GB 13015-1991 Pollution Control Standard for Waste Containing Polychlorinated Biphenyls
Some standard content:
National Standard of the People's Republic of China
Control standard on polychlorinatedbiphenyl wastes for wastes
Control standard on poly chlorinatedbiphenyl for wastes
GB13015—91
This standard is specially formulated for the management and treatment of biphenyl waste, to protect the environment and protect human health. 1 Subject content and scope of application
1.1 Subject content
This standard specifies the standard values ??for pollution control of waste containing polychlorinated biphenyl and the disposal methods of waste containing polychlorinated biphenyl. 1.2 Scope of application||tt ||This standard applies to the collection, storage, transportation, recycling, treatment and disposal of PCB-containing waste. 2 Terminology
2.1 Waste containing harmful PCBs refers to waste containing PCBs equal to or greater than the pollution control standard value and PCBs used as impregnating agents in waste power capacitors.
2.2 General PCB-containing waste refers to PCB-containing waste that is less than the pollution control standard value. 3 Standard value
Standard value item for pollution control of waste containing PCBs
from
PCB content
4 Disposal of waste containing PCBs| |tt||Standard value, mg/kg
50
4.1 Generally, waste containing PCBs should be stacked in the site designated by the environmental protection administrative department of the local people's government. 4.2 Disposal of waste containing hazardous PCBs: 4.2.1 Hazardous wastes with PCB content ≥50~≤500mg/kg are allowed to be disposed of by safe land filling technology or high-temperature burning technology.
4.2.2 Hazardous waste with a PCB content >500 mg/kg and PCBs used as impregnating agents in waste power capacitors must be disposed of using high-temperature incineration technology.
4.2.3 Temporary storage or sealing of wastes containing hazardous PCBs: When wastes containing hazardous PCBs are temporarily and unconditionally processed and disposed of, they should be temporarily stored or sealed in a centralized manner; the construction of centralized temporary storage or sealing warehouses should comply with Relevant regulations of the environmental protection administrative department of the People's Government. 5 Standard implementation
5.1 This standard is supervised and implemented by the environmental protection administrative department of the People's Government. It was approved by the State Environmental Protection Administration on 1991-06-27 and implemented on 1992-03-01
GB13015-91| |tt||5.2 When this standard cannot meet local environmental protection requirements, the people's governments of provinces, autonomous regions, and municipalities directly under the Central Government may formulate local standards that are stricter than this standard in accordance with relevant national regulations and report them to the environmental protection department of the State Council for filing6
Monitoring Method
See Appendix A (reference).
GB13015-91
Appendix A
Determination of polyfluorobiphenyls (PCBs) in waste
(reference)
It is a global environmental pollutant. It is a mixture of various chlorinated biphenyls. Most of the polychlorinated biphenyls used in domestic production are "trichlorobiphenyl" (PCB), which is used as an impregnating agent for power capacitors. The physical and chemical properties of polychlorinated biphenyls are similar to those of organofluorine pesticides, and they interfere with each other during gas chromatography measurement. Therefore, gas chromatography is used for quantification and thin layer chromatography for confirmatory testing. A1 Gas Chromatography
A1.1 This method uses alkaline hydrolysis to destroy the organochlorine pesticide BHC, steam distillation-liquid-liquid extraction (purification with sulfuric acid if necessary), and then determines it using electron capture detector gas chromatography. | |tt | Redistill again or purify with neutral aluminum oxide chromatography column. A1.2.2 Sulfuric acid: first grade pure.
A1.2.3 Potassium hydroxide: first grade pure.
A1.2.4 Anhydrous sodium sulfate; take 100g, add 50mL n-hexane, shake and filter, then add 25mL n-hexane, shake and filter, air-dry, and bake at 150°C for 15 hours.
A1.2.5 Absorbent cotton: Extract and treat with acetone for later use. A1.2.6 Standard solution of organofluorine pesticides: P, P\-DDE, prepared at 1.00PPm, and other organochlorine pesticides prepared at appropriate concentrations. A1.2.7 Polychlorinated bipin standard solution: Environmental analysis standard trichlorobiphenyl (PCB.) of the Environmental Science Committee of the Chinese Academy of Sciences (developed by the Institute of Environmental Chemistry, Chinese Academy of Sciences), prepared into a 5 mg/mL stock solution, and diluted to different concentrations standard solution. Or use PCB: n-hexane solution standard material (200PPm) (developed by the Ecological Environment Research Center of the Chinese Academy of Sciences) and dilute it into standard solutions of different concentrations. A1.3 Instrument
a.
Steam distillation-liquid-liquid extraction hood. See Figure A1. b.
Gas chromatograph with electron capture detector. c.
d.
e.
Electric heating jacket.
Voltage regulating transformer.
Drying tube.
A1.4 test
GB13015
5—91
E
Figure A1 Steam distillation-liquid-liquid extraction device
test The collection and preparation of samples (samples) are carried out in accordance with the provisions of Section 1.5 of Chapter 1 of the "Testing and Monitoring Methods for Harmful Characteristics of Industrial Solid Wastes" (Trial) issued by the State Environmental Protection Administration No. 86) Environmental Supervisory Office No. 114 ||tt ||A1.5.1 Alkaline hydrolysis and distillation
Accurately weigh 10 to 40g of air-dried waste sample (also weigh about 20g and dry it at 60°C for 24h to measure the moisture content), put it into a 10.00mL round In the bottom flask, add 250 mL of 1 mol/L potassium hydroxide solution, add a small amount of zeolite, install and connect A and B as shown in Figure A1, and heat to reflux for 1 hour (heat with a heating jacket and control the temperature with a voltage regulating transformer). Cool to room temperature, remove part B, add 5 mL of n-hexane to C, connect parts A, C, and D, heat and distill for 90 minutes, with a flow rate of 80 to 100 drops per minute (the heating and temperature control methods are the same as above) and the distillation is completed. Cool to room temperature, transfer the liquid in C into the separatory funnel, then connect parts A, C, and D, add 10 mL of distilled water from the upper part of the condenser tube to rinse, then merge the washing liquid in C into the separatory funnel, and shake thoroughly. Discard the water layer, then add a small amount of n-hexane and wash C2 times, combine the n-hexane layers (if there are many impurities, purify with sulfuric acid, add the same volume of sulfuric acid as the n-hexane extract, shake for 1 min, and let stand for layering) , discard the sulfuric acid layer. The number of purifications depends on the amount of impurities in the extract, usually 1 to 3 times. Then add 0.1mol/L sodium hydroxide solution of the same volume as n-hexane, shake for 1 minute, and let stand for layering. , discard the lower water layer), pass the n-hexane extract in the separatory funnel through a 5cm high anhydrous sodium sulfate dehydration column with absorbent cotton plugged at the bottom. Wash the separatory funnel 3 times with a small amount of n-hexane, and pass it through each time. Dehydration column, collect in 5 or 10mL volumetric flask, dilute to volume for chromatographic measurement.
A1.5.2 Chromatographic conditions
a.
Stationary phase: 5%SE-30/ChromosorbW (AW.DMCS), 80~100 ears. Chromatographic column: 2m long, 3mm inner diameter glass column. b.
c.
The column temperature is 195℃.
dGasification temperature: 250℃.
Detection temperature: 240℃.
e.
f.
Carrier gas: high purity nitrogen, flow rate is 70mL/min. A1.5.3 Quantitative determination
Dilute the PCB standard solution to different concentrations and inject quantitatively to determine the linear range of the electron capture detector. When measuring the sample, compare the peak height obtained by quantitative injection (should be within the linear range) with the peak height of the standard solution of similar concentration to calculate the PCB content.
A1.6 calculation
GB13015-91
PCB content (mg/kg) = N scale×Vz×hm×VhsXV#XW
where : N standard - standard solution concentration tg/mL
V standard - standard solution chromatographic injection volume, uL: h select sample extraction solution peak height, mm;
V - after concentration of the extract solution Volume, mL
h standard---peak height of standard solution, mm;
V sample--sample extraction liquid chromatography injection volume, uL; W---weight of sample, g (Calculated based on the weight of the sample dried at 60°C). A1.7 Accuracy and precision
The recovery rate of this method is 101% ~ 116%, and the coefficient of variation is 4.9%. Note: Regarding the quantitative calculation method of polychlorinated biphenyl, there are many expression methods because it is a mixture. In view of the fact that domestic waste is mainly contaminated by "trioxybiphenyl\(PCB)", if the peak shape of the sample and standard material (PCB,) There is no big difference, you can use a specific peak height, with P,The retention value of P\DDE is 100. Select the peak with a relative retention value of 38\ or use the full peak height or select several peak heights and calculate the content. A2 thin layer chromatography
A2.1 The physical and chemical properties of polychlorinated biphenyls are similar to those of organochlorine pesticides, so confirmatory tests are indispensable when analyzing and measuring. The same gas chromatography method uses alkaline hydrolysis to destroy organochlorine pesticides, steam distillation-liquid-liquid extraction, and sulfuric acid purification, and then uses a combination of adsorption thin-layer and reverse-phase distribution thin-layer chromatography to compare with the standard and conduct a confirmation experiment. A2.2 Reagent
A2.2.1 n-hexane: Redistillate with an all-glass still and collect the 68-70C fraction. A2.2.2 Methanol: analytical grade.
A2.2.3
Axillary paraffin: Level 2.
Silica Gel: Qingdao Marine Chemical Plant.
A2.2.4
Silicone GFas: E.Merck.
A2.2.5
A2.2.6
Chromogen: Dissolve 2g of silver nitrate in 10mL of distilled water, add an appropriate amount of methanol to 100mL, and mix well. A2.2.7
PCB standard solution: the same as the PCB standard solution used in gas chromatography. A2.2.8 Preparation of thin-layer plate:
a.
Adsorption silica gel thin-layer plate: Weigh 15g of silica gel G or GF254 and add about 40ml of distilled water, and spread it according to the conventional method (200tmm×200mm) Thin-layer plates with a thickness of 0.25 mm were heated and activated at 105°C for 1 hour, and stored in an anhydrous calcium chloride desiccator for later use. b. Reverse-phase distribution silica gel thin layer plate: Weigh 27g of silica gel G or GF254 in a stoppered Erlenmeyer flask, add 3 liquid paraffin and 60mL = methyl chloride, shake, and spread into a thin layer (200mm×200mm) with a thickness of 0.25mm. plate, air-dry at room temperature, and store in an airtight container until further use.
A2.3 instrument
UV lamp: wavelength 254~360nm.
a.
b.
Microsyringe.
Paving instrument.
c
d. Sprayer.
e. Expansion cylinder: 200mm×190mm×100mm. A2.4
A2.4.1 Adsorption thin layer chromatography qualitative test
CB13015--91
Place the sample solution and standard solution for gas chromatography measurement at each point. Place different amounts on the silica gel G or GF254 thin-layer plate, use n-hexane as the developing agent, and expand 10 to 12cm using the rising method. Take out the thin-layer plate. After airing at room temperature, place the silica gel G plate under a UV lamp at a distance of 10cm. Irradiate for about 30 minutes, then spray with methanol solution of silver nitrate to develop color, put it under the UV lamp again in the same way, and irradiate for 1 minute, take out and observe the R position after the spots have expanded, compare the sample with the standard solution to determine the quality, or put the silica gel GF254 plate , under ultraviolet light, observe the R: value position after the spots are expanded, and compare the sample with the standard solution to make a qualitative determination. A2.4.2 Reversed-phase distribution thin-layer chromatography confirmation test uses a reverse-phase distribution thin-layer plate. The developing agent is methanol: water = 9:1. The other operating steps are the same as those for the adsorption thin layer (if necessary, one or three times of development can be performed) . Observe the R value position after the spots are expanded, and compare the sample with the standard solution to confirm. After the adsorption thin layer is spread out, the R values ??of various polyfluorobiphenyls are close to each other and appear as a circular spot. When the sample contains P,P'-DDE, its R value is close to that of polyazobiphenyls and interferes with polychlorinated biphenyls (see Figure A2). Therefore, the R value of adsorption thin layer chromatography cannot be used to confirm polychlorinated biphenyls. Benzene should also be confirmed by combining reversed phase distribution thin layer chromatography characteristics. 0.8 | | tt | | 0.6 | | tt | ||1—P,P-DDT: 2O.P-DDT; 3-P, P'-DDE, 4-Aroclor1242; 5-PCBs; 6—Aroclor1254; 7—PC13g various polychlorinated biphenyls through reversed phase distribution After the thin layer chromatography was developed, several circular spots in a series and overlapping each other appeared (spot R, the value temporarily varies with the number of chlorine contained in the polyazobiphenyl, see Figure A3), which is the polyazobiphenyl. It has unique chromatographic behavior characteristics, which can be used for confirmation tests. However, organochlorine pesticides such as P, P\-DDE only detect a spot and do not interfere with the confirmation of polyfluorobiphenyls. -1.0
+0.9
0.8
-0.7
+0.6
.5
0.4
0.3|| tt||-0.2
o
GB13015-91
o
8
88
0.1
fo123+ 6+#90n
Figure A3 Thin layer chromatography of PCB and DDE on reversed phase distribution silica gel GF254
1—P,P'-DDT;2--O,P-DDT;3- P,P'-DDE;4Aroclor1232,5--Aroclor1242;6-PCBs;7-KC-400;8-Aroclor1254;9-PCBs;10-Aroclor1260;11Decachlorobiphenyl
Note: R value The minimum detectable amount is different due to factors such as experimental conditions, so the standard solution should be used for qualitative confirmation. The experimental data of R: value and minimum detection base given here (see Table A1, Table A2) are for reference only. Table A1PCB and DDE adsorption thin layer R, value and minimum detection amount Ri value
product
name
silica gel G
P, P-DDT||tt ||O,P'-DDT
P,P'-DDE
P,P\-DDD
Aroclor1232
Araclor1242
PCBa|| tt||KC-400
Aroclor1254
0.37
0.43
0.51
0.53
0.53
0.54|| tt||Silicone GF914
0.30
0.37
0.45
0.20
0.39
0.42
0.42||tt ||0.44
0.47
minimum detection amount, g
silica gel G
a
b
0.1~0.2||tt ||a
b
0.05~~0.1
a
b
0.1~0.2
b
0.15 ~0.30
a
b
0.15~0.30
a
b
0.2~0.4
Silicone GF254| |tt||0.1
0.1
0.05
0.36
0.25
0.15
0.15
0.25||tt ||0.20
Product
Name
PCB
Aroclor126c
Decacyanobiphenyl
Silicone G
0: 51
GB13015—91
Continued Table A1
Rr value
Silicone GF2s4
0. 47
0.48
Origin
Note: A series shows spots after being left for 8 hours after irradiation, B series shows spots immediately. Silicone G
a
Minimum detection period
Silica gel GF254
b
0. 2~0. 4
Table A2PCB Reverse phase distribution with DDE and other thin layer R value and minimum detection amount Rr value
product
name
silica gel G
P,P'-DDT||tt ||P'-DDT
P,P'-DDE
Aroclor1242
PCB3
Aroclor1254
PCB;
0.41|| tt||0.38
0.35
d
0.27~0.69
c
d
0.25~0.70
e
d
0.13~0.47
e||tt ||d
0.15~0.48
Note: c is the R value from the lower end of the spot, d is the R value from the upper end of the spot. Additional notes:
This standard is proposed by the National Environmental Protection Administration. Silicone GFi34
0.48
0.41
0.34
c
d
0.200.50
c||tt| |d
0.23~0.52
c
d
0.18~0.35
c
d
0.19~0.38
This standard is drafted by the Ecological Environment Research Center of the Chinese Academy of Sciences. The National Environmental Protection Administration is responsible for interpreting this standard. The main drafters of this standard are Wang Jide and Zhuang Shuihui. Minimum detection amount, μg
0. 20www.bzxz.net
0.45
Silica gel GF254
Silica gel G
0.2
0.1||tt| |0.2
1
1
1
1
0.4
0. 2
0. 4|| tt||1
0.5
0. 4
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