CN106757151A - Cathode copper is produced using copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin - Google Patents
Cathode copper is produced using copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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Abstract
Field is utilized the invention belongs to changing waste into resources, and in particular to a kind of utilization copper-contained sludge produces cathode copper and separates the low energy consumption method of nickel, arsenic and tin.For prior art high energy consumption, pollution is big, the rate of recovery of copper is low, anode is easily passivated and cannot a step realize the problem that copper, nickel, tin are separate, cathode copper is produced the invention provides a kind of utilization copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin, through the cathode copper high purity 99.99% that the method production is obtained, the rate of recovery of copper can reach 92%, and can reducing energy consumption more than 22%.
Description
Technical field
The invention belongs to utilization of waste as resource field, and in particular to one kind produces cathode copper and divides using copper-contained sludge
From the low energy consumption method of nickel, arsenic and tin.
Background technology
At present, domestic and international scientific research personnel mainly uses following three kinds of methods to copper-contained sludge recycling：With blast furnace
It is the pyrolytic semlting absorption method for representing；The chemical recycling and calcining-acidleach absorption method of sulfuric acid stirring acidleach.Above-mentioned three kinds of sides
Method there is a problem of big and small to some extent, and such as pyrolytic semlting absorption method has high energy consumption, unfriendly to environment, and suitable
With scope it is small the shortcomings of；Although the chemical recycling reaction time of sulfuric acid stirring acidleach is shorter, the leaching rate of copper is higher, due to
Substantial amounts of sulfuric acid is used, it has stronger corrosivity to environment, and because sludge components are complicated, the separation of solid and liquid after sulfuric acid leaching
Extremely difficult, the rate of recovery of copper is low；Although calcining-acidleach absorption method process is simple, easy to operate, technique power consumption is higher, generation
Mantoquita is impure more.
Therefore, for above-mentioned technical problem, applicant has submitted an entitled one kind to State Intellectual Property Office a few days ago
Using the patent (Publication No. CN104233370A) of the method for copper-contained sludge production cathode copper, it is comprised the following steps：(1) burn
Knot：The bronze medal sludge of the crystallization water 80% will be contained it will be placed in differential sintering machine and be sintered, sintering will be until obtain cellular or graininess
Agglomerate；(2) oxygen-enriched side-blowing melting：The cellular or graininess agglomerate that will be obtained in step (1), with quartz, lime stone
And carbon mixing, smelting furnace is transferred to, the air for being continually fed into oxygen volumetric concentration 90% is calcined, wherein calcining heat
It it is 1200-1250 DEG C, oxygen-rich oxide blows to the blister copper and the mixture of matte for obtaining copper content 85-95%；(3) essence is turned round
Refining：The blister copper and the mixture of matte that step (2) is obtained are transferred in revolution refining furnace, in the mixture to blister copper and matte
Quartz, lime stone, carbon and heavy oil are added, is calcined to air is continually fed into mixture, wherein calcining heat is
1100-1200 DEG C, calcining obtains the anode copper coin of cupric 98%；(4) electrorefining：Using the anode copper coin in step (3) as
Anode, fine copper is laminated as negative electrode, and the mixed solution of sulfuric acid and copper sulphate carries out reverse current electrolysis as electrolyte, is controlled
The temperature of electrolyte processed is 60-70 DEG C, and electrolysis obtains cathode copper of the present invention.Influence of the method to environment is smaller, and
The content of copper is up to 99.99% in the electrolysis copper products for obtaining, and the rate of recovery of copper is up to more than 85%.But, applicant is in reality
Found in the production of border, the refining slag that step (3) is produced also containing 30~50% copper, 1~2% nickel and 3~5% tin, such as
Fruit repeats refining slag not only can significantly waste nickel therein and tin if above-mentioned steps production cathode copper, and can cause
Integrated artistic power consumption is higher, is unfavorable for its large-scale popularization and application, and because the refining slag for producing is impure more, if press with
Preceding electrolytic method is electrolysed, and extremely easily produces the phenomenon of anodic passivity.
Further, since the earth of positive pole that electrolysis is produced is except tin is contained, it also contains a small amount of nickel and copper, and existing method does not have
Further three is separated.
Therefore, it is necessary to provide that a kind of process is simple, energy consumption are low, pollution is small while the rate of recovery of copper is high, and can be effectively real
Now separate copper, nickel, the technique of tin.
The content of the invention
In order to solve technical problem present in prior art, copper-contained sludge is utilized it is an object of the invention to provide one kind
Produce cathode copper and separate the low energy consumption method of nickel, arsenic and tin, to solve disadvantages described above.
Cathode copper is produced the invention provides a kind of utilization copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin, bag
Include following steps：
S1, copper-contained sludge is sintered, until the agglomerate water content for obtaining is 1~5%；
S2, by above-mentioned agglomerate move into smelting furnace, add flux, while being continually fed into oxygen volumetric concentration 30~40%
Air is calcined, and obtains blister copper, wherein the temperature calcined is 1200~1250 DEG C；
S3, by above-mentioned blister copper move into refining furnace, add heavy oil while be continually fed into oxygen volumetric concentration 90~99.9%
Air mixing dissolve copper, add reducing agent and quartz, obtain anode copper coin and refining slag that copper content is 98%, wherein
The temperature of calcining is 1100~1200 DEG C；
S4, using above-mentioned anode copper coin as anode, copper sheet is placed in the mixed liquor of sulfuric acid and copper sulphate as negative electrode
In, it is continually fed into electric current and is electrolysed, control electrolysis temperature for 60~70 DEG C, electrolysis obtains catholyte copper；
S5, by step S3) during the refining slag that obtains moves into blast furnace calcining obtain the black copper sun that copper content is 60~70%
Pole plate, calcining heat is 1200~1250 DEG C；
S6, using above-mentioned black copper positive plate as anode, copper sheet is placed in the electrolyte of sulfuric acid and copper sulphate as negative electrode
In, 700~800 parts of 50~80 parts of thiocarbamide and gelatine are added toward electrolyte, it is passed through cycle forward and reverse electric current and is electrolysed, obtain
Catholyte copper simultaneously retains electrolyte and the earth of positive pole；Wherein, the concentration of copper ion is 40~50g/L in the electrolyte, described
The temperature of electrolyte is 60~80 DEG C, and the current density is 150~200A/m2；
S7, the above-mentioned earth of positive pole is washed with deionized 1~3 time, retains cleaning solution, the earth of positive pole after washing is milled to
200~400 mesh, are moved into leaching pond after crossing vibratory sieve, add hydrogen peroxide, while being passed through air, leach copper and mickel, and filtering is protected
Reserved filtrate and Fu Xi filter residues；
S8, by step S7) gained filtrate and cleaning solution mix, and adds NaOH regulation pH to 6~7, stands 2~4h shapes
Precipitation cuprum nickeliferous is obtained into precipitation, after filtering, the precipitation cuprum nickeliferous is washed with deionized 1~3 time；
S9, by above-mentioned washing after precipitation cuprum nickeliferous add water regulation pH to 9~10 after add copper ion 0.6~0.8
The ethylene glycol of amount, stirring, filtering, retain filtrate and precipitation again；
S10, toward step S9) obtained by filtrate in add the sulfuric acid solution of 1~3mol/L to adjust pH to 7~8, generate hydrogen-oxygen
Change copper precipitation；
S11, by step S9) precipitation that obtains is washed with deionized 1~3 time, is filtrated to get nickel hydroxide precipitate, add
The sulfuric acid solution of 1~3mol/L is allowed to dissolve, and nickel sulfate is obtained after being evaporated.
Preferably, the step S2) in flux include 3~4kg/t of lime stone Cu, 6~8kg/t of quartz Cu and carbon
10~12kg/t Cu.
Preferably, the step S3) in reducing agent consumption be 2~6kg/t Cu, quartz consumption be 4~8kg/t
Cu, the consumption of heavy oil are 3~4kg/t Cu.
Preferably, the step S6) in the temperature of electrolyte be 63~70 DEG C, the density of forward and reverse electric current for 180~
190A/m2, the concentration of copper ion is 42~47g/L in electrolyte.
Preferably, the step S6) in the temperature of electrolyte be 68 DEG C, the density of forward and reverse electric current is 185A/m2, electrolysis
The concentration of copper ion is 45g/L in liquid.
Preferably, the step S6) described in the cycle be 10~12s.
Preferably, the step S6) also include that the stabilizer is in electrolyte the step of to stabilizer is added in electrolyte
In mass fraction be 1~5 part.
Preferably, stabilizer mass fraction in the electrolytic solution is 3 parts.
Preferably, the stabilizer presses 1 by diethylene-triamine pentaacetic acid and DL- aminocaproic lactams:(0.01~
0.04) weight is than composition.
Preferably, the stabilizer presses 1 by diethylene-triamine pentaacetic acid and DL- aminocaproic lactams:0.03 weight
Than composition.
In actual production, by copper-contained sludge is sintered, melting, refining and electrolysis can realize returning most copper
Receive, but the refining slag produced in refining process is also containing 45~55% copper, 1~2% nickel and 3~5% tin, if directly
Connect it is discarded will directly contribute waste and the pollution to environment, but if refining slag is repeated be sintered, melting, refining and electricity
Solution preocess can be because consuming energy larger and causing integrated artistic to consume if copper is further reclaimed in sintering, melting and refining process
Can be higher, and the waste of nickel and tin is caused, it is unfavorable for inexpensive production.
In order to solve the above-mentioned technical problem, the present invention first by copper-contained sludge is sintered, melting, refining and electrolysis treatment realization
Major part to copper is reclaimed, then the refining slag that will be produced in refining process directly casts black copper positive plate in blast furnace again,
And using the black copper positive plate as anode, copper sheet carries out re-electrolysis production tough cathode as negative electrode, realizes to copper again
Secondary recovery.It is solved refining slag is sintered, melting and refining without refining slag is re-started into sintering, melting and refining
The problem of high energy consumption caused by process.But because refining slag is impure more, cast black copper positive plate carry out electrolysis be easy to
Hinder copper ion and spread to electrolyte because the precipitation of nickel forms the continuous and covering of densification in anode surface, so as to lead
The passivation of anode is caused, and then influences the quality of production efficiency and product.Inventor in electrolytic process it was unexpectedly observed that be passed through week
Phase, forward and reverse electric current can effectively solve the problem that the problem of anodic passivity.Through statistics, the application method can reduce by 22~30% energy consumption.
By the cycle of the reverse 1s of 10~12s of forward direction toward electric current is passed through in electrolyte, anodic passivity can be preferably avoided.
But inventor is had found with the carrying out of electrolysis, nickel in positive plate concentration in the electrolytic solution is raised, and it can make
The viscosity of electrolyte is raised, and the rising of viscosity is unfavorable for the diffusion of copper ion, therefore, phase after electrolysis, even if being passed through the cycle
Forward and reverse electric current is electrolysed, and anode also inevitably produces passivation phenomenon, causes the purity of global copper and the rate of recovery not
It is high.Copper is electrolysed in sulfuric acid and lost one before this and be electronically generated univalent copper ion, then proceedes to generate bivalent cupric ion, the latter's ratio
The former is slow.Therefore, copper is inevitable along with cupprous generation and accumulation in anodic dissolution processes.And monovalence copper is very not
Stabilization, it can occur disproportionated reaction, and the copper for being generated can be deposited on cathode surface in electrolytic process in the way of electrophoresis, from
And burr is produced, make cathode surface coarse.Stabilizer of the present invention is pressed by diethylene-triamine pentaacetic acid and DL- aminocaproic lactams
1：The weight of (0.01~0.04) is than composition.Wherein, diethylene-triamine pentaacetic acid presence on the one hand can network and nickel ion,
Prevent anode from continuing to be passivated, on the other hand can also stablize univalent copper ion, be favorably improved planarization and the densification of cathode surface
Property.In addition, addition DL- aminocaproic lactams can accelerate the generation of bivalent cupric ion, the accumulation of univalent copper ion is reduced.
Experiment is proved, while addition diethylene-triamine pentaacetic acid and DL- aminocaproic lactams can put forward the rate of recovery of copper
To 82.2~92.6%, the purity of copper reaches 94.25~99.99% to height, and in the case of being added without stabilizer, the rate of recovery of copper
68% is reduced to, purity is 90.49%.The rate of recovery and purity for being individually added into DL- aminocaproic lactam copper are respectively 68.3%
With 91.32%；It is 72.5% to be individually added into the rate of recovery of diethylene-triamine pentaacetic acid copper, and purity is 94.68%.This explanation,
Both compounding uses have the effect of Synergistic.Wherein, diethylene-triamine pentaacetic acid and DL- aminocaproic lactams press 1：
Than compounding use effect preferably, the rate of recovery of copper can reach 92.6%, high purity 99.99% to 0.03 weight.
Compared with prior art, the inventive method has the advantage that：
1) the cathode copper high purity 99.99% obtained through the inventive method production, the rate of recovery of copper can reach 92%, drop
Low energy consumption more than 22%, and the separation of copper, nickel, tin can be effectively realized, it is significantly better than disclosed preparation in the prior art and is electrolysed
The method of copper.
2) present invention is combined using cycle forward and reverse electric current with stabilizer, its passivation phenomenon that can significantly inhibit anode, and
And cause that the rate of recovery and purity of copper are greatly improved.
Specific embodiment：
Below by way of the description of specific embodiment, the invention will be further described, but this is not to limit of the invention
System, those skilled in the art's basic thought of the invention, various modifications may be made or improves, but without departing from this
The basic thought of invention, within the scope of the present invention.
Embodiment 1, produce cathode copper using copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin
The methods described of the embodiment of the present invention 1 is comprised the steps of：
S1, copper-contained sludge is sintered, until the agglomerate water content for obtaining is 1%；
S2, above-mentioned agglomerate is moved into smelting furnace, add lime stone 3kg/t Cu, quartz 6kg/t Cu and carbon
10kg/t Cu, while the air for being continually fed into oxygen volumetric concentration 30% is calcined, obtain blister copper, wherein the temperature calcined
It is 1200 DEG C；
S3, by above-mentioned blister copper move into refining furnace, add heavy oil 3kg/t Cu while be continually fed into oxygen volumetric concentration
90% air mixing dissolves copper, adds carbon dust 2kg/t Cu and quartz 4kg/t Cu, obtains the sun that copper content is 98%
Pole copper coin and refining slag, wherein the temperature calcined is 1100 DEG C；
S4, using above-mentioned anode copper coin as anode, copper sheet is placed in the mixed liquor of sulfuric acid and copper sulphate as negative electrode
In, it is continually fed into electric current and is electrolysed, control electrolysis temperature for 60 DEG C, electrolysis obtains No. 1 cathode copper；
S5, by step S3) during the refining slag that obtains moves into blast furnace calcining obtain the black copper positive plate that copper content is 60%,
Calcining heat is 1200 DEG C；
S6, using above-mentioned black copper positive plate as anode, copper sheet is placed in the electrolyte of sulfuric acid and copper sulphate as negative electrode
In, 700 parts of 50 parts of thiocarbamide and gelatine are added toward electrolyte, it is passed through electric current by the cycle of the reverse 1s of positive 10s and is electrolysed, obtain
To No. 2 cathode coppers and retain electrolyte and the earth of positive pole；Wherein, the concentration of copper ion is 40g/L, the electrolysis in the electrolyte
The temperature of liquid is 60 DEG C, and the current density is 150A/m2；
S7, the above-mentioned earth of positive pole is washed with deionized 1 time, retains cleaning solution, the earth of positive pole after washing is milled to 200
Mesh, crosses after vibratory sieve to move into and leaches in pond, adds hydrogen peroxide, while be passed through air, leaches copper and mickel, filtering, retain filtrate and
Rich tin filter residue；
S8, by step S7) gained filtrate and cleaning solution mix, and adds NaOH regulation pH to 6, stand 2h and form heavy
Form sediment, precipitation cuprum nickeliferous is obtained after filtering, the precipitation cuprum nickeliferous is washed with deionized 1 time；
S9, by above-mentioned washing after precipitation cuprum nickeliferous add the second two that 0.6 times of copper ion amount is added after water regulation pH to 9
Alcohol, stirring, filtering retains filtrate and precipitation；
S10, toward step S9) obtained by filtrate in add the sulfuric acid solution of 1mol/L to adjust pH to 7, generation Kocide SD sinks
Form sediment；
S11, by step S9) precipitation that obtains is washed with deionized 1 time, is filtrated to get nickel hydroxide precipitate, add
The sulfuric acid solution of 1mol/L is allowed to dissolve, and nickel sulfate is obtained after being evaporated.
22% energy consumption can be reduced through the methods described of embodiment 1 production cathode copper, the cathode copper purity that electrolysis is obtained is
90.49%, the rate of recovery of copper is 68%.
Embodiment 2, produce cathode copper using copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin
The methods described of the embodiment of the present invention 2 is comprised the steps of：
S1, copper-contained sludge is sintered, until the agglomerate water content for obtaining is 3%；
S2, above-mentioned agglomerate is moved into smelting furnace, add lime stone 3.5kg/t Cu, quartz 7kg/t Cu and carbon
11kg/t Cu, while the air for being continually fed into oxygen volumetric concentration 35% is calcined, obtain blister copper, wherein the temperature calcined
It is 1200 DEG C；
S3, by above-mentioned blister copper move into refining furnace, add heavy oil 3.5kg/t Cu while be continually fed into oxygen volumetric concentration
90% air mixing dissolves copper, adds carbon dust 2kg/t Cu and quartz 4kg/t Cu, obtains the sun that copper content is 98%
Pole copper coin and refining slag, wherein the temperature calcined is 1100 DEG C；
S4, using above-mentioned anode copper coin as anode, copper sheet is placed in the mixed liquor of sulfuric acid and copper sulphate as negative electrode
In, it is continually fed into electric current and is electrolysed, control electrolysis temperature for 60 DEG C, electrolysis obtains No. 1 cathode copper；
S5, by step S3) during the refining slag that obtains moves into blast furnace calcining obtain the black copper positive plate that copper content is 60%,
Calcining heat is 1200 DEG C；
S6, using above-mentioned black copper positive plate as anode, copper sheet is placed in the electrolyte of sulfuric acid and copper sulphate as negative electrode
In, 3 parts of 60 parts of thiocarbamide, 750 parts of gelatine and stabilizer are added toward electrolyte, it is passed through electric current by the cycle of the reverse 1s of positive 12s
It is electrolysed, obtains cathode copper and retain electrolyte and the earth of positive pole；Wherein, the concentration of copper ion is 45g/L in the electrolyte,
The temperature of the electrolyte is 70 DEG C, and the current density is 185A/m2, the stabilizer by diethylene-triamine pentaacetic acid and
DL- aminocaproic lactams press 1：0.03 weight is than composition；
S7, the above-mentioned earth of positive pole is washed with deionized 2 times, retains cleaning solution, the earth of positive pole after washing is milled to 300
Mesh, crosses after vibratory sieve to move into and leaches in pond, adds hydrogen peroxide, while be passed through air, leaches copper and mickel, filtering, retain filtrate and
Rich tin filter residue；
S8, by step S7) gained filtrate and cleaning solution mix, and adds NaOH regulation pH to 7, stand 3h and form heavy
Form sediment, precipitation cuprum nickeliferous is obtained after filtering, the precipitation cuprum nickeliferous is washed with deionized 2 times；
S9, by above-mentioned washing after precipitation cuprum nickeliferous add the second that 0.7 times of copper ion amount is added after water regulation pH to 10
Glycol, stirring, filtering retains filtrate and precipitation；
S10, toward step S9) obtained by filtrate in add the sulfuric acid solution of 2mol/L to adjust pH to 7.5, generate Kocide SD
Precipitation；
S11, by step S9) precipitation that obtains is washed with deionized 2 times, is filtrated to get nickel hydroxide precipitate, add
The sulfuric acid solution of 2mol/L is allowed to dissolve, and nickel sulfate is obtained after being evaporated.
30% energy consumption can be reduced through the methods described of embodiment 2 production cathode copper, the cathode copper purity that electrolysis is obtained is high
Up to 99.99%, the rate of recovery of copper is 92.6%.
Embodiment 3, produce cathode copper using copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin
The methods described of the embodiment of the present invention 3 is comprised the steps of：
S1, copper-contained sludge is sintered, until the agglomerate water content for obtaining is 3%；
S2, above-mentioned agglomerate is moved into smelting furnace, add lime stone 3.5kg/t Cu, quartz 7kg/t Cu and carbon
11kg/t Cu, while the air for being continually fed into oxygen volumetric concentration 35% is calcined, obtain blister copper, wherein the temperature calcined
It is 1200 DEG C；
S3, by above-mentioned blister copper move into refining furnace, add heavy oil 3.5kg/t Cu while be continually fed into oxygen volumetric concentration
90% air mixing dissolves copper, adds carbon dust 2kg/t Cu and quartz 4kg/t Cu, obtains the sun that copper content is 98%
Pole copper coin and refining slag, wherein the temperature calcined is 1100 DEG C；
S4, using above-mentioned anode copper coin as anode, copper sheet is placed in the mixed liquor of sulfuric acid and copper sulphate as negative electrode
In, it is continually fed into electric current and is electrolysed, control electrolysis temperature for 60 DEG C, electrolysis obtains No. 1 cathode copper；
S5, by step S3) during the refining slag that obtains moves into blast furnace calcining obtain the black copper positive plate that copper content is 60%,
Calcining heat is 1200 DEG C；
S6, using above-mentioned black copper positive plate as anode, copper sheet is placed in the electrolyte of sulfuric acid and copper sulphate as negative electrode
In, 3 parts of 60 parts of thiocarbamide, 750 parts of gelatine and stabilizer are added toward electrolyte, it is passed through electric current by the cycle of the reverse 1s of positive 11s
It is electrolysed, obtains cathode copper and retain electrolyte and the earth of positive pole；Wherein, the concentration of copper ion is 45g/L in the electrolyte,
The temperature of the electrolyte is 70 DEG C, and the current density is 185A/m2, the stabilizer by diethylene-triamine pentaacetic acid and
DL- aminocaproic lactams press 1：0.03 weight is than composition；
S7, the above-mentioned earth of positive pole is washed with deionized 2 times, retains cleaning solution, the earth of positive pole after washing is milled to 300
Mesh, crosses after vibratory sieve to move into and leaches in pond, adds hydrogen peroxide, while be passed through air, leaches copper and mickel, filtering, retain filtrate and
Rich tin filter residue；
S8, by step S7) gained filtrate and cleaning solution mix, and adds NaOH regulation pH to 7, stand 3h and form heavy
Form sediment, precipitation cuprum nickeliferous is obtained after filtering, the precipitation cuprum nickeliferous is washed with deionized 2 times；
S9, by above-mentioned washing after precipitation cuprum nickeliferous add the second that 0.7 times of copper ion amount is added after water regulation pH to 10
Glycol, stirring, filtering retains filtrate and precipitation；
S10, toward step S9) obtained by filtrate in add the sulfuric acid solution of 2mol/L to adjust pH to 7.5, generate Kocide SD
Precipitation；
S11, by step S9) precipitation that obtains is washed with deionized 2 times, is filtrated to get nickel hydroxide precipitate, add
The sulfuric acid solution of 2mol/L is allowed to dissolve, and nickel sulfate is obtained after being evaporated.
25% energy consumption can be reduced through the methods described of embodiment 3 production cathode copper, the cathode copper purity that electrolysis is obtained is high
Up to 99.92%, the rate of recovery of copper is 88%.
Influence of the combination of test example one, different stabilizers to the rate of recovery of copper
On the basis of embodiment 2,4 kinds of combinations of different stabilizers are set, it is investigated to copper recovery and the shadow of purity
Ring, investigate result as shown in table 1.
Table 1 investigates result
| Stabilizer | Copper recovery | The purity of copper |
| It is added without stabilizer | 68% | 90.49% |
| Diethylene-triamine pentaacetic acid | 72.5% | 94.68% |
| DL- aminocaproic lactams | 68.3% | 91.32% |
| Diethylene-triamine pentaacetic acid：DL- aminocaproic lactam=1：0.03 | 92.6% | 99.99% |
| Diethylene-triamine pentaacetic acid：DL- aminocaproic lactam=1：1 | 82.2% | 94.25% |
As seen from Table 1, it is 68% through the rate of recovery of the inventive method production copper when being added without stabilizer, purity is
90.99%, and the rate of recovery for being individually added into DL- aminocaproic lactam copper is only 68.3%, purity is 91.32%, and is added without
Stabilizer is compared without significant change, and this explanation, the addition of DL- aminocaproic lactams is little to the rate of recovery and impurities affect of copper.
Compared with stabilizer is added without, after being individually added into diethylene-triamine pentaacetic acid, the rate of recovery of copper improves 4.5%, and purity is carried
It is high by 4.19%, and diethylene-triamine pentaacetic acid and DL- aminocaproic lactams are added simultaneously, the rate of recovery of copper can improve 14.2
~24.6%, purity can improve 3.76%~9.50%, especially when both are with 1:0.03 ratio addition can make the rate of recovery of copper
92.6% is reached, this explanation, both compounding uses have the effect of Synergistic.
Claims (10)
1. produce cathode copper using copper-contained sludge and separate the low energy consumption method of nickel, arsenic and tin, it is characterised in that including following step
Suddenly：
S1, copper-contained sludge is sintered, until the agglomerate water content for obtaining is 1~5%；
S2, by above-mentioned agglomerate move into smelting furnace, add flux, while being continually fed into the air of oxygen volumetric concentration 30~40%
Calcined, obtained blister copper, wherein the temperature calcined is 1200~1250 DEG C；
S3, above-mentioned blister copper is moved into refining furnace, the sky of oxygen volumetric concentration 90~99.9% is continually fed into while adding heavy oil
Gas mixing dissolves copper, adds reducing agent and quartz, anode copper coin and refining slag that copper content is 98% is obtained, wherein calcining
Temperature be 1100~1200 DEG C；
S4, using above-mentioned anode copper coin as anode, copper sheet is placed in the mixed liquor of sulfuric acid and copper sulphate as negative electrode, holds
It is continuous to be passed through electric current and be electrolysed, control electrolysis temperature for 60~70 DEG C, it is electrolysed and obtains catholyte copper；
S5, by step S3) during the refining slag that obtains moves into blast furnace calcining obtain the black copper positive plate that copper content is 60~70%,
Calcining heat is 1200~1250 DEG C；
S6, using above-mentioned black copper positive plate as anode, copper sheet is placed in the electrolyte of sulfuric acid and copper sulphate as negative electrode,
700~800 parts of 50~80 parts of thiocarbamide and gelatine are added toward electrolyte, cycle forward and reverse electric current is passed through and is electrolysed, obtain the moon
Pole cathode copper simultaneously retains electrolyte and the earth of positive pole；Wherein, the concentration of copper ion is 40~50g/L, the electricity in the electrolyte
The temperature for solving liquid is 60~80 DEG C, and the current density is 150~200A/m2；
S7, the above-mentioned earth of positive pole is washed with deionized 1~3 time, retains cleaning solution, the earth of positive pole after washing is milled to 200
~400 mesh, move into leaching pond after crossing vibratory sieve, add hydrogen peroxide, while being passed through air, leach copper and mickel, and filtering retains and filters
Liquid and Fu Xi filter residues；
S8, by step S7) gained filtrate and cleaning solution mix, and adds NaOH regulation pH to 6~7, stand 2~4h and form heavy
Form sediment, precipitation cuprum nickeliferous is obtained after filtering, the precipitation cuprum nickeliferous is washed with deionized 1~3 time；
S9, by above-mentioned washing after precipitation cuprum nickeliferous add water regulation pH to 9~10 after add 0.6~0.8 times of copper ion amount
Ethylene glycol, stirring, filtering, retain filtrate and precipitation；
S10, toward step S9) obtained by filtrate in add the sulfuric acid solution of 1~3mol/L to adjust pH to 7~8, generate Kocide SD
Precipitation；
S11, by step S9) precipitation that obtains is washed with deionized 1~3 time, is filtrated to get nickel hydroxide precipitate, add 1~
The sulfuric acid solution of 3mol/L is allowed to dissolve, and nickel sulfate is obtained after being evaporated.
2. the method for claim 1, it is characterised in that the step S2) in flux include 3~4kg/t of lime stone
Cu, 6~8kg/t of quartz Cu and 10~12kg/t of carbon Cu.
3. the method for claim 1, it is characterised in that the step S3) in the consumption of reducing agent be 2~6kg/t
Cu, the consumption of quartz be 4~8kg/t Cu, heavy oil consumption be 3~4kg/t Cu.
4. the method for claim 1, it is characterised in that the step S6) in the temperature of electrolyte be 63~70 DEG C, just
The density of reverse current is 180~190A/m2, the concentration of copper ion is 42~47g/L in electrolyte.
5. method as claimed in claim 4, it is characterised in that the step S6) in the temperature of electrolyte be 68 DEG C, it is forward and reverse
The density of electric current is 185A/m2, and the concentration of copper ion is 45g/L in electrolyte.
6. the method for claim 1, it is characterised in that the step S6) described in the cycle be 10~12s.
7. the method for claim 1, it is characterised in that the step S6) also include to adding stabilizer in electrolyte
The step of, stabilizer mass fraction in the electrolytic solution is 1~5 part.
8. method as claimed in claim 7, it is characterised in that stabilizer mass fraction in the electrolytic solution is 3 parts.
9. method as claimed in claim 7 or 8, it is characterised in that the stabilizer is by diethylene-triamine pentaacetic acid and DL-
Aminocaproic lactam presses 1:The weight of (0.01~0.04) is than composition.
10. method as claimed in claim 9, it is characterised in that the stabilizer is by diethylene-triamine pentaacetic acid and DL- ammonia
Base caprolactam presses 1:0.03 weight is than composition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018095162A1 (en) * | 2016-11-23 | 2018-05-31 | 肇庆市飞南金属有限公司 | Low energy consumption method for preparing electrolytic copper from copper-containing sludge |
| CN108385133A (en) * | 2018-03-13 | 2018-08-10 | 肇庆市飞南金属有限公司 | A kind of low energy consumption method producing cathode copper using copper-contained sludge |
| CN110055421A (en) * | 2019-04-28 | 2019-07-26 | 广东飞南资源利用股份有限公司 | A kind of preprocess method of high tin copper anode mud |
| CN111394582A (en) * | 2020-05-09 | 2020-07-10 | 广东飞南资源利用股份有限公司 | Copper-nickel sludge resource recycling process |
| CN114635038A (en) * | 2022-02-18 | 2022-06-17 | 永兴长隆环保科技有限公司 | Method for recovering and preparing refined tin from tin-containing waste residues |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974689A (en) * | 2010-09-26 | 2011-02-16 | 金川集团有限公司 | Method for processing material containing copper |
| CN102002594A (en) * | 2010-12-17 | 2011-04-06 | 赖小洪 | Method for recycling tin |
| CN102242268A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for treating black copper slag through electrolytic method |
| CN102345143A (en) * | 2011-10-09 | 2012-02-08 | 中南大学 | Method for separating copper, arsenic and nickel and purifying copper electrolyte |
| CN104233370A (en) * | 2014-09-02 | 2014-12-24 | 肇庆市飞南金属有限公司 | Method for producing electrolytic copper by utilizing copper-containing sludge |
-
2016
- 2016-11-23 CN CN201611046435.5A patent/CN106757151A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974689A (en) * | 2010-09-26 | 2011-02-16 | 金川集团有限公司 | Method for processing material containing copper |
| CN102002594A (en) * | 2010-12-17 | 2011-04-06 | 赖小洪 | Method for recycling tin |
| CN102242268A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for treating black copper slag through electrolytic method |
| CN102345143A (en) * | 2011-10-09 | 2012-02-08 | 中南大学 | Method for separating copper, arsenic and nickel and purifying copper electrolyte |
| CN104233370A (en) * | 2014-09-02 | 2014-12-24 | 肇庆市飞南金属有限公司 | Method for producing electrolytic copper by utilizing copper-containing sludge |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018095162A1 (en) * | 2016-11-23 | 2018-05-31 | 肇庆市飞南金属有限公司 | Low energy consumption method for preparing electrolytic copper from copper-containing sludge |
| CN108385133A (en) * | 2018-03-13 | 2018-08-10 | 肇庆市飞南金属有限公司 | A kind of low energy consumption method producing cathode copper using copper-contained sludge |
| CN110055421A (en) * | 2019-04-28 | 2019-07-26 | 广东飞南资源利用股份有限公司 | A kind of preprocess method of high tin copper anode mud |
| CN111394582A (en) * | 2020-05-09 | 2020-07-10 | 广东飞南资源利用股份有限公司 | Copper-nickel sludge resource recycling process |
| CN111394582B (en) * | 2020-05-09 | 2022-02-01 | 广东飞南资源利用股份有限公司 | Copper-nickel sludge resource recycling process |
| CN114635038A (en) * | 2022-02-18 | 2022-06-17 | 永兴长隆环保科技有限公司 | Method for recovering and preparing refined tin from tin-containing waste residues |
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