离子交换电雾检测测定CO2吸收液中一乙醇胺、二乙醇胺、N-甲基二乙醇胺

渐江大学学报(理学版第38卷第4期Journal of Zhejiang University( Science Edition)Vol 38 No 42011年7http://www.journalszju.edu.cn/sciJul. 2011DOI:10.3785/.issn.10089497.2011.04.015离子交换电雾检测测定CO2吸收液中乙醇胺、二乙醇胺、N-甲基二乙醇胺叶明立12,陈郁3(1.淅江大学化学系,浙江杭州310028;2.戴安中国有限公司上海实验室,上海201203;3.杭州职业技术学院,浙江杭州310018)犢要:建立了阳离子交换-电雾检测器测定CO吸收液中一乙醇胺、二乙醇胺、N甲基二乙酶胺的分析方渎,实验禾Ion Pac CS17阳离子交换柱,选用甲酸与乙腈溶液为淋洗液,并考察了色谱柱种类、淋洗液种类与浓度对分离测定有机醇胺的彩响.所测3种有机醇胺的检出限分别为0.21、0.04、0.32gg·mL1,线性范围在1.0~100gg·mL-,相关系数分别为0.996、0.9993和0.9992,加标回收奉为87%~98%.用所建立的方法测定了CO2吸收液中有机胺质量浓度,结果令人满意关键词:阳离子交换;电雾检测器;有机醇胺中图分类号:O657.7文献标志码:A文章编号:1008-9497(2011)04433-03YE Ming-li.2, CHEN Yu(1. Department of Chemistry, Zhejiang University, Hangzhou 310028, Chinas2. Shanghai Lab, Dionex China Co LTD, Shanghai 201203, China: 3. Hangzhou Vocational and TechnicalCollege, Hangzhou 310018, China)Determination of monoethanolamine, diethanolamine and diethanolmethylamine in the absorption liquid of co, by ionhromatography with charged aerosol detector Journal of Zhejiang University( Science Edition), 2011, 38(4): 433-435Abstract: A method was developed for the determination of monoethanolamine, diethanolamine and Diethanolmethylamine in the absorption liquid of CO, by cation-exchange ion chromatography with charged aerosol detector(CAD). Chromatographic separation was performed on a Dionex lon Pac CS17(250X 4 mm), fomic acid and aceton-trile were used as eluent, respectively. The effects of the types of column, eluent, eluent concentration of organic alcoholamines were investigated. The linear ranges of the method for three alcohol amines were 1. 0-100 ug.mL , thecorrelation coefficients were 0. 9996, 0. 9993 and 0. 9992, and the detection limits(S/N=3)were 0. 21, 0.040. 32 ug. I respectively. The method was successfully applied to determine organic alcohol amines in real sam-ple. The recoveries of three organic alcohol amines after spiking were from 87% to 98%Key Words: cation-exchange; charged aerosol detector; organic alcohol amine要为一乙醇胺(MEA)、二乙醇胺(DEA)、N甲基二乙0引言醇胺(MDEA))为吸收剂的CO2吸收法广泛应用于天然气、炼厂气、合成气及烟气等各种气体净化工艺CO2是主要的温室气体之一,减少CO2排放量中-2,在醇胺类CO2吸收剂研究与生产过程中对的有效途径就是从各种排放气体中分离回收CO2,有机胺成分及质量浓度测定有着重要的意义用于生产尿素、纯碱等化工产品.因此,从各种排放有机胺类化合物,主要采用气质联用GC气体中分离提纯CO2并加以利用,不仅具有重要的Ms,反相液相色谱HPLC5等方法分析,但由于环境效益,而且具有经济效益,以有机胺水溶液(主醇胺类化合物热不稳定,易分解,采用GCMS分析收稿日期:2011-03-20基金项目:淅江省自然科学基金资助项目(Y2110945R4080124Y507252);浙江省分析测作者简介:叶明立(1978-),男,硕士,主要从事分析测试方法的研究通信作者E-mail:chenyu0571@163.comTH中国煤化工CNMHG434浙江大学学报(理学版)第38卷不是太适合;而在反相液相色谱柱上,醇胺类保留很2.2乙腈体积分数对分离的影响弱,需要进行复杂的衍生才能进行测定有机胺具有一定的疏水性,加入有机溶剂可减电雾检测器(CAD)是新型通用型检测器-81,少有机胺与固定相疏水表面的吸附作用,改善峰形色谱淋洗液及被分析物经雾化器雾化,其中分析物与分离度.在流速恒定情况下,通过5%、10%液滴在室温下干燥形成溶质颗粒,与带正电荷的氮15%20%和30%等不同体积分数乙腈作对比实气颗粒反向相遇,经碰撞使溶质颗粒带上正电,用检验发现适度增加乙腈的体积分数,可以改善峰型,测器测出带电溶质的信号电流由此产生的信号电提高塔板数但对3种有机胺出峰时间影响不大在流与溶质的质量浓度呈正比CAD可实际应用于任流动相中加入体积分数为10%乙腈较适宜何非挥发或半挥发化合物的分析检测2.3甲酸体积分数对分离的影响本方法根据MEA、DEA、MDEA的理化性质,阳离子交换分离机理中,淋洗液离子体积分数越采用阳离子交换色谱柱-10分离、CAD电雾检测器高淋洗液从固定相置换溶质离子越有效,溶质离子测定CO2吸收液中醇胺类化合物,结果令人满意.的洗脱时间越短.在流速、乙腈体积分数恒定情况下改变甲酸体积分数0.02%、0.05%、0.1%、0.2%1材料与方法0.3%作对比试验.甲酸体积分数在0.1%时,3种有机胺达到完全分离,且出峰时间比较适宜1.1仪器与试剂2.4线性关系、线性范围及检出限Dionex ics5000色谱仪(美国戴安公司),配用标准品配制7种不同质量浓度的混合标准溶PEE泵, Chromeleon色谱工作站; CORONA UL液MEA、DEA与MDEA质量浓度分别为1.0、TRA电雾检测器;AS自动进样器2.0、5.0、10.0、20.0、50.0、100g·mL1,对上述乙醇胺(MEA)、二乙醇胺(DEA)、N甲基二溶液各测定3次后,取其峰面积的平均值,以峰面乙醇胺(MDEA),均为分析纯试剂,购自上海医药积为纵坐标,标准液质量浓度为横坐标建立标准工集团有限公司,实验用水为超纯水作曲线,3种物质的线性回归方程如表1所示.可以1.2色谱条件看出,3种物质在1.0~100g·mL时峰面积与质量采用 Ion Pac CG17(50mm×0.4mm)保护柱和浓度呈线性响应,相关系数为0.9992~0.9996.以信Ion Pac CS17(250mm×0.4mm)分离柱.流动相为噪比(S/N)为3计算检出限,MEA、DEA、MDEA的V(乙腈):v(甲酸)=10:90等度淋洗流速为检出限分别为0.21、0.04、0.32g·mL1.4mL·min';进样体积5μL,柱温30℃.表1方法的线性关系电雾检测器参数:氮气压力24kPa;雾化温度Table 1 Aggression equation of the analyte determined25℃;检测范围设置为100pA被测物回归方程线性范围2结果与讨论Analyte regression equation相关系数r(g·mL-)Lanear rangeMEAY=0.0268X-0.00020.99961.0~1002.1色谱柱的选择MEA、DEA、MDEA在酸性情况下均以阳离子DEAY=0.09910.9993的形式存在,但也表现一定的疏水性.因此采用阳离X-0.00081.0~100子交换机理与反相机理相结合的混合基质色谱柱对Y=0.0311MDEA0.99921.0~1其进行分离X+0.0013选择 Acclaim WCX1柱、 Acclaim Trinity PlEE Y, peak area; X: mass concentration of analyte, Hg.mL柱和 Ion Pac CS17柱作为分离柱进行实验. Acclaim2.5重现性WCX-1柱流失比较严重,CAD检测器背景噪音达吸取 MEA DEA MDEA质量浓度为50g·mL1到50pA,不适合用于该方法 Acclaim Trinity P1的混合标准溶液,重复进样11次,记录色谱图(见图柱,CAD检测器背景噪音<5pA,但调整流动相仍1).它们保留时间的相对标准偏差分别为0.04%、无法使3种有机胺达到基线分离. Ion Pac CS17柱0.03%、0.08%对3种有机胺保留合适,且背景噪音<5pA.因此,1.21%、0.81%中国煤化工差分别为选择 Ion Pac CS17柱作为分离柱为1.60%、0.61%、YHECNMHGE偏差分别虽塊第4期叶明立,等:离子交换电雾检测测定CO2吸收液中一乙醇胺、二乙醇胺、N甲基二乙醇胺4351003结论g50本方法采用阳离子色谱法-电雾检测器测定0.0CO2吸收液中的有机胺,进一步优化了分离条件,在等淋洗条件下分离一乙醇胺、二乙醇胺、N甲基0.010203.040506.07.0809010.0二乙醇胺.在此色谱条件下,一乙醇胺、二乙醇胺、图1标准溶液的色谱图N-甲基二乙醇胺有较好的线性和重现性以及较为Fig. 1 Chromatogram of standard solution理想的检测下限,也解决了部分有机胺电导响应灵l:MEA(50g·mL1),2:DEA(5g·mL-1),3:MDEA敏度不高等问题,可以应用于CO2吸收液实际样品的测定2.6样品测定及回收率样品稀释100倍,经过0.22pm滤膜过滤后,参考文献( References)按“1.2”节色谱条件进行测定,外标法定量,其分析结果见表2为确保检验方法的准确性,在原样品中[1] LIN Po-hsun, KO Chih-chiang, LI Meng-hui. Ternary加入3个不同质量浓度标准工作溶液,经过同样的diffusion coefficients of diethanolamine and N-methyl样品前处理步骤,进行加标回收试验,回收率结果见diethanolaminein aqueous solutions containing dieth-品中 MEA, DEA, MDEA的质量浓度夏 Equilibr0765 elamine. 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