.4970.490L40.4940.5215.46%0.1960.2075.71%0.1950.23218.81%0.09800.10810.29%0.09910.1055.83%L50.00%0.00%0.980.977-0.42%0.980.973-0.78%0.4950.5072.44%L60.4950.4880.1960.2075.54%0.1960.1981.04%0.1000.1066.41%0.1000.0987L70.00%0.00%0.9910.92%0.9720.9760.45%0.4970.503L80.4920.4670.1960.2043.91%0.1970.197-0.06%0.09950.1000.24%0.09880.1055.92%标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L10.00%0.00%1.26%-0.22%0.5070.5070.03%L20.5070.5110.88%0.2000.1980.2000.1960.1010.1020.77%0.10100.0971-3.91%L30.00%0.00%0.9790.9880.92%0.9770.970-0.73%0.5050.5345.65%L40.5040.5060.40%0.2010.2199.05%0.1990.2157.98%0.10000.1088.01%0.10110.1064.61%L50.00%0.00%0.9990.991-0.88%0.5050.5101.09%L60.5050.503-0.39%0.2000.2031.30%0.2000.1960.100012.05%0.1020.102-0.20%L70.00%0.00%0.9920.5070.502L80.5010.489-2.43%0.2000.2073.73%0.2010.200-0.38%0.1010.1042.73%0.1010.100标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L10.00%0.00%0.9840.9850.08%0.9840.979-0.56%0.4940.4970.64%L20.4940.490-0.78%0.1950.1950.1950.2013.08%0.09870.0980-0.69%0.09870.0985-0.25%L30.00%0.00%0.9520.9580.61%0.9510.9530.22%0.4930.5123.89%L40.4900.5012.29%0.1950.2023.75%0.1940.2076.96%0.09800.1056.67%0.09840.1045.71%L50.00%0.00%0.9740.9770.26%0.9740.9780.40%0.4910.490-0.30%L60.4910.4971.21%0.1950.1991.81%0.1950.194-0.45%0.10200.1042.31%0.09940.0965-2.89%L70.00%0.00%0.9840.9850.09%0.9650.934-3.20%0.4940.495L80.4880.4770.1950.1992.23%0.1950.185-5.02%0.09870.0982-0.51%0.09810.0977-0.41%标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L10.00%0.00%0.9800.9910.9800.976-0.37%0.4920.5022.00%L20.4920.4840.1940.2002.85%0.1940.2003.02%0.09830.0979-0.36%0.09830.1012.54%L30.00%0.00%0.9480.9500.9470.9500.27%0.4910.5073.22%L40.4880.4920.77%0.1950.1950.00%0.1930.2035.45%0.09700.09831.34%0.09800.1012.67%L51.05%0.00%0.9700.9640.9700.968-0.24%0.4890.487-0.99%L60.4890.4961.45%0.1940.1982.24%0.1940.1950.59%0.09900.1023.49%0.09900.1023.05%L70.00%0.00%0.9800.9921.20%0.9610.907-5.62%0.4920.5113.88%L80.4860.457-5.96%0.1940.2170.1950.180-7.83%0.098313.85%0.09770.0938-4.01%标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L10.00%0.00%0.9800.9820.23%0.9800.9961.59%0.4920.4960.77%L20.4920.469-4.65%0.1940.1940.02%0.1940.2003.20%0.09830.09890.64%0.09830.1012.54%L30.00%0.00%0.9480.9510.36%0.9470.941-0.68%0.4910.5103.96%L40.4880.484-0.74%0.1950.1910.1930.1993.06%0.09700.1003.37%0.09800.104L50.00%0.00%0.9700.9740.42%0.9700.9932.37%0.4890.489L60.4890.4930.80%0.1940.1950.53%0.1940.2013.76%0.09900.1022.54%0.09900.103L70.00%0.00%0.9800.9810.09%0.9610.9460.4920.491-0.29%L80.4860.4780.1940.2034.42%0.1950.1970.93%0.09830.1012.95%0.09770.0963标准值、测定值单位：μmol/mol实验室标准值测定均值相对偏差%实验室标准值测定均值相对偏差%L10.00%0.00%0.9820.977-0.51%0.9823.46%0.4930.492-0.29%L20.4930.473-4.05%0.1940.193-0.30%0.1940.2097.73%0.09850.1034.34%0.09850.1012.74%L30.00%0.00%0.9510.9510.03%0.9490.9611.28%0.4930.5052.42%L40.4890.4900.1940.1982.00%0.1930.2014.20%0.09700.09770.71%0.09820.109L50.00%0.00%0.9720.967-0.47%0.9720.968-0.37%0.4900.4920.43%L60.4900.490-0.05%0.1940.2003.22%0.1940.1961.09%0.09920.1000.78%0.09920.1000.36%L70.00%0.00%0.9820.9860.41%0.9630.9882.57%0.4930.4960.55%L80.4870.5114.93%0.1940.2024.33%0.1950.1970.97%0.09850.1045.39%0.09790.09830.39% --5表465μmol/mol～30-5 2-12-12-1 2-12-1 2-1 2-12-1某炼厂采用天然气制氢工艺生产质子交换膜燃料电池车用氢气。对该厂生产管线低压取样，氢气中氦气、氩气、氮气和烃类含量分析结果/(µmol/mol)552时间/min某炼厂苯乙烯车间采用乙苯脱氢法制苯乙烯，乙苯在催化剂作用下经脱氢反应得到苯乙烯，同时得到副产品氢气，除此以外，会副产甲烷、乙烷和乙烯。副产品氢气纯度一般在80%-90%,为提供质子交换膜燃料电池应用的纯度的氢气，进一步采用变压吸附(PSA)工艺纯化。对该厂生产管线低压取样，氢气中烃类含量分析结果列于表56,对应色谱图见图9。分析项目GB/T37244指标检测结果方法检测下限甲烷2乙烷2乙烯24采用国际标准和国外先进标准的程度，以及与国际、国外同类标准水平的对比情况，或与测试的国外样品、样机的有关数据对比情况GB/T37244推荐采用GB/T27894.3《天然气在一定不确定度下用气相色谱法测定组分第3部分：用两根填充柱测定氢、氦气、氧气、氮气、二氧气化碳和直至C8的烃类》测定燃料氢气中的氦气；采用GB/T3634.2《氢气第2部分：纯氢、高纯氢和超纯氢》测定氮气和氩气；采用GB/T8984《气体中一氧气化碳、二氧气化碳和碳氢化合物的测定气相色谱法》测定总烃。GB/T27894.3采用氩气作载气测定天然气中的氦气组分，而当测定氢气中的氦气组分时，大量的氢气会导致其和氦气无法分离，因此方法不适用与FCV用氢气中氦气的测定。GB/T3634.2是对纯氢、高纯氢和超纯氢的分析，要求对氩气的检测限低于0.2μmol/mol,对氮气的检测限低于0.4μmol/mol,而GB/T37244对燃料氢气的指标要求为总氮气和氩气<100μmol/mol,前者分析方法采用氦气离子化检测器完成，成3634.1《氢气第1部分工业氢》附录A测定工业氢中氧气、氩气和氮气含量的方法面临无法实现氩气和氧气分离的问题，需要在系统中增加脱氧气柱，利用差减法得到氩气含量。本方法基于双阀和双柱气相色谱系统，结合热导和氢火焰离子化检测器测定质子交换膜燃料电池汽车用氢气中氦气、氩气、氮气和烃类的含量，氦气检测下限达10μmol/mol,氩气和氮气检测下限达5μmol/mol,本标准与现行法律、法规、政策统一、协调一致，并与现行有效的国家标准和行业标准有很好的协调性，本标准在编制过程中参考并引用ISO21087analysis-Anexchangemembrane[PEM]fuelc为了使标准得到更好更有效的实施，应组织相关管理人员、技术人员和操作人员进行标准宣贯培训，使所有的技术人员和操作人员都能灵活掌握本标准的详细条款和具体要求，并在实际工作中得到认真地贯彻1D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.0D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:X^2.3628.Cycle:150040030020001000020000300004000050000BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-9.6354E-04(X-4.6053E+05),%S=66.4;RepeatsSD=-8.5556E-04(X-3.8479E+05),%S=73.627总3D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.0D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:X^2.3628.Cycle:150040030020001000020000300004000050000BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-9.6354E-04(X-4.6053E+05),%S=66.4;RepeatsSD=-8.5556E-04(X-3.8479E+05),%S=73.64果7总5D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.076总7D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.0D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:X^2.3628.Cycle:150040030020001000020000300004000050000BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-9.6354E-04(X-4.6053E+05),%S=66.4;RepeatsSD=-8.5556E-04(X-3.8479E+05),%S=73.687总9D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.07总D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.0D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:X^2.3628.Cycle:150040030020001000020000300004000050000BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-9.6354E-04(X-4.6053E+05),%S=66.4;RepeatsSD=-8.5556E-04(X-3.8479E+05),%S=73.67总D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.0D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:X^2.3628.Cycle:150040030020001000020000300004000050000BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-9.6354E-04(X-4.6053E+05),%S=66.4;RepeatsSD=-8.5556E-04(X-3.8479E+05),%S=73.67总y=Ln(X^0.5685)D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-1.0978E-02(X-1.2234E+02),%S=0.2;RepeatsSD=-6.7113E-03(X-1.3136E+02),%S=1.0D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:X^2.3628.Cycle:150040030020001000020000300004000050000BetweenLabsBetweenLabsWithinLabsWithinLabsBetweenLabsSD=-9.6354E-04(X-4.6053E+05),%S=66.4;RepeatsSD=-8.5556E-04(X-3.8479E+05),%S=73.66总D02.xx,RRDataforAinBbyC,ComponentD,xx/xx/xxCurrenttransformation:NONE.Cycle:10.90.80.70.60.50.40.30.2405060708090100BetweenLabsBetweenLabsWithinLab