CN102409175A - Method for treating purification copper-removing slag of nickel electrolysis anode solution - Google Patents
Method for treating purification copper-removing slag of nickel electrolysis anode solution Download PDFInfo
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Abstract
The invention discloses a method for treating the purification copper-removing slag of a nickel electrolysis anode solution. The method comprises the following steps: treating the copper-removing slag generated in the nickel thiocarbonate method copper-removing process with a copper-containing solution to leach nickel in the copper-removing slag, obtain copper-removing slag of which copper-nickel ratio is above 150 and convert the leachate to a nickel-containing solution, then using the nickel-containing solution to react with a thiocarbonate solution and prepare nickel thiocarbonate, and using the prepared nickel thiocarbonate to remove copper in the nickel electrolysis anode solution. In the copper-removing process, only copper in the nickel electrolysis anode solution is required to be removed completely without considering the copper-nickel ratio of the copper-removing slag. A lot of copper-removing agent is added to ensure that even the highest concentration of copper in the solution can be removed completely. Therefore, the copper concentration of the solution is not required to be accurately controlled before the copper-removing process and the operations are performed easily. Meanwhile, a lot of copper-removing agent is added and the copper-removing solution with extremely lower copper concentration can be obtained, compared with the copper-removing effect by adding a defined amount of the copper-removing agent. As whether nickel exceeds the standard is not considered, the copper-removing operation can be easily controlled.
Description
Technical field
The present invention relates to copper nickel hydrometallurgy field, particularly purify the technological method that removes separating copper nickel the copper ashes from nickle electrolysis anode solution.
Background technology
In China's electricity nickel standard (GB/T 6516-1997 Ni9996) foreign matter content is required very strictness, particularly the content requirement to impurity copper is lower than 0.01%.But, therefore want the degree of depth and remove the difficult problem that copper in the nickle electrolysis anode solution becomes the domestic and international metallurgical boundary of long-term puzzlement because copper nickel belongs to the quite similar element of chemical property.To this difficult problem, China classifies this research as key research projects twice in " eight or five " and the ninth five-year plan, and hope can be developed the new process for copper that removes.On the one hand copper content is reduced and satisfy production requirement, increase substantially on the other hand,, so just can reach the purpose of simplifying technical process and reducing cost so that copper ashes can directly get into the copper production system as copper ore concentrates except that copper nickel ratio in the copper ashes.Develop new copper removal technology key and be the synthetic new Tong Shiji that removes.Domestic scholars is attempted the whole bag of tricks, remove process for copper like active nickel sulfide, nickel thiosulfate, active sulphur powder etc., but the copper removal problem is not well solved still.
Thiocarbonic acid SOH nickel as a kind of be the decoppering agent that the basis obtains with the molecular designing, can remove the copper in the copper nickle electrolysis anode solution efficiently.When an amount of thiocarbonic acid SOH nickel and nickle electrolysis anode solution mix, can the copper concentration in the solution be reduced to below the 3mg/L, except that copper nickel ratio in the copper ashes is higher than 15, can satisfy the industrial production requirement.
Obtain above result, must guarantee that the add-on of thiocarbonic acid SOH nickel is suitable, can not be too much or very little.Because although excessive decoppering agent can the degree of depth be removed copper, can be very low except that copper nickel ratio in the copper ashes; And when the decoppering agent add-on was not enough, the copper in the solution then can not the degree of depth be removed.And to guarantee that key that thiocarbonic acid SOH nickel accurately adds is in the whole copper removal process that copper content and pH value of solution value all need maintain a comparatively maintenance level in the nickle electrolysis anode solution.But raw mineral materials complicacy and unstable in Industrial processes because in the nickel smelting process can cause the concentration of copper in the nickle electrolysis anode solution to produce fluctuation.Copper concentration is monitored so that in order accurately to add thiocarbonic acid SOH nickel in real time in just must be to nickle electrolysis anode solution when copper removal is operated.But in actual mechanical process, carry out monitoring in real time accurately, and then the add-on of accurately controlling thiocarbonic acid SOH nickel is a very thing of difficulty, is difficult to realize the copper concentration in a large amount of fluent solutions.
Because thiocarbonic acid SOH nickel is active high, speed of response is fast, can remove the copper in the solution fast.Therefore, in industrial production, adopt to add excess of sulfur, let it fast the copper degree of depth removed, guarantee that earlier the copper in the solution arrives production requirement for nickelous carbonate.Adopt such operating method, can break away from the restriction of the copper removal weak effect that causes because the thiocarbonic acid SOH nickel add-on that the copper concentration analysis is forbidden to cause is inaccurate.So just need not to copper in the solution before the copper removal carry out precise real-time monitoring, only need to add excessive thiocarbonic acid SOH nickel and guarantee the copper degree of depth in the solution removed and get final product.Because only need control, make the entire operation process become and be easy to operate and control to the copper removal degree of depth one end.
Because a large amount of adding of decoppering agent, make to remove and contain the intact thiocarbonic acid SOH nickel of part unreacted in the copper ashes that it is very high to cause removing in the copper ashes nickel content, does not reach copper nickel fully than the requirement that is higher than 15, need further focus on suitable subsequent disposal requirement.
Summary of the invention
Copper nickel has proposed to obtain the high method of removing copper ashes of copper nickel to further handling except that copper ashes to reduce nickel content than extremely low problem in the copper ashes to the objective of the invention is to remove removing that the excessive adding of decoppering agent causes in the process for copper to thiocarbonic acid SOH nickel.Obtain under the excessive adding condition of decoppering agent owing to remove copper ashes, therefore remove in the copper ashes and also contain the unreacted thiocarbonic acid SOH nickel of part.Because thiocarbonic acid SOH nickel is a kind of active very long compound of hold-time, so the activity of removing copper ashes that obtains is still very high, still can continue and copper bearing solution reaction.
A kind of method of handling the nickle electrolysis anode solution purification except that copper ashes: earlier copper-containing solution pH value being adjusted to 2.5～7.0, is that 0.7～1 adding is reacted except that copper ashes mixes by the mol ratio except that copper in nickel in the copper ashes and the copper-containing solution then; Describedly remove that copper nickel mass ratio is 0.5～15 in the copper ashes; Control reaction temperature is 20 ℃～90 ℃, and the reaction times is 5～120 minutes.
Negatively charged ion is SO in the described copper-containing solution
4 2-, Cl
-, NO
3 -In one or more mixture, the concentration of copper is not less than 0.5g/L.
The described copper ashes that removes is the copper ashes that removes that nickle electrolysis anode solution adopts the generation of thiocarbonic acid SOH nickel copper removal.Its staple comprises NiS, NiCS
3, NiCS
4, NiCS
5, NiC
2S
5, NiC
3S
7In one or more mixture, all the other are CuS, CuCS
3, CuCS
4, CuCS
5, CuC
2S
5, CuC
3S
7In one or more mixture.
It is following that described thiocarbonic acid SOH nickel and nickle electrolysis anode solution reaction copper removal produce the method for removing copper ashes:
PH value with nickle electrolysis anode solution is adjusted to 2.5～6.5 earlier; Add the reaction of excessive thiocarbonic acid SOH nickel and the copper in the solution, control reaction temperature is 25～90 ℃, and the reaction times is 5～120min; Reaction equation is following:
NiC
aS
2a+b+ Cu
2+=CuC
aS
2a+b+ Ni
2+(wherein a, b is the integer more than or equal to 1)
Preferably the mol ratio according to copper in thio-carbonate and the solution is 1.5～2.0 adding thiocarbonic acid SOH nickel hybrid reactions.
The processing nickle electrolysis anode solution purifies except that isolating solid phase after the copper ashes reaction and further handles.The solid phase of separating is the copper sulphur compound, directly carries out pyrometallurgical smelting as copper ore concentrates, perhaps prepares copper sulfate electrolyte through wet oxidation.Separate the solution containing nickel that solid phase obtains after reaction is accomplished, the solution containing nickel staple is NiSO
4, NiCl
2, Ni (NO
3)
2In one or more mixture; Regulator solution pH value to 3.0～7.0 obtain thiocarbonic acid SOH nickel with the thiocarbonate prepared in reaction then; Thiocarbonic acid SOH nickel that obtains and nickle electrolysis anode solution reaction carrying out copper removal; Separate the copper ashes that removes that obtains after copper-stripping reaction is accomplished, get into the next round circular treatment again.
The synthetic ultimate principle of thiocarbonate is:
With dissolvable sulfide and CS
2During mixing, following reaction takes place in the solution:
S
2-+CS
2＝CS
3 2-
Work as CS
3 2-Continue and CS
2During contact, following reaction can take place:
CS
3 2-+ (n-1) CS
2=C
nS
2n+1 2-(n is>=2 integer)
When the synthetic more high-sulfur of needs during for the decoppering agent of degree, following reaction capable of using:
CS
3 2-+ yS=CS
3+y 2-(y is>=1 integer)
C
nS
2n+1 2-+ mS=C
nS
M+2n+1 2-(m is>=1, and n is>=2 integer)
With solubility polysulfide and CS
2During mixing, following reaction takes place in the solution:
S
x 2-+ CS
2=CS
2+x 2-(x is>=2 integer)
Work as CS
2+x 2-Continue and CS
2During contact, following reaction can take place:
CS
2+x 2-+ (n-1) CS
2=C
nS
2n+x 2-(n is>=2, and x is>=2 integer)
The synthetic of thiocarbonic acid SOH nickel undertaken by following mode:
In the thio-carbonate solution that any one mode of (1)-(6) prepares below adopting one or more continue and the synthetic thiocarbonic acid SOH nickel of solution containing nickel reaction again;
(1) with dissolvable sulfide solution and CS
2Fully reacted 5～24 hours by stoichiometry, obtaining negatively charged ion is CS
3 2-Thio-carbonate solution;
(2) solution that mode (1) is obtained continues and CS
2Reacted 5～24 hours, obtaining negatively charged ion after the reaction is C
nS
2n+1 2-With CS
3 2-Mixture, perhaps C
nS
2n+1 2-Thio-carbonate solution, wherein n is>=2 integer;
(3) solution that mode (1) is obtained continues and sulphur thorough mixing stirring reaction 10～24 hours, and obtaining negatively charged ion after the reaction is CS
3+y 2-With CS
3 2-Mixture, perhaps CS
3+y 2-Thio-carbonate solution, wherein y is>=1 integer;
(4) only contain C with what mode (2) obtained
nS
2n+1 2-Solution continue and sulphur thorough mixing stirring reaction 10～24 hours, obtaining negatively charged ion after reacting completely is C
nS
M+2n+1 2-Thio-carbonate solution, wherein m is>=1, n is>=2 integer;
(5) with solubility polysulfide solution and CS
2Fully reacted 5～24 hours by stoichiometry, obtaining negatively charged ion is CS
2+x 2-Thio-carbonate solution, wherein x is>=2 integer;
(6) solution that mode (5) is obtained continues and CS
2Reacted 5～24 hours, obtaining negatively charged ion after reacting completely is C
nS
2n+x 2-Thio-carbonate solution, n wherein, x is>=2 integer;
Described dissolvable sulfide comprises sulfide Na
2S, K
2Among the S one or both, the solubility polysulfide comprises Na
2S
x, K
2S
xIn one or both, x is>=2 integer.
Through obtaining thio-carbonate solution so that upper type is synthetic, its negatively charged ion can use general formula to be C
aS
2a+b 2-The form of (wherein a, b is the integer more than or equal to 1) is represented.
The synthetic thio-carbonate solution is synthesizing thiocarbonic acid SOH nickel through following method:
Reactional equation is following:
C
aS
2a+b 2-+ Ni
2+=NiC
aS
2a+b(wherein a, b is the integer more than or equal to 1)
Compound method is: the pH value with solution containing nickel is adjusted to 3.0～7.0 earlier; Mol ratio by nickel in thio-carbonate and the solution is that 0.5～1.0 adding thio-carbonate solution reaction generates thiocarbonic acid SOH nickel deposition then, and continues stirring reaction 10～30 minutes.
Described solution containing nickel is NiSO
4, NiCl
2, Ni (NO
3)
2The mixture of one or more in the solution also can be a nickle electrolysis anode solution.
Through above step, the final synthetic thiocarbonic acid SOH nickel that obtains.
Technical superiority of the present invention:
Advantage of the present invention is mainly reflected in:
(1) the copper removal process is easy to control and operation: adopt method of the present invention, in the copper removal process, only need accomplish the copper degree of depth in the nickle electrolysis anode solution removed and get final product, need not take into account except that the copper nickel in the copper ashes and compare so as to see who is superior.Also can the degree of depth remove when decoppering agent guarantees to occur in the solution copper of maximum concentration even only need add.So just needn't make precise monitoring constantly to copper concentration in the liquid before the copper removal, operation is easy to carry out.Simultaneously because a large amount of decoppering agents that add, compare and add fashionable copper removal effect in right amount, can obtain liquid behind the copper removal of copper concentration extremely low (less than 2mg/L) on the contrary.Need not consider can exceed standard except that nickel in the copper ashes, the copper removal operation becomes and is easy to control.
(2) can reach high copper nickel ratio except that after the copper ashes simple process; More help sending the copper metallurgy: though the copper nickel that removes copper ashes that under the excessive decoppering agent condition of adding, produces is lower than very; But after the further processing of the present invention, can bring up to more than 150, be transformed into the compound of copper basically except that copper nickel ratio in the copper ashes; Only need through simple press filtration, even need not wash and also can satisfy subsequent disposal and get copper nickel ratio and require.
(3) the main nickeliferous and little copper of solution after handling fully can directly be used to prepare decoppering agent thiocarbonic acid SOH nickel again.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
In the nickel smelting process, copper nickel mixing vulcanised ore concentrate obtains high nickel matte through the flash stove with after bessemerizing, and wearable is floating after the slow cooling separates the nickel sulfide concentrate that obtains, and then becomes nickelous sulfide electrolytic anode piece through the reverberatory furnace founding; Nickelous sulfide electrolytic anode piece produces thick nickel sulfate solution through electrolytic dissolution in acidic solution.Contain other impurity such as a certain amount of iron, copper, cobalt in the thick nickel sulfate solution, need just can enter into electrolysis production electrolytic nickel step behind the further purification and impurity removal.
At first thick nickel sulfate solution is through oxidation neutralizing hydrolysis deironing; Can together remove the copper of part in the solution during deironing; Need iron in the nickel sulfate solution after the deironing and copper content be controlled to certain level through the control deferrization process in the actual industrial production, deferrization process control quality is directly connected to the content of copper in the nickel sulfate electrolyte.Nickel sulfate solution after the deironing is the sulfuric acid nickle electrolysis anode solution described in the present invention, and copper does not exceed standard in the electrolytic nickel product in order to make, and we need remove through the copper degree of depth that adds in the further solution of decoppering agent.
For example, when we carried out copper removal research with the sulfuric acid nickle electrolysis anode solution that produces on certain factory industry production line, the copper concentration in its solution kept in 0.3～1.0g/L scope.Adition process according to decoppering agent is easy to control principle, and we need only the peak according to fluctuation range in the copper removal process again, add excessive thiocarbonic acid SOH nickel and get final product.After reacting completely, the copper in the solution reaches requirement fully, and this handles by method of the present invention and remove copper ashes.
Embodiment 1
PH value with nickle electrolysis anode solution is adjusted to 4 earlier; Add the reaction of excessive thiocarbonic acid SOH nickel and the copper in the solution, control reaction temperature is 90 ℃, and the reaction times is 60min, obtains removing copper ashes.To join 84 liters of pH be 5.0 than the copper ashes that removes that is 0.5 with 10Kg copper nickel, and copper concentration is the CuSO of 80g/L
4In the solution, remove in the copper ashes that the mol ratio of copper is 0.7 in the nickel and copper-containing solution, control reaction temperature is 25 ℃, react after 120 minutes, separation obtain copper nickel than be 151 except that copper ashes, and nickel concentration is 52.7g/L, copper concentration is the NiSO of 0.33g/L
4Solution.Then with the Na of 5.8Kg
2S is dissolved in earlier in the 70L water, adds the CS of 4.7L again
2Solution after reaction is carried out 10 hours, obtains the Na of 74mol
2CS
3Solution.Again with NiSO
4Solution reaction prepares thiocarbonic acid SOH nickel; Last with contain 70mol copper, pH is that 5.0 nickle electrolysis anode solution carries out copper removal 60 ℃ of reactions, copper concentration is 1.2mg/L behind the copper removal, removes that copper nickel ratio is 1.2 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 2
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 1 be 7.0 except that copper ashes joins 80 liters of pH, copper concentration is the CuSO that contains of 60g/L
4And Cu
2SO
4Mixing solutions in, remove in the copper ashes that the mol ratio of copper is 0.8 in the nickel and copper-containing solution, control reaction temperature is 50 ℃, react after 80 minutes, separation obtain copper nickel than be 200 except that copper ashes, and nickel concentration is 34.6g/L, copper concentration is the NiSO of 0.002g/L
4Solution.Then with the Na of 3.58Kg
2S is dissolved in earlier in the 50L water, adds the CS of 5.55L again
2Solution after reaction is carried out 10 hours, obtains the Na of 46mol
2C
2S
5Solution.Again with NiSO
4Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 43mol copper, pH is that 4.2 nickle electrolysis anode solution carries out copper removal 20 ℃ of reactions, copper concentration is 1.1mg/L behind the copper removal, removes that copper nickel ratio is 2.2 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 3
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 1.5 be 2.5 except that copper ashes joins 54 liters of pH, copper concentration is the CuCl of 52g/L
2In the solution, remove in the copper ashes that the mol ratio of copper is 1.0 in the nickel and copper-containing solution, control reaction temperature is 90 ℃, react after 60 minutes, separation obtain copper nickel than be 178 except that copper ashes, and nickel concentration is 36.9g/L, copper concentration is the NiCl of 0.67g/L
2Solution.Then with the K of 3.63Kg
2S is dissolved in earlier in the 50L water, adds the CS of 3.98L again
2Solution after reaction is carried out 20 hours, obtains the K of 33mol
2C
2S
5Solution.Again with NiCl
2Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 32mol copper, pH is that 6.0 nickle electrolysis anode solution carries out copper removal 90 ℃ of reactions, copper concentration is 0.98mg/L behind the copper removal, removes that copper nickel ratio is 1.6 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 4
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 2 be 3.5 except that copper ashes joins 41 liters of pH, copper concentration is the Cu (NO of 48g/L
3)
2In the solution, remove in the copper ashes that the mol ratio of copper is 0.85 in the nickel and copper-containing solution, control reaction temperature is 75 ℃, react after 45 minutes, separation obtain copper nickel than be 186 except that copper ashes, and nickel concentration is 37g/L, copper concentration is the Ni (NO of 1.1g/L
3)
2Solution.Then with the Na of 1.95Kg
2S is dissolved in earlier in the 20L water, adds the CS of 3.02L again
2Solution after reaction is carried out 10 hours, obtains the Na of 25mol
2C
2S
5Solution.Again with Ni (NO
3)
2Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 24mol copper, pH is that 4.3 nickle electrolysis anode solution carries out copper removal 70 ℃ of reactions, copper concentration is 1.3mg/L behind the copper removal, removes that copper nickel ratio is 5 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 5
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 3 be 2.5 except that copper ashes joins 42 liters of pH, copper concentration is the CuSO of 35g/L
4In the solution, remove in the copper ashes that the mol ratio of copper is 0.75 in the nickel and copper-containing solution, control reaction temperature is 90 ℃, react after 60 minutes, separation obtain copper nickel than be 164 except that copper ashes, and nickel concentration is 29g/L, copper concentration is the NiSO of 0.04g/L
4Solution.Then with the Na of 1.56Kg
2S is dissolved in earlier in the 20L water, adds the CS of 1.21L again
2Solution after reaction is carried out 20 hours, obtains the Na of 20mol
2CS
3Solution.Again with NiSO
4Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 18mol copper, pH is that 5.5 nickle electrolysis anode solution carries out copper removal 75 ℃ of reactions, copper concentration is 1.2mg/L behind the copper removal, removes that copper nickel ratio is 2.4 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 6
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 5 be 2.5 except that copper ashes joins 59 liters of pH, copper concentration is the CuCl of 22g/L
2In the solution, remove in the copper ashes that the mol ratio of copper is 0.7 in the nickel and copper-containing solution, control reaction temperature is 60 ℃, react after 50 minutes, separation obtain copper nickel than be 203 except that copper ashes, and nickel concentration is 17g/L, copper concentration is the NiCl of 0.16g/L
2Solution.Then with the Na of 1.33Kg
2S is dissolved in earlier in the 20L water, adds the CS of 2.05L again
2Solution after reaction is carried out 15 hours, again with 0.6Kg sulfur reaction 10 hours, obtains the Na of 17mol
2C
2S
6Solution.Again with NiCl
2Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 16.5mol copper, pH is that 6.0 nickle electrolysis anode solution carries out copper removal 90 ℃ of reactions, copper concentration is 1.6mg/L behind the copper removal, removes that copper nickel ratio is 15 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 7
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 2.5 be 3.5 except that copper ashes joins 107 liters of pH, copper concentration is the CuCl that contains of 31g/L
2In the mixing solutions of CuCl, remove in the copper ashes that the mol ratio of copper is 0.83 in the nickel and copper-containing solution, control reaction temperature is 80 ℃; React after 30 minutes; Separate obtain copper nickel than be 176 except that copper ashes, and nickel concentration is 16.8g/L, copper concentration is the NiCl of 0.023g/L
2Solution.Then with the Na of 2.34Kg
2S is dissolved in earlier in the 30L water, adds the CS of 1.81L again
2Solution after reaction is carried out 20 hours, again with 2.0Kg sulfur reaction 20 hours, obtains the Na of 30mol
2CS
5Solution.Again with NiCl
2Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 29mol copper, pH is that 5.0 nickle electrolysis anode solution carries out copper removal 60 ℃ of reactions, copper concentration is 1.0mg/L behind the copper removal, removes that copper nickel ratio is 5 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 8
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 7 be 3.5 except that copper ashes joins 71 liters of pH, copper concentration is the CuSO of 15g/L
4In the solution, remove in the copper ashes that the mol ratio of copper is 0.93 in the nickel and copper-containing solution, control reaction temperature is 75 ℃, react after 55 minutes, separation obtain copper nickel than be 162 except that copper ashes, and nickel concentration is 9.9g/L, copper concentration is the NiSO of 0.42g/L
4Solution.Then with the K of 1.21Kg
2S is dissolved in earlier in the 15L water, adds the CS of 0.7L again
2Solution after reaction is carried out 10 hours, obtains the K of 11mol
2CS
3Solution.Again with NiSO
4Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 10mol copper, pH is that 5.5 nickle electrolysis anode solution carries out copper removal 62 ℃ of reactions, copper concentration is 1.4mg/L behind the copper removal, removes that copper nickel ratio is 3.2 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 9
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 9 be 3.6 except that copper ashes joins 99 liters of pH, copper concentration is the CuSO of 5g/L
4In the solution, remove in the copper ashes that the mol ratio of copper is 0.88 in the nickel and copper-containing solution, control reaction temperature is 70 ℃, react after 75 minutes, separation obtain copper nickel than be 177 except that copper ashes, and nickel concentration is 3.8g/L, copper concentration is the NiSO of 0.001g/L
4Solution.Then with the K of 0.66Kg
2S is dissolved in earlier in the 5L water, adds the CS of 0.75L again
2Solution after reaction is carried out 10 hours, obtains the K of 6mol
2C
2S
5Solution.Again with NiSO
4Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 5.5mol copper, pH is that 5.5 nickle electrolysis anode solution carries out copper removal 65 ℃ of reactions, copper concentration is 1.2mg/L behind the copper removal, removes that copper nickel ratio is 2.2 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Embodiment 10
Remove copper ashes and produce with embodiment 1, with 10Kg copper nickel than be 15 be 3.8 except that copper ashes joins 841 liters of pH, copper concentration is the CuSO of 0.5g/L
4In the solution, remove in the copper ashes that the mol ratio of copper is 0.76 in the nickel and copper-containing solution, control reaction temperature is 66 ℃, react after 65 minutes, separation obtain copper nickel than be 182 except that copper ashes, and nickel concentration is the NiSO of 0.5g/L
4, copper concentration is the NiSO of 0.0022g/L
4Solution.Then with the Na of 0.51Kg
2S is dissolved in earlier in the 5L water, adds the CS of 0.81L again
2Solution after reaction is carried out 15 hours, obtains the Na of 6.5mol
2C
2S
5Solution.Again with NiSO
4Solution reaction prepares thiocarbonic acid SOH nickel; Then with contain 6mol copper, pH is that 5.2 nickle electrolysis anode solution carries out copper removal 65 ℃ of reactions, copper concentration is 1.5mg/L behind the copper removal, removes that copper nickel ratio is 6 in the copper ashes; To continue to fall nickel except that copper ashes with the copper-containing solution processing.
Claims (8)
1. handle the method that the nickle electrolysis anode solution purification removes copper ashes for one kind, it is characterized in that: earlier copper-containing solution pH value being adjusted to 2.5～7.0, is that 0.7～1 adding is reacted except that copper ashes mixes by the mol ratio except that copper in nickel in the copper ashes and the copper-containing solution then; Describedly remove that copper nickel mass ratio is 0.5～15 in the copper ashes; Control reaction temperature is 20 ℃～90 ℃, and the reaction times is 5～120 minutes.
2. method according to claim 1 is characterized in that: negatively charged ion is SO in the described copper-containing solution
4 2-, Cl
-, NO
3 -In one or more mixture, the concentration of copper is not less than 0.5g/L.
3. method according to claim 1 is characterized in that: the described copper ashes that removes is the copper ashes that removes that nickle electrolysis anode solution adopts the generation of thiocarbonic acid SOH nickel copper removal.
4. method according to claim 3 is characterized in that: it is following that described thiocarbonic acid SOH nickel and nickle electrolysis anode solution reaction copper removal produce the method for removing copper ashes:
PH value with nickle electrolysis anode solution is adjusted to 2.5～6.5 earlier; Add the reaction of excessive thiocarbonic acid SOH nickel and the copper in the solution again, control reaction temperature is 25～90 ℃, and the reaction times is 5～120min.
5. method according to claim 4 is characterized in that: the mol ratio according to copper in thio-carbonate and the solution is 1.5～2.0 adding thiocarbonic acid SOH nickel hybrid reactions.
6. method according to claim 1 is characterized in that: isolate solid phase after the reaction and further handle.
7. method according to claim 6 is characterized in that: the solid phase of separating is the copper sulphur compound, directly carries out pyrometallurgical smelting as copper ore concentrates, perhaps prepares copper sulfate electrolyte through wet oxidation.
8. according to claim 1 or 6 or 7 described methods, it is characterized in that: separate the solution containing nickel that solid phase obtains after reaction is accomplished, regulator solution pH value to 3.0～7.0 obtain thiocarbonic acid SOH nickel with the thiocarbonate prepared in reaction then.
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| CN102864307A (en) * | 2012-09-20 | 2013-01-09 | 中南大学 | Deep decoppering method by nickel thiocarbonate/nickel-containing solution two-section reflux reaction |
| CN104962738A (en) * | 2015-07-17 | 2015-10-07 | 中南大学 | Copper electrolyte purifying technology |
| CN105803203A (en) * | 2014-12-30 | 2016-07-27 | 北京有色金属研究总院 | Method for multicycle selective leaching of copper, zinc and nickel from sludge in waste water produced by copper smelting |
| CN106834740A (en) * | 2016-12-30 | 2017-06-13 | 四川师范大学 | The method for decoppering of nickel solution |
| CN109797410A (en) * | 2019-03-20 | 2019-05-24 | 金川集团股份有限公司 | A kind of two sections of impurity removal process of nickel sulfide soluble anode nickel electrowinning purification |
| CN113061724A (en) * | 2021-03-09 | 2021-07-02 | 金川集团股份有限公司 | Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings |
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| CN109797410A (en) * | 2019-03-20 | 2019-05-24 | 金川集团股份有限公司 | A kind of two sections of impurity removal process of nickel sulfide soluble anode nickel electrowinning purification |
| CN113061724A (en) * | 2021-03-09 | 2021-07-02 | 金川集团股份有限公司 | Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings |
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