阅读说明：本技术 一种甲胺水溶液中组分含量的测定方法 (Method for measuring component content in methylamine aqueous solution ) 是由 王敬 艾连峰 张海超 马育松 李玮 于 2020-12-16 设计创作，主要内容包括：本发明属于物质检测技术领域。本发明提供了一种甲胺水溶液中组分含量的测定方法。本发明使用气相色谱仪获取标准曲线,将待测样品重复进入色谱仪中,和标准曲线比对,即可获得测量结果。本发明方法可将主组分进行有效分离,专属性强,经济实效,重现性好,准确度高,并能准确有效地测定一甲胺、二甲胺和三甲胺的含量,进而实现甲胺水溶液的质量可控,填补了现有技术的空白。(The invention belongs to the technical field of substance detection. The invention provides a method for measuring the content of components in methylamine water solution. The method uses the gas chromatograph to obtain the standard curve, repeatedly enters the chromatograph to be measured into the sample to be measured, and compares the standard curve with the sample to be measured, so that the measurement result can be obtained. The method can effectively separate the main components, has strong specificity, economic and practical effects, good reproducibility and high accuracy, and can accurately and effectively measure the contents of monomethylamine, dimethylamine and trimethylamine, thereby realizing the quality control of the methylamine aqueous solution and filling the blank of the prior art.)

1. A method for measuring the content of components in methylamine water solution is characterized by comprising the following steps:

(1) the standard substance is vaporized and enters a chromatographic column, and parameters are adjusted to obtain a standard curve;

(2) testing a methylamine water solution sample to obtain a determination result of the component content;

the methylamine water solution comprises one or more of monomethylamine, dimethylamine and trimethylamine.

2. The method according to claim 1, wherein the mass concentration of the standard substance in the step (1) is 145 to 155. mu.g/mL.

3. The method according to claim 1 or 2, wherein the detector for vaporization in the step (1) is a hydrogen flame ionization detector, and the temperature of the vaporization chamber for vaporization is 155 to 165 ℃.

4. The method according to claim 3, wherein the temperature of the hydrogen flame ionization detector is 175 to 185 ℃.

5. The method for detecting amine compounds in the claim 1, wherein the chromatographic column in the step (1) is an Agilent CP-Volamine amine compound analysis dedicated capillary column.

6. The method according to claim 1 or 5, wherein the column box temperature of the column in the step (1) is 75 to 85 ℃.

7. The assay of claim 6, wherein the step (1) is performed by split-flow injection, and the split-flow injection has a split-flow ratio of 1: 5 to 15.

8. The method according to claim 1, 2, 4, 5 or 7, wherein the carrier introduced in the step (1) is a mixed gas comprising hydrogen, air and an inert gas;

the volume ratio of the hydrogen to the air to the inert gas is (0.7-1): (9-11): (0.8 to 1.2).

9. The method according to claim 8, wherein the flow rate of the carrier is 0.5 to 1.5 mL/min.

10. The method according to claim 9, wherein the amount of the aqueous methylamine solution sample in the step (2) is 0.5 to 0.7. mu.L.

Technical Field

The invention relates to the technical field of substance detection, in particular to a method for determining the content of components in a methylamine aqueous solution.

Background

Monomethylamine (CH)₃NH₂) Dimethylamine (CH)₃)₂NH]And Trimethylamine [ Trimethylamine, (CH)₃)₃N]The water solution is medium-strong alkaline, the explosion limit of monomethylamine is 4.9-20.7%, dimethylamine is 2.8-14.4%, trimethylamine is 2-11.6%, and the vapor pressure at 20 ℃ is 173.9kPa (1307.2 mmHg). Because of their low boiling point and high vapor pressure, they are volatile during manufacture and use. Monomethylamine, dimethylamine and trimethylamine are important organic chemical raw materials, are used as raw materials for synthesizing a plurality of other compounds, can produce about hundred million kilograms per year, are widely used in various industries of national economy, and are main raw materials of pesticides, medicines, synthetic dyes, synthetic resins, chemical fibers, photographic materials, solvents, explosives, high-energy fuels, surfactants and vulcanization accelerators. Organic amine compounds are harmful to health and environment, are easy to cause harm to eyes, skin, mucous membranes and the like of human bodies, and may cause cancer after human tissues absorb certain amine compounds. For example, skin contact with liquid dimethylamine can cause necrosis, eye contact can cause corneal loss, haze; the dimethylamine is absorbed by the human body for a long time, so that the chromosome structure of the bone marrow is abnormal; triethylamine has strong irritation to respiratory tract, and can cause pulmonary edema and even death after inhalation, and chemical burn can be caused by oral administration, oral cavity, esophagus and stomach corrosion, eye and skin contact.

Currently, organic amines are commonly detected by gas chromatography, high performance liquid chromatography and spectrophotometry, but the methods still have respective disadvantages. The spectrophotometry has more interference factors, and can not realize the simultaneous detection of amine substances with different components. Since the volatile amine substances have no double bonds, the substances need to be derivatized to be detected by using high performance liquid chromatography in combination with an ultraviolet detector, and the derivatization step is very complicated. For gas chromatography, it is difficult to separate various mixed amine compounds under conventional chromatographic column conditions, and especially, the analysis of the acute amine compounds with good water solubility has poor peak, severe tailing phenomenon and poor reproducibility. Therefore, the existing detection method cannot well satisfy the analysis and detection of amines, and a more efficient and accurate detection and separation method needs to be developed.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a method for measuring the content of components in a methylamine aqueous solution.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a method for measuring the content of components in methylamine water solution, which comprises the following steps:

(1) the standard substance is vaporized and enters a chromatographic column, and parameters are adjusted to obtain a standard curve;

(2) testing a methylamine water solution sample to obtain a determination result of the component content;

the methylamine water solution comprises one or more of monomethylamine, dimethylamine and trimethylamine.

Preferably, the mass concentration of the standard substance in the step (1) is 145-155 mu g/mL.

Preferably, the detector for vaporization in the step (1) is a hydrogen flame ionization detector, and the temperature of the vaporization chamber for vaporization is 155-165 ℃.

Preferably, the temperature of the hydrogen flame ionization detector is 175-185 ℃.

Preferably, the chromatographic column in the step (1) is an Agilent CP-Volamine amine compound analysis special capillary column.

Preferably, the temperature of the chromatographic column in the step (1) is 75-85 ℃.

Preferably, the entering mode in the step (1) is split injection, and the split ratio of the split injection is 1: 5 to 15.

Preferably, the carrier entering in the step (1) is a mixed gas, and the mixed gas comprises hydrogen, air and an inert gas;

the volume ratio of the hydrogen to the air to the inert gas is (0.7-1): (9-11): (0.8 to 1.2).

Preferably, the flow rate of the carrier is 0.5-1.5 mL/min.

Preferably, the sample amount of the methylamine water solution sample in the step (2) is 0.5-0.7 μ L.

The invention provides a method for measuring the content of components in methylamine water solution, which comprises the steps of measuring by a gas chromatograph, obtaining a standard curve, repeatedly feeding a sample to be measured into the chromatograph, and comparing with the standard curve to obtain a measurement result. The method can effectively separate the main components, has strong specificity, economic and practical effects, good reproducibility and high accuracy, and can accurately and effectively measure the contents of monomethylamine, dimethylamine and trimethylamine, thereby realizing the quality control of the methylamine aqueous solution and filling the blank of the prior art.

Drawings

FIG. 1 is a blank solution specificity chromatogram;

FIG. 2 is a standard solution specificity chromatogram;

FIG. 3 is a chromatogram of a sample solution;

FIG. 4 is a detection limit chromatogram of a mixed standard solution of monomethylamine, dimethylamine and trimethylamine;

FIG. 5 is a quantitative limit chromatogram of a mixed standard solution of monomethylamine, dimethylamine and trimethylamine.

Detailed Description

The invention provides a method for measuring the content of components in methylamine water solution, which comprises the following steps:

(1) the standard substance is vaporized and enters a chromatographic column, and parameters are adjusted to obtain a standard curve;

(2) testing a methylamine water solution sample to obtain a determination result of the component content;

the methylamine water solution comprises one or more of monomethylamine, dimethylamine and trimethylamine.

In the invention, the mass concentration of the standard substance in the step (1) is preferably 145-155 [ mu ] g/mL, more preferably 146-154 [ mu ] g/mL, and even more preferably 148-152 [ mu ] g/mL.

In the invention, the detector for vaporization in the step (1) is preferably a hydrogen flame ionization detector, and the temperature of the vaporization chamber for vaporization is preferably 155-165 ℃, more preferably 156-164 ℃, and more preferably 158-162 ℃.

In the invention, the temperature of the hydrogen flame ionization detector is preferably 175-185 ℃, more preferably 176-184 ℃, and even more preferably 178-182 ℃.

In the invention, the chromatographic column in the step (1) is preferably a capillary column special for analyzing Agilent CP-Volamine amine compounds.

In the invention, the temperature of the chromatographic column in the step (1) is preferably 75-85 ℃, more preferably 76-84 ℃, and even more preferably 78-82 ℃.

In the present invention, the entering manner in step (1) is preferably split injection, and the split ratio of the split injection is preferably 1: 5-15, and more preferably 1: 8-12, more preferably 1: 9 to 11.

In the present invention, the carrier introduced in the step (1) is preferably a mixed gas, and the mixed gas preferably contains hydrogen, air and an inert gas, and the inert gas is preferably nitrogen, helium or argon.

In the invention, the volume ratio of the hydrogen to the air to the inert gas is preferably (0.7-1): (9-11): (0.8-1.2), more preferably (0.8-0.9): (9.4-10.6): (0.9 to 1.1), more preferably (0.84 to 0.86): (9.8-10.2): (0.95-1.05).

In the present invention, the flow rate of the carrier is preferably 0.5 to 1.5mL/min, more preferably 0.6 to 1.4mL/min, and still more preferably 0.8 to 1.2 mL/min.

In the present invention, the amount of the methylamine aqueous solution sample in the step (2) is preferably 0.5 to 0.7. mu.L, more preferably 0.52 to 0.68. mu.L, and still more preferably 0.55 to 0.65. mu.L.

The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.

Example 1

The measurement method provided in the present application was performed for the measurement of the standard solution.

The concentrations of monomethylamine, dimethylamine and trimethylamine used in this application were all 2000. mu.g/mL.

And (3) specificity determination:

accurately measuring 0.75mL of monomethylamine, 0.75mL of dimethylamine and 0.75mL of trimethylamine into a 10mL volumetric flask respectively, diluting the solution to a scale with water, shaking up to prepare a standard solution containing monomethylamine, dimethylamine and trimethylamine, wherein the mass concentration of the standard solution is 150 mug/mL, and the standard solution is to be measured.

Precisely measuring 0.6 mu L of each of a blank solution, a standard solution and a test solution, carrying out GC analysis, recording a chromatogram, recording the blank solution as figure 1, the standard solution as figure 2 and the test solution as figure 3, wherein as can be seen from the figures, the blank and other components in the test solution do not cause interference on a target object. And the target peak and other miscellaneous peaks in the standard solution can reach the baseline separation and meet the specificity requirement.

And (3) measuring a linear relation: linear working fluid: the same volumes of monomethylamine, dimethylamine and trimethylamine, 0.25mL, 0.5mL, 1mL, 2mL, 4mL, 5mL and 10mL, respectively, are weighed and placed in 7 10mL volumetric flasks, water is added to dilute the mixture until the scales are evenly shaken, and linear working solutions of 50. mu.g/mL, 100. mu.g/mL, 200. mu.g/mL, 400. mu.g/mL, 800. mu.g/mL, 1000. mu.g/mL and 2000. mu.g/mL are prepared.

Precisely measuring 0.6 mu L of linear working solution with each concentration, injecting the linear working solution into a chromatograph, recording a chromatogram, and calculating the linear relation between the peak areas and the concentrations of the monomethylamine, the dimethylamine and the trimethylamine. The results are reported in table 1.

TABLE 1 Standard Curve

As can be seen from Table 1, the correlation coefficients of monomethylamine, dimethylamine and trimethylamine are all greater than 0.990 in the range of 50-2000. mu.g/mL, and the linear relationship is good.

Determination of the limit of quantitation and detection: accurately measuring 0.25mL and 0.75mL of monomethylamine, dimethylamine and trimethylamine into a 10mL volumetric flask respectively, diluting with water to scale, shaking up, and preparing into mixed standard solutions with the concentrations of monomethylamine, dimethylamine and trimethylamine being 50 mu g/mL and 150 mu g/mL respectively.

Precisely measuring 0.6 μ L of the mixed standard solution, injecting into a chromatograph, and recording chromatogram. Fig. 4 is a detection limit chromatogram of the mixed standard solution, and fig. 5 is a quantification limit chromatogram of the mixed standard solution.

The detection limit and the quantification limit of the measurement method provided by the present application were counted, and the results are shown in table 2.

TABLE 2 statistical results

The detection limit of the method is determined according to the verification guiding principle of an analysis method of 2020-edition pharmacopoeia 9101, the measured object with known concentration is actually measured in a practical sample standard adding mode by adopting an intuitive method, the peak area is recorded and compared with the corresponding standard peak area, the lowest concentration which can be reliably detected is tested, and the signal-to-noise ratio is more than or equal to 3 at the moment. The measured results show that the S/N of the instrument to the mixed standard solution of monomethylamine, dimethylamine and trimethylamine with the concentration of 50 mu g/mL is respectively 5.8, 8.5 and 17.0, and the following conditions are met: the detection limit S/N is equal to or greater than 3. The peak area RSD value range of the 6 needle quantitative limit concentration continuous sampling method is 6.01-6.69%. Therefore, the detection limit of the method is 50. mu.g/mL, and the quantification limit is 150. mu.g/mL.

And (3) repeatability determination: precisely measuring 0.6 mu L of the test solution, injecting into a chromatograph, recording the chromatogram, respectively calculating the content RSD% of the 6 test solutions prepared in parallel, and recording the result in the table 3.

TABLE 3 repeatability tests

The results show that the contents of RSD of the solutions of 6 samples prepared in parallel are respectively 2.60%, 0.13% and 1.50%, and are all less than 5%, and the repeatability of the method is good.

And (3) testing intermediate precision: another tester precisely measures 6 parts of the sample, precisely measures 0.6 mu L of the sample, injects the sample into a chromatograph, records a chromatogram, and respectively calculates the RSD content of the solution of the sample of 6 parts prepared in parallel. The results are shown in Table 4.

TABLE 4 intermediate precision experiment

And (4) conclusion: the RSD range of 12 test samples prepared by two analysts in parallel is 0.33-2.79 and less than 11%, and the intermediate precision of the method is good.

And (3) testing accuracy: mixing standard working solution: accurately weighing 0.60mL, 0.75mL and 0.90mL of monomethylamine, dimethylamine and trimethylamine into a 10mL volumetric flask respectively, diluting the volumetric flask with water to scale, shaking up, and preparing mixed standard working solution with the concentrations of the monomethylamine, the dimethylamine and the trimethylamine being 120 mu g/mL, 150 mu g/mL and 180 mu g/mL respectively.

Precisely measuring 0.6 mu L of mixed standard working solution, injecting the mixed standard working solution into a chromatograph, recording a chromatogram, respectively calculating the content RSD of each concentration accuracy solution of monomethylamine, dimethylamine and trimethylamine, and recording the result in a table 5.

TABLE 5 accuracy test

And (4) conclusion: the range of the standard recovery rate of the three levels is 91.58% -105.79%, the requirement that the average recovery rate is between 80% -120% is met, the RSD range is 1.21% -5.14%, and is less than 10%, and the accuracy of the method is good.

And (3) stability testing: mixing standard working solution: respectively and precisely measuring 0.75mL of monomethylamine, dimethylamine and trimethylamine reference substance stock solution into a 10mL volumetric flask, diluting the solution to a scale with water, and shaking up the solution to prepare a mixed standard working solution with the concentration of the monomethylamine, the dimethylamine and the trimethylamine being 150 mu g/mL.

Measuring 0.6 mu L of mixed standard working solution in 0, 2, 4, 8 and 24h respectively, injecting into a chromatograph, recording a chromatogram, calculating RSD of the peak areas of monomethylamine, dimethylamine and trimethylamine respectively, and inspecting the solution stability. The results of the measurements are reported in table 6.

TABLE 6 control working fluid stability

Time (hr)	Peak area of monomethylamine	Area of dimethylamine peak	Area of trimethylamine peak
				0	29.06	35.69	38.89
2	30.08	37.80	40.32
				4	29.42	35.66	36.33
8	29.35	36.51	37.07
				24	27.93	35.67	38.03
RSD(％)	2.70	2.57	4.09

The conclusion is that the reference substance working solution is placed for 24 hours at room temperature, the peak areas RSD of the monomethylamine, the dimethylamine and the trimethylamine are respectively 2.70 percent, 2.57 percent and 4.09 percent, which are all less than 10 percent, and the solution stability is good.

And (3) durability test: precisely measuring 0.6 μ L of the sample, injecting into a chromatograph at different injection port temperatures, and recording chromatogram. The results are reported in table 7.

TABLE 7 durability of test articles

The results show that at different injection port temperatures (140 ℃, 160 ℃ and 180 ℃ respectively), the degrees of separation between the target peaks of the sample solution are all larger than 1.5, the theoretical plate numbers are all larger than 2000, and the calculated result RSD value is smaller than 10%, thus the durability of the method is good.

Vaporizing a standard solution with the mass concentration of 150 mug/mL in a vaporizing chamber at 160 ℃, and introducing the standard solution into a chromatographic column, wherein the chromatographic column is a capillary column special for analyzing Agilent CP-Volamine amine compounds, the temperature of a hydrogen flame ionization detector is 180 ℃, the temperature of a chromatographic column box is 80 ℃, and the volume ratio of hydrogen to air to nitrogen in a carrier is 0.8: 10: 1.1, according to the flow division ratio of 1: 10, the flow rate of the carrier is 1 mL/min.

A test sample with unknown concentration is weighed and measured according to the method, and the sample amount is 0.6 mu L. The content of each component in the test article is recorded in table 8.

Example 2

Vaporizing a standard solution with the mass concentration of 145 mug/mL in a vaporizing chamber at 165 ℃ and introducing the standard solution into a chromatographic column, wherein the chromatographic column is a capillary column special for analyzing Agilent CP-Volamine amine compounds, the temperature of a hydrogen flame ionization detector is 185 ℃, the temperature of a chromatographic column box is 75 ℃, and the volume ratio of hydrogen to air to helium in a carrier is 1: 9: 0.9, according to the flow dividing ratio of 1: 8, the flow rate of the carrier is 1.2 mL/min.

A test sample with unknown concentration is weighed and measured according to the method, and the sample amount is 0.5 mu L. The content of each component in the test article is recorded in table 8.

Example 3

Vaporizing a standard solution with the mass concentration of 155 mu g/mL in a vaporizing chamber at 155 ℃ and introducing the standard solution into a chromatographic column, wherein the chromatographic column is a capillary column special for analyzing Agilent CP-Volamine amine compounds, the temperature of a hydrogen flame ionization detector is 175 ℃, the temperature of a chromatographic column box is 85 ℃, and the volume ratio of hydrogen to air to argon in a carrier is 0.8: 11: 1.2, according to the flow division ratio of 1: 12, the flow rate of the carrier is 0.8 mL/min.

A test sample with unknown concentration is weighed and measured according to the method, and the sample amount is 0.7 mu L. The content of each component in the test article is recorded in table 8.

Table 8 measurement results

The above embodiments show that the method for determining the content of the components in the methylamine aqueous solution provided by the invention comprises the steps of firstly obtaining a standard curve, repeatedly feeding a sample to be measured into a chromatograph, and comparing the sample to be measured with the standard curve to obtain a measurement result. The method can effectively separate the main components, has strong specificity, economic and practical effects, good reproducibility and high accuracy, and can accurately and effectively measure the contents of monomethylamine, dimethylamine and trimethylamine, thereby realizing the quality control of the methylamine aqueous solution and filling the blank of the prior art.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.