CN114002346A - Method for detecting methyl ethyl ketone peroxide in air of workplace - Google Patents
Method for detecting methyl ethyl ketone peroxide in air of workplace Download PDFInfo
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- CN114002346A CN114002346A CN202111225917.8A CN202111225917A CN114002346A CN 114002346 A CN114002346 A CN 114002346A CN 202111225917 A CN202111225917 A CN 202111225917A CN 114002346 A CN114002346 A CN 114002346A
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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
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- G—PHYSICS
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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
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Abstract
The invention provides a method for measuring the content of methyl ethyl ketone peroxide in air of a workplace, belonging to the technical field of occupational health detection; an air sampler is used for sampling at fixed points, a 401 organic support tube is used as a solid adsorbent, acetone is used as desorption liquid, optimized chromatographic conditions are provided, and the concentration of methyl ethyl ketone peroxide in the air of a working place is detected by adopting solvent desorption-gas chromatography. The invention has simple operation and lower cost, and is convenient for collecting and analyzing a large amount of samples.
Description
Technical Field
The invention belongs to the technical field of occupational health detection, and particularly relates to a method for determining the concentration of methyl ethyl ketone peroxide in air of a workplace.
Background
Methyl Ethyl Ketone Peroxide (MEKP) is an organic substance, can be dissolved in organic solvents such as benzene, alcohol, ether and ester, and is insoluble in water. Methyl ethyl ketone peroxide is industrially used as a normal-temperature curing agent for unsaturated polyester resins, an initiator for organic synthesis, a bleaching agent, and a bactericide. Studies have shown that methyl ethyl ketone peroxide vapor or mist is highly irritating to the respiratory tract and also damaging to the eyes and skin. The first part of the occupational exposure limits of harmful factors in workplaces of the current national standards: the occupational exposure limits are specified in the chemical hazards (GBZ 2.1.1-2019). The National Institute for Occupational Safety and Health (NIOSH) established a visible absorption spectrophotometry method for determining the concentration in the air of its workplace. In the detection method, most of ketone compounds except acetone have higher detection results under higher concentration, and other peroxides or strong oxides also interfere the color reaction.
The invention patent (application number CN201210035608.9) discloses a method for measuring the content of methyl ethyl ketone peroxide in air of a workplace, and the pretreatment process of a sample is complex, so that the method is not beneficial to analyzing a large amount of samples to be measured quickly. Therefore, a method for accurately and efficiently measuring the concentration of the methyl ethyl ketone peroxide in the air of a workplace needs to be researched and developed, real and reliable data are provided for occupational health evaluation, and meanwhile, the blank of the related field is filled.
Disclosure of Invention
The invention aims to provide a method for measuring the content of methyl ethyl ketone peroxide in air of a workplace, and aims to solve the technical problems that the sample pretreatment process is complex, the analysis of a large number of samples to be detected is not facilitated, and the detection result is high in the existing detection method.
In order to achieve the purpose, the specific technical scheme of the method for measuring the content of the methyl ethyl ketone peroxide in the air of the workplace comprises the following steps:
the technical scheme provided by the invention is that an air sampler is used for sampling at fixed points, a 401 organic support tube is used as a solid adsorbent, acetone is used as desorption liquid, optimized chromatographic conditions are provided, and the concentration of methyl ethyl ketone peroxide in air of a working place is detected by adopting a solvent desorption-gas chromatography method, and the method specifically comprises the following steps:
step S1, connecting 401 an organic support tube at the sampling point to be detected by using an air sampling pump, wherein the air sampling pump in the steps is required to meet the following conditions: the flow rate is 0-500 ml/min. The 401 organic carrier tube is of a solvent desorption type and contains 100mg/50mg of the 401 organic carrier. The method comprises the following steps of short-time sampling: opening 401 two ends of the organic carrier tube at a sampling point, and collecting a 15min air sample at a flow rate of 100 ml/min; sampling for a long time: and (4) opening the two ends of the organic support pipe 401 at a sampling point, and collecting an air sample for 2-8 h at the flow rate of 50 ml/min. After sampling, immediately closing the two ends of the organic support tube 401, recording the sample number, placing the sample in a clean container for transportation and storage, and sending the sample to a laboratory for detection;
and step S2, opening the 401 organic support tube collected in the step, respectively pouring the front section and the rear section of the 401 organic support body collected in the 401 organic support tube into a solvent desorption bottle, respectively adding 1.0ml of acetone, sealing, shaking for 1min, and desorbing for 30 min. Shaking up, and determining the desorption solution. If the concentration of the substance to be detected in the desorption solution exceeds the determination range, diluting with acetone and determining, and multiplying the dilution times during calculation;
and step S3, adding the desorption solution obtained in the step into a gas chromatograph for analysis by using a micro-sampler, determining the quality by retention time, determining the quantity by using the peak area of the chromatographic peak of the substance to be detected, and dividing the detection result by the standard sampling volume to obtain the concentration of the methyl ethyl ketone peroxide in the air of the workplace. The range of the micro sample injector is 5 μ L or 10 μ L. Specific gas chromatography apparatus conditions are detailed in the embodiments.
The method for measuring the content of methyl ethyl ketone peroxide in the air of the workplace has the following advantages:
(1) the method provided by the invention is simple and convenient to operate, has lower cost and is convenient for collecting and analyzing a large number of samples;
(2) by utilizing the method provided by the invention to carry out sample pretreatment, the loss of the components to be detected is less, and the detection accuracy is high;
(3) the chromatographic conditions provided by the invention can realize lower detection limit, higher sensitivity and higher analysis speed, and the solvent peak and the object to be detected have good separation effect and wider linear range of the standard curve, thereby being suitable for quickly and effectively analyzing samples with different concentrations.
(4) Can effectively eliminate the deviation of experimental results caused by the coexistence of ketone, peroxide and other substances.
Drawings
FIG. 1 is a flow chart of a method of determining the methyl ethyl ketone peroxide content of workplace air in accordance with the present invention.
Detailed Description
In order to better understand the purpose, structure and function of the present invention, the following describes the method for determining the content of methyl ethyl ketone peroxide in the air of a workplace in detail with reference to the attached drawings.
(1) Main instrument and equipment for experiment
1. An Agilent 7890B gas chromatograph, which is provided with a split/non-split sample inlet and a hydrogen Flame Ionization Detector (FID);
2. mettler electronic balance, model: MS105 DU;
3. the air sampler can adjust the sampling flow, the flow control range is 0-500 mL/min, and the air sampler is provided with a bracket;
4. a microsyringe with the measuring range of 5 muL or 10 muL;
5. compressed air pump, type: SPB-3;
6. hydrogen generator, type: TH-300, the purity of the generated hydrogen is more than 99.99%;
7. capillary gas chromatography column, type: HP-5(30 m.times.0.25 mm.times.0.25 μm);
8. the volume of the solvent desorption bottle is 5mL, and the solvent desorption bottle is provided with a sealing rubber gasket and a desorption bottle cap;
9. 401 organic carrier tube, solvent desorption type, the internal charge 100mg/50mg 401 organic carrier;
10. several 10mL volumetric flasks with a tolerance of. + -. 0.02 mL.
(2) Reagent for experiment
1. Methyl ethyl ketone peroxide (chromatically pure), manufacturer: tianjin Yongda chemical reagents, Inc.;
2. acetone (chromatographically pure), manufacturer: tianjin Guangfu Fine chemical research institute;
3. the gas chromatography carrier gas is high-purity nitrogen with the purity of more than 99.99 percent.
(3) Sampling instrument calibration
According to the specification of technical Specification of air sampling instruments at operation sites (GB/T17061-.
(4) In situ sampling
Placing a bracket at a sampling point, adjusting the height of the bracket to a respiratory belt of an operator, placing an air sampler on the bracket, adjusting the flow after fixing the sampler, connecting 401 a body tube of the bracket for sampling, collecting 15min air samples at the flow of 100mL/min, or collecting 2-8 h air samples at the flow of 50mL/min, and simultaneously making a sampling blank. And simultaneously recording the information of the field sampling volume, the sampling point temperature, the air pressure and the like. Immediately after the sampling is finished, the two ends of the organic support tube are closed 401, and the organic support tube is sent to a laboratory for measurement as soon as possible.
(5) Sample pretreatment
Opening the 401 organic carrier tube collected in the step, respectively pouring the front section and the rear section of the 401 organic carrier tube collected in the step into a solvent desorption bottle, respectively adding 1.0ml of acetone, sealing, shaking for 1min, and desorbing for 20-40 min. Shaking up, and determining the desorption solution. If the concentration exceeds the detection range, the concentration is measured after diluted with acetone.
(6) Gas chromatography conditions
Connecting a gas path of a gas chromatograph, turning on a carrier gas, a hydrogen generator and an air pump, respectively adjusting the output pressure and flow of the gas to the range required by the experiment, turning on a power supply of the gas chromatograph, and adjusting the parameters of the gas chromatograph to the following states: detector temperature: 220 ℃; sample inlet temperature: 220 ℃; the temperature of the chromatographic column adopts programmed temperature rise: the initial temperature is 45 ℃, the temperature is kept for 1min, the temperature is raised to 100 ℃ at the speed of 20 ℃/min, and the temperature is kept for 1 min; the carrier gas adopts a constant flow mode, and the flow rate of the carrier gas is 1.0 mL/min; the hydrogen flow is 30 ml/min; the air flow is 400 ml/min; the tail blowing flow is 25 ml/min; the sample introduction mode adopts split sample introduction, and the split ratio is 100: 1.
Under the conditions, the peak shape is good, the separation of the solvent and the substance to be detected can be effectively realized, and the requirement of quantitative detection can be met.
(7) Drawing of standard curve
Adding about 5mL of acetone into a 10mL volumetric flask, accurately weighing, adding a certain amount of methyl ethyl ketone peroxide by using a microsyringe, accurately weighing again, and adding acetone to a scale to obtain the standard stock solution. Dividing the volume of the volumetric flask by the difference value of the two times of weighing to obtain the concentration of the standard stock solution, sequentially diluting the standard stock solution to the following concentration, and preparing the standard series of methyl ethyl ketone peroxide in acetone. The standard curve formulation is shown in table 1:
TABLE 1 Standard Curve preparation
Repeatedly measuring each concentration for 3 times, wherein the sample injection volume is 1.0 mu L, the sample injection volume is qualitative according to retention time, the sample injection volume is quantitative according to peak area mean value, a standard curve is drawn according to the concentration to peak area mean value, and a standard curve regression equation is obtained: 2.0990x-2.2356, correlation coefficient: 0.9999.
(8) sample analysis
And (3) analyzing and determining the sample to be detected and the blank desorption solution of the sample under the same conditions of the standard series, repeatedly determining each sample for 3 times, taking the average value of the peak areas of the 3 times of determination to bring the average value into a regression equation of a standard curve, and subtracting the blank desorption solution of the sample from the concentration of the sample to be detected to obtain the concentration of the substance to be detected.
(9) Determination of desorption efficiency
Taking 6 blank 401 organic support tubes, adding a certain amount of methyl ethyl ketone peroxide respectively, and measuring the desorption efficiency, wherein the measurement results are shown in a table 2:
TABLE 2 determination of desorption efficiency
The results of six measurements show that: the desorption efficiency was between 97.9% and 99.2%, with an average value of 98.6%.
(10) Calculation of results
And substituting the temperature, the air pressure and the sampling volume into a standard sampling volume, and converting the sampling volume into the standard sampling volume according to the regulation of 'sampling specification for detecting harmful substances in air of a workplace' (GBZ 159 and 2004) according to the following formula when the temperature of the sampling point is lower than 5 ℃ and higher than 35 ℃ and the atmospheric pressure is lower than 98.8kPa and higher than 103.4 kPa:
in the formula:
V0-a standard sampling volume, L;
Vt-a sample volume, L, at a temperature of t ℃ and an atmospheric pressure of P;
t-temperature at the sampling point, ° C;
p-atmospheric pressure at the sample point, kPa.
And multiplying the measured value by the volume of the desorption liquid to obtain the content of the methyl ethyl ketone peroxide, dividing the data by the desorption efficiency to obtain the corrected content, and dividing the value by the standard sampling volume to calculate the concentration of the methyl ethyl ketone peroxide in the air of the operation place. The specific calculation method is as follows:
in the formula:
c-concentration of methyl ethyl ketone peroxide in air of work place, mg/m3；
c1Concentration of methyl ethyl ketone peroxide adsorbed by the organic supporter at the front section of the organic supporter tube 410 after sampling, μ g/mL;
c2concentration of methyl ethyl ketone peroxide adsorbed by the organic supporter at the rear section of the organic supporter tube 410 after sampling, μ g/mL;
v-volume of sample solution, mL;
d-desorption efficiency,%;
V0-represents the standard sample volume, L.
(11) Method performance index
The detection limit of the method is 1.43 mu g/mL (concentration corresponding to triple noise), and the lowest detection concentration is 0.95mg/m3(the sampling volume is 1.5L), the measurement range is 1.4-500 mu g/mL, and the penetration capacity>20mg, desorption efficiency>90 percent, and the performance indexes can meet the relevant requirements of the development specifications of the detection method.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (5)
1. A method for detecting methyl ethyl ketone peroxide in air of a workplace is characterized in that an air sampler is used for sampling at a fixed point, a 401 organic support tube is used as a solid adsorbent, acetone is used as desorption liquid, optimized chromatographic conditions are provided, and the concentration of the methyl ethyl ketone peroxide in the air of the workplace is detected by adopting solvent desorption-gas chromatography.
2. The method for detecting methyl ethyl ketone peroxide in workplace air according to claim 1, which is characterized by comprising the following steps in sequence:
s1, connecting a 401 organic support tube at a sampling point to be detected by using an air sampling pump, wherein the 401 organic support tube is of a solvent desorption type, a 100mg/50mg 401 organic support is filled in the 401 organic support tube, after sampling, immediately closing two ends of the 401 organic support tube, recording a sample number, placing the 401 organic support tube in a clean container for transportation and storage, and sending the sample to a laboratory for detection;
step S2, opening the 401 organic carrier tube collected in the above step, respectively pouring the front and rear sections of the 401 organic carrier tube collected in the step S into a solvent desorption bottle, respectively adding 1.0ml of acetone, sealing, shaking for 1min, and desorbing for 30 min; shaking up, and determining desorption solution;
if the concentration of the substance to be detected in the desorption solution exceeds the determination range, diluting with acetone and determining, and multiplying the dilution times during calculation;
and step S3, adding the desorption solution obtained in the step into a gas chromatograph for analysis by using a micro-sampler, determining the quality by retention time, determining the quantity by using the peak area of the chromatographic peak of the substance to be detected, and dividing the detection result by the standard sampling volume to obtain the concentration of the methyl ethyl ketone peroxide in the air of the workplace.
3. The method for detecting methyl ethyl ketone peroxide in workplace air according to claim 2, wherein the air sampling pump in step S1 satisfies the following conditions: the flow rate is 0-500 ml/min.
4. The method for detecting methyl ethyl ketone peroxide in workplace air according to claim 2, wherein the step S1 is divided into short-time sampling: opening 401 two ends of the organic carrier tube at a sampling point, and collecting a 15min air sample at a flow rate of 100 ml/min;
sampling for a long time: and (4) opening the two ends of the organic support pipe 401 at a sampling point, and collecting an air sample for 2-8 h at the flow rate of 50 ml/min.
5. The method for detecting methyl ethyl ketone peroxide in workplace air according to claim 2, wherein in step S3, the range of the microsampler is 5 μ L or 10 μ L.
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Citations (4)
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| CN103257137A (en) * | 2012-02-17 | 2013-08-21 | 谱尼测试科技股份有限公司 | Method of determining content of methyl ethyl ketone peroxide in workplace air through UV spectrophotometer |
| CN104569250A (en) * | 2014-12-08 | 2015-04-29 | 江苏泰洁检测技术有限公司 | Method for determining concentration of pyridine in heterocyclic compound of workplace |
| CN107607639A (en) * | 2017-08-28 | 2018-01-19 | 浙江云广检测技术服务有限公司 | A kind of method that Solvent desorption Gas phase chromatography method surveys Air toxic substance |
| CN109406700A (en) * | 2018-08-30 | 2019-03-01 | 国网吉林省电力有限公司电力科学研究院 | The detection method of dimethyl sulfoxide concentration in air of workplace |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103257137A (en) * | 2012-02-17 | 2013-08-21 | 谱尼测试科技股份有限公司 | Method of determining content of methyl ethyl ketone peroxide in workplace air through UV spectrophotometer |
| CN104569250A (en) * | 2014-12-08 | 2015-04-29 | 江苏泰洁检测技术有限公司 | Method for determining concentration of pyridine in heterocyclic compound of workplace |
| CN107607639A (en) * | 2017-08-28 | 2018-01-19 | 浙江云广检测技术服务有限公司 | A kind of method that Solvent desorption Gas phase chromatography method surveys Air toxic substance |
| CN109406700A (en) * | 2018-08-30 | 2019-03-01 | 国网吉林省电力有限公司电力科学研究院 | The detection method of dimethyl sulfoxide concentration in air of workplace |
Non-Patent Citations (2)
| Title |
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