GB 14470.2-2002Discharge standard for water pollutants from ordnance industry - Initiating explosive material and relative composition (English PDF)

3.1 Initiating explosive material and their relative composition

Explosives or pyrotechnic compositions used, or mainly used, in initiating explosive devices, chiefly including primary explosives, igniting compositions and delay compositions.

3.2 Picric acid

Chemical name: 2,4,6-trinitrophenol.

3.3 Double salt of basic lead picrate and lead azide

Also called K·D double salt initiating explosive.

3.4 Co-precipitated product of lead azide and lead trinitroresorcinate

Also called D·S co-precipitated initiating explosive.

4.1 Standard values

This standard specifies, for different time periods, the maximum allowable daily average discharge concentrations of water pollutants from the initiating explosive material industry and the maximum allowable water discharge per unit product for water used directly in production.

4.1.1 Projects built before 30 June 2003

Enterprises whose projects were built before 30 June 2003 and that went into production after completion shall comply with the standard specified in Table 1.

Table 1 - Maximum allowable daily average discharge concentrations of water pollutants and maximum allowable water discharge per unit product for initiating explosive material manufacturing enterprises whose projects were built before 30 June 2003 and went into production after completion.

Columns: water discharge per unit product (L/kg); pH; chemical oxygen demand (COD); biochemical oxygen demand (BOD5); colour (dilution factor); total lead; nitrophenols (as picric acid); sodium azide (as N3-); hydrazine (as N2H4); thiocyanate (as SCN-); iron(II, III) cyanide complexes (as [Fe(CN)6]3-); sulfide (as S2-). Concentrations in mg/L except pH and colour; a dash means no limit specified.

Diazodinitrophenol: 220; 6-9; 250; 80; 180; -; 6.0; -; -; -; -; 2.0.

Lead azide: 60; 6-9; 150; 30; -; 3.0; -; 5.0; -; -; -; -.

Lead trinitroresorcinate: 60; 6-9; 150; 30; 100; 5.0; 4.0; -; -; -; -; -.

D·S co-precipitated initiating explosive: 60; 6-9; 150; 30; 100; 5.0; 4.0; 5.0; -; -; -; -.

K·D double salt initiating explosive: 60; 6-9; 150; 30; 150; 5.0; 4.0; 5.0; -; -; -; -.

Thiocyanate: 20; 6-9; 150; 30; -; 3.0; -; -; -; 5.0; -; -.

Lead ferrocyanide: 80; 6-9; 150; 30; -; 3.0; -; -; -; -; 5.0; -.

Sodium azide: 20; 6-9; 200; 80; -; -; -; 3.0; 3.0; -; -; -.

Trinitroresorcinol: 50; 6-9; 150; 30; 150; -; 4.0; -; -; -; -; -.

4.1.2 Enterprises built from 1 July 2003 and new, expanded or rebuilt projects

Enterprises built from 1 July 2003, and new, expanded or rebuilt projects of existing enterprises, shall comply with the standard specified in Table 2.

Table 2 - Maximum allowable daily average discharge concentrations of water pollutants and maximum allowable water discharge per unit product for initiating explosive material manufacturing enterprises built from 1 July 2003 and their new, rebuilt and expanded projects.

Columns: water discharge per unit product (L/kg); pH; chemical oxygen demand (COD); biochemical oxygen demand (BOD5); colour (dilution factor); total lead; nitrophenols (as picric acid); sodium azide (as N3-); hydrazine (as N2H4); thiocyanate (as SCN-); iron(II, III) cyanide complexes (as [Fe(CN)6]3-); sulfide (as S2-). Concentrations in mg/L except pH and colour; a dash means no limit specified.

Diazodinitrophenol: 220; 6-9; 150; 40; 120; -; 3.0; -; -; -; -; 1.0.

Lead azide: 60; 6-9; 150; 30; -; 1.0; -; 5.0; -; -; -; -.

Lead trinitroresorcinate: 60; 6-9; 150; 30; 80; 1.0; 3.0; -; -; -; -; -.

D·S co-precipitated initiating explosive: 60; 6-9; 150; 30; 80; 1.0; 3.0; 5.0; -; -; -; -.

K·D double salt initiating explosive: 60; 6-9; 150; 30; 120; 1.0; 3.0; 5.0; -; -; -; -.

Thiocyanate: 20; 6-9; 150; 30; -; 1.0; -; -; -; 3.0; -; -.

Lead ferrocyanide: 80; 6-9; 150; 30; -; 1.0; -; -; -; -; 5.0; -.

Sodium azide: 15; 6-9; 150; 40; -; -; -; 3.0; 3.0; -; -; -.

Trinitroresorcinol: 50; 6-9; 150; 30; 120; -; 3.0; -; -; -; -; -.

4.2 Discharge into urban sewerage systems with secondary treatment plants

For wastewater discharged into urban sewerage systems served by a secondary sewage treatment plant, the characteristic pollutants nitrophenols, azides, hydrazine, thiocyanate, iron(II, III) cyanide complexes and total lead shall comply with this standard; the other parameters shall meet the influent requirements of the sewage treatment plant specified locally.

6.1 Sampling points

For monitoring of the three parameters total lead, azides and hydrazine, samples shall be taken at the workshop discharge outlet; all other parameters shall be sampled at the plant's main discharge outlet. Discharge outlets shall be provided with outlet signs and wastewater flow metering devices.

6.2 Sampling frequency

The sampling frequency shall be determined according to the production cycle. Where the production cycle is within 8 h, samples shall be taken once every two hours; where the production cycle exceeds 8 h, samples shall be taken once every four hours. The maximum allowable discharge concentration is calculated as a daily average.

6.3 Water discharge volume

The water discharge volume counts only water discharged directly from production; the maximum allowable water discharge is calculated as a monthly average.

6.4 Statistics

The quantities of raw materials used, product output and similar data of the enterprise shall be based on the statutory monthly or annual reports.

6.5 Determination methods

The determination methods adopted in this standard shall be as specified in Table 3.

Table 3 - Monitoring methods for pollutant parameters (No.; parameter; determination method; method source):

1 pH value; glass electrode method; GB 6920

2 Total lead; dithizone spectrophotometric method; GB 7470

3 Total lead; atomic absorption spectrophotometry; GB 7475

4 Biochemical oxygen demand (BOD5); dilution and seeding method; GB 7488

5 Colour; dilution factor method; GB 11903

6 Chemical oxygen demand (COD); dichromate method; GB 11914

7 Thiocyanate; isonicotinic acid-pyrazolone spectrophotometric method; GB/T 13897

8 Iron(II, III) cyanide complexes; atomic absorption spectrophotometry; GB/T 13898

9 Iron(II, III) cyanide complexes; ferric trichloride spectrophotometric method; GB/T 13899

10 Hydrazine; p-dimethylaminobenzaldehyde spectrophotometric method; GB/T 15507

11 Sulfide; methylene blue spectrophotometric method; GB/T 16489

12 Nitrophenols; spectrophotometric method; see Annex A

13 Azides; limit colorimetric method; see note 1)

Note 1): See National discharge standards for pollutants - Compilation notes and analytical methods (2), Environmental Protection Bureau Standards Division, Ministry of Urban and Rural Construction and Environmental Protection, 1984. For the determination of azides in wastewater from K·D double salt initiating explosive and sodium azide production, the "Analytical method for wastewater from lead azide, lead trinitroresorcinate and D·S co-precipitated initiating explosive production" in that book shall be followed provisionally. When analysing wastewater from sodium azide production, the addition of sodium azide standard solution B shall be changed from 2.5 mL to 1.5 mL.

A.1 Scope

The analytical method specified in this annex is used for the determination of the content of nitrophenols in wastewater at the discharge outlet of initiating explosive material manufacturing plants.

A.2 Principle

Nitrophenols in wastewater from initiating explosive materials form ion-association complexes with trioctylmethylammonium chloride, and the ion-association complexes formed with the several main nitrophenols have similar absorption coefficients at a wavelength of 410 nm. After extraction with dichloroethane, the total quantity of nitrophenols in the wastewater is determined spectrophotometrically.

A.3 Reagents

All reagents used in the method specified in this annex are of analytical grade; the water used is deionized water or water of equivalent purity.

A.3.1 Sodium sulfite (Na2SO3).

A.3.2 Sodium sulfite solution: 100 g/L.

A.3.3 Sulfuric acid solution: 1+2.

A.3.4 Trioctylmethylammonium chloride solution: 12.5 g/L.

A.3.5 Sodium hydroxide solution: 50 g/L.

A.3.6 Dichloroethane.

A.3.7 Sodium bicarbonate-sodium sulfate solution: weigh 25 g of sodium bicarbonate and 10 g of sodium sulfate, dissolve in water and dilute to 1 L.

A.3.8 Picric acid standard solutions.

A.3.8.1 Picric acid standard stock solution: weigh 0.2000 g of picric acid dried at 70 °C for 3 h, add 10 mL of sodium hydroxide solution (A.3.5) and 20 mL of water; after dissolution, transfer to a 1 L volumetric flask, dilute to the mark with water and mix. Store in the dark. 1.00 mL of this solution contains 200 µg of picric acid.

A.3.8.2 Picric acid standard working solution: transfer 10.00 mL of the picric acid standard stock solution to a 200 mL volumetric flask, dilute to the mark with water and mix. 1.00 mL of this solution contains 10.0 µg of picric acid.

A.4 Apparatus

General laboratory apparatus and a spectrophotometer.

A.5 Sampling and samples

Sodium sulfite (A.3.1) is placed beforehand in a glass sampling bottle in an amount of 10 g per litre of water sample. The wastewater sample is collected at the plant discharge outlet, its pH is adjusted to 8-9 with sodium hydroxide solution (A.3.5), and it is kept refrigerated at 2 °C to 5 °C. The samples shall be analysed within 24 h.

A.6 Analytical procedure

A.6.1 Test portion

Take two equal volumes of homogeneous sample filtered through dry filter paper (volume not more than 50 mL, measured to 0.1 mL, containing less than 100 µg of nitrophenols) as test portions.