CN104694978A - Waste electrolyte treatment method and device - Google Patents
Waste electrolyte treatment method and device Download PDFInfo
- Publication number
- CN104694978A CN104694978A CN201310653956.7A CN201310653956A CN104694978A CN 104694978 A CN104694978 A CN 104694978A CN 201310653956 A CN201310653956 A CN 201310653956A CN 104694978 A CN104694978 A CN 104694978A
- Authority
- CN
- China
- Prior art keywords
- electrolyzer
- decopper
- ing
- copper
- fluid inlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a waste electrolyte treatment method. The method comprises the following steps of a, treating waste electrolyte to obtain a primary copper-removed finished solution with a copper ion concentration of 35-45g/L, b, treating the primary copper-removed finished solution by a continuous electrowinning method utilizing an insoluble anode and a stainless steel cathode to obtain A-level copper and a secondary copper-removed finished solution, and c, treating the secondary copper-removed finished solution by the continuous electrowinning method utilizing an insoluble anode and an electrolysis remnant pole as a cathode to obtain electro-deposited copper, a black copper plate, black copper powder and black copper mud. The invention also provides a waste electrolyte treatment device. The method utilizes the primary copper-removed finished solution with low copper ion content as a raw material, the insoluble anode and the stainless steel cathode to produce the A-level copper so that a production cost is reduced and resource waste is reduced.
Description
Technical field
The invention belongs to copper electrolyte technical field, particularly relate to a kind for the treatment of process and treatment unit of waste electrolyte.
Background technology
Electrolytic copper adopts electrolytic process to produce the copper obtained, and quality is high, can be used for making electric product.The general process of electrolytic copper is as follows: blister copper is made in advance slab as anode, negative electrode is made with the beginning level sheet that stainless steel plate or pure copper sheet make, using the mixed solution of sulfuric acid and copper sulfate as electrolytic solution, after energising, copper becomes cupric ion to movable cathode from anode dissolution, obtain electronics after reaching negative electrode and separate out at negative electrode, obtaining electrolytic copper.In electrolytic refining course of copper, the composition of electrolytic solution constantly changes, and not only copper ion concentration constantly rises, and sulfuric acid concentration reduces gradually, and impurity also wherein constantly accumulates.In order to maintain copper, acid content and impurity concentration in electrolytic solution all within the limits prescribed, just must purify electrolytic solution and adjust, to ensure normally carrying out of electrolytic process.This part electrolytic solution of purification and adjustment is needed just to be referred to as waste electrolyte.
The purification of waste electrolyte is completed by decopper(ing), removing impurities operation, at present conventional cleaning section generally comprises following step: first by waste electrolyte through vacuum-evaporation, freezing and crystallizing and vacuum band-type filter machine process, obtain thick copper sulfate, heavy solution and crystalline mother solution; Thick copper sulfate copper content is about 23%, can direct marketing; Heavy solution can be mixed into row relax or again for generating crude nickle sulphate with waste electrolyte; And crystalline mother solution can continue to adopt continuous decopper(ing) dearsenification method to carry out electrolysis decopper(ing), obtain electro deposited copper, black copper powder, black copper mud etc. successively in a cell, whole liquid after electrolysis decopper(ing) for the production of single nickel salt, see the purification process schematic flow sheet of Fig. 1, Fig. 1 waste electrolyte disclosed in prior art.When adopting continuous decopper(ing) dearsenification method to carry out electrolysis decopper(ing) to crystalline mother solution, general using insoluble anode as anode, adopting electrolysis residual pole carries out electrolysis as negative electrode, electro deposited copper, black copper powder, black copper mud etc. can be obtained, wherein, electro deposited copper purity can reach more than 99%, and about electro deposited copper output accounts for the half of electro deposited copper, black copper powder, black copper mud ultimate production, but, electro deposited copper cannot use as product because purity is lower, can only be used for again preparing burden, melting, cast produce positive plate, reduce production efficiency, add production cost.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process and treatment unit of waste electrolyte, the treatment process of waste electrolyte provided by the invention can meet the A level copper of cathode copper GB for raw material prepares with the whole liquid of the decopper(ing) that copper content is lower, reduce production cost, decrease the waste of resource.
The invention provides a kind for the treatment of process of waste electrolyte, comprise the following steps:
A) process waste electrolyte, obtain the whole liquid of decopper(ing), in a described decopper(ing) solution, copper ion concentration is 35g/L ~ 45g/L;
B) using insoluble anode as anode, using stainless steel cathode as negative electrode, adopt continuous electrodeposition method to process the whole liquid of a described decopper(ing), obtain A level copper and the whole liquid of secondary decopper(ing);
C) using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of described secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.
Preferably, in described step b), the flow of the whole liquid of a described decopper(ing) is 20L/min ~ 28L/min; The temperature of described electrolytic deposition is 50 DEG C ~ 70 DEG C; The current density of described electrolytic deposition is 180A/m
2~ 200A/m
2; The described concentration stating cupric ion in the whole liquid of secondary decopper(ing) is 15g/L ~ 25g/L.
Preferably, in described step b), the whole liquid of described decopper(ing) carries out electrolytic deposition through the electrolyzer of 3 or 4 series connection successively, described each electrolyzer all using insoluble anode as anode, using stainless steel cathode as negative electrode.
Preferably, before described step b), also comprise and add additive in the whole liquid of a described decopper(ing), described additive is gelatine and thiocarbamide.
Preferably, the consumption of described gelatine is 20g/t ~ 30g/t, and the consumption of described thiocarbamide is 40g/t ~ 50g/t.
Preferably, in described step b), the feed liquor mode of the whole liquid of a described decopper(ing) is bottom in and top out.
Preferably, described step a) is specially:
Adopt strike to process waste electrolyte, obtain A level copper and the whole liquid of decopper(ing);
Or,
Described step a) is specially:
Waste electrolyte is carried out vacuum-evaporation, freezing and crystallizing and filtration treatment successively, obtains copper sulfate and the whole liquid of decopper(ing).
Present invention also offers a kind of waste electrolyte treatment unit, comprising:
First decopper(ing) device;
The second electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device, described second electrolyzer using insoluble anode as anode, using stainless steel cathode as negative electrode;
The 3rd electrolyzer that fluid inlet is connected with the liquid outlet of described second electrolyzer, described 3rd electrolyzer using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode.
Preferably, described second electrolyzer comprises:
The 2nd A electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device;
The 2nd B electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd A electrolyzer;
The 2nd C electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd B electrolyzer.
Preferably, the shunt pipe be connected with the liquid outlet of the 2nd C electrolyzer is also comprised.
Preferably, the fluid inlet of described 2nd A electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd B electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd C electrolyzer is lower than liquid outlet.
Preferably, described second electrolyzer comprises:
The 2nd A electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device;
The 2nd B electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd A electrolyzer;
The 2nd C electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd B electrolyzer;
The 2nd D electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd C electrolyzer.
Preferably, the shunt pipe be connected with the liquid outlet of the 2nd D electrolyzer is also comprised.
Preferably, the fluid inlet of described 2nd A electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd B electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd C electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd D electrolyzer is lower than liquid outlet.
Preferably, described first decopper(ing) device comprises the first electrolyzer, described first electrolyzer using insoluble anode as anode, using stainless steel cathode as negative electrode;
Or,
Described first decopper(ing) device comprises:
Vacuum-evaporator unit;
The freezing and crystallizing device be connected with the discharge port of described vacuum-evaporator unit; With
The filtration unit be connected with the discharge port of described freezing and crystallizing device.
Preferably, also comprise additive storage tank, the liquid outlet of described additive storage tank is connected with the fluid inlet of described second electrolyzer.
Compared with prior art, the treatment process of waste electrolyte provided by the invention, first processes waste electrolyte, and obtain the whole liquid of decopper(ing), in a described decopper(ing) solution, copper ion concentration is 35g/L ~ 45g/L; Then using insoluble anode as anode, using stainless steel cathode as negative electrode, adopt continuous electrodeposition method to process the whole liquid of a described decopper(ing), obtain A level copper and the whole liquid of secondary decopper(ing); Last using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of described secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.First the present invention carries out first time process to waste electrolyte, and obtain the whole liquid of decopper(ing), the process of this first time can be produce copper sulfate, also can be to produce A level copper, and object reduces copper ion concentration in waste electrolyte, makes it as 35g/L ~ 45g/L; Then using insoluble anode as anode, using stainless steel cathode as negative electrode, continuous electrodeposition method is adopted to process the whole liquid of a described decopper(ing), using stainless steel cathode as negative electrode, continuous electrodeposition method is adopted to be met cathode copper GB completely, main grade even can reach 99.999%, and total impurities grade is at the A level copper of about 25ppm; Again using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.The present invention with the whole liquid of decopper(ing) that content of copper ion is lower for raw material, using insoluble anode as anode, A level copper is produced using stainless steel cathode as negative electrode, not only reduce production cost, decrease the waste of resource, and the A level copper obtained meets cathode copper GB completely, main grade even can reach 99.999%, and total impurities grade is at about 25ppm.Experimental result shows, adopts method provided by the invention can obtain meeting the A level copper of cathode copper GB.
Accompanying drawing explanation
The purification process schematic flow sheet of Fig. 1 waste electrolyte disclosed in prior art;
The structural representation of the waste electrolyte treatment unit that Fig. 2 provides for the embodiment of the present invention.
Embodiment
The invention provides a kind for the treatment of process of waste electrolyte, comprise the following steps:
A) process waste electrolyte, obtain the whole liquid of decopper(ing), in a described decopper(ing) solution, copper ion concentration is 35g/L ~ 45g/L;
B) using insoluble anode as anode, using stainless steel cathode as negative electrode, adopt continuous electrodeposition method to process the whole liquid of a described decopper(ing), obtain A level copper and the whole liquid of secondary decopper(ing);
C) using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of described secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.
In the present invention, described waste electrolyte refers to need to reduce impurity, and regulate the electrolytic solution of copper, acid balance, specifically refer to the waste electrolyte obtained in electrolytic copper process, the present invention there is no particular restriction to it.Preferably, in described waste electrolyte, copper ion concentration is preferably 40g/L ~ 60g/L, is more preferably 42g/L ~ 58g/L.
First the present invention carries out first time decopper(ing) process to waste electrolyte, obtain the whole liquid of decopper(ing), the method of the present invention to described first time decopper(ing) process there is no particular restriction, because in waste electrolyte, copper ion concentration is higher, the object of first time decopper(ing) process is to reduce the copper ion concentration in waste electrolyte, obtains the copper products that value added is higher.
In the present invention, described first time decopper(ing) process for process waste electrolyte, can obtain copper sulfate, and detailed process is as follows:
Waste electrolyte is carried out vacuum-evaporation, freezing and crystallizing and filtration treatment successively, obtains copper sulfate and the whole liquid of decopper(ing).
The present invention preferably carries out vacuum-evaporation well known to those skilled in the art, freezing and crystallizing and filtration treatment successively to waste electrolyte, can obtain thick copper sulfate and the whole liquid of decopper(ing).The present invention is not particularly limited the processing parameter of described vacuum-evaporation, freezing and crystallizing and filtration treatment and concrete steps, and the step that those skilled in the art commonly use and parameter, can obtain copper sulfate.After above-mentioned process, in the copper sulfate obtained, copper content is preferably 20% ~ 30%; In the whole liquid of decopper(ing), copper ion concentration is preferably 35g/L ~ 45g/L, is more preferably 38g/L ~ 42g/L.
In the present invention, described first time decopper(ing) process can for process waste electrolyte, and obtain cloudy A level copper and the whole liquid of decopper(ing), detailed process is as follows:
Adopt strike to process waste electrolyte, obtain A level copper and the whole liquid of decopper(ing).
The present invention, preferably using insoluble anode as anode, using stainless steel cathode as negative electrode, adopts strike to process described waste electrolyte, obtains A level copper and the whole liquid of decopper(ing).The present invention is not particularly limited the processing parameter of described strike and concrete steps, carries out electrolysis to waste electrolyte, obtains A level copper.After above-mentioned process, in the whole liquid of the decopper(ing) obtained, copper ion concentration is preferably 35g/L ~ 45g/L, is more preferably 38g/L ~ 42g/L.In the present invention, described insoluble anode is preferably lead anode.
In the present invention, when in waste electrolyte, copper ion concentration is higher, when being 50g/L ~ 60g/L as it, preferably adopt strike to process it, obtain A level copper and the whole liquid of decopper(ing); When its copper ion concentration is lower, as during for 40g/L ~ 50g/L, preferably successively vacuum-evaporation, freezing and crystallizing and filtration treatment are carried out to it, obtain copper sulfate and the whole liquid of decopper(ing).
After obtaining the whole liquid of decopper(ing), using insoluble anode as anode, using stainless steel cathode as negative electrode, adopt continuous electrodeposition method to process the whole liquid of a described decopper(ing), obtain A level copper and the whole liquid of secondary decopper(ing).The present invention replaces adopting electrolysis residual pole or starting sheet with stainless steel cathode, prepares A level copper with the whole liquid of decopper(ing) for raw material carries out continuous electrodeposition method.
In the present invention, the whole liquid of described decopper(ing) preferably carries out electrolytic deposition through the electrolyzers of 3 or 4 series connection successively, described each electrolyzer all using insoluble anode as anode, using stainless steel cathode as negative electrode.Specifically, when first time, decopper(ing) was treated to strike production A level copper, the whole liquid of the decopper(ing) obtained preferably carries out electrolytic deposition through the electrolyzer of 4 series connection successively; When first time, decopper(ing) was treated to production copper sulfate, the whole liquid of the decopper(ing) obtained preferably carries out electrolytic deposition through the electrolyzer of 3 series connection successively.
When carrying out electrolytic deposition in the electrolyzer of above-mentioned series connection, the liquid flow rate, temperature, current density etc. of each groove are all identical, and the present invention only carries out the explanation of above-mentioned each parameter for first electrolyzer.When carrying out the process of second time decopper(ing), the flow of the whole liquid of a described decopper(ing) is preferably 20L/min ~ 28L/min, is more preferably 21L/min ~ 25L/min; The temperature of described electrolytic deposition is preferably 50 DEG C ~ 70 DEG C, is more preferably 60 DEG C ~ 68 DEG C; The current density of described electrolytic deposition is preferably 180A/m
2~ 200A/m
2, be more preferably 190A/m
2~ 198A/m
2.
Using insoluble anode as anode, using stainless steel cathode as negative electrode, after adopting continuous electrodeposition method to process the whole liquid of a described decopper(ing), obtain A level copper and the whole liquid of secondary decopper(ing), the A level copper obtained meets cathode copper GB completely, and main grade even can reach 99.999%, and total impurities grade is at about 25ppm, in the whole liquid of the secondary decopper(ing) obtained, the concentration of cupric ion is preferably 15g/L ~ 25g/L, is more preferably 18g/L ~ 23g/L.
Before the process of second time decopper(ing) is carried out to the whole liquid of decopper(ing), preferably in the whole liquid of a described decopper(ing), add additive, while making decopper(ing), remove the impurity such as arsenic, bismuth, antimony.Described additive is preferably gelatine and thiocarbamide, and wherein, the consumption of described gelatine is preferably 20g/t ~ 30g/t, is more preferably 28g/t; The consumption of described thiocarbamide is preferably 40g/t ~ 50g/t, is more preferably 45g/t.
Carrying out in second time decopper(ing) treating processes to the whole liquid of a described decopper(ing), the feed liquor mode of the whole liquid of a described decopper(ing) is bottom in and top out, namely the whole liquid of decopper(ing) enters below first electrolyzer, flow out from top after electrolysis, enter below second electrolyzer again, carry out successively, the present invention does not repeat them here.Adopt the feed liquor mode of bottom in and top out, the A level copper that main taste is higher can be obtained.
After obtaining the whole liquid of secondary decopper(ing), using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of described secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.Wherein, adopting electrolysis residual pole refers to the remaining part of anode copper electrolysis.In the present invention, the whole liquid of described secondary decopper(ing) preferably carries out electrolytic deposition through the electrolyzers of 6 or 7 series connection successively, described each electrolyzer all using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode.Specifically, when a decopper(ing) electrolyzer that end, liquid was connected through 4, the whole liquid of secondary decopper(ing) is through the electrolyzer of 6 series connection, and wherein, front 3 electrolyzers are for the production of electro deposited copper, and rear 3 electrolyzers are for the production of products such as black copper plate, black copper powder and black copper mud; When a decopper(ing) electrolyzer that end, liquid was connected through 3, the whole liquid of secondary decopper(ing) is through the electrolyzer of 7 series connection, and wherein, front 4 electrolyzers are for the production of electro deposited copper, and rear 3 electrolyzers are for the production of products such as black copper plate, black copper powder and black copper mud.
That is, in the treating processes of waste electrolyte provided by the invention, waste electrolyte obtains after the whole liquid of decopper(ing) through first time decopper(ing) process, preferably carry out electrolytic deposition through the electrolyzer of 10 series connection successively, prepare the products such as A level copper, electro deposited copper, black copper plate, black copper powder and black copper mud respectively.By these 10 electrolyzers in order number consecutively be No. 1 electrolyzer, No. 2 electrolyzer to 10 electrolyzers, specifically have following two kinds for the treatment of processs:
The first:
1 ~ No. 3 groove, all using insoluble anode as anode, using stainless steel cathode as negative electrode, obtains A level copper to after a whole liquid electrolysis treatment of decopper(ing);
4 ~ No. 10 grooves are all using insoluble anode as anode, and using adopting electrolysis residual pole as negative electrode, 4 ~ No. 7 grooves carry out electrolysis treatment, obtain electro deposited copper; 8 ~ No. 10 grooves carry out electrolysis treatment, obtain black copper plate, black copper powder and black copper mud.
The second:
1 ~ No. 4 groove, all using insoluble anode as anode, using stainless steel cathode as negative electrode, obtains A level copper to after a whole liquid electrolysis treatment of decopper(ing);
5 ~ No. 10 grooves are all using insoluble anode as anode, and using adopting electrolysis residual pole as negative electrode, 5 ~ No. 7 grooves carry out electrolysis treatment, obtain electro deposited copper; 8 ~ No. 10 grooves carry out electrolysis treatment, obtain black copper plate, black copper powder and black copper mud.
The present invention is to using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, the processing parameter of continuous electrodeposition method process is carried out to the whole liquid of described secondary decopper(ing) and operation steps is not particularly limited, parameter well known to those skilled in the art and step, electro deposited copper, black copper plate, black copper powder and black copper mud can be obtained, wherein, electro deposited copper, black copper plate can be used for producing positive plate, and black copper powder and black copper mud can be sent into preparation room and again utilize after treatment.Preferably, the present invention preferably carries out adding cupric ion in the process processed carrying out continuous electrodeposition method, thus improves the decreasing ratio to arsenic.
After third time decopper(ing) process, namely the whole liquid of secondary decopper(ing) is after No. 10 electrolyzers, and in the whole liquid of the decopper(ing) obtained, content of copper ion is preferably lower than 0.5g/L.
In the present invention, in order to the follow-up removing impurities effect of boudoir, when waste electrolyte flow is large, copper content height time, the whole liquid of secondary decopper(ing) can not enter subsequent disposal, and directly again carrying out entering subsequent disposal again after decopper(ing) prepares A level copper prepares electro deposited copper etc.
In third time decopper(ing) process, for reaching the object of revulsion removing impurities, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
First the present invention carries out first time process to waste electrolyte, and obtain the whole liquid of decopper(ing), the process of this first time can be produce copper sulfate, also can be to produce A level copper, and object reduces copper ion concentration in waste electrolyte, makes it as 35g/L ~ 45g/L; Then using insoluble anode as anode, using stainless steel cathode as negative electrode, continuous electrodeposition method is adopted to process the whole liquid of a described decopper(ing), using stainless steel cathode as negative electrode, continuous electrodeposition method is adopted to be met cathode copper GB completely, main grade even can reach 99.999%, and total impurities grade is at the A level copper of about 25ppm; Again using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.The present invention with the whole liquid of decopper(ing) that content of copper ion is lower for raw material, using insoluble anode as anode, A level copper is produced using stainless steel cathode as negative electrode, not only reduce production cost, decrease the waste of resource, and the A level copper obtained meets cathode copper GB completely, main grade even can reach 99.999%, and total impurities grade is at about 25ppm.Experimental result shows, adopts method provided by the invention can obtain meeting the A level copper of cathode copper GB.
Present invention also offers a kind of waste electrolyte treatment unit, comprising:
First decopper(ing) device;
The second electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device, described second electrolyzer using insoluble anode as anode, using stainless steel cathode as negative electrode;
The 3rd electrolyzer that fluid inlet is connected with the liquid outlet of described second electrolyzer, described 3rd electrolyzer using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode.
See the structural representation of the waste electrolyte treatment unit that Fig. 2, Fig. 2 provide for the embodiment of the present invention, wherein, 1 is the first decopper(ing) device, and 2 is the second electrolyzer, and 3 is the 3rd electrolyzer.
In the present invention, the object of the first decopper(ing) device 1 is to carry out first time decopper(ing) process to waste electrolyte, according to the difference of first time decopper(ing) treatment process, described first decopper(ing) device can be the first electrolyzer, described first electrolyzer is using insoluble anode as anode, using stainless steel cathode as negative electrode, waste electrolyte carries out electrolysis in the first electrolyzer, obtains A level copper and the whole liquid of decopper(ing); Described first decopper(ing) device also can comprise:
Vacuum-evaporator unit;
The freezing and crystallizing device be connected with the discharge port of described vacuum-evaporator unit; With
The filtration unit be connected with the discharge port of described freezing and crystallizing device.
Waste electrolyte processes through vacuum-evaporator unit, freezing and crystallizing device and filtration unit successively, obtains copper sulfate and the whole liquid of decopper(ing).The concrete structure of the present invention to described first electrolyzer or vacuum-evaporator unit, freezing and crystallizing device and filtration unit is not particularly limited, related device well known to those skilled in the art.
The fluid inlet of the second electrolyzer provided by the invention is connected with the liquid outlet of the first decopper(ing) device, and it is using insoluble anode as anode, using stainless steel cathode as negative electrode.Enter in the second electrolyzer through the whole liquid of decopper(ing) of the first decopper(ing) device and carry out electrolysis, obtain A level copper and the whole liquid of the second decopper(ing).In the present invention, described second electrolyzer comprises:
The 2nd A electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device;
The 2nd B electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd A electrolyzer;
The 2nd C electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd B electrolyzer.
That is, the second electrolyzer comprise 3 be successively connected the 2nd A electrolyzer, the 2nd B electrolyzer and the 2nd C electrolyzers, each electrolyzer all using insoluble anode as anode, using stainless steel cathode as negative electrode.One time the whole liquid of decopper(ing) carries out electrolysis successively in the 2nd A electrolyzer, the 2nd B electrolyzer and the 2nd C electrolyzer, obtains A level copper and the whole liquid of secondary decopper(ing).
In other embodiments, the fluid inlet of the 2nd A electrolyzer, the 2nd B electrolyzer and the 2nd C electrolyzer, all lower than its liquid outlet, makes the feed liquor mode of liquid be bottom in and top out, thus is more conducive to removing of cupric ion in waste electrolyte.
In other embodiments, also comprise the shunt pipe be connected with the liquid outlet of the 2nd C electrolyzer, when waste electrolyte flow is larger, or when content of copper ion is higher, the whole liquid of the secondary decopper(ing) obtained after the 2nd C electrolytic tank electrolysis enters the whole liquid storage tank of decopper(ing) through this shunt pipe or carries out other process.
In another embodiment, described second electrolyzer can also comprise:
The 2nd A electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device;
The 2nd B electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd A electrolyzer;
The 2nd C electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd B electrolyzer;
The 2nd D electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd C electrolyzer.
That is, the second electrolyzer comprise 3 be successively connected the 2nd A electrolyzer, the 2nd B electrolyzer, the 2nd C electrolyzer and the 2nd D electrolyzers, each electrolyzer all using insoluble anode as anode, using stainless steel cathode as negative electrode.One time the whole liquid of decopper(ing) carries out electrolysis successively in the 2nd A electrolyzer, the 2nd B electrolyzer, the 2nd C electrolyzer and the 2nd D electrolyzer, obtains A level copper and the whole liquid of secondary decopper(ing).
In other embodiments, the fluid inlet of the 2nd A electrolyzer, the 2nd B electrolyzer, the 2nd C electrolyzer and the 2nd D electrolyzer, all lower than its liquid outlet, makes the feed liquor mode of liquid be bottom in and top out, thus is more conducive to removing of cupric ion in waste electrolyte.
In other embodiments, described waste electrolyte treatment unit also comprises the shunt pipe be connected with the liquid outlet of the 2nd D electrolyzer, when waste electrolyte flow is larger, or when content of copper ion is higher, the whole liquid of the secondary decopper(ing) obtained after the 2nd D electrolytic tank electrolysis enters the whole liquid storage tank of decopper(ing) through this shunt pipe or carries out other process.
In other embodiments, described waste electrolyte treatment unit also comprises additive storage tank, the liquid outlet of described additive storage tank is connected with the fluid inlet of described second electrolyzer, and additive mixes with the whole liquid of decopper(ing) by additive storage tank, then enters in the second electrolyzer and carries out electrolysis.
Waste electrolyte treatment unit provided by the invention also comprises the 3rd electrolyzer, and the fluid inlet of the 3rd electrolyzer is connected with the liquid outlet of described second electrolyzer, described 3rd electrolyzer using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode.The whole liquid of secondary decopper(ing) of the second electrolyzer enters in the 3rd electrolyzer and carries out electrolysis, obtains the whole liquid of electro deposited copper, black copper plate, black copper powder, black copper mud and decopper(ing).
In the present invention, described 3rd electrolyzer can comprise 6 electrolyzers or 7 electrolyzers of connecting successively, each electrolyzer all using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode.Specifically, when the second electrolyzer comprises the electrolyzer of 4 series connection, the 3rd electrolyzer comprises the electrolyzer of 6 series connection, and wherein, front 3 electrolyzers are for the production of electro deposited copper, and rear 3 electrolyzers are for the production of products such as black copper plate, black copper powder and black copper mud; When the second electrolyzer comprises the electrolyzer of 3 series connection, the 3rd electrolyzer comprises the electrolyzer of 7 series connection, and wherein, front 4 electrolyzers are for the production of electro deposited copper, and rear 3 electrolyzers are for the production of products such as black copper plate, black copper powder and black copper mud.
That is, in the present invention, described second electrolyzer and the 3rd electrolyzer are specifically as follows the electrolyzer of 10 series connection, waste electrolyte is after the first decopper(ing) device, electrolyzer successively through 10 series connection carries out electrolytic deposition, prepares the products such as A level copper, electro deposited copper, black copper plate, black copper powder and black copper mud respectively.By these 10 electrolyzers in order number consecutively be No. 1 electrolyzer, No. 2 electrolyzer to 10 electrolyzers, specifically have following two kinds of concrete structures:
The first:
1 ~ No. 3 groove, all using insoluble anode as anode, using stainless steel cathode as negative electrode, obtains A level copper to after a whole liquid electrolysis treatment of decopper(ing);
4 ~ No. 10 grooves are all using insoluble anode as anode, and using adopting electrolysis residual pole as negative electrode, 4 ~ No. 7 grooves carry out electrolysis treatment, obtain electro deposited copper; 8 ~ No. 10 grooves carry out electrolysis treatment, obtain black copper plate, black copper powder and black copper mud.
The second:
1 ~ No. 4 groove, all using insoluble anode as anode, using stainless steel cathode as negative electrode, obtains A level copper to after a whole liquid electrolysis treatment of decopper(ing);
5 ~ No. 10 grooves are all using insoluble anode as anode, and using adopting electrolysis residual pole as negative electrode, 5 ~ No. 7 grooves carry out electrolysis treatment, obtain electro deposited copper; 8 ~ No. 10 grooves carry out electrolysis treatment, obtain black copper plate, black copper powder and black copper mud.
Principle of work and the workflow of waste electrolyte treatment unit provided by the invention are as follows:
Waste electrolyte carries out first time decopper(ing) process through the first decopper(ing) device, obtains the whole liquid of decopper(ing);
One time the whole liquid of decopper(ing) passes through using insoluble anode as anode, and the second electrolyzer using stainless steel cathode as negative electrode carries out electrolysis treatment, obtains A level copper and the whole liquid of secondary decopper(ing);
The whole liquid of secondary decopper(ing) is through with using insoluble anode as anode, and the 3rd electrolyzer using adopting electrolysis residual pole as negative electrode carries out electrolysis treatment, obtains the whole liquid of electro deposited copper, black copper plate, black copper powder, black copper mud and decopper(ing).
The present invention with the whole liquid of decopper(ing) that content of copper ion is lower for raw material, using insoluble anode as anode, A level copper is produced using stainless steel cathode as negative electrode, not only reduce production cost, decrease the waste of resource, and the A level copper obtained meets cathode copper GB completely, main grade even can reach 99.999%, and total impurities grade is at about 25ppm.Experimental result shows, adopts method provided by the invention can obtain meeting the A level copper of cathode copper GB.
In order to further illustrate the present invention, be described below in conjunction with the treatment process of embodiment to waste electrolyte provided by the invention, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Take copper ion concentration as 51g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L waste electrolyte be raw material, strike is adopted to carry out electrolysis to waste electrolyte, obtain A level copper and the whole liquid of decopper(ing), in the whole liquid of decopper(ing), copper ion concentration is 42g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L;
1 ~ No. 10 electrolyzer is connected successively, take the feed liquor mode of bottom in and top out, wherein, 1 ~ No. 3 groove with insoluble Plante type plate for anode, take stainless steel polar plate as negative electrode, 4 ~ No. 10 grooves are with insoluble Plante type plate for anode, and the area of negative electrode is 800mm*900mm, is that negative electrode carries out electrolysis with adopting electrolysis residual pole, before carrying out electrolysis, in the whole liquid of decopper(ing), add 28g/t gelatine and 45g/t thiocarbamide, electrolytic process parameter and result see table 1, the electrolytic parameter that table 1 provides for the embodiment of the present invention 1 and result.In electrolytic process, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
The electrolytic parameter that table 1 embodiment of the present invention 1 provides and result
In table 1, outlet copper ion concentration is No. 10 electrolyzer outlet cupric ion copper concentration, and separating by extraction, antimony decreasing ratio and bismuth decreasing ratio are the decreasing ratio of each material in the whole liquid of decopper(ing) that No. 10 electrolyzers obtain.
As shown in Table 1, the A level copper that method provided by the invention prepares can meet cathode copper Standard, and the decreasing ratio of arsenic, antimony, bismuth is higher.
Embodiment 2
Take copper ion concentration as 51g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L waste electrolyte be raw material, strike is adopted to carry out electrolysis to waste electrolyte, obtain A level copper and the whole liquid of decopper(ing), in the whole liquid of decopper(ing), copper ion concentration is 42g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L;
1 ~ No. 10 electrolyzer is connected successively, take the feed liquor mode of bottom in and top out, wherein, 1 ~ No. 3 groove with insoluble Plante type plate for anode, take stainless steel polar plate as negative electrode, 4 ~ No. 10 grooves are with insoluble Plante type plate for anode, and the area of negative electrode is 800mm*900mm, is that negative electrode carries out electrolysis with adopting electrolysis residual pole, before carrying out electrolysis, in the whole liquid of decopper(ing), add 28g/t gelatine and 45g/t thiocarbamide, electrolytic process parameter and result see table 2, the electrolytic parameter that table 2 provides for the embodiment of the present invention 2 and result.In electrolytic process, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
The electrolytic parameter that table 2 embodiment of the present invention 2 provides and result
In table 2, outlet copper ion concentration is No. 10 electrolyzer outlet cupric ion copper concentration, and separating by extraction, antimony decreasing ratio and bismuth decreasing ratio are the decreasing ratio of each material in the whole liquid of decopper(ing) that No. 10 electrolyzers obtain.
As shown in Table 2, the A level copper that method provided by the invention prepares can meet cathode copper Standard, and the decreasing ratio of arsenic, antimony, bismuth is higher.
Embodiment 3
Take copper ion concentration as 51g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L waste electrolyte be raw material, strike is adopted to carry out electrolysis to waste electrolyte, obtain A level copper and the whole liquid of decopper(ing), in the whole liquid of decopper(ing), copper ion concentration is 42g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L;
1 ~ No. 10 electrolyzer is connected successively, take the feed liquor mode of bottom in and top out, wherein, 1 ~ No. 3 groove with insoluble Plante type plate for anode, take stainless steel polar plate as negative electrode, 4 ~ No. 10 grooves with insoluble Plante type plate for anode, the area of negative electrode is 800mm*900mm, be that negative electrode carries out electrolysis with adopting electrolysis residual pole, before carrying out electrolysis, in the whole liquid of decopper(ing), add additive 28g/t gelatine and 45g/t thiocarbamide, electrolytic process parameter and result see table 3, the electrolytic parameter that table 3 provides for the embodiment of the present invention and result.In electrolytic process, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
The electrolytic parameter that table 3 embodiment of the present invention 3 provides and result
In table 3, outlet copper ion concentration is No. 10 electrolyzer outlet cupric ion copper concentration, and separating by extraction, antimony decreasing ratio and bismuth decreasing ratio are the decreasing ratio of each material in the whole liquid of decopper(ing) that No. 10 electrolyzers obtain.
As shown in Table 3, the A level copper that method provided by the invention prepares can meet cathode copper Standard, and the decreasing ratio of arsenic, antimony, bismuth is higher.
Embodiment 4
Take copper ion concentration as 51g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L waste electrolyte be raw material, strike is adopted to carry out electrolysis to waste electrolyte, obtain A level copper and the whole liquid of decopper(ing), in the whole liquid of decopper(ing), copper ion concentration is 42g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L;
1 ~ No. 10 electrolyzer is connected successively, take the feed liquor mode of bottom in and top out, wherein, 1 ~ No. 3 groove with insoluble titanium pole plate for anode, take stainless steel polar plate as negative electrode, 4 ~ No. 10 grooves with insoluble Plante type plate for anode, the area of negative electrode is 800mm*900mm, be that negative electrode carries out electrolysis with adopting electrolysis residual pole, before carrying out electrolysis, in the whole liquid of decopper(ing), add additive 28g/t gelatine and 45g/t thiocarbamide, electrolytic process parameter and result see table 4, the electrolytic parameter that table 4 provides for the embodiment of the present invention 4 and result.In electrolytic process, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
The electrolytic parameter that table 4 embodiment of the present invention 4 provides and result
In table 4, outlet copper ion concentration is No. 10 electrolyzer outlet cupric ion copper concentration, and separating by extraction, antimony decreasing ratio and bismuth decreasing ratio are the decreasing ratio of each material in the whole liquid of decopper(ing) that No. 10 electrolyzers obtain.
As shown in Table 4, the A level copper that method provided by the invention prepares can meet cathode copper Standard, and the decreasing ratio of arsenic, antimony, bismuth is higher.
In addition, the decopper(ing) electricity effect of the present embodiment is 88%.
Embodiment 5
Take copper ion concentration as 51g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L waste electrolyte be raw material, strike is adopted to carry out electrolysis to waste electrolyte, obtain A level copper and the whole liquid of decopper(ing), in the whole liquid of decopper(ing), copper ion concentration is 38g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L;
1 ~ No. 10 electrolyzer is connected successively, take the feed liquor mode of bottom in and top out, wherein, 1 ~ No. 3 groove with insoluble titanium pole plate for anode, take stainless steel polar plate as negative electrode, 4 ~ No. 10 grooves with insoluble Plante type plate for anode, the area of negative electrode is 800mm*900mm, be that negative electrode carries out electrolysis with adopting electrolysis residual pole, before carrying out electrolysis, in the whole liquid of decopper(ing), add additive 28g/t gelatine and 45g/t thiocarbamide, electrolytic process parameter and result see table 5, the electrolytic parameter that table 5 provides for the embodiment of the present invention 5 and result.In electrolytic process, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
The electrolytic parameter that table 5 embodiment of the present invention 5 provides and result
In table 5, outlet copper ion concentration is No. 10 electrolyzer outlet cupric ion copper concentration, and separating by extraction, antimony decreasing ratio and bismuth decreasing ratio are the decreasing ratio of each material in the whole liquid of decopper(ing) that No. 10 electrolyzers obtain.
As shown in Table 5, the A level copper that method provided by the invention prepares can meet cathode copper Standard, and the decreasing ratio of arsenic, antimony, bismuth is higher.
Comparative example 1
Take copper ion concentration as 51g/L, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L waste electrolyte be raw material, strike is adopted to carry out electrolysis to waste electrolyte, obtain A level copper and the whole liquid of decopper(ing), in the whole liquid of decopper(ing), copper ion concentration is 38g/L,, arsenic 5000g/L, antimony 180g/L, bismuth 240g/L, nickel 15000g/L, iron 2000g/L;
1 ~ No. 10 electrolyzer is connected successively, take the feed liquor mode of bottom in and top out, wherein, 1 ~ No. 10 groove is with insoluble Plante type plate for anode, and the area of negative electrode is 800mm*900mm, is that negative electrode carries out electrolysis with adopting electrolysis residual pole, before carrying out electrolysis, in the whole liquid of decopper(ing), add 28g/t gelatine and 45g/t thiocarbamide, electrolytic process parameter and result see table 6, the electrolytic parameter that table 6 provides for comparative example 1 of the present invention and result.In electrolytic process, the 7th, 8, No. 9 copper liberation cell all adds the whole liquid of decopper(ing), and its flow is 1/9 of inlet flow rate.
The electrolytic parameter that table 6 comparative example 1 of the present invention provides and result
| Project | |
| Electric current (A) | 8000 |
| Flow (L/min) | 23 |
| Import copper (g/L) | 38 |
| Outlet copper (g/L) | ＜0.5 |
| Separating by extraction (%) | 65～75 |
| Antimony decreasing ratio (%) | 70～80 |
| Bismuth decreasing ratio (%) | 95～98 |
In table 5, outlet copper ion concentration is No. 10 electrolyzer outlet cupric ion copper concentration, and separating by extraction, antimony decreasing ratio and bismuth decreasing ratio are the decreasing ratio of each material in the whole liquid of decopper(ing) that No. 10 electrolyzers obtain.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (16)
1. a treatment process for waste electrolyte, comprises the following steps:
A) process waste electrolyte, obtain the whole liquid of decopper(ing), in a described decopper(ing) solution, copper ion concentration is 35g/L ~ 45g/L;
B) using insoluble anode as anode, using stainless steel cathode as negative electrode, adopt continuous electrodeposition method to process the whole liquid of a described decopper(ing), obtain A level copper and the whole liquid of secondary decopper(ing);
C) using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode, adopt continuous electrodeposition method to process the whole liquid of described secondary decopper(ing), obtain electro deposited copper, black copper plate, black copper powder and black copper mud.
2. treatment process according to claim 1, is characterized in that, in described step b), the flow of the whole liquid of a described decopper(ing) is 20L/min ~ 28L/min; The temperature of described electrolytic deposition is 50 DEG C ~ 70 DEG C; The current density of described electrolytic deposition is 180A/m
2~ 200A/m
2; The described concentration stating cupric ion in the whole liquid of secondary decopper(ing) is 15g/L ~ 25g/L.
3. treatment process according to claim 2, it is characterized in that, in described step b), the whole liquid of a described decopper(ing) carries out electrolytic deposition through the electrolyzer of 3 or 4 series connection successively, described each electrolyzer all using insoluble anode as anode, using stainless steel cathode as negative electrode.
4. treatment process according to claim 1, is characterized in that, before described step b), also comprise and add additive in the whole liquid of a described decopper(ing), described additive is gelatine and thiocarbamide.
5. treatment process according to claim 4, is characterized in that, the consumption of described gelatine is 20g/t ~ 30g/t, and the consumption of described thiocarbamide is 40g/t ~ 50g/t.
6. treatment process according to claim 1, is characterized in that, in described step b), the feed liquor mode of the whole liquid of a described decopper(ing) is bottom in and top out.
7. treatment process according to claim 1, is characterized in that, described step a) is specially:
Adopt strike to process waste electrolyte, obtain A level copper and the whole liquid of decopper(ing);
Or,
Described step a) is specially:
Waste electrolyte is carried out vacuum-evaporation, freezing and crystallizing and filtration treatment successively, obtains copper sulfate and the whole liquid of decopper(ing).
8. a waste electrolyte treatment unit, comprising:
First decopper(ing) device;
The second electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device, described second electrolyzer using insoluble anode as anode, using stainless steel cathode as negative electrode;
The 3rd electrolyzer that fluid inlet is connected with the liquid outlet of described second electrolyzer, described 3rd electrolyzer using insoluble anode as anode, using adopting electrolysis residual pole as negative electrode.
9. treatment unit according to claim 8, is characterized in that, described second electrolyzer comprises:
The 2nd A electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device;
The 2nd B electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd A electrolyzer;
The 2nd C electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd B electrolyzer.
10. treatment unit according to claim 9, is characterized in that, also comprises the shunt pipe be connected with the liquid outlet of the 2nd C electrolyzer.
11. treatment unit according to claim 9 or 10 any one, it is characterized in that, the fluid inlet of described 2nd A electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd B electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd C electrolyzer is lower than liquid outlet.
12. treatment unit according to claim 8, is characterized in that, described second electrolyzer comprises:
The 2nd A electrolyzer that fluid inlet is connected with the liquid outlet of described first decopper(ing) device;
The 2nd B electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd A electrolyzer;
The 2nd C electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd B electrolyzer;
The 2nd D electrolyzer that fluid inlet is connected with the liquid outlet of described 2nd C electrolyzer.
13. treatment unit according to claim 12, is characterized in that, also comprise the shunt pipe be connected with the liquid outlet of the 2nd D electrolyzer.
14. treatment unit according to claim 12 or 13 any one, it is characterized in that, the fluid inlet of described 2nd A electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd B electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd C electrolyzer is lower than liquid outlet; The fluid inlet of the 2nd D electrolyzer is lower than liquid outlet.
15. treatment unit according to claim 8, is characterized in that, described first decopper(ing) device comprises the first electrolyzer, described first electrolyzer using insoluble anode as anode, using stainless steel cathode as negative electrode;
Or,
Described first decopper(ing) device comprises:
Vacuum-evaporator unit;
The freezing and crystallizing device be connected with the discharge port of described vacuum-evaporator unit; With
The filtration unit be connected with the discharge port of described freezing and crystallizing device.
16. treatment unit according to claim 8, is characterized in that, also comprise additive storage tank, and the liquid outlet of described additive storage tank is connected with the fluid inlet of described second electrolyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653956.7A CN104694978B (en) | 2013-12-05 | 2013-12-05 | The processing method and processing unit of a kind of waste electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310653956.7A CN104694978B (en) | 2013-12-05 | 2013-12-05 | The processing method and processing unit of a kind of waste electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104694978A true CN104694978A (en) | 2015-06-10 |
| CN104694978B CN104694978B (en) | 2018-03-23 |
Family
ID=53342511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310653956.7A Active CN104694978B (en) | 2013-12-05 | 2013-12-05 | The processing method and processing unit of a kind of waste electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104694978B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420753A (en) * | 2015-12-29 | 2016-03-23 | 重庆紫光国际化工有限责任公司 | Method and device for maintaining activity of electrolyte during process of acrylonitrile electrolysis for preparing adiponitrile |
| CN106086942A (en) * | 2016-08-05 | 2016-11-09 | 江西众合装备技术有限公司 | A kind of cleaning copper electrolyte minus plate black copper mud stripping off device |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN113881967A (en) * | 2021-09-22 | 2022-01-04 | 中国恩菲工程技术有限公司 | Impurity removal method for lead electrolyte |
| CN115074784A (en) * | 2021-03-10 | 2022-09-20 | 中国科学院过程工程研究所 | Method for efficiently removing arsenic through electrolysis in refined copper electrolyte |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01159392A (en) * | 1987-12-16 | 1989-06-22 | Fujikura Ltd | Production of high purity electrolytic copper |
| JPH0222489A (en) * | 1988-07-08 | 1990-01-25 | Furukawa Electric Co Ltd:The | Method for electrolytically refining high purity copper |
| JPH02185990A (en) * | 1989-01-11 | 1990-07-20 | Dowa Mining Co Ltd | Ultrahigh purity copper and production thereof |
| JPH03260083A (en) * | 1990-03-12 | 1991-11-20 | Furukawa Electric Co Ltd:The | Production of high purity copper |
| CN1186875A (en) * | 1996-12-29 | 1998-07-08 | 中南工业大学 | Method and device for on-line control of organic additive in electrolytic deposition process of metal |
| KR20010091517A (en) * | 2000-03-16 | 2001-10-23 | 박호군 | Cementation apparatus of high purity copper |
| CN101003857A (en) * | 2006-10-31 | 2007-07-25 | 东华大学 | Method for extracting metal copper from electronical wastes |
| CN101033508A (en) * | 2007-04-16 | 2007-09-12 | 中南大学 | Method of preparing high purity copper by bacteria leaching primary sulfide ore |
| CN101049979A (en) * | 2007-05-16 | 2007-10-10 | 梅州市金雁铜业公司 | Method for extracting nickel sulfate from waste solution of copper electrolysis |
| CN101550488A (en) * | 2009-05-13 | 2009-10-07 | 中南大学 | Method of preparing high pure cathode copper by using PCB acid chlorine copper etching solution sewage |
| CN101928957A (en) * | 2010-10-04 | 2010-12-29 | 普宁市长欣五金有限公司 | Method for electrolyzing refined copper at room temperature |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN102453931A (en) * | 2011-01-18 | 2012-05-16 | 嘉兴科菲冶金科技股份有限公司 | Technology for treating and purifying copper electrolyte by vortex electrolysis |
| CN102766887A (en) * | 2012-08-16 | 2012-11-07 | 张家港市江城冶化科技有限公司 | Method for manufacturing stainless steel negative plate |
| CN102776527A (en) * | 2012-07-31 | 2012-11-14 | 安徽嘉伟再生资源有限公司 | Novel clean, energy-saving and environment-friendly technology for extracting high-grade copper plate by utilizing waste containing copper |
| CN102899686A (en) * | 2011-12-19 | 2013-01-30 | 河南科技大学 | Impurity removal method for copper electrolyte |
| CN103132101A (en) * | 2012-10-22 | 2013-06-05 | 广西有色再生金属有限公司 | Copper electrolyte decoppering method by utilizing copper electrolytic residual anodes as cathodes and device thereof |
| CN202968708U (en) * | 2012-11-28 | 2013-06-05 | 浙江和鼎铜业有限公司 | Automation copper electrolysis production line |
| CN103194769A (en) * | 2013-04-22 | 2013-07-10 | 北京工业大学 | Electrolytic device and method for recovering high-purity copper from waste circuit board |
| CN103334123A (en) * | 2013-07-24 | 2013-10-02 | 阳谷祥光铜业有限公司 | Copper electrolysis system and running method |
-
2013
- 2013-12-05 CN CN201310653956.7A patent/CN104694978B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01159392A (en) * | 1987-12-16 | 1989-06-22 | Fujikura Ltd | Production of high purity electrolytic copper |
| JPH0222489A (en) * | 1988-07-08 | 1990-01-25 | Furukawa Electric Co Ltd:The | Method for electrolytically refining high purity copper |
| JPH02185990A (en) * | 1989-01-11 | 1990-07-20 | Dowa Mining Co Ltd | Ultrahigh purity copper and production thereof |
| JPH03260083A (en) * | 1990-03-12 | 1991-11-20 | Furukawa Electric Co Ltd:The | Production of high purity copper |
| CN1186875A (en) * | 1996-12-29 | 1998-07-08 | 中南工业大学 | Method and device for on-line control of organic additive in electrolytic deposition process of metal |
| KR20010091517A (en) * | 2000-03-16 | 2001-10-23 | 박호군 | Cementation apparatus of high purity copper |
| CN101003857A (en) * | 2006-10-31 | 2007-07-25 | 东华大学 | Method for extracting metal copper from electronical wastes |
| CN101033508A (en) * | 2007-04-16 | 2007-09-12 | 中南大学 | Method of preparing high purity copper by bacteria leaching primary sulfide ore |
| CN101049979A (en) * | 2007-05-16 | 2007-10-10 | 梅州市金雁铜业公司 | Method for extracting nickel sulfate from waste solution of copper electrolysis |
| CN101550488A (en) * | 2009-05-13 | 2009-10-07 | 中南大学 | Method of preparing high pure cathode copper by using PCB acid chlorine copper etching solution sewage |
| CN101928957A (en) * | 2010-10-04 | 2010-12-29 | 普宁市长欣五金有限公司 | Method for electrolyzing refined copper at room temperature |
| CN102453931A (en) * | 2011-01-18 | 2012-05-16 | 嘉兴科菲冶金科技股份有限公司 | Technology for treating and purifying copper electrolyte by vortex electrolysis |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN102899686A (en) * | 2011-12-19 | 2013-01-30 | 河南科技大学 | Impurity removal method for copper electrolyte |
| CN102776527A (en) * | 2012-07-31 | 2012-11-14 | 安徽嘉伟再生资源有限公司 | Novel clean, energy-saving and environment-friendly technology for extracting high-grade copper plate by utilizing waste containing copper |
| CN102766887A (en) * | 2012-08-16 | 2012-11-07 | 张家港市江城冶化科技有限公司 | Method for manufacturing stainless steel negative plate |
| CN103132101A (en) * | 2012-10-22 | 2013-06-05 | 广西有色再生金属有限公司 | Copper electrolyte decoppering method by utilizing copper electrolytic residual anodes as cathodes and device thereof |
| CN202968708U (en) * | 2012-11-28 | 2013-06-05 | 浙江和鼎铜业有限公司 | Automation copper electrolysis production line |
| CN103194769A (en) * | 2013-04-22 | 2013-07-10 | 北京工业大学 | Electrolytic device and method for recovering high-purity copper from waste circuit board |
| CN103334123A (en) * | 2013-07-24 | 2013-10-02 | 阳谷祥光铜业有限公司 | Copper electrolysis system and running method |
Non-Patent Citations (7)
| Title |
|---|
| 吴文明: "金隆电积脱铜脱砷生产实践", 《有色冶炼》 * |
| 聂仲文: "浅析贵溪冶炼厂A级铜生产实践", 《湿法冶金》 * |
| 聂仲文: "贵冶铜电解液净化生产实践", 《有色冶炼》 * |
| 肖炳瑞: "铜电解精炼过程杂质的溶出及脱除", 《铜业工程》 * |
| 褚仁雪: "连续脱铜电解研讨", 《有色冶炼》 * |
| 邢卫国: "二次脱铜过程中砷行为分析和工艺控制", 《有色金属(冶炼部分)》 * |
| 陈白珍等: "控制阴极电势电积法脱铜砷", 《中国有色金属学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420753A (en) * | 2015-12-29 | 2016-03-23 | 重庆紫光国际化工有限责任公司 | Method and device for maintaining activity of electrolyte during process of acrylonitrile electrolysis for preparing adiponitrile |
| CN106086942A (en) * | 2016-08-05 | 2016-11-09 | 江西众合装备技术有限公司 | A kind of cleaning copper electrolyte minus plate black copper mud stripping off device |
| CN111501065A (en) * | 2020-04-27 | 2020-08-07 | 阳谷祥光铜业有限公司 | Method for purifying copper electrolyte |
| CN115074784A (en) * | 2021-03-10 | 2022-09-20 | 中国科学院过程工程研究所 | Method for efficiently removing arsenic through electrolysis in refined copper electrolyte |
| CN113881967A (en) * | 2021-09-22 | 2022-01-04 | 中国恩菲工程技术有限公司 | Impurity removal method for lead electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104694978B (en) | 2018-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104694978A (en) | Waste electrolyte treatment method and device | |
| CN101906654B (en) | Method for purifying copper electrolyte with minimal chemical reacting dose | |
| CN104894607A (en) | Method for purifying waste copper sulfate electrolyte | |
| CN105506670B (en) | A kind of device and operation method of cupric electrolysis or copper electrodeposition | |
| CN109252190B (en) | Method for recovering 99.98% copper powder from etching solution and preparing 99.999% cathode copper | |
| CN110387560B (en) | Method for preparing 5N high-purity copper through one-time electrolysis | |
| CN103334123A (en) | Copper electrolysis system and running method | |
| CN113957459A (en) | Method for producing bromine and caustic soda by electrolyzing sodium bromide through ion membrane | |
| CN105565342A (en) | Refining agent for refining primary brine in chlorine alkali industry and application of refining agent | |
| CN103265094A (en) | Method for recycling nitric acid and copper from waste water generated in production of printed circuit board | |
| CN105441974B (en) | A kind of method for producing electro deposited nickel | |
| CN107419111B (en) | A kind of method that production zinc powder is leached in the in-pulp electrolysis of alloy zinc gray | |
| CN203200349U (en) | Diaphragm electrolytic cell for preparing high-purity cobalt | |
| CN103710541A (en) | Wet process for producing electrolytic manganese dioxide | |
| CN103498169A (en) | Preparation method for reducing sulfur impurities in electrolytic nickel | |
| CN110938842A (en) | Copper electrolyte purification method | |
| CN1932083A (en) | Silver electrolyzing process | |
| CN103710732A (en) | Waste copper sulfate electrolyte purification system and method | |
| CN104018185A (en) | Compound technology for removing As, Sb, Bi by utilizing copper electrolyte | |
| CN107022769A (en) | A kind of method and device that high-purity monohydrate lithium hydroxide is extracted from the material containing lithium carbonate | |
| CN203474910U (en) | Copper electrolysis system | |
| CN109809502A (en) | A method of nickel sulfate is produced using electro deposited nickel anolyte | |
| CN109536992A (en) | A kind of method of two de- two products purifying copper electrolytes | |
| CN102051635B (en) | Method for producing metal cobalt by adopting high-current density sulfuric acid electrolyte | |
| CN102234816A (en) | Method for extracting copper from copper electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |