CN102586803A - Method for preparing low-lead electrolytic manganese metal - Google Patents
Method for preparing low-lead electrolytic manganese metal Download PDFInfo
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- CN102586803A CN102586803A CN2012100840096A CN201210084009A CN102586803A CN 102586803 A CN102586803 A CN 102586803A CN 2012100840096 A CN2012100840096 A CN 2012100840096A CN 201210084009 A CN201210084009 A CN 201210084009A CN 102586803 A CN102586803 A CN 102586803A
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Abstract
The invention relates to a method for preparing low-lead electrolytic manganese metal. The technical scheme is that ceric sulfate [Ce(SO4)2-4H2O] is used as an antioxidant to perform electrolysis and production of the low-lead electrolytic manganese metal when the cathode-current density is controlled in a range of 350-400 A/m2 and the anodic-current density is controlled in a range of 600-700 A/m2, lead content in the electrolytic manganese metal is less than 5 ug/g, thereby meeting the requirements to electrolytic manganese metal products in the production of high-end alloy products.
Description
Technical field
The present invention relates to the production of manganese metal, especially a kind of working method of low plumbous electrolytic metal Mn.
Background technology
In existing industrial production electrolytic metal Mn, adopt stainless steel plate as negative electrode, plumbous antimony tin silver quad alloy is as anode, and the aqueous solution that uses manganous sulfate and ammonium sulfate is as electrolytic solution and add oxidation inhibitor and carry out electrolysis, and electrolytic metal Mn is folded on negative electrode.
Oxidation inhibitor mainly adopts tin anhydride (SeO at present
2) or sulfurous gas (SO
2), but the former when making oxidation inhibitor in the electrolytic metal product plumbous (Pb) content reach 30～60ug/g, selenium (Se) content reaches 0.05～0.07%.When the latter makes oxidation inhibitor in the electrolytic metal product plumbous (Pb) content reach 40～80ug/g, sulphur (S) content reaches 0.04～0.06%.Tin anhydride (SeO
2) belonging to highly toxic product, the production process control and management is strict, and sulfurous gas is poisonous, has intense stimulus property smell, bigger to human harm aborning.
Except that above-mentioned two kinds of oxidation inhibitor; Adopt hydroxy acid, glycerine, formic acid, telluric acid, formaldehyde, thiocyanate-, alcohol, Hydrocerol A, ammonium acetate and ammonium oxalate etc. in addition; Plumbous (Pb) content reaches 60～150ug/g in the electrolytic metal manganese product that these oxidation inhibitor adding electrolysis production go out; And anode and cathode current efficiency is low, and foreign matter content is high in the product.
In high-end alloy product production to electrolytic metal Mn in lead content require to be lower than 5ug/g.Above-mentioned oxidation inhibitor adding is carried out the low plumbous electrolytic metal manganese product of electrolysis production and can not be satisfied.
Summary of the invention
The purpose of this invention is to provide a kind of reagent and make the working method that low plumbous electrolytic metal Mn is produced in the oxidation inhibitor electrolysis, make that lead content is lower than 5ug/g in the electrolytic metal Mn, satisfy high-end alloy product produce in to the electrolytic metal Mn requirement of products.
Technical scheme of the present invention:
For achieving the above object, draw up following solution to the problems described above, just cathode current density is controlled at 350-400A/m
2Be controlled at 600-700A/m with anodic current density
2The time, adopt ceric sulfate [Ce (SO
4)
24H
2O] do the production that low plumbous electrolytic metal Mn is produced in the oxidation inhibitor electrolysis.
In addition, characteristic of the present invention also has, and ceric sulfate (in Ce) concentration is controlled at 5-15ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 1-5ug/g.
In addition, characteristic of the present invention also has, and ceric sulfate (in Ce) concentration is controlled at 10-19ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1-5ug/g, plumbous (Pb) content 4.1-5ug/g of the electrolytic metal product of electrolysis production.
In addition, characteristic of the present invention also has, and ceric sulfate (in Ce) concentration is controlled at 20-29ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1-5ug/g, plumbous (Pb) content 3.1-4ug/g of the electrolytic metal product of electrolysis production.
In addition, characteristic of the present invention also has, and ceric sulfate (in Ce) concentration is controlled at 30-39ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1-5ug/g, plumbous (Pb) content 2.1-3ug/g of the electrolytic metal product of electrolysis production.
In addition, characteristic of the present invention also has, and ceric sulfate (in Ce) concentration is controlled at 40-49ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1-5ug/g, plumbous (Pb) content 1.1-2ug/g of the electrolytic metal product of electrolysis production.
In addition, characteristic of the present invention also has, and ceric sulfate (in Ce) concentration is controlled at 50-70ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1-5ug/g, plumbous (Pb) content≤1ug/g of the electrolytic metal product of electrolysis production.
In addition, the characteristic of the inventive method also has, and electrolysis feed liquor manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34-36g/l, and ammonium sulfate concentrations is controlled at 105-115g/l.
In addition, the characteristic of the inventive method also has, and cathode compartment pH value is controlled at 7.5-8.5 in the electrolytic process, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13-16g/l, temperature is controlled at 40-45 ℃, and electrolysing period is 24 hours.
Provided by the present inventionly be; Under above-mentioned ceric sulfate (in Ce) concentration, tin anhydride (in Se) concentration, manganous sulfate concentration and ammonium sulfate concentrations condition, carry out the method for the low plumbous electrolytic metal Mn of electrolysis production, the electrolytic metal manganese product lead content≤5ug/g of electrolysis production.
Advantage of the present invention:
1, lead content all is lower than in the product that traditional technology produces lead content more than 10 times less than 5ug/g in the electrolytic metal manganese product produced of the present invention.
2, the used oxidation inhibitor ceric sulfate of the present invention is lower than traditional technology oxidation inhibitor tin anhydride or sulfurous gas toxicity, and is safe in utilization in the production, less to human harm, and storage is convenient.
3, veneer output of the present invention can improve usage ratio of equipment a little more than traditional processing technology under identical shared device device, reduces the investment of shared device.
4, the present invention produces easy control, and the cerium content of bringing in the product all is lower than the impurity of bringing in the traditional technology (selenium, sulphur).
Embodiment
The present invention uses and adopts stainless steel plate as negative electrode, and plumbous antimony tin silver quad alloy is as anode, and cathode current density is controlled at 350-400A/m
2Be controlled at 600-700A/m with anodic current density
2
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 10-70ug/g in the electrolysis feed liquor manganese sulfate solution of the present invention, and ceric sulfate (in Ce) concentration is controlled at 5-15ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage.
Electrolysis feed liquor of the present invention consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34-36g/l, and ammonium sulfate concentrations is controlled at 105-115g/L, adds continuously in the electrolytic process.
Cathode compartment pH value is controlled at 7.5-8.5 in the electrolytic process of the present invention, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13-16g/l, temperature is controlled at 40-45 ℃, and electrolysing period is 24 hours.
Embodiment 1
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 10ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 5ug/g.Ceric sulfate (in Ce) concentration is controlled at 15ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 5ug/g.
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 36g/l, and ammonium sulfate concentrations is controlled at 105g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 350A/m in the electrolytic process
2Be controlled at 600A/m with anodic current density
2Cathode compartment pH value is controlled at 7.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 16g/l, temperature is controlled at 40 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 1, and experimental tank number is 1-3; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 4-5; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.020g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 6-7.
Table 1
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 1 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 2
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 15ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 2.5ug/g.Ceric sulfate (in Ce) concentration is controlled at 10ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 2.5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 35g/l, and ammonium sulfate concentrations is controlled at 110g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 380A/m in the electrolytic process
2Be controlled at 650A/m with anodic current density
2Cathode compartment pH value is controlled at 8.0, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 15g/l, temperature is controlled at 42 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 2, and experimental tank number is 8-10; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 11-12; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.025g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 13-14.
Table 2
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 2 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 3
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 19ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1ug/g.Ceric sulfate (in Ce) concentration is controlled at 5ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 1ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34g/l, and ammonium sulfate concentrations is controlled at 115g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 400A/m in the electrolytic process
2Be controlled at 700A/m with anodic current density
2Cathode compartment pH value is controlled at 8.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13g/l, temperature is controlled at 45 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 2, and experimental tank number is 15-17; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 18-19; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.029g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 20-21.
Table 3
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 3 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 4
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 20ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 5ug/g.Ceric sulfate (in Ce) concentration is controlled at 15ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 36g/l, and ammonium sulfate concentrations is controlled at 105g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 350A/m in the electrolytic process
2Be controlled at 600A/m with anodic current density
2Cathode compartment pH value is controlled at 7.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 16g/l, temperature is controlled at 40 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 4, and experimental tank number is 22-24; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 25-26; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.030g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 27-28.
Table 4
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 4 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 5
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 25ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 2.5ug/g.Ceric sulfate (in Ce) concentration is controlled at 10ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 2.5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 35g/l, and ammonium sulfate concentrations is controlled at 110g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 380A/m in the electrolytic process
2Be controlled at 650A/m with anodic current density
2Cathode compartment pH value is controlled at 8.0, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 15g/l, temperature is controlled at 42 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 5, and experimental tank number is 29-31; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 32-33; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.0325g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 34-35.
Table 5
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 5 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 6
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 29ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1ug/g.Ceric sulfate (in Ce) concentration is controlled at 5ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 1ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34g/l, and ammonium sulfate concentrations is controlled at 115g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 400A/m in the electrolytic process
2Be controlled at 700A/m with anodic current density
2Cathode compartment pH value is controlled at 8.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13g/l, temperature is controlled at 45 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 6, and experimental tank number is 36-38; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 39-40; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.035g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 41-42.
Table 6
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 6 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 7
In the electrolyzer (long 4.5 meters, dark 11 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 30ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 5ug/g.Ceric sulfate (in Ce) concentration is controlled at 15ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 36g/l, and ammonium sulfate concentrations is controlled at 105g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 350A/m in the electrolytic process
2Be controlled at 600A/m with anodic current density
2Cathode compartment pH value is controlled at 7.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 16g/l, temperature is controlled at 40 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 7, and experimental tank number is 43-45; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 46-47; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.036g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 48-49.
Table 7
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 7 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 8
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 35ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 2.5ug/g.Ceric sulfate (in Ce) concentration is controlled at 10ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 2.5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 35g/l, and ammonium sulfate concentrations is controlled at 110g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 380A/m in the electrolytic process
2Be controlled at 650A/m with anodic current density
2Cathode compartment pH value is controlled at 8.0, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 15g/l, temperature is controlled at 42 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 8, and experimental tank number is 50-52; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 53-54; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.0375g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 55-56.
Table 8
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 8 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 9
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 39ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1ug/g.Ceric sulfate (in Ce) concentration is controlled at 5ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 1ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34g/l, and ammonium sulfate concentrations is controlled at 115g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 400A/m in the electrolytic process
2Be controlled at 700A/m with anodic current density
2Cathode compartment pH value is controlled at 8.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13g/l, temperature is controlled at 45 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 9, and experimental tank number is 57-59; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 60-61; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.03g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 62-63.
Table 9
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 9 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 10
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 40ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 5ug/g.Ceric sulfate (in Ce) concentration is controlled at 15ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 36g/l, and ammonium sulfate concentrations is controlled at 105g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 350A/m in the electrolytic process
2Be controlled at 600A/m with anodic current density
2Cathode compartment pH value is controlled at 7.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 16g/l, temperature is controlled at 40 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 10, and experimental tank number is 64-66; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 67-68; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.040g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 69-70.
Table 10
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 10 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 11
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 45ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 2.5ug/g.Ceric sulfate (in Ce) concentration is controlled at 10ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 2.5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 35g/l, and ammonium sulfate concentrations is controlled at 110g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 380A/m in the electrolytic process
2Be controlled at 650A/m with anodic current density
2Cathode compartment pH value is controlled at 8.0, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 15g/l, temperature is controlled at 42 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 11, and experimental tank number is 71-73; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 74-75; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.0430g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 76-77.
Table 11
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 11 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 12
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 49ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1ug/g.Ceric sulfate (in Ce) concentration is controlled at 5ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 1ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34g/l, and ammonium sulfate concentrations is controlled at 115g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 400A/m in the electrolytic process
2Be controlled at 700A/m with anodic current density
2Cathode compartment pH value is controlled at 8.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13g/l, temperature is controlled at 45 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 12, and experimental tank number is 78-80; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 81-82; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.045g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 83-84.
Table 12
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 12 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 13
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 50ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 5ug/g.Ceric sulfate (in Ce) concentration is controlled at 5ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 36g/l, and ammonium sulfate concentrations is controlled at 105g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 350A/m in the electrolytic process
2Be controlled at 600A/m with anodic current density
2Cathode compartment pH value is controlled at 7.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 16g/l, temperature is controlled at 40 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 13, and experimental tank number is 85-87; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 88-89; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.045g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 90-91.
Table 13
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 13 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 14
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 60ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 2.5ug/g.Ceric sulfate (in Ce) concentration is controlled at 10ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 2.5ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 35g/l, and ammonium sulfate concentrations is controlled at 110g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 380A/m in the electrolytic process
2Be controlled at 650A/m with anodic current density
2Cathode compartment pH value is controlled at 8.0, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 15g/l, temperature is controlled at 42 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 14, and experimental tank number is 92-94; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 95-96; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.050g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 97-98.
Table 14
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 14 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Embodiment 15
In the electrolyzer (long 4.5 meters, dark 1.1 meters, wide 0.8 meter), anode is plumbous antimony tin silver quad alloy, and negative electrode is a stainless steel plate.
Oxidation inhibitor ceric sulfate (in Ce) concentration is controlled at 70ug/g in the electrolysis feed liquor manganese sulfate solution, and tin anhydride (in Se) concentration is controlled at 1ug/g.Ceric sulfate (in Ce) concentration is controlled at 5ug/g in the preceding cathode compartment electrolytic solution of electrolysis tankage, and tin anhydride (in Se) concentration is controlled at 1ug/g
The electrolysis feed liquor consists of, and manganese sulfate solution is (with Mn
2+Meter) concentration is controlled at 34g/l, and ammonium sulfate concentrations is controlled at 115g/l, adds continuously in the electrolytic process.
Cathode current density is controlled at 400A/m in the electrolytic process
2Be controlled at 700A/m with anodic current density
2Cathode compartment pH value is controlled at 8.5, and manganese sulfate solution is (with Mn
2+Meter) be controlled at 13g/l, temperature is controlled at 45 ℃, and electrolysing period is 24 hours.
Product is undertaken by normal postprocessing working procedures after going out groove, and its physico-chemical analysis result is shown in table 15, and experimental tank number is 99-101; Comparison groove 1 oxidation inhibitor adopts tin anhydride, and all the other conditions are identical with experimental tank, and groove number is 102-103; Comparison groove 2 oxidation inhibitor adopt sulfurous gas, and sulfur dioxide concentration is controlled at 0.055g/l in the electrolysis feed liquor manganese sulfate solution, does not add tin anhydride before the electrolysis tankage, and all the other conditions are identical with experimental tank, and groove number is 104-105.
Table 15
Trace element analysis result in the table: pb detects with ICP; Ce, SeO
2Detect with volumetry; Sulphur detects with infrared high frequency carbon and sulfur analytical instrument; ND representes not detect.
Can know that from table 15 lead content is starkly lower than comparison groove in the product of the present invention, other micro-summation all is lower than comparison groove.
Claims (8)
1. the preparation method of one kind low plumbous electrolytic metal Mn, it is characterized in that: cathode current density is controlled at 350-400A/m
2Be controlled at 600-700A/m with anodic current density
2The time, adopt ceric sulfate [Ce (SO
4)
24H
2O] make the low plumbous electrolytic metal Mn of oxidation inhibitor electrolysis production.
2. the preparation method of low plumbous electrolytic metal Mn as claimed in claim 1 is characterized in that: before the electrolysis tankage in the cathode compartment electrolytic solution ceric sulfate concentration be controlled at 5-15 ug/g in Ce, tin anhydride concentration is controlled at 1-5ug/g in Se.
3. according to claim 1 or claim 2 the preparation method of low plumbous electrolytic metal Mn; It is characterized in that: ceric sulfate concentration is controlled at 10-19ug/g in Ce in the electrolysis feed liquor manganese sulfate solution in said electrolysis; Tin anhydride concentration is controlled at 1-5ug/g in Se, the electrolytic metal product lead content 4.1-5ug/g of electrolysis production.
4. according to claim 1 or claim 2 the preparation method of low plumbous electrolytic metal Mn; It is characterized in that: ceric sulfate concentration is controlled at 20-29ug/g in Ce in the electrolysis feed liquor manganese sulfate solution in said electrolysis; Tin anhydride concentration is controlled at 1-5ug/g in Se, the electrolytic metal product lead content 3.1-4ug/g of electrolysis production.
5. according to claim 1 or claim 2 the preparation method of low plumbous electrolytic metal Mn; It is characterized in that: ceric sulfate concentration is controlled at 30-39ug/g in Ce in the electrolysis feed liquor manganese sulfate solution in said electrolysis; Tin anhydride concentration is controlled at 1-5ug/g in Se, the electrolytic metal product lead content 2.1-3ug/g of electrolysis production.
6. according to claim 1 or claim 2 the preparation method of low plumbous electrolytic metal Mn; It is characterized in that: ceric sulfate concentration is controlled at 40-49ug/g in Ce in the electrolysis feed liquor manganese sulfate solution in said electrolysis; Tin anhydride concentration is controlled at 1-5ug/g in Se, the electrolytic metal product lead content 1.1-2ug/g of electrolysis production.
7. according to claim 1 or claim 2 the preparation method of low plumbous electrolytic metal Mn; It is characterized in that: ceric sulfate concentration is controlled at 50-70ug/g in Ce in the electrolysis feed liquor manganese sulfate solution in said electrolysis; Tin anhydride concentration is controlled at 1-5ug/g in Se, the electrolytic metal product lead content≤1ug/g of electrolysis production.
8. like the preparation method of claim 1,2,3,4,5,6 or 7 described low plumbous electrolytic metal Mns, it is characterized in that: electrolysis feed liquor manganese sulfate solution concentration is with Mn
2+Meter is controlled at 34-36 g/l, and ammonium sulfate concentrations is controlled at 105-115 g/l; Cathode compartment pH value is controlled at 7.5-8.5 in the electrolytic process, and manganese sulfate solution concentration is with Mn
2+Meter is controlled at 13-16 g/l, and temperature is controlled at 40-45 ℃, and electrolysing period is 24 hours.
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| CN114752965A (en) * | 2022-03-28 | 2022-07-15 | 南方锰业集团有限责任公司大新锰矿分公司 | Preparation method of low-selenium high-purity electrolytic manganese |
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| CN114752965A (en) * | 2022-03-28 | 2022-07-15 | 南方锰业集团有限责任公司大新锰矿分公司 | Preparation method of low-selenium high-purity electrolytic manganese |
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