CN102094215B - Horizontal movement type continuous electrolytic method and device of lead in regenerative lead-containing material - Google Patents
Horizontal movement type continuous electrolytic method and device of lead in regenerative lead-containing material Download PDFInfo
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- CN102094215B CN102094215B CN2011100020815A CN201110002081A CN102094215B CN 102094215 B CN102094215 B CN 102094215B CN 2011100020815 A CN2011100020815 A CN 2011100020815A CN 201110002081 A CN201110002081 A CN 201110002081A CN 102094215 B CN102094215 B CN 102094215B
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title abstract description 33
- 230000001172 regenerating effect Effects 0.000 title abstract 3
- 238000003860 storage Methods 0.000 claims abstract description 22
- 230000008929 regeneration Effects 0.000 claims abstract description 21
- 238000011069 regeneration method Methods 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 37
- 230000005540 biological transmission Effects 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 230000007246 mechanism Effects 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 210000005056 cell body Anatomy 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- 239000002253 acid Substances 0.000 abstract description 11
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- 239000002699 waste material Substances 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 239000011505 plaster Substances 0.000 description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 238000007599 discharging Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 7
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
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- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
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- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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Abstract
The invention relates to a horizontal movement type continuous electrolytic method of lead in a regenerative lead-containing material and the method uses the lead-containing paste in waste lead acid storage batteries and the lead-containing paste generated in the production process of the lead acid storage batteries as raw material to perform electrolytic regeneration. In the electrolytic process, alkaline electrolyte is used, a cathode and an anode are arranged in a horizontal manner, the lead-containing paste to be treated is filled in a cathode disk to perform continuous horizontal movements; and the lead-containing paste is reduced to obtain lead and realize the continuous electrolytic regeneration of lead. The invention also provides a horizontal movement type continuous electrolytic device of lead in the regenerative lead-containing material. By adopting the method and device of the invention, the continuous production can be realized, the gas lock effect can be avoided or greatly reduced, the current distribution of the cathode and the anode can be improved, the cell voltage can be improved and the production efficiency can be effectively increased.
Description
Technical field
The present invention relates to lead resource wet reclamation technical field, particularly relate to plumbous method and apparatus in a kind of continuous electrolysis regeneration lead-containing material.
Background technology
At present, lead acid cell has obtained being widely used, but has also brought the handling problem of this battery after inefficacy is scrapped thereupon.Because the singularity of lead material as if not fine being located in of this refuse battery managed and utilization, both can work the mischief to ecotope, also was simultaneously a loss greatly of lead resource.Therefore lead-acid accumulator and other lead-containing material (like the plumbiferous cream pug that produces in the lead storage battery production process) must reasonably be handled and utilized.For the recycling treatment of lead-acid accumulator and lead-containing material, developed the thermal process of large-scale production, Wet technique is research and development to some extent also.The pyrogenic process technology has obtained using more widely, but its treatment temp is high, and the lead resource recovery is lower, and it is serious that lead steam and sulfurous gas discharge the environmental pollution that is produced simultaneously, produced serious consequence.Method that the wet method electrolytic regeneration is plumbous and technology are because of treatment temp low (room temperature and normal temperature), and environmental pollution is little, and characteristics such as lead recovery height have been subjected to bigger attention.Should technology mainly concentrate on acid system and alkaline process two big technologies at present.The principle that adopts the electrolysis tech of alkaline medium is to utilize the cathodic reduction reaction of materials such as plumbous vitriol, plumbous oxide.Conventional new electrobath and electrolysis mode at intermittence have been adopted at present in this process implementing; Its weak point is: (1) is because the cathode and anode in the electrolyzer adopts vertically placement; Cause the oxygen of anode generation and the hydrogen partial of different electrolysis stage negative electrode generation to be separated out from bottom to top; Make the electrolytic solution between the anode and cathode be filled with great amount of bubbles, form the vapour lock layer, increase bath voltage and energy consumption, the interfering current uniform distribution; (2) during electrolysis, electrode is vertically placed, and material shelling and cause yin, yang intereelectrode short-circuit in the cathode frame is generally selected big cathode and anode spacing (like 8cm), causes bath voltage high, and electrolysis energy consumption is big; (3) vertically place owing to electrode; In the big or electrolysis later stage when electric current, cathode hydrogen evolution produces great amount of bubbles can make the lead powder bed of material of cathode surface wash away, loosen, and causes in extraneous solution, disperseing the spongy lead swimmer; Be prone to cause intereelectrode short-circuit; Plumbous product also can fall into bottom of electrolytic tank simultaneously, causes and collects difficulty, and increase desilting frequency also constitutes a latent danger; (4) produce the batch operation pattern that adopted, electrolysis need be cut off the electricity supply after finishing, and from electric groove, hangs out the very big negative plate of quality and takes out plumbous mud, and the labor operation amount is excessive, influences production efficiency simultaneously.
Summary of the invention
In order to overcome the step mode of production, anode vapour lock effect, the more high deficiency of bath voltage that the lead resource method exists in the existing electrolytic regeneration lead-containing material; The present invention proposes a kind of mode of operation that can realize the serialization electrolysis production, can avoid or alleviate the vapour lock effect significantly, reduce bath voltage and the horizontal movable type continuous electrolysis regeneration lead-containing material of effectively enhancing productivity in plumbous method and device.
The technical solution adopted for the present invention to solve the technical problems is:
Plumbous method in a kind of horizontal movable type continuous electrolysis regeneration lead-containing material; The lead plaster mud that contains with in lead-acid accumulator and the lead acid cell production process is that raw material carries out electrolytic regeneration, in the electrolytic process, adopts alkaline electrolyte; Anode and cathode is all arranged in a horizontal manner; The pending lead plaster mud full-filling continuous horizontal on cathode disc that contains moves, and is become plumbous by electrolytic reduction simultaneously, realizes plumbous serialization electrolytic regeneration;
During the electrolysis operation, will contain the even full-filling of lead plaster mud earlier in cathode disc, put into electrolytic solution to cathode disc one by one from feeding mouth through the charging mechanism then, place above the transmission crawler belt,, make cathode disc transmission forward continuously through the transmission of drive device drives crawler belt; When cathode disc is transmitted crawler-tread to electrolyzer discharge port, take out cathode disc through the discharging mechanism; Electrolysate is processed lead pig through aftertreatment.
Further, be that 4～40% sodium hydroxide solution is an electrolytic solution with temperature at 20 ℃～70 ℃, massfraction, the interpole gap of control anode and negative electrode is 1～5cm, the control cathode apparent current density is 100～600A/m
2
Further again, the said lead plaster mud that contains is for containing lead plaster mud after removing sulfate radical.
Or the said lead plaster mud that contains is for containing lead plaster mud without what remove that sulfate radical handles.For containing lead plaster mud, need regularly to adopt crystallization process to remove sodium sulfate wherein to electrolytic solution without removing the situation that sulfate radical is handled.
Described contain lead plaster mud in full-filling to cathode disc before, use earlier massfraction be 10～30% sodium hydroxide solution material furnishing paste, and make the density that contains lead plaster mud reach 2～5g/cm
3
Further, the method for described electrolysate aftertreatment is that the material on the cathode disc that takes out after electrolysis is finished takes off, and changes the product storage tank over to, in nitrogen atmosphere, carries out the briquetting dehydration, gets into lead smelting furnace then, is fused into plumbous liquid, is cast into lead pig at last.
Plumbous device in a kind of horizontal movable type continuous electrolysis regeneration lead-containing material; Said device comprises horizontal movable type negative electrode, anode, cell body and electrolyte circulation system; Said horizontal movable type negative electrode comprises double coaxial crawler belt, negative electrode conducting copper and cathode disc composition; Said double coaxial crawler belt horizontal arrangement drives the rotating shaft transmission in the electrolyzer bottom through external motor and speed change system, moves ahead continuously; Below said negative electrode conducting copper was arranged in the middle of the double crawler belt, copper bar top was provided with the level trough of placing liquid static eliminator; Said cathode disc level places on the double crawler belt, and the cathode disc bottom is provided with conducting rod; Said conducting rod passes the intermediate space of said coaxial double crawler belt and is electrically connected with liquid static eliminator during said copper bar top water is risen as high as the banks.
Further, above negative electrode, said frame is provided with height regulating rod and regulates the spacing between anode and the negative electrode said anode through the frame horizontal arrangement; Said anode comprises anode housing, inner structure part and bus, and said inner structure part is electrically connected with housing, and said bus is positioned at the both sides of anode housing, and said bus is connected with main copper bar conduction.
Further, said cell body adopts alkaline-resisting material, said electrolyzer two ends be provided with cathode disc into and out of mechanism.
Further again; Said electrolyte circulation system comprises high-order storage tank and the low level storage tank that is provided with the heating cooling apparatus; Described high-order storage tank is connected with electrolyte outlet with the electrolytic solution import of electrolyzer respectively with the low level storage tank, and described high-order storage tank is connected with the low level storage tank through recycle pump; Described electrolytic solution is realized circulation between high-order storage tank, electrolyzer, low level storage tank.
Technical conceive of the present invention is: adopt negative electrode horizontal movable type continuous electrolysis mode; The cathode and anode average level is placed in the electrolyzer, and wherein negative electrode is arranged on the electrolyzer bottom, drives the negative electrode material disc through crawler belt and moves ahead; Adopt liquid static eliminator to electrically connect, realize the regeneration of negative electrode material continuous electrolysis; The anode water plain cloth places negative electrode top, adopts the electrode structure of being convenient to gas evolution, and bubble is directly derived, and avoids or significantly alleviates the vapour lock effect; The quick effusion of the horizontal positioned of negative electrode material and anode gas bubble can reduce cathode and anode spacing as much as possible, the uniform distribution that helps reducing bath voltage He improve the anode and cathode electric current.
Beneficial effect of the present invention mainly shows:
(1) anode and cathode adopts horizontal arranging mode, and the oxygen bubbles of separating out on the anode can directly be overflowed, and is difficult for causing the vapour lock effect of electrolytic solution between cathode and anode, can reduce bath voltage more significantly, helps anode and cathode electric current uniform distribution;
(2) anode and cathode adopts horizontal arranging mode, and the flat full-filling of pending lead plaster muddy water poor electric contact and plumbous mud between lead plaster mud and the negative electrode conductive pane (plate) can not occur from disengaging of negative electrode frame or the phenomenon that falls down in cathode disc;
(3) cathode and anode spacing can be reduced to lower degree, like 1～2cm, helps further reducing bath voltage;
(4) adopt the crawler belt transmission to drive the negative electrode material disc and move continuously, the production process continous-stable, simple to operate, can significantly enhance productivity.
Contain lead plaster mud cathodic reduction average cell voltage about 2.5V with respect to traditional; Adopt the bath voltage of the present invention's technology can be reduced to (there is something special can be reduced to below the 1.7V) below the 2.0V; It is variant that concrete direct current consumption is formed different numerical value according to the lead plaster raw material; With common waste lead acid battery lead cream metering, direct current consumption is saved more than about 50kWh/t Pb.
Description of drawings
Fig. 1 is the structural representation of horizontal movable type electrolyzer.
Fig. 2 is the schematic cross-section of negative electrode conducting copper.
Fig. 3 is the anode construction synoptic diagram.
Fig. 4 is the circulation of elecrolyte synoptic diagram.
Embodiment
Below in conjunction with accompanying drawing the present invention is further described.
Embodiment 1
With reference to Fig. 1～Fig. 4, plumbous method in a kind of horizontal movable type continuous electrolysis regeneration lead-containing material is that raw material carries out electrolytic regeneration with the lead plaster mud that contains that produces in lead-acid accumulator and the lead acid cell production process; In the electrolytic process; Adopt alkaline electrolyte, anode and cathode arranges in a horizontal manner that all the pending lead plaster mud full-filling continuous horizontal on cathode disc that contains moves; Become plumbous by electrolytic reduction simultaneously, realize plumbous serialization electrolytic regeneration;
During the electrolysis operation, will contain the even full-filling of lead plaster mud earlier in cathode disc, put into electrolytic solution to cathode disc one by one from feeding mouth through the charging mechanism then, place above the transmission crawler belt,, make cathode disc transmission continuously forward through the transmission of drive device drives crawler belt; When cathode disc is transmitted crawler-tread to electrolyzer discharge port, take out cathode disc through the discharging mechanism; Electrolysate is processed lead pig through aftertreatment.
With temperature is that 20 ℃～70 ℃, massfraction are that 4～40% sodium hydroxide solution is an electrolytic solution, the interpole gap 1～5cm between control anode frame and cathode disc, and the control cathode apparent current density is 100～600A/m
2
The said lead plaster mud that contains is for containing lead plaster mud after removing sulfate radical.Or the said lead plaster mud that contains is for containing lead plaster mud without what remove that sulfate radical handles.For containing lead plaster mud, need regularly to adopt crystallization process to remove sodium sulfate wherein to electrolytic solution without removing the situation that sulfate radical is handled.
Described contain lead plaster mud in full-filling to cathode disc before, using earlier massfraction is that 10～30% sodium hydroxide solution carries out pre-treatment, makes the density that contains lead plaster mud reach 2～5g/cm
3
The method of described electrolysate aftertreatment is that the material on the cathode disc that takes out after electrolysis is finished takes off, and changes the product storage tank over to, in nitrogen atmosphere, carries out the briquetting dehydration, gets into lead smelting furnace then, is fused into plumbous liquid, is cast into lead pig at last.
With reference to Fig. 1～Fig. 4; Plumbous device in a kind of horizontal movable type continuous electrolysis regeneration lead-containing material; Comprise the cathode disc 7 of treating electrolytic lead-containing material in order to the electrolyzer 1 of placement alkaline electrolyte with in order to placement; The bottom of said electrolyzer 1 is provided with transmission crawler belt 3, and said transmission crawler belt 3 two ends are sleeved in the rotating shaft 2, and said rotating shaft 2 is in transmission connection with drive unit;
Said double coaxial crawler belt 3 horizontal arrangement drive the rotating shaft transmission in the electrolyzer bottom through external motor and speed change system, move ahead continuously; Below said negative electrode conducting copper 4 was arranged in the middle of the double crawler belt, copper bar top was provided with the horizontal notch of placing liquid static eliminator; Said cathode disc 7 levels place on the double crawler belt, and cathode disc 7 bottoms are provided with conducting rod; Said conducting rod passes the intermediate space of said coaxial double crawler belt and is electrically connected with liquid static eliminator 10 in the said copper bar notch.
One end of said double coaxial transmission crawler belt 3 is a feeding mouth; The other end is a discharge port; The top of said feeding mouth is provided with in order to cathode disc is put into from top to bottom the charging mechanism 9 of feeding mouth, and the top of said discharge port is provided with in order to cathode disc is seen from top to bottom off the discharging mechanism 5 of discharge port;
The below is provided with negative electrode conducting copper 4 in the middle of the said double coaxial transmission crawler belt 3; The top of said negative electrode conducting copper 4 is provided with the level trough of placing liquid static eliminator 10; The bottom of said cathode disc 7 is provided with conducting rod, and the intermediate space that said conducting rod passes said coaxial double crawler belt is electrically connected with said liquid static eliminator 10.
The top of said transmission crawler belt 3 is provided with the anode frame 6 of horizontal arrangement, and said anode frame 6 comprises anode housing 11, inner rip 12 and bus 13, and bus 13 is positioned at the both sides of anode housing 11, and it is connected with main copper bar conduction.The inner rip 12 that the centre of said anode housing 11 equidistantly distributes and is in tilted layout.
In the said rotating shaft 2 transmitting gear is installed, said transmitting gear and driving toothed gear engagement, said driving toothed gear is installed on the output shaft of motor 8.
Said anode frame 6 connects height regulating rod, and said height regulating rod can slide up and down to be installed on the frame.For example can realize altitude mixture control up and down, can realize the adjusting of the interpole gap between negative electrode and the anode through leading screw and nut mechanism.
Make raw material with lead plaster after the preparatory desulfurization of waste lead accumulator, adopt electrolyzer as shown in Figure 1 to realize regeneration plumbous in the lead plaster.Wherein, cell body, anode frame, cathode disc all adopt stainless material.The cathode disc specification: long 1000mm * wide 300mm * high 15mm, cathode disc bottom centre are welded with diameter
current conducting rod; Electrolyzer specification: 16m * 1.4m * 0.9m;
Electrolytic trial: with the refuse battery lead plaster after the preparatory desulfurization, get the caustic soda soln of an amount of 10% mass concentration, in stirrer, the lead plaster volume density is adjusted to 2.5g/cm
3Through analyzing, material wherein consists of: PbO
2Content is 34.1%, and PbO content is 51.2%, sodium hydroxide 0.9%, and water 13.8% is coated on this lead plaster pug the quality of cathode disc and weighing lead plaster then, and making the lead plaster amount of loading in each cathode disc is 10kg.
Through electrolyzer feeding mouth lifting device, cathode disc is put on the crawler belt one by one, set motor speed; Make crawler belt with the transmission continuously forward of 0.68m/h speed; When cathode disc during by crawler-tread to electrolyzer discharge port, cathode disc breaks away from power supply through lifting device, and the single-deck electrolysis finishes.Then the material on this cathode disc is taken off, and this product is carried out the briquetting dehydration in nitrogen atmosphere, get into lead smelting furnace again, under 400 ℃, be fused into plumbous liquid, be cast into the electrolysis lead pig at last.In electrolytic process, electrolytic solution is the sodium hydroxide solution of 15% mass concentration, and electrolyte temperature is 50 ℃; The circulation of elecrolyte flow is 0.5L/s, and cathode and anode spacing is 2cm, and negative electrode average apparent current density is 500A/m
2
Utilize above-mentioned electrolyzer, bath voltage, current efficiency and the direct current energy consumption of method plumbous in this horizontal movable type continuous electrolysis regeneration lead-containing material are investigated.After electrolysis was stable, 45 cathode discs of continuously feeding also had 45 continuous dischargings of cathode disc simultaneously.The total mass of the lead plaster mud in 45 cathode discs being investigated is 450kg, and the electrolytic time is 20 hours.Bath voltage 1.92V～1.95V.After the electrolysis discharging, obtain lead pig 339kg through aftertreatment, plumbous according to one's analysis purity 99.99% reaches the plumbous standard of 1#.According to calculating, the current efficiency of above-mentioned electrolytic process is 92.0%, and yield plumbous in the lead plaster mud is 97.75%, and power consumption is 768.45kWh/ ton plumbous (average cell voltage is in 1.93V).
Embodiment 3
In the present embodiment, electrolytic trial: with the refuse battery lead plaster after the preparatory desulfurization, get the caustic soda soln of an amount of 10% mass concentration, in stirrer, the lead plaster volume density is adjusted to 2.5g/cm
3Through analyzing, material wherein consists of PbO
2Content is 34.1%, and PbO content is 51.2%, sodium hydroxide 0.9%, water 13.8%, then this lead plaster pug full-filling in the quality of cathode disc and weighing lead plaster, making the lead plaster amount of loading in each cathode disc is 10kg.
Through electrolyzer feeding mouth lifting device, cathode disc is put on the crawler belt one by one, set motor speed; Make crawler belt with the transmission continuously forward of 0.55m/h speed; When cathode disc during by crawler-tread to electrolyzer discharge port, cathode disc breaks away from power supply through lifting device, and the single-deck electrolysis finishes.Then the material on this cathode disc is taken off, and this product is carried out the briquetting dehydration in nitrogen atmosphere, get into lead smelting furnace again, be fused into plumbous liquid, be cast into the electrolysis lead pig at last at 400 ℃.In electrolytic process, electrolytic solution is the sodium hydroxide solution of 20% mass concentration, and electrolyte temperature is 50 ℃; The circulation of elecrolyte flow is 0.5L/s, and cathode and anode spacing is 3cm, and negative electrode average apparent current density is 400A/m
2
Utilize above-mentioned electrolyzer, bath voltage, current efficiency and the direct current energy consumption of method plumbous in this horizontal movable type continuous electrolysis regeneration lead-containing material are investigated.After electrolysis was stable, 45 cathode discs of continuously feeding also had 45 continuous dischargings of cathode disc simultaneously.The total mass of the lead plaster mud in 45 cathode discs being investigated is 450kg, and the electrolytic time is 24.9 hours.Bath voltage 1.96V～1.98V.After the electrolysis discharging, obtain lead pig 340kg through aftertreatment, plumbous according to one's analysis purity 99.99% reaches the plumbous standard of 1#.According to calculating, the current efficiency of above-mentioned electrolytic process is 92.3%, and yield plumbous in the lead plaster mud is 98.04%, and power consumption is 779.08kWh/ ton plumbous (average cell voltage is in 1.97V).
Other schemes of present embodiment are all identical with embodiment 2.
Embodiment 4
With reference to Fig. 1～Fig. 4, in the present embodiment, electrolytic trial: with the lead plaster in the production of the lead storage battery after the preparatory desulfurization, get the caustic soda soln of an amount of 10% mass concentration, in stirrer, the lead plaster volume density is adjusted to 2.8g/cm
3Through analyzing, material wherein consists of PbO
2Content is 1.9%, and PbO content is 84.5%, sodium hydroxide 0.8%, and water 12.8% is coated on this lead plaster mud the quality of cathode disc and weighing lead plaster then, and making the lead plaster amount of loading in each cathode disc is 10kg.
Through electrolyzer feeding mouth lifting device, cathode disc is put on the crawler belt one by one, set motor speed; Make crawler belt with the transmission continuously forward of 0.90m/h speed; When cathode disc during by crawler-tread to electrolyzer discharge port, cathode disc breaks away from power supply through lifting device, and the single-deck electrolysis finishes.Then the material on this cathode disc is taken off, and this product is carried out the briquetting dehydration in nitrogen atmosphere, get into lead smelting furnace again, be fused into plumbous liquid, be cast into the electrolysis lead pig at last at 400 ℃.In electrolytic process, electrolytic solution is the sodium hydroxide solution of 10% mass concentration, and electrolyte temperature is 50 ℃; Circulation of elecrolyte flow 0.5L/s, interpole gap 2cm, negative electrode average apparent current density 500A/m
2
Utilize above-mentioned electrolyzer, bath voltage, current efficiency and the direct current energy consumption of method plumbous in this horizontal movable type continuous electrolysis regeneration lead-containing material are investigated.After electrolysis was stable, 45 cathode discs of continuously feeding also had 45 continuous dischargings of cathode disc simultaneously.The total mass of the lead plaster mud in 45 cathode discs being investigated is 450kg, and the electrolytic time is 15 hours.Bath voltage is 1.86V～1.90V.After the electrolysis discharging, obtain lead pig 354kg through aftertreatment, plumbous according to one's analysis purity 99.99% reaches the plumbous standard of 1#.According to calculating, the current efficiency of above-mentioned electrolytic process is 93.97%, and yield plumbous in the lead plaster mud is 98.22%, and power consumption is 534.85kWh/ ton plumbous (average cell voltage is in 1.87V).
Other schemes of present embodiment are all identical with embodiment 2.
Claims (4)
1. plumbous device in the horizontal movable type continuous electrolysis regeneration lead-containing material; It is characterized in that: said device comprises moving cathode, anode, cell body and electrolyte circulation system; Said moving cathode comprises double coaxial crawler belt, negative electrode conducting copper and cathode disc composition; Said double coaxial crawler belt horizontal arrangement drives the rotating shaft transmission in the electrolyzer bottom through external motor and speed change system, moves ahead continuously; Below said negative electrode conducting copper was arranged in the middle of the double crawler belt, copper bar top was provided with the level trough of placing liquid static eliminator; Said cathode disc level places on the double crawler belt, and the cathode disc bottom is provided with conducting rod; Said conducting rod passes the intermediate space of said coaxial double crawler belt and is electrically connected with liquid static eliminator during said copper bar top water is risen as high as the banks.
2. device as claimed in claim 1 is characterized in that: above negative electrode, said frame is provided with height regulating rod and regulates the distance between anode and the negative electrode said anode through the frame horizontal arrangement; Said anode comprises anode housing, inner structure part and bus, and said inner structure part is electrically connected with housing, and said bus is positioned at the both sides of anode housing, and said bus is connected with main copper bar conduction.
3. device as claimed in claim 2 is characterized in that: said cell body adopts alkaline-resisting material, said electrolyzer two ends be provided with cathode disc into and out of mechanism.
4. like the described device of one of claim 1～3; It is characterized in that: said electrolyte circulation system comprises low level storage tank and the high-order storage tank that is provided with the heating cooling apparatus; Described high-order storage tank is connected with electrolyte outlet with the electrolytic solution import of electrolyzer respectively with the low level storage tank, and described high-order storage tank is connected with the low level storage tank through recycle pump; Described electrolytic solution is realized circulation between high-order storage tank, electrolyzer, low level storage tank.
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| CN102677095B (en) * | 2012-01-15 | 2014-08-06 | 河南科技大学 | Method for recovering lead in lead plaster of waste lead-acid storage batteries |
| CN107268027A (en) * | 2017-06-23 | 2017-10-20 | 湘潭大学 | A kind of method and apparatus of the continuous rotary electrolysis of lead solution |
| CN108220999B (en) * | 2018-01-22 | 2019-11-12 | 中南大学 | A kind of device recycling cadmium containing the method for recycling cadmium in cadmium fumes and from cadmium-ammonia solution from metallurgy |
| CN111270075B (en) * | 2020-03-04 | 2022-02-11 | 云南祥云飞龙再生科技股份有限公司 | Process for preparing lead by solid-phase electrolysis of waste lead battery paste |
| CN113388862A (en) * | 2020-03-13 | 2021-09-14 | 刘强 | Continuous solid-phase electrolysis device for lead-containing substance of waste lead-acid storage battery |
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| DE3402338A1 (en) * | 1984-01-24 | 1985-07-25 | HAGEN Batterie AG, 4770 Soest | METHOD FOR RECOVERING LEAD FROM OLD LEAD ACCUMULATORS SCRAP AND REDUCTION PLATE HERE |
| CN1470675A (en) * | 2002-07-22 | 2004-01-28 | 佟永顺 | Waste lead battery lead recovery process |
| CN101368280A (en) * | 2007-08-17 | 2009-02-18 | 洛阳森韵热工设备有限公司 | Electrolyzer for recovering lead from lead plaster |
| CN101760757A (en) * | 2009-12-09 | 2010-06-30 | 王树楷 | Method for producing lead by executing electrolysis and alkaline leaching on lead sulfate material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3402338A1 (en) * | 1984-01-24 | 1985-07-25 | HAGEN Batterie AG, 4770 Soest | METHOD FOR RECOVERING LEAD FROM OLD LEAD ACCUMULATORS SCRAP AND REDUCTION PLATE HERE |
| CN1470675A (en) * | 2002-07-22 | 2004-01-28 | 佟永顺 | Waste lead battery lead recovery process |
| CN101368280A (en) * | 2007-08-17 | 2009-02-18 | 洛阳森韵热工设备有限公司 | Electrolyzer for recovering lead from lead plaster |
| CN101760757A (en) * | 2009-12-09 | 2010-06-30 | 王树楷 | Method for producing lead by executing electrolysis and alkaline leaching on lead sulfate material |
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