CN112684037A - Detection method for determining organic amine in ambient air and waste gas - Google Patents
Detection method for determining organic amine in ambient air and waste gas Download PDFInfo
- Publication number
- CN112684037A CN112684037A CN202011449767.4A CN202011449767A CN112684037A CN 112684037 A CN112684037 A CN 112684037A CN 202011449767 A CN202011449767 A CN 202011449767A CN 112684037 A CN112684037 A CN 112684037A
- Authority
- CN
- China
- Prior art keywords
- sample
- triethylamine
- monoethylamine
- diethylamine
- temperature
- 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.)
- Granted
Links
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- 239000012080 ambient air Substances 0.000 title claims abstract description 34
- 239000002912 waste gas Substances 0.000 title claims abstract description 31
- 150000001412 amines Chemical class 0.000 title claims abstract description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 168
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 98
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000523 sample Substances 0.000 claims description 87
- 239000000243 solution Substances 0.000 claims description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000003570 air Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005070 sampling Methods 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 230000007613 environmental effect Effects 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012496 blank sample Substances 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003795 desorption Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 15
- 238000010586 diagram Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Sampling And Sample Adjustment (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a detection method for measuring organic amine in ambient air and waste gas, which comprises the following steps: s1, collecting samples, S2, and carrying out experiment by an experimental instrument according to the following experimental conditions: s3, processing a sample; s4, establishing a working curve: preparing a standard sample curve according to the sample processing process in the step S3, sequentially injecting samples from low to high in concentration, and establishing a working curve by taking the concentration mg/L of the standard series as a horizontal coordinate and the peak area of the corresponding chromatographic peak as a vertical coordinate. In the invention, the detection limits of the methods for monoethylamine, diethylamine and triethylamine in the ambient air are respectively 0.1mg/m3、0.2mg/m3、0.2mg/m3The detection limits of the method for fixing the monoethylamine, the diethylamine and the triethylamine in the waste gas of the pollution source are respectively 0.2mg/m3、0.3mg/m3、0.3mg/m3Adding a label to the sampleThe recovery rate ranges from 82.5% to 116%, from 85.3% to 131% and from 72.0% to 121%, and the relative standard deviation ranges from 13.5%, from 16.3% and from 21.7%, respectively.
Description
Technical Field
The invention relates to the technical field of detection of monoethylamine, diethylamine and triethylamine in ambient air and waste gas, in particular to a detection method for detecting organic amine in ambient air and waste gas.
Background
Monoethylamine, diethylamine and triethylamine belong to organic amine, have strong ammoniacal irritant gases, can be slightly dissolved in water, the boiling points are respectively 16.6 ℃, 55.5 ℃ and 89.5 ℃, the organic amine is used as a raw material or an intermediate product in the production of rubber vulcanization accelerators, synthetic fibers and resins, insecticides, organic dyes, vitamin-reinforced feeds, plant growth regulation and pharmaceutical preparations, and the monoethylamine and the diethylamine are extremely volatile due to low boiling points, are easy to cause pollution to the surrounding environment and influence human health, have large toxicity and high activity, so that the analysis and determination of the monoethylamine, the diethylamine and the triethylamine are very important in the fields of environmental engineering, food and pesticides.
The method for measuring the organic amine in the water comprises a direct sample injection method, a headspace-gas chromatography and the like, but the prior art lacks a detection method for measuring monoethylamine, diethylamine and triethylamine in samples of ambient air and waste gas, so that a detection method for measuring the contents of monoethylamine, diethylamine and triethylamine in the ambient air and the waste gas is lacked.
Disclosure of Invention
In order to solve the problems mentioned in the background art, a detection method for measuring organic amine in ambient air and waste gas is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a detection method for determining organic amine in ambient air and waste gas comprises the following steps:
s1, sample collection:
air sample: adsorbing an environmental air sample and an air sample of a fixed pollution source inorganization emission monitoring point at a sampling point by using a silica tube, and collecting a 15min sample at a flow rate of 500ml/min by using an air sampler, wherein the sampling volume is 7.5L;
an exhaust gas sample: adsorbing the fixed pollution source waste gas sample on a silicon rubber tube at a sampling point, and collecting a 10min sample at a flow rate of 500ml/min by using a flue gas sampler, wherein the sampling volume is 5.0L;
blank sample: opening two ends of the silicone tube at a sampling point and immediately closing the silicone tube to obtain a blank sample;
s2, experimental conditions of the experimental instrument are as follows:
an experimental instrument: a headspace sample injector and a gas chromatograph;
the experimental conditions are as follows:
the conditions for the headspace sampler were as follows: heating equilibrium temperature: 75 ℃; headspace equilibrium time: 1 min; transmission line temperature: 105 ℃; temperature of the sample injection needle: 100 ℃; heating balance time: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1 mL;
the gas chromatograph operating conditions were as follows: capillary chromatographic column: HP-5MS (30 m.times.0.25 mm.times.0.25 μm); carrier gas: purity ≧ 99.999% of nitrogen, column flow rate: 1.0 mL/min; split-flow sample injection with a split-flow ratio of 10: 1; sample inlet temperature: 200 ℃; temperature rising procedure: the initial temperature is 40 ℃, the temperature is kept for 5min, and then the temperature is increased to 220 ℃ at the speed of 20 ℃/min; GC analysis time: 14 min;
s3, sample treatment: sequentially weighing 3.2g of sodium chloride and 1.0g of potassium sulfate in a headspace bottle, respectively pouring the front and rear end alkaline silica gels into two solvent headspace bottles, adding 10mL of 0.06mol/L dilute sulfuric acid solution, shaking uniformly, adding 500 mu L of 50% w/v sodium hydroxide solution and 100 mu L of 0.91g/mL ammonia water solution, immediately sealing the headspace bottle, shaking slightly until the salt is dissolved, carrying out ultrasonic desorption for 20min, and determining the content of organic amine according to an experimental instrument and experimental conditions in the step S2;
s4, establishing a working curve:
for ambient air and unstructured exhaust gas concentrations of 0-2.0 mg/L: respectively taking 20mg/L monoethylamine, diethylamine and triethylamine mixed standard use solutions, preparing at least 6-point standard series by using 0.06mol/L dilute sulfuric acid solution, wherein the mass concentrations of the monoethylamine, diethylamine and triethylamine are 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L in sequence;
for the fixed pollutant source organized waste gas with the concentration of 0.5-40.0 mg/L: respectively taking 20mg/L monoethylamine, diethylamine and triethylamine mixed standard use solutions, preparing at least 6-point standard series by using 0.06mol/L dilute sulfuric acid solution, wherein the mass concentrations of the monoethylamine, diethylamine and triethylamine are 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L, 20.0mg/L and 40.0mg/L in sequence;
preparing a standard sample curve according to the sample treatment process in the step S3, sequentially injecting samples according to the concentration of a mixed standard use solution of monoethylamine, diethylamine and triethylamine from low to high, and establishing a working curve by taking the concentration mg/L of a standard series as a horizontal coordinate and the peak area of a corresponding chromatographic peak as a vertical coordinate.
As a further description of the above technical solution:
the silicone tube is of a solvent analysis type, and 200mg/100mg of alkaline silica gel is filled in the silicone tube.
As a further description of the above technical solution:
the flow range of the air sample injector is 0.1L/min-1.0L/min.
As a further description of the above technical solution:
the flow range of the flue gas sampler is 0.1L/min-2.0L/min.
As a further description of the above technical solution:
the headspace bottle is a glass bottle with the volume of 22ml, and is provided with a sealing cover with a polytetrafluoroethylene coating and a sealing gasket.
As a further description of the above technical solution:
and (3) burning the sodium chloride and the potassium sulfate in a muffle furnace at 400 ℃ for 4h, and cooling to room temperature for later use.
As a further description of the above technical solution:
in step S3, 1.6mL of concentrated sulfuric acid is removed and added to the experimental water, and the solution is cooled, diluted and diluted to a volume of 500mL to obtain a 0.06mol/L dilute sulfuric acid solution.
As a further description of the above technical solution:
in step S3, 50g of sodium hydroxide was dissolved in 50mL of experimental water to obtain a 50% w/v sodium hydroxide solution.
As a further description of the above technical solution:
the experimental water is one of deionized water or distilled water.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the invention, the detection limits of the method for determining monoethylamine, diethylamine and triethylamine in ambient air by the method are respectively 0.1mg/m3、0.2mg/m3、0.2mg/m3The detection limits of the method for fixing the monoethylamine, the diethylamine and the triethylamine in the waste gas of the pollution source are respectively 0.2mg/m3、0.3mg/m3、0.3mg/m3The sample adding standard recovery rate ranges from 82.5% to 116%, 85.3% to 131%, 72.0% to 121%, and the relative standard deviation ranges from 13.5%, 16.3% and 21.7%, respectively.
2. In the invention, the conditions of the headspace sample injector are optimized as follows: "heating equilibrium temperature: 75 ℃; the balance time is as follows: 1 min; transmission line temperature: 105 ℃; temperature of the sample injection needle: 100 ℃; constant temperature time of the headspace bottle: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1 mL' to ensure the accuracy of the sample measuring result, obtain reliable accuracy and precision, and is suitable for the analysis and detection of monoethylamine, diethylamine and triethylamine in the environment air and the fixed pollution source waste gas.
Drawings
FIG. 1 shows standard gas chromatograms of monoethylamine, diethylamine and triethylamine of a detection method for determining organic amines in ambient air and exhaust gas according to an embodiment of the present invention;
FIG. 2 is a schematic diagram showing the working curve of monoethylamine in an ambient air matrix sample according to an embodiment of the present invention;
FIG. 3 is a schematic diagram showing the operating curves of diethylamine in an ambient air matrix sample of a detection method for determining organic amines in ambient air and exhaust gas according to an embodiment of the present invention;
FIG. 4 is a schematic diagram showing the operating curves of triethylamine in an ambient air matrix sample according to an embodiment of the present invention;
FIG. 5 is a schematic diagram showing the operating curve of monoethylamine in an exhaust gas matrix sample of a detection method for determining organic amine in ambient air and exhaust gas according to an embodiment of the present invention;
FIG. 6 is a schematic diagram showing a working curve of diethylamine in an exhaust gas matrix sample of a detection method for determining organic amine in ambient air and exhaust gas according to an embodiment of the present invention;
FIG. 7 is a schematic diagram showing the operating curves of triethylamine in the exhaust gas matrix sample of the detection method for determining organic amine in the ambient air and the exhaust gas according to the embodiment of the invention;
FIG. 8 is a schematic diagram showing the peak area changes of triethylamine at different heating equilibrium temperatures according to the detection method for determining organic amine in ambient air and waste gas provided by the embodiment of the invention;
fig. 9 shows a schematic diagram of the peak area change of triethylamine at different injection needle temperatures according to the detection method for determining organic amine in ambient air and waste gas provided by the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Referring to fig. 1-7, the present invention provides a technical solution: a detection method for determining organic amine in ambient air and waste gas comprises the following steps:
s1, sample collection:
air sample: adsorbing an environmental air sample and an air sample of a fixed pollution source inorganization emission monitoring point at a sampling point by using a silica tube, and collecting a 15min sample at a flow rate of 500ml/min by using an air sampler, wherein the sampling volume is 7.5L;
an exhaust gas sample: adsorbing the fixed pollution source waste gas sample on a silicon rubber tube at a sampling point, and collecting a 10min sample at a flow rate of 500ml/min by using a flue gas sampler, wherein the sampling volume is 5.0L;
blank sample: opening two ends of the silicone tube at a sampling point and immediately closing the silicone tube to obtain a blank sample;
wherein, the silicone tube is solvent analysis type, and 200mg/100mg of alkaline silica gel is filled in the silicone tube;
wherein the flow range of the air sample injector is 0.1L/min-1.0L/min;
wherein the flow range of the flue gas sampler is 0.1L/min-2.0L/min;
s2, experimental conditions of the experimental instrument are as follows:
an experimental instrument: a headspace sample injector and a gas chromatograph;
the experimental conditions are as follows:
the conditions for the headspace sampler were as follows: heating equilibrium temperature: 75 ℃; headspace equilibrium time: 1 min; transmission line temperature: 105 ℃; temperature of the sample injection needle: 100 ℃; heating balance time: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1 mL;
the gas chromatograph operating conditions were as follows: capillary chromatographic column: HP-5MS (30 m.times.0.25 mm.times.0.25 μm); carrier gas: purity ≧ 99.999% of nitrogen, column flow rate: 1.0 mL/min; split-flow sample injection with a split-flow ratio of 10: 1; sample inlet temperature: 200 ℃; temperature rising procedure: the initial temperature is 40 ℃, the temperature is kept for 5min, and then the temperature is increased to 220 ℃ at the speed of 20 ℃/min; GC analysis time: 14 min;
s3, sample treatment: sequentially weighing 3.2g of sodium chloride and 1.0g of potassium sulfate in a headspace bottle, respectively pouring the front and rear end alkaline silica gels into two solvent headspace bottles, adding 10mL of 0.06mol/L dilute sulfuric acid solution, shaking uniformly, adding 500 mu L of 50% w/v sodium hydroxide solution and 100 mu L of 0.91g/mL ammonia water solution, immediately sealing the headspace bottle, shaking slightly until the salt is dissolved, carrying out ultrasonic desorption for 20min, and carrying out determination on the content of organic amine according to an experimental instrument and experimental conditions in the step S2, namely content determination of monoethylamine, diethylamine and triethylamine;
wherein, sodium chloride and potassium sulfate are burned for 4 hours in a muffle furnace at 400 ℃, and cooled to room temperature for standby;
wherein the headspace bottle is a glass bottle with the volume of 22ml, and is provided with a sealing cover with a polytetrafluoroethylene coating and a sealing gasket;
wherein, 1.6mL of concentrated sulfuric acid is transferred and added into experimental water, and the mixture is cooled, diluted and fixed to the volume of 500mL to obtain a 0.06mol/L dilute sulfuric acid solution;
wherein 50g of sodium hydroxide is dissolved in 50mL of experimental water to obtain a 50% w/v sodium hydroxide solution;
wherein the experimental water is one of deionized water or distilled water;
s4, establishing a working curve:
for ambient air and unstructured exhaust gas concentrations of 0-2.0 mg/L: respectively taking 20mg/L monoethylamine, diethylamine and triethylamine mixed standard use solutions, preparing at least 6-point standard series by using 0.06mol/L dilute sulfuric acid solution, wherein the mass concentrations of the monoethylamine, diethylamine and triethylamine are 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L in sequence;
for the fixed pollutant source organized waste gas with the concentration of 0.5-40.0 mg/L: respectively taking 20mg/L monoethylamine, diethylamine and triethylamine mixed standard use solutions, preparing at least 6-point standard series by using 0.06mol/L dilute sulfuric acid solution, wherein the mass concentrations of the monoethylamine, diethylamine and triethylamine are 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L, 20.0mg/L and 40.0mg/L in sequence;
wherein, 100 mu L of monoethylamine, diethylamine and triethylamine standard solution of 2000mg/L are respectively taken and diluted to 10mL by dilute sulphuric acid solution, and 20mg/L of mixed standard use solution of monoethylamine, diethylamine and triethylamine is prepared;
preparing a standard sample curve according to the sample treatment process in the step S3, sequentially injecting samples according to the concentration of a mixed standard use solution of monoethylamine, diethylamine and triethylamine from low to high, and establishing a working curve by taking the concentration mg/L of a standard series as a horizontal coordinate and the peak area of a corresponding chromatographic peak as a vertical coordinate.
Referring to fig. 1, a standard gas chromatogram of 20.0mg/L mixed standard concentrations of monoethylamine, diethylamine and triethylamine shows that the retention time of monoethylamine is 2.699min, the retention time of diethylamine is 3.135min and the retention time of triethylamine is 4.312 min;
comparison of method performance for monoethylamine, diethylamine and triethylamine in ambient air and waste samples:
(1) standard curve, correlation coefficient and detection limit of the method: referring to fig. 2-7, peak areas of 6 different mass concentrations were studied under two substrate samples of ambient air and exhaust gas, respectively, and a standard curve was established with the mass concentration as abscissa x and the peak area as ordinate y, and the correlation coefficients and correlation coefficients of the working curve equation are shown in table 1 below:
TABLE 1 Standard curves, correlation coefficients and method detection limits for monoethylamine, diethylamine and triethylamine in ambient air and exhaust gases
According to the lowest detectable monoethylamine, diethylamine and triethylamine concentration of the instrument, according to the method for determining detection limit of 'the technical guide of revision of environmental detection and analysis method Standard', repeating the whole process of test operation for 7 times, blank labeling of the sample, wherein the concentration of the labeled sample is 0.05mg/L, converting the measurement result into the concentration of the sample to obtain the standard deviation(s), and calculating the detection limits of the environmental air matrix sample monoethylamine, diethylamine and triethylamine to be 0.1mg/m3、0.2mg/m3And 0.2mg/m3The detection limits of the waste gas substrate samples monoethylamine, diethylamine and triethylamine are respectively 0.2mg/m3、0.3mg/m3And 0.3mg/m3The results are shown in table 2 below:
table 2 detection limit results for two substrate samples of ambient air and exhaust gas (n ═ 7)
(2) The method has the following accuracy and precision: after the blank silicone tube samples in the whole process are respectively adopted for labeling, the whole procedure is measured for 6 times according to the standard method steps, and the measurement precision and the accuracy are shown in the following table 3:
table 3 precision and accuracy test results (n ═ 6)
As can be seen from Table 3, the relative standard deviations of the measurement results of the monoethylamine, the diethylamine and the triethylamine are respectively 4.2% -6.0%, 4.6% -13.1% and 3.8% -9.0%, the range of the standard recovery rates of the addition are respectively 82.0-96.0%, 69.0-94.5% and 80.0-114%, the method meets the quality control requirements of the analysis and test, and the method has reliable precision and accuracy;
after the fixed pollution source waste gas sample F ethylamine 01-05-01-06 is subjected to standard addition, the whole procedure is measured for 6 times according to the standard method steps, and the measurement precision and accuracy are as follows:
TABLE 4 precision and accuracy test results (n ═ 6)
As can be seen from Table 4, the relative standard deviations of the results of the monoethylamine, diethylamine and triethylamine measurements after the sample is subjected to the standard addition are respectively 13.5%, 16.3% and 21.7%, and the ranges of the recovery rates of the standard addition are respectively 82.5% -116%, 85.3% -131% and 72.0% -121%, which indicates that the method has good precision and accuracy and meets the requirements of quality control of analysis and test.
And (3) sample analysis: the method is used for detecting the environmental air and fixed pollution source waste gas samples of the factory boundary of an enterprise, the absorption of an alkaline silicone tube, the desorption of a solution, the headspace sampling and the separation and detection of gas chromatography are carried out, each group of data is analyzed 6 times at equal time sampling intervals, the relative standard deviation RSD of the parallel sample determination results of the waste gas samples is less than 25 percent, the relative standard deviation RSD of the parallel sample determination results of the air samples of the factory boundary is less than 40 percent, and the content results of the analysis and detection of monoethylamine, diethylamine and triethylamine are shown in the following table 5 and table 6:
table 5 measurement results of monoethylamine, diethylamine and triethylamine in the actual exhaust gas sample (n ═ 6)
Table 6 results of measurement of monoethylamine, diethylamine and triethylamine in actual samples of air (n ═ 6)
The contents of monoethylamine, diethylamine and triethylamine in the ambient air and the waste gas are determined by establishing an alkaline silica gel tube adsorption-headspace/gas chromatography, and the result shows that: the detection limit of the method for determining monoethylamine, diethylamine and triethylamine in the ambient air is 0.1mg/m respectively3、0.2mg/m3、0.2mg/m3The detection limits of the method for fixing the monoethylamine, the diethylamine and the triethylamine in the waste gas of the pollution source are respectively 0.2mg/m3、0.3mg/m3、0.3mg/m3The sample adding standard recovery rate ranges from 82.5% to 116%, 85.3% to 131%, 72.0% to 121%, and the relative standard deviation ranges from 13.5%, 16.3% and 21.7%, respectively.
Example two
Specifically, as shown in fig. 8, in step S2, a mixed standard solution with a concentration of 1.0mg/L is prepared and injected for analysis, and other conditions of the headspace injector, i.e., "headspace equilibrium time: 1 min; transmission line temperature: 105 ℃; temperature of the sample injection needle: 100 ℃; heating balance time: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1mL is unchanged, and the peak area changes of triethylamine at the heating equilibrium temperatures of 55, 65, 75, 85 and 95 ℃ are examined;
when the temperature rises, the Henry constant is increased, the distribution coefficient of triethylamine in gas and liquid is changed, when the heating equilibrium temperature rises, the peak area of triethylamine gradually becomes larger, but the pressure of a headspace bottle is increased along with the rise of the equilibrium temperature, the headspace bottle is easy to break due to overhigh pressure, the difficulty of sampling analysis is increased due to overhigh air pressure, the analysis accuracy is influenced, and the sensitivity of the analysis is proper when the heating equilibrium temperature is 75 ℃;
specifically, as shown in fig. 9, in step S2, a mixed standard solution with a concentration of 1.0mg/L is prepared and injected for analysis, and other conditions of the headspace injector, i.e., "headspace equilibrium time: 1 min; transmission line temperature: 105 ℃; heating balance time: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1mL is unchanged, and the peak area changes of triethylamine at the temperature of 80, 90, 100, 110 and 120 ℃ of the injection needle are inspected;
if the temperature of the sample injection needle is too low, triethylamine is incompletely volatilized; when the temperature of the injection needle is too high, triethylamine is easy to decompose, the peak area of triethylamine is gradually increased along with the increase of the temperature of the injection needle, and when the temperature of the injection needle is selected to be 100 ℃, the peak area is not changed greatly, so that the temperature of the injection needle is selected to be 100 ℃ in an experiment;
therefore, the invention optimizes the headspace sampler conditions as follows: "heating equilibrium temperature: 75 ℃; the balance time is as follows: 1 min; transmission line temperature: 105 ℃; temperature of the sample injection needle: 100 ℃; constant temperature time of the headspace bottle: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1 mL' to ensure the accuracy of the sample measuring result, obtain reliable accuracy and precision, and is suitable for the analysis and detection of monoethylamine, diethylamine and triethylamine in the environment air and the fixed pollution source waste gas.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The detection method for detecting the organic amine in the ambient air and the waste gas is characterized by comprising the following steps of:
s1, sample collection:
air sample: adsorbing an environmental air sample and an air sample of a fixed pollution source inorganization emission monitoring point at a sampling point by using a silica tube, and collecting a 15min sample at a flow rate of 500ml/min by using an air sampler, wherein the sampling volume is 7.5L;
an exhaust gas sample: adsorbing the fixed pollution source waste gas sample on a silicon rubber tube at a sampling point, and collecting a 10min sample at a flow rate of 500ml/min by using a flue gas sampler, wherein the sampling volume is 5.0L;
blank sample: opening two ends of the silicone tube at a sampling point and immediately closing the silicone tube to obtain a blank sample;
s2, experimental conditions of the experimental instrument are as follows:
an experimental instrument: a headspace sample injector and a gas chromatograph;
the experimental conditions are as follows:
the conditions for the headspace sampler were as follows: heating equilibrium temperature: 75 ℃; headspace equilibrium time: 1 min;
transmission line temperature: 105 ℃; temperature of the sample injection needle: 100 ℃; heating balance time: 30 min; sample introduction time: 0.5 min; sample introduction volume: 1 mL;
the gas chromatograph operating conditions were as follows: capillary chromatographic column: HP-5MS (30 m.times.0.25 mm.times.0.25 μm); carrier gas: purity ≧ 99.999% of nitrogen, column flow rate: 1.0 mL/min; split-flow sample injection with a split-flow ratio of 10: 1; sample inlet temperature: 200 ℃; temperature rising procedure: the initial temperature is 40 ℃, the temperature is kept for 5min, and then the temperature is increased to 220 ℃ at the speed of 20 ℃/min; GC analysis time: 14 min;
s3, sample treatment: sequentially weighing 3.2g of sodium chloride and 1.0g of potassium sulfate in a headspace bottle, respectively pouring the front and rear end alkaline silica gels into two solvent headspace bottles, adding 10mL of 0.06mol/L dilute sulfuric acid solution, shaking uniformly, adding 500 mu L of 50% w/v sodium hydroxide solution and 100 mu L of 0.91g/mL ammonia water solution, immediately sealing the headspace bottle, shaking slightly until the salt is dissolved, carrying out ultrasonic desorption for 20min, and determining the content of organic amine according to an experimental instrument and experimental conditions in the step S2;
s4, establishing a working curve:
for ambient air and unstructured exhaust gas concentrations of 0-2.0 mg/L: respectively taking 20mg/L monoethylamine, diethylamine and triethylamine mixed standard use solutions, preparing at least 6-point standard series by using 0.06mol/L dilute sulfuric acid solution, wherein the mass concentrations of the monoethylamine, diethylamine and triethylamine are 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L and 2.0mg/L in sequence;
for the fixed pollutant source organized waste gas with the concentration of 0.5-40.0 mg/L: respectively taking 20mg/L monoethylamine, diethylamine and triethylamine mixed standard use solutions, preparing at least 6-point standard series by using 0.06mol/L dilute sulfuric acid solution, wherein the mass concentrations of the monoethylamine, diethylamine and triethylamine are 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L, 20.0mg/L and 40.0mg/L in sequence;
preparing a standard sample curve according to the sample treatment process in the step S3, sequentially injecting samples according to the concentration of a mixed standard use solution of monoethylamine, diethylamine and triethylamine from low to high, and establishing a working curve by taking the concentration mg/L of a standard series as a horizontal coordinate and the peak area of a corresponding chromatographic peak as a vertical coordinate.
2. The method as claimed in claim 1, wherein the silica gel tube is solvent-resolved, and the silica gel tube contains 200mg/100mg alkaline silica gel.
3. The method of claim 1, wherein the air injector has a flow rate in the range of 0.1L/min to 1.0L/min.
4. The method of claim 1, wherein the flow rate of the flue gas sampler is in the range of 0.1L/min to 2.0L/min.
5. The method of claim 1, wherein the headspace bottle is a 22ml glass bottle with a teflon-coated sealing cap and gasket.
6. The detection method for detecting the organic amine in the ambient air and the waste gas as claimed in claim 1, wherein the sodium chloride and the potassium sulfate are burned in a muffle furnace at 400 ℃ for 4h and cooled to room temperature for standby.
7. The method for detecting organic amine in ambient air and waste gas according to claim 1, wherein in step S3, 1.6mL of concentrated sulfuric acid is removed and added to the experimental water, and the solution is cooled, diluted and diluted to 500mL to obtain 0.06mol/L of dilute sulfuric acid solution.
8. The method of claim 1, wherein 50g of NaOH is dissolved in 50mL of test water to obtain 50% w/v NaOH solution in step S3.
9. The method of claim 1, wherein the test water is one of deionized water or distilled water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011449767.4A CN112684037B (en) | 2020-12-09 | 2020-12-09 | Detection method for determining organic amine in ambient air and waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011449767.4A CN112684037B (en) | 2020-12-09 | 2020-12-09 | Detection method for determining organic amine in ambient air and waste gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112684037A true CN112684037A (en) | 2021-04-20 |
| CN112684037B CN112684037B (en) | 2024-03-12 |
Family
ID=75448834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011449767.4A Active CN112684037B (en) | 2020-12-09 | 2020-12-09 | Detection method for determining organic amine in ambient air and waste gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112684037B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113624886A (en) * | 2021-08-20 | 2021-11-09 | 山东省环境保护科学研究设计院有限公司 | Method for measuring concentration of triethylamine in air of workplace |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050037386A1 (en) * | 2003-05-05 | 2005-02-17 | Drug Risk Solutions, L.L.C. | Composition and processes for analysis of pharmacologic agents in biological samples |
| CN103776931A (en) * | 2014-01-26 | 2014-05-07 | 山东安和安全技术研究院有限公司 | Measuring method of ethylamine in workplace air |
| CN107941926A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | A kind of assay method of triethylamine content |
-
2020
- 2020-12-09 CN CN202011449767.4A patent/CN112684037B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050037386A1 (en) * | 2003-05-05 | 2005-02-17 | Drug Risk Solutions, L.L.C. | Composition and processes for analysis of pharmacologic agents in biological samples |
| CN103776931A (en) * | 2014-01-26 | 2014-05-07 | 山东安和安全技术研究院有限公司 | Measuring method of ethylamine in workplace air |
| CN107941926A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | A kind of assay method of triethylamine content |
Non-Patent Citations (3)
| Title |
|---|
| IKUO UETA等: "Determination of Volatile Amines Using Needle-Type Extraction Coupled with Gas Chromatography–Barrier Discharge Ionization Detection", 《CHROMATOGRAPHIA》 * |
| 孙冬杰等: "毛细管色谱柱气相色谱法测定工作场所空气中三乙胺", 《中国卫生工程学》 * |
| 张存良等: "顶空-气相色谱法测定固定污染源废气中三甲胺的含量", 《理化检验（化学分册）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113624886A (en) * | 2021-08-20 | 2021-11-09 | 山东省环境保护科学研究设计院有限公司 | Method for measuring concentration of triethylamine in air of workplace |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112684037B (en) | 2024-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103226137B (en) | Method for determination of low-concentration H2S in air | |
| CN112684037A (en) | Detection method for determining organic amine in ambient air and waste gas | |
| CN108593606B (en) | Method for testing germanium content in coal by utilizing atomic fluorescence spectroscopy | |
| CN109001290A (en) | The measuring method of the nitrogen isotope ratio of nitrate granules object in a kind of atmospheric aerosol | |
| CN112129855A (en) | Method for measuring chloroacetic acid concentration in air by gas chromatography and application thereof | |
| CN110118840A (en) | The measuring method of organic amine in a kind of atmosphere PM2.5 | |
| CN111537631A (en) | Anti-oxidation sulfur dioxide ion chromatographic detection method | |
| CN110057934A (en) | A method of with ferrocene and bicyclopentadiene in GC-MS detection soil | |
| CN113740459B (en) | Method for detecting epichlorohydrin in domestic drinking water | |
| CN113607852B (en) | Method for measuring turpentine in soil | |
| CN111983062B (en) | Method for detecting trace DMAEA in air | |
| Yassaa et al. | Development and application of a headspace solid‐phase microextraction and gas chromatography/mass spectrometry method for the determination of dimethylsulfide emitted by eight marine phytoplankton species | |
| CN115266280B (en) | Method for detecting nitrogen and oxygen isotopes of nitrate | |
| CN113358769A (en) | Method for determining benzene series in water | |
| CN114660190A (en) | Method for detecting pesticide residue of weedicide in soil | |
| CN1624454A (en) | Determination method of microelement mercury in ferti lizer | |
| CN113624886A (en) | Method for measuring concentration of triethylamine in air of workplace | |
| CN108414661B (en) | Derivatization gas chromatography-mass spectrometry method for detecting ammonia content in biological sample | |
| CN112255323A (en) | Novel chlorine-enhanced ionization reagent for liquid chromatography-mass spectrometry detection and application thereof | |
| Dercksen et al. | Quantitative analysis of volatile sulfur compounds in beer using a membrane extraction interface | |
| CN111024858A (en) | Method for detecting alkane in drinking water | |
| CN114814040B (en) | Method for detecting residual quantity of methyl bromide in tea | |
| CN113960239B (en) | Method for detecting content of methyltrimethoxysilane by internal standard method | |
| CN115201367B (en) | Method for detecting sulfur-containing organic compounds in pollution sources | |
| CN115931747A (en) | Non-equilibrium analysis method for acid volatile sulfide in marine sediment |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |