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HJ 1006-2018Stationary source emission - Determination of volatile halogenated hydrocarbons - Bags sampling-gas chromatography (English PDF)

固定污染源废气挥发性卤代烃的测定气袋采样-气相色谱法

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

December 26, 2018

Implementation date

June 1, 2019

Scope

HJ 1006-2018 is the English-translated version of 固定污染源废气挥发性卤代烃的测定气袋采样-气相色谱法.

HJ 1006-2018 — Air bag sampling - gas chromatography 1 Scope of application this standard specifies gas chromatography for the determination of volatile halogenated hydrocarbons in fixed source exhaust gases.

This standard is applicable to methyl chloride, vinyl chloride, methyl bromide, ethyl bromide, chloropropene, dichloromethane in fixed pollution source exhaust gas.

Chloroprene, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethylene, 1,2-dichloropropane, epichlorohydrin, Determination of 14 volatile halogenated hydrocarbons such as tetrachloroethylene.

When the injection volume is 1.0 ml, the detection limit of the method is 0.0003 mg/m3 to 0.6 mg/m3, and the lower limit of determination is 0.0012 mg/m3 to 2.4 mg/m3, see Appendix A for details.

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Document preview — HJ 1006-2018

National Standard of the People's Republic of China

Classification: Z 25

Issued by: Ministry of Ecology and Environment

Foreword
1 Determination of volatile halogenated hydrocarbons from fixed pollution sources
2 Normative references
3 Principle of the method
4 Reagents and materials
5 Methyl chloride, vinyl chloride, epichlorohydrin 50.0
36 Samples

Foreword

To protect the "Environmental Protection Law of the People's Republic of China" and the "Air Pollution Control Law of the People's Republic of China" this standard is formulated to ensure the health of human body and to regulate the determination of volatile halogenated hydrocarbons in fixed source waste gas.

This standard specifies gas chromatography for the determination of volatile halogenated hydrocarbons in fixed source exhaust gases.

Appendix A of this standard is a normative appendix, and Appendix B is an informative appendix.

This standard is the first release.

This standard is formulated by the Department of Eco-Environmental Monitoring, the Department of Regulations and Standards of the Ministry of Ecology and Environment.

This standard was drafted. Dalian Environmental Monitoring Center.

This standard is verified by. Shenyang Environmental Monitoring Center Station, Qingdao Environmental Monitoring Center Station, and Anshan City Environmental Monitoring Xinzhan, Tianjin Ecological Environment Monitoring Center, Fushun Environmental Monitoring Center Station and Xiamen Environmental Monitoring Center Station.

This standard is approved by the Ministry of Ecology and Environment on December 26, 2018.

This standard has been implemented since June 1, 2019.

This standard is explained by the Ministry of Ecology and Environment.

1 Determination of volatile halogenated hydrocarbons from fixed pollution sources

Air bag sampling - gas chromatography

1 Scope of application this standard specifies gas chromatography for the determination of volatile halogenated hydrocarbons in fixed source exhaust gases.

This standard is applicable to methyl chloride, vinyl chloride, methyl bromide, ethyl bromide, chloropropene, dichloromethane in fixed pollution source exhaust gas.

When the injection volume is 1.0 ml, the detection limit of the method is 0.0003 mg/m3 to 0.6 mg/m3, and the lower limit of determination is 0.0012 mg/m3 to 2.4 mg/m3, see Appendix A for details.

2 Normative references

This standard refers to the following documents or their terms. For undated references, the valid version applies to this standard.

GB/T 16157 Determination of particulate matter in fixed pollution source exhaust gas and sampling method of gaseous pollutants HJ 732 Sampling air bag method for fixed volatile waste gas HJ/T 48 soot sampler technical conditions HJ/T 397 Fixed Source Exhaust Gas Monitoring Technical Specification

3 Principle of the method

The volatile halogenated hydrocarbons in the fixed pollution source are collected in air bags, directly injected, separated by gas chromatography, and electron trapped.

Detected by an detector (ECD), characterized by retention time, and quantified by external standard method.

4 Reagents and materials

4.1 Volatile halogenated hydrocarbon standard gas. Purchase commercially available certified standard gas. See Table 1 for reference concentrations.

Table 1 Reference concentration of each component in the mixed gas

Serial number compound name Standard gas volume fraction (µmol/mol) 1 carbon tetrachloride, tetrachloroethylene 0.0100 2 chloroform, trichloroethylene 0.100 3 chloroprene 1.00 4 dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, methyl bromide, ethyl bromide, chloropropene 10.0 2 continued Serial number compound name Standard gas volume fraction (µmol/mol)

5 Methyl chloride, vinyl chloride, epichlorohydrin 50.0

4.2 Nitrogen. purity >= 99.999%.

5 instruments and equipment

5.1 Gas Chromatograph. with split/splitless inlet, electron capture detector (ECD).

5.2 Quartz capillary column. 30 m × 0.25 mm × 1.40 µm, stationary phase 6% cyanopropyl phenyl and 94% dimethyl polysilicon Oxytomane. Other equivalent capillary columns can also be used.

5.3 Air bag. Polyvinyl fluoride (PVF) material or other equivalent material air bag.

5.4 Air bag sampling system. see Figure 1.

1-exhaust pipe; 2-glass wool filter; 3-Teflon connecting pipe; 4-heated sampling pipe; 5-fast joint male head; 6-fast joint female head;

7-air bag; 8-vacuum box; 9-valve; 10--activated carbon filter; 11-exhaust pump.

Figure 1 Air bag sampling system

5.5 Sampling tube. hard glass or polyethylene. The inner diameter should be greater than 6 mm and should be attached to a temperature above 120 °C.

Insulation jacket.

5.6 Smoke sampler. It has the module to measure the moisture content of the flue gas and the temperature of the flue gas. The performance of the instrument complies with the requirements of HJ/T 48.

5.7 Gas dilution unit. Accuracy is better or better than 2%.

5.8 Oven. The temperature can reach 130 ° C with an accuracy of ± 1 ° C.

5.9 Hermetic syringe. 1.0 ml.

5.10 Common instruments and equipment used in general laboratories.

36 Samples

6.1 Sample collection

6.1.1 Fixed pollution source exhaust sampling position and sampling point, sampling frequency, sampling time and sampling operation Relevant provisions of GB/T 16157, HJ/T 397 and HJ 732.

6.1.2 Connect the air bag sampling device (5.4) as shown in Figure 1. Start the air pump and turn off the air pump after the bag is full.

Remove the sampling bag seal. If the temperature of the exhaust gas in the exhaust pipe is higher than the ambient temperature during sampling, turn on the sampling tube (5.5) for heating.

For the power supply, heat the sampling tube (5.5) to 120 °C ± 5 °C.

6.1.3 Determine the moisture content in the exhaust pipe by the smoke sampler (5.6). The operation steps are related to GB/T 16157.

Provisions.

Note. This method can only collect samples with temperatures below 150 °C.

6.2 Transport blank sample Take a sample and collect an air bag of the same batch, fill it in the laboratory with nitrogen, and bring it to the sampling site without sample collection.

Shipped back to the laboratory along with the sample as a blank sample for transport.

6.3 Sample preservation Samples were stored in the dark after collection and analyzed within 24 h after sampling.

6.4 Laboratory blank samples Take a sample of the same batch of an air bag, fill the laboratory with nitrogen, save the laboratory in the dark, as a laboratory empty White sample.

7 Analysis steps

7.1 Instrument Reference Conditions Inlet temperature. 150 ° C; detector temperature. 280 ° C; column flow. 1.5 ml/min; split ratio. 5.1;

Flow rate. 60 ml/min; temperature program. 38 ° C for 1.8 min, ramp up to 120 ° C at 10 ° C/min, then 15 ° C /min The rate is raised to 240 ° C for 2 min.

Injection volume. 1.0 ml.

7.2 Calibration

7.2.1 Establishment of the standard curve the volatile halogenated hydrocarbon standard gas (4.1) is diluted 100 times, 50 times, 20 by gas dilution device (5.7) Times, 10 times and 5 times, formulated into a series of standard use gas (currently used), according to the instrument reference conditions for injection analysis. Take the volume fraction of the target is the abscissa, and the corresponding peak area or peak height is plotted on the ordinate to establish a standard curve.

47.2.2 Standard chromatogram

The standard sample reference chromatogram of 14 volatile halogenated hydrocarbons under the reference conditions of this standard is shown in Figure 2.

1-chloromethane; 2-chloroethylene; 3-bromomethane; 4-bromoethane; 5-chloropropene; 6-dichloromethane; 7-chlorobutadiene; 8-trichloromethane;

9-carbon tetrachloride; 10-1,2-dichloroethane; 11-trichloroethylene; 12-1,2-dichloropropane; 13-epichlorohydrin; 14-tetrachloroethylene.

Figure 2 Standard sample reference chromatogram of 14 volatile halogenated hydrocarbons

7.3 Sample determination the inner wall of the sample air bag must be observed before sample analysis. If there is droplet condensation, the air bag should be placed in the oven.

After heating at 50 ° C for 1 min or more, it was confirmed that the droplet condensation phenomenon was eliminated, and the air bag sampling analysis was quickly taken out.

Pipette 1.0 ml of the sample with a gas tight syringe (5.9) and inject it into the gas chromatograph (5.1) or through 1.0 ml.

Quantitative loop or autosampler injection, measured according to the same conditions as the establishment of the standard curve, record the retention time of the chromatographic peak, Peak area or peak height.

7.4 Blank test

Transport blank samples (6.2) and laboratory blank samples (6.4) were determined according to the same procedure as for sample determination (7.3).

8 Calculation and representation of results

8.1 Qualitative analysis Qualitative according to the retention time of the target compound.

8.2 Calculation of results the mass concentration rho of the volatile halogenated hydrocarbon (based on the dry gas volume in the standard state) is calculated according to formula (1).

4.22) 1 ( × -

Xsw

DM phi

Where. rho--the mass concentration of volatile halogenated hydrocarbons in the sample, mg/m3;

M--the molar mass of a target compound, g/mol;

D--sample dilution factor;

5phi--the volume fraction of a target compound obtained from a standard curve, µmol/mol;

Xsw--volume percentage of moisture content in exhaust gas, %;

22.4--The molar volume of gaseous molecules in the standard state, L/mol.

8.3 Result representation the retention of the number of digits after the decimal point of the measurement result is consistent with the method detection limit, and at most three significant digits are reserved.

9 Precision and accuracy 9.1 precision Six laboratories performed six repeated measurements on low, medium and high blank spiked samples, respectively.

The standard deviations were 4.4% to 13%, 2.4% to 12%, and 1.8% to 8.4%, respectively; the relative standard deviations between laboratories were 1.9% to 7.3%, 2.1% to 7.7%, and 1.8% to 5.6%; the repeatability limits are. 0.0001 mg/m3 to 0.4 mg/m3, 0.0005 mg/m3 to 1.5 mg/m3 and 0.0017 mg/m3 to 5.0 mg/m3; the reproducibility limits are. 0.0001 mg/m3~ 0.4 mg/m3, 0.0006 mg/m3 to 1.5 mg/m3 and 0.0022 mg/m3 to 5.1 mg/m3.

Refer to Appendix B for details of the method precision summary data.

9.2 Accuracy

Six laboratories performed six repeated measurements on low, medium and high blank spiked samples, and added standard recovery.

The average values are 77.4% to 83.9%, 80.7% to 93.5%, and 92.4% to 100%, respectively.

The method accuracy summary data is detailed in Appendix B.

10 Quality Assurance and Quality Control

10.1 At least one transport blank sample and one laboratory blank sample shall be prepared for each batch of samples, and the measured value shall be lower than the method detection.

limit.

10.2 The correlation coefficient of the standard curve is r >= 0.99; for each batch (<= 20 samples), a curve intermediate check point shall be determined.

The relative error of the concentration corresponding to the standard curve and the standard curve should be within ±20%.

11 Waste treatment

The waste generated by the experiment shall be collected and stored in a separate manner, safely disposed of as required or entrusted to a qualified unit for disposal.

12 Precautions

12.1 When the sampling air bag is used repeatedly, a blank test should be carried out after cleaning. If the measurement result is lower than the method detection limit, the air bag can continue to be used, otherwise it must be discarded.

12.2 The position of the inlet of the sampling pipe should be as close as possible to the center of the discharge pipe, and the length of the sampling pipe should be as short as possible.

6 Appendix A

(normative appendix) Target detection limit and lower limit of measurement the method detection limits and lower limit of determination for 14 targets are shown in Table A.1.

Table A.1 Detection limits and lower limit of determination of target

No. Compound name English name CAS No.

The detection limit

(mg/m3)

Lower limit of measurement (mg/m3) 1 methyl chloride Methyl chloride 74-87-3 0.4 1.6

2 Vinyl chloride 75-01-4 0.3 1.2 3 methyl bromide Methyl bromide 74-83-9 0.2 0.8

4 Bromoethane 74-96-4 0.2 0.8

5 Chloropropene Allyl chloride 107-05-1 0.09 0.36

6 Dichloromethane Dichloromethane 75-09-2 0.3 1.2 7 chloroprene 2-Chloro-1,3-butadiene 126-99-8 0.02 0.08 8 chloroform Chloroform 67-66-3 0.003 0.012

9 Carbon tetrachloride Carbon tetrachloride 56-23-5 0.0003 0.0012 10 1,2-Dichloroethane 1,2-Dichloroethane 107-06-2 0.2 0.8

11 Trichloroethylene Trichloroethylene 79-01-6 0.005 0.02 12 1,2-dichloropropane 1,2-Dichloropropane 78-87-5 0.4 1.6

13 Epichlorohydrin Epichlorohydrin 106-89-8 0.6 2.4

14 Tetrachloroethylene 127-18-4 0.0004 0.0016

7 Appendix B

(informative appendix) Method precision and accuracy the precision summary data of the method is shown in Table B.1, and the accuracy summary data is shown in Table B.2.

Table B.1 Precision summary data

Compound blank spiked sample concentration determination average Value (mg/m3) Laboratory room Relative standard deviation(%) Laboratory room Relative standard deviation(%) Repeatability limit r (mg/m3) Reproducibility limit Name (µmol/mol) (mg/m3) (mg/m3) Methyl chloride 0.625 1.41 1.15 5.3~8.4 4.4 0.2 0.3 2.5 5.64 4.55 2.4~6.4 2.1 0.6 0.6 10 22.5 20.8 1.9~5.0 2.6 2 2.4 Vinyl chloride 0.625 1.74 1.37 6.0~8.8 4.4 0.3 0.3 2.5 6.98 5.75 3.8~6.4 2.7 0.9 0.9 10 27.9 25.9 1.8~6.9 2.3 2.5 2.9 Methyl bromide 0.125 0.53 0.41 4.7~9.8 2.2 0.1 0.1 0.5 2.12 1.86 6.5~9.1 7 0.4 0.5 2 8.48 8.18 3.5~5.0 3 1 1.1 Bromoethane 0.125 0.61 0.48 5.6~8.2 2.2 0.1 0.1 0.5 2.43 2.26 2.7~9.1 5.3 0.4 0.5 2 9.73 9.39 2.5~7.9 3.3 1.4 1.6 Chloropropene 0.125 0.427 0.341 6.1~9.4 4.4 0.07 0.08 0.5 1.71 1.54 5.6~10 3.5 0.32 0.33 2 6.83 6.46 3.0~7.8 1.8 1 0.98 Dichloromethane 0.125 0.47 0.37 5.1~8.8 2.6 0.1 0.1 0.5 1.9 1.69 6.4~9.4 2.9 0.4 0.4 2 7.58 7.39 3.3~5.9 4 0.9 1.2 Chloroprene 0.0125 0.049 0.039 5.1~11 2.4 0.01 0.01 0.05 0.198 0.176 6.4~9.4 3 0.04 0.04 0.2 0.791 0.735 3.3~4.9 2.1 0.09 0.09 Trichloromethane 0.00125 0.0067 0.0056 4.4~9.3 6.1 0.001 0.001 0.005 0.0266 0.0239 5.1~9.7 5 0.005 0.006 0.02 0.107 0.102 2.5~6.2 3.9 0.013 0.016 Carbon tetrachloride 0.000125 0.00086 0.0007 4.9~8.2 1.9 0.0001 0.0001 0.0005 0.00343 0.00319 4.0~6.9 4.9 0.0005 0.0006 0.002 0.0137 0.0134 3.4~5.6 3.9 0.0017 0.0022 1,2-dichloroethane 0.125 0.55 0.44 4.6~10 3.3 0.1 0.1 0.5 2.21 1.95 6.9~12 3 0.5 0.5 2 8.84 8.48 4.0~8.4 2.9 1.5 1.5 8 continued Compound blank spiked sample concentration determination average Value (mg/m3) Laboratory room Relative standard deviation(%) Laboratory room Relative standard deviation(%) Repeatability limit r (mg/m3) Reproducibility limit Name (µmol/mol) (mg/m3) (mg/m3) Trichloroethylene 0.00125 0.0073 0.006 5.3~9.3 7.3 0.001 0.002 0.005 0.0293 0.0274 3.7~8.5 5.1 0.006 0.006 0.02 0.117 0.113 3.1~7.7 5.2 0.015 0.021 1,2-dichloropropane 0.125 0.63 0.5 5.2~8.6 3.6 0.1 0.1 0.5 2.52 2.3 6.1~8.3 3.8 0.4 0.5 2 10.1 9.84 3.5~8.3 4.4 1.5 1.8 Epichlorohydrin 0.625 2.58 2.01 5.4~9.3 3.4 0.4 0.4 2.5 10.3 8.8 5.1~7.6 2.4 1.5 1.5 10 41.3 39.4 3.5~5.4 2.1 5 5.1 Tetrachloroethylene 0.000125 0.00093 0.00078 6.5~13 3 0.0002 0.0002 0.0005 0.0037 0.00329 6.6~8.1 7.7 0.0007 0.0009 0.002 0.0148 0.0148 2.3~6.8 5.6 0.0018 0.0028

Table B.2 Accuracy summary data

Compound name

Blank spiked sample concentration Mean value (mg/m3) (%) (%) _2 SP ± (%) (µmol/mol) (mg/m3) Methyl chloride 0.625 1.41 1.15 81.6 3.7 81.6±7.4 2.50 5.64 4.55 80.7 1.7 80.7±3.4 10.0 22.5 20.8 92.4 2.5 92.4±5.0 Vinyl chloride 0.625 1.74 1.37 78.7 3.4 78.7±6.8 2.50 6.98 5.75 82.4 2.2 82.4±4.4 10.0 27.9 25.9 92.8 2.2 92.8±4.4 Methyl bromide 0.125 0.53 0.41 77.4 1.7 77.4±3.4 0.500 2.12 1.86 87.7 6.1 87.7±12.2 2.00 8.48 8.18 96.5 2.9 96.5±5.8 Bromoethane 0.125 0.61 0.48 78.7 1.6 78.7±3.2 0.500 2.43 2.26 93.0 5.0 93.0±10.0 2.00 9.73 9.39 96.5 3.1 96.5±6.2 Chloropropene 0.125 0.427 0.341 79.9 3.6 79.9±7.2 0.500 1.71 1.54 90.1 3.2 90.1±6.4 2.00 6.83 6.46 94.6 1.7 94.6±3.4 Dichloromethane 0.125 0.47 0.37 78.7 3.4 78.7±6.8 0.500 1.90 1.69 88.9 2.6 88.9±5.2 2.00 7.58 7.39 97.5 3.8 97.5±7.6 Chloroprene 0.0125 0.049 0.039 79.6 2.0 79.6±4.0 0.0500 0.198 0.176 88.9 2.7 88.9±5.4 9 continued Compound name Blank spiked sample concentration Mean value (mg/m3) (%) (%) _2 SP ± (%) (µmol/mol) (mg/m3) Chloroprene 0.200 0.791 0.735 92.9 2.0 92.9±4.0 Trichloromethane 0.00125 0.0067 0.0056 83.4 5.2 83.4±10.4 0.00500 0.0266 0.0239 89.8 4.4 89.8±8.8 0.0200 0.107 0.102 95.3 3.7 95.3±7.4 Carbon tetrachloride 0.000125 0.00086 0.00070 81.4 1.5 81.4±3.0 0.000500 0.00343 0.00319 93.0 4.4 93.0±8.8 0.00200 0.0137 0.0134 97.8 3.8 97.8±7.6 1,2-dichloroethane 0.125 0.55 0.44 80.0 2.6 80.0±5.2 0.500 2.21 1.95 88.2 2.6 88.2±5.2 2.00 8.84 8.48 95.9 2.7 95.9±5.4 Trichloroethylene 0.00125 0.0073 0.0060 82.2 5.8 82.2±11.6 0.00500 0.0293 0.0274 93.5 4.7 93.5±9.4 0.0200 0.117 0.113 96.6 5.1 96.6±10.2 1,2-dichloropropane 0.125 0.63 0.50 79.4 2.9 79.4±5.8 0.500 2.52 2.30 91.3 3.5 91.3±7.0 2.00 10.1 9.84 97.4 4.2 97.4±8.4 Epichlorohydrin 0.625 2.58 2.01 77.9 2.6 77.9±5.2 2.50 10.3 8.80 85.4 2.0 85.4±4.0 10.0 41.3 39.4 95.4 2.0 95.4±4.0 Tetrachloroethylene 0.000125 0.00093 0.00078 83.9 2.6 83.9±5.2 0.000500 0.00370 0.00329 88.9 7.0 88.9±14.0 0.00200 0.0148 0.0148 100 5.6 100±11.2

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This preview omits tables, figures, formulas and parts of the technical clauses. The complete document — 9 pages — is available in the English PDF.

Referenced standards

Normative references

GB/T 16157Determination of particulates and sampling methods of gaseous pollutants emitted from exhaust gas of stationary source

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