第38卷第4期Jon五聲n筆m學(xué)學(xué)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(cè)測(cè)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(xué)化學(xué)系,浙江杭州310028;2.戴安中國(guó)有限公司上海實(shí)驗(yàn)室,上海2012033.杭州職業(yè)技術(shù)學(xué)院,浙江杭州310018)犢要:建立了陽(yáng)離子交換-電霧檢測(cè)器測(cè)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(shí)驗(yàn)采用 Ion Pac CS17陽(yáng)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(lèi)、淋洗液種類(lèi)與濃度對(duì)分離測(cè)定有機(jī)醇胺的影響.所測(cè)3種有機(jī)醇胺的檢出限分別為0.21、0.04、0.32gg·mL,線(xiàn)性范圍在1.0~100gg·mL-',相關(guān)系數(shù)分別為0.9996、0.9993和0.9992,加標(biāo)回收奉為87%~98%.用所建立的方法測(cè)定了CO2吸收液中有機(jī)胺質(zhì)量濃度,結(jié)果令人滿(mǎn)意關(guān)鍵詞:陽(yáng)離子交換;電霧檢測(cè)器;有機(jī)醇胺中圖分類(lèi)號(hào):O657.7文獻(xiàn)標(biāo)志碼:A章編號(hào):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(yīng)用于天然氣、煉廠(chǎng)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(lèi)CO2吸收劑研究與生產(chǎn)過(guò)程中,對(duì)的有效途徑就是從各種排放氣體中分離回收CO2,有機(jī)胺成分及質(zhì)量濃度測(cè)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(jī)胺類(lèi)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(jì)效益,以有機(jī)胺水溶液(主醇胺類(lèi)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(xiàng)目:浙江省自然科學(xué)基金資助項(xiàng)目(Y2110945R4080124Y507252);浙江省分析測(cè)試基金資助項(xiàng)目(2007F70061)作者簡(jiǎn)介:葉明立(1978-),男,碩士,主要從事分析測(cè)試方法的研究通信作者,E-mail:chenyu57@163.com434浙江大學(xué)學(xué)報(bào)(理學(xué)版)第38卷不是太適合;而在反相液相色譜柱上,醇胺類(lèi)保留很2.2乙腈體積分?jǐn)?shù)對(duì)分離的影響弱,需要進(jìn)行復(fù)雜的衍生才能進(jìn)行測(cè)定有機(jī)胺具有一定的疏水性,加入有機(jī)溶劑可減電霧檢測(cè)器(CAD)是新型通用型檢測(cè)器81,少有機(jī)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(guò)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?jǐn)?shù)乙腈作對(duì)比實(shí)氣顆粒反向相遇,經(jīng)碰撞使溶質(zhì)顆粒帶上正電,用檢驗(yàn).發(fā)現(xiàn)適度增加乙腈的體積分?jǐn)?shù),可以改善峰型,測(cè)器測(cè)出帶電溶質(zhì)的信號(hào)電流,由此產(chǎn)生的信號(hào)電提高塔板數(shù),但對(duì)3種有機(jī)胺出峰時(shí)間影響不大.在流與溶質(zhì)的質(zhì)量濃度呈正比.CAD可實(shí)際應(yīng)用于任流動(dòng)相中加入體積分?jǐn)?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(cè).2.3甲酸體積分?jǐn)?shù)對(duì)分離的影響本方法根據(jù)MEA、DEA、MDEA的理化性質(zhì),陽(yáng)離子交換分離機(jī)理中,淋洗液離子體積分?jǐn)?shù)越采用陽(yáng)離子交換色譜柱9-10分離、CAD電霧檢測(cè)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(cè)定CO2吸收液中醇胺類(lèi)化合物,結(jié)果令人滿(mǎn)意的洗脫時(shí)間越短.在流速、乙腈體積分?jǐn)?shù)恒定情況下,改變甲酸體積分?jǐn)?shù)0.02%、0.05%、0.1%、0.2%1材料與方法0.3%作對(duì)比試驗(yàn)甲酸體積分?jǐn)?shù)在0.1%時(shí),3種有機(jī)胺達(dá)到完全分離,且出峰時(shí)間比較適宜1.1儀器與試劑2.4線(xiàn)性關(guān)系、線(xiàn)性范圍及檢出限D(zhuǎn)ionex ics-5000色譜儀(美國(guó)戴安公司),配用標(biāo)準(zhǔn)品配制7種不同質(zhì)量濃度的混合標(biāo)準(zhǔn)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(cè)器;AS自動(dòng)進(jìn)樣器2.0、5.0、10.0、20.0、50.0、100g·mL1,對(duì)上述乙醇胺(MEA)、二乙醇胺(DEA)、N甲基二溶液各測(cè)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?cè)噭┵?gòu)自上海醫(yī)藥積為縱坐標(biāo),標(biāo)準(zhǔn)液質(zhì)量濃度為橫坐標(biāo)建立標(biāo)準(zhǔn)工集團(tuán)有限公司,實(shí)驗(yàn)用水為超純水作曲線(xiàn),3種物質(zhì)的線(xiàn)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(shí)峰面積與質(zhì)量采用 Ion Pac CG17(50mm×0.4mm)保護(hù)柱和濃度呈線(xiàn)性響應(yīng),相關(guān)系數(shù)為0992~0.9996.以信IonPac CS17(250mm×0.4mm)分離柱.流動(dòng)相為噪比(S/N)為3計(jì)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(jìn)樣體積5μL,柱溫30℃表1方法的線(xiàn)性關(guān)系電霧檢測(cè)器參數(shù):氮?dú)鈮毫?4kPa;霧化溫度Table 1 Aggression equation of the analyte determined25℃;檢測(cè)范圍設(shè)置為100pA被測(cè)物回歸方程線(xiàn)性范圍Analyte regression equation相關(guān)系數(shù)r(pg·mL-1)2結(jié)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(yáng)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(yáng)離X-0.0008子交換機(jī)理與反相機(jī)理相結(jié)合的混合基質(zhì)色譜柱對(duì)MDEAY=0.03110.9992X+0.00131.0~1其進(jìn)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(jìn)行實(shí)驗(yàn). Acclaim2.5重現(xiàn)性WCX-1柱流失比較嚴(yán)重,CAD檢測(cè)器背景噪音達(dá)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(biāo)準(zhǔn)溶液,重復(fù)進(jìn)樣11次,記錄色譜圖(見(jiàn)圖柱,CAD檢測(cè)器背景噪音<5pA,但調(diào)整流動(dòng)相仍1).它們保留時(shí)間的相對(duì)標(biāo)準(zhǔn)偏差分別為0.04%無(wú)法使3種有機(jī)胺達(dá)到基線(xiàn)分離. IonPac CS17柱0.03%、0.08%,峰面積的相對(duì)標(biāo)準(zhǔn)偏差分別為對(duì)3種有機(jī)胺保留合適,且背景噪音<5pA.因此,1.21%、0.81%、0.61%,峰高的相對(duì)標(biāo)準(zhǔn)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(cè)測(cè)定CO2吸收液中一乙醇胺、二乙醇胺、N甲基二乙醇胺4351003結(jié)論本方法采用陽(yáng)離子色譜法電霧檢測(cè)器測(cè)定00CO2吸收液中的有機(jī)胺,進(jìn)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(biāo)準(zhǔn)溶液的色譜圖N甲基二乙醇胺有較好的線(xiàn)性和重現(xiàn)性以及較為Fig 1 Chromatogram of standard solution理想的檢測(cè)下限,也解決了部分有機(jī)胺電導(dǎo)響應(yīng)靈1;MEA(50·mL-1),2;DEA(5rg·mL-1),3:MDEA敏度不高等問(wèn)題,可以應(yīng)用于CO2吸收液實(shí)際樣品的測(cè)定2.6樣品測(cè)定及回收率樣品稀釋100倍,經(jīng)過(guò)0.22gm濾膜過(guò)濾后,參考文獻(xiàn)( References)按“1.2”節(jié)色譜條件進(jìn)行測(cè)定,外標(biāo)法定量,其分析結(jié)果見(jiàn)表2.為確保檢驗(yàn)方法的準(zhǔn)確性,在原樣品中[1] LIN Po-hsun, KO Chih-chiang, LI Meng-hui. 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