离子色谱法同时测定脱硫液中8种有机胺类物质

doi:10.3724/SP.J.1123.2023.09024

摘要/Abstract

摘要：

有机胺脱硫工艺因高效、经济等优点,应用越来越广泛。不同配比的有机胺对二氧化硫脱除效果不同。因此,对脱硫液中的不同有机胺成分进行准确测定具有重要意义。离子色谱法检测有机胺不需要衍生步骤,前处理简单,并且可同时测定多种有机胺。本研究采用离子色谱法同时测定乙醇胺(MEA)、二乙基乙醇胺(DEEA)、N-甲基二乙醇胺(MDEA)、2-氨基-2-甲基-1-丙醇(AMP)、羟乙基乙二胺(AEEA)、哌嗪(PZ)、N-羟乙基哌嗪(HEPZ)、二乙烯三胺(DETA)等8种有机胺。实验对比不同型号色谱柱、淋洗液和柱温条件对8种有机胺的分离效果,最终采用IonPac CS17色谱柱,柱温35 ℃,甲基磺酸(MSA)水溶液梯度淋洗,抑制电导法进行测定。脱硫液样品采用超纯水稀释,过0.22 μm尼龙微孔滤膜和OnGuard Ⅱ RP柱后进样分析,样品前处理简便。8种有机胺在一定范围内具有良好的线性关系,判定系数R²≥0.9980。以信噪比(S/N)=3时对应的有机胺质量浓度为检出限(LOD),以S/N=10时对应的有机胺质量浓度为定量限(LOQ)。在进样量1.0 μL时,LOD即可达到0.02~0.08 mg/L, LOQ为0.07~0.27 mg/L。实际样品的加标回收率为93.0%~111%,相对标准偏差(RSD, n=5)为0.31%~1.2%,说明方法具有良好的准确性和精密度,适用于脱硫液中多种有机胺的测定。

关键词: 离子色谱, 有机胺类物质, 脱硫液

Abstract:

The applications of organic-amine desulfurization have steadily increased owing to its high efficiency, low cost, and low energy consumption. Different proportions of organic amines exert different effects on sulfur dioxide removal. Therefore, the accurate determination of different organic amines in the desulfurization solution is of great importance. The ion-chromatographic method for the detection of organic amines does not require a derivatization step, has simple pretreatment procedures, and allows for the simultaneous determination of many types of organic amines. In this study, a method based on ion chromatography was developed for the simultaneous determination of ethanolamine (MEA), diethylethanolamine (DEEA), n-methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP), hydroxyethylethylenediamine (AEEA), piperazine (PZ), n-hydroxyethylpiperazine (HEPZ), and diethylenetriamine (DETA). The separation efficiency of the eight organic amines in different types of columns, leaching solutions, and column temperatures were compared. The determination was performed using an IonPac CS17 column with column temperature of 35 ℃ and gradient leaching with methyl sulfonic acid (MSA) solution via the inhibition conductance method. Samples of the desulfurization solution were analyzed using ultrapure water filtered through a 0.22 μm nylon microporous filter membrane and an OnGuard Ⅱ RP column; thus, the pretreatment steps are simple. The eight organic amines showed a good linear relationship within a certain concentration range, and the coefficient of determinations (R²) were greater than 0.998. The limits of detection (LODs) and quantification (LOQs) were determined from the mass concentrations of the organic amines corresponding to signal-to-noise ratios (S/N) of 3 and 10, respectively. LODs of 0.02-0.08 mg/L and LOQs of 0.07-0.27 mg/L were determined from a 1.0 μL sample injection. The actual recoveries ranged from 93.0% to 111%, and the relative standard deviations (RSDs, n=5) ranged from 0.31% to 1.2%. The results indicated that the proposed method has good accuracy and precision; thus, it is suitable for the determination of various organic amines in desulfurization solution.

Key words: ion chromatography (IC), organic amines, desulfurization solution

中图分类号:

O658

高立红, 姜振邦, 郑洪国, 厉文辉. 离子色谱法同时测定脱硫液中8种有机胺类物质[J]. 色谱, 2024, 42(5): 452-457.

GAO Lihong, JIANG Zhenbang, ZHENG Hongguo, LI Wenhui. Simultaneous determination of eight organic amines in desulfurization solution by ion chromatography[J]. Chinese Journal of Chromatography, 2024, 42(5): 452-457.

图/表 6

图1 CS19和CS17色谱柱分离8种有机胺的色谱图

Fig. 1 Chromatograms of the eight organic amines by CS19 and CS17 columns MEA: monoethanolamine; AMP: 2-amino-2-methyl-1-propanol; MDEA: N-methyldiethanolamine; DEEA: diethylethanolamine; AEEA: aminoethylethanolamine; PZ: piperazine; HEPZ: 1-(2-hydroxyethyl)piperazine; DETA: diethylenetriamine.

图2 不同柱温条件下8种有机胺的色谱图

Fig. 2 Chromatograms of the eight organic amines at different column temperatures Elution program: 0-8 min, 3 mmol/L; 8-25 min, 3-17 mmol/L; 25-33 min, 17 mmol/L; 33-33.1 min, 17-3 mmol/L; 33.1-38 min, 3 mmol/L.

图3 不同淋洗液梯度洗脱程序下8种有机胺的色谱图

Fig. 3 Chromatograms of the eight organic amines under different gradient eluent programs Gradient eluent program: a. 0-8 min, 3 mmol/L; 8-25 min, 3-17 mmol/L; 25-33 min, 17 mmol/L; 33-33.1 min, 17-3 mmol/L; 33.1-38 min, 3 mmol/L. b. 0-20 min, 2 mmol/L; 20-34 min, 2-17 mmol/L; 34-41 min, 17 mmol/L; 41-41.1 min, 17-2 mmol/L; 41.1-45 min, 2 mmol/L. c. 0-19 min, 1 mmol/L; 19-34 min, 1-17 mmol/L; 34-41 min, 17 mmol/L; 41-41.1 min, 17-1 mmol/L; 41.1-45 min, 1 mmol/L.

表1 8种有机胺的线性范围、判定系数、检出限和定量限

Table 1 Linear ranges, coefficients of determination (R2), LODs and LOQs of the eight organic amines

Compound	Linear range/(mg/L)	R²	Linear equation	LOD/(mg/L)	LOQ/(mg/L)
MEA	10-200	0.9993	y=0.0071x-0.0011	0.05	0.17
AMP	10-200	0.9999	y=0.0044x-0.0137	0.08	0.27
MDEA	10-200	0.9994	y=0.0023x+0.0065	0.05	0.17
DEEA	10-200	0.9999	y=0.0036x-0.0060	0.04	0.14
AEEA	10-200	0.9980	y=0.0036x+0.0164	0.02	0.07
PZ	10-200	0.9990	y=0.0046x+0.0102	0.02	0.07
HEPZ	10-200	0.9992	y=0.0046x+0.0357	0.03	0.10
DETA	10-200	0.9988	y=0.0068x+0.0512	0.04	0.14

表2 8种有机胺在脱硫液中的加标回收率(n=5)

Table 2 Spiked recoveries of the eight organic amines in desulfurization solution (n=5)

Compound	Background/ (g/L)	Added/ (g/L)	Found/ (g/L)	Recovery/ %	RSD/ %	Compound	Background/ (g/L)	Added/ (g/L)	Found/ (g/L)	Recovery/ %	RSD/ %
MEA	8.45	5.0	13.4	99.0	0.51	AEEA	nd	1.0	1.10	110	0.87
		7.5	15.7	96.7	0.97			5.0	5.27	105	0.47
		16	24.0	97.2	0.85			20	20.5	103	0.88
AMP	nd	1.0	0.97	97.0	0.93	PZ	nd	1.0	0.98	98.0	0.93
		5.0	5.29	105	0.46			5.0	5.23	104	0.43
		20	19.2	96.0	1.2			20	19.8	99.0	0.98
MDEA	10.1	5.0	15.0	98.0	0.40	HEPZ	6.10	2.5	8.68	103	0.31
		10	19.6	95.0	0.78			5.0	11.2	102	0.34
		20	29.3	96.0	0.95			12	17.9	98.3	0.63
DEEA	nd	1.0	0.93	93.0	0.75	DETA	nd	1.0	1.07	107	0.84
		5.0	5.01	100	0.52			5.0	5.57	111	0.47
		20	19.6	98.0	1.0			20	20.3	102	0.68

表3 脱硫液样品中有机胺的含量

Table 3 Contents of organic amines in desulfurization solution samples g/L

No.	MEA	AMP	MDEA	DEEA	AEEA	PZ	HEPZ	DETA
1	101	<LOD	168	<LOD	<LOD	<LOD	56.5	<LOD
2	85.3	<LOD	140	<LOD	<LOD	<LOD	38.8	<LOD
3	82.0	<LOD	131	<LOD	<LOD	<LOD	33.2	<LOD
4	8.45	<LOD	10.1	<LOD	<LOD	<LOD	6.10	<LOD

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