Some standard content:
HG/T2961-1999
This standard is a non-equivalent revision of the chemical industry standard HG/T2961-1979 (1997) "Cuprous Oxide" using the American Society for Testing and Materials ASTMD912:1981 (1986) "Cuprous Oxide for Antifouling Paints" and ASTMD283--84 (90) "Test Methods for Cuprous Oxide and Copper Powder Pigments". This standard has the following main differences compared with ASTMD912:1981 (1986) and ASTMD283:1984 (1990): This standard divides products into three grades: superior, first-class, and qualified. Among them, the indicators of superior products fully meet the requirements of ASTMD912:1981(1986), and the total copper, total reduction rate and 45μm sieve residue are stricter than ASTMD912:1981(1986) indicators according to the characteristics of domestic products and user requirements.
Indicator items are more metal copper content and moisture indicators than ASTMD912:1981(1986). In fact, ASTMD912:1981(1986) also needs to measure this item to calculate the cuprous oxide content, but it does not control this item. Compared with HG/T2961--1979(1997), this standard has made the following important modifications: stability, acetone solubles, chlorides, non-copper metals and total nitric acid insolubles on 75μm sieve and corresponding test methods have been added, and the products are divided into three grades: superior products, first-class products and qualified products. This standard adopts type inspection, and does not conduct batch inspection for indicators that can be stably controlled in production. This standard shall replace HG/T2961-1979 (1997) from the date of implementation. This standard was proposed by the Technical Supervision Department of the former Ministry of Chemical Industry of the People's Republic of China. This standard is under the jurisdiction of the Inorganic Chemical Branch of the National Technical Committee for Chemical Standardization. The drafting units of this standard are: Tianjin Chemical Research Institute of the Ministry of Chemical Industry and Jiangsu Taixing Smelter. The main drafters of this standard are: Fan Guoqiang, Xu Jinzhang, Zhang Guohua, Qian Ya. This standard was first issued as the national standard GB1620-1979 "Cuprous Oxide" in January 1980, and was adjusted to the chemical industry standard in 1992. The original GB1620-1979 was abolished in 1997 and renumbered as HG/T2961-1979 (1997) in 1998. This standard is entrusted to the Inorganic Chemical Branch of the National Technical Committee for Chemical Standardization for interpretation. 301
1 Scope
Chemical Industry Standard of the People's Republic of China
Cuprous Oxide
Industry
Cuprous Oxide for Industrial UseHG/T2961---1999
Replaces HG/T 2961--1979(1997)
This standard specifies the requirements, test methods, inspection rules, marking, packaging, transportation and storage of industrial cuprous oxide. This standard applies to industrial cuprous oxide, which is mainly used in ship antifouling paint, glass, pesticides, etc. Molecular formula: Cu20
Relative molecular mass: 143.09 (according to the 1995 international relative atomic mass) 2 Referenced 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/T 6011988
GB/T 602 ---1988
GB/T 603—1988
GB/T1250—1989
GB/T 6678—1986
GB/T 6682—1992
Chemical reagents Preparation of standard solutions for titration analysis (volume analysis) Chemical reagents
Chemical reagents
Preparation of standard solutions for impurity determination (neqISO6353-1:1982) Preparation of preparations and products used in test methods (neqISO6353-1:1982) Expression and determination methods of limit values General rules for sampling of chemical products
Specifications and test methods for water used in analytical laboratories (neqISO3696:1987) HG/T2323—1992
3 Requirements
Industrial zinc chloride
Appearance: orange-red to dark red powder.
Industrial cuprous oxide should meet the requirements of Table 1.
Requirements in Table 1
Total reduction rate (in CuzO)
Content of metallic copper (Cu)
Superior product
Content of cuprous oxide (in CuzO)
Content of total copper (Cu)
Content of chloride (in CI)
Content of sulfate (in SO.)
Content of acetone-soluble matter
Approved by the State Administration of Petroleum and Chemical Industry on August 12, 1999 302
First-class product
Qualified product
Implemented on October 1, 2000
Reduction rate reduction after stability test
Sieve residue (45μm)
75 μm nitric acid insoluble matter on sieve
Non-copper metal content
Test method
HG/T 2961—1999
Table 1 (end)
Superior quality
Qualified quality
The reagents and water used in this standard, unless otherwise specified, refer to analytical pure reagents and grade 3 water specified in GB/T6682. The standard titration solutions, impurity standard solutions, preparations and products used in the test, unless otherwise specified, are prepared in accordance with the provisions of GB/T601, GB/T602 and GB/T603.
Safety tips: The strong acids and alkalis used in this standard are corrosive, so be careful when handling them to avoid splashing; volatile organic solvents are harmful to human health and flammable, so be careful to operate them in a fume hood and avoid contact with open flames. 4.1 Determination of total reduction rate
4.1.1 Method summary
Add ferric chloride to the sample to oxidize cuprous and copper to divalent cupric. At the same time, the reduced divalent iron is titrated with cerium salt, and the excess cerium salt is back-titrated with standard titration solution of ferrous ammonium sulfate. Calculate the total reduction rate. 4.1.2 Reagents and solutions
4.1.2.1 Sulfuric acid solution: 1+9.
4.1.2.2 Ferric chloride solution.
75g ferric trifluoride (FeCl3·6H,O) is dissolved in a mixture of 150mL hydrochloric acid and 400mL water, and 5mL of 30% hydrogen peroxide is added. The excess hydrogen peroxide is removed by boiling. 4.1.2.3 Standard titration solution of cerium sulfate: c[Ce(SO4)2] is about 0.1 mol/L. 4.1.2.4 Standard titration solution of ammonium ferrous sulfate: cLFe(NH4)2(SO.)2] is about 0.03mol/L. Weigh 12g of ammonium ferrous sulfate [Fe(NH4),SO·6H,O] and dissolve it in 300mL of (1+9) sulfuric acid solution, place it in a volumetric flask and dilute it to 1I with water. This solution is calibrated with high-standard sulfuric acid titration solution using o-phenanthroline as indicator before daily use. 4.1.2.5 o-phenanthroline indicator solution: 5g/L. 4.1.3 Analysis steps
Weigh 0.14g~~0.15g sample (accurate to 0.0002g), place in a 250mL conical flask, add appropriate amount of glass beads with a diameter of 4mm~5mm, and add 10mL of ferric chloride solution. Shake until the sample is completely dissolved, then add 50mL of water, immediately titrate with standard antimony sulfate solution, add 2 drops of 1-phenanthroline indicator when it is close to the end point, continue to titrate until the solution changes from orange-red to cyan-blue, then back-titrate with standard ferrous sulfate solution until the solution turns orange-red, which is the end point. 4.1.4 Expression of analysis results
Total reduction rate (in terms of CuzO) (X,) is calculated according to formula (1): X = (cVi-Va) × 0. 071 55 × 100 (1)
-Actual concentration of standard titration solution of cerium sulfate, mol/L; Wherein: ci-
C2-——Actual concentration of standard titration solution of ammonium ferrous sulfate, mol/L; Vi-——Volume of standard titration solution of cerium sulfate consumed by titration test solution, mL; V2-——Volume of standard titration solution of ammonium ferrous sulfate consumed by titration test solution, mL; Mass of sample, g;
HG/T 2961-1999
0. 07155..
-with 1.00 mL standard titration solution of cerium sulfate (cCe(S0)2·4H2O=1.000 mol/L) is equivalent to the mass of cuprous oxide (CuzO) expressed in grams. 4.1.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the two parallel determination results shall not exceed 0.3%. 4.2 Determination of metallic copper content
4.2.1 Method summary
The sample is added with extraction solution at low temperature to dissolve all copper oxides. After filtering and separating from metallic copper, the copper is oxidized with ferric chloride, and the reduced divalent iron is titrated with high iodine salt to calculate the metallic copper content. 4.2.2 Reagents and solutionsWww.bzxZ.net
4.2.2.1 Denatured ethanol: 995 ml of 95% ethanol, add 5 ml of benzene. 4.2.2.2 Extraction solution: 40 g of stannous chloride (SnCl2·2H2O) is dissolved in 40 ml of hydrochloric acid, and then 1000 ml of denatured ethanol is added and mixed thoroughly.
4.2.2.3 Ferric chloride solution: 75g ferric chloride (FeCl:·6H0) is dissolved in a mixture of 150mL hydrochloric acid and 400mL water, 5mL of 30% hydrogen peroxide is added, and the excess hydrogen peroxide is removed by boiling. 4.2.2.4 Standard titration solution of bis(2-hydroxy-2-thiocyanate): c[Ce(SO.),] is about 0.1mol/L. 4.2.2.5 O-phenanthroline indicator solution: 5g/L. 4.2.2.6 Acid-washed asbestos.
4.2.3 Analysis steps
Weigh 0.5g of sample (accurate to 0.0002g), place it in a 500mL conical flask, add appropriate amount of 4mm5mm diameter glass beads, add 25mL of denatured ethanol, add appropriate amount of dry ice, shake, and always keep the solution at about 0℃. Add 100mL of extraction solution and shake for 2 min~~5min. After the copper oxide is completely dissolved, filter it with acid-washed asbestos in a Gooch crucible. The thickness of the acid-washed asbestos layer should be enough to prevent the penetration of fine copper powder. Wash the flask twice with 100mL of denatured ethanol, and rinse and filter out the residue, then wash it with water twice, and then transfer the residue and the acid-washed asbestos into the original conical flask. Add 25mL of ferric chloride solution, shake, add 50mL of water and 2 drops of o-phenanthroline indicator after the residue is dissolved, and titrate with sulfuric acid high standard titration solution until the solution changes from orange-red to cyan blue. 4.2.4 Expression of analysis results
The content of metallic copper (X,) expressed as mass percentage is calculated according to formula (2): X2 = × 0. 031 77
Wherein: c---actual concentration of standard cerium sulfate titration solution, mol/L; (2))
V---volume of standard cerium sulfate titration solution consumed by the titration test solution, mL; 0.03177--mass of copper (Cu) equivalent to 1.00mL standard cerium sulfate titration solution 1c[Ce(SO)2·4HzO］1.000moi/L) expressed in grams;
m--mass of the sample, g.
4.2.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.1%. 4.3 Calculation of cuprous oxide content
The cuprous oxide content (X:) expressed as a mass percentage is calculated according to formula (3): X: X1 - 2.252X2
Wherein: X1--total reduction rate calculated based on cuprous oxide, %; X2--metallic copper content, %;
-coefficient of converting metallic copper to cuprous oxide. 4.4 Determination of total copper
4.4.1 Electrodeposition method (arbitration method)
4.4.1.1 Summary of the method
HG/T 2961---1999
After the sample is dissolved with nitric acid and perchloric acid, copper is completely electrodeposited with a rotating platinum electrode at a certain current, and the total copper content is weighed and calculated. The solution after electrodeposition is used to determine non-copper metals. 4.4.1.2 Reagents and solutions
4.4.1.2.1 Nitric acid;
4.4.1.2.2 Perchloric acid;
4.4.1.2.3 Ammonium sulfate;
4.4.1.2.4 Acetone.
4.4.1.3 Instruments and equipment
Electrolytic analyzer: equipped with a rotating platinum electrode. 4.4.1.4 Analysis steps
Accurately weigh 1.0g of sample (accurate to 0.0001g) and place it in a 300mL beaker. Add 10mL nitric acid and boil for 3min. Add 10ml perchloric acid and heat until it smokes for 5min. After cooling, dilute with water to about 150ml and add 1ml nitric acid and 1g ammonium sulfate. Weigh the rotating platinum electrode (accurate to 0.0001.g), put it in the solution, and electrolyze for 2h with a current of 2A. Electroplate copper onto a rotating platinum electrode, dilute with water and continue electrolysis for 15 minutes. Remove the electrode and retain the electrolyte (solution A) for the determination of other non-copper metals. Wash the platinum electrode with water and acetone and dry at 105℃~～110℃ to constant weight. 4.4.1.5 Expression of analysis results
The total copper content (X.) expressed as mass percentage is calculated according to formula (4): X.=m=m2×100
Where: m1\-
The mass of the copper deposited on the rotating platinum electrode, g; The mass of the rotating platinum electrode, g;
The mass of the sample, g.
4.4.1.6 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.3%. 4.4.2 Iodometric method
4.4.2.1 Summary of the method
After the sample is dissolved in nitric and sulfuric acid, it is cooled to a constant volume and dry filtered. Quantitatively remove the filtrate, adjust it to weak acidity with ammonia water and acetic acid, add masking agent sodium fluoride, add potassium iodide, titrate the released iodine, and calculate the total copper content. 4.4.2.2 Reagents and solutions
4.4.2.2.1 Nitric acid;
4.4.2.2.2 Sulfuric acid;
4.4.2.2.3 Potassium iodide;
4.4.2.2.4 Acetic acid: 36%,
Ammonia solution: 1+1;
4. 2.2. 2. 5
Sodium fluoride solution: 50g/I;
4.4.2.2.6
4.4.2.2.7
Ammonium thiocyanate solution: 250g/1.
4.4.2.2.8 Sodium thiosulfate standard titration solution: c(NazS,O.) is approximately 0.1mol/L; Soluble starch indicator solution: 5g/L.
4. 4. 2. 2. 9
4.4.2.3 Analysis steps
Weigh 1g of sample (accurate to 0.0002g), add 20mL of water, 5mL of nitric acid, and 2.5mL of sulfuric acid, heat to dissolve and evaporate until white smoke escapes, cool, transfer to a 100mL volumetric flask, dilute to scale, dry filter with qualitative filter paper, and discard the previous filtrate. Take 10mL of filtrate, add 10mL of water, neutralize with ammonia water, and continue to neutralize until the precipitate is dissolved after the precipitate is formed. Add 5mL of acetic acid and 8mL of sodium fluoride solution. Then add 305
HG/T 2961--1999
2g of potassium iodide. Titrate with 0.1N sodium thiosulfate standard titration solution until the solution turns light yellow. Add 5mL of starch solution and continue to titrate until the blue color disappears. Add 5 mL of ammonium thiocyanate solution. The solution turns blue again. Continue titrating with sodium thiosulfate standard titration solution until the blue color disappears.
4.4.2.4 Expression of analysis results
The total copper content (X4) expressed as mass percentage is calculated according to formula (5): X = V×0.06355×100
m×100
Wherein: c-..—actual concentration of sodium thiosulfate standard titration solution, mol/L; V
—consumption of sodium thiosulfate standard titration solution, mL; m—mass of the sample, g;
0.06355—mass of copper (Cu) in grams equivalent to 1.00 mL of sodium thiosulfate standard titration solution [c(NazSz:)-1.000 mol/L].
4.4.2.5 Allowable difference
The arithmetic mean of the parallel determination results shall be taken as the determination result. The absolute difference between the two parallel determination results shall not exceed 0.3%. 4.5 Determination of chloride content
4.5.1 Reagents and solutions
4.5.1.1 Nitric acid;
4.5.1.2 Silver nitrate solution: 50g/L;
4.5.1.3 Saturated sodium carbonate solution.
4.5.2 Instruments and equipment
Glass sand floor: G4.
4.5.3 Analysis steps
4.5.3.1 Preparation of test solution B
Accurately weigh about 10g of the sample, add excess nitric acid, and heat slightly until the sample decomposes. Dilute with water to about 150mL, add excess saturated sodium carbonate solution, and heat to boiling. Transfer the solution to a 500mL volumetric flask and dilute to scale with water. Let it settle (solution B). 4.5.3.2 Determination
Pipette 50ml (solution B) into a 250mL beaker, adjust it to slightly acidic with nitric acid, and add a few drops of silver nitrate solution. If no precipitate is formed, report that there is no chloride. If a precipitate is formed, slowly add excess silver nitrate solution, heat to boil after the precipitate settles, filter it with a glass sand pot, and wash it with cold water. Dry at 130℃ to constant weight. 4.5.4 Expression of analysis results
The chloride content (in terms of CI) expressed as mass percentage (X,) is calculated according to formula (6): ml X0.247
m×50/500×100
Where: m--mass of silver chloride, g;
m--mass of sample, g;
0.247---coefficient of silver chloride converted to chloride (CI). 4.5.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the two parallel determination results shall not exceed 0.1%. 4.6 Determination of sulfate content
4.6.1 Reagents and solutions
4.6.1.1 Nitric acid.
4.6.1.2 Barium chloride solution: 100g/L.
Weigh 117g of barium chloride (BaCl2·HzO) and dissolve it in water and dilute to 1L. 306
·（6)
4.6.1.3 Hydrochloric acid solution: 1+1.
4.6.2 Instruments and equipment
Glass sand: G4.
4.6.3 Analysis steps
HG/T 2961—1999
Pipette 50mL (solution B) into a 250ml beaker, adjust it to slightly acidic with nitric acid, dilute it with water to about 200mL, add about 1ml of hydrochloric acid solution, heat it to boiling and slowly add 10ml of barium chloride solution. Let it stand and settle. Filter it with a glass sand crucible, wash the precipitate, and dry it at 105℃~110℃ to constant weight.
4.6.4 Expression of analytical results
The sulfate content (in terms of SO4) expressed as a mass percentage (Xe) is calculated according to formula (7): Xe
where: m
-mass of barium sulfate, g;
-mass of the sample, g;
m × 50/500
Coefficient for converting sulfuric acid to sulfate (in terms of SO4). X 100
4.6.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the two parallel determination results shall not exceed 0.1%. 4.7 Determination of moisture
(7)
4.7.1 Summary of the method
Place the sample in a round-bottom flask, add xylene, and heat the flask with a non-open flame to remove the moisture in the sample with the xylene vapor. The steam is in the condenser, and the water condenses and layers in the collector, and the water volume is read. 4.7.2 Reagents and solutions
Xylene.
4.7.3 Instruments and equipment
Moisture analyzer: It consists of a short-necked round-bottom flask (500mL), a condensed water collector (10mL, with 0.1mL graduation) and a condenser (see Figure 1).
Condenser
Condensate collector
Short-necked round-bottom flask
Figure 1 Moisture analyzer
4.7.4 Analysis steps
HG/T 2961—1999
Weigh 50g of sample (accurate to 0.01g), place it in the flask of the moisture analyzer, add 100mL of xylene, heat on an air bath to make the solution in the flask boil, and continue for half an hour. Stop heating when the amount of water in the condensate collector no longer increases. If there are water droplets on the condenser wall, wash them off with xylene. Read the milliliters of water in the collector. 4.7.5 Expression of analysis results
The water content (X,) expressed as a mass percentage is calculated according to formula (8): ×100
Density of water, regarded as 1g/mL at room temperature;
Wherein: p-—
-the amount of water collected, mL;
The mass of the sample, g.
4.7.6 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the two parallel determination results shall not exceed 0.1%. 4.8 Determination of acetone soluble content
4.8.1 Reagents and solutions
Acetone.
...(8)
4.8.2 Analysis steps
Accurately weigh 5.0g of the sample and place it in a 250mL conical flask with a glass stopper. Add 100 mL of acetone, shake vigorously for 15 min, and let it settle. Filter the solution through slow filter paper into a 250 mL beaker, and wash the conical flask and filter paper thoroughly with acetone to wash out all the acetone-soluble substances. Evaporate the acetone containing the soluble substances on a water bath to reduce the volume to about 30 mL, then transfer it to a 100 mL beaker with constant weight, and wash the beaker with a small amount of acetone. Evaporate all the acetone and dry it in an oven at 105°C to constant weight. 4.8.3 Expression of analytical results
The acetone-soluble substance content (X.) expressed as mass percentage is calculated according to formula (9): Xgml×100
...(9)
Where: m1—mass of residue, g;
m—mass of sample, g.
4.8.4 Allowable difference
Take the arithmetic mean of the parallel determination results as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.1%. 4.9 Stability test
4.9.1 Reagents and solutions
Sulfuric acid solution: 11%.
4.9.2 Instruments and equipment
4.9.2.1 Surface III: $100 mm×15 mm. 4.9.2.2 Dryer: See Figure 2.
11% sulfuric acid
Figure 2 Dryer
4.9.3 Analysis steps
HG/T 2961-1999
Weigh about 100g of sample, spread it on surface III, and place it in a dryer with about 200mL of sulfuric acid solution at the bottom (relative humidity is about 95%), and cover it tightly. Place the dryer in a constant temperature oven at 40℃ and heat it for 72h. Take out the sample from the oven and determine the total reduction rate according to 4.1. Weigh 50g of the remaining sample and determine the moisture content according to 4.7. 4.9.4 Expression of analysis results
The total reduction rate reduction (X.) expressed as a mass percentage is calculated according to formula (10): X, = XX/100-X2 100-.
Where: Xb—
Total reduction rate before stability test;
X. —-—Total reduction rate after stability test; X,
Moisture content determined according to 4.7.
4.9.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the two parallel determination results shall not exceed 0.5%. 4.10 Determination of sieve residue (45um) content
4.10.1 Reagents and solutions
Ethanol.
4.10.2 Instruments and equipment
4.10.2.1 Test sieve: sieve hole diameter 45μm; 4.10.2.2 Stainless steel brush: No. 4.
4.10.3 Analysis steps
·(10)
Weigh about 10g of sample (accurate to 0.01g), put it into a sieve that has been weighed constant and moistened with ethanol, moisten the sample with ethanol, immerse the bottom of the sieve in water, gently scrub it with a stainless steel brush several times, replace the washing water until the washing water is clear and there is no sample on the stainless steel brush, rinse it with water twice, rinse it with ethanol once, dry it at (105±2)℃ for 3 hours, put it in a desiccator, cool it to room temperature, and weigh it until constant weight. 4.10.4 Expression of analysis results
The content of residue on 45μm sieve expressed as mass percentage (X1.) is calculated according to formula (11): Xio= m=m2×100
Wherein: mr—
Mass of test sieve and residue, g;
Mass of test sieve, g;
Mass of sample, g.
4.10.5 Allowable difference
The arithmetic mean of the results of parallel determinations is taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.1%. 4.1 Determination of nitric acid insoluble matter content on 175μm sieve 4.11.1 Reagents and solutions
4.11.1.1 Ethanol;
4.11.1.2 Nitric acid solution: 1+3.
4.11.2 Instruments and equipment
4.11.2.1 Test sieve: sieve hole diameter 75um; 4.11.2.2 Glass sand crucible: pore size 5μm～15μm; 4.11.2.3 Brush: No. 4.
4.11.3 Analysis steps
Weigh 10g sample (accurate to 0.01g), replace 45um test sieve with 75μm test sieve, and after testing according to 4.10.3, transfer all the residue on the sieve into a 250ml beaker, add 50mL nitric acid solution, and boil for 5min. Filter with glass sand that has been washed with nitric acid solution and constant weight, wash the residue with hot water, and dry at 105℃～110℃ to constant weight. 309
4.11.4 Expression of analysis results
HG/T 2961-1999
The content of nitric acid insoluble matter on the 75μm sieve expressed as mass percentage (Xn) shall be calculated according to formula (12): Xn
m-m2×100
--mass of glass sand crucible and nitric acid insoluble matter, g; where: mi---
-mass of glass sand crucible, g;
mass of sample, more.
4.11.5 Allowable difference
The arithmetic mean of the parallel determination results shall be taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.02%. 4.12 Determination of non-copper metal content
4.12.1 Summary of method
(12)
After the sample is dissolved in acid, copper is separated by electrolysis. The electrolyte is evaporated to remove perchloric acid and nitric acid, dissolved in water, and iron is separated by precipitation by adding ammonia water-ammonium chloride. After acid dissolution, it is titrated with high sodium chloride. Cobalt, nickel and zinc are further separated from the filtrate. Determine by corresponding methods. Report the total amount of the above non-copper metals.
4.12.2 Reagents and solutions
4.12.2.1 Sulfuric acid.
4.12.2.2 Hydrochloric acid.
4.12.2.3 Ammonium chloride
4.12.2.4 Sulfuric acid solution: 1+1.
4.12.2.5 Hydrochloric acid solution: 1+1.
4.12.2.6 Ammonium chloride solution: 50g/1.
4. 12. 2.7
Potassium ferrocyanide solution: 50g/1.
Stannous chloride solution: 50g/1.
4. 12. 2. 8
Mercuric chloride solution: 40g/1..
4. 12. 2. 9
Potassium ferrocyanide standard titration solution: cLK.Fe(CN). ］ is about 0.05mol/L. 4. 12. 2. 10
Prepare and calibrate according to 5.1.2.5 of HG/T23231992. 4. 12. 2. 11
Standard titration solution of perchloric acid: c[Ce(SO4)] is about 0.1 mol/L. O-phenanthroline indicator: 0.5% solution.
4. 12. 2. 12
Diphenylamine indicator: 10 g/L.
4. 12. 2. 13
Weigh 1 g of diphenylamine and dissolve it in 100 mL of sulfuric acid. 4.12.3 Analysis steps
-4.12.3.1 Separation
Add 5 mL of sulfuric acid to solution A after the total copper content is determined by filtration electrolysis, and evaporate it to dryness to remove all perchloric acid and nitric acid, add about 150 ml of water, and then add ammonia water to neutralize and add 5 mL excess. Add 10 g of ammonium chloride and boil the solution slightly for 3 minutes. Allow the precipitate to settle, filter with slow filter paper and wash the precipitate with ammonium chloride solution, retain the filtrate (solution C) for determination in 4.12.3.3. 4.12.3.2 Determination of iron content
Dissolve the precipitate on the filter paper with hot hydrochloric acid solution and collect the solution in a conical flask. Add stannous chloride solution until the yellow color of the solution disappears and the excess is 1-2 drops, add 5mL mercuric chloride solution and let stand for 3min. Add 2 drops of o-phenanthroline indicator and titrate with standard titration solution of sodium sulfate. The iron content (XF) expressed as mass percentage is calculated according to formula (13): ×100
Where: C——actual concentration of standard titration solution of sodium sulfate, mol/L; V------volume of standard titration solution of sodium sulfate consumed, mlL; 310
·(13)
m.4．4.． .4Mass of the sample, g.
4.12.3.3 Determination of cobalt and nickel
HG/T2961—1999
Evaporate solution C to 15mL~20mL. If the solution is colored, it indicates the presence of nickel or cobalt, or both, which must be removed before determining zinc. It can be processed and determined according to the relevant standard procedures and the total amount is reported. 4.12.3.4 Determination of zinc
Neutralize the solution treated in 4.12.3.3 with sulfuric acid solution and add 15ml in excess. Dilute with water to 300ml. Add 5 drops of diphenylamine indicator, heat to 75℃, and titrate with potassium ferrocyanide standard titration solution. The color changes from blue to green-yellow at the end point. The zinc content (Xzn) expressed in mass percentage is calculated according to formula (14): Xzm=×100
-actual concentration of potassium ferrocyanide standard titration solution, mol/I Where: C-——
V--volume of potassium ferrocyanide standard titration solution consumed by titrating the test solution, mL; m·4.4.1.4 Mass of sample, g
4.12.4 Expression of analysis results
The non-copper metal content (X12) expressed in mass percentage is calculated according to formula (15): Xi12 = Xre + XGN + X2n
Where: Xre--iron content, %;
XGN--cobalt and nickel content, %;
Xzn--zinc content, %.
5 Inspection rules
·(15)
5.1 All items specified in this standard are type inspection items, among which cuprous oxide, total copper, total reduction rate, metallic copper, sieve residue and moisture are factory inspection items and must be inspected batch by batch. Under normal production conditions, type inspection shall be carried out at least once every three months. 5.2 Each batch of products shall not exceed 10t.
5.3 Determine the number of sampling units in accordance with the provisions of 6.6 of GB/T6678-1986. Each packaging bag is a sampling unit. When sampling, use a sampler to obliquely insert from the top of the packaging bag to 3/4 of the material layer to collect samples. Mix the samples evenly, reduce them to about 500g by quartering method, and immediately put them into two clean and dry wide-mouth bottles and seal them. Label the bottles with the following: manufacturer name, product name, batch number, sampling date and name of the sampler. One bottle is used as a laboratory sample and the other is kept for three months for future reference. 5.4 Industrial cuprous oxide shall be inspected by the quality supervision and inspection department of the manufacturer in accordance with the provisions of this standard. The manufacturer shall ensure that each batch of products shipped out of the factory meets the requirements of this standard. If any index of the test results does not meet the requirements of this standard, samples shall be taken from twice the amount of packaging for re-testing. Even if only one index does not meet the requirements of this standard in the re-testing results, the entire batch of products shall be unqualified. 5.5 Under the storage and transportation conditions in accordance with this standard, the manufacturer shall ensure that the cuprous oxide content of each batch of cuprous oxide shipped out of the factory is not lower than the index specified in this standard within three months from the date of packaging; within six months or more, it shall be ensured that the cuprous oxide content does not decrease by more than 1% specified in this standard.
5.6 The rounded value comparison method specified in 5.2 of GB/T1250-1989 shall be used to determine whether the test results meet the standards. 6 Marking and labeling
6.1 The packaging of industrial cuprous oxide shall be firmly and clearly marked, including: manufacturer name, factory address, product name, trademark, net content, grade, and this standard number.
6.2 Each batch of products leaving the factory should have a quality certificate. The content includes: manufacturer name, factory address, product name, trademark, net content, grade, batch number or production date, proof that the product quality complies with this standard and the number of this standard. 7 Packaging, transportation and storage
7.1 Industrial cuprous oxide is packaged in three types: iron barrels, plastic barrels or composite paper bags. The iron barrel packaging is lined with a layer of polyethylene film bag with a thickness of not less than 0.07mm. The net content of each barrel of iron barrel packaging is 25kg or 50kg; the net content of each barrel of plastic barrel packaging is 25kg; the composite paper bag packaging uses three layers of kraft paper (80g/m2) with an inner layer of aluminum foil, and the net content of each bag is 25kg. 7.2 The inner bag of the iron drum or plastic drum should be tied with vinyl rope or rope of equivalent quality, or sealed with other equivalent methods to ensure tight sealing. The lid of the iron drum should be sealed firmly; composite paper bag packaging should be sealed with folded mouth. 7.3 Industrial cuprous oxide products should be stored in good ventilation and should not be mixed with oxidants. 7.4. When transporting industrial cuprous oxide products, care should be taken to prevent sun exposure and rain, and keep the packaging intact. 3123 Analysis steps
Weigh 10g of sample (accurate to 0.01g), replace the 45um test sieve with a 75μm test sieve, and after testing according to 4.10.3, transfer all the residue on the sieve into a 250ml beaker, add 50mL nitric acid solution, and boil for 5min. Filter with glass sand that has been washed with nitric acid solution and has a constant weight, wash the residue with hot water, and dry at 105℃~110℃ to a constant weight. 309
4.11.4 Expression of analysis results
HG/T 2961-1999
The content of nitric acid insoluble matter on the 75μm sieve expressed as mass percentage (Xn) shall be calculated according to formula (12): Xn
m-m2×100
--mass of glass sand crucible and nitric acid insoluble matter, g; where: mi---
-mass of glass sand crucible, g;
mass of sample, more.
4.11.5 Allowable difference
The arithmetic mean of the parallel determination results shall be taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.02%. 4.12 Determination of non-copper metal content
4.12.1 Summary of method
(12)
After the sample is dissolved in acid, copper is separated by electrolysis. The electrolyte is evaporated to remove perchloric acid and nitric acid, dissolved in water, and iron is separated by precipitation by adding ammonia water-ammonium chloride. After acid dissolution, it is titrated with high sodium chloride. Cobalt, nickel and zinc are further separated from the filtrate. Determine by corresponding methods. Report the total amount of the above non-copper metals.
4.12.2 Reagents and solutions
4.12.2.1 Sulfuric acid.
4.12.2.2 Hydrochloric acid.
4.12.2.3 Ammonium chloride
4.12.2.4 Sulfuric acid solution: 1+1.
4.12.2.5 Hydrochloric acid solution: 1+1.
4.12.2.6 Ammonium chloride solution: 50g/1.
4. 12. 2.7
Potassium ferrocyanide solution: 50g/1.
Stannous chloride solution: 50g/1.
4. 12. 2. 8
Mercuric chloride solution: 40g/1..
4. 12. 2. 9
Potassium ferrocyanide standard titration solution: cLK.Fe(CN). ］ is about 0.05mol/L. 4. 12. 2. 10
Prepare and calibrate according to 5.1.2.5 of HG/T23231992. 4. 12. 2. 11
Standard titration solution of perchloric acid: c[Ce(SO4)] is about 0.1 mol/L. O-phenanthroline indicator: 0.5% solution.
4. 12. 2. 12
Diphenylamine indicator: 10 g/L.
4. 12. 2. 13
Weigh 1 g of diphenylamine and dissolve it in 100 mL of sulfuric acid. 4.12.3 Analysis steps
-4.12.3.1 Separation
Add 5 mL of sulfuric acid to solution A after the total copper content is determined by filtration electrolysis, and evaporate it to dryness to remove all perchloric acid and nitric acid, add about 150 ml of water, and then add ammonia water to neutralize and add 5 mL excess. Add 10 g of ammonium chloride and boil the solution slightly for 3 minutes. Allow the precipitate to settle, filter with slow filter paper and wash the precipitate with ammonium chloride solution, retain the filtrate (solution C) for determination in 4.12.3.3. 4.12.3.2 Determination of iron content
Dissolve the precipitate on the filter paper with hot hydrochloric acid solution and collect the solution in a conical flask. Add stannous chloride solution until the yellow color of the solution disappears and the excess is 1-2 drops, add 5mL mercuric chloride solution and let stand for 3min. Add 2 drops of o-phenanthroline indicator and titrate with standard titration solution of sodium sulfate. The iron content (XF) expressed as mass percentage is calculated according to formula (13): ×100
Where: C——actual concentration of standard titration solution of sodium sulfate, mol/L; V------volume of standard titration solution of sodium sulfate consumed, mlL; 310
·(13)
m.4．4.． .4Mass of the sample, g.
4.12.3.3 Determination of cobalt and nickel
HG/T2961—1999
Evaporate solution C to 15mL~20mL. If the solution is colored, it indicates the presence of nickel or cobalt, or both, which must be removed before determining zinc. It can be processed and determined according to the relevant standard procedures and the total amount is reported. 4.12.3.4 Determination of zinc
Neutralize the solution treated in 4.12.3.3 with sulfuric acid solution and add 15ml in excess. Dilute with water to 300ml. Add 5 drops of diphenylamine indicator, heat to 75℃, and titrate with potassium ferrocyanide standard titration solution. The color changes from blue to green-yellow at the end point. The zinc content (Xzn) expressed in mass percentage is calculated according to formula (14): Xzm=×100
-actual concentration of potassium ferrocyanide standard titration solution, mol/I Where: C-——
V--volume of potassium ferrocyanide standard titration solution consumed by titration test solution, mL; m·4.4.1.4 Mass of sample, g
4.12.4 Expression of analysis results
The non-copper metal content (X12) expressed in mass percentage is calculated according to formula (15): Xi12 = Xre + XGN + X2n
Where: Xre--iron content, %;
XGN--cobalt and nickel content, %;
Xzn--zinc content, %.
5 Inspection rules
·(15)
5.1 All items specified in this standard are type inspection items, among which cuprous oxide, total copper, total reduction rate, metallic copper, sieve residue and moisture are factory inspection items and must be inspected batch by batch. Under normal production conditions, type inspection shall be carried out at least once every three months. 5.2 Each batch of products shall not exceed 10t.
5.3 Determine the number of sampling units in accordance with the provisions of 6.6 of GB/T6678-1986. Each packaging bag is a sampling unit. When sampling, use a sampler to obliquely insert from the top of the packaging bag to 3/4 of the material layer to collect samples. Mix the samples evenly, reduce them to about 500g by quartering method, and immediately put them into two clean and dry wide-mouth bottles and seal them. Label the bottles with the following: manufacturer name, product name, batch number, sampling date and name of the sampler. One bottle is used as a laboratory sample and the other is kept for three months for future reference. 5.4 Industrial cuprous oxide shall be inspected by the quality supervision and inspection department of the manufacturer in accordance with the provisions of this standard. The manufacturer shall ensure that each batch of products shipped out of the factory meets the requirements of this standard. If any index of the test results does not meet the requirements of this standard, samples shall be taken from twice the amount of packaging for re-testing. Even if only one index does not meet the requirements of this standard in the re-testing results, the entire batch of products shall be unqualified. 5.5 Under the storage and transportation conditions in accordance with this standard, the manufacturer shall ensure that the cuprous oxide content of each batch of cuprous oxide shipped out of the factory is not lower than the index specified in this standard within three months from the date of packaging; within six months or more, it shall be ensured that the cuprous oxide content does not decrease by more than 1% specified in this standard.
5.6 The rounded value comparison method specified in 5.2 of GB/T1250-1989 shall be used to determine whether the test results meet the standards. 6 Marking and labeling
6.1 The packaging of industrial cuprous oxide shall be firmly and clearly marked, including: manufacturer name, factory address, product name, trademark, net content, grade, and this standard number.
6.2 Each batch of products leaving the factory should have a quality certificate. The content includes: manufacturer name, factory address, product name, trademark, net content, grade, batch number or production date, proof that the product quality complies with this standard and the number of this standard. 7 Packaging, transportation and storage
7.1 Industrial cuprous oxide is packaged in three types: iron barrels, plastic barrels or composite paper bags. The iron barrel packaging is lined with a layer of polyethylene film bag with a thickness of not less than 0.07mm. The net content of each barrel of iron barrel packaging is 25kg or 50kg; the net content of each barrel of plastic barrel packaging is 25kg; the composite paper bag packaging uses three layers of kraft paper (80g/m2) with an inner layer of aluminum foil, and the net content of each bag is 25kg. 7.2 The inner bag of the iron drum or plastic drum should be tied with vinyl rope or rope of equivalent quality, or sealed with other equivalent methods to ensure tight sealing. The lid of the iron drum should be sealed firmly; composite paper bag packaging should be sealed with folded mouth. 7.3 Industrial cuprous oxide products should be stored in good ventilation and should not be mixed with oxidants. 7.4. When transporting industrial cuprous oxide products, care should be taken to prevent sun exposure and rain, and keep the packaging intact. 3123 Analysis steps
Weigh 10g of sample (accurate to 0.01g), replace the 45um test sieve with a 75μm test sieve, and after testing according to 4.10.3, transfer all the residue on the sieve into a 250ml beaker, add 50mL nitric acid solution, and boil for 5min. Filter with glass sand that has been washed with nitric acid solution and has a constant weight, wash the residue with hot water, and dry at 105℃~110℃ to a constant weight. 309
4.11.4 Expression of analysis results
HG/T 2961-1999
The content of nitric acid insoluble matter on the 75μm sieve expressed as mass percentage (Xn) shall be calculated according to formula (12): Xn
m-m2×100
--mass of glass sand crucible and nitric acid insoluble matter, g; where: mi---
-mass of glass sand crucible, g;
mass of sample, more.
4.11.5 Allowable difference
The arithmetic mean of the parallel determination results shall be taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.02%. 4.12 Determination of non-copper metal content
4.12.1 Summary of method
(12)
After the sample is dissolved in acid, copper is separated by electrolysis. The electrolyte is evaporated to remove perchloric acid and nitric acid, dissolved in water, and iron is separated by precipitation by adding ammonia water-ammonium chloride. After acid dissolution, it is titrated with high sodium chloride. Cobalt, nickel and zinc are further separated from the filtrate. Determine by corresponding methods. Report the total amount of the above non-copper metals.
4.12.2 Reagents and solutions
4.12.2.1 Sulfuric acid.
4.12.2.2 Hydrochloric acid.
4.12.2.3 Ammonium chloride
4.12.2.4 Sulfuric acid solution: 1+1.
4.12.2.5 Hydrochloric acid solution: 1+1.
4.12.2.6 Ammonium chloride solution: 50g/1.
4. 12. 2.7
Potassium ferrocyanide solution: 50g/1.
Stannous chloride solution: 50g/1.
4. 12. 2. 8
Mercuric chloride solution: 40g/1..
4. 12. 2. 9
Potassium ferrocyanide standard titration solution: cLK.Fe(CN). ］ is about 0.05mol/L. 4. 12. 2. 10
Prepare and calibrate according to 5.1.2.5 of HG/T23231992. 4. 12. 2. 11
Standard titration solution of perchloric acid: c[Ce(SO4)] is about 0.1 mol/L. O-phenanthroline indicator: 0.5% solution.
4. 12. 2. 12
Diphenylamine indicator: 10 g/L.
4. 12. 2. 13
Weigh 1 g of diphenylamine and dissolve it in 100 mL of sulfuric acid. 4.12.3 Analysis steps
-4.12.3.1 Separation
Add 5 mL of sulfuric acid to solution A after the total copper content is determined by filtration electrolysis, and evaporate it to dryness to remove all perchloric acid and nitric acid, add about 150 ml of water, and then add ammonia water to neutralize and add 5 mL excess. Add 10 g of ammonium chloride and boil the solution slightly for 3 minutes. Allow the precipitate to settle, filter with slow filter paper and wash the precipitate with ammonium chloride solution, retain the filtrate (solution C) for determination in 4.12.3.3. 4.12.3.2 Determination of iron content
Dissolve the precipitate on the filter paper with hot hydrochloric acid solution and collect the solution in a conical flask. Add stannous chloride solution until the yellow color of the solution disappears and the excess is 1-2 drops, add 5mL mercuric chloride solution and let stand for 3min. Add 2 drops of o-phenanthroline indicator and titrate with standard titration solution of sodium sulfate. The iron content (XF) expressed as mass percentage is calculated according to formula (13): ×100
Where: C——actual concentration of standard titration solution of sodium sulfate, mol/L; V------volume of standard titration solution of sodium sulfate consumed, mlL; 310
·(13)
m.4．4.． .4Mass of the sample, g.
4.12.3.3 Determination of cobalt and nickel
HG/T2961—1999
Evaporate solution C to 15mL~20mL. If the solution is colored, it indicates the presence of nickel or cobalt, or both, which must be removed before determining zinc. It can be processed and determined according to the relevant standard procedures and the total amount is reported. 4.12.3.4 Determination of zinc
Neutralize the solution treated in 4.12.3.3 with sulfuric acid solution and add 15ml in excess. Dilute with water to 300ml. Add 5 drops of diphenylamine indicator, heat to 75℃, and titrate with potassium ferrocyanide standard titration solution. The color changes from blue to green-yellow at the end point. The zinc content (Xzn) expressed in mass percentage is calculated according to formula (14): Xzm=×100
-actual concentration of potassium ferrocyanide standard titration solution, mol/I Where: C-——
V--volume of potassium ferrocyanide standard titration solution consumed by titration test solution, mL; m·4.4.1.4 Mass of sample, g
4.12.4 Expression of analysis results
The non-copper metal content (X12) expressed in mass percentage is calculated according to formula (15): Xi12 = Xre + XGN + X2n
Where: Xre--iron content, %;
XGN--cobalt and nickel content, %;
Xzn--zinc content, %.
5 Inspection rules
·(15)
5.1 All items specified in this standard are type inspection items, among which cuprous oxide, total copper, total reduction rate, metallic copper, sieve residue and moisture are factory inspection items and must be inspected batch by batch. Under normal production conditions, type inspection shall be carried out at least once every three months. 5.2 Each batch of products shall not exceed 10t.
5.3 Determine the number of sampling units in accordance with the provisions of 6.6 of GB/T6678-1986. Each packaging bag is a sampling unit. When sampling, use a sampler to obliquely insert from the top of the packaging bag to 3/4 of the material layer to collect samples. Mix the samples evenly, reduce them to about 500g by quartering method, and immediately put them into two clean and dry wide-mouth bottles and seal them. Label the bottles with the following: manufacturer name, product name, batch number, sampling date and name of the sampler. One bottle is used as a laboratory sample and the other is kept for three months for future reference. 5.4 Industrial cuprous oxide shall be inspected by the quality supervision and inspection department of the manufacturer in accordance with the provisions of this standard. The manufacturer shall ensure that each batch of products shipped out of the factory meets the requirements of this standard. If any index of the test results does not meet the requirements of this standard, samples shall be taken from twice the amount of packaging for re-testing. Even if only one index does not meet the requirements of this standard in the re-testing results, the entire batch of products shall be unqualified. 5.5 Under the storage and transportation conditions in accordance with this standard, the manufacturer shall ensure that the cuprous oxide content of each batch of cuprous oxide shipped out of the factory is not lower than the index specified in this standard within three months from the date of packaging; within six months or more, it shall be ensured that the cuprous oxide content does not decrease by more than 1% specified in this standard.
5.6 The rounded value comparison method specified in 5.2 of GB/T1250-1989 shall be used to determine whether the test results meet the standards. 6 Marking and labeling
6.1 The packaging of industrial cuprous oxide shall be firmly and clearly marked, including: manufacturer name, factory address, product name, trademark, net content, grade, and this standard number.
6.2 Each batch of products leaving the factory should have a quality certificate. The content includes: manufacturer name, factory address, product name, trademark, net content, grade, batch number or production date, proof that the product quality complies with this standard and the number of this standard. 7 Packaging, transportation and storage
7.1 Industrial cuprous oxide is packaged in three types: iron barrels, plastic barrels or composite paper bags. The iron barrel packaging is lined with a layer of polyethylene film bag with a thickness of not less than 0.07mm. The net content of each barrel of iron barrel packaging is 25kg or 50kg; the net content of each barrel of plastic barrel packaging is 25kg; the composite paper bag packaging uses three layers of kraft paper (80g/m2) with an inner layer of aluminum foil, and the net content of each bag is 25kg. 7.2 The inner bag of the iron drum or plastic drum should be tied with vinyl rope or rope of equivalent quality, or sealed with other equivalent methods to ensure tight sealing. The lid of the iron drum should be sealed firmly; composite paper bag packaging should be sealed with folded mouth. 7.3 Industrial cuprous oxide products should be stored in good ventilation and should not be mixed with oxidants. 7.4. When transporting industrial cuprous oxide products, care should be taken to prevent sun exposure and rain, and keep the packaging intact. 312Add 50mL nitric acid solution to the beaker and boil for 5min. Filter with glass sand that has been washed with nitric acid solution and has reached constant weight, wash the residue with hot water, and dry at 105℃～110℃ to constant weight. 309
4.11.4 Expression of analysis results
HG/T 2961-1999
The content of nitric acid insoluble matter on 75μm sieve expressed as mass percentage (Xn) is calculated according to formula (12): Xn
m-m2×100
--mass of glass sand crucible and nitric acid insoluble matter, g; where: mi---
-mass of glass sand crucible, g;
mass of sample, more.
4.11.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.02%. 4.12 Determination of non-copper metal content
4.12.1 Summary of method
(12)
After the sample is dissolved in acid, copper is separated by electrolysis. The electrolyte is evaporated to remove perchloric acid and nitric acid, dissolved in water, and iron is separated by precipitation by adding ammonia water-ammonium chloride. After acid dissolution, it is titrated with high sodium chloride. Cobalt, nickel and zinc are further separated from the filtrate. Determine by corresponding methods. Report the total amount of the above non-copper metals.
4.12.2 Reagents and solutions
4.12.2.1 Sulfuric acid.
4.12.2.2 Hydrochloric acid.
4.12.2.3 Ammonium chloride
4.12.2.4 Sulfuric acid solution: 1+1.
4.12.2.5 Hydrochloric acid solution: 1+1.
4.12.2.6 Ammonium chloride solution: 50g/1.
4. 12. 2.7
Potassium ferrocyanide solution: 50g/1.
Stannous chloride solution: 50g/1.
4. 12. 2. 8
Mercuric chloride solution: 40g/1..
4. 12. 2. 9
Potassium ferrocyanide standard titration solution: cLK.Fe(CN). ］ is about 0.05mol/L. 4. 12. 2. 10
Prepare and calibrate according to 5.1.2.5 of HG/T23231992. 4. 12. 2. 11
Standard titration solution of perchloric acid: c[Ce(SO4)] is about 0.1 mol/L. O-phenanthroline indicator: 0.5% solution.
4. 12. 2. 12
Diphenylamine indicator: 10 g/L.
4. 12. 2. 13
Weigh 1 g of diphenylamine and dissolve it in 100 mL of sulfuric acid. 4.12.3 Analysis steps
-4.12.3.1 Separation
Add 5 mL of sulfuric acid to solution A after the total copper content is determined by filtration electrolysis, and evaporate it to dryness to remove all perchloric acid and nitric acid, add about 150 ml of water, and then add ammonia water to neutralize and add 5 mL excess. Add 10 g of ammonium chloride and boil the solution slightly for 3 minutes. Allow the precipitate to settle, filter with slow filter paper and wash the precipitate with ammonium chloride solution, retain the filtrate (solution C) for determination in 4.12.3.3. 4.12.3.2 Determination of iron content
Dissolve the precipitate on the filter paper with hot hydrochloric acid solution and collect the solution in a conical flask. Add stannous chloride solution until the yellow color of the solution disappears and the excess is 1-2 drops, add 5mL mercuric chloride solution and let stand for 3min. Add 2 drops of o-phenanthroline indicator and titrate with standard titration solution of sodium sulfate. The iron content (XF) expressed as mass percentage is calculated according to formula (13): ×100
Where: C——actual concentration of standard titration solution of sodium sulfate, mol/L; V------volume of standard titration solution of sodium sulfate consumed, mlL; 310
·(13)
m.4．4.． .4Mass of the sample, g.
4.12.3.3 Determination of cobalt and nickel
HG/T2961—1999
Evaporate solution C to 15mL~20mL. If the solution is colored, it indicates the presence of nickel or cobalt, or both, which must be removed before determining zinc. It can be processed and determined according to the relevant standard procedures and the total amount is reported. 4.12.3.4 Determination of zinc
Neutralize the solution treated in 4.12.3.3 with sulfuric acid solution and add 15ml in excess. Dilute with water to 300ml. Add 5 drops of diphenylamine indicator, heat to 75℃, and titrate with potassium ferrocyanide standard titration solution. The color changes from blue to green-yellow at the end point. The zinc content (Xzn) expressed in mass percentage is calculated according to formula (14): Xzm=×100
-actual concentration of potassium ferrocyanide standard titration solution, mol/I Where: C-——
V--volume of potassium ferrocyanide standard titration solution consumed by titrating the test solution, mL; m·4.4.1.4 Mass of sample, g
4.12.4 Expression of analysis results
The non-copper metal content (X12) expressed in mass percentage is calculated according to formula (15): Xi12 = Xre + XGN + X2n
Where: Xre--iron content, %;
XGN--cobalt and nickel content, %;
Xzn--zinc content, %.
5 Inspection rules
·(15)
5.1 All items specified in this standard are type inspection items, among which cuprous oxide, total copper, total reduction rate, metallic copper, sieve residue and moisture are factory inspection items and must be inspected batch by batch. Under normal production conditions, type inspection shall be carried out at least once every three months. 5.2 Each batch of products shall not exceed 10t.
5.3 Determine the number of sampling units in accordance with the provisions of 6.6 of GB/T6678-1986. Each packaging bag is a sampling unit. When sampling, use a sampler to obliquely insert from the top of the packaging bag to 3/4 of the material layer to collect samples. Mix the samples evenly, reduce them to about 500g by quartering method, and immediately put them into two clean and dry wide-mouth bottles and seal them. Label the bottles with the following: manufacturer name, product name, batch number, sampling date and name of the sampler. One bottle is used as a laboratory sample and the other is kept for three months for future reference. 5.4 Industrial cuprous oxide shall be inspected by the quality supervision and inspection department of the manufacturer in accordance with the provisions of this standard. The manufacturer shall ensure that each batch of products shipped out of the factory meets the requirements of this standard. If any index of the test results does not meet the requirements of this standard, samples shall be taken from twice the amount of packaging for re-testing. Even if only one index does not meet the requirements of this standard in the re-testing results, the entire batch of products shall be unqualified. 5.5 Under the storage and transportation conditions in accordance with this standard, the manufacturer shall ensure that the cuprous oxide content of each batch of cuprous oxide shipped out of the factory is not lower than the index specified in this standard within three months from the date of packaging; within six months or more, it shall be ensured that the cuprous oxide content does not decrease by more than 1% specified in this standard.
5.6 The rounded value comparison method specified in 5.2 of GB/T1250-1989 shall be used to determine whether the test results meet the standards. 6 Marking and labeling
6.1 The packaging of industrial cuprous oxide shall be firmly and clearly marked, including: manufacturer name, factory address, product name, trademark, net content, grade, and this standard number.
6.2 Each batch of products leaving the factory should have a quality certificate. The content includes: manufacturer name, factory address, product name, trademark, net content, grade, batch number or production date, proof that the product quality complies with this standard and the number of this standard. 7 Packaging, transportation and storage
7.1 Industrial cuprous oxide is packaged in three types: iron barrels, plastic barrels or composite paper bags. The iron barrel packaging is lined with a layer of polyethylene film bag with a thickness of not less than 0.07mm. The net content of each barrel of iron barrel packaging is 25kg or 50kg; the net content of each barrel of plastic barrel packaging is 25kg; the composite paper bag packaging uses three layers of kraft paper (80g/m2) with an inner layer of aluminum foil, and the net content of each bag is 25kg. 7.2 The inner bag of the iron drum or plastic drum should be tied with vinyl rope or rope of equivalent quality, or sealed with other equivalent methods to ensure tight sealing. The lid of the iron drum should be sealed firmly; composite paper bag packaging should be sealed with folded mouth. 7.3 Industrial cuprous oxide products should be stored in good ventilation and should not be mixed with oxidants. 7.4. When transporting industrial cuprous oxide products, care should be taken to prevent sun exposure and rain, and keep the packaging intact. 312Add 50mL nitric acid solution to the beaker and boil for 5min. Filter with glass sand that has been washed with nitric acid solution and has reached constant weight, wash the residue with hot water, and dry at 105℃～110℃ to constant weight. 309
4.11.4 Expression of analysis results
HG/T 2961-1999
The content of nitric acid insoluble matter on 75μm sieve expressed as mass percentage (Xn) is calculated according to formula (12): Xn
m-m2×100
--mass of glass sand crucible and nitric acid insoluble matter, g; where: mi---
-mass of glass sand crucible, g;
mass of sample, more.
4.11.5 Allowable difference
The arithmetic mean of the parallel determination results is taken as the determination result. The absolute difference between the results of two parallel determinations shall not exceed 0.02%. 4.12 Determination of non-copper metal content
4.12.1 Summary of method
(12)
After the sample is dissolved in acid, copper is separated by electrolysis. The electrolyte is evaporated to remove perchloric acid and nitric acid, dissolved in water, and iron is separated by precipitation by adding ammonia water-ammonium chloride. After acid dissolution, it is titrated with high sodium chloride. Cobalt, nickel and zinc are further separated from the filtrate. Determine by corresponding methods. Report the total amount of the above non-copper metals.
4.12.2 Reagents and solutions
4.12.2.1 Sulfuric acid.
4.12.2.2 Hydrochloric acid.
4.12.2.3 Ammonium chloride
4.12.2.4 Sulfuric acid solution: 1+1.
4.12.2.5 Hydrochloric acid solution: 1+1.
4.12.2.6 Ammonium chloride solution: 50g/1.
4. 12. 2.7
Potassium ferrocyanide solution: 50g/1.
Stannous chloride solution: 50g/1.
4. 12. 2. 8
Mercuric chloride solution: 40g/1..
4. 12. 2. 9
Potassium ferrocyanide standard titration solution: cLK.Fe(CN). ］ is about 0.05mol/L. 4. 12. 2. 10
Prepare and calibrate according to 5.1.2.5 of HG/T23231992. 4. 12. 2. 11
Standard titration solution of perchloric acid: c[Ce(SO4)] is about 0.1 mol/L. O-phenanthroline indicator: 0.5% solution.
4. 12. 2. 12
Diphenylamine indicator: 10 g/L.
4. 12. 2. 13
Weigh 1 g of diphenylamine and dissolve it in 100 mL of sulfuric acid. 4.12.3 Analysis steps
-4.12.3.1 Separation
Add 5 mL of sulfuric acid to solution A after the total copper content is determined by filtration electrolysis, and evaporate it to dryness to remove all perchloric acid and nitric acid, add about 150 ml of water, and then add ammonia water to neutralize and add 5 mL excess. Add 10 g of ammonium chloride and boil the solution slightly for 3 minutes. Allow the precipitate to settle, filter with slow filter paper and wash the precipitate with ammonium chloride solution, retain the filtrate (solution C) for determination in 4.12.3.3. 4.12.3.2 Determination of iron content
Dissolve the precipitate on the filter paper with hot hydrochloric acid solution and collect the solution in a conical flask. Add stannous chloride solution until the yellow color of the solution disappears and the excess is 1-2 drops, add 5mL mercuric chloride solution and let stand for 3min. Add 2 drops of o-phenanthroline indicator and titrate with standard titration solution of sodium sulfate. The iron content (XF) expressed as mass percentage is calculated according to formula (13): ×100
Where: C——actual concentration of standard titration
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