CN114019041A - Method for detecting residual amount of triphosgene in industrial waste liquid - Google Patents
Method for detecting residual amount of triphosgene in industrial waste liquid Download PDFInfo
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Abstract
The invention discloses a method for detecting the residual amount of triphosgene in industrial waste liquid, which comprises the steps of preparing a standard reference substance solution, preparing a sample solution of a sample to be tested, detecting a triphosgene derivative by adopting a high performance liquid chromatography-mass spectrometry combined method, and then calculating the residual amount of the triphosgene by using an external standard method. According to the triphosgene detection method provided by the invention, the amount of triphosgene is obtained by detecting the amount of a derivative by utilizing the complete specificity of the reaction of the triphosgene and the derivative reagent; proved by methodology, the method can detect that the content of the triphosgene in the industrial waste liquid is at least lower than 2ng, and meet the requirement on the triphosgene discharge standard in the industrial waste liquid; the method has high precision, and the retention time RSD% is 0.02%; the method has good specificity, and the triphosgene derivative chromatogram is not interfered by other peaks; the method has the advantages that the linearity of the triphosgene derivative is good within the range of 2ng/mL-20 ng/mL; the triphosgene derivative has at least 12 hr stability in the recovering solution, high stability and high recovering rate.
Description
Technical Field
The invention relates to the technical field of chemical analysis, in particular to a method for detecting the residual amount of triphosgene in industrial waste liquid.
Background
Triphosgene, also known as phosgene solid, known by the chemical name bis (trichloromethyl) carbonate, BTC for short, is a white crystalline compound with a phosgene-like odor and has the molecular formula of CO (OCCl)3)2. The triphosgene has reaction activity similar to that of phosgene, can react with alcohol, aldehyde, amine, amide, carboxylic acid, phenol, hydroxylamine and other compounds, can also be cyclized and condensed to prepare heterocyclic compounds, can be used for carbonylation reaction, cyclized condensation, certain polymerization reaction and the like, and can be applied to the production of all chemical products using phosgene and diphosgene. Since triphosgene is a stable solid compound, can be stored in a sealed manner at room temperature, and is safer to transport and store, the triphosgene has been widely used in industrial production instead of phosgene, and has been successfully applied to various fields such as pesticides, medicines, perfumes, dyes, high polymer materials and the like. However, triphosgene can generate substances such as carbon monoxide, carbon dioxide, hydrogen chloride, phosgene and the like in a reaction link, and phosgene which is a main decomposition product is high-toxicity asphyxia harmful gas, so that a large amount of phosgene is absorbed in a short time, systemic diseases mainly comprising respiratory system damage are easily caused, and pulmonary edema or death occurs in serious patients. In order to control the risk of triphosgene pollution, the residual amount of triphosgene in the industrial waste liquid needs to be detected to determine whether the waste liquid discharge standard is met. At present, no effective test method aiming at the residual amount of the triphosgene in the industrial waste liquid is found in the field, so that the establishment of the method which is simple to operate, accurate in result, high in sensitivity and capable of being used for analyzing the residual amount of the triphosgene in the industrial waste liquid is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for detecting the residual amount of triphosgene in industrial waste liquid, which can accurately detect the residual amount of triphosgene in the industrial waste liquid, and has the advantages of high sensitivity, good precision and detection limit meeting the detection requirement.
In order to solve the technical problem, the method for detecting the residual amount of triphosgene in the industrial waste liquid provided by the invention comprises the following steps:
1) preparing a sample solution of a test sample: taking a certain amount of industrial waste liquid and acetonitrile solvent into a volumetric flask, adding a derivatization reagent after dissolving, adding a mixed solution of acetonitrile and dimethyl sulfoxide into the volumetric flask after completely reacting under specific conditions (temperature and ultrasound), and obtaining a test article stock solution; taking a certain amount of the test article stock solution in another volumetric flask, adding a diluent to a constant volume and shaking up to obtain a test article sample solution;
2) preparing a standard reference substance solution: taking a certain amount of triphosgene and acetonitrile solvent into a volumetric flask, adding a derivatization reagent after dissolving, adding a mixed solution of acetonitrile and dimethyl sulfoxide into the volumetric flask after completely reacting under specific conditions (temperature and ultrasound), and obtaining a standard reference substance stock solution; taking a certain amount of standard reference substance stock solution in another volumetric flask, adding a diluent to a constant volume, and shaking up to obtain a standard reference substance solution;
3) respectively detecting the sample solution of the test sample and the standard reference solution by adopting a high performance liquid chromatography-mass spectrometer, and recording the detection results;
4) calculating the content of triphosgene derivatives in the sample solution of the test sample by using an external standard method, calculating the amount of triphosgene by using a reaction formula of the triphosgene and a derivatization reagent, and calculating the residual amount of the triphosgene in the industrial waste liquid according to the concentration of the sample solution of the test sample.
Based on the characteristics that triphosgene is not reserved in a reversed-phase chromatographic system and does not respond on a mass spectrum detector, the triphosgene is firstly subjected to derivatization treatment to prepare a triphosgene derivative, and the triphosgene derivative has good reservation on a conventional reversed-phase chromatographic column and can be ionized, so that the triphosgene derivative can be used for detection by a high performance liquid chromatography-mass spectrum combined method; the high performance liquid chromatography-mass spectrometry combined method uses high performance liquid chromatography as a separation means and mass spectrometry as an identification tool to analyze and process triphosgene derivatives, and the specific process of the analysis and the processing is generally as follows: preparing a series of standard reference substance solutions with concentration by using the standard reference substance stock solution, continuously feeding samples, recording a chromatogram, performing linear regression by using the mass concentration and the peak area of the chromatogram to obtain an equation and a correlation coefficient, and preparing a standard curve; and then injecting the prepared sample solution of the test sample, recording a chromatogram, integrating the chromatographic peak of the triphosgene derivative in the chromatogram to obtain a peak area, finally calculating the content of the triphosgene derivative in the sample solution of the test sample according to an external standard method, calculating the amount of the triphosgene by utilizing the reaction formula of the triphosgene and a derivatization reagent, and calculating the residual amount of the triphosgene in the industrial waste liquid according to the concentration of the sample solution of the test sample.
In a specific embodiment, the derivatizing agent is benzylamine. The triphosgene and benzylamine can basically realize complete reaction, and even a small amount of residual triphosgene in the industrial waste liquid can also basically realize complete reaction with benzylamine to generate a triphosgene derivative for detection, namely, the determination of the residual triphosgene in the industrial waste liquid can be met.
In a specific embodiment, the specific conditions refer to a reaction temperature of 30-40 ℃, an ultrasonic power of 50W, and a reaction time of 10-60min, preferably, the reaction time is 30 min.
In a specific embodiment, in the mixed solution of acetonitrile and dimethyl sulfoxide, the volume ratio of acetonitrile to dimethyl sulfoxide is 1: 1.
In a specific embodiment, the diluent is a mixture of water and dimethyl sulfoxide, wherein the volume ratio of water to dimethyl sulfoxide is 1: 1.
In one specific embodiment, the detection conditions are as follows:
chromatographic conditions are as follows:
the chromatographic column adopts a C18 chromatographic column;
the mobile phase comprises a mobile phase A and a mobile phase B, wherein the mobile phase A is a formic acid aqueous solution, and the volume concentration of formic acid is 0.05% -0.2%; the mobile phase B is an acetonitrile solution of formic acid, wherein the volume concentration of the formic acid is 0.05% -0.2%;
gradient elution was used, the gradient elution procedure was performed as follows: the volume percentage of the mobile phase A is decreased from 70% to 10% in 0-10min when the mobile phase A + the mobile phase B is equal to 100%; keeping the volume percentage of the mobile phase A at 10 percent for 10-12 min; the volume percentage of the mobile phase A is increased from 10 percent to 70 percent within 12-13 min; 13-18min, the volume percentage of the mobile phase A is kept to be 70%;
mass spectrum conditions:
an electrospray ionization source is adopted, and the temperature of an ion source is 280-320 ℃;
adopting a positive ion scanning mode;
the flow rate of the drying gas is 8-13L/min, and the temperature of the drying gas is 350 ℃;
atomizer pressure 35 psi;
the capillary voltage is 3000V;
the voltage of the taper hole is 70-150W;
the quantitative ion m/z was 241.0.
In a specific embodiment, the chromatographic conditions are such that the column temperature of the chromatographic column is from 40 to 60 ℃ and the flow rate is from 0.8 to 1.5 mL/min.
In a specific embodiment, the chromatographic conditions are such that the column temperature is 50 ℃ and the flow rate is 1.0 mL/min.
In a specific embodiment, the sample size in the chromatographic conditions is 5. mu.L.
In a specific embodiment, the mass spectrometry conditions are such that the ion source temperature is 300 ℃, the dry gas flow is 12L/min, and the cone hole voltage is 70V.
According to the triphosgene detection method provided by the invention, the amount of triphosgene is obtained by detecting the amount of a derivative by utilizing the complete specificity of the reaction of the triphosgene and the derivative reagent; proved by methodology, the method can detect that the content of the triphosgene in the industrial waste liquid is at least lower than 2ng, and meet the requirement on the triphosgene discharge standard in the industrial waste liquid; the method has high precision, and the retention time RSD% is 0.02%; the method has good specificity, and the triphosgene derivative chromatogram is not interfered by other peaks; the method has the advantages that the linearity of the triphosgene derivative is good within the range of 2ng/mL-20 ng/mL; the triphosgene derivative has at least 12 hr stability in the recovering solution, high stability and high recovering rate.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the present invention are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a chromatogram of a blank solution in an example of the present invention;
FIG. 2 is a chromatogram of a standard control solution at a concentration of 10ng/mL in an example of the invention;
FIG. 3 is a sample solution chromatogram of a test sample in an example of the present invention;
FIG. 4 is a chromatogram of a sample spiking solution according to an embodiment of the present invention;
FIG. 5 is a chromatogram of a triphosgene derivative concentration of 1.0ng/mL in a detection limit and quantitation limit experiment in an example of the present invention;
FIG. 6 is a chromatogram of a triphosgene derivative concentration of 2.0ng/mL in a detection limit and quantitation limit experiment in an example of the present invention.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The inventor of the application finds out and obtains a method for detecting the residual amount of the triphosgene in the industrial waste liquid through extensive research and a large number of experiments, the detected amount provided by the method is at least lower than 2ng, and the requirement of the industrial waste liquid on the emission standard of the triphosgene is met.
The experimental conditions in the examples of the invention are as follows:
the instrument comprises the following steps: agilent 1260 high performance liquid chromatography-MS 6120 single quadrupole mass spectrometer; mettler Toledo XSE205DU analytical balance;
the chromatographic conditions were as follows:
a chromatographic column: waters Xbridge C18 (150X 4.6mm,3.5 μm);
mobile phase: mobile phase A + mobile phase B is 100%; the mobile phase A is an aqueous solution containing 0.1% formic acid; mobile phase B was 0.1% formic acid in acetonitrile;
gradient elution procedure: the volume percentage of the mobile phase A is decreased from 70% to 10% in 0-10min when the mobile phase A + the mobile phase B is equal to 100%; keeping the volume percentage of the mobile phase A at 10 percent for 10-12 min; the volume percentage of the mobile phase A is increased from 10 percent to 70 percent within 12-13 min; 13-18min, the volume percentage of the mobile phase A is kept to be 70%;
flow rate: 1.0 mL/min;
column temperature: 50 ℃;
sample introduction amount: 5 μ L.
The mass spectrometry conditions were as follows:
an ionization source: electrospray (ESI) ionization source, positive ion scan mode;
ion source temperature: 300 ℃;
flow rate of drying gas: 12L/min;
temperature of the drying gas: 350 ℃;
atomizer pressure: 35 psi;
capillary voltage: 3000V;
taper hole voltage: 70V;
241.0 is the quantity of ions m/z.
Example A content of triphosgene in Industrial waste liquid
1) Preparation of standard control solution: weighing 50mg of triphosgene into a 50mL volumetric flask, adding 25mL of acetonitrile solvent for dissolving, adding 300mg of benzylamine after dissolving, carrying out ultrasonic treatment for 30min (ultrasonic power is 50W) at 35 +/-5 ℃, and adding 25mL of mixed solution of acetonitrile and dimethyl sulfoxide (volume ratio of the acetonitrile to the dimethyl sulfoxide is 1:1) after reaction is completed to obtain standard reference substance stock solution with concentration of 1 mg/mL; taking a standard reference substance stock solution, diluting the stock solution with a diluent (a mixed solution of water and dimethyl sulfoxide, the volume ratio of the two is 1: 1; the diluent in the application is the solution without special indication), and preparing a standard reference substance solution with the following concentration: 2.0ng/mL,5.0ng/mL,8.0ng/mL,10.0ng/mL,12.0ng/mL and 20.0 ng/mL.
2) Preparing a sample solution of a test sample: taking 50mg of industrial waste liquid into a 50mL volumetric flask, adding 25mL of acetonitrile solvent for dissolving, adding 300mg of benzylamine after dissolving, carrying out ultrasonic treatment for 30min (ultrasonic power is 50W) at 35 +/-5 ℃, and adding 25mL of mixed liquid of acetonitrile and dimethyl sulfoxide (volume ratio of the acetonitrile to the dimethyl sulfoxide is 1:1) after reaction is completed to obtain a stock solution of a test sample with the concentration of 1 mg/mL; taking 1mL and 10mL volumetric flasks of the stock solution of the test sample, and shaking up with a diluent to a constant volume to obtain a sample solution of the test sample with the concentration of 0.1 mg/mL.
3) Preparing blank solution: weighing 30mg of benzylamine in a 5mL volumetric flask, adding a diluent for dissolution, diluting to a constant volume with the diluent, and shaking up to obtain a solution with the benzylamine concentration of 6 mg/mL; transferring 1mL of the solution with the benzylamine concentration of 6mg/mL into a 100mL volumetric flask, diluting with the diluent again to constant volume, and shaking up to obtain a solution with the benzylamine concentration of 0.06 mg/mL; transferring 50 mu L of the solution with the benzylamine concentration of 0.06mg/mL into a 100mL volumetric flask, diluting with the diluent again to constant volume, and shaking up to obtain a solution with the benzylamine concentration of 0.03 mu g/mL, namely a blank solution.
4) And respectively measuring the standard reference substance solution, the test substance solution and the blank solution by adopting the established detection conditions, and recording the chromatogram. And according to an external standard method, calculating to obtain that the content of triphosgene in the sample solution of the test sample is 0.8 ng.
Example two methodological validation
1) Specificity experiments
Preparing a sample and a standard solution: taking 50mg of industrial waste liquid into a 50mL volumetric flask, adding 25mL of acetonitrile solvent for dissolving, adding 300mg of benzylamine after dissolving, carrying out ultrasonic treatment for 30min (ultrasonic power is 50W) at 35 +/-5 ℃, and adding 25mL of mixed liquid of acetonitrile and dimethyl sulfoxide (volume ratio of the acetonitrile to the dimethyl sulfoxide is 1:1) after reaction is completed to obtain a stock solution of a test sample with the concentration of 1 mg/mL; taking 1mL of the stock solution of the test sample and 1mL of the standard reference substance solution of 100ng/mL into a 10mL volumetric flask, and shaking up with a diluent in constant volume to obtain the test sample labeling solution with the concentration of 0.1 mg/mL.
Taking the blank solution prepared in the example 1, the standard reference solution with the concentration of 10ng/mL, the sample solution of the test sample with the concentration of 0.1mg/mL and the sample adding standard solution of the test sample, and sequentially sampling to acquire a chromatogram;
the experimental results show that: the blank solution has no interference, and other peaks in the sample have no interference to the triphosgene derivative chromatographic peak, and the method has good specificity.
2) Precision experiment
Preparing a standard solution for a precision experiment according to the preparation method of the standard reference substance solution in the first embodiment, wherein the prepared concentration is 10.0 ng/mL; and (3) continuously injecting the prepared standard solution for 5 times under the detection condition of high performance liquid chromatography-mass spectrometry, recording retention time and peak area, and evaluating the result, wherein the recorded result is detailed in table 1.
TABLE 1 System precision Experimental results
| Number of needle insertions | 1 | 2 | 3 | 4 | 5 | Average | RSD％ |
| Peak area | 5.393 | 5.393 | 5.392 | 5.392 | 5.394 | 5.393 | 0.02％ |
| Retention time (min) | 60827 | 60804 | 61226 | 60849 | 60805 | 60902 | 0.30％ |
The experimental results show that: the method has good precision and meets the test requirements.
3) Linear and range experiments
A series of linear and range experimental standard solutions were prepared according to the formulation method for the standard control solution in example one, at concentrations of 2.0ng/mL,5.0ng/mL,8.0ng/mL,10.0ng/mL,12.0ng/mL, and 20.0ng/mL in this order. The prepared series of standard solutions are subjected to sample injection in sequence under the condition of high performance liquid chromatography-mass spectrometry combined detection, test results are recorded, linear regression is carried out according to mass concentration and peak area, a regression equation and relevant coefficients are obtained, and the test results are detailed in table 2.
TABLE 2 results of the linearity and Range experiments
The experimental results show that at least in the range of 2.0-20.0ng/mL, the linearity is good.
4) Detection limit and quantitative limit experiment
Preparing a series of standard solutions for concentration detection limit and quantitative limit experiments according to the preparation method of the standard reference substance solution in the first embodiment, sequentially injecting samples under the detection condition of high performance liquid chromatography-mass spectrometry, and recording chromatograms, which are detailed in fig. 5 and 6;
the experimental results show that when the concentration of the triphosgene derivative is 2.0ng/mL, the main peak height is 10 times of the baseline noise, and when the concentration of the triphosgene derivative is 1.0ng/mL, the main peak height is 2-3 times of the baseline noise.
5) Standard recovery rate experiment
Preparing a recovery rate stock solution of a recovery rate experiment according to the preparation method of the standard reference substance solution in the first embodiment, wherein the concentration of the recovery rate stock solution is 100 ng/mL;
preparing a sample solution to be tested for a recovery rate experiment according to the preparation method of the sample solution to be tested in the first embodiment, wherein the concentration of the sample solution to be tested is 0.1 mg/mL;
preparing a sample stock solution for a recovery rate experiment according to the preparation method of the sample stock solution in the first embodiment, wherein the concentration of the sample stock solution is 1mg/mL, taking 3 parts of the sample stock solution for the 1mL recovery rate experiment, respectively adding into 3 10mL volumetric flasks, respectively adding 0.5mL, 1.0mL and 1.5mL of the recovery rate stock solutions, respectively adding a diluent, fixing the volume, and shaking uniformly to obtain 50%, 100% and 150% recovery rate solutions;
sequentially testing the sample solution of the sample to be tested and the three solutions with the standard recovery rate under the detection condition of high performance liquid chromatography-mass spectrometry, calculating the concentration of each peak in the three solutions with the standard recovery rate by installing an external standard method, wherein the calculation results are shown in Table 3,
TABLE 3 results of recovery test with addition of standard
The experimental result shows that the recovery rate is good, the accuracy is high, and the test requirement is met.
6) Stability test
And (3) taking a 100% standard adding recovery rate solution in the standard adding recovery rate experiment to perform a stability experiment, injecting samples in 0,4,6 and 12 hours respectively, recording a chromatogram, and obtaining results shown in table 4 in detail.
Table 4 stability test results
The experimental results show that the triphosgene derivative solution is stable at room temperature for at least 12 hours.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for detecting the residual amount of triphosgene in industrial waste liquid is characterized by comprising the following steps:
1) preparing a sample solution of a test sample: taking a certain amount of industrial waste liquid and acetonitrile solvent into a volumetric flask, adding a derivatization reagent after dissolving, adding a mixed solution of acetonitrile and dimethyl sulfoxide into the volumetric flask after completely reacting under specific conditions (temperature and ultrasound), and obtaining a test article stock solution; taking a certain amount of the test article stock solution in another volumetric flask, adding a diluent to a constant volume and shaking up to obtain a test article sample solution;
2) preparing a standard reference substance solution: taking a certain amount of triphosgene and acetonitrile solvent into a volumetric flask, adding a derivatization reagent after dissolving, adding a mixed solution of acetonitrile and dimethyl sulfoxide into the volumetric flask after completely reacting under specific conditions (temperature and ultrasound), and obtaining a standard reference substance stock solution; taking a certain amount of standard reference substance stock solution in another volumetric flask, adding a diluent to a constant volume, and shaking up to obtain a standard reference substance solution;
3) respectively detecting the sample solution of the test sample and the standard reference solution by adopting a high performance liquid chromatography-mass spectrometer, and recording the detection results;
4) calculating the content of triphosgene derivatives in the sample solution of the test sample by using an external standard method, calculating the amount of triphosgene by using a reaction formula of the triphosgene and a derivatization reagent, and calculating the residual amount of the triphosgene in the industrial waste liquid according to the concentration of the sample solution of the test sample.
2. The method of claim 1, wherein the derivatizing agent is benzylamine.
3. The method of claim 1, wherein the specific conditions are a reaction temperature of 30-40 ℃, an ultrasonic power of 50W, and a reaction time of 10-60 min.
4. The method according to claim 1, wherein the volume ratio of acetonitrile to dimethylsulfoxide in the mixed solution of acetonitrile and dimethylsulfoxide is 1: 1.
5. The method of claim 1, wherein the diluent is a mixture of water and dimethylsulfoxide, wherein the volume ratio of water to dimethylsulfoxide is 1: 1.
6. The method of claim 1, wherein the detection conditions are as follows:
chromatographic conditions are as follows:
the chromatographic column adopts a C18 chromatographic column;
the mobile phase comprises a mobile phase A and a mobile phase B, wherein the mobile phase A is a formic acid aqueous solution, and the volume concentration of formic acid is 0.05% -0.2%; the mobile phase B is an acetonitrile solution of formic acid, wherein the volume concentration of the formic acid is 0.05% -0.2%;
gradient elution was used, the gradient elution procedure was performed as follows: the volume percentage of the mobile phase A is decreased from 70% to 10% in 0-10min when the mobile phase A + the mobile phase B is equal to 100%; keeping the volume percentage of the mobile phase A at 10 percent for 10-12 min; the volume percentage of the mobile phase A is increased from 10 percent to 70 percent within 12-13 min; 13-18min, the volume percentage of the mobile phase A is kept to be 70%;
mass spectrum conditions:
an electrospray ionization source is adopted, and the temperature of an ion source is 280-320 ℃;
adopting a positive ion scanning mode;
the flow rate of the drying gas is 8-13L/min, and the temperature of the drying gas is 350 ℃;
atomizer pressure 35 psi;
the capillary voltage is 3000V;
the voltage of the taper hole is 70-150W;
the quantitative ion m/z was 241.0.
7. The method of claim 6, wherein the chromatographic conditions are such that the column temperature is 40-60 ℃ and the flow rate is 0.8-1.5 mL/min.
8. The method of claim 7, wherein the chromatographic conditions comprise a column temperature of 50 ℃ and a flow rate of 1.0 mL/min.
9. The method of claim 6, wherein the chromatographic conditions are such that a sample size of 5 μ L is applied.
10. The method of claim 6, wherein the mass spectrometry conditions are an ion source temperature of 300 ℃, a dry gas flow of 12L/min, and a cone-hole voltage of 70V.
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