第38卷第4期Jon五聲n筆m學學圖uo2011年7月http://www.journalszju.educn/sciDOI:10.3785/j.issn.1008-9497.2011.04.015離子交換電霧檢測測定CO2吸收液中乙醇胺、二乙醇胺、N-甲基二乙醇胺葉明立12,陳郁3(1.浙江大學化學系,浙江杭州310028;2.戴安中國有限公司上海實驗室,上海2012033.杭州職業(yè)技術學院,浙江杭州310018)犢要:建立了陽離子交換-電霧檢測器測定CO吸收液中一乙醇胺、二乙醇胺、N甲基二乙醇胺的分析方瀆,實驗采用 Ion Pac CS17陽離于交換柱,選用甲酸與乙腈溶液為淋洗液,并考察了色譜柱種類、淋洗液種類與濃度對分離測定有機醇胺的影響.所測3種有機醇胺的檢出限分別為0.21、0.04、0.32gg·mL,線性范圍在1.0~100gg·mL-',相關系數(shù)分別為0.9996、0.9993和0.9992,加標回收奉為87%~98%.用所建立的方法測定了CO2吸收液中有機胺質(zhì)量濃度,結果令人滿意關鍵詞:陽離子交換;電霧檢測器;有機醇胺中圖分類號:O657.7文獻標志碼:A章編號:10089497(2011)04-433-03YE Ming-li 2, CHEN Yu(1. Department of Chemistry, Zhejiang University, Hangzhou 310028, China;2. 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 Ion 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 1.0100 ugcorrelation coefficients were 0. 9996, 0. 9993 and 0. 9992, and the detection limits(S/N=3)were 0. 21, 0.040. 32 ug.mL 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要為一乙醇胺(MEA)、二乙醇胺(DEA)、N甲基二乙0引言醇胺(MDEA))為吸收劑的CO2吸收法廣泛應用于天然氣、煉廠氣、合成氣及煙氣等各種氣體凈化工藝CO2是主要的溫室氣體之一,減少CO2排放量中1-2).在醇胺類CO2吸收劑研究與生產(chǎn)過程中,對的有效途徑就是從各種排放氣體中分離回收CO2,有機胺成分及質(zhì)量濃度測定有著重要的意義用于生產(chǎn)尿素純堿等化工產(chǎn)品.因此,從各種排放有機胺類化合物,主要采用氣質(zhì)聯(lián)用GC氣體中分離提純CO2并加以利用,不僅具有重要的MS4,反相液相色譜HPLC5等方法分析,但由于環(huán)境效益,而且具有經(jīng)濟效益,以有機胺水溶液(主醇胺類化合物熱不穩(wěn)定,易分解,采用GCMS分析收稿日期:2011-03-20.基金項目:浙江省自然科學基金資助項目(Y2110945R4080124Y507252);浙江省分析測試基金資助項目(2007F70061)作者簡介:葉明立(1978-),男,碩士,主要從事分析測試方法的研究通信作者,E-mail:chenyu57@163.com434浙江大學學報(理學版)第38卷不是太適合;而在反相液相色譜柱上,醇胺類保留很2.2乙腈體積分數(shù)對分離的影響弱,需要進行復雜的衍生才能進行測定有機胺具有一定的疏水性,加入有機溶劑可減電霧檢測器(CAD)是新型通用型檢測器81,少有機胺與固定相疏水表面的吸附作用,改善峰形色譜淋洗液及被分析物經(jīng)霧化器霧化,其中分析物與分離度,在流速恒定情況下,通過5%、10%、液滴在室溫下干燥形成溶質(zhì)顆粒,與帶正電荷的氮15%、20%和30%等不同體積分數(shù)乙腈作對比實氣顆粒反向相遇,經(jīng)碰撞使溶質(zhì)顆粒帶上正電,用檢驗.發(fā)現(xiàn)適度增加乙腈的體積分數(shù),可以改善峰型,測器測出帶電溶質(zhì)的信號電流,由此產(chǎn)生的信號電提高塔板數(shù),但對3種有機胺出峰時間影響不大.在流與溶質(zhì)的質(zhì)量濃度呈正比.CAD可實際應用于任流動相中加入體積分數(shù)為10%乙腈較適宜何非揮發(fā)或半揮發(fā)化合物的分析檢測.2.3甲酸體積分數(shù)對分離的影響本方法根據(jù)MEA、DEA、MDEA的理化性質(zhì),陽離子交換分離機理中,淋洗液離子體積分數(shù)越采用陽離子交換色譜柱9-10分離、CAD電霧檢測器高淋洗液從固定相置換溶質(zhì)離子越有效溶質(zhì)離子測定CO2吸收液中醇胺類化合物,結果令人滿意的洗脫時間越短.在流速、乙腈體積分數(shù)恒定情況下,改變甲酸體積分數(shù)0.02%、0.05%、0.1%、0.2%1材料與方法0.3%作對比試驗甲酸體積分數(shù)在0.1%時,3種有機胺達到完全分離,且出峰時間比較適宜1.1儀器與試劑2.4線性關系、線性范圍及檢出限Dionex ics-5000色譜儀(美國戴安公司),配用標準品配制7種不同質(zhì)量濃度的混合標準溶PEEK泵, Chromeleon色譜工作站; CORONA UL-液MEA、DEA與MDEA質(zhì)量濃度分別為1.0、TRA電霧檢測器;AS自動進樣器2.0、5.0、10.0、20.0、50.0、100g·mL1,對上述乙醇胺(MEA)、二乙醇胺(DEA)、N甲基二溶液各測定3次后,取其峰面積的平均值,以峰面乙醇胺(MDEA),均為分析純試劑購自上海醫(yī)藥積為縱坐標,標準液質(zhì)量濃度為橫坐標建立標準工集團有限公司,實驗用水為超純水作曲線,3種物質(zhì)的線性回歸方程如表1所示.可以1.2色譜條件看出,3種物質(zhì)在1.0~100g·mL時峰面積與質(zhì)量采用 Ion Pac CG17(50mm×0.4mm)保護柱和濃度呈線性響應,相關系數(shù)為0992~0.9996.以信IonPac CS17(250mm×0.4mm)分離柱.流動相為噪比(S/N)為3計算檢出限,MEA、DEA、MDEA的V(乙腈):V(甲酸)=10:90等度淋洗流速為檢出限分別為0.21、0.04、0.32四g·mL1.1.4mL·min-';進樣體積5μL,柱溫30℃表1方法的線性關系電霧檢測器參數(shù):氮氣壓力24kPa;霧化溫度Table 1 Aggression equation of the analyte determined25℃;檢測范圍設置為100pA被測物回歸方程線性范圍Analyte regression equation相關系數(shù)r(pg·mL-1)2結果與討論Linear rangeMEAY=0.02682.1色譜柱的選擇X-0.00020.99961.0~100MEA、DEA、MDEA在酸性情況下均以陽離子Y=0.0991DEA0.99931.0~1的形式存在,但也表現(xiàn)一定的疏水性.因此采用陽離X-0.0008子交換機理與反相機理相結合的混合基質(zhì)色譜柱對MDEAY=0.03110.9992X+0.00131.0~1其進行分離選擇 Acclaim WCX-1柱、 Acclaim Trinity P1it Y peak area: X, mass concentration of analyte, Hg. mL-I柱和 Ion Pac CS17柱作為分離柱進行實驗. Acclaim2.5重現(xiàn)性WCX-1柱流失比較嚴重,CAD檢測器背景噪音達吸取MEA、 DEA MDEA質(zhì)量濃度為50g·m1到50pA,不適合用于該方法 Acclaim Trinity P1的混合標準溶液,重復進樣11次,記錄色譜圖(見圖柱,CAD檢測器背景噪音<5pA,但調(diào)整流動相仍1).它們保留時間的相對標準偏差分別為0.04%無法使3種有機胺達到基線分離. IonPac CS17柱0.03%、0.08%,峰面積的相對標準偏差分別為對3種有機胺保留合適,且背景噪音<5pA.因此,1.21%、0.81%、0.61%,峰高的相對標準偏差分別選擇 Ion Pac cs17柱作為分離柱為1.60%、0.61%、1.29%,重現(xiàn)性較好第4期葉明立,等:離子交換電霧檢測測定CO2吸收液中一乙醇胺、二乙醇胺、N甲基二乙醇胺4351003結論本方法采用陽離子色譜法電霧檢測器測定00CO2吸收液中的有機胺,進一步優(yōu)化了分離條件,在等淋洗條件下分離一乙醇胺、二乙醇胺、N甲基001020304050600809010二乙醇胺.在此色譜條件下,一乙醇胺、二乙醇胺圖1標準溶液的色譜圖N甲基二乙醇胺有較好的線性和重現(xiàn)性以及較為Fig 1 Chromatogram of standard solution理想的檢測下限,也解決了部分有機胺電導響應靈1;MEA(50·mL-1),2;DEA(5rg·mL-1),3:MDEA敏度不高等問題,可以應用于CO2吸收液實際樣品的測定2.6樣品測定及回收率樣品稀釋100倍,經(jīng)過0.22gm濾膜過濾后,參考文獻( References)按“1.2”節(jié)色譜條件進行測定,外標法定量,其分析結果見表2.為確保檢驗方法的準確性,在原樣品中[1] LIN Po-hsun, KO Chih-chiang, LI Meng-hui. 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