Method for analyzing and detecting vinylamine mixture

Abstract

The invention provides an analysis and detection method of an intermediate mixed product for preparation of vinylamine by amination, and relates to the technical field of vinylamine substance analysis and detection. The analysis method comprises the following steps: chromatogram setting; preparing a standard substance solution containing an internal standard substance, carrying out gas chromatographic analysis, and establishing a standard curve; and carrying out gas chromatographic analysis on the sample to be detected, and obtaining the content of each vinylamine substance by adopting an internal standard method-standard curve according to a detection result. According to the method, the vinylamine substances are comprehensively and rapidly detected by adopting a column separation method after sample introduction of gas chromatography, repeated sample introduction is not needed, sample introduction after sample derivatization treatment is not needed, the analysis and detection efficiency is improved, and the defects in the prior art are overcome. The method can be used for qualitatively and quantitatively analyzing and detecting more than 18 vinylamine mixtures, is wide in coverage range, and meets the requirements of monitoring the reaction process in actual research and development and / or production.

Description

Technical Field

[0001] The invention relates to the technical field of analysis and detection of ethyleneamine mixtures, and in particular to an analysis and detection method for an ethyleneamine mixture product obtained by preparing ethyleneamine through hydroamination. Background Art

[0002] Ethyleneamine is a general term for a class of organic amine fine chemical products, which mainly include acyclic polymers of ethylenediamine and cyclic amine products derived from piperazine. Acyclic polymers include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenediamine (TEDA), hydroxyethylethylenediamine (AEEA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA), etc., and cyclic amines include piperazine (PIP), hydroxyethylpiperazine (HEP), aminoethylpiperazine (AEP), etc. The various substances of ethyleneamine are widely used in organic synthesis, medicine, pesticides, surfactants, papermaking, epoxy resin curing agents, etc.

[0003] At present, the main methods for synthesizing ethyleneamine products are the ethylene dichloride (EDC) method and the ethanolamine (MEA) method. Among them, the ethanolamine method is that ethanolamine and ammonia undergo a hydrogen amination reaction under the action of a catalyst to produce ethyleneamine. Due to the complexity of the reaction, a mixture of various ethyleneamine substances is generated during the amination process, and a specific single substance product needs to be separated in multiple steps.

[0004] The chemical structures and molecular weights of many ethyleneamines are highly similar, such as N-methylethylenediamine and N-ethylethylenediamine, methylethanolamine and ethylethanolamine, etc., which leads to little difference in their separation in the chromatographic column. In addition, ethyleneamines are alkaline, which easily leads to tailing in some traditional chromatographic columns. This makes it very difficult to conduct qualitative and quantitative analysis of the various substances in the mixed product obtained after the amination reaction. Usually, multiple different chromatographic analyses are required to obtain more comprehensive results. If necessary, derivatization is required for analysis, which increases the number of detection and analysis and the complexity of the detection and analysis operations.

[0005] In the prior art, conventional methods are used to analyze and detect the mixed products obtained in the process of preparing ethyleneamine. In existing reports, the total number of quantitative ethyleneamine product substances obtained by analysis and detection does not exceed 10, and the detection range is relatively narrow. For example, in "Gas Chromatographic Analysis of Reaction Liquid of Ethanolamine Reduction and Amination to Ethylenediamine" "Physical and Chemical Testing-Chemical Volume", 2011, 47(6):711-712, gas chromatography was used to determine the contents of ethanolamine, ethylenediamine, piperazine and diethylenetriamine in the reaction, wherein a single chiral chromatographic column was used. In patent CN108067289A, gas chromatography was used to analyze 7 substances such as ethanolamine, ethylenediamine, piperazine, diethylenetriamine, and hydroxyethylethylenediamine.

[0006] In the preparation and production of ethyleneamine, the analysis of the mixed ethyleneamine products after the reactor is not frequently carried out due to its complexity. Most of the time, the quality analysis is carried out on the specific single products obtained after subsequent separation. The lack of analytical detection of the mixture after the reactor is not conducive to the monitoring of the reaction unit during industrial production and / or research and development, and is not conducive to timely regulation of the reaction unit according to the product distribution. Therefore, it is of great significance to establish a simple, fast and comprehensive analytical detection method for the mixed ethyleneamine products obtained by preparing ethyleneamine for process monitoring and real-time process control in actual factory production and / or research and development. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention provides an analytical detection method for preparing vinylamine by amination, which can quickly, comprehensively and accurately detect the content of 18 vinylamine substances. The method does not require complicated derivatization pretreatment, directly analyzes by gas chromatography, covers a wide range of vinylamine substances, and meets the needs of process monitoring and process control for product distribution monitoring in actual industrial production and / or research and development.

[0008] To achieve the above objectives, the technical solution of the present invention is implemented through the following technical solutions:

[0009] An analytical detection method for an ethyleneamine mixture, the analytical detection method comprising the following steps:

[0010] S1. Setting of gas chromatograph: setting a liquid phase injection port, connecting a Y-type splitter through a blank capillary column after the injection port, and then connecting two different chromatographic columns, and connecting the two chromatographic columns to their respective detectors for detection, and the two chromatographic columns are respectively a high polarity column and a non-polar column;

[0011] S2. Prepare a standard solution containing an internal standard, perform gas chromatography analysis using the above-mentioned gas chromatograph, and establish a standard curve;

[0012] S3. The sample to be tested containing the ethyleneamine mixture is subjected to gas chromatography analysis using the above-mentioned gas chromatograph, and the quantitative results of each substance in the ethyleneamine mixture are obtained by adopting the internal standard method-standard curve according to the test results.

[0013] Preferably, the Y-type splitter is an ultra-high inert universal press-fit Y-type splitter;

[0014] Preferably, the two chromatographic columns with different polarities are respectively a high-polarity chromatographic column with an alkali-modified polyethylene glycol stationary phase and a non-polar dimethylpolysiloxane chromatographic column, and their respective carrier gas flow rates are set in linkage with the injection port pressure and the total carrier gas flow rate.

[0015] Preferably, in step S1, the detector is a hydrogen flame ionization detector, the carrier gas is N2 or He, the fuel gas is hydrogen, and the auxiliary fuel is air.

[0016] Preferably, the chromatographic conditions of the gas chromatography analysis in steps S2 and S3 are: injection port temperature 280°C; injection volume 2 μL; split ratio 30:1; column box program temperature conditions: initial column temperature 60-80°C, maintained for 0.5 min, increased to 200°C at a rate of 20°C / min, maintained for 10 min, then increased to 210°C at a rate of 10°C / min, maintained for 2 min; detector temperature 300°C.

[0017] Preferably, the standard solution containing the internal standard in step S2 uses methanol as solvent, 3-diethylamino-1-propylamine as the internal standard, and the concentration of the prepared internal standard is 0.020 g / g.

[0018] Preferably, the ethyleneamine substance in step S3 includes any one or more of methylamine, ethylamine, N-methylethylenediamine, N-ethylethylenediamine, ethylenediamine, 1-methylpiperazine, piperazine, N-ethylpiperazine, methylethanolamine, N-ethylethanolamine, monoethanolamine, diethylenetriamine, N-aminoethylpiperazine, 1-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)ethylenediamine, diethanolamine, triethylenetetramine, and tris(2-aminoethyl)amine.

[0019] Preferably, the method for establishing a standard curve in step S2 comprises the following steps:

[0020] S2-1, preparing standard stock solutions of different concentrations, wherein the standard stock solutions are single or mixed solutions of one or more substances, and the substances in the mixed solutions are mixed arbitrarily according to mass concentration;

[0021] S2-2, prepare a series of standard injection solutions of different concentrations, weigh 0.100g, 0.250g, 0.500g, 0.750g, and 1.000g of the standard stock solution respectively, dilute to 1.000g with methanol, and then add 2.000g of the internal standard solution to each of them to prepare a series of standard injection solutions;

[0022] S2-3, respectively performing gas chromatography detection on the standard injection solutions of the series of concentrations, and establishing a standard curve according to the detection results and the concentration of each substance in the series of standard samples.

[0023] The present invention provides an analytical detection method for preparing ethyleneamine by hydroamination, which has the following advantages over the prior art:

[0024] (1) The present invention uses a Y-type splitter to split the sample to be tested through two different chromatographic columns for separation, thereby avoiding the influence of overlapping chromatographic peaks of similar components caused by a single chromatographic column. The two chromatographic columns used in the embodiment of the present invention are a base-modified polyethylene glycol stationary phase high-polarity chromatographic column and a dimethyl polysiloxane non-polar chromatographic column, specifically, Shimadzu's SH-PolarX capillary chromatographic column and Agilent's HP-1 capillary chromatographic column. Experimental verification shows that the analytical detection method of the present invention has a good separation effect, high analytical detection repeatability, good durability, and can well meet the detection requirements.

[0025] (2) The method of the present invention can simultaneously determine 18 kinds of ethyleneamine substances, covering a wide range. The 18 substances have a good linear relationship with the chromatographic peak area within the corresponding mass concentration range, and are highly practical;

[0026] (3) The method of the present invention adopts the internal standard method-standard curve to obtain the content of each substance of ethyleneamines, and the influence of experimental conditions is eliminated by adding internal standard substances, thereby improving the accuracy and reliability of the measurement results. The method is simple to operate, does not require derivatization, and directly injects samples for analysis, thereby improving the detection efficiency, and the results are accurate and reliable, with good precision and stability, meeting the needs of actual research and development and / or industrial production process monitoring. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The gas chromatograms of the simulated ethyleneamine mixture sample solution in Example 1 of the present invention, wherein A is the SH-PolarX chromatographic column spectrum and B is the HP-1 chromatographic column spectrum;

[0028] Figure 2 The gas chromatogram of the ethyleneamine mixed product sample obtained by amination in Example 1 of the present invention, wherein A is a SH-PolarX chromatographic column spectrum, and B is a HP-1 chromatographic column spectrum;

[0029] Figure 3 The gas chromatogram of the simulated ethyleneamine mixture sample in Comparative Example 1 of the present invention on a single chromatographic column SH-PolarX;

[0030] Figure 4 This is a gas chromatogram of the simulated ethyleneamine mixture sample in Comparative Example 2 of the present invention on a single chromatographic column HP-1. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Embodiment 1:

[0033] Analysis and detection of ethyleneamine mixture by dual chromatographic columns:

[0034] 1. Gas chromatography conditions:

[0035] Gas chromatograph: Agilent GC8860;

[0036] A liquid phase injection port is provided, and two chromatographic columns with different polarities are connected to the injection port through an ultra-high inert universal press-fit Y-type splitter, and two respective hydrogen flame ionization detectors are connected to the two chromatographic columns;

[0037] The two chromatographic columns with different polarities are: high polarity capillary column: Shimadzu SH-PolarX (30m*0.32mm*1μm) and non-polar capillary column: Agilent HP-1

[0038] (30m*0.53mm*2.65μm);

[0039] Column flow rate: 0.90 mL / min for SH-PolarX column and 6.67 mL / min for HP-1 column;

[0040] Inlet temperature: 280°C;

[0041] Hydrogen flame ionization detector temperature: 300°C;

[0042] Carrier gas: high purity nitrogen;

[0043] Column temperature: Initial column temperature was 80°C, maintained for 0.5 min, increased to 200°C at a rate of 20°C / min, maintained for 10 min, then increased to 210°C at a rate of 10°C / min, maintained for 2 min.

[0044] Split ratio: 30:1;

[0045] Injection volume: 2 μL;

[0046] Hydrogen flow rate: 30 mL / min;

[0047] Air flow rate: 400mL / min;

[0048] 2. Preparation of ethyleneamine standard curve:

[0049] 2.1 Preparation of standard stock solution

[0050] According to industrial needs, 18 kinds of ethyleneamine substances are obtained by hydroamination of ethanolamine to prepare ethyleneamine, which are divided into 3 groups, numbered A, B, and C. Group A contains ethanolamine, N-methylethylenediamine, N-ethylethylenediamine, 1-methylpiperazine, N-aminoethylpiperazine, diethylenetriamine, and methylethanolamine; Group B contains methylamine, ethylamine, ethylenediamine, piperazine, N-(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, and N-ethylethanolamine; Group C contains N-ethylpiperazine, diethanolamine, triethylenetetramine, and tris(2-aminoethyl)amine. Among them, use a ten-thousandth balance to weigh the required substances. In group A, accurately weigh 7.000g of ethanolamine, 0.080g of N-methylethylenediamine, 0.050g of N-ethylethylenediamine, 0.020g of 1-methylpiperazine, 0.500g of N-aminoethylpiperazine, 1.200g of diethylenetriamine, and 0.020g of methylethanolamine, and add the solvent methanol to prepare a 10.000g standard stock solution; in group B, accurately weigh 0.010g of methylamine, 0.010g of ethylamine, and 1.70 0.050 g of N-ethylpiperazine, 0.020 g of diethanolamine, 0.200 g of triethylenetetramine, and 0.050 g of tris(2-aminoethyl)amine were accurately weighed and added with methanol as solvent to prepare a 10.000 g standard stock solution.

[0051] 2.2 Preparation of internal standard solution 3-diethylamino-1-propylamine solution

[0052] Accurately weigh 2.000 g of 3-diethylamino-1-propylamine, add 98.000 g of methanol solvent to prepare 100.000 g of 0.020 g / g internal standard solution.

[0053] 2.3 Preparation and analysis of standard injection solution

[0054] For the standard stock solution of group A, accurately weigh 0.100g, 0.250g, 0.500g, 0.750g, and 1.000g of the standard stock solution of group A, dilute each to 1.000g with methanol, and then add 2.000g of internal standard solution to prepare the series standard injections of group A. Repeat the above series standard injection operation steps of group A to obtain series standard injections of groups B and C. Under the above gas chromatography conditions, the gas chromatography was used to measure respectively, and each standard injection was repeated 3 times. The standard curve of each substance was established according to the peak area and the content of the internal standard. The results are shown in Table 1:

[0055] Table 1. Standard curve parameters for each substance

[0056] Components Regression curve <![CDATA[R 2 ]]> Methylamine y=0.0045x 0.99998 Ethylamine y=0.0069x 0.99989 N-Methylethylenediamine y=0.0066x 0.99994 N-Ethylethylenediamine y=0.0072x 0.99997 Ethylenediamine y=0.0054x 0.99987 Piperazine y=0.0080x 0.99987 1-Methylpiperazine y=0.0087x 0.99998 N-Ethylpiperazine y=0.0091x 0.99997 Methylethanolamine y=0.0059x 0.99996 N-Ethylethanolamine y=0.0075x 0.99994 Monoethanolamine y=0.0045x 0.99994 Diethylenetriamine y=0.0064x 0.99971 N-Aminoethylpiperazine y=0.0069x 0.99982 1-(2-Hydroxyethyl)piperazine y=0.0062x 0.99969 N-(2-Hydroxyethyl)ethylenediamine y=0.0025x 0.99013 Diethanolamine y=0.0058x 0.99949 Triethylenetetramine y=0.0072x 0.99995 Tris(2-aminoethyl)amine y=0.0072x 1.00000

[0057] Within the designed experimental range, the correlation coefficients R of 18 ethyleneamine substances 2 It is between 0.99013 and 1.00000, with a good linear relationship, thus resulting in high detection accuracy.

[0058] 3. Analysis of ethyleneamine mixture simulation samples:

[0059] To simulate amination to generate a mixed product of ethyleneamine, appropriate amounts of methylamine, ethylamine, N-methylethylenediamine, N-ethylethylenediamine, ethylenediamine, 1-methylpiperazine, piperazine, N-ethylpiperazine, methylethanolamine, N-ethylethanolamine, monoethanolamine, diethylenetriamine, N-aminoethylpiperazine, 1-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)ethylenediamine, diethanolamine, triethylenetetramine, tris(2-aminoethyl)amine were weighed and dissolved with methanol to prepare a simulated sample solution of the ethyleneamine mixture. Accurately weigh 1.000g of the simulated sample solution of the ethyleneamine mixture, and add 2.000g of 0.020g / g internal standard solution to prepare a simulated sample injection solution of the ethyleneamine mixture. The above-mentioned gas chromatography conditions were used for gas chromatography analysis and determination, and the content of each substance was obtained in combination with the standard curve. The results are shown in Table 2;

[0060] 4. Analysis of mixed products of ethyleneamine produced by amination:

[0061] The ethyleneamine mixed product obtained by the experiment of preparing ethyleneamine by hydrogen amination of ethanolamine carried out by the inventor was used as the analysis object. The specific amination reaction method is shown in CN118253311A. 1.000g of ethyleneamine mixed product sample was accurately weighed, and then 2.000g of 0.020g / g internal standard solution was added to analyze the actual ethyleneamine mixed product. The gas chromatography analysis was carried out under the above-mentioned gas chromatography conditions, and the qualitative and quantitative analysis of each specific ethyleneamine substance was obtained in combination with the standard curve. The results are shown in Table 2. In addition to the qualitative and quantitative 18 ethyleneamine substances, multiple unknown peaks appeared in the analysis spectrum, and the peak area sum of all unknown peaks accounted for less than 3% of the total peak area of ​​the analysis spectrum (excluding solvent peaks).

[0062] 5. Repeatability experiment:

[0063] Preparation of standard injection solution: accurately weigh appropriate amounts of methylamine, ethylamine, N-methylethylenediamine, N-ethylethylenediamine, ethylenediamine, 1-methylpiperazine, piperazine, N-ethylpiperazine, methylethanolamine, N-ethylethanolamine, monoethanolamine, diethylenetriamine, N-aminoethylpiperazine, 1-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)ethylenediamine, diethanolamine, triethylenetetramine, tris(2-aminoethyl)amine, dilute and dissolve with methanol to prepare a standard solution. Accurately weigh 1.000g of the standard solution, add 2.000g of 0.020g / g internal standard solution to prepare a standard injection solution. The above-mentioned gas chromatography conditions were used for gas chromatography analysis and determination, and the determination was repeated 3 times. The peak area of ​​each component was recorded, and the relative standard deviation (RSD) of the peak area of ​​each component was calculated. The results are shown in Table 2. The RSD of each component was low, and the high precision of the method was verified.

[0064] Table 2

[0065]

[0066] 6. Spike recovery experiment:

[0067] The ethyleneamine mixed product obtained by the hydrogenation of ethanolamine to prepare ethyleneamine carried out by the inventor was used as the analysis object. Two portions of 0.500g of the product were accurately weighed, and 0.500g of the solvent methanol was added to one portion, and then 2.000g of 0.020g / g internal standard solution was added; 0.500g of the standard solution in the repeatability experiment was added to the other portion of the product, and then 2.000g of 0.020g / g internal standard solution was added to conduct a sample spike experiment. The gas chromatography was repeated 3 times under the above gas chromatography conditions to obtain the average value. The results are shown in Table 3:

[0068] Table 3

[0069]

[0070]

[0071] As shown in Table 3, the recoveries of the 18 target substances in this method ranged from 88.8% to 113.2%, indicating good accuracy and meeting the requirements of quantitative analysis.

[0072] Comparative Example 1:

[0073] Analysis and detection of ethyleneamine mixture simulated sample using single SH-PolarX column:

[0074] 1-1. Gas chromatography conditions:

[0075] Gas chromatograph: GC8860;

[0076] Chromatographic column: Shimadzu SH-PolarX (30m*0.32mm*1μm);

[0077] Column flow rate: 1.8 mL / min;

[0078] Inlet temperature: 280°C;

[0079] Hydrogen flame ionization detector temperature: 300°C;

[0080] Carrier gas: high purity nitrogen;

[0081] Column temperature: Initially, the column temperature was 60°C, raised to 180°C at a rate of 10°C / min, maintained for 5 min, then raised to 210°C at a rate of 20°C / min, maintained for 2 min.

[0082] Split ratio: 20:1;

[0083] Injection volume: 2 μL;

[0084] Hydrogen flow rate: 30 mL / min;

[0085] Air flow rate: 400mL / min;

[0086] 1-2. Analysis of simulated samples of ethyleneamine mixture

[0087] The simulated sample solution of the ethyleneamine mixture of Example 1-3 was used as the analysis object. 1.000 g of the simulated sample solution was taken and 2.000 g of 0.020 g / g internal standard solution was added to prepare the simulated sample injection solution. The gas phase analysis of a single chromatographic column was performed under the above gas chromatography conditions. The gas phase spectrum is shown in Figure 3 From the figure, we can see that 13 out of 18 ethyleneamine substances are eluted in the SH-PolarX column under the gas phase conditions, and 5 ethyleneamine substances are not eluted in the column. It is difficult to fully analyze the 18 ethyleneamine substances with a single SH-PolarX column.

[0088] Comparative Example 2:

[0089] Analysis and detection of ethyleneamine mixture simulation sample single HP-1 column:

[0090] 2-1. Gas chromatography conditions:

[0091] Gas chromatograph: GC8860;

[0092] Chromatographic column: Agilent HP-1 (30m*0.53mm*2.65μm);

[0093] Column flow rate: 2.5 mL / min;

[0094] Inlet temperature: 280°C;

[0095] Hydrogen flame ionization detector temperature: 300°C;

[0096] Carrier gas: high purity nitrogen;

[0097] Column temperature: Initial column temperature was 80°C, maintained for 0.5 min, increased to 200°C at a rate of 20°C / min, maintained for 10 min, then increased to 210°C at a rate of 10°C / min, maintained for 2 min.

[0098] Split ratio: 20:1;

[0099] Injection volume: 2 μL;

[0100] Hydrogen flow rate: 30 mL / min;

[0101] Air flow rate: 400mL / min;

[0102] 2-2. Analysis of simulated samples of ethyleneamine mixture

[0103] The injection solution is the simulated sample injection solution of the ethyleneamine mixture in Comparative Example 1-2, and the gas phase analysis of a single chromatographic column is performed under the above-mentioned gas chromatography conditions. The gas phase spectrum is shown in Figure 4 From the figure, it can be seen that under the gas phase conditions, 14 out of 18 ethyleneamine substances are eluted in the HP-1 chromatographic column, of which 4 ethyleneamine substances do not elute in the chromatographic column. In addition, among the 14 chromatographic peaks, 4 chromatographic peaks overlap. It is difficult to fully analyze the 18 ethyleneamine substances with a single HP-1.

[0104] From Comparative Examples 1 and 2, it can be seen that it is difficult for all ethylene amine substances to emit peaks using a single chromatographic column. Even if they do, substances with similar properties are prone to double peaks, resulting in inaccurate quantification. A single chromatographic column cannot perform qualitative and quantitative analysis of substances in a ethylene amine mixture well and comprehensively.

[0105] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for analyzing and detecting an ethyleneamine mixture, characterized in that: The analytical detection method comprises the following steps: S1. Setting of gas chromatograph: setting a liquid phase injection port, connecting a Y-type splitter through a blank capillary column after the injection port, and then connecting two different chromatographic columns, and connecting the two chromatographic columns to their respective detectors for detection, and the two chromatographic columns are respectively a high polarity column and a non-polar column; S2. Prepare a standard solution containing an internal standard, perform gas chromatography analysis using the above-mentioned gas chromatograph, and establish a standard curve; S3. The sample to be tested containing the ethyleneamine mixture is subjected to gas chromatography analysis using the above-mentioned gas chromatograph, and the quantitative results of each substance in the ethyleneamine mixture are obtained by adopting the internal standard method-standard curve according to the test results.

2. The analysis and detection method according to claim 1, characterized in that: The Y-type splitter is an ultra-high inert universal press-fit Y-type splitter.

3. The analysis and detection method according to claim 1, characterized in that: The two chromatographic columns with different polarities are respectively a alkali-modified polyethylene glycol stationary phase high-polarity chromatographic column and a dimethylpolysiloxane chromatographic column, and their respective carrier gas flow rates are linked to set by the injection port pressure and the total carrier gas flow rate.

4. The analysis and detection method according to claim 1, characterized in that: In step S1, the detector is a hydrogen flame ionization detector, the carrier gas is N2 or He, the fuel gas is hydrogen, and the auxiliary fuel gas is air.

5. The analysis and detection method according to claim 1, characterized in that: The chromatographic conditions of the gas chromatography analysis in steps S2 and S3 are: injection port temperature 280°C; injection volume 2μL; split ratio 30:1; column box program temperature conditions: initial column temperature 60-80°C, maintained for 0.5min, increased to 200°C at a rate of 20°C / min, maintained for 10min, then increased to 210°C at a rate of 10°C / min, maintained for 2min; detector temperature 300°C.

6. The analysis and detection method according to claim 1, characterized in that: The standard solution containing the internal standard in step S2 uses methanol as solvent, 3-diethylamino-1-propylamine as the internal standard, and the concentration of the prepared internal standard is 0.020 g / g.

7. The analysis and detection method according to claim 1, characterized in that: The ethyleneamine substances in step S3 include any one or more of methylamine, ethylamine, N-methylethylenediamine, N-ethylethylenediamine, ethylenediamine, 1-methylpiperazine, piperazine, N-ethylpiperazine, methylethanolamine, N-ethylethanolamine, monoethanolamine, diethylenetriamine, N-aminoethylpiperazine, 1-(2-hydroxyethyl)piperazine, N-(2-hydroxyethyl)ethylenediamine, diethanolamine, triethylenetetramine, and tris(2-aminoethyl)amine.

8. The analysis and detection method according to claim 1, characterized in that: The method for establishing a standard curve in step S2 comprises the following steps: S2-1, prepare standard stock solutions of different concentrations, wherein the standard stock solutions are single or mixed solutions of one or more substances, and the substances in the mixed solutions are mixed arbitrarily according to mass concentration; S2-2, prepare a series of standard injection solutions of different concentrations, weigh 0.100g, 0.250g, 0.500g, 0.750g, and 1.000g of the standard stock solution, dilute to 1.000g with solvent, and then add 2.000g of internal standard solution to each of them to prepare a series of standard injection solutions; S2-3, respectively performing gas chromatography detection on the standard injection solutions of the series of concentrations, and establishing a standard curve according to the detection results and the concentration of each substance in the series of standard samples.

Images