CN107621507B - Liquid chromatography analysis method for simultaneously quantifying glycine and iminodiacetic acid in diethanolamine dehydrogenation product - Google Patents
Liquid chromatography analysis method for simultaneously quantifying glycine and iminodiacetic acid in diethanolamine dehydrogenation product Download PDFInfo
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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Abstract
The invention discloses a liquid phase analysis method for simultaneously quantifying glycine and iminodiacetic acid in a diethanolamine dehydrogenation product, which comprises the steps of carrying out liquid phase chromatographic analysis after carrying out derivatization reaction on p-toluenesulfonylchloronitrile serving as a derivatization agent and amino acid in the diethanolamine dehydrogenation product, and respectively drawing standard curves by using peak areas of iminodiacetic acid derivatives and glycine derivatives to the concentrations of iminodiacetic acid and glycine. The peak area of an iminodiacetic acid (IDA) standard and the concentration of a standard substance are in linear correlation within the range of 0.5 g/L-2.500 g/L, the peak area of a glycine (Gly) standard substance and the concentration of the standard substance are in linear correlation within the range of 0.01 g/L-0.15 g/L, the correlation coefficients are all larger than 0.9990, and the relative standard deviation is smaller than 1.3%. The method has accurate analysis result, simple and convenient analysis steps and high analysis sensitivity, can be used for quantitative analysis of the product iminodiacetic acid and the byproduct glycine in the dehydrogenation reaction of the diethanolamine, can also be used for qualitative analysis of the product by liquid chromatography-mass spectrometry, and has important guiding significance for scientific research and industrial production of preparing the iminodiacetic acid by catalytic dehydrogenation of the diethanolamine.
Description
Technical Field
The invention relates to a quantitative analysis method capable of simultaneously measuring glycine and iminodiacetic acid in a diethanolamine dehydrogenation product.
Background
Iminodiacetic acid (IDA) is an important chemical raw material, is an important chemical fine intermediate with wide application, can be used as an intermediate of pesticide, and can also be used in electroplating industry, electronics, dye, water treatment and other fields.
The current common analytical methods for iminodiacetic acid are: potentiometric titration, ion chromatography, ultraviolet spectrophotometry, gas chromatography pre-column derivatization, reversed phase high performance liquid chromatography, and the like.
(1) Potentiometric titration method: research on a copper zirconium iminodiacetate catalyst prepared by Li Yanni diethanolamine oxidative dehydrogenation [ D ] Zhejiang: university of chekiang, 2011: 21-23; liuchangfei method of separating a mixture of glycine and iminodiacetic acid using electrodialysis [ P ]. chinese patent: 101792397A, 2010-8-4. When the potentiometric titration method is adopted, the content obtained by measurement is the content of all acids (including glycine, iminodiacetic acid and the like) in the sample, but the method has low sensitivity and poor accuracy of analysis results.
(2) Ion chromatography: the method for the on-line pretreatment and the post-column derivatization of the Jie ion chromatography is developed. [D] Zhejiang: zhejiang university, 2015: 63-68; although the analysis method is simple and convenient to operate and high in sensitivity, the sample solution needs to be continuously diluted, so that the analysis accuracy is influenced.
(3) Ultraviolet spectrophotometry: bhattacharyya S, Saha n.pecophotometric amplification of immunogenic acid in presence of primary amino acids, [ J ] Talanta,1976, 23: 331- > 332; huxin, luobu, an analytical method of iminodiacetic acid component in mother liquor of PMIDA: CN102706986A [ P ]. 2012. According to the analysis method, the sodium nitrite or the alum and the IDA are used for generating the complex, and the content of the iminodiacetic acid in the sample is calculated according to the comparison of the ultraviolet absorbance As of the complex in the sample and the ultraviolet absorbance Ar of the complex in a reference substance. The method has long preparation time in the early stage and complex operation, needs to detect a reference substance and a sample with a blank experiment respectively, needs to continuously adjust the dilution times until the absorbance is more than 0.01, and has complex steps.
(4) Gas chromatography pre-column derivatization: arren C, galec E.quantitative determination of nitrile and related aminopolycarboxylic acids in inorganic waters, Analysis by gas chromatography, [ J ]. chromatography, 1972, 64: 219, 237. because iminodiacetic acid and glycine have high molecular boiling points and cannot be directly gasified in gas chromatography, it is usually necessary to perform derivatization treatment and then to perform sample injection analysis. The derivatization reaction is more complex and has more side reactions than liquid chromatography, and the derivatization reaction is not as high in sensitivity and low in detection limit as the liquid chromatography.
(5) Reversed phase high performance liquid chromatography using strong anion chromatographic column: j, 2012,24(1):138-141, in the industrial production of glycine crystallization mother liquor. The method can rapidly determine the content of iminodiacetic acid, and has the advantages of high sensitivity and simple operation. However, the method can only be used for measuring iminodiacetic acid and glycine in the glycine mother liquor. For the dehydrogenation reaction of diethanol amine, as reaction products comprise various byproducts besides iminodiacetic acid and glycine, under the described chromatographic conditions, main and side reaction products can not be completely separated, the separation degree can not reach the quantitative requirement, and the iminodiacetic acid peak has obvious tailing asymmetry, so that the content of two substances in a sample can not be accurately measured.
Reversed phase high performance liquid chromatography using C18 column: glycine and iminodiacetic acid have neither chromogenic groups nor fluorescence, but belong to primary amine and secondary amine respectively, and chromogenic groups can be introduced into a compound structure through derivatization reaction, so that detection by using ultraviolet absorption in liquid chromatography is realized. The literature of this method is: fangfang, Weirongqin, novel pre-column derivatization reagent high performance liquid chromatography research on glyphosate [ J ] biological processing procedure, 2014, 12 (3): 69-72 parts of; HPLC detection of free amino acids [ J ] in raspberry by Zhaoyinglian.2, 4-dinitrofluorobenzene column pre-derivative 2015,36(6): 178-; butchun swallow, zhao jade, high performance liquid chromatography analysis of novel derivatizing reagent pre-column derivatizing amino acids [ J ] analytical test bulletin, 2008,27 (7): 681 685; on-line post-column derivatization-high performance liquid chromatography-fluorescence detection method for simultaneously determining 16 sulfonamide residues in beef [ J ] chromatography, 2016, 34 (04): 422-428. the derivatizing agents used in the methods are generally o-phthalaldehyde, phenyl isothiocyanate, 2,4 dinitrofluorobenzene. The reagent has the defects of high derivatization reaction temperature, harsh derivatization conditions, toxic derivatization reagent and the like. But the p-methyl benzene sulfonyl chloride has the advantages of high reaction activity, low price, rapid reaction, simple and convenient operation and the like. The method is applied to the quantitative analysis of iminodiacetic acid and glycine, not only can quickly and accurately detect the content of iminodiacetic acid and glycine, but also can apply the sample solution to the near-step conjecture of liquid chromatography-mass spectrometry analysis to obtain a possible reaction mechanism.
Disclosure of Invention
The invention aims to provide a quantitative analysis method which can overcome the defect of absorption interference of the conventional liquid phase end, has mild reaction conditions and can simultaneously determine glycine and iminodiacetic acid in a diethanolamine dehydrogenation product
The technical scheme of the invention is that a liquid chromatography analysis method for simultaneously quantifying glycine and iminodiacetic acid in a diethanolamine dehydrogenation product is characterized in that:
(1) liquid chromatography conditions:
(a) a chromatographic column: a VP-ODS chromatography column;
(b) mobile phase: the paint consists of A, B two components, wherein the component A: 85-90% (V) of ammonium acetate solution with the concentration of 0.02-0.04 mol/L, and the pH value of the ammonium acetate solution is 4.0-6.0; and B component: 10-15% (V) of acetonitrile;
(c) flow rate of mobile phase: 0.5-1.5 mL.min-1；
(d) Detection wavelength: 220-240 nm;
(e) column temperature: 30-40 ℃;
(2) drawing a glycine standard curve;
preparing glycine standard solutions with different concentrations, adding sufficient p-toluenesulfonyl chloroacetonitrile for reaction, fixing the volume by using a borax buffer solution, filtering after reaction in a constant-temperature water bath, taking a filtrate, carrying out sample injection according to selected chromatographic conditions for liquid chromatographic analysis, and drawing by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate to obtain a glycine standard curve;
the curvilinear regression equation is:
NGly(A)＝7765.6CGly+96.0531，
in the formula: n is a radical ofGlyIs the peak area of the glycine derivative, CGlyThe concentration of glycine, the linear correlation coefficient R is 0.9993,
(3) drawing a standard curve of iminodiacetic acid;
preparing iminodiacetic acid standard solutions with different concentrations, adding sufficient p-toluenesulfonylchloronitrile for reaction, fixing the volume by using borax buffer solution, filtering after reaction in a constant-temperature water bath, taking filtrate, injecting sample for liquid chromatography analysis according to selected chromatographic conditions, and drawing by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate to obtain an iminodiacetic acid standard curve;
the curvilinear regression equation is:
NIDA(A)＝3791.3CIDA+54.1012, linear correlation coefficient R0.9992;
in the formula: n is a radical ofIDAIs the peak area of a derivative of iminodiacetic acid, CIDAThe concentration of iminodiacetic acid, the linear correlation coefficient R is 0.9993,
(4) preparation and measurement of a diethanolamine dehydrogenation product sample:
taking supernatant after dehydrogenation reaction of diethanolamine, diluting with ultrapure water, adjusting the pH value of the supernatant to be consistent with that of a standard solution, ultrasonically oscillating and uniformly mixing, and then fixing the volume with the ultrapure water; absorbing the diluted sample solution, adding a p-toluenesulfonyl chloride acetonitrile solution, fixing the volume by using a borax buffer solution, reacting in a constant-temperature water bath, filtering, and carrying out liquid chromatography analysis by sample injection according to the same chromatographic conditions of standard solution analysis; obtaining a liquid chromatogram of a diethanolamine dehydrogenation product sample to obtain peak areas of glycine and iminodiacetic acid; and respectively substituting peak areas of glycine and iminodiacetic acid measured in the diethanolamine dehydrogenation product sample into regression equations of the glycine and the iminodiacetic acid, and multiplying the peak areas by the diluted times to obtain the concentration of the glycine and the concentration of the iminodiacetic acid in the diethanolamine dehydrogenation product sample.
CGly＝n×(NGly(A)-96.0531)/7765.6
CIDA＝n×(NIDA(A)-54.1012)/3791.3
In the formula, CGlyIs grams of glycine per liter of diethanolamine dehydrogenation product (g/L), CIDAIn grams of iminodiacetic acid per liter of diethanolamine dehydrogenation product (g/L), N is the dilution factor of the diethanolamine dehydrogenation product, NGly(A)Is the peak area and N of the glycine derivative in the dehydrogenation product of diethanolamineIDA(A)Is the peak area of the iminodiacetic acid derivative in the diethanolamine dehydrogenation product.
The method has the following technical effects that p-toluenesulfonyl chloride with high reaction activity and low cost is found as a derivatization reagent, and an optimal condition is found for derivatization reaction; the derivatization reaction has the advantages of simple operation, mild reaction conditions, good stability and the like; the method solves the problem that glycine, iminodiacetic acid and other byproducts in the dehydrogenation product of the diethanolamine cannot be separated on an ODS column, can realize complete separation between the iminodiacetic acid, the glycine and other components in the product, has small absorption interference and high sensitivity, and can provide guidance for mechanism speculation and production optimization process conditions for preparing the iminodiacetic acid by catalytic dehydrogenation of the diethanolamine.
Drawings
Figure 1 glycine standard curve.
FIG. 2 Iminodiacetic acid standard curve.
FIG. 3 separation chromatogram of diethanolamine dehydrogenation product sample.
Detailed Description
Glycine and iminodiacetic acid have neither chromogenic group nor fluorescence, but belong to primary amine and secondary amine respectively, and are easy to generate Hisberg reaction; after Hisberg reaction with a benzenesulfonyl chloride compound, introducing a chromogenic group into a compound structure, thereby realizing detection by using ultraviolet absorption in liquid chromatography; the invention adopts p-methyl benzene sulfonyl chloride as a derivatization agent, and the reaction principle is shown as the following formula:
compared with other derivatization agents, the p-methyl benzene sulfonyl chloride has the advantages of low price, rapid reaction, less byproducts and the like, but the hydrolysis reaction of the p-methyl benzene sulfonyl chloride in water can not be avoided; in order to inhibit the hydrolysis reaction of the compound maximally, the invention finds that the optimal reaction conditions are as follows through a series of optimization experiments: a borax buffer solution with the temperature of 35-55 ℃ and the pH value of 10-12, and the reaction time of 10-20 min; the method and the analysis steps have the advantages of simple and convenient operation, mild reaction conditions, good stability, quick analysis, high accuracy and the like; in a certain concentration range, an external standard method is adopted for quantification, the concentrations of iminodiacetic acid and glycine and the peak area of a derivative are in a strict linear relationship, the linear correlation coefficient is more than 0.9990, and the content of the glycine and the iminodiacetic acid in a diethanolamine dehydrogenation product can be quantified.
A liquid chromatography analysis method for simultaneously quantifying glycine and iminodiacetic acid in a diethanolamine dehydrogenation product,
1. chromatographic analysis conditions:
an Agilent Technologies-1200 high performance liquid chromatograph, a VP-ODS chromatographic column, a mobile phase, wherein the A component concentration of the mobile phase is 0.03mol/L, and the mobile phase consists of 87 percent (V) (pH value is 5.50) of ammonium acetate solution and 100 percent acetonitrile solution of the B component; flow rate of mobile phase 1/ml.min-1(ii) a The column temperature is 30 ℃; the detection wavelength is 235 nm; sample introduction amount: 20 μ L.
2. Preparation of a standard solution:
accurately preparing 0.9, 1.2, 1.5, 1.8 and 2.1g/L iminodiacetic acid standard solution and 0.02, 0.04, 0.06, 0.08 and 0.1g/L glycine standard solution; taking 1mL of the standard solution, adding 4.4mL of prepared p-toluenesulfonylchloronitrile solution (with a molar concentration of 0.015) into each standard solution, fixing the volume to 15mL by using borax buffer solution with the pH value of 11, reacting in a constant-temperature water bath kettle at 45 ℃ for 15min, filtering by using a needle filter, taking the filtrate, injecting 20 mu L of the sample according to the selected chromatographic conditions, and carrying out liquid chromatography analysis. Plotting the peak area as ordinate and the concentration as abscissa to obtain FIG. 1 and FIG. 2
FIG. 1 is a standard curve of glycine (Gly) with peak area A/mAu on the abscissa and concentration C/g.L of glycine on the ordinate-1，
The regression equation is: n is a radical ofGly(A)＝7765.6CGly+96.0531, linear correlation coefficient R is 0.9993,
FIG. 2 is a standard curve of iminodiacetic acid (IDA) with peak area A/mAu on the abscissa and concentration C/g.L of iminodiacetic acid on the ordinate-1，
The regression equation is NIDA(A)＝3791.3CIDA+54.1012, linear correlation coefficient R0.9992.
3. Preparation and measurement of sample solution:
sucking 1mL of solution to be detected into a 50mL volumetric flask, diluting with ultrapure water, adjusting the pH value to 3 (consistent with the pH value of the standard solution), ultrasonically shaking and uniformly mixing, and then fixing the volume with the ultrapure water; sucking 1mL of the diluted sample solution, adding 4.4mL of prepared p-toluenesulfonyl chloroacetonitrile solution (with a molar concentration of 0.015), diluting to 15mL by using a borax buffer solution with a pH value of 11, reacting in a constant temperature water bath at 45 ℃ for 15min, and filtering by using a syringe filter. The same chromatographic conditions were used for standard solution analysis, and 20. mu.L of sample was injected for liquid chromatography.
FIG. 3 is a separation chromatogram of a sample of a catalytic dehydrogenation product of diethanolamine, wherein the retention time and peak area of each peak are specifically shown in Table 1:
retention time and peak area of each peak in the liquid chromatogram of sample separation (Table 1)
| Retention time/min | area/mAu | Name of substance |
| 3.222 | 110.7 | |
| 3.54 | 112 | P-methylbenzenesulfonyl chloride |
| 6.822 | 2044.5 | Hydrolysis product of p-methylbenzenesulfonyl chloride |
| 8.234 | 6302.7 | Iminodiacetic acid derivatives |
| 13.157 | 224.3 | Glycine derivatives |
| 18.726 | 680.1 |
And respectively substituting the peak areas of the glycine and the iminodiacetic acid measured in the sample into regression equations of the glycine and the iminodiacetic acid, and multiplying the regression equations by the diluted times to calculate that the concentration of the glycine in the sample is 1.435g/L and the concentration of the iminodiacetic acid is 85.495 g/L.
4. Recovery and relative standard deviation of spiked
Selecting a sample solution with proper concentration (taking a diethanolamine dehydrogenation product as a standard), adding 3 levels of Gly and IDA standard substances, and carrying out a standard addition recovery experiment, wherein the Gly 3 addition levels are respectively as follows: 0.0102, 0.0201, 0.0301 g/L; the IDA 3 addition levels were: 0.0996, 0.2004, 0.2507g/L, and the results are shown in tables 2 and 3, with 5 repeated injections per addition level.
Gly recovery results (Table 2)
IDA recovery results are given in Tab.3
In order to ensure the accuracy of the measured data, in the process of completely drawing the standard curve to the concentration measurement of the solution to be measured, for the standard solution and the solution to be measured with different concentrations, all steps and chromatographic conditions in the measurement process are completely the same, especially the conditions required by the derivatization reaction.
Claims (1)
1. A liquid chromatography analysis method for simultaneously quantifying glycine and iminodiacetic acid in a diethanolamine dehydrogenation product is characterized by comprising the following steps:
(1) liquid chromatography conditions:
(a) a chromatographic column: a VP-ODS chromatography column;
(b) mobile phase: the paint consists of A, B two components, wherein the component A: 85-90% (V) of ammonium acetate solution with the concentration of 0.02-0.04 mol/L, and the pH value of the ammonium acetate solution is 4.0-6.0; and B component: 10-15% (V) of acetonitrile;
(c) flow rate of mobile phase: 0.5-1.5 mL.min-1；
(d) Detection wavelength: 220-240 nm;
(e) column temperature: 30-40 ℃;
(2) drawing a glycine standard curve;
preparing glycine standard solutions with different concentrations, adding sufficient p-toluenesulfonylchloronitrile solution for reaction, fixing the volume by using borax buffer solution, filtering after reaction in a constant-temperature water bath, taking filtrate, injecting sample for liquid chromatography analysis according to selected chromatographic conditions, and drawing by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate to obtain a glycine standard curve;
the curvilinear regression equation is:
NGly(A)＝7765.6CGly+96.0531，
in the formula: n is a radical ofGlyIs the peak area of the glycine derivative, CGlyThe concentration of glycine, the linear correlation coefficient R is 0.9993,
(3) drawing an iminodiacetic acid curve;
preparing iminodiacetic acid standard solutions with different concentrations, adding sufficient p-toluenesulfonylchloronitrile for reaction, fixing the volume by using borax buffer solution, filtering after reaction in a constant-temperature water bath, taking filtrate, injecting sample for liquid chromatography analysis according to selected chromatographic conditions, and drawing by taking a peak area as a vertical coordinate and a concentration as a horizontal coordinate to obtain an iminodiacetic acid standard curve;
the curvilinear regression equation is:
NIDA(A)＝3791.3CIDA+54.1012，
in the formula: n is a radical ofIDAIs the peak area of the iminodiacetic acid derivative, CIDAThe concentration of iminodiacetic acid, the linear correlation coefficient R is 0.9993,
(4) preparation and measurement of a diethanolamine dehydrogenation product sample:
taking supernatant after dehydrogenation reaction of diethanolamine, diluting with ultrapure water, adjusting the pH value of the supernatant to be consistent with that of a standard solution, ultrasonically oscillating and uniformly mixing, and then fixing the volume with the ultrapure water; absorbing the diluted sample solution, adding a p-toluenesulfonyl chloride acetonitrile solution, fixing the volume by using a borax buffer solution, reacting in a constant-temperature water bath, filtering, and carrying out liquid chromatography analysis by sample injection according to the same chromatographic conditions of standard solution analysis; obtaining a diethanolamine dehydrogenation product sample curve, and measuring peak areas of a glycine derivative and an iminodiacetic acid derivative; respectively substituting peak areas of the glycine derivative and the iminodiacetic acid derivative measured in the diethanolamine dehydrogenation product sample into regression equations of the glycine and the iminodiacetic acid, and multiplying the diluted times to obtain the glycine concentration and the iminodiacetic acid concentration in the diethanolamine dehydrogenation product sample:
CGly＝n×(NGly(A)-96.0531)/7765.6
CIDA＝n×(NIDA(A)-54.1012)/3791.3
in the formula, CGlyIs grams of glycine per liter of diethanolamine dehydrogenation product (g/L), CIDAIn grams of iminodiacetic acid per liter of diethanolamine dehydrogenation product (g/L), N is the dilution factor of the diethanolamine dehydrogenation product, NGly(A)Is the peak area and N of the glycine derivative in the dehydrogenation product of diethanolamineIDA(A)Is the peak area of the iminodiacetic acid derivative in the diethanolamine dehydrogenation product.
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