CN103498051B - Method for recovering copper and nickel from nickel-iron-copper alloy waste - Google Patents
Method for recovering copper and nickel from nickel-iron-copper alloy waste Download PDFInfo
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- CN103498051B CN103498051B CN201310455464.7A CN201310455464A CN103498051B CN 103498051 B CN103498051 B CN 103498051B CN 201310455464 A CN201310455464 A CN 201310455464A CN 103498051 B CN103498051 B CN 103498051B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000010949 copper Substances 0.000 title claims abstract description 81
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title abstract description 10
- GOECOOJIPSGIIV-UHFFFAOYSA-N copper iron nickel Chemical compound [Fe].[Ni].[Cu] GOECOOJIPSGIIV-UHFFFAOYSA-N 0.000 title abstract 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000010935 stainless steel Substances 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 39
- 239000008151 electrolyte solution Substances 0.000 claims description 32
- 238000005868 electrolysis reaction Methods 0.000 claims description 26
- 230000008021 deposition Effects 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 5
- 239000013589 supplement Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052935 jarosite Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- -1 bath voltage be 1.6V Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- 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
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- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for recovering copper and nickel from nickel-iron-copper alloy waste, belonging to the technical field of resource comprehensive utilization. The method comprises the following steps: oxidation for iron removal: heating the nickel-iron-copper alloy waste to obtain molten-state nickel-iron-copper alloy waste, then adding a slag former, and spraying oxidation gas to obtain molten metal and slag; first-stage electrolytic refining to recover copper: casting the obtained molten metal into a soluble anode, and then electrolyzing by taking a soluble anode plate as an anode, a stainless steel plate as a cathode and copper sulfate as electrolyte to obtain copper on the cathode; second-stage electrolytic refining to recover nickel: heating the electrolyte after the electrolytic refining to remove iron and copper and then feeding into a nickel electrolytic tank as the electrolyte for recovering nickel, and electrolyzing by taking an insoluble titanium plate as an anode and a stainless steel plate as a cathode to obtain nickel on the cathode. According to the method provided by the invention, the three processes of alloy structure damage, anode plate casting and oxidation for iron removal are coupled together, so that the energy saving effect of the process is remarkable.
Description
Technical field
The present invention relates to a kind of method reclaiming copper, nickel from ferronickel copper alloy scrap, belong to technical field of resource comprehensive utilization.
Background technology
China's nickel supply is made up of two parts, and a part newly produces nickel ore concentrate supply, and this part accounts for 72.9% of nickel aggregate supply, and another part accounts for 27.1% from regeneration nickel, and along with the development of economic construction and Iron And Steel Industry, the demand of nickel constantly increases.Within 2010, estimate that Chinese nickel consumption reaches after 400,000 tons/year, China becomes nickel country of consumption the biggest in the world.Within 2010, Chinese nickel metal foundation reserves only have about 2,300,000 tons, over 2010 ~ 2013 years, Chinese nickel minerals exploration does not have major progress, if just according to consuming like this, after 10 years, the nickel ore resource of China incites somebody to action approach exhaustion gradually, and copper resource situation is similar with it.Alleviate the resource pressure of China's copper, nickel resources, the utilising efficiency to secondary resource need be strengthened.
Corronel waste material material is increasing year by year simultaneously, the alloy components damaged in the waste material produced in the waste material produced when mainly comprising mechanical workout, smelting process, industrial sector and part etc.In addition, the nickel-copper alloy waste material major part that domestic market circulates is bought on ground from Taiwan of Japan, Korea S and China etc., it is the waste material of electronic component factory output, its chemical composition, based on nickel, copper, strengthens there is comparatively positive effect to alleviation China nickel, copper resource pressure undoubtedly to this recycling.But the Land use systems at present about this alloyed scrap is add as alloying element additive in the rear alloy manufacture craft of classification, and utilization ratio is on the low side and economy performance is poor.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the present invention uses for reference the thought of Complicated Copper raw material electrorefining, a kind of method reclaiming copper, nickel from ferronickel copper alloy scrap is provided, remelting iron removal by oxidation-two sections of electrolytic refining processes are adopted to reclaim the method for wherein nickel, copper, ferronickel copper alloy structure is broken in remelting mode, and reclaims wherein copper, iron in the mode of segmentation electrolysis control cell dimension and low bath voltage.Alloy structure effectively destroys by the present invention, positive plate is cast and iron removal by oxidation three technique is coupled as one, energy saving technology Be very effective, and reclaim wherein copper, iron by segmentation electrolysis mode, waste resource overall availability is high, commercial introduction application prospect is good, and the present invention is achieved through the following technical solutions.
From ferronickel copper alloy scrap, reclaim a method for copper, nickel, its concrete steps are as follows:
(1) iron removal by oxidation: first ferronickel copper alloy scrap is warming up to 1500 ~ 1650 DEG C and obtains molten state ferronickel copper alloy scrap, then in molten state ferronickel copper alloy scrap, add slag former and spray into oxidizing gas, after keeping this thermotonus 10 ~ 120min, obtaining molten metal and slag;
(2) one sections of electrorefinings reclaim copper: the molten metal that step (1) obtains is cast into soluble anode, then be anode by this soluble anode plate, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, bath voltage be 1.6 ~ 3.0V, electrolyte temperature is 45 ~ 60 DEG C, with the copper electrolysis cells of interpole gap 60 ~ 95mm in carry out electrolysis, and at this electrolytic process intermittent iron supplement Cu
2+, make electrolytic solution Cu
2+ionic concn maintains 20 ~ 80g/L, can prepare copper after cathode deposition period terminates on negative electrode;
(3) second segment electrorefining reclaims nickel: will deliver to electrolytic nickel cell as the electrolytic solution reclaiming nickel after the electrolytic solution intensification deironing and copper removal of step (2) electrorefining, with insoluble titanium plate for anode, stainless steel plate is negative electrode, bath voltage be 2.4 ~ 2.8V, electrolyte temperature is 40 ~ 65 DEG C, be the electrolytic nickel cell of 80 ~ 100mm with interpole gap in carry out electrolysis, nickel can be prepared on negative electrode after cathode deposition period terminates.
Described ferronickel copper alloy scrap comprises the component of following mass percent: Fe0.5 ~ 20%, Cu60 ~ 80%, Ni3 ~ 20%.
Described slag former is SiO
2, one or both arbitrary proportion mixtures in blast furnace slag, add-on is 0.5 ~ 2.5 times of weight of iron in ferronickel copper alloy.
Described oxidizing gas is air, oxygen-rich air or oxygen, and spraying into pressure is 0.01 ~ 0.8MPa.
In described step (2), cupric electrolysis groove width and high size are respectively 1.0 ~ 3.0 times of the wide and long size of soluble anode.
The Cu added in described step (2)
2+for CuSO
4, CuCl
2in one or both arbitrary proportion mixtures.
The cathode deposition period of described one section of electrorefining, second segment electrorefining is 7 ~ 10 days.
In above-mentioned steps (3), the process of electrolytic solution intensification deironing is:
First regulate electrolytic solution PH to about 1.5 with sodium carbonate, temperature rises to 90 ~ 95 DEG C, with carbon compositing catalyst, blasts atmospheric oxidation, reaction 3h, generates sodium jarosite filtration and realizes preliminary deironing; And then regulate PH to about 2.0, with hydrogen peroxide by Fe with sodium carbonate
2+be oxidized to Fe
3+, after then generating sodium jarosite filtration, deironing rate is to more than 99%.
In above-mentioned steps (3), the process of electrolytic solution copper removal is:
Technique adopts sulfurization-precipitation method copper removal, controls to start between pH value 2.0 ~ 3.0 in process, between terminal pH value 3.5 ~ 4.0, makes copper sulfuration generate precipitation and remove.
Above-mentioned same interpole gap is anode and anode, distance between negative electrode and negative electrode.
The invention has the beneficial effects as follows: alloy structure destroys by (1), positive plate is cast and iron removal by oxidation three technique is coupled as one, energy saving technology Be very effective; (2) reclaim copper, nickel in alloyed scrap by segmentation electrolysis mode, reclaiming product is electrolytic copper and electrolytic nickel, and added value of product is high; (3) method universality is strong, laterally can extend to the process of other similar structures alloyed scraps; (4) technological process is simple to operate, and production cost is low.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
As shown in Figure 1, should reclaim the method for copper, nickel from ferronickel copper alloy scrap, its concrete steps are as follows:
(1) iron removal by oxidation: first ferronickel copper alloy scrap is warming up to 1500 DEG C and obtains molten state ferronickel copper alloy scrap, then in molten state ferronickel copper alloy scrap, add slag former and spray into oxidizing gas, molten metal and slag is obtained after keeping this thermotonus 10min, ferronickel copper alloy scrap comprises the component of following mass percent: Fe0.5%, Cu80%, Ni19.5%; Slag former is SiO
2, add-on is 0.5 times of weight of iron in ferronickel copper alloy; Oxidizing gas is air, and spraying into pressure is 0.01MPa;
(2) one sections of electrorefinings reclaim copper: the molten metal that step (1) obtains is cast into soluble anode, then be anode by this soluble anode plate, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, bath voltage be 1.6V, electrolyte temperature is 45 DEG C, with the copper electrolysis cells of interpole gap 60mm in carry out electrolysis, and at this electrolytic process intermittent iron supplement Cu
2+, make electrolytic solution Cu
2+ionic concn maintains 20g/L, and can prepare copper on negative electrode after cathode deposition period terminates, wherein soluble anode is of a size of 670 × 870 × 10mm, and cupric electrolysis groove width and high size are respectively 1.0 times of the wide and long size of soluble anode; The Cu added
2+for CuSO
4; Cathode deposition period is 7 days;
(3) second segment electrorefining reclaims nickel: will deliver to electrolytic nickel cell as the electrolytic solution reclaiming nickel after the electrolytic solution intensification deironing and copper removal of step (2) electrorefining, with insoluble titanium plate for anode, stainless steel plate is negative electrode, bath voltage be 2.4V, electrolyte temperature is 40 DEG C, be the electrolytic nickel cell of 80mm with interpole gap in carry out electrolysis, can prepare nickel on negative electrode after cathode deposition period terminates, wherein cathode deposition period is 7 days.
In above-mentioned steps (3), the process of electrolytic solution intensification deironing is:
First regulate electrolytic solution PH to about 1.5 with sodium carbonate, temperature rises to 90 DEG C, with carbon compositing catalyst, blasts atmospheric oxidation, reaction 3h, generates sodium jarosite filtration and realizes preliminary deironing; And then regulate PH to about 2.0, with hydrogen peroxide by Fe with sodium carbonate
2+be oxidized to Fe
3+, generate sodium jarosite and filter rear deironing rate to more than 99%.
In above-mentioned steps (3), the process of electrolytic solution copper removal is:
Technique adopts sulfurization-precipitation method copper removal, controls to start pH value 2.0, terminal pH value 3.5 in process, makes copper sulfuration generate precipitation and remove.
The copper that this electrolysis obtains, nickel detect by analysis, and copper purity is 99.91%, and nickel purity is 99.993%.
Embodiment 2
As shown in Figure 1, should reclaim the method for copper, nickel from ferronickel copper alloy scrap, its concrete steps are as follows:
(1) iron removal by oxidation: first ferronickel copper alloy scrap is warming up to 1650 DEG C and obtains molten state ferronickel copper alloy scrap, then in molten state ferronickel copper alloy scrap, add slag former and spray into oxidizing gas, molten metal and slag is obtained after keeping this thermotonus 120min, wherein ferronickel copper alloy scrap comprises the component of following mass percent: Fe20%, Cu60%, Ni20%; Slag former is the SiO of quality 1:1
2with blast furnace slag mixture, add-on is 2.5 times of weight of iron in ferronickel copper alloy; Oxidizing gas is oxygen-rich air, and spraying into pressure is 0.8MPa;
(2) one sections of electrorefinings reclaim copper: the molten metal that step (1) obtains is cast into soluble anode, then be anode by this soluble anode plate, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, bath voltage be 3.0V, electrolyte temperature is 60 DEG C, with the copper electrolysis cells of interpole gap 95mm in carry out electrolysis, and at this electrolytic process intermittent iron supplement Cu
2+, make electrolytic solution Cu
2+ionic concn maintains 80g/L, and can prepare copper on negative electrode after cathode deposition period terminates, wherein soluble anode is of a size of 700 × 900 × 10mm, and cupric electrolysis groove width and high size are respectively 3.0 times of the wide and long size of soluble anode; The Cu added
2+for the CuSO of quality 1:1
4and CuCl
2mixture; Cathode deposition period is 10 days;
(3) second segment electrorefining reclaims nickel: will deliver to electrolytic nickel cell as the electrolytic solution reclaiming nickel after the electrolytic solution intensification deironing and copper removal of step (2) electrorefining, with insoluble titanium plate for anode, stainless steel plate is negative electrode, bath voltage be 2.8V, electrolyte temperature is 65 DEG C, be the electrolytic nickel cell of 100mm with interpole gap in carry out electrolysis, can prepare nickel on negative electrode after cathode deposition period terminates, cathode deposition period is 10 days.
In above-mentioned steps (3), the process of electrolytic solution intensification deironing is:
First regulate electrolytic solution PH to about 1.5 with sodium carbonate, temperature rises to 95 DEG C, with carbon compositing catalyst, blasts atmospheric oxidation, reaction 3h, generates sodium jarosite filtration and realizes preliminary deironing; And then regulate PH to about 2.0, with hydrogen peroxide by Fe with sodium carbonate
2+be oxidized to Fe
3+, generate sodium jarosite and filter rear deironing rate to more than 99%.
In above-mentioned steps (3), the process of electrolytic solution copper removal is:
Technique adopts sulfurization-precipitation method copper removal, controls to start pH value 3.0, terminal pH value 4.0 in process, makes copper sulfuration generate precipitation and remove.
The copper that this electrolysis obtains, nickel detect by analysis, and copper purity is 99.95%, and nickel purity is 99.998%.
Embodiment 3
As shown in Figure 1, should reclaim the method for copper, nickel from ferronickel copper alloy scrap, its concrete steps are as follows:
(1) iron removal by oxidation: first ferronickel copper alloy scrap is warming up to 1600 DEG C and obtains molten state ferronickel copper alloy scrap, then in molten state ferronickel copper alloy scrap, add slag former and spray into oxidizing gas, molten metal and slag is obtained after keeping this thermotonus 80min, wherein ferronickel copper alloy scrap comprises the component of following mass percent: Fe19%, Cu78%, Ni3%; Described slag former is blast furnace slag, and add-on is 1.5 times of weight of iron in ferronickel copper alloy; Described oxidizing gas is oxygen, and spraying into pressure is 0.5MPa;
(2) one sections of electrorefinings reclaim copper: the molten metal that step (1) obtains is cast into soluble anode, then be anode by this soluble anode plate, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, bath voltage be 2.4V, electrolyte temperature is 50 DEG C, with the copper electrolysis cells of interpole gap 85mm in carry out electrolysis, and at this electrolytic process intermittent iron supplement Cu
2+, make electrolytic solution Cu
2+ionic concn maintains 60g/L, can prepare copper after cathode deposition period terminates on negative electrode, and wherein soluble anode is 720 × 900 × 10mm, and cupric electrolysis groove width and high size are respectively 2.0 times of the wide and long size of soluble anode; The Cu added
2+for CuCl
2; Cathode deposition period is 9 days;
(3) second segment electrorefining reclaims nickel: will deliver to electrolytic nickel cell as the electrolytic solution reclaiming nickel after the electrolytic solution intensification deironing and copper removal of step (2) electrorefining, with insoluble titanium plate for anode, stainless steel plate is negative electrode, bath voltage be 2.6V, electrolyte temperature is 55 DEG C, be the electrolytic nickel cell of 90mm with interpole gap in carry out electrolysis, can prepare nickel on negative electrode after cathode deposition period terminates, cathode deposition period is 9 days.
In above-mentioned steps (3), the process of electrolytic solution intensification deironing is:
First regulate electrolytic solution PH to about 1.5 with sodium carbonate, temperature rises to 93 DEG C, with carbon compositing catalyst, blasts atmospheric oxidation, reaction 3h, generates sodium jarosite filtration and realizes preliminary deironing; And then regulate PH to about 2.0, with hydrogen peroxide by Fe with sodium carbonate
2+be oxidized to Fe
3+, generate sodium jarosite and filter rear deironing rate to more than 99%.
In above-mentioned steps (3), the process of electrolytic solution copper removal is:
Technique adopts sulfurization-precipitation method copper removal, controls to start pH value 2.5, terminal pH value 3.8 in process, makes copper sulfuration generate precipitation and remove.
The copper that this electrolysis obtains, nickel detect by analysis, and copper purity is 99.93%, and nickel purity is 99.997%.
Claims (6)
1. from ferronickel copper alloy scrap, reclaim a method for copper, nickel, it is characterized in that concrete steps are as follows:
(1) iron removal by oxidation: first ferronickel copper alloy scrap is warming up to 1500 ~ 1650 DEG C and obtains molten state ferronickel copper alloy scrap, then in molten state ferronickel copper alloy scrap, add slag former and spray into oxidizing gas, after keeping this thermotonus 10 ~ 120min, obtaining molten metal and slag; Described slag former is SiO
2, one or both arbitrary proportion mixtures in blast furnace slag, add-on is 0.5 ~ 2.5 times of weight of iron in ferronickel copper alloy;
(2) one sections of electrorefinings reclaim copper: the molten metal that step (1) obtains is cast into soluble anode, then be anode by this soluble anode plate, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, bath voltage be 1.6 ~ 3.0V, electrolyte temperature is 45 ~ 60 DEG C, with the copper electrolysis cells of interpole gap 60 ~ 95mm in carry out electrolysis, and at this electrolytic process intermittent iron supplement Cu
2+, make electrolytic solution Cu
2+ionic concn maintains 20 ~ 80g/L, can prepare copper after cathode deposition period terminates on negative electrode;
(3) second segment electrorefining reclaims nickel: will deliver to electrolytic nickel cell as the electrolytic solution reclaiming nickel after the electrolytic solution intensification deironing and copper removal of step (2) electrorefining, with insoluble titanium plate for anode, stainless steel plate is negative electrode, bath voltage be 2.4 ~ 2.8V, electrolyte temperature is 40 ~ 65 DEG C, be the electrolytic nickel cell of 80 ~ 100mm with interpole gap in carry out electrolysis, nickel can be prepared on negative electrode after cathode deposition period terminates.
2. the method reclaiming copper, nickel from ferronickel copper alloy scrap according to claim 1, is characterized in that: described ferronickel copper alloy scrap comprises the component of following mass percent: Fe0.5 ~ 20%, Cu60 ~ 80%, Ni3 ~ 20%.
3. the method reclaiming copper, nickel from ferronickel copper alloy scrap according to claim 1 and 2, is characterized in that: described oxidizing gas is air, oxygen-rich air or oxygen, and spraying into pressure is 0.01 ~ 0.8MPa.
4. the method reclaiming copper, nickel from ferronickel copper alloy scrap according to claim 1 and 2, is characterized in that: in described step (2), cupric electrolysis groove width and high size are respectively 1.0 ~ 3.0 times of the wide and long size of soluble anode.
5. the method reclaiming copper, nickel from ferronickel copper alloy scrap according to claim 1 and 2, is characterized in that: the Cu added in described step (2)
2+for CuSO
4, CuCl
2in one or both arbitrary proportion mixtures.
6. the method reclaiming copper, nickel from ferronickel copper alloy scrap according to claim 1 and 2, is characterized in that: the cathode deposition period of described one section of electrorefining, second segment electrorefining is 7 ~ 10 days.
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| CN201310455464.7A CN103498051B (en) | 2013-09-30 | 2013-09-30 | Method for recovering copper and nickel from nickel-iron-copper alloy waste |
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| CN201310455464.7A CN103498051B (en) | 2013-09-30 | 2013-09-30 | Method for recovering copper and nickel from nickel-iron-copper alloy waste |
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| CN104263937A (en) * | 2014-09-04 | 2015-01-07 | 龙济时代(北京)新能源科技有限公司 | Treatment method for nickel, copper and tin alloy waste material |
| CN105154919B (en) * | 2015-10-14 | 2017-10-31 | 池州西恩新材料科技有限公司 | It is a kind of that copper, the technique of nickel are reclaimed from corronil |
| CN108950215A (en) * | 2018-07-27 | 2018-12-07 | 湖南金业环保科技有限公司 | Low-grade nickle contained discarded material processing method |
| CN109609766B (en) * | 2018-12-10 | 2020-11-03 | 江西理工大学 | Method for removing iron and recovering copper from waste iron bronze |
| CN109518225B (en) * | 2019-01-16 | 2020-10-02 | 北京矿冶科技集团有限公司 | Method for separating ferrous iron and cobalt nickel in solution |
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| US1382361A (en) * | 1920-02-25 | 1921-06-21 | Hybinette Noak Victor | Refining copper-nickel matte |
| US1569137A (en) * | 1920-08-26 | 1926-01-12 | Nat Trust Company Ltd | Refining of copper-nickel matte |
| CN1029746C (en) * | 1993-08-10 | 1995-09-13 | 李学刚 | Process for one-stage electrolytic extraction of copper |
| CN103160855A (en) * | 2011-12-15 | 2013-06-19 | 广东先导稀材股份有限公司 | Preparation method of high-purity indium |
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