CN112505208A - Detection method for trace organic impurities in high-purity carbonate solvent and application thereof - Google Patents

Detection method for trace organic impurities in high-purity carbonate solvent and application thereof Download PDF

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CN112505208A
CN112505208A CN202011183432.2A CN202011183432A CN112505208A CN 112505208 A CN112505208 A CN 112505208A CN 202011183432 A CN202011183432 A CN 202011183432A CN 112505208 A CN112505208 A CN 112505208A
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detected
sample
gcms
detection method
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燕增伟
汪德家
张勇
魏娟
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Shandong Haike Xinyuan Material Technology Co Ltd
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Shandong Haike Xinyuan Material Technology Co Ltd
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
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    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/08—Preparation using an enricher
    • G—PHYSICS
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    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8624—Detection of slopes or peaks; baseline correction
    • G01N30/8631—Peaks
    • G01N30/8634—Peak quality criteria
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8696—Details of Software
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8872—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample impurities

Abstract

The invention discloses a detection method of trace organic impurities in a high-purity carbonate solvent and application thereof, belonging to the technical field of impurity detection in organic solvents. The detection method comprises a first process and/or a second process: the first process comprises the following steps: 1) setting GCMS analysis parameters; 2) detecting the solvent to be detected by adopting different sample introduction modes; 3) collecting a total ion current chromatogram map of a solvent to be detected; 4) comparing to determine components in the solvent to be detected; 5) calculating the content of each component in the solvent to be detected by adopting an area normalization method; the second process comprises the following steps: a. setting GCMS analysis parameters; b. extracting and desorbing the solvent to be detected; c. detecting the desorption solution by adopting the method in the step 2), and determining and calculating the content of each component in the desorption solution by adopting the methods in the steps 3) to 5) in the first flow. The detection method provided by the invention has the advantages of high sensitivity and wide range, and can effectively detect the organic impurities in the high-purity carbonate solvent.

Description

Detection method for trace organic impurities in high-purity carbonate solvent and application thereof
Technical Field
The invention belongs to the technical field of impurity detection in organic solvents, and particularly relates to a detection method of trace organic impurities in a high-purity carbonate solvent and application thereof.
Background
Some impurity molecules in the carbonate high-purity solvent often influence the service performance of the electrolyte and obviously influence the quality of the electrolytes with different functions. With the development and progress of lithium battery technology, the battery industry has also made higher demands on the purity of high purity solvents in electrolytes, and the level of impurities in the solvents has been changed from ppm level to ppb level, which has prompted solvent manufacturers to continuously improve the product grade and impurity detection capability.
The detection method of the gas chromatography-mass spectrometry combined analysis technology mainly utilizes the separation function of gas compounds and the powerful high-sensitivity qualitative and quantitative function of a mass spectrometry detector. Because the defects of gas chromatography, such as incapability of qualitative analysis and insufficient sensitivity, are overcome by the powerful function of mass spectrometry, particularly the powerful qualitative function, most organic compounds can be analyzed by different chromatographic separation and detection technologies. However, in the case of a complex matrix or high-purity substances with trace impurities, some compounds which are not easily separated and ionized exist, so that the qualitative analysis of the impurities is difficult or incomplete. The impurity molecules of the carbonate solvents are difficult to directly characterize, especially the trace light components with special functional groups. Therefore, it is important to provide a method capable of effectively detecting impurities in a carbonate solvent.
Disclosure of Invention
The invention aims to provide a method for detecting complex matrixes and trace organic impurities in a high-purity carbonate solvent and application thereof, which have the advantages of high detection sensitivity and wide range and can effectively detect the complex matrixes and the trace organic impurities in the high-purity carbonate solvent.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for detecting trace organic impurities in a high-purity carbonate solvent, which comprises the following steps:
the first process comprises the following steps:
1) setting GCMS analysis parameters;
2) detecting the solvent to be detected by adopting different sample introduction modes;
the different carrying modes comprise four sample feeding modes, namely a sample feeding mode I, a sample feeding mode II, a sample feeding mode III and/or a sample feeding mode IV;
the first sample introduction mode is as follows: absorbing the solvent to be detected by using a microsyringe, discharging the solvent to be detected to 0-10 mu L, and inserting the microsyringe into a GCMS sample inlet to push a push rod to sample;
the sample introduction mode II is as follows: absorbing the solvent to be detected by using a microsyringe, discharging the solvent to be detected to a zero position, pulling to 0-2 mu L, inserting the microsyringe into a GCMS sample inlet, delaying for 0-10 s, and pushing a push rod to sample;
the sample introduction mode III is as follows: absorbing a solvent to be detected by a microsyringe, discharging the solvent to be detected to a zero position, inserting the microsyringe into a GCMS sample inlet, pulling a push rod to 0-2 mu L, and then injecting the sample by the push rod;
the fourth sampling mode is as follows: after a solvent to be detected is sucked by a microsyringe and then is discharged to a zero position, inserting the microsyringe into a GCMS sample inlet and delaying for 0-10 s, and pushing a push rod for sample injection to prevent pressure from pushing the push rod out;
3) collecting a total ion current chromatogram of a solvent to be detected by a GCMS system;
4) analyzing mass spectrograms of the spectral peaks through GCMS software and a spectral library, and comparing the mass spectrograms with mass spectrograms of the spectral library to determine components in the solvent to be detected;
5) calculating the content of each component in the solvent to be detected by adopting an area normalization method after the area of each component chromatographic peak is calculated by adopting GCMS software;
the second process comprises the following steps:
a. setting GCMS analysis parameters;
b. extracting and desorbing the solvent to be detected to obtain desorption liquid;
c. detecting the desorption solution in the step b by adopting the method in the step 2) in the first flow, and determining and calculating the content of each component in the desorption solution by adopting the methods in the steps 3) to 5) in the first flow.
Preferably, the extraction method in the step b is to mix an extraction rod with a solvent to be tested, stir and adsorb a target compound; the inner part of the extraction rod is a magnetic core quartz rod, and the outer layer is a coating of polyacrylate or a porous silica gel layer; the thickness of the coating is 1-10 mu m.
Preferably, the method also comprises adding soluble salt for promoting adsorption; the soluble salt comprises formate, acetate, sodium hydrogen phthalate, potassium hydrogen phthalate, zinc chloride and calcium chloride; the mass ratio of the soluble salt to the solvent to be detected is 0-1: 1 to 2.
Preferably, the rotating speed of the stirring is 10-1000 rpm, and the time is 5-60 min.
Preferably, the temperature during the extraction in the step b is 10-50 ℃.
Preferably, the desorption method in the step b is ultrasonic treatment for 1-10 min after an analytic solvent is added; the power of the ultrasonic wave is 10-1000 w.
Preferably, the resolving solvent is one or more of toluene, chloroform, carbon tetrachloride, dichloromethane, petroleum hydrocarbon, n-hexane and n-heptane.
The invention also provides application of the detection method in the scheme in detection of trace organic impurities in a high-purity carbonate solvent.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by adopting a direct sample introduction delay and partial gasification sample introduction mode of the solvent to be detected and a solvent delay detection technology, the sample introduction amount is controlled, errors and interference caused by a conventional dilution method are avoided, the analysis of high-content components is realized, the qualitative capability of molecules which are difficult to be determined is increased, the detection degree is increased, and the interference is reduced; meanwhile, the detection capability of direct solvent sample introduction of trace impurity molecules is improved, and the detection range and the detection limit of the impurity molecules are expanded.
Meanwhile, the invention can effectively enrich and detect the volatile and semi-volatile impurity molecules in the sample by the technology of enriching and pretreating the impurity molecules in the solvent sample through solid-phase microextraction, can further improve the detection limit of impurities, and simultaneously solves the problem of interference of a solvent peak on detection of partial impurities.
The detection method provided by the invention has the advantages of simple and controllable process, easiness in realization, no interference and no blank background influence in the analysis process, and the rapidity and the reliability of analysis are realized.
Drawings
FIG. 1 is a total ion chromatogram of five target compounds of example 1 (in FIG. 1, the peak positions are EMC, VC, DEC, EC, PC, from left to right);
FIG. 2 is a total ion current chromatogram of the target compound in example 2;
FIG. 3 is a chromatogram of the total ion current of the solvent to be tested in example 2;
FIG. 4 is a comparison graph of the impurity mass spectrum and the standard mass spectrum of the solvent to be tested in example 2 at 9.26 min;
FIG. 5 is a chromatogram of the test sample in example 3 before enrichment;
FIG. 6 is a chromatogram after enrichment of the solvent to be tested in example 3;
FIG. 7 is a mass spectrum of the impurity peak of the solvent to be tested at 2.35min in example 3.
Detailed Description
The invention provides a method for detecting trace organic impurities in a high-purity carbonate solvent, which comprises the following steps:
the first process comprises the following steps:
1) setting GCMS analysis parameters;
2) detecting the solvent to be detected by adopting different sample introduction modes;
the different carrying modes comprise four sample feeding modes, namely a sample feeding mode I, a sample feeding mode II, a sample feeding mode III and/or a sample feeding mode IV;
the first sample introduction mode is as follows: absorbing the solvent to be detected by using a microsyringe, discharging the solvent to be detected to 0-10 mu L, and inserting the microsyringe into a GCMS sample inlet to push a push rod to sample;
the sample introduction mode II is as follows: absorbing the solvent to be detected by using a microsyringe, discharging the solvent to be detected to a zero position, pulling to 0-2 mu L, inserting the microsyringe into a GCMS sample inlet, delaying for 0-10 s, and pushing a push rod to sample;
the sample introduction mode III is as follows: absorbing a solvent to be detected by a microsyringe, discharging the solvent to be detected to a zero position, inserting the microsyringe into a GCMS sample inlet, pulling a push rod to 0-2 mu L, and then injecting the sample by the push rod;
the fourth sampling mode is as follows: after a solvent to be detected is sucked by a microsyringe and then is discharged to a zero position, inserting the microsyringe into a GCMS sample inlet and delaying for 0-10 s, and pushing a push rod for sample injection to prevent pressure from pushing the push rod out;
3) collecting a total ion current chromatogram of a solvent to be detected by a GCMS system;
4) analyzing mass spectrograms of the spectral peaks through GCMS software and a spectral library, and comparing the mass spectrograms with mass spectrograms of the spectral library to determine components in the solvent to be detected;
5) calculating the content of each component in the solvent to be detected by adopting an area normalization method after the area of each component chromatographic peak is calculated by adopting GCMS software;
the second process comprises the following steps:
a. setting GCMS analysis parameters;
b. extracting and desorbing the solvent to be detected to obtain desorption liquid;
c. detecting the desorption solution in the step b by adopting the method in the step 2) in the first flow, and determining and calculating the content of each component in the desorption solution by adopting the methods in the steps 3) to 5) in the first flow.
The method for detecting the trace organic impurities in the high-purity carbonate solvent provided by the invention adopts four different sample injection modes to detect the solvent to be detected, controls the sample injection amount through a direct sample injection delay or partial gasification sample injection mode of the solvent sample to be detected and a solvent delay detection technology, can reduce the damage to a mass spectrum caused by a large amount of solvent entering a chromatographic system, and avoids errors and interference caused by a conventional dilution method. The method not only realizes the analysis of high-content components and increases the qualitative capability of some molecules which are difficult to be determined qualitatively, but also increases the detection degree and reduces the interference; meanwhile, the detection capability of direct solvent sample introduction of trace impurity molecules is improved, and the detection range and the detection limit of the impurity molecules are expanded.
The method for detecting the trace organic impurities in the high-purity carbonate solvent, provided by the invention, comprises the following steps of carrying out a second process after the second process is finished; the second process comprises the following steps:
a. setting GCMS analysis parameters;
b. extracting and desorbing the solvent to be detected to obtain desorption liquid;
c. detecting the desorption solution in the step b by adopting the method in the step 2) in the first flow, and determining and calculating the content of each component in the desorption solution by adopting the methods in the steps 3) to 5) in the first flow.
The invention extracts and desorbs the solvent to be detected to obtain desorption liquid. In the invention, the extraction method is preferably to mix an extraction rod with a solvent to be tested, stir and adsorb a target compound; the inner part of the extraction rod is preferably a magnetic core quartz rod, and the outer layer is preferably a coating of polyacrylate or a porous silica gel layer; the thickness of the coating is preferably 1-10 mu m. In the present invention, in order to enable sufficient extraction, it is preferable to further add a soluble salt that promotes adsorption; the soluble salts preferably include formate, acetate, sodium hydrogen phthalate, potassium hydrogen phthalate, zinc chloride and calcium chloride; in the present invention, the formate is preferably sodium formate or potassium formate, and the acetate is preferably sodium acetate or potassium acetate; the mass ratio of the soluble salt to the solvent to be detected is preferably 0-1: 1 to 2. In the invention, the rotation speed of the stirring is preferably 10-1000 rpm, more preferably 500-600 rpm; the stirring time is preferably 5-60 min, and more preferably 25-45 min. In the invention, the temperature during the extraction is preferably 10-50 ℃.
In the invention, the desorption method is preferably ultrasonic treatment for 1-10 min after an analytic solvent is added; the power of the ultrasonic wave is preferably 10-1000 w. In the present invention, the resolving solvent is preferably one or more of toluene, chloroform, carbon tetrachloride, dichloromethane, petroleum hydrocarbon, n-hexane and n-heptane.
For low trace volatile and semi-volatile substances, the sensitivity of common gas phase detection is insufficient, and the mass spectrum has the limitation of a solvent peak.
The sources of the materials, reagents and instruments used in the present invention are not particularly limited, and those commonly available in the art can be used.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Analysis of 5 standard target compounds:
the instrument conditions were as follows:
conditions of gas chromatograph
A chromatographic column: HP-5(30 m.times.0.25 mm.times.0.25 μm) capillary column; carrier gas flow (helium): 1 mL/min;
column box temperature program: 50 ℃ (5min) → 20 ℃/min (7.5min) → 200 ℃ (3 min);
a vaporization chamber: 250 ℃; pressing the column in front: 60 kPa; and (3) sample introduction mode: split-flow sample injection with a split-flow ratio of 50: 1; purging flow rate: 2 mL/min.
Conditions of the Mass spectrometer
An ion source: an EI source; electron energy: 70 eV; ion source temperature: 200 ℃; interface temperature: 250 ℃;
solvent retardation: 3.5min, or adopting a mass spectrum data acquisition method without solvent delay and segment delay; the scanning mode is as follows: performing full scanning qualitative, wherein the scanning range is (35-270) amu; SIM scanning and quantifying;
(1) standard solvent compounds were formulated using five standard solvents of EMC, VC, DEC, EC and PC as per 3: 1: 4: 1: 1, then detecting a standard sample according to the gas phase analysis conditions, the mass spectrum conditions and the detection method described above, wherein the sample injection amount of the standard sample is 0.0 mu L, delaying 3S sample injection, and obtaining a chromatogram as shown in figure 1.
(2) And (3) taking a mass spectrogram at the maximum peak position from the spectrogram obtained in the step (1), retrieving a molecular structure and a matching degree, selecting a compound with the most suitable matching degree for qualitative use, and also selecting characteristic fragment ion for quantitative use to obtain qualitative results, wherein the specific results are ethyl methyl carbonate, vinylene carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate from left to right, and two minimum unknown peaks are excluded (impurity peaks with retention time at 4.35min and 5.45 min).
Example 2
Analysis of compounds in the actual electrolyte system:
(1) the content of various solvents and additives in the unknown electrolyte is analyzed by using an actual electrolyte and adopting the same analysis method and a sample injection mode, and the chromatogram results are shown in figure 2. As can be seen from FIG. 2, the electrolyte mainly contains DEC, PC and a small amount of EMC, and does not contain a solvent such as VC additive and EC.
(2) The specific results of calculating each component in the unknown electrolyte according to the peak area of each component in the standard sample are shown in table 1:
TABLE 1 test results of the respective components of the electrolyte
Serial number Compound (I) Concentration in sample (%)
1 Methyl Ethyl carbonate EMC 0.22
2 Vinylene carbonate VC N.D
3 Diethyl carbonate DEC 46.83
4 Ethylene carbonate EC N.D
5 Propylene carbonate PC 12.85
As can be seen from Table 1, the method qualitatively quantifies the content of different solvents in the electrolyte, and the electrolyte does not contain two solvents of VC and EC, mainly two solvents of DEC and PC and a small amount of EMC solvent.
(3) And (3) analyzing impurities in the carbonate solvent or the electrolyte, and determining the impurities according to the sample injection method. For example, as shown in fig. 3, the direct chromatographic analysis result of the industrial-grade ethylene carbonate EC shows that the matching degree between the mass spectrum of the impurity peak at 9.26min and the standard spectrum reaches more than 95%, as shown in fig. 4. It can be seen from FIG. 4 that it is 2-bromoethanol.
Example 3
Enrichment analysis of unknown compounds in a certain solvent system:
(1) a high-purity solvent (Aladdin dimethyl carbonate DMC 99%) purchased from the market is adopted, an acrylate extraction rod is adopted for magnetic stirring and soaking for 30min, after the stirring speed is 1000rpm, the rod is taken out and is placed into a glass bottle, 2-5 mL of chromatographic grade n-hexane is added, ultrasonic desorption is carried out for 3min, and the solution is used for standby.
(2) And (3) continuously soaking the extracted high-purity solvent for 3-30 min by adopting a silica gel layer extraction rod through magnetic stirring at a stirring speed of 1000rpm, taking out the extraction rod, placing the extraction rod in used n-hexane for ultrasonic desorption for 3min, and taking the solution as a GCMS analysis sample for sample injection analysis.
(3) And (4) analyzing the impurities in the solvent after enrichment and analysis, performing chromatographic analysis according to the above several sample injection methods, and determining the impurities. FIG. 5 is a chromatogram prior to enrichment due to low content and the presence of background interference; the chromatographic analysis result after the solvent impurity enrichment by using the extraction rod is shown in fig. 6, and the mass spectrogram of the impurity peak at 2.35min is shown in fig. 7.
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.

Claims (8)

1. A method for detecting trace organic impurities in a high-purity carbonate solvent is characterized by comprising a first process and/or a second process:
the first process comprises the following steps:
1) setting GCMS analysis parameters;
2) detecting the solvent to be detected by adopting different sample introduction modes;
the different carrying modes comprise four sample feeding modes, namely a sample feeding mode I, a sample feeding mode II, a sample feeding mode III and/or a sample feeding mode IV;
the first sample introduction mode is as follows: absorbing the solvent to be detected by using a microsyringe, discharging the solvent to be detected to 0-10 mu L, and inserting the microsyringe into a GCMS sample inlet to push a push rod to sample;
the sample introduction mode II is as follows: absorbing the solvent to be detected by using a microsyringe, discharging the solvent to be detected to a zero position, pulling to 0-2 mu L, inserting the microsyringe into a GCMS sample inlet, delaying for 0-10 s, and pushing a push rod to sample;
the sample introduction mode III is as follows: absorbing a solvent to be detected by a microsyringe, discharging the solvent to be detected to a zero position, inserting the microsyringe into a GCMS sample inlet, pulling a push rod to 0-2 mu L, and then injecting the sample by the push rod;
the fourth sampling mode is as follows: after a solvent to be detected is sucked by a microsyringe and then is discharged to a zero position, inserting the microsyringe into a GCMS sample inlet and delaying for 0-10 s, and pushing a push rod for sample injection to prevent pressure from pushing the push rod out;
3) collecting a total ion current chromatogram of a solvent to be detected by a GCMS system;
4) analyzing mass spectrograms of the spectral peaks through GCMS software and a spectral library, and comparing the mass spectrograms with mass spectrograms of the spectral library to determine components in the solvent to be detected;
5) calculating the content of each component in the solvent to be detected by adopting an area normalization method after the area of each component chromatographic peak is calculated by adopting GCMS software;
the second process comprises the following steps:
a. setting GCMS analysis parameters;
b. extracting and desorbing the solvent to be detected to obtain desorption liquid;
c. detecting the desorption solution in the step b by adopting the method in the step 2) in the first flow, and determining and calculating the content of each component in the desorption solution by adopting the methods in the steps 3) to 5) in the first flow.
2. The detection method according to claim 1, wherein the extraction in step b is performed by mixing an extraction rod with a solvent to be detected, stirring and adsorbing the target compound; the inner part of the extraction rod is a magnetic core quartz rod, and the outer layer is a coating of polyacrylate or a porous silica gel layer; the thickness of the coating is 1-10 mu m.
3. The detection method according to claim 2, further comprising adding a soluble salt that promotes adsorption; the soluble salt comprises formate, acetate, sodium hydrogen phthalate, potassium hydrogen phthalate, zinc chloride and calcium chloride; the mass ratio of the soluble salt to the solvent to be detected is 0-1: 1 to 2.
4. The detection method according to claim 2, wherein the rotation speed of the stirring is 10 to 1000rpm, and the time is 5 to 60 min.
5. The detection method according to claim 1, wherein the temperature at the time of extraction in the step b is 10 to 50 ℃.
6. The detection method according to claim 1, wherein the desorption method in the step b is ultrasonic treatment for 1-10 min after an analytic solvent is added; the power of the ultrasonic wave is 10-1000 w.
7. The detection method according to claim 6, wherein the analytic solvent is one or more of toluene, chloroform, carbon tetrachloride, methylene chloride, petroleum hydrocarbon, n-hexane and n-heptane.
8. The use of the detection method of any one of claims 1 to 7 for detecting trace organic impurities in a high purity carbonate solvent.
CN202011183432.2A 2020-10-29 2020-10-29 Detection method for trace organic impurities in high-purity carbonate solvent and application thereof Pending CN112505208A (en)

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Application publication date: 20210316