CN109655550A - The measuring method of 2- methyl naphthalene concentration in workplace air - Google Patents
The measuring method of 2- methyl naphthalene concentration in workplace air Download PDFInfo
- Publication number
- CN109655550A CN109655550A CN201910071425.4A CN201910071425A CN109655550A CN 109655550 A CN109655550 A CN 109655550A CN 201910071425 A CN201910071425 A CN 201910071425A CN 109655550 A CN109655550 A CN 109655550A
- Authority
- CN
- China
- Prior art keywords
- sample
- methyl naphthalene
- concentration
- air
- tested
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2273—Atmospheric sampling
-
- 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
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- 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
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention provides a kind of measuring method of 2- methyl naphthalene concentration in workplace air, comprising the following steps: (1) prepares a series of 2- methyl naphthalene standard solution of concentration, carry out gas-chromatography test, draw standard curve；(2) in workplace to be tested using activated carbon sampling pipe acquisition air sample as sample to be tested, then the front and back section active carbon for the activated carbon sampling pipe for adopting sample is added in solvent and is desorbed, obtained sample to be tested stripping liquid carries out gas-chromatography test；(3) gas-chromatography test is carried out using the sample to be tested stripping liquid that the identical gas-chromatography test condition with step (1) obtains step (2), the concentration of 2- methyl naphthalene in sample to be tested stripping liquid is calculated to obtain by the standard curve that step (1) is drawn；(4) in data processing stripping liquid 2- methyl naphthalene concentration conversion at 2- methyl naphthalene in air concentration.The present invention can Accurate Determining 2- methyl naphthalene concentration, filled up the blank in the field.
Description
Technical field
The invention belongs to workplace noxious material determination techniques fields, and in particular to 2- methyl naphthalene in workplace air
The measuring method of concentration.
Background technique
With the development of industry, the swift and violent growth of the aggregation of urban population, coal and petroleum, atmosphere pollution are increasingly tighter
Weight, especially petrochemical industry develops the type and quantity for having sharply increased pollutants in air on a large scale.Chemical materials
Use and process make to be flooded with more organic volatiles in workplace, the major part in them has been found to have
There is carcinogenicity, and aromatic hydrocarbon therein has even more serious injury to human body.Since the industrial revolution, West Europe, the U.S. and Japan
Equal developed countries' air pollution episode is increasing, such as London smog episode, India's Bhopal toxic gas leakage event, beauty
State's Los Angeles type smog event, asthma Event of Yokkaichi, Japan etc..These examples not only severely compromise residents ' health, but also cause
Mortality.
After harmful substance reaches a certain concentration in air, human health will be damaged.To workplace air toxicity
The monitoring and detection of concentration, can not only promote evaluate Workplace operating environment, while also can improvement environmental condition and
Its harm that may be generated to human body is solved, productivity effect is improved.In recent years, in order to safeguard labors'equity, labourer's body is protected
Body health, China has also put into effect many policies and standard successively, has leaked labourer in the dense of workplace air chemical substance cruelly
Degree has digitized rigid requirement." chemical substance measuring method ", " workplace noxious material measurement have been revised one by one
Standard determination method " etc. relevant national standard, make to be likely to be present in workplace air more than 200 kind chemical substances have
Relatively unambiguous detection regulation, this also makes the air detection in China work to have stepped into standardization.
With the development of industrialization society, 2- methyl naphthalene using more and more extensive, the concentration of 2- methyl naphthalene is in air
Ascendant trend.Living area mixes the pollution by 2- methyl naphthalene in varying degrees with industrial area in some cities.Methyl naphthalene, naphthalene nucleus
On have a hydrogen atom by methyl substituted naphthalene homologue, be one of high temperature coal-tar converted products, there are two types of isomers, i.e. 1-
Methyl naphthalene (also referred to as alpha-methyl-naphthalene) and 2- methyl naphthalene (also referred to as beta-methylnaphthalene), mainly from the pair in coal tar and petroleum refining process
Rectifying separation is made in product.It is irritant to eye, the upper respiratory tract and skin to contact 2- methyl naphthalene, pain can be caused, nausea, vomitted
It spits, diarrhea, anaemia, jaundice, floaty euphoria, dysopia, convulsions and stupor.
However, China not yet formulates the related detecting method of 2- methyl naphthalene in workplace air at present, this research base
In results of laboratory and professional field investigation, foundation is provided for standardized experiment room detection method, while being also formulation China
2- methyl naphthalene measurement standard provides reference.
Summary of the invention
The present invention provides one kind for the undetectable technical problem of 2- methyl naphthalene in workplace air in the prior art
The measuring method of 2- methyl naphthalene concentration in workplace air, can Accurate Determining 2- methyl naphthalene concentration, filled up the field
Blank.
The present invention adopts the following technical scheme:
The measuring method of 2- methyl naphthalene concentration in a kind of workplace air, comprising the following steps:
(1) it draws standard curve: preparing a series of 2- methyl naphthalene standard solution of concentration, carry out gas-chromatography test, with
The peak area measured draws standard curve to 2- methyl naphthalene concentration of standard solution；
(2) sampling of activated carbon sampling pipe is handled with desorption: being acquired in workplace to be tested using activated carbon sampling pipe
Air sample is as sample to be tested, while setting does not acquire the blank control of air sample, then adopts the activated carbon for adopting sample
The front and back section active carbon of sample pipe is added in solvent and is desorbed, obtained sample to be tested stripping liquid and blank control stripping liquid into
The test of row gas-chromatography；
(3) sample test: using with step (1) identical gas-chromatography test condition to step (2) obtain to test sample
Product stripping liquid and blank control stripping liquid carry out gas-chromatography test, and the peak area value of sample to be tested stripping liquid subtracts blank control
Peak area value after, the concentration of 2- methyl naphthalene in sample to be tested stripping liquid is calculated to obtain by the standard curve that step (1) is drawn；
(4) data processing: the sampling volume of activated carbon sampling pipe in step (2) is converted into standard by formula (1) first and is adopted
Sample volume:
In formula:
V0--- standard sample volume, unit are to rise (L)；
Vt--- the sampling volume when temperature is t DEG C, and atmospheric pressure is P, unit are to rise (L)；
The temperature of t --- sampled point, unit are degree Celsius (DEG C)；
The atmospheric pressure of P --- sampled point, unit are kPa (kPa)；
Right back-pushed-type (2) calculates the concentration of 2- methyl naphthalene in air:
C --- the concentration of 2- methyl naphthalene in air, unit are every cubic metre of milligram (mg/m3)；
c1--- the concentration of 2- methyl naphthalene in the sample to be tested stripping liquid measured, unit are micrograms per millilitre (μ g/mL)；
V --- the volume of sample to be tested stripping liquid, unit are milliliter (mL)；
V0--- standard sample volume, unit are to rise (L)；
D --- desorption efficiency, %.
Preferably, gas Chromatographic Determination condition is as follows in the step (1) and step (3):
HP-5 chromatographic column；Sample volume: 1.0-2.0 μ L；Column temperature: 100-140 DEG C；Fid detector temperature: 180-250 DEG C；Into
Sample mouth temperature: 200-250 DEG C；Split ratio: 2:1-10:1；Carrier gas: nitrogen；Air mass flow: 250-350mL/min；
Hydrogen flowing quantity: 25-35mL/min；Make-up gas flow (N2) (combination): 25-35mL/min；Flow rate of carrier gas:
2-4mL/min。
Preferably, in the step (2), following two mode can be used in the sampling of activated carbon sampling pipe: (a) short time is adopted
Sample: in sampled point, with activated carbon sampling pipe with 0.1-0.3L/min flow collection 15min air sample；(b) it samples for a long time:
In sampled point, with activated carbon sampling pipe with 0.05-0.2L/min flow collection 2h-8h air sample.
Preferably, in the step (2), desorption processing solvent for use is carbon disulfide.
Beneficial effects of the present invention are as follows:
Detection for pernicious gas ingredient in air, the factor for influencing its accurate quantitative analysis is mainly the success of sample to be tested
Preparation is precisely separating with detection process, and the method for sampling of the present invention, first sampling efficiency are 100%, and use two
For nitric sulfid as solvent, desorption efficiency is up to 94%, then preferred gas-chromatography test condition, so that 2- methyl naphthalene and therewith companion
Raw 1- methyl naphthalene efficiently separates, and the detection of 2- methyl naphthalene will not be interfered quantitative.Through further verifying of the invention, can see
Out, invention accuracy of the invention and precision meet the requirement of national standard test pernicious gas ingredient, and detection limit is low.
In addition, the present invention follows " People's Republic of China's law on prevention and cure of occupational disease " and its with set of rules, Occupational health
Standard.The present invention includes acquisition and laboratory testing two parts of field sample, in strict accordance with " occupational health standard stipulation guide
4th part: chemical substance measuring method in workplace air " (GBZ/T 210.4-2008) and " have in workplace air
Evil matter monitoring sampling specification " GBZ 159 determine method all technical content carry out.The property of the sampling instrument used
The regulation of GB/T 17061 can be met with technical indicator.Therefore, the present invention has ideally filled up workplace 2- methyl naphthalene concentration
The blank for detecting this field, meets national standard, and application value is high.
Detailed description of the invention
Fig. 1 is the naphthalene tested using gas chromatograph-mass spectrometer, the spectrogram of 1- methyl naphthalene and 2- methyl naphthalene mixed solution；
Fig. 2 is the spectrogram of the 2- methyl naphthalene obtained using gas chromatograph；
Fig. 3 is the naphthalene obtained using gas chromatograph, the spectrogram of 1- methyl naphthalene and 2- methyl naphthalene mixed solution；
Fig. 4 is the chromatogram that crude benzol washers acquire that sample obtains；
Fig. 5 is the partial enlarged view of Fig. 4；
Fig. 6 is the chromatogram that crude benzol distills that work acquisition sample obtains；
Fig. 7 is the partial enlarged view of Fig. 6.
Specific embodiment
In order to keep technical purpose of the invention, technical scheme and beneficial effects clearer, with reference to the accompanying drawing and specifically
Embodiment is further illustrated technical solution of the present invention.
Lower mask body introduces the measuring method of 2- methyl naphthalene concentration in workplace air of the present invention.
1.1 summarizing
First Principles of the invention are to follow " People's Republic of China's law on prevention and cure of occupational disease " and its with set of rules, national duty
Industry sanitary standard comprising the acquisition of field sample and laboratory testing two parts, in strict accordance with " occupational health standard stipulation refers to
Southern 4th part: chemical substance measuring method in workplace air " (GBZ/T 210.4-2008) and " in workplace air
The sampling specification of supervision on hazardous substances " GBZ 159-2004 determine method all technical content carry out.The sampling used
The performance and technical indicator of instrument meet the regulation of GB/T 17061.
2.1 experimental section
Instrument
Agilent gas chromatograph 7890B is equipped with hydrogen flame ionization detector (FID) detector；
7693 autosamplers；
HP-5 chromatographic column (30m × 0.32mm × 0.25 μm)；
Micro syringe, 10 μ L；
The automated injection bottle of polytetrafluoroethyllining lining lid；
Assay balance, sensibility reciprocal 0.01mg；
Activated carbon sampling pipe, solvent desorption type, built-in 100mg/50mg activated carbon；
QC-4 air sampler, 100~500mL/min of flow；
SKC 220-1000TC air sampler, 20~500mL/min of flow；
Solvent desorption bottle, 5mL；
The pipette of 1mL and other suitable sizes；
10mL and the volumetric flask of other suitable sizes are used for configuration standard solution；
Nitrogen cylinder (purity 99.999%)；
Hydrogen gas cylinder (purity 99.999%).
Reagent
Carbon disulfide (chromatographically pure), Tianjin Kermel Chemical Reagent Co., Ltd.；1- methyl naphthalene, (chromatographically pure), Beijing
Lark prestige Science and Technology Ltd.；2- methyl naphthalene (chromatographically pure), Aladdin reagent (Shanghai) Co., Ltd.；Naphthalene (chromatographically pure), Tianjin
Ke Miou chemical reagent Co., Ltd, city.
The preparation of stock solution
Precise 0.00532g2- methyl naphthalene, is dissolved in 5mL carbon disulfide, is quantitatively transferred in 10mL volumetric flask, uses
Carbon disulfide is diluted to scale, this is 2- methyl naphthalene standard reserving solution.
2.1.1 Specification Curve of Increasing
With carbon disulfide difference dilution standard stock solution at a series of 2- methyl naphthalene standard solution of concentration.It is grasped referring to instrument
Make condition, gas chromatograph is adjusted to optimum determining state, 1.0 μ L of sample introduction, measures each standard liquid series respectively.It is each dense
Degree is repeated three times.Standard curve is drawn to 2- methyl naphthalene concentration (μ g/mL) with the peak area mean value measured.
Chromatographiccondition selection
According to GBZ/210.4-2008 " occupational health standard formulation guide Part IV: chemicals in workplace air
Matter measuring method ", be to the selection of chromatographic column, column temperature, temperature of vaporization chamber and detector temperature, carrier gas flux, detector and its
He tests operating condition, to obtain optimum determining as a result, but general column temperature to separating degree should be maximum.According to phase patibhaga-nimitta
Molten principle carries out the selection of chromatographic column fixer, i.e., when similar with stationary liquid polarity, structure, functional group by isolated substance, two
The active force of person is strong, and retention time is just grown, and separating effect is all right.
(1) chromatographic column selects
Chromatographic column tests in test the chromatographic columns such as DB-1, DB-WAX, DB-FFAP, HP-5, compares through overtesting, most
Select HP-5 chromatographic column (30m × 0.25mm × 0.25 μm) eventually.HP-5 column is usually the preferred column for analyzing unknown sample, tool
There are extraordinary inertia and thermal stability, column bleed is very low.Therefore, the detection limit of detector is also lower.Naphthalene compounds tool
There is a low pole, therefore this kind of compound, when being tested with HP-5 type capillary gas chromatographic column, in comparison, separating effect is preferable,
Peak shape is symmetrical.
(2) column temperature selects
100 DEG C of different starting column temperatures, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C are selected, difference originates separation when column temperature
Difference, starting column temperature is higher, and 1- methyl naphthalene and 2- methyl naphthalene are just less susceptible to separate, and retention time becomes smaller, and takes into account sensitivity
With analysis speed, selecting column temperature herein is 120 DEG C, retention time 4.054min.
(3) gas Chromatographic Determination condition selects optimum condition, as follows:
HP-5 chromatographic column；Sample volume: 1.0 μ L；Column temperature: 120 DEG C；Fid detector temperature: 250 DEG C；Injector temperature: 220
℃；Split ratio: 5:1；Carrier gas: nitrogen；Air mass flow: 300mL/min；Hydrogen flowing quantity: 30mL/min；Make-up gas flow (N2)
(combination): 30mL/min；Flow rate of carrier gas: 3mL/min.
Specification Curve of Increasing
Make retarder thinner with carbon disulfide, by standard reserving solution be configured to concentration be 16.6 μ g/mL, 33.3 μ g/mL,
The standard series of 133.0 μ g/mL, 532.0 μ g/mL.Using quantified by external standard method.Sample introduction is analyzed under above-mentioned optimum chromatogram condition,
The solution of each concentration is measured in parallel three times, and taking average peak area response is ordinate, and the concentration (μ g/mL) of each component is cross
Coordinate draws standard curve.1.0 μ L of sample introduction carries out regression analysis, regression equation: y=3.29x- with the peak area measured
5.32, the linearly dependent coefficient of compound is 0.99996, and linear relationship is good, and the range that standard curve is included covers 0.0 μ
The μ g/mL of g/mL~532.0 can satisfy measurement and require.Standard series is shown in Table 1.
1 2- methyl naphthalene standard liquid series of table
2.1.2 the acquisition of workplace air sample and processing
Spot sampling is executed according to GBZ 159-2004 " the sampling specification of supervision on hazardous substances in workplace air ".?
Sampled point acquires air sample with explosion-proof air sampler QC-4 and SKC 220-1000TC.It samples front opening and seals sampling pipe,
Prepare one be about in caliber half hole, when aperture, wears goggles, using sampling pipe holder, to reduce to greatest extent
The danger of glass breaking, all sampling pipes require to be same batch.The less part of sampling pipe adsorbent as backup be placed on from
The nearest place of sampling pump, sampling pipe is connected on sampling pump, and such sampling pipe is in sampling about in the vertical plane of entrance
On, adjustment sampling pump, sampling pipe holder and pipeline location avoid interfering worker's normal work and safety.By entering for sampling pipe support
Mouth directly acquires air sample, and the air sample of acquisition cannot pass through any hose before through sampling pipe.Short time sampling:
Sampled point, with activated carbon sampling pipe with 0.2L/min flow collection 15min air sample；It samples for a long time: in sampled point, with work
Property carbon sampling pipe is with 0.05L/min flow collection 2h-8h air sample.After sampling, sampling pipe is closed immediately, sets clean container
Middle transport and preservation.After sampling carries out appropriate time, takes out sorbent tubes and sealed using plastic end cover.Every group of sample to be tested is at least
One blank sample is set as control, for blank sample in addition to not having air to pass through, other conditions are identical as sample to be tested.
Each sample to be tested sampled air volume (L), sampling time (min) and sampling flow (L/min) are recorded, and is adopted
Other potential interferences that may be present during sample.Before analysis, active carbon in two sections before and after activated carbon sampling pipe is poured into respectively
In tool plug test tube, 1.0mL CS is added2, shake frequently, room temperature desorbs 30~60min, herein after preferred desorption 30min, takes solution
Imbibition, if stripping liquid concentration is more than the range of linearity, uses CS for measuring2It is measured after dilution.
2.1.3 workplace air sample detection
It, may be right according to the physicochemical property of interfering substance that may be present in 2- methyl naphthalene production process and each substance
The substance that this method measurement 2- methyl naphthalene concentration generates interference mainly has naphthalene, 1- methyl naphthalene.For the peak position out for determining 2- methyl naphthalene
It sets, spy has done following interference experiment
Firstly, carrying out qualitative and exclusive PCR, sample used using 7890B/5977A type gas chromatograph-mass spectrometer (GC-MS)
Be formulated for the standard items of naphthalene, 1- methyl naphthalene and 2- methyl naphthalene three solution (respectively precise 0.0420g naphthalene,
0.425g1- methyl naphthalene and 0.389g2- methyl naphthalene, are dissolved in carbon disulfide, are quantitatively transferred in 10mL volumetric flask, use curing
Carbon is diluted to scale), gas Chromatographic Determination condition are as follows: HP-5MS chromaticness fused-silica capillary column (30.0m × 0.25mm ×
0.25μm)；Carrier gas: ultrapure helium, flow 1.0m L/min；Injector temperature: 220 DEG C；Ion source temperature: 230 DEG C；Sample introduction
Amount: 1 μ L；Split ratio: 5:1；Column temperature condition:, keeping 1min by 90 DEG C of initial temperature, rises to 200 DEG C with the rate of 10 DEG C/min, protects
Hold 1min；Solvent delay 3 minutes；Scan pattern: Scan.GC-MS analyzes the result is shown in Figure 1.It should be noted that for chaff interferent
Matter is qualitative, and present invention instrument used herein is 7890B/5977A type gas chromatograph-mass spectrometer (GC-MS), remaining is used everywhere
7890B gas chromatograph carries out gas Chromatographic Determination, due to instrument difference, does not lead to best gas Chromatographic Determination condition not
Together, and obtained spectrogram goes out that peak position is different, but the peak sequence of different compounds does not change because of instrument difference, because
It is qualitative that this has no effect on makings.
It can be clearly separated out naphthalene by Fig. 1, but 1- methyl naphthalene and 2- methyl naphthalene are isomers, and in NIST
It is more close to compose matching rate in library, it can not be to the accurate structured qualitative analysis of the two, so check experiment synthesis is needed accurately to sentence
Disconnected 1- methyl naphthalene and 2- methyl naphthalene.
Check experiment selects 7890B type gas chromatograph, (accurate to claim using the solution that 2- methyl naphthalene standard items are prepared first
0.326g2- methyl naphthalene is measured, is dissolved in carbon disulfide, is quantitatively transferred in 10mL volumetric flask, be diluted to scale with carbon disulfide)
Measurement obtains Fig. 2 under the conditions of following gas Chromatographic Determination, then using naphthalene, the standard items of 1- methyl naphthalene and 2- methyl naphthalene three
(precise 0.0420g naphthalene, 0.425g1- methyl naphthalene and 0.389g2- methyl naphthalene respectively, are dissolved in two sulphur to the solution being formulated
Change in carbon, be quantitatively transferred in 10mL volumetric flask, be diluted to scale with carbon disulfide) in gas Chromatographic Determination identical with Fig. 2
Under the conditions of measurement obtain Fig. 3.The retention time of 2- methyl naphthalene is 4.054 as can be seen from Figure 2, and complex chart 1, Fig. 2 and Fig. 3 can
To learn: naphthalene elder generation appearance, retention time 2.732, subsequent 2- methyl naphthalene, retention time 4.054, what is finally come out is 1- first
Base naphthalene, retention time 4.341.And 1- methyl naphthalene and 2- methyl naphthalene are clearly separated, therefore gas-chromatography item of the invention
Part can be such that 2- methyl naphthalene and various interfering substances efficiently separates, and will not interfere to the measurement of 2- methyl naphthalene.
For the exposure of evaluation work place worker's 2- methyl naphthalene, and investigation may be exposed by 2- methyl naphthalene and be caused
Health hazard, prevent occupational disease, guarantee Workers ' Health, we are using method of the invention to there may be 2- first
The chemical industry subsidiary factory of certain Coking Company of base naphthalene occupational has carried out the on-site test of workplace.Following 3 kinds of samplings
The table 2 that mode obtains to table 4 is all made of following general operation and is detected:
After the air sample for taking workplace with activated carbon sampling pipe, the stripping liquid desorbed is adopted as sample to be tested
Sample to be tested is measured with gas Chromatographic Determination condition identical with standard liquid series described in 2.1.1 and blank sample desorbs to obtain
Stripping liquid, after the sample to be tested peak area value measured subtracts the peak area value of blank control, 2- methyl naphthalene is obtained by standard curve
Concentration (μ g/mL).Wherein, gas Chromatographic Determination condition specifically:
HP-5 chromatographic column；Sample volume: 1.0 μ L；Column temperature: 120 DEG C；Fid detector temperature: 250 DEG C；Injector temperature: 220
℃；Split ratio: 5:1；Carrier gas: nitrogen；Air mass flow: 300mL/min；Hydrogen flowing quantity: 30mL/min；Make-up gas flow (N2)
(combination): 30mL/min；Flow rate of carrier gas: 3mL/min.
When sampling, in sampled point, activated carbon sampling pipe both ends are opened, acquire air sample.We have selected the short time to adopt
Sample (flow velocity 0.20L/min samples 15min) and sampling for a long time (flow velocity 0.05L/min samples 480min).It is detected
It the results are shown in Table 2 and 3.
2- methyl naphthalene Concentration Testing (short time sampling) in 2 workplace air of table
Note: this method concentration limit is 0.70mg/m3(acquire the calculating of 3.0L air).
This chemical industry subsidiary factory grab sampling collects 15 parts of samples altogether, and short time sampled result is as shown in table 2.This detection knot
Fruit discovery collects in sample amounting to 15 parts of fixed points, the presence of 2- methyl naphthalene is not detected, and illustrates that equipment, pipeline, valve connect
It is closed good to meet place.
2- methyl naphthalene Concentration Testing (sampling for a long time) in 3 workplace air of table
Note: this method concentration limit is 0.09mg/m3(acquire the calculating of 24L air).
This chemical industry subsidiary factory long-time sampled result is as shown in table 3, collects 9 parts of sample standard deviations altogether and 2- methyl naphthalene is not detected
In the presence of illustrating that equipment, pipeline, valve junction are closed good.
Personal sampler then is worn for the worker of workplace, is sampled (flow velocity 0.1L/ with biggish flow
Min, block sampling 480min).Testing result: this chemical industry subsidiary factory personal sampling collects 5 parts of samples altogether, wherein crude benzol washers
Gas chromatographic detection result with crude benzol distillation work can detecte the presence of 2- methyl naphthalene, summarized results as shown in Fig. 4 to 7
As shown in table 4.
2- methyl naphthalene Concentration Testing (personal sampling) in 4 workplace air of table
Note: concentration limit 0.04mg/m3(acquire the calculating of 48L air).
Wherein, crude benzol washers and the corresponding 2- methyl naphthalene concentration calculation process of crude benzol distillation work are as follows:
The sampling volume of workplace air sample is lower than 5 DEG C in sampled point temperature and is lower than higher than 35 DEG C, atmospheric pressure
98.8kPa and be higher than 103.4kPa when, sampling volume should be converted into standard sample volume by formula (1).Due to we scene
Sample temperature is 16.3 DEG C, atmosphere 99.7kPa, therefore does not have to sampling volume being converted into standard sample volume.
The concentration of 2- methyl naphthalene in air is calculated by formula (2):
C --- the concentration of 2- methyl naphthalene in air, unit are every cubic metre of milligram (mg/m3)；
c1--- the concentration of 2- methyl naphthalene in the front and back section sample solution measured, unit is micrograms per millilitre (μ g/mL)；
V --- the volume of sample stripping liquid, unit are milliliter (mL)；
V0--- standard sample volume, unit are to rise (L)；
D --- desorption efficiency, %.
Wherein, desorption efficiency is obtained by following tests:
Take activated carbon sampling pipe points three groups, every group of standard solution for being separately added into three dosage, additional amount is basic, normal, high
Three concentration, stand overnight, and next day desorbs and measures the object amount to be measured of each tube.
18 activated carbon sampling pipes are taken, is divided into 3 groups, every group 6,1.0,2.0 and 5.0 μ L is added with micro syringe respectively
2- methyl naphthalene standard solution, amount contained by every group of activated carbon sampling pipe is respectively 15.1,30.2 and 75.6 μ g 2- methyl naphthalenes,
It is measured after 4 DEG C of refrigerator storages are stood overnight, measured value is shown in Table 2-5, by calculating as it can be seen that average desorption efficiency is
94.0%, it is greater than 75%, complies with standard formulation and require.
5 desorption efficiency test result (n=6) of table
According to gas chromatogram as a result, being calculated after substitution numerical value:
Crude benzol washers:
Crude benzol distills work:
The concentration of 2- methyl naphthalene is 0.19mg/m in crude benzol washers' air3, similarly crude benzol distills 2- methyl in work air
The concentration of naphthalene is 0.17mg/m3。
This testing result: this chemical industry subsidiary factory personal sampling collects 5 parts of samples altogether, detects in crude benzol workshop section micro
2- methyl naphthalene there are such as Fig. 4 to Fig. 7, can be seen that from Fig. 5 and 7, the retention time of 2- methyl naphthalene is respectively under its chromatogram
4.072 and 4.073, Fig. 4 and Fig. 6 are original image, and Fig. 5 and Fig. 7 are respectively that Fig. 4 and Fig. 6 removes the enlarged drawing after solvent peak, from figure
It can be seen that detecting micro 2- methyl naphthalene, its amplified appearance since baseline, most postpeak to base in although
Knot beam, peak type is all high and narrow and symmetrical, illustrates that separating degree and sensitivity of the invention are preferable.By on-site test it is considered that
May due to by crude benzol reflux pump, by debenzolizing tower, distillation pump, regenerator, distillation pump, crude benzol slot, rich oil slot etc. be because of equipment, pipe
Road, valve junction airtightness are bad to lead to have micro 2- methyl naphthalene to escape.
The verifying such as sampling efficiency, accuracy, detection limit has been carried out to the method for the invention below.
3.1 sampling efficiencies and break through volume
This experiment samples distribution method.Under conditions of room temperature is 20~25 DEG C, relative humidity is 85%~95%, with 6
30L aluminum-plastic composite membrane gas sampling bag prepares different quality concentration series hybrid standard gas, and every kind of mass concentration uses activated carbon
Sampling pipe acquires 15min with 0.20L/min and acquires 480min with 0.05L/min, measures to be measured group of forward and backward pipe active carbon respectively
Divide level, carries out 6 measurements.Measurement result is shown in 2-6, the results showed that the in-site modeling concentration sample configured, activity
The sampling efficiency of charcoal sampling pipe is 100%, and sampling efficiency is greater than 90%, increase at any time, front tube activated carbon adsorption 2- first
The amount of base naphthalene also increases, and when adsorbance saturation, then penetrates into rear pipe activated carbon sampling pipe.Pipe measures after sometime putting
Amount be equal to front tube measured amount when, front tube measured amount be break through volume, the results show that the break through volume of 2- methyl naphthalene be greater than
1.28mg (100mg active carbon) complies with standard formulation and requires.
6 sampling efficiency of table and break through volume test result
3.2 sample stability
Sampling pipe is taken, the 2- methyl naphthalene of same amount is injected separately into, the both ends of pipe are then put on into plastic cap, room temperature decentralization
It sets.6 are first taken to analyze immediately, other change respectively at several days post analysis, the loss of test sample, i.e. decline loss late.
24 activated carbon sampling pipes are divided into 4 groups, every group 6, every is added suitable 15.1 μ g2- methyl naphthalene standard solution,
4 DEG C of refrigerator storages are placed, each desorption measurement in the 1st, 3,5,7 day.The stability of 30.2 μ g 2- methyl naphthalenes of addition is measured with method
Test.It the results are shown in Table 2-7.The 7th day measured value rate of descent < 10% of the sample saved under room temperature, shows that sample can be protected at normal temperature
Deposit 7d.
7 stability test result of table
The experiment of 3.3 detection limits
Detection limit refers to that under certain confidence level, measuring method can detect the minimum concentration or amount of determinand.This
Test uses standard deviation method.
The regulation of detection limit is estimated about gas chromatography, minimum detectable activity refers to that detector be able to generate and noise signal
The minimum of the substance of required injection chromatographic column when the response signal distinguished.It is 30.2 μ to concentration under optimum chromatogram condition
The standard solution METHOD FOR CONTINUOUS DETERMINATION of g/mL 11 times, acquiring mean concentration is 29.8 μ g/mL, and standard deviation (S) is 0.21 μ g/mL, is pressed
Formula detection limit DL (μ g/mL)=3S × 30.2/30.2 is calculated, and is acquired measurement liquid detection and is limited to 0.62 μ g/mL (with 3 times of standards
Difference meter), lower limit of quantitation is 2.1 μ g/mL (in terms of 10 times of standard deviations), when acquisition 3.0L sample, when desorption volume is 1.0mL, most
Low basis weight concentration is 0.70mg/m3。
The experiment of 3.4 preci-sion and accuracies
Precision test, high, medium and low 3 concentration within the scope of selection criteria curve determination, carries out 6 in 3 days~5 days
Secondary replication calculates its relative standard deviation (RSD).It is required that RSD is less than or equal to 10%.Accuracy test selects sample mark-on
Absorption method.
Precision refers to that for detection method to the reproducibility of the multiple measurement result of homogeneous sample, it does not consider institute under certain condition
The error size between data and true value is obtained, and only indicates the dispersion degree of numerical value.Precision is decided by accidental error.According to
GBZ/T210.4-2008 " occupational health standard formulation guide Part IV: chemical substance measuring method in workplace air ",
Precision measurement will include sample treatment and measurement overall process.High, medium and low 3 concentration within the scope of selection criteria curve determination,
6 replications are carried out in 3 days~5 days, calculate its relative standard deviation (RSD)[23].It is required that RSD is less than or equal to 10%.
(1) withinrun precision
The 2- methyl naphthalene standard solution of 1.0 μ L, 2.0 μ L, 5.0 μ L is taken to be added in blank activated carbon sampling pipe, at method
Reason is configured to the 2- methyl naphthalene sample stripping liquid of high, medium and low 3 contents containing 30.2 μ g, 75.6 μ g, 151.2 μ g, in 4 DEG C of ice
Case storage is stood overnight, with l mL CS2Measurement carries out concentration mensuration after desorbing charcoal pipe, and each concentration is measured in parallel 6 parts, as a result
It is shown in Table 2-2, by calculating as it can be seen that relative standard deviation is respectively 3.6%, 3.7%, 2.5%, respectively less than 5%, complies with standard system
Provisioning request.
8 withinrun precision test result (n=6) of table
(2) betweenrun precision
2- methyl naphthalene standard solution, the same withinrun precision of additive amount, by side are separately added into blank activated carbon sampling pipe
Method processing, is placed in 4 DEG C of refrigerator storages, daily with l.0mL CS2Desorption charcoal pipe and the standard curve for substituting into same day production calculate
Content, carrying out 6 replication relative standard deviations altogether is respectively 3.9%, 4.0%, 3.4%, respectively less than 5%, is complied with standard
It formulates and requires.It is shown in Table 2-3, is shown by calculated result, relative standard deviation is respectively 3.9%, 4.0%, 3.4%, respectively less than
5%, it complies with standard formulation and requires.
9 betweenrun precision test result (n=6) of table
3.5 accuracy
The 2- methyl naphthalene standard of 1.0,2.0 and 10.0 μ L is added with micro syringe respectively into 9 activated carbon sampling pipes
Solution, is separately added into the 2- methyl naphthalene standard solution containing 15.1 μ g, 30.2 μ g, 151.2 μ g, and each concentration respectively adds 3 activated carbon
Sampling pipe is measured after 4 DEG C of refrigerator storages are stood overnight.L mL CS is used respectively2It measures after desorption active carbon, as a result sees
Table 2-4.The results show that this method average recovery rate is 97.8%, between 95%~105%, satisfaction is all satisfied GBZ/T
210.4-2008 " occupational health standard formulation guide Part IV: chemical substance measuring method in workplace air " is wanted
It asks.
10 accuracy test result (n=3) of table
It should be noted last that: technical solution of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or locally replace that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (4)
1. the measuring method of 2- methyl naphthalene concentration in a kind of workplace air, which comprises the following steps:
(1) it draws standard curve: preparing a series of 2- methyl naphthalene standard solution of concentration, gas-chromatography test is carried out, to measure
Peak area to 2- methyl naphthalene concentration of standard solution draw standard curve；
(2) sampling of activated carbon sampling pipe is handled with desorption: acquiring air using activated carbon sampling pipe in workplace to be tested
Sample is as sample to be tested, while setting does not acquire the blank control of air sample, then will adopt the activated carbon sampling pipe of sample
Front and back section active carbon be added in solvent and desorbed, obtained sample to be tested stripping liquid and blank control stripping liquid carries out gas
The test of phase chromatography；
(3) sample test: using the sample to be tested solution that identical gas-chromatography test condition obtains step (2) with step (1)
Imbibition and blank control stripping liquid carry out gas-chromatography test, and the peak area value of sample to be tested stripping liquid subtracts the peak of blank control
After area value, the concentration of 2- methyl naphthalene in sample to be tested stripping liquid is calculated to obtain by the standard curve that step (1) is drawn；
(4) sampling volume of activated carbon sampling pipe in step (2) data processing: is converted into standard sample body by formula (1) first
Product:
In formula:
V0--- standard sample volume；
Vt--- the sampling volume when temperature is t DEG C, and atmospheric pressure is P；
The temperature of t --- sampled point；
The atmospheric pressure of P --- sampled point；
Right back-pushed-type (2) calculates the concentration of 2- methyl naphthalene in air:
C --- the concentration of 2- methyl naphthalene in air；
c1--- the concentration of 2- methyl naphthalene in the sample to be tested stripping liquid measured；
V --- the volume of sample to be tested stripping liquid；
V0--- standard sample volume；
D --- desorption efficiency.
2. the measuring method of 2- methyl naphthalene concentration in workplace air according to claim 1, which is characterized in that described
Gas Chromatographic Determination condition is as follows in step (1) and step (3):
HP-5 chromatographic column；Sample volume: 1.0-2.0 μ L；Column temperature: 100-140 DEG C；Fid detector temperature: 180-250 DEG C；Injection port
Temperature: 200-250 DEG C；Split ratio: 2:1-10:1；Carrier gas: nitrogen；Air mass flow: 250-350mL/min；Hydrogen flowing quantity: 25-
35mL/min；Make-up gas flow: 25-35mL/min；Flow rate of carrier gas: 2-4mL/min.
3. the measuring method of 2- methyl naphthalene concentration in workplace air according to claim 1, which is characterized in that described
In step (2), following two mode can be used in the sampling of activated carbon sampling pipe: (a) short time is sampled: in sampled point, using activated carbon
Sampling pipe is with 0.1-0.3L/min flow collection 15min air sample；(b) it samples: in sampled point, being sampled with activated carbon for a long time
Pipe is with 0.05-0.2L/min flow collection 2h-8h air sample.
4. the measuring method of 2- methyl naphthalene concentration in workplace air according to claim 1, which is characterized in that described
In step (2), desorption processing solvent for use is carbon disulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910071425.4A CN109655550A (en) | 2019-01-25 | 2019-01-25 | The measuring method of 2- methyl naphthalene concentration in workplace air |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910071425.4A CN109655550A (en) | 2019-01-25 | 2019-01-25 | The measuring method of 2- methyl naphthalene concentration in workplace air |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109655550A true CN109655550A (en) | 2019-04-19 |
Family
ID=66121428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910071425.4A Pending CN109655550A (en) | 2019-01-25 | 2019-01-25 | The measuring method of 2- methyl naphthalene concentration in workplace air |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109655550A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111693596A (en) * | 2020-06-05 | 2020-09-22 | 清华大学 | Non-target testing method for gaseous pollutants in building |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62193645A (en) * | 1986-02-19 | 1987-08-25 | Agency Of Ind Science & Technol | Adsorbent |
| CN101718762A (en) * | 2009-11-27 | 2010-06-02 | 攀枝花新钢钒股份有限公司 | Method for measuring washed mixed distillate parameter value of industrial naphthalene raw material with gas chromatography |
| CN102338780A (en) * | 2010-07-28 | 2012-02-01 | 中国科学院大连化学物理研究所 | Method for discriminating cigarette brands |
| CN104020243A (en) * | 2014-06-17 | 2014-09-03 | 中国石油化工股份有限公司 | Detection method for solvent gasoline in air in working place |
| CN106146245A (en) * | 2015-03-28 | 2016-11-23 | 鞍钢股份有限公司 | Method for producing beta-methylnaphthalene by adopting continuous azeotropic distillation process |
-
2019
- 2019-01-25 CN CN201910071425.4A patent/CN109655550A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62193645A (en) * | 1986-02-19 | 1987-08-25 | Agency Of Ind Science & Technol | Adsorbent |
| CN101718762A (en) * | 2009-11-27 | 2010-06-02 | 攀枝花新钢钒股份有限公司 | Method for measuring washed mixed distillate parameter value of industrial naphthalene raw material with gas chromatography |
| CN102338780A (en) * | 2010-07-28 | 2012-02-01 | 中国科学院大连化学物理研究所 | Method for discriminating cigarette brands |
| CN104020243A (en) * | 2014-06-17 | 2014-09-03 | 中国石油化工股份有限公司 | Detection method for solvent gasoline in air in working place |
| CN106146245A (en) * | 2015-03-28 | 2016-11-23 | 鞍钢股份有限公司 | Method for producing beta-methylnaphthalene by adopting continuous azeotropic distillation process |
Non-Patent Citations (6)
| Title |
|---|
| DAVID KIM 等: "Mathematical description of the uptake of hydrocarbons in jet fuel into the stratum corneum of human volunteers", 《TOXICOLOGY LETTERS》 * |
| JEZEWSKA, ANNA: "2-Metylonaftalen-metoda oznaczania", 《PODSTAWY I METODY OCENY ŚRODOWISKA PRACY》 * |
| JEZEWSKA, ANNA: "2-Metylonaftalen-metoda oznaczania", 《PODSTAWYI METODY OCENY ŚRODOWISKA PRACY》 * |
| 申鼎 等: "针对某焦化企业2-甲基萘存在的职业卫生调查与分析", 《开封大学学报》 * |
| 臧立华 等: "复合肥生产中有机污染气体的气相色谱/质谱分析", 《山东轻工业学院学报》 * |
| 陈月萌 等: "毛细管气相色谱法测定工作场所空气中３种多环芳烃", 《理化检验-化学分册》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111693596A (en) * | 2020-06-05 | 2020-09-22 | 清华大学 | Non-target testing method for gaseous pollutants in building |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110187037A (en) | The measurement system and method for 57 kinds of volatile organic contents in surrounding air | |
| CN103323543B (en) | Method for detecting 17 polycyclic aromatic hydrocarbons in cigarette gas | |
| CN102128906A (en) | Method for detecting volatile organic compound in cigarette filter | |
| CN107561182A (en) | Volatility and the detection method of semi-volatile organic compounds in cigarette mainstream flue gas | |
| CN104020243B (en) | Detection method for solvent gasoline in air in working place | |
| CN108303477A (en) | A kind of heating do not burn cigarette main flume in the compounds such as alcohols detection method | |
| CN109655550A (en) | The measuring method of 2- methyl naphthalene concentration in workplace air | |
| CN109668972A (en) | The detection method of volatile organic matter in Petrochemical Enterprises air and waste gas | |
| CN104914184A (en) | Cold trap capturing-gas chromatography/mass spectrum combined detection method for furan in cigarette mainstream smoke | |
| CN105572285A (en) | Method for measuring semi-volatile substances in mainstream smoke of cigarettes | |
| Hill et al. | Gas-chromatographic determination of vinyl chloride in air samples collected on charcoal | |
| Grubner et al. | Gas chromatographic determination of nicotine in gases and liquids with suppression of adsorption effects | |
| CN105806968A (en) | Gas chromatography method for simultaneously detecting n-heptane, isooctane, ethyl acetate and isopropanol and use thereof | |
| CN103698433A (en) | Method for detecting chloroethylene in sidestream smoke of cigarettes | |
| CN110514752A (en) | The extracting method of additive and its non-targeted screening method in a kind of paper food packaging materials | |
| CN103235053B (en) | Method for determining tributyl phosphate in dry food packaging paper | |
| CN110376325A (en) | Semi-volatile Organic Compounds In Underground Water detection method | |
| CN110187035A (en) | The analyzing detecting method of Drinking Water glyphosate | |
| Park et al. | Toluene distribution of glue sniffers' biological fluid samples in Korea | |
| Qazi et al. | A new method for monitoring personal exposure to ethylene oxide in the occupational environment | |
| CN111983062B (en) | Method for detecting trace DMAEA in air | |
| CN104764812A (en) | Detection method for determining alcohol compounds through gas chromatography | |
| CN104634904B (en) | Concentration of aniline assay method in a kind of workplace aromatic amine | |
| CN109298122B (en) | Method for detecting purity of R-glyceraldehyde acetonide finished product | |
| CN102680624A (en) | Method for detecting methyl acetate in adhesive for smoke |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190419 |
|
| RJ01 | Rejection of invention patent application after publication |