CN107064378B - The detection method of a variety of halogen acetic acids in air or exhaust gas - Google Patents
The detection method of a variety of halogen acetic acids in air or exhaust gas Download PDFInfo
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Abstract
The invention belongs to technical field of environmental detection, and in particular to the detection method of a variety of halogen acetic acids in a kind of air or exhaust gas.Halogen acetic acid in air or exhaust gas is absorbed into sampling by the porous glass plate absorption bottle equipped with NaOH aqueous solution or ultrapure water；It is extracted again by the methyl tertiary butyl ether(MTBE) containing internal standard compound, and using methyl tertiary butyl ether(MTBE) as carrier solvent, and esterification occurs with methanol under metallic catalyst, metalloporphyrin and benzene sulfonic acid base phenolic resin composite catalyzing, using the gas chromatograph for determination peak area for having electron capture organ, result measurement is carried out.The present invention realizes disposable comprehensively quick while measuring a variety of halogenated acetic acids in air or exhaust gas, and measurement method precision is high, accuracy is good, detection limit is low.
Description
Technical field
The invention belongs to technical field of environmental detection, and in particular to the detection side of a variety of halogen acetic acids in a kind of air or exhaust gas
Method.
Background technique
Halogen acetic acid (HAAs) is the important intermediate for preparing organic synthesis chemical industry and pesticide, is had a wide range of application, main to wrap
Include nine kinds: chloroacetic acid, a bromoacetic acid, dichloroacetic acid, trichloroacetic acid, monobromo chloroacetic acid, monobromo dichloroacetic acid, dibromo second
Acid, a chlorine dibromoacetic acid, tribromoacetic acid, halogen acetic acid have carcinogenic, teratogenesis to human body, cause deformation effect.And lack at present air and
The detection method of a variety of halogen acetic acids in exhaust gas.The gas-chromatography that Shao Shengwen etc. reports chloroacetic acid in air of workplace is surveyed
Determine method, inquires into GC conditions, sample acquisition and processing method, but be only limitted to chloroacetic acid, and be only capable of determination of the environment
Air can not be suitable for exhaust gas and measure, and other eight kinds of halogen acetic acid classes measurements have not been reported in air.Halogen acetic acid measurement side in exhaust gas
The hardly seen report of method.
Since halogen acetic acid is to the strong three-induced effect of human body, social extensive concern is caused.It studies a variety of in air or exhaust gas
The distribution situation of halogen acetic acid is very urgent in the detection method and then understanding gas medium of halogen acetic acid, therefore develops a kind of measurement
The detection method of a variety of halogen acetic acids is imperative in air or exhaust gas.
Summary of the invention
The object of the present invention is to provide a kind of detection method of a variety of halogen acetic acids in air or exhaust gas, detection limit is low, accurate
Degree is high, accuracy is good, detection rates are fast, sample collecting efficiency height, catalyst are reusable, it is at low cost, avoid container
Corrosion.
The detection method of a variety of halogen acetic acids in air or exhaust gas of the present invention, steps are as follows:
(1) halogen acetic acid in air or exhaust gas is inhaled by the porous glass plate absorption bottle equipped with NaOH aqueous solution or ultrapure water
Receive sampling；
(2) it is extracted again by the methyl tertiary butyl ether(MTBE) containing internal standard compound, and using methyl tertiary butyl ether(MTBE) as carrier solvent, and
Esterification occurs with methanol under metallic catalyst, metalloporphyrin and benzene sulfonic acid base phenolic resin composite catalyzing, using with electricity
The gas chromatograph for determination peak area of sub- acquirer carries out result measurement.
The concentration of NaOH aqueous solution described in step (1) is 0.01-1mol/L.
The number of porous glass plate absorption bottle described in step (1) is 1 or 2.
Internal standard compound described in step (2) is 1,2,3- trichloropropane.
Metallic catalyst described in step (2) is copper sulphate, copper chloride, iron chloride, ferric sulfate, copper oxide, three oxidations
One of two iron, aluminum oxide or zirconium oxychloride.
Metalloporphyrin described in step (2) is to chlorine tetraphenyl copper porphyrin, immobilized right to chlorine tetraphenyl ferriporphyrin, carrier
Chlorine tetraphenyl copper porphyrin or carrier are immobilized to one of chlorine tetraphenyl ferriporphyrin.
The carrier is one of molecular sieve, zeolite, porous ceramics, sepiolite, polyvinyl chloride or polystyrene.
The additive amount of metalloporphyrin described in step (2) is the 0.1-10ppm of carrier solvent quality.
The mass ratio of metallic catalyst, metalloporphyrin and benzene sulfonic acid base phenolic resin described in step (2) is 10-
1000:0.03-3:1-500.
Halogen acetic acid in air or exhaust gas is passed through into the porous equipped with 0.01~1mol/LNaOH aqueous solution or ultrapure water
Plate absorption bottle absorbs sampling, so that nine kinds of halogen acetic acids is changed into halogen acetic acid salt by NaOH aqueous solution to substantially increase absorption effect
Rate, halogen acetic acid good water solubility can also be absorbed by ultrapure water.It is extracted again by the methyl tertiary butyl ether(MTBE) containing internal standard compound, and with
Methyl tertiary butyl ether(MTBE) be carrier solvent and under metallic catalyst, metalloporphyrin and benzene sulfonic acid base phenolic resin efficient catalytic with first
Esterification occurs for alcohol, using the gas chromatograph for determination peak area for having electron capture organ, confirms using by actual tests
Nine kinds of halogen acetic acids and correlation between the peak area ratio and concentration ratio of internal standard compound and correlated fitting parameter carry out result measurement.
Present invention firstly provides use " by filling 0.01~1mol/LNaOH aqueous solution or ultrapure water as the more of absorbing liquid
Hole glass plate absorption bottle sampling-internal standard compound and halogen acetic acid standard substance jointly after extraction and metallic catalyst, metalloporphyrin and
The sample pre-treatments of derivative-gas chromatographic analysis under benzene sulfonic acid base phenolic resin efficient catalytic " and prepare standard specimen with electricity
A series of whole process analysis such as gas-chromatography (GC-ECD) analysis of sub- acquisition detector, it is thus identified that nine kinds of halogen acetic acids and internal standard compound
Peak area ratio and concentration ratio between correlation and correlated fitting parameter, establish working curve.And using identical process point
Nine kinds of halogen acetic acid compound samples to be tested are analysed, C is utilizedim=AimCism/kAism-bCism/ k (wherein m=1 or 2) and Ci=(Ci1
+Ci2-2C0)×40×10-3÷ V measures the various halogen acetic acid concentration in air or exhaust gas.
It is as follows to measure process:
Nine kinds of halogen acetic acid compounds wait for test sample in porous glass plate absorption bottle acquisition air and exhaust gas equipped with specific absorption liquid
The aqueous solution of product → preparation various concentration halogen acetic acid standard substance → plus internal standard compound and extractant methyl tertiary butyl ether(MTBE) extraction with
Special catalyst esterification is derivative → into GC-ECD standard specimen analysis → fitting operations curve → nine kinds of confirmation halogen acetic acid and internal standard compound
Peak area ratio and concentration ratio between linear dependence and nine kinds of halogen acetic acid compounds in fitting parameter → air and exhaust gas
Absorbing liquid sample pre-treatments to be measured and GC-ECD chromatography obtain peak area Ai→ utilize Cim=AimCism/kAism-bCism/k
(wherein m=1 or 2) and Ci=(Ci1+Ci2-2C0)×40×10-3÷ V measures various halogen acetic acid concentration.
The detection method of a variety of halogen acetic acids in air or exhaust gas of the present invention, the specific steps are as follows:
One, sample acquires
It is 0.01~1mol/LNaOH aqueous solution or 40ml ultrapure water conduct that 40ml concentration is filled in porous glass plate absorption bottle
Absorbing liquid absorbs the halogen acetic acid class compound in acquisition air or exhaust gas.It is adopted using single or two porous glass plate absorption bottles of series connection
Porous glass plate absorption bottle is connected by sample with air sampler or flue gas sampler, and setting gas production flow is 0.2~1L/min, adopts
Collect 20min~100min.
Above-mentioned absorbing liquid can be NaOH aqueous solution, be also possible to ultrapure water, and wherein the concentration of NaOH aqueous solution is 0.01
~1mol/L.Nine kinds of halogen acetic acid class compounds are soluble easily in water.When halogen acetic acid class compound concentration is low in air or exhaust gas, water is selected
Or 0.01~1mol/L NaOH aqueous solution is as absorbing liquid.When halogen acetic acid class compound concentration is higher in air or exhaust gas, select
0.01~1mol/L NaOH aqueous solution makes halogen acetic acid be changed into halogen acetic acid salt as absorbing liquid, increases water-soluble.
Sample uses the halogen acetic acid in ultrapure water acquisition air；It is acquired using 0.01~1mol/L NaOH aqueous solution
Halogen acetic acid in air and exhaust gas.
Two, the drafting of working curve
Nine kinds of halogen acetic acid standard substances are added into the NaOH aqueous solution that concentration is 0.01~1mol/L, it is dense to be configured to 40ml
Degree is respectively 0.5 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 1000 μ g/L,
2000 nine kinds of μ g/L halogen acetic acid standard alkaline type aqueous solutions.2ml concentrated sulfuric acid tune pH is added less than 0.5 to above-mentioned alkaline aqueous solution, makes
Obtaining halogen acetic acid is by halogen acetic acid without existing in the form of halogen acetic acid root anion.Then it is rapidly added the 8g sodium chloride vibration dried
Dissolution is swung, the methyl tertiary butyl ether(MTBE) extract liquor extraction 3min, quiet of 1,2,3- trichloropropane of internal standard compound (4000 μ g/L) is contained with 4ml
Set 3min.Upper layer ether liquid 3ml is pipetted into tool plug test tube, be added methanol 0.5ml, and add 0.1~10mg metallic catalyst and
0.1~10ppm metalloporphyrin and 0.01-5mg benzene sulfonic acid base phenolic resin (PAFR) are used as composite catalyst, and substitution has strong
Corrosive concentrated sulfuric acid is made catalyst halogen acetic acid and is reacted with methanol, and the corrosion of reaction vessel is avoided.This method is due to nothing
Need the traditional esterifications reaction concentrated sulfuric acid make catalyst thus be omitted the necessary subsequent progress of sulphuric acid catalysis institute saturated sodium-chloride it is molten
Liquid washing and sodium bicarbonate lye in and air bleeding step, improve work efficiency, avoid saturated sodium chloride solution washing and carbon
In sour hydrogen soda lye and the carbon dioxide gas of generation takes away easy volatile solvent methyl tertiary butyl ether(MTBE) and the ester of reaction generation is made
At loss of material, improve test accuracy；Metallic catalyst and benzene sulfonic acid base phenolic resin (PAFR) catalyst are repeatable
It recycles, metalloporphyrin dosage is few, and at low cost, esterification yield is higher than under ternary complex catalyst composite catalyzing
99.5%.Sealing compound seals tool plug test tube, and 50 DEG C of water-bath magnetic agitations react 1h, transfer the material into brown sample injection bottle after cooling
In, utilize the gas chromatograph for determination for having electron capture detector.
Metallic catalyst described in above-mentioned steps can be copper sulphate or copper chloride, iron chloride or ferric sulfate, be also possible to
One of copper oxide, di-iron trioxide, aluminum oxide, zirconium oxychloride.
Metalloporphyrin described in above-mentioned steps can be to chlorine tetraphenyl copper porphyrin or to chlorine tetraphenyl ferriporphyrin, can also be with
It is to chlorine tetraphenyl copper porphyrin or the immobilized porphyrin constituted to chlorine tetraphenyl ferriporphyrin and high molecular material.The carrier is point
One of sub- sieve, zeolite, porous ceramics, sepiolite, polyvinyl chloride or polystyrene.
Benzene sulfonic acid base phenolic resin (PAFR) is added into metallic catalyst and the effect of metalloporphyrin is: being improved
The esterification reaction of organic acid yield of halogen acetic acid, is increased to 99.5% or more for esterifying efficiency in methyl tertiary butyl ether(MTBE) medium, so inspection
It is high to survey device response, to obtain lower method detection limit；The esterification reaction of organic acid rate of halogen acetic acid, halogen second are accelerated simultaneously
The sour esterification reaction of organic acid time is foreshortened to the 1h of ternary complex catalyst, halogen acetic acid esterification by the 1.5-2h of single metallic catalyst
Reaction rate improves 50%-100%.Under ternary complex catalyst composite catalyzing, halogen acetic acid esterification reaction of organic acid yield and reaction
Rate significantly improves, and the reaction time is only that 1h is achieved with esterification yield higher than 99.5%.
In the reacting of nine kinds of halogen acetic acids and the methanol being catalyzed to metallic catalyst, benzene sulfonic acid base phenolic resin is added
(PAFR), nine kinds of halogen acetic acid methyl esters yields improve 15%-35%, and reaction rate accelerates 40%-75%.After metalloporphyrin is added
Reaction rate accelerates 10%-36%.
It is as follows that gas-chromatography instrument condition is set: injector temperature: 210 DEG C；Gas-chromatography temperature programming: initial temperature 40
DEG C keep 5min, be raised to 65 DEG C with 2.5 DEG C/min, 85 DEG C of holding 3min be raised to 10 DEG C/min, are raised to 205 DEG C with 20 DEG C/min
Keep 2min；Detector temperature: 290 DEG C；Chromatographic column: DB-1701 capillary chromatographic column (30m × 0.32mmi.d. × 0.25 μm
Film thickness)；Carrier gas: 99.99% high pure nitrogen；Carrier gas mobility: 2.0ml/min, make-up gas flow velocity: 30ml/min；Input mode: point
Flow into sample, split ratio 3:1；Sample volume: 2.0ul.
The successively sample introduction from low concentration to high concentration, obtains the gas chromatogram of nine kinds of halogen acetic acids of various concentration.With nine kinds
The concentration of halogenated acetic acids compound and internal standard compound ratio is abscissa, and halogenated acetic acids compound object is with internal standard compound peak area ratio
Ordinate establishes working curve.
Peak area ratio (the y=A of nine kinds of halogen acetic acids and internal standard compoundi/Ais) and concentration ratio (x=Ci/Cis) between related school
Positive equation are as follows: y=kx+b.
In formula, AiFor the peak area (wherein i=1~9) of various halogen acetic acids；AisFor the peak area of internal standard compound；CimOnly for m
(concentration of various halogen acetic acids, μ g/L in wherein i=1~9, m=1 or 2) porous glass plate absorption bottle absorbing liquid；CisFor internal standard compound
Concentration, μ g/L；K is the slope of working curve；B is the intercept of working curve.
Ci=AiCis/kAis-bCis/k
Only (concentration of various halogen acetic acids uses m in wherein i=1~9, m=1 or 2) porous glass plate absorption bottle absorbing liquid
Following formula calculates:
Cim=AimCism/kAism-bCism/k
(wherein: i is nine kinds of halogen acetic acid serial numbers, i=1~9；M is porous glass plate absorption bottle serial number, m=1~2.)
In formula, AimFor m only (various halogen acetic acids in wherein i=1~9, m=1 or 2) porous glass plate absorption bottle absorbing liquid
Peak area；AismFor the peak area of internal standard compound in m only porous glass plate absorption bottle absorbing liquid；CimFor m only porous glass plate absorption bottle
The concentration of various halogen acetic acids in absorbing liquid, μ g/L；CismFor the concentration of internal standard compound in m only porous glass plate absorption bottle absorbing liquid, μ
g/L；K is the slope of working curve；B is the intercept of working curve.
Three, the measurement of sample
NaOH absorbing liquid or water absorbing liquid that sampling finishes are transferred in separatory funnel, it is small that 2ml concentrated sulfuric acid tune pH is added
In 0.5, halogen acetic acid salt is made to be converted into halogen acetic acid, is then rapidly added the 8g sodium chloride oscillation dissolution dried, internal standard is contained with 4ml
The methyl tertiary butyl ether(MTBE) extract liquor extraction 3min of object 1,2,3- trichloropropane (4000 μ g/L), 3min is stood.Take the upper layer 3ml ether liquid
Into 15ml tool plug test tube, methanol 0.5ml is added, and add the metal porphin of 0.1~10mg metallic catalyst and 0.1~10ppm
Quinoline and 0.01-5mg benzene sulfonic acid base phenolic resin (PAFR) are used as composite catalyst, have in substitution traditional esterifications reaction strong rotten
The concentrated sulfuric acid of corrosion is made catalyst halogen acetic acid and is reacted with methanol, and the corrosion of reaction vessel is avoided.This method is due to being not necessarily to
The concentrated sulfuric acid make catalyst thus be omitted sulphuric acid catalysis institute must subsequent progress saturated sodium chloride solution wash and bicarbonate
It in soda lye and air bleeding step, improves work efficiency, avoids saturated sodium chloride solution washing and sodium bicarbonate lye neutralizes
Loss of material caused by the ester that the carbon dioxide gas of generation takes away easy volatile solvent methyl tertiary butyl ether(MTBE) and reaction generates,
Improve test accuracy；Catalyst is repeatable to be recycled, at low cost, is esterified under ternary complex catalyst composite catalyzing anti-
Product yield is higher than 99.5%.Sealing compound seals tool plug test tube, and 50 DEG C of water-bath magnetic agitations are reacted 1h, transferred the material into after cooling
In brown sample injection bottle, the gas chromatograph for determination for having electron capture detector is utilized.
Specimen Determination step institute can be with working curve plot step institute using composite catalyst using composite catalyst
It is identical, it is also possible to different, it is preferable to use identical composite catalyst.
Metallic catalyst described in above-mentioned steps can be copper sulphate or copper chloride, iron chloride or ferric sulfate, be also possible to
One of copper oxide, di-iron trioxide, aluminum oxide, zirconium oxychloride.
Metalloporphyrin described in above-mentioned steps can be to chlorine tetraphenyl copper porphyrin or to chlorine tetraphenyl ferriporphyrin, can also be with
It is to chlorine tetraphenyl copper porphyrin or the immobilized porphyrin constituted to chlorine tetraphenyl ferriporphyrin and high molecular material.With above-mentioned metalloporphyrin
The carrier for constituting supported metalloporphyrin catalyst has: molecular sieve, zeolite, porous ceramics, sepiolite, polyvinyl chloride, polystyrene
Deng.
End of reaction, metallic catalyst and benzene sulfonic acid base phenolic resin (PAFR) in ternary complex catalyst can repeat
Circulation catalysis uses, and has saved cost.
The concentration of various halogen acetic acids is calculated using following formula in surrounding air or exhaust gas:
Ci=(Ci1+Ci2-2C0)×40×10-3÷V
CiFor the concentration of various halogen acetic acids in surrounding air or exhaust gas, mg/m3, (wherein: i is nine kinds of halogen acetic acid serial numbers, i=
1~9；M is porous glass plate absorption bottle serial number, m=1~2).
Ci1Various halogen acetic acid concentration in the absorption fluid samples prepared for first porous glass plate absorption bottle, μ g/L, (wherein: i
For nine kinds of halogen acetic acid serial numbers, i=1~9).
Ci2Various halogen acetic acid concentration in the absorption fluid samples prepared for second porous glass plate absorption bottle, μ g/L, (wherein: i
For nine kinds of halogen acetic acid serial numbers, i=1~9).
C0Various halogen acetic acid concentration in the sample prepared for two porous glass plate absorption bottle absorbing liquid laboratory blank samples,
μ g/L, since reagent blank is free of halogen acetic acid, C in most cases0It is in most cases zero.
V is the sampling volume under standard state (101.325KPa, 273K), L.
40 be absorbing liquid volume, mL.
Four, the determination of detection limit and Determination Limit
When absorbing liquid sample gas volume is 20L, with the detection limit of 3 times of each substances of signal-to-noise ratio computation: chloroacetic acid: 1.02
×10-4~1.89 × 10-4mg/m3, a bromoacetic acid: 1.35 × 10-4~2.31 × 10-4mg/m3, dichloroacetic acid: 1.2 × 10-5~
2.7×10-5mg/m3, trichloroacetic acid: 1.5 × 10-6~3.6 × 10-6mg/m3, monobromo chloroacetic acid: 2.1 × 10-6~3.4 ×
10-6mg/m3, monobromo dichloroacetic acid: 2.1 × 10-6~3.5 × 10-6mg/m3, dibromoacetic acid: 1.5 × 10-6~3.1 × 10-6mg/
m3, a chlorine dibromoacetic acid: 2.9 × 10-6~4.9 × 10-6mg/m3, tribromoacetic acid: 5.1 × 10-6~7.2 × 10-6mg/m3。
The Determination Limit of each substance: chloroacetic acid: 4.08 × 10 is calculated with 4 times of detection limits-4~7.56 × 10-4mg/m3, one
Bromoacetic acid: 5.4 × 10-4~9.24 × 10-4mg/m3, dichloroacetic acid: 4.8 × 10-5~1.08 × 10-4mg/m3, trichloroacetic acid: 6
×10-6~1.44 × 10-5mg/m3, monobromo chloroacetic acid: 8.4 × 10-6~1.36 × 10-5mg/m3, monobromo dichloroacetic acid: 8.4
×10-6~1.4 × 10-5mg/m3, dibromoacetic acid: 6 × 10-6~1.24 × 10-5mg/m3, a chlorine dibromoacetic acid: 1.16 × 10-5
~1.96 × 10-5mg/m3, tribromoacetic acid: 2.04 × 10-5~2.88 × 10-5mg/m3。
Five, the measurement of precision
Preparing six parts of 40mL concentration is 150 μ g/L, nine kinds of halogen acetic acid standard sample absorbing liquids, and according to sample analysis step
6 parallel determinations are carried out after carrying out pre-treatment, calculate the relative standard deviation of 6 measurements.The relative standard deviation of each substance are as follows:
Chloroacetic acid: 1.7%~3.8%, bromoacetic acid: 2.8%~3.5%, dichloroacetic acid: 2.3%~4.2%, trichloroacetic acid:
2.6%~3.4%, monobromo chloroacetic acid: 3.9%~4.5%, monobromo dichloroacetic acid: 2.1%~4.6%, dibromoacetic acid:
2.6%~5.2%, one chlorine dibromoacetic acid: 2.8%~4.1%, tribromoacetic acid: 3.8%~4.6%.Each substance relative standard is inclined
Difference is respectively less than 5.2%, and method precision is high, favorable reproducibility.
Six, accuracy
Nine kinds of halogen acetic acid hybrid standard sample absorbing liquids that 40mL concentration is 80 μ g/L are prepared, according to sample analysis step,
The rate of recovery of various halogen acetic acids is calculated, each substance recovery is respectively as follows: chloroacetic acid: 96.9%~101%, bromoacetic acid:
98.1~102%%, dichloroacetic acid: 97.4%~102%, trichloroacetic acid: 98.6%~103%, monobromo chloroacetic acid:
96.7%~101%, monobromo dichloroacetic acid: 97.5%~99.5%, dibromoacetic acid: 97.2%~102%, chlorine dibromo second
Acid: 98.1%~99.7%, tribromoacetic acid: 99.6%~101%.The rate of recovery of each substance is 96.7%~103%, quantitative to tie
Fruit accuracy is good.
Compared with prior art, the present invention having the following beneficial effects:
1, the sampling of a variety of halogenated acetic acids in air or exhaust gas can be disposably completed at the same time.Halogen acetic acid good water solubility, it is readily soluble
Yu Shui selects 0.01~1mol/L NaOH aqueous solution as absorbing liquid, halogen acetic acid is made to be changed into halogen acetic acid salt, increases water solubility,
Absorbing liquid is good to air off gas absorbability, and gaseous sample collecting efficiency is high.
2, it realizes disposable comprehensively quick while measuring a variety of halogenated acetic acids in air or exhaust gas.Measurement method precision
Height, each substance relative standard deviation are respectively less than 5.2%.Method accuracy is good, and the rate of recovery of each substance is 96.7%~103%.
3, using metallic catalyst and add metalloporphyrin and benzene sulfonic acid base phenolic resin (PAFR) substitution have deep-etching
Property the concentrated sulfuric acid make catalyst halogen acetic acid and methanol esterification occur, avoid the corrosion of reaction vessel；This method by
In without the concentrated sulfuric acid make catalyst thus be omitted the necessary subsequent progress of traditional sulphuric acid catalysis technique institute saturated sodium-chloride it is molten
Liquid washing and sodium bicarbonate lye in and air bleeding step, improve work efficiency, avoid saturated sodium chloride solution washing and carbon
In sour hydrogen soda lye and the carbon dioxide gas of generation takes away easy volatile solvent methyl tertiary butyl ether(MTBE), internal standard compound 1,2,3- trichlorine third
Loss of material caused by the ester that alkane and reaction generate, improves test accuracy；Metallic catalyst and benzene sulfonic acid base phenolic aldehyde tree
Rouge is repeatable to be recycled, and metalloporphyrin dosage is at low cost down to ppm grades；Under ternary complex catalyst composite catalyzing, halogen second
Sour esterification reaction of organic acid yield is significantly improved with reaction rate, and the reaction time is only that 1h is achieved with esterification higher than 99.5%
Yield.
4, detection limit is low, method high sensitivity.Wherein chloroacetic acid minimum detectability is 1.02 × 10-4mg/m3, and document
GBZ/T160.59-2004 (air of industry location noxious material measures carboxylic acid compound) detection is limited to 0.1mg/m3, the present invention
Chloroacetic acid detection limit ratio GBZ/T160.59-2004 detection limit is 979.4 times low.Due to using metallic catalyst in continuous mode,
As carrier solvent and metalloporphyrin and benzene sulfonic acid base phenolic resin are added as composite catalyst using methyl tertiary butyl ether(MTBE), will be esterified
Efficiency is increased to 99.5% or more, so the relative detector response of halogen acetic acid esterification products to be measured is higher, method high sensitivity, inspection
Rising limit is low.
5, internal standard compound 1,2,3- trichloropropanes are added in sample with methyl tertiary butyl ether(MTBE) simultaneously before extraction, internal standard compound 1,
2,3- trichloropropane and the extraction of halogen acetic acid common experience extractant methyl tertiary butyl ether(MTBE) and esterification derivative-gas chromatographic analysis.
Internal standard compound 1,2,3- trichloropropane are added in sample with methyl tertiary butyl ether(MTBE) simultaneously before extraction, internal standard compound and determinand two
Person extracts the same enrichment of same loss with extractant, helps to maintain the ratio of internal standard compound and determinand in extract liquor to stablize,
Effectively prevent bad dry of measurement result precision caused by the factors such as extractant methyl tertiary butyl ether(MTBE) oscillation extraction is insufficient
It disturbs, test result favorable reproducibility.
6, working curve and sample analysis are all made of inner mark method ration, and quantitative more accurate, repeatability is more preferable, are effectively reduced
The operation of operator requires threshold.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
It is respectively adopted with connecting equipped with volume for the porous glass plate absorption bottle absorption of the 0.1mol/L NaOH aqueous solution of 40ml for two
Collect the halogen acetic acid class compound in stationary source exhaust gas.Concatenated porous glass plate absorption bottle is connected with flue gas sampler, if
Setting gas production flow is that 0.5L/min acquires waste gas of pollutant 40min, acquires gaseous sample 20L.
It is that nine kinds of halogen acetic acid standard substances are added in 0.1mol/LNaOH aqueous solution to concentration, is configured to 40ml concentration difference
For 0.5 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 1000 μ g/L, 2000 μ g/L
Nine kinds of halogen acetic acid standard alkaline type aqueous solutions.2ml concentrated sulfuric acid tune pH is added into above-mentioned alkaline aqueous solution less than 0.5, makes halogen acetic acid
Salt is converted into halogen acetic acid, is then rapidly added the 8g sodium chloride oscillation dissolution dried, contains 1,2,3- trichlorine third of internal standard compound with 4ml
The methyl tertiary butyl ether(MTBE) extract liquor extraction 3min of alkane (4000 μ g/L), 3min is stood.Upper layer ether liquid 3ml is pipetted to tool plug test tube
In, CH is added3OH0.5ml, metallic catalyst copper sulphate 1mg, and add carrier solvent quality 0.1ppm to chlorine tetraphenyl
Ferriporphyrin and 1.5mg benzene sulfonic acid base phenolic resin (PAFR).Sealing compound seals tool plug test tube, and 50 DEG C of water-bath magnetic agitations are anti-
1h is answered, upper materials are transferred in brown sample injection bottle after cooling, utilizes the gas chromatograph for determination peak for having electron capture organ
Area.
It is as follows that gas-chromatography instrument condition is set: injector temperature: 210 DEG C；Gas-chromatography temperature programming: initial temperature 40
DEG C keep 5min, be raised to 65 DEG C with 2.5 DEG C/min, 85 DEG C of holding 3min be raised to 10 DEG C/min, are raised to 205 DEG C with 20 DEG C/min
Keep 2min；Detector temperature: 290 DEG C；Chromatographic column: DB-1701 capillary chromatographic column (30m × 0.32mmi.d. × 0.25 μm
Film thickness)；Carrier gas: 99.99% high pure nitrogen；Carrier gas mobility: 2.0ml/min, make-up gas flow velocity: 30ml/min；Input mode: point
Flow into sample, split ratio 3:1；Sample volume: 2.0ul.
The successively sample introduction from low concentration to high concentration, obtains the gas chromatogram of nine kinds of halogen acetic acids of various concentration.With nine kinds
The concentration of halogenated acetic acids compound and internal standard compound ratio is abscissa, and halogenated acetic acids compound object is with internal standard compound peak area ratio
Ordinate establishes working curve.
Peak area ratio (the y=A of nine kinds of halogen acetic acids and internal standard compoundi/Ais) and concentration ratio (x=Ci/Cis) between related school
Positive equation are as follows: y=kx+b.
In formula, AiFor the peak area of various halogen acetic acids；AisFor the peak area of internal standard compound；CimIt is only (m=1 or 2) porous for m
The concentration of various halogen acetic acids, mg/m in glass plate absorption bottle absorbing liquid3；CisFor the concentration of internal standard compound, mg/m3；K is working curve
Slope；B is the intercept of working curve.
Ci=AiCis/kAis-bCis/k
Only (concentration of various halogen acetic acids uses m in wherein i=1~9, m=1 or 2) porous glass plate absorption bottle absorbing liquid
Following formula calculates:
Cim=AimCism/kAism-bCism/k
(wherein: i is nine kinds of halogen acetic acid serial numbers, i=1~9；M is porous glass plate absorption bottle serial number, m=1~2.)
In formula, AimFor m only (various halogen acetic acids in wherein i=1~9, m=1 or 2) porous glass plate absorption bottle absorbing liquid
Peak area；AismFor the peak area of internal standard compound in m only porous glass plate absorption bottle absorbing liquid；CimFor m only porous glass plate absorption bottle
The concentration of various halogen acetic acids in absorbing liquid, μ g/L；CismFor the concentration of internal standard compound in m only porous glass plate absorption bottle absorbing liquid, μ
g/L；K is the slope of working curve；B is the intercept of working curve.
The linear fit regression equation and correlated fitting parameter of nine kinds of halogen acetic acids are shown in Table 1.
The linear fit regression equation and correlated fitting parameter of 1 nine kinds of halogen acetic acids of table
The NaOH absorbing liquid that sampling finishes is transferred in separatory funnel, 2ml concentrated sulfuric acid tune pH is added less than 0.5, makes halogen
Acetate is converted into halogen acetic acid, is then rapidly added the 8g sodium chloride oscillation dissolution dried, contains internal standard compound 1,2,3- tri- with 4ml
The methyl tertiary butyl ether(MTBE) extract liquor extraction 3min of chloropropane (4000 μ g/L), 3min is stood.Upper layer ether liquid 3ml is extracted to tool plug examination
CH is added in Guan Zhong3OH0.5ml, metallic catalyst copper sulphate 1mg, and add carrier solvent quality 0.1ppm to four benzene of chlorine
Base ferriporphyrin and 1.5mg benzene sulfonic acid base phenolic resin (PAFR), 50 DEG C of water-bath magnetic agitations react 1h, by upper layer substance after cooling
Material is transferred in brown sample injection bottle, and air inlet analysis of hplc calculates.
The concentration of various halogen acetic acids is calculated using following formula in exhaust gas:
Ci=(Ci1+Ci2-2C0)×40×10-3÷V
CiFor the concentration of halogen acetic acids various in exhaust gas, mg/m3, (wherein: i is nine kinds of halogen acetic acid serial numbers, i=1~9；M is more
Hole glass plate absorption bottle serial number, m=1~2).
Ci1For various halogen acetic acid concentration in the absorbing liquid of first porous glass plate absorption bottle preparation, μ g/L.
Ci2For various halogen acetic acid concentration in the absorbing liquid of second porous glass plate absorption bottle preparation, μ g/L.
C0Various halogen acetic acid concentration in the sample prepared for two porous glass plate absorption bottle absorbing liquid laboratory blank samples,
μ g/L, since the blank of agents useful for same is free of halogen acetic acid, C0Numerical value is zero.
V is the sampling volume under standard state (101.325KPa, 273K), L.
40 be absorbing liquid volume, mL.
Various halogen acetic acid concentration Cs in exhaust gasiMeasurement result it is as follows: chloroacetic acid 3.2893mg/m3, a bromoacetic acid
1.2152mg/m3, dichloroacetic acid 3.2923mg/m3, trichloroacetic acid 1.4237mg/m3, monobromo chloroacetic acid 0.1065mg/m3, one
Bromine dichloroacetic acid 0.2561mg/m3, dibromoacetic acid 0.3591mg/m3, a chlorine dibromoacetic acid 0.2875mg/m3, tribromoacetic acid
0.3256mg/m3。
Embodiment 2
It is respectively adopted with connecting equipped with volume for the porous glass plate absorption bottle absorption of the 0.5mol/LNaOH aqueous solution of 40ml for two
Collect the halogen acetic acid class compound in stationary source exhaust gas.Concatenated porous glass plate absorption bottle is connected with flue gas sampler, if
Setting gas production flow is that 0.4L/min acquires waste gas of pollutant 50min, acquires sample 20L.According to same as Example 1 after sampling
Sample analysis step, the concentration of nine kinds of halogen acetic acids in analytical calculation Concentration in Fixed Pollutants Source cylinder exhaust gas.Working curve draw and to
It is ferric sulfate, additional amount 8mg that sample, which measures metallic catalyst used,；And add carrier solvent quality 6ppm to chlorine four
Phenyl copper porphyrin and 0.8mg benzene sulfonic acid base phenolic resin (PAFR).
Exhaust gas halogen acetic acid measurement result is as follows: chloroacetic acid 0.3151mg/m3, a bromoacetic acid 0.1823, dichloroacetic acid
0.1012mg/m3, trichloroacetic acid 0.3325mg/m3, monobromo chloroacetic acid 0.2056mg/m3, monobromo dichloroacetic acid 0.2013mg/
m3, dibromoacetic acid 0.1692mg/m3, a chlorine dibromoacetic acid 0.4253mg/m3, tribromoacetic acid 0.3217mg/m3。
Embodiment 3
It is fixed dirty that acquisition is absorbed with single porous glass plate absorption bottle only equipped with volume for the 1mol/LNaOH aqueous solution of 40ml
Halogen acetic acid class compound in the exhaust gas of dye source.Porous glass plate absorption bottle is connected with flue gas sampler, setting gas production flow is
0.4L/min acquires waste gas of pollutant 50min, acquires gaseous sample 20L.According to sample analysis same as Example 1 after sampling
Step, nine kinds of halogen acetic acid concentration in analytical calculation stationary source exhaust gas.Working curve is drawn and sample to be tested measurement gold used
Metal catalyst iron chloride additional amount is 7mg；And it is immobilized to chlorine tetraphenyl copper porphyrin and 0.5mg benzene sulfonic acid base phenol to add sepiolite
Urea formaldehyde (PAFR), wherein be the 5ppm of carrier solvent quality to chlorine tetraphenyl copper porphyrin content.
Exhaust gas halogen acetic acid measurement result is as follows: chloroacetic acid 0.1593mg/m3, a bromoacetic acid 0.0621mg/m3, two chloroethenes
Sour 0.0754mg/m3, trichloroacetic acid 0.0363mg/m3, monobromo chloroacetic acid 0.0275mg/m3, monobromo dichloroacetic acid
0.0121mg/m3, dibromoacetic acid 0.0182mg/m3, a chlorine dibromoacetic acid 0.0134mg/m3, tribromoacetic acid 0.0216mg/m3。
Embodiment 4
It is respectively adopted with connecting equipped with volume for the porous glass plate absorption bottle absorption of the 0.8mol/LNaOH aqueous solution of 40ml for two
Collect the halogen acetic acid class compound in stationary source exhaust gas.Concatenated porous glass plate absorption bottle is connected with flue gas sampler, if
Setting gas production flow is that 0.4L/min acquires waste gas of pollutant 50min, acquires sample 20L.Working curve draws metal catalytic used
Agent is ferric sulfate, additional amount 8mg；And add carrier solvent quality 6ppm to chlorine tetraphenyl copper porphyrin and 0.8mg benzene
Sulfonic group phenolic resin (PAFR).It is copper sulphate that sample to be tested, which measures metallic catalyst used, additional amount 1.5mg, and is added
The 0.5ppm of carrier solvent quality to chlorine tetraphenyl ferriporphyrin and 1.3mg benzene sulfonic acid base phenolic resin (PAFR).After sampling
According to sample analysis step same as Example 1, nine kinds of halogen acetic acid concentration in analytical calculation Concentration in Fixed Pollutants Source cylinder exhaust gas.
Exhaust gas halogen acetic acid measurement result is as follows: chloroacetic acid 0.2669mg/m3, a bromoacetic acid 0.2713mg/m3, two chloroethenes
Sour 0.1325mg/m3, trichloroacetic acid 0.1695mg/m3, monobromo chloroacetic acid 0.2378mg/m3, monobromo dichloroacetic acid
0.1981mg/m3, dibromoacetic acid 0.1322mg/m3, a chlorine dibromoacetic acid 0.2167mg/m3, tribromoacetic acid 0.2659mg/m3。
Embodiment 5
With single halogen acetic acid class chemical combination only absorbed equipped with the porous glass plate absorption bottle that volume is 40ml pure water in acquisition atmosphere
Object.Porous glass plate absorption bottle is connected with air sampler, setting gas production flow is that 0.4L/min acquires waste gas of pollutant
50min acquires sample 20L.According to sample analysis step same as Example 1 after sampling, nine kinds of halogen in analytical calculation atmosphere
Acetic acid concentration.Working curve is drawn and sample to be tested measurement metallic catalyst used is aluminum oxide, additional amount 3mg；And
It is immobilized to chlorine tetraphenyl ferriporphyrin and 2mg benzene sulfonic acid base phenolic resin (PAFR) to add polyvinyl chloride, wherein to chlorine tetraphenyl
Ferriporphyrin content is the 8ppm of carrier solvent quality.
Atmosphere halogen acetic acid measurement result is as follows: chloroacetic acid 0.0015mg/m3, a bromoacetic acid 0.0032mg/m3, two chloroethenes
Sour 0.0021mg/m3, trichloroacetic acid 0.0002mg/m3, monobromo chloroacetic acid 0.00006mg/m3, monobromo dichloroacetic acid
0.0001mg/m3, dibromoacetic acid 0.0009mg/m3, a chlorine dibromoacetic acid 0.0003mg/m3, tribromoacetic acid 0.0001mg/m3。
Embodiment 6
Acquisition atmosphere is absorbed with single porous glass plate absorption bottle only equipped with volume for the 0.5mol/LNaOH aqueous solution of 40ml
In halogen acetic acid class compound.Porous glass plate absorption bottle is connected with air sampler, setting gas production flow is adopted for 0.5L/min
Collect waste gas of pollutant 40min, acquires sample 20L.According to sample analysis step same as Example 1, analytical calculation after sampling
Nine kinds of halogen acetic acid concentration in atmosphere.Working curve is drawn and sample to be tested measurement metallic catalyst used is zirconium oxychloride, is added
Entering amount is 0.5mg；And the 0.2ppm of carrier solvent quality is added to chlorine tetraphenyl copper porphyrin and 1.5mg benzene sulfonic acid base phenolic aldehyde tree
Rouge (PAFR).
Atmosphere halogen acetic acid measurement result is as follows: chloroacetic acid 0.0011mg/m3, a bromoacetic acid 0.0015mg/m3, two chloroethenes
Sour 0.0015mg/m3, trichloroacetic acid 0.0001mg/m3, monobromo chloroacetic acid 0.00003mg/m3, monobromo dichloroacetic acid
0.0002mg/m3, dibromoacetic acid 0.0011mg/m3, a chlorine dibromoacetic acid 0.0012mg/m3, tribromoacetic acid 0.0003mg/m3。
Claims (8)
1. the detection method of a variety of halogen acetic acids in a kind of air or exhaust gas, it is characterised in that steps are as follows:
(1) halogen acetic acid in air or exhaust gas is adopted by the porous glass plate absorption bottle absorption equipped with NaOH aqueous solution or ultrapure water
Sample；
(2) it is extracted again by the methyl tertiary butyl ether(MTBE) containing internal standard compound, and using methyl tertiary butyl ether(MTBE) as carrier solvent, and in metal
Esterification occurs with methanol under catalyst, metalloporphyrin and benzene sulfonic acid base phenolic resin composite catalyzing, is caught using with electronics
The gas chromatograph for determination peak area of device is obtained, result measurement is carried out；
The mass ratio of metallic catalyst, metalloporphyrin and benzene sulfonic acid base phenolic resin described in step (2) is 10-1000:
0.03-3:1-500；
A variety of halogen acetic acids are nine kinds of halogen acetic acids, specially chloroacetic acid, a bromoacetic acid, dichloroacetic acid, trichloroacetic acid, one chlorine of monobromo
Acetic acid, monobromo dichloroacetic acid, dibromoacetic acid, a chlorine dibromoacetic acid, tribromoacetic acid.
2. the detection method of a variety of halogen acetic acids in air according to claim 1 or exhaust gas, it is characterised in that in step (1)
The concentration of the NaOH aqueous solution is 0.01-1mol/L.
3. the detection method of a variety of halogen acetic acids in air according to claim 1 or exhaust gas, it is characterised in that in step (1)
The number of the porous glass plate absorption bottle is 1 or 2.
4. the detection method of a variety of halogen acetic acids in air according to claim 1 or exhaust gas, it is characterised in that in step (2)
The internal standard compound is 1,2,3- trichloropropane.
5. the detection method of a variety of halogen acetic acids in air according to claim 1 or exhaust gas, it is characterised in that in step (2)
The metallic catalyst be copper sulphate, copper chloride, iron chloride, ferric sulfate, copper oxide, di-iron trioxide, aluminum oxide or
One of zirconium oxychloride.
6. the detection method of a variety of halogen acetic acids in air according to claim 1 or exhaust gas, it is characterised in that in step (2)
The metalloporphyrin be to chlorine tetraphenyl copper porphyrin, it is immobilized to chlorine tetraphenyl ferriporphyrin, carrier to chlorine tetraphenyl copper porphyrin or
Carrier is immobilized to one of chlorine tetraphenyl ferriporphyrin.
7. the detection method of a variety of halogen acetic acids in air according to claim 6 or exhaust gas, it is characterised in that the load
Body is one of molecular sieve, zeolite, porous ceramics, sepiolite, polyvinyl chloride or polystyrene.
8. the detection method of a variety of halogen acetic acids in air according to claim 1 or exhaust gas, it is characterised in that in step (2)
The additive amount of the metalloporphyrin is the 0.1-10ppm of carrier solvent quality.
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| CN101131381A (en) * | 2007-09-27 | 2008-02-27 | 上海交通大学 | Method for detecting halogen acetic acid in drinking water |
| CN105717208A (en) * | 2016-01-28 | 2016-06-29 | 哈尔滨工业大学 | Method for synchronously determining content of trihalomethane and haloacetic acid in drinking water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101131381A (en) * | 2007-09-27 | 2008-02-27 | 上海交通大学 | Method for detecting halogen acetic acid in drinking water |
| CN105717208A (en) * | 2016-01-28 | 2016-06-29 | 哈尔滨工业大学 | Method for synchronously determining content of trihalomethane and haloacetic acid in drinking water |
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| Analysis of haloacetic acids in water and air (aerosols) from indoor swimming pools using HS-SPME/GC/ECD;CHRISTOPHER S.A.et al.;《Journal of environmental science and health》;20121231;第47卷;176-183页 |
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