Some standard content:
GB18188.1—2000
This standard is prepared in accordance with the Environmental Protection Law of the People's Republic of China and the Marine Environment Protection Law of the People's Republic of China. This standard refers to the technical contents of standards and guidelines such as the International Maritime Organization's Guide to the Application of Oil Spill Dispersants Including Environmental Considerations, the UK's Oil Spill Dispersant Specifications, the US Federal Regulations 40CFR300J\Use of Dispersants and Other Chemicals and Appendix C of 40CFR300, Canada's Guide to the Approval and Application of Oil Spill Dispersants, and Japan's Performance Test Standards for Oil Spill Treatment Agents. It is completed on the basis of summarizing the technical conditions of oil spill dispersants at home and abroad and the scientific and technological progress in this field, combined with national conditions and through necessary experimental verification. This standard will provide unified quality standards and technical requirements for the use of oil spill dispersants in the waters under the jurisdiction of the People's Republic of China. GB18188.118188.2--2000 includes two parts under the general title of "Oil Spill Dispersants": Part 1 "Technical Conditions for Oil Spill Dispersants"; Part 2 "Guidelines for the Use of Oil Spill Dispersants". This standard is Part 1. Appendix A, Appendix B, Appendix C and Appendix D of this standard are all appendices to the standard. This standard is proposed by the Ministry of Transport of the People's Republic of China. This standard is under the jurisdiction of the Maritime Safety Administration of the People's Republic of China. The drafting units of this standard are: Water Transport Research Institute of the Ministry of Transport, Maritime Safety Administration of the People's Republic of China, and Standard Metrology Institute of the Ministry of Transport. The main drafters of this standard are: Zhang Xiuzhi, E Hailiang, Hu Huanxiu, Li Yun, and Zhao Qian. 248
National Standard of the People's Republic of China
Oil spill dispersant
Technical conditions
Oil spill dispersant--Technical regulationsGB 18188.1—2000
This standard specifies the classification, performance indicators, test methods, inspection rules, signs, labels, instructions for use, packaging, storage and disposal of expired products of oil spill dispersants.
This standard applies to oil spill dispersants used in waters under the jurisdiction of the People's Republic of China. 2 Reference standards
The provisions contained in the following standards constitute the provisions of this standard through reference in this standard. When this standard is published, the versions shown are valid. All standards will be revised, and parties using this standard should explore the possibility of using the latest version of the following standards. GB/T265-1988 Determination of kinematic viscosity and calculation of dynamic viscosity of petroleum products GB/T267—1988 Determination of flash point and fire point of petroleum products (open cup method) GB/T7488—1987 Determination of five-day biochemical oxygen demand (BODs) of water quality Dilution and inoculation method
GB/T11914-1989 Determination of chemical oxygen demand of water quality Dichromate method GB/T 13267—1991
3 Definitions
This standard adopts the following definitions.
Determination of acute toxicity of substances to freshwater fish (zebrafish) 3.1 Oil spill dispersant Chemical preparations that can emulsify, disperse or dissolve floating oil on the water surface in water bodies. Oil spill dispersants are composed of a mixture of surfactants and solvents.
3.2 the water areas under the jurisdiction of the People's Republic of China
This standard refers to the waters to which the Marine Environment Protection Law and the Water Pollution Prevention and Control Law apply. 4 Classification
Oil spill dispersants are divided into two categories: conventional dispersants and concentrated dispersants. 4.1 Conventional dispersants are composed of a mixture of fat solvents and surfactants, and the content of surfactants does not exceed 30%. Conventional dispersants cannot be used after dilution with water.
4.2 Concentrated dispersants usually contain oxidized aliphatic hydrocarbon solvents, and the content of surfactants is generally 50% to 75%. Concentrated dispersants are divided into two types: dilutable or non-dilutable. 5 Performance indicators
The performance indicators of oil spill dispersants are shown in Table 1.
Approved by the State Administration of Quality and Technical Supervision on September 7, 2000, and implemented on October 1, 2001
6 Test methods
Emulsification rate, %
GB 18188.1—2000
Table 1 Performance indicators of oil spill dispersants
Kinematic viscosity (30C).mm/s
10 min
Acute toxicity to fish - half lethal time at specified concentration, hBOD
Biodegradability BOD, %
6.1 See Table 2 for the test methods of oil spill dispersants. Table 2
Flash point, C
Kinematic viscosity (30C).mm2/s
Emulsification rate, %
10 min
Acute toxicity to fish - half lethal time at specified concentration.hBOD
BiodegradabilityCOD, %
Performance index
Clear, transparent, no stratification
Test method
pH test paper
GB/T 267
GB/T265
Appendix A (Appendix to the standard) Emulsification rate test method Appendix B (Appendix to the standard) Fish acute toxicity test method Appendix C (Appendix to the standard) Biodegradability test method The test results of each item of oil spill dispersant shall meet the performance index requirements of Chapter 5. 6.2
Inspection rules
The inspection of oil spill dispersant includes type inspection and factory inspection. 7.1 Type inspection
7.1.1 Oil spill dispersants produced, sold or used in the territory of the People's Republic of China shall be subject to type inspection in the following circumstances: a) New products apply for type inspection;
6) Raw materials or processes have changed significantly after formal production; c) Type approved products are re-inspected regularly or the approval body deems it necessary to conduct re-inspection and puts forward re-inspection requirements. 7.1.2 The national oil spill dispersant type approval body authorized by the environmental protection department of the State Council is responsible for the type inspection of oil spill dispersants. The sampling method is shown in Appendix D (Appendix to the standard), and the inspection items and test methods are in accordance with the provisions of 6.1. 7.1.3 Products whose test results all meet the performance indicators specified in Chapter 5 are qualified products; products with more than two test results that do not meet the indicators are unqualified products. If one test result does not meet the indicators, re-sampling and inspection are allowed. If the re-inspection results meet the indicators, the product is qualified; if the re-inspection results still do not meet the indicators, the product is unqualified. 7.2 Factory inspectionbzxZ.net
GB 18188.1-2000
7.2.1 The manufacturer shall conduct factory inspection for each production batch. Samples shall be taken according to Appendix D, and factory inspection shall be conducted according to the five test methods specified in Chapter 5, including appearance, pH, burning point, viscosity, and emulsification rate. 7.2.2 Products whose five test results all meet the relevant indicators specified in Chapter 5 are qualified products: Products with more than two unqualified test results shall not be shipped! '. If one test result does not meet the indicator, re-sample from the doubled packaging barrel for inspection. If one test result still does not meet the indicator, the entire batch of products shall not be shipped. 8.1 ... The main contents of the instruction manual include: a) Overview of product name and type, product features, main uses and safety protection measures; b) Main ingredients and mechanism for treating oil spills; e) Performance parameters; 9) Usage method and restricted use conditions; e) Storage environment, shelf life and disposal measures for expired products; f) Possible impact of the product on the ecological environment, toxicological information, possible harm to people and first aid measures, and protection requirements for operators; g) Other matters that need to be explained to users. 9 Packaging and storage
9.1 Packaging
Oil spill dispersants should be sealed and packaged in galvanized barrels or ethylene plastic barrels, and should not be packaged in polyvinyl chloride barrels. The maximum volume of the packaging barrel is 200L. It can also be stored in bulk in carbon steel or fiberglass tanks for a short period of time. 9.2 Storage
9.2.1 Oil spill dispersants should be stored in a dry, ventilated warehouse or shaded area to avoid direct sunlight. 9.2.2 The storage validity period of oil spill dispersants in sealed original packaging is five years. Sealed original packaging products that have exceeded the storage period of five years are allowed to undergo type inspection again and continue to be used within the approved period. The bulk storage period of oil spill dispersants shall not exceed one year. Oil spill dispersants shall not be mixed with water or stored with different types of oil spill dispersants or other chemical preparations. 10 Disposal of expired products
Expired products should be disposed of in one of the following three ways: a) return to the manufacturer for treatment or reuse; b) send to a chemical incineration facility for incineration
c) dispose of in accordance with other measures approved by the environmental protection department. 251
A1 Principle
GB 18188.1—2000
Appendix A
(Appendix to the standard)
Emulsification rate test method
Oil and water are insoluble. The function of oil spill dispersants is to emulsify oil into fine particles and disperse them in water. Due to the floating property of oil in water, the oil content in the lower emulsion will decrease with the increase of standing time. Under specific test conditions, the ratio of the amount of oil in the emulsion to the amount of oil added is called the emulsification rate. This test stipulates that a dispersant is added to 1.000g of the test oil floating on the surface of 50mL artificial seawater in a certain proportion, and after oscillation and emulsification, it is left to stand for 30s and 10min respectively, and 20mL of the lower layer is emulsified, and the oil concentration therein is determined, and the emulsification rate of 30s (indicating the emulsification ability of the oil spill dispersant) and the emulsification rate of 10min (indicating the emulsification stability of the oil spill dispersant) are calculated. A2 reagent
a) Standard oil: Shengli crude oil (pre-extracted at 100C); h) Chloroform (analytical grade);
c) Artificial seawater: 30g of commercially available coarse sea salt is dissolved in 1L of distilled water and filtered. Note: If the emulsification performance of the oil spill dispersant for a specific oil is to be evaluated, this specific oil should be used as the standard oil. A3 Instruments
a) Electronic balance: sensitivity 1mg;
b) Conical separatory funnel: 50, 100ml;c) Plastic oil limit ring: diameter 25-40mm;d) Beaker: 20mL;
e) Measuring cylinder: 20, 50mL;
f) Syringe: 2, 5mL
g) Needle: 3, 10cm;
h) Volumetric flask: 10, 25mL;
i) Oscillator: frequency 240Hz, amplitude 40mmj) Visible spectrophotometer.
A4 Test steps
A4.1 Use a 50ml measuring cylinder to add 50mL of artificial seawater to each of the two 100mL separatory funnels, and place the plastic oil limit ring on the water surface.
A4.2 Use a 2mL syringe to extract 1g of standard oil, remove the tares on an electronic balance, and squeeze it into the plastic oil limit ring in one of the separatory funnels in A4.1. Weigh the empty syringe ml (accurate to 0.001g). m: is the amount of standard oil added. Repeat the above operation and add standard oil to the plastic oil limit ring in the other separatory funnel.
A4.3 Use a 2mL syringe with a 3cm needle to extract the oil spill dispersant, remove the tares on an electronic balance, and evenly add the calculated amount of oil spill dispersant to the oil surface in the plastic oil limit ring. Weigh m2 (accurate to 0.001g), m2 is the amount of oil spill dispersant added. The amount of conventional dispersant added is 20% of the standard oil, that is, 0.200g of dispersant is added to 1.000g of oil; the amount of concentrated dispersant added is 4% of the standard oil, that is, 0.040g of dispersant is added to 1.000g of oil. The allowable error of the ratio of oil spill dispersant to standard oil is ±10%. A4.4 After oscillating the two separating funnels at the same time for 3 minutes, quickly take them out, transfer them vertically to the separating funnel stand, and let them stand for 10 minutes. Do not shake the separating funnel during this process.
GB 18188.12000
A4.5 Repeat A4.1~A4.3. Add artificial seawater, standard oil and oil spill dispersant to the other two separating funnels, oscillate according to A4.4 and let them stand for 30 seconds.
A4.6 After the two components of A4.4 and A4.5 have been standing for the specified time, promptly release 20mL of emulsion from the bottom into a 20ml measuring cylinder and read the volume to 0.1 mL.
A4.7 Pour the emulsion in A4.6 into four 50mL separating funnels respectively, and use the corresponding measuring cylinder to add the same volume of chloroform as the emulsion (use chloroform to carefully rinse the oil adhering to the wall of the measuring cylinder), shake and extract for 5 minutes, and let it stand for 30 minutes to separate. A4.8 Use a 5mL syringe with a 10cm needle to draw about 0.2ml of air, and quickly pass through the water layer into the extraction layer. After squeezing out the air in the syringe, wait for a while, draw out 1ml of extract, quickly raise it to the surface of the water, squeeze out a little and wipe the needle with filter paper. Use this extract to wash the syringe and colorimetric blood. Repeat the above operation once. A4.9 According to the sampling method in A4.8, draw about 3mL of extract and place it in colorimetric III for testing. Note
1 Do not bring water when drawing the extract with a syringe. If water droplets are found on the syringe or colorimetric blood wall, immediately replace it with a clean and dry syringe or colorimetric blood and resample.
2 During the emulsification test, the ambient temperature and artificial seawater temperature are 20~23A4.10 At a wavelength of 650nm, use trichloromethane as a reference to test the absorbance of the A4.9 extract. If the absorbance of the extract exceeds the test range, dilute the concentration of the extract with trichloromethane to within the test range. A5 Make a standard curve
Accurately weigh 500mg of standard oil and dissolve it in 25mL of trichloromethane to obtain a 20000mg/L stock solution. Prepare a series of test oil-chloroform solutions of different concentrations as needed. For example, take 1, 2, 3, and 4.5 ml of stock solution, dilute to 10 ml, and prepare a series of standard solutions with corresponding concentrations of 2000, 4000, 6000, 8000, and 10000 mg/l. Measure the absorbance of the series of standard solutions at a wavelength of 650 nm with a 0.5 cm colorimetric blood, draw a standard curve of oil concentration and absorbance, or perform regression calculation to obtain the correlation coefficient, slope, and intercept. A6 Result Calculation
The test results of emulsification rate at 30 s and 10 min are expressed in percentage. a) Calculation formula for emulsification rate of conventional dispersant: 51.2Ca
6×100%
m, X 106
b) Calculation formula for emulsification rate of concentrated dispersant: T
Wherein; T——emulsification rate,%;
m-standard oil addition amount, g;
×100%
m X 106
C-oil concentration obtained from the standard curve by the absorbance value of the extract or calculated according to the regression coefficient, mg/L; (-extract dilution multiple;
51.2-the sum of the volumes (mL) of artificial seawater, oil and conventional dispersant; 51-the sum of the volumes (mL) of artificial seawater and oil. (AI)
B1 Principle
GB 18188.1—2000
Appendix B
(Appendix to the standard)
Test method for acute toxicity of fish
The toxicity of oil spill dispersants to aquatic organisms is usually evaluated by the test results of acute toxicity of fish. The test fish are placed in different concentrations of oil spill dispersants for 24h or 96h, and the concentration of the test solution at which half of the test fish die is obtained, which is the 24h or 96h half-lethal concentration: or the time when half of the test fish die in a certain concentration of oil spill dispersant solution is measured, which is called the half-lethal time at this concentration. This standard recommends the use of a test to determine the half-lethal time at a certain concentration. Conventional dispersants The concentration of the test solution is 3000mg/L; the concentration of the concentrated dispersant test solution is 600mg/L. B2 Instruments
a) Test tank;
b) Adjustable speed electric stirrer;
c) Speed measuring instrument;
d) Thermometer;
e) Air pump or oil-free air compressor and other air-purifying equipment;f) Balance: Sensitivity 100mg,
g) Beaker: 501000mL;
h) Domestication pond: The volume is adapted to the number of domesticated fish, ensuring 1g fish/liter of water or a larger volume of water;i) Large water tank: store sufficient test water;i) Dissolved oxygen measuring instrument.
Test device
The test device is shown in Figure B1.
1 Electric stirrer; 2—plexiglass cylinder, 3 test cylinder Figure B1 Test device
The inner diameter of the plexiglass cylinder 2 is 7~8cm, and the height is about 30cm. There is a pore zone at each end of the cylinder, about 3cm wide. This pore zone is evenly and densely covered with small circular holes, and the outer layer is covered with a soft screen. The upper edge of the upper pore zone is 8cm away from the top of the cylinder, and the lower edge of the lower pore zone is 2cm away from the bottom of the cylinder. The plexiglass cylinder is placed in the center of the glass test cylinder 3, and the diameter of the test cylinder is about 30cm and the height is about 30cm. The stirring blade of the electric stirrer 1 (2~254
GB 18188.1--2000
4 pieces) are located in the middle of the plexiglass cylinder. The blades cannot touch the inner wall of the cylinder during stirring. Adjust the position of the stirring blades so that a vortex is formed in the cylinder during stirring, and the test liquid is sucked in from the upper pore zone and pressed out from the lower pore zone, causing the test liquid to flow from bottom to top in the cylinder. B4 Test fish
B4.1 The test fish are zebrafish born in the same year, with a body length of about 30mm and a weight of about 0.3g. The maximum body length of the fish in a test should not exceed 1.5 times the minimum body length of the fish.
B4.2 The test fish should be domesticated indoors for at least one week. Feed once a day during the domestication period, and stop feeding 24 hours before the test. If the mortality rate of the fish before the test exceeds 10%, the batch of fish cannot be used for the test. The environmental parameters for zebrafish egg rearing and reproduction shall comply with the provisions of Appendix D of GB/T132671991.
B5 Test water
Use tap water that has been aerated naturally for two days or artificially. The water temperature of the acclimatization pool should be consistent with the test water temperature (20-26℃). In the same drinking test, the water temperature change should not exceed ±1℃.
B6 Test steps
B6.1 Use test water (B5) to prepare a certain concentration of test substrate: a) the concentration of conventional dispersant is 3000 mg/L; b) the concentration of concentrated dispersant is 600 mg/L. Add about 15L of test water to the test tank, so that the water surface reaches the upper edge of the upper pore zone of the organic glass cylinder in the tank, and determine the water volume. Start the stirrer and adjust the speed to 200-400r/min, then add the calculated amount of oil spill dispersant to the rotating part of the organic glass cylinder to make it reach the test degree and stir evenly.
B6.2 Select 10X3 test fish (B4) from the other ponds and place them in three 1000mL beakers, 10 fish in each beaker. After the test preparation is completed, use a soft scoop net to transfer the test fish to two test reds and one blank. Move quickly and do not expose the fish to the air for a long time.
Note: The blank test device should meet the requirements of B3 and only add test water. B6.3 During the test period, if a fish is found to be motionless and not breathing, gently touch its tail with a glass rod. If the fish does not react, it is considered dead and should be fished out in time.
B7 Records
The test records include the following:
a) Test fish species, source and purchase time; b) Maximum, minimum and average weight and length of test fish; c) Test solution concentration;
d) Test fish release time;
e) Record abnormal performance, poisoning symptoms and death time of test fish at any time; f) Record the number of surviving test fish and water temperature in the test tank and blank tank every 2 hours; g) Accurately record the time when 5 test fish died. B8 Result processing
B8.1 If the mortality rate of test fish in the blank test exceeds 10%, the test result is unusable. B8.2 Take the average of the half-lethal time of two parallel tests as the test result. 255
C1 Principle
GB 18188.1--2000
Appendix C
(Appendix to the standard)
Test method for biodegradability
Biodegradation refers to the process in which organic matter is completely converted into inorganic matter by organisms (microorganisms) through intermediate metabolism under aerobic conditions. The whole process of biodegradation is very slow, so specific conditions and methods are usually used to evaluate the biodegradability of organic matter. This standard adopts the method of comparing the correlation between five-day biochemical oxygen demand (BODs) and chemical oxygen demand (COD). Prepare a certain concentration of oil spill dispersant aqueous solution (300 mg/L for conventional dispersant and 200 mg/L for concentrated dispersant), determine its BOD: and COD respectively, and calculate the evaluation index of oil spill dispersant biodegradability. C2 BOD: determination
Test according to the provisions of GB/T7488. C3 COD determination
Test in accordance with the provisions of GB/T11914. C4 Calculation
Oil spill dispersant biodegradability assessment index calculation formula: D
×100%
Wherein: D——oil spill dispersant biodegradability assessment index, %; BOD:
15-day biochemical oxygen demand, mg/L;
COD——chemical oxygen demand, mg/L.
Appendix D
(Appendix of Standard Male)
Sampling method
D1 Principle
Sampling should be taken from the quantitative products according to the regulations for type inspection and factory inspection. The quality of the sample should be representative of the quality of the inspection batch products. D2 Sampling method
D2.1 Randomly select 10% of the packaging barrels from an inspection batch of products, and carefully remove dust and impurities on the barrel covers to avoid contamination of the products when opening the covers
Note: The inspection batch for factory inspection is one production batch; the inspection batch for type inspection can be composed of one or several production batches. D2.2 Use a sampling tube to take samples along the upper, middle and lower parts of the vertical line of the center of the packaging barrel drawn out in D2.1. The sampling volume at each sampling point is equal, and then all samples are evenly mixed.
GB18188.12000
D2.3 Take 500mLX2 samples from the mixed sample, divide them into two clean and dry ground-mouth glass bottles or polyethylene plastic bottles, and seal them with polytetrafluoroethylene film. The sampler seals the sample. D2.4 Attach a label to the outside of the sampling bottle, indicating the manufacturer name, product name, batch number, sampling date, sampling agency and sampler. 257), respectively determine its BOD: and COD, calculate the evaluation index of the biodegradability of the oil spill dispersant. C2 BOD: determination
Test according to the provisions of GB/T7488. C3 COD determination
Test according to the provisions of GB/T11914. C4 Calculation
Oil spill dispersant biodegradability evaluation index calculation formula: D
×100%
Where: D——oil spill dispersant biodegradability evaluation index, %; BOD:
——15-day biochemical oxygen demand, mg/L;
COD——chemical oxygen demand, mg/L.
Appendix D
(Appendix of Biao Xiong)
Sampling method
D1 Principle
Sampling shall be carried out according to regulations from the quantitative products for type inspection and factory inspection. The quality of the samples shall be representative of the quality of the products in the inspection batch. D2 Sampling method
D2.1 Randomly select 10% of the packaging barrels from an inspection batch of products, and carefully remove dust and impurities on the barrel covers to avoid contamination of the products when opening the covers
Note: The inspection batch for factory inspection is one production batch; the inspection batch for type inspection can be composed of one or several production batches. D2.2 Use a sampling tube to take samples from the upper, middle and lower parts of the vertical line at the center of the packaging barrel drawn out in D2.1. The sampling volume at each sampling point shall be equal, and then all samples shall be evenly mixed.
GB18188.12000
D2.3 Take 500mLX2 samples from the mixed sample and pack them into two clean and dry ground-mouth glass bottles or polyethylene plastic bottles, and seal them with polytetrafluoroethylene membranes. The sampler seals the sample. D2.4 Attach a label to the outside of the sampling bottle, indicating the manufacturer name, product name, batch number, sampling date, sampling agency and sampler. 257), respectively determine its BOD: and COD, calculate the evaluation index of the biodegradability of the oil spill dispersant. C2 BOD: determination
Test according to the provisions of GB/T7488. C3 COD determination
Test according to the provisions of GB/T11914. C4 Calculation
Oil spill dispersant biodegradability evaluation index calculation formula: D
×100%
Where: D——oil spill dispersant biodegradability evaluation index, %; BOD:
——15-day biochemical oxygen demand, mg/L;
COD——chemical oxygen demand, mg/L.
Appendix D
(Appendix of Biao Xiong)
Sampling method
D1 Principle
Sampling shall be carried out according to regulations from the quantitative products for type inspection and factory inspection. The quality of the samples shall be representative of the quality of the products in the inspection batch. D2 Sampling method
D2.1 Randomly select 10% of the packaging barrels from an inspection batch of products, and carefully remove dust and impurities on the barrel covers to avoid contamination of the products when opening the covers
Note: The inspection batch for factory inspection is one production batch; the inspection batch for type inspection can be composed of one or several production batches. D2.2 Use a sampling tube to take samples from the upper, middle and lower parts of the vertical line at the center of the packaging barrel drawn out in D2.1. The sampling volume at each sampling point shall be equal, and then all samples shall be evenly mixed.
GB18188.12000
D2.3 Take 500mLX2 samples from the mixed sample and pack them into two clean and dry ground-mouth glass bottles or polyethylene plastic bottles, and seal them with polytetrafluoroethylene membranes. The sampler seals the sample. D2.4 Attach a label to the outside of the sampling bottle, indicating the manufacturer name, product name, batch number, sampling date, sampling agency and sampler. 257
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