CN203440460U - Environmental-friendly electrolytic nickel or electrolytic cobalt continuous stable production process device - Google Patents
Environmental-friendly electrolytic nickel or electrolytic cobalt continuous stable production process device Download PDFInfo
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- CN203440460U CN203440460U CN201320491593.7U CN201320491593U CN203440460U CN 203440460 U CN203440460 U CN 203440460U CN 201320491593 U CN201320491593 U CN 201320491593U CN 203440460 U CN203440460 U CN 203440460U
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- acid mist
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Abstract
The utility model relates to an environmental-friendly electrolytic nickel or electrolytic cobalt continuous stable production process device. The device comprises a cathode frame and an anode frame, wherein the cathode frame and the anode frame of the device are arranged in the winning cell; a permeable membrane is arranged between the cathode frame and the anode frame; an overhead tank is arranged on one side of the winning cell; the overhead tank is connected with the winning cell through a liquid supply main pipe; a low tank is arranged at the other end of the winning cell; the low tank is connected with the overhead tank through a pipeline; an oxygen-containing acid mist adsorption tube is arranged at the upper end of the cathode frame; an acid mist adsorption tower is connected with an exhaust fan; the exhaust fan is connected with the oxygen-containing acid mist adsorption tube. The device changes the condition of the harsh environment caused by direct and unorganized discharging of acid mist generated in a conventional electrowinning device in the electrowinning process and avoids the problem that when a gas collecting hood and the like are adopted to extract the acid mist, liquid formed on the gas collecting hood drips on a copper bar or a copper rod to corrode copper so that the quality of a nickel product is affected. Negative pressure type air draft is adopted and resources are saved.
Description
Technical field
The utility model relates to the electrolytic deposition equipment in chemical technology field, is specially a kind of electrolytic nickel or electrolytic cobalt continuous and stable production process unit of environment-friendly type.
Background technology
Domestic contrast advanced person's nickel production method is to adopt refining wet method smelting process to produce metallic nickel, in production process, according to the chemical property of nickel, being easy to other metals close by current potential or that current potential is higher pollutes, adopt diaphragm type electrolysis structure, with diaphragm bag 3, electrolytic solution is divided into cathodic area 1 and positive column 2, by catholyte header tank, mode anticathode district (in diaphragm bag) electrolysis liquid by gravity flow, guarantees that catholyte liquid level exceeds anolyte liquid level 25-30mm.Object is that the solution that makes the solution in cathodic area can flow into ，Er positive column, positive column can not enter cathodic area, can guarantee the pure of catholyte like this, thereby guarantee the quality of electric nickel.
But in actual production process, in electrolytic process, the size of anode and cathode interpole gap directly affects the quality of electric nickel, interpole gap is excessive, and nickel ion is separated out difficulty, and electric nickel production efficiency is low, interpole gap is too small, in production process, easily there is again negative plate bonding diaphragm bag, pierce through the phenomenons such as diaphragm bag, cause electric nickel center fullness, the problems such as pore, reduce the quality of electric nickel.
In the patent No., be once to record in CN 201801606 U, in theory, by the header tank feed liquid way that flows automatically, anticathode district adds electrolytic solution, can effectively guarantee the moon, the liquid level of anolyte, guarantee the quality of electric nickel, but find by actual production, original solution flows to feed flow house steward certainly by header tank, directly hose connection to the separating tube of electrolytic solution by PVC, because Winning cell planar horizontal is lack of standardization, cause header tank different from the difference of altitude of separating tube, uneven for flow quantity height, the Winning cell that liquid supply rate is low, the easy dilution of nickel ion, in electrolytic deposition process, form a large amount of alkali formula nickel, cause nickel plate plate face greening blackout, reduced electric nickel quality, the Winning cell that feed flow is too fast, the high soltion viscosity of nickel ion content is large, the hydrogen that plate face is separated out is difficult to overflow, cause plate face to occur pore.And the excessive waste that also causes catholyte of flow.
In the device of traditional electro deposited nickel or electrodeposited cobalt, due at anode H
2o loses electronics and generates oxygen and hydrogen ion, and oxygen is overflowed, and hydrogen ion is enrichment gradually, and nickel ion in solution obtains electronics on negative electrode, separate out electro deposited nickel, in to the process of electro deposited nickel or electrodeposited cobalt, positive column hydrogen ion enrichment, this process is for making acid-respons process, oxygen and steam that anode produces overflow from liquid, and bubble surface is brought a small amount of acid in air under tension force effect, form acid mist, make the direct amorphous operating space that enters of acid mist producing, had a strong impact on production environment.Also the plant and equipment of steel construction are had to very large corrodibility, reduced the work-ing life of plant and equipment, also affect the healthy of workman simultaneously.
Also there is at present the acid fog recovery device of developing, such as application number is in the nickel electrodeposition acid mist absorption apparatus adopting in 200720187328.4, it adopts gas skirt to extract acid mist, like this, certainly will gas skirt be set each anode upper end, also needing in addition to add pump-line just can make acid mist discharge, do like this, first, in electrolytic process, negative electrode and anode all can discharge gas, can take part acid out of, acid mist can form water smoke in cover, then the water droplet forming can drop onto on the copper bar or copper bar in electrolyzer, can corrode copper, also can affect the quality of product nickel, and, at anode, add gas skirt, maintainer is difficult to enter the inside and keeps in repair, after need to hanging the son of uncapping, could operate, can increase labour intensity like this.
Summary of the invention
The utility model is just for above technical problem, provide and can extend plant and equipment work-ing life, and can improve preferably Working environment, make at the uniform velocity electrolysis of electrolytic solution, guarantee preferably electrolytic nickel or the electrolytic cobalt continuous and stable production process unit of a kind of environment-friendly type of electric nickel quality.
To achieve these goals, the technical solution adopted in the utility model is such:
A kind of electrolytic nickel of environment-friendly type or electrolytic cobalt continuous and stable production process unit, comprise Winning cell, negative electrode frame, anode frame, the recycle system and acid mist recovery system, negative electrode frame and anode frame are all arranged in Winning cell, between negative electrode frame and anode frame, permeable membrane is set, cloudy, anode frame is closed structure, all negative electrode frames and anode frame all adopt screw rod to link together, on negative electrode frame, electrolyte entrance is set, the acid mist arranging on anode frame absorbs mouth, acid mist absorbs mouth and is connected with acid mist absorption tube, and be connected with acid mist recovery system by this acid mist absorption mouthful, the anolyte outlet that anode frame lower end arranges, each anolyte is connected with collecting pipe to outlet, and be connected with the recycle system by collecting pipe, anode in negative electrode and positive electrode frame in negative electrode frame, interpole gap between the two poles of the earth is 70-130mm.
The recycle system comprises header tank, Lower tank and heavy nickel groove, Lower tank is connected with the catholyte collecting pipe in Winning cell by pipeline two, Lower tank is connected with header tank with heavy nickel groove respectively, header tank enters in Winning cell by feed flow house steward, there is difference of altitude in feed flow house steward and pipeline two, feed flow house steward is than pipeline two height, because negative electrode frame is airtight frame, but on negative electrode frame, electrolyte entrance is set, electrolytic solution enters negative electrode frame by entrance, between negative electrode frame and anode frame, permeable membrane is set, this infiltration membrane permeability is moderate, the woven dacron that is 3751 through many experiments proof employing model can meet the demand of this technique, electrolytic solution enters anode frame by permeable membrane, liquid level between negative electrode frame and anode frame is poor is 15-25mm.Due to the feed flow house steward at Winning cell and pipeline two formation U-shaped tubuloses, and have difference of altitude between the two, make electrolytic solution at the uniform velocity enter Winning cell, and due to the infiltrative special selection of permeable membrane, make electrolytic solution at the uniform velocity enter anode frame and carry out electrolysis, guaranteed the quality of electric nickel.
Traditional nickel electrodeposition, in sulfate system, generally adopts alloy lead anode, this anode is in the process of electrolysis, and surface forms one deck plumbous oxide anonite membrane, and this film is not very fine and close, the oxygen easily being produced in electrolytic process rushes, and is suspended in the PbO in electrolytic solution
2particulate is also very easily attached to the surface of electro deposited nickel, in electrolytic process, be wrapped in cathode nickel plate, increase the lead tolerance of metallic nickel, reduce the quality of electrolytic nickel, so traditional nickel electrodeposition all needs to adopt the mode of barrier film that anode and cathode is separated, disclosed technique all adopts diaphragm bag, every negative electrode, every anode, in each Winning cell, settle a lot of diaphragm bags, diaphragm bag will support with diaphragm frame, occupied a large amount of space in groove, be unfavorable for increasing groove utilization ratio, and after employing diaphragm bag, interpole gap between anode and cathode can expand, and adopt this electrowinning plant, all anode and cathode are all fixed together, negative and positive are closed structure very, between anode and cathode, can not interact, in same width Winning cell, the current efficiency of this electrowinning plant is high, in the process of electrolysis, the pH value stabilization in the cathodic area of this electrowinning plant.
Acid mist recovery system comprises acid fog absorption tower, vacuum fan and circulation groove, and acid fog absorption tower is connected with the acid mist absorption tube in Winning cell by the vacuum fan connecting, and acid fog absorption tower is connected with circulation groove.Because the anode frame of electro deposited nickel or electrodeposited cobalt is closed structure, acid mist relief outlet is set on anode frame, due in electrolytic nickel or electrodeposited cobalt, the H of positive column
2o loses electronics and generates oxygen and H
+, and in positive column, acid concentration raises gradually, and this process is for making acid-respons process, and at negative electrode, nickel ion obtains electronics, and the reaction mechanism of electro deposited nickel is as follows:
Anodic reaction: H
2o-2e
-=1/2O
2↑+2H
+
Cathodic reaction: Ni2
++ 2e=Ni
Then the acid mist of generation is entered to air draft passage by acid mist relief outlet, aperture is offered in the side of this air draft passage, acid mist is in aperture admission passage, all enter acid fog absorption tower under the effect of vacuum fan after, process, this system also comprises circulation groove, from acid fog absorption tower material out, be pumped to circulation groove, in circulation groove, add sodium carbonate, make the nickel ion recycling being mingled with in acid mist.The principle absorbing is as follows:
Na
2CO
3+H
2SO
4=Na
2SO
4+CO
2↑+H
2O
The composition of oxygen acid mist is H
2sO
4, NiSO
4and O
2, the add-on of described sodium carbonate is according to reaction formula H
2sO
4+ Na
2cO
3=Na
2sO
4+ H
2o+CO
2after ↑ proportioning, add.Oxygen containing acid mist is treated, detects rear discharge up to standard.The single nickel salt being mingled with in the acid mist of playback simultaneously, has overcome acid mist and has directly discharged the defect of the work under bad environment causing.
Direct Closed suction from anode frame, and be different from adding gas skirt on Winning cell, also be different from and on anode, add gas skirt and enter collection and confinement of gases pipeline, adopt gas skirt to collect acid mist (as shown in Figure 3), not only can occupy Winning cell space, make anode and cathode in groove put into quantity minimizing, and bad operation.If the gas in gas skirt is not discharged in time, also can form water droplet at gas skirt, drop on copper bar or copper bar, affect the quality of electrolytic nickel, the quality of product can be had a greatly reduced quality.
Permeable membrane is selected corrosion resistant woven dacron, as preferably, adopts the woven dacron that model is 3751.The selection of permeable membrane is more crucial, as permeable membrane poor permeability, can affect the speed of electrodeposition, if perviousness is very good, electrolytic solution enters anode frame very soon, can not keep liquid level poor, does not also reach electrodeposition effect.
The processing condition of electrolytic nickel or electrolytic cobalt are: in configured electrolytic solution, nickel >75g/L, cobalt < 0.005 g/L, copper < 0.001 g/L, zinc < 0.001 g/L, manganese < 0.001 g/L, iron < 0.001g/L, cadmium < 0.001g/L, plumbous < 0.004 g/L, Mg is 8.0, Ca < 0.25g/L, Cr < 0.002g/L, Na is 20-30g/L, organism < 0.002g/L, H
2bO
3for 8.0-12.0g/L, Cl
-< 0.08g/L, pH=2.5-4.5(pH test paper is measured), electrolytic condition is: current density is 300～500A/m
2, electrolyte temperature is 60 ℃, circulation of elecrolyte amount is 40m
3/ t.Ni, bath voltage is 3.6-4.5v, direct current consumption is 4500-5500 Kw.h, current efficiency >90%, nickel recovery >99%, anode and cathode liquid level difference is 15mm-25mm.
In Winning cell, all negative electrode frame and anode frames all adopt screw rod to connect as one, and facilitate integrated moving, and Winning cell all can be worked at an arbitrary position, and the quantity of screw rod can be one, also can adopt many and be fixed.
Positively effect of the present utility model is embodied in:
(1), changed in old electrowinning plant the direct amorphous discharge of acid mist producing for electrolytic deposition process and the severe situation of environment causing, avoid adopting the extraction acid mist devices such as gas skirt and the fluid drips that causes forming on gas skirt is fallen the quality of corroding copper on copper bar or copper bar and affecting product nickel.
(2), adopt suction type exhausting, economize on resources, also avoid Liao anolyte compartment to add too much gas skirt, and make operation site disorderly and unsystematic.
(3), from stream mode, make electrolytic solution at the uniform velocity enter Winning cell, unique perviousness of permeable membrane makes electrolytic solution at the uniform velocity enter anode frame, has guaranteed the quality of electrolytic nickel.
(4), two interpolar spacing are less, have increased groove utilization ratio, pH value stabilization in Winning cell, current efficiency is high, brownout, constant product quality.
Accompanying drawing explanation
Fig. 1 is the apparatus structure schematic diagram in the utility model;
Fig. 2 is that the acid mist in the utility model is discharged schematic diagram;
Wherein, 1---Winning cell, 2---air draft pipe, 3---aperture, 4---acid fog absorption tower, 5---circulation groove, 6---negative electrode frame, 7---anode frame, 8---permeable membrane, 9---vacuum fan, 10---header tank, 11---the heavy nickel groove of Lower tank, 12---readjustment tank, 13---.
Embodiment
Below in conjunction with embodiment, the utility model is further described in detail, the embodiment providing does not limit the scope of the invention, and the utility model will expand to any new feature or any new combination disclosing in this manual.
Embodiment 1:
Electrolytic nickel in the present invention or the device of electrolytic cobalt, comprise Winning cell, negative electrode frame, anode frame, the recycle system and acid mist recovery system, negative electrode frame and anode frame are all arranged in Winning cell, between negative electrode frame and anode frame, permeable membrane is set, cloudy, anode frame is closed structure, all negative electrode frames and anode frame all adopt screw rod to link together, on negative electrode frame, electrolyte entrance is set, the acid mist arranging on anode frame absorbs mouth, acid mist absorbs mouth and is connected with acid mist absorption tube, and be connected with acid mist recovery system by this acid mist absorption mouthful, the anolyte outlet that anode frame lower end arranges, each anolyte is connected with collecting pipe to outlet, and be connected with the recycle system by collecting pipe, anode in negative electrode and positive electrode frame in negative electrode frame, interpole gap between the two poles of the earth is 70-130mm.
The recycle system comprises header tank, Lower tank and heavy nickel groove, Lower tank is connected with the catholyte collecting pipe in Winning cell by pipeline two, Lower tank is connected with header tank with heavy nickel groove respectively, header tank enters in Winning cell by feed flow house steward, there is difference of altitude in feed flow house steward and pipeline two, feed flow house steward is than pipeline two height, because negative electrode frame is airtight frame, but on negative electrode frame, electrolyte entrance is set, electrolytic solution enters negative electrode frame by electrolyte entrance, between negative electrode frame and anode frame, permeable membrane is set, this infiltration membrane permeability is moderate, the woven dacron that is 3751 through many experiments proof employing model can meet the demand of this technique, electrolytic solution enters anode frame by permeable membrane, liquid level between negative electrode frame and anode frame is poor is 15-25mm.Due to the feed flow house steward at Winning cell and pipeline two formation U-shaped tubuloses, and have difference of altitude between the two, make electrolytic solution at the uniform velocity enter Winning cell, and due to the infiltrative special selection of permeable membrane, make electrolytic solution at the uniform velocity enter anode frame and carry out electrolysis, guaranteed the quality of electric nickel.
Adopt this electrowinning plant, all anode and cathode frames are all fixed together, and negative and positive are closed structure very, between anode and cathode, can not interact, in same width Winning cell, the current efficiency of this electrowinning plant is high, in the process of electrolysis, the pH value stabilization in the cathodic area of this electrowinning plant.
Acid mist recovery system comprises acid fog absorption tower, vacuum fan and circulation groove, and acid fog absorption tower is connected with the acid mist absorption tube in Winning cell by the vacuum fan connecting, and acid fog absorption tower is connected with circulation groove.Because the anode frame of electro deposited nickel or electrodeposited cobalt is closed structure, acid mist relief outlet is set on anode frame, then the acid mist of generation is entered to air draft passage by acid mist relief outlet, aperture is offered in the side of this air draft passage, acid mist is in aperture admission passage, under the effect of vacuum fan, all entering acid fog absorption tower processes, this system also comprises circulation groove, from acid fog absorption tower material out, be pumped to circulation groove, in circulation groove, add sodium carbonate, make the nickel ion recycling being mingled with in acid mist.Oxygen containing acid mist is treated, detects rear discharge up to standard.The single nickel salt being mingled with in the acid mist of playback simultaneously, has overcome acid mist and has directly discharged the defect of the work under bad environment causing, and the permeable membrane of selecting is woven dacron, and its model is 3751.
The processing condition of electrolytic nickel or electrolytic cobalt are: in configured electrolytic solution, nickel >75g/L, cobalt < 0.005 g/L, copper < 0.001 g/L, zinc < 0.001 g/L, manganese < 0.001 g/L, iron < 0.001g/L, cadmium < 0.001g/L, plumbous < 0.004 g/L, Mg is 8.0, Ca < 0.25g/L, Cr < 0.002g/L, Na is 20-30g/L, organism < 0.002g/L, H
2bO
3for 8.0-12.0g/L, Cl
-< 0.08g/L, pH value=2.5-4.5(pH test paper is measured), electrolytic condition is: current density is 300～500A/m
2, electrolyte temperature is 60 ℃, circulation of elecrolyte amount is 40m
3/ t.Ni, bath voltage is 3.6-4.5v, direct current consumption is 4500-5500 Kw.h, current efficiency >90%, nickel recovery >99%, anode and cathode liquid level difference is 15mm-25mm.
Embodiment 2:
In configured bath composition, the content of nickel is 80g/L, cobalt 0.004 g/L, copper 0.0005 g/L, zinc 0.0005g/L, manganese 0.0005 g/L, iron 0.0005g/L, cadmium 0.0005g/L, plumbous 0.003 g/L, Mg is 8.0, Ca0.24g/L, Cr0.001g/L, Na is 25g/L, organism 0.001g/L, H
2bO
3for 11.0g/L, Cl
-0.07g/L, pH=3(pH test paper is measured); Electrolytic condition is: current density 400A/m
2, 60 ℃ of electrolyte temperatures, circulation of elecrolyte amount 40m
3/ t.Ni, bath voltage 4.0v, direct current consumption 5000 Kw.h, current efficiency >90%, nickel recovery >99%, anode and cathode liquid level difference is 20mm.
Negative electrode frame and anode frame are set in Winning cell, 3751 permeable membrane is set between negative electrode frame and anode frame, electrolytic solution in header tank enters Winning cell by feed flow house steward, then by the electrolyte entrance arranging on negative electrode frame, catholyte enters negative electrode frame, the permeable membrane arranging by centre again enters anode frame, anolyte after electrolysis is from the bottom anode liquid outlet of anode frame, by arm, enter collecting pipe again, collecting pipe is connected with Lower tank, again under the effect of magnetic drive pump, part enters heavy nickel groove from Lower tank liquid out, add again sodium carbonate to deposit, finally send flame filter press to filter, another part liquid enters header tank through readjustment, in header tank, mix with the pure nickel sulfate solution from extraction, after being mixed into the electrolytic solution that meets previous process condition, again enter feed flow house steward.
The cathode nickel producing in negative electrode frame becomes electrolytic nickel product, the constant product quality of electrolytic nickel through washing.
Claims (7)
1. the electrolytic nickel of an environment-friendly type or electrolytic cobalt continuous and stable production process unit, comprise the negative electrode frame and the anode frame that are arranged in Winning cell, it is characterized in that: negative electrode frame and anode frame are arranged in Winning cell, between negative electrode frame and anode frame, permeable membrane is set, a side at Winning cell arranges header tank, header tank is connected with Winning cell by feed flow house steward, other one end at Winning cell arranges Lower tank, Lower tank is connected with header tank by pipeline, oxygen acid mist absorption tube is set in the upper end of negative electrode frame, acid fog absorption tower is connected with vacuum fan, vacuum fan is connected with oxygen acid mist absorption tube.
2. electrolytic nickel according to claim 1 or electrolytic cobalt continuous and stable production process unit, is characterized in that: the lower end of described acid fog absorption tower is connected with the upper end of circulation groove, and the lower end of circulation groove is connected with the upper end of acid fog absorption tower by pump.
3. electrolytic nickel according to claim 1 or electrolytic cobalt continuous and stable production process unit, is characterized in that: described negative electrode frame and the interpole gap between anode frame are 70-130mm.
4. electrolytic nickel according to claim 1 or electrolytic cobalt continuous and stable production process unit, is characterized in that: on described negative electrode frame, electrolyte entrance is set, oxygen acid mist relief outlet is also set on negative electrode frame.
5. electrolytic nickel according to claim 1 or electrolytic cobalt continuous and stable production process unit, is characterized in that: the anolyte arranging on described anode frame exports, and anolyte outlet is connected with arm, and arm is connected with the house steward of confluxing.
6. electrolytic nickel according to claim 1 or electrolytic cobalt continuous and stable production process unit, is characterized in that: described Lower tank is connected with heavy nickel groove after being connected with pump again.
7. electrolytic nickel according to claim 1 or electrolytic cobalt continuous and stable production process unit, is characterized in that: between the described feed flow house steward who is connected with header tank and the pipeline of anolyte collecting pipe, have difference of altitude.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201320491593.7U CN203440460U (en) | 2013-08-13 | 2013-08-13 | Environmental-friendly electrolytic nickel or electrolytic cobalt continuous stable production process device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201320491593.7U CN203440460U (en) | 2013-08-13 | 2013-08-13 | Environmental-friendly electrolytic nickel or electrolytic cobalt continuous stable production process device |
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| CN203440460U true CN203440460U (en) | 2014-02-19 |
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ID=50091528
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274577A (en) * | 2014-05-28 | 2016-01-27 | 北京有色金属研究总院 | High purity metal preparation electrolysis bath and use method thereof |
| CN110373686A (en) * | 2019-07-24 | 2019-10-25 | 中国环境科学研究院 | A kind of potroom groove face acid mist source cut down clean preparation method and system |
| CN111690953A (en) * | 2020-07-14 | 2020-09-22 | 西安泰金工业电化学技术有限公司 | Insoluble frame-shaped anode structure capable of collecting acid mist |
-
2013
- 2013-08-13 CN CN201320491593.7U patent/CN203440460U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274577A (en) * | 2014-05-28 | 2016-01-27 | 北京有色金属研究总院 | High purity metal preparation electrolysis bath and use method thereof |
| CN110373686A (en) * | 2019-07-24 | 2019-10-25 | 中国环境科学研究院 | A kind of potroom groove face acid mist source cut down clean preparation method and system |
| CN111690953A (en) * | 2020-07-14 | 2020-09-22 | 西安泰金工业电化学技术有限公司 | Insoluble frame-shaped anode structure capable of collecting acid mist |
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