CN112442591A - Copper-nickel leaching and iron separation method for copper-nickel sulfide ore - Google Patents
Copper-nickel leaching and iron separation method for copper-nickel sulfide ore Download PDFInfo
- Publication number
- CN112442591A CN112442591A CN201910814901.7A CN201910814901A CN112442591A CN 112442591 A CN112442591 A CN 112442591A CN 201910814901 A CN201910814901 A CN 201910814901A CN 112442591 A CN112442591 A CN 112442591A
- Authority
- CN
- China
- Prior art keywords
- copper
- nickel
- leaching
- sulfide ore
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a copper-nickel leaching and iron separation method for copper-nickel sulfide ore. The method is characterized in that an oxidant, namely oxychloride, is added into the copper-nickel sulfide ore, so that copper and nickel elements are leached out, and iron elements are precipitated. The method adopts the oxychloride as the oxidant, does not additionally introduce harmful ions, can realize the complete leaching of the copper and nickel ions by a simple process, simultaneously directly separates out the iron in a precipitation form, and has the advantages of mild reaction conditions, short reaction time, simple equipment, simple operation, low cost and suitability for popularization and application.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a copper-nickel leaching and iron separation method for copper-nickel sulfide ore.
Background
The nickel and copper elements are essential basic materials and important strategic materials for national economy, social development, national defense industrial construction and scientific and technical development, the copper-nickel sulfide ore is a main nickel source, the copper is an important source, and the smelting of the copper-nickel ore is an important step for producing the nickel and copper simple substances. The smelting of the copper nickel sulfide ore is divided into a fire method and a wet method, and the fire method has wide application. The energy consumption and the environmental problem in the pyrometallurgy are solved to a certain extent by the hydrometallurgy, and the leaching process is an important step in the hydrometallurgy.
The leaching process of the copper-nickel sulfide ore can be mainly divided into acid leaching, ammonia leaching, chlorine leaching and bacterial leaching according to different leaching agents. The oxidant for ammonia leaching and acid leaching is oxygen, the oxidant for chlorine leaching is chlorine, and the oxidant for bacteria leaching is oxidase produced by bacteria. In addition, the use of oxidizing agents such as dichromate, ozone, and potassium permanganate as leaching agents has also been studied. According to different leaching raw materials, the method can be divided into concentrate leaching and high nickel matte leaching. The chlorine leaching method of the high nickel matte is a forming process in industry, and is used as a subsequent process of pyrometallurgy, the efficiency of leaching the high nickel matte by the chlorine is high, the recovery rate is high, and the effective separation of copper and nickel can be realized. At the same time, however, chlorine is expensive and has high requirements on the corrosion resistance of the equipment, so that the production cost is high. The leaching process using oxygen and bacterial oxidase as oxidants has low efficiency, and other ions such as chromate and manganese ions can be introduced in the process using dichromate, potassium permanganate and the like as oxidants, so that the difficulty in subsequent treatment is increased.
Therefore, a simple leaching process with high leaching efficiency, controllable cost and no harmful ion generation needs to be found.
Disclosure of Invention
The invention aims to provide a copper-nickel leaching and iron separating method for copper-nickel sulfide ore, which has the advantages of convenient operation, mild reaction condition, low cost, no additional introduction of harmful ions, complete leaching of copper and nickel, and fixation of iron element in a precipitation form to realize direct separation.
In order to solve the technical problems, the invention provides the following technical scheme:
the method for leaching copper nickel ions from copper nickel sulfide ore is characterized by adding oxidant oxychloride into copper nickel sulfide ore to make copper and nickel be leached out and make iron produce precipitate.
According to the scheme, when the oxidant is sodium chlorate, the method comprises the following specific steps:
(1) mixing copper nickel sulfide ore, sodium chlorate and distilled water and ball milling;
(2) drying the ball-milled sample in the step (1) at room temperature to 60-80% of dehydration;
(3) heating the dried sample in the step (2) for reaction; (ii) a
(4) Putting the sample reacted in the step (3) into distilled water, leaching copper and nickel, dissolving the sample in the distilled water, and generating precipitate NaFe by iron3(SO4)2(OH)6。
The oxidant sodium chlorate and the copper nickel sulphide ore are mixed and ball-milled, so that the oxidant sodium chlorate and the copper nickel sulphide ore can be promoted to be fully crushed and then closely contacted, and the existence of water reduces the oxidability of the sodium chlorate and avoids direct reaction after the sodium chlorate and the copper nickel sulphide ore are mixed; then evaporating at room temperature to remove 60-80% of water so that the mixture is converted into a quasi-solid state with low water content from slurry, and the residual water exists as a reactant; oxidation-reduction reaction occurs during heating, S element is oxidized, copper ions and nickel ions are directly leached out in distilled water, and iron ions are used for precipitating NaFe3(SO4)2(OH)6The form is fixed.
According to the scheme, the mass ratio of the copper nickel sulfide ore to the distilled water in the step (1) is 1: (1-1.5); the mass ratio of the copper nickel sulfide ore to the sodium chlorate is 1: (0.85-1.30).
According to the scheme, the ball milling conditions in the step (1) are as follows: the rotation speed is 200-400 rpm, and the time is 50-100 min.
According to the scheme, the heating reaction conditions in the step (3) are as follows: the temperature is 100-400 ℃, and the time is 100-150 min.
According to the scheme, the leaching time in the step (4) is 20-40 min.
According to the scheme, the leaching process in the step (4) selects an ultrasonic wave, oscillation or stirring mode.
According to the scheme, when the oxidant is sodium chlorite, the method comprises the following specific steps:
(1) preparing a sodium chlorite solution with the concentration of 0.1-0.5 mol/L;
(2) and (2) mixing and reacting the copper-nickel sulfide ore with the sodium chlorite solution prepared in the step (1) at normal temperature, leaching copper and nickel into an aqueous solution after the reaction is finished, and generating precipitated ferroferric oxide from iron.
The concentration of a sodium chlorite solution is regulated, the sodium chlorite reacts with the copper nickel sulfide ore mildly, the S element is oxidized, copper ions and nickel ions are directly leached in distilled water, and iron ions are fixed in a form of precipitated ferroferric oxide.
According to the scheme, the mass ratio of the copper nickel sulfide ore to the sodium chlorite is 1 (1.35-4.45).
According to the scheme, the reaction process in the step (2) selects an ultrasonic wave, oscillation or stirring mode.
According to the scheme, the reaction time in the step (2) is 10-30 min.
The invention has the beneficial effects that:
the invention can realize the complete leaching of copper and nickel elements by adding the oxychloride as the oxidant into the copper-nickel sulfide ore concentrate, and simultaneously, the iron element is fixed by the precipitate so as to directly realize the separation of the copper-nickel element and the iron element. The method has the advantages of mild reaction conditions, short reaction time, simple equipment, simple operation, low cost, no additional introduction of harmful ions in the reaction process and suitability for popularization and application.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of leaching residues obtained after copper nickel sulfide ores are treated by an oxidant sodium chlorate in example 1.
FIG. 2 is an XRD pattern of leached residues obtained after copper nickel sulfide ore is treated with sodium chlorite as an oxidant in example 3.
The specific implementation mode is as follows:
in order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples.
Example 1:
the main component of a copper nickel sulfide ore is nickel pyrite ((Ni, Fe)9S8) Chalcopyrite (CuFeS)2) And pyrite (FeS)2). The contents of Ni, Cu and Fe in the sample were 4.97%, 4.73% and 30.24%, respectively. 1g of ore sample and 1.01g of sodium chlorate are taken and added into a ball milling tank, 1g of water is added, and the ball milling is carried out for 60min under the condition of low rotating speed of 300 rpm. Taking out the ground sample in a dry stateDrying for 24h at room temperature in a dryer, removing 60% of water, heating for 2h at 200 ℃ in a muffle furnace, quantitatively taking a sample after heating, putting the sample into a conical flask, adding distilled water, and leaching for 30min at normal temperature and normal pressure in a water bath oscillator, wherein Ni and Cu are leached into the distilled water, leaching residues are precipitates of Fe, and Fe is directly separated from Ni and Cu. The measured leaching rates are respectively as follows: 99.63% of Ni, 99.74% of Cu and 0% of Fe.
FIG. 1 is an XRD spectrum of the leached residue after the reaction in this example, which shows that the main component of the leached residue is jarosite (NaFe)3(SO4)2(OH)6)。
The sodium chlorate has excellent leaching effect on the copper-nickel sulfide ore, can realize the complete leaching of copper and nickel elements and the fixation of iron elements by leaching for 30min at normal temperature and normal pressure, and the iron elements completely form sodium jarosite insoluble salt to be fixed in solid insoluble substances.
Example 2:
the main component of a copper nickel sulfide ore is chalcopyrite (CuFeS)2) Pyrite (FeS)2) Violarite (FeNi)2S4). The Ni, Cu and Fe contents in the sample were 4.72%, 4.40% and 26.55%, respectively. 1g of ore sample and 1.2g of sodium chlorate are taken and added into a ball milling tank, 1g of water is added, and the ball milling is carried out for 80min under the condition of low rotating speed of 200 rpm. Taking out the ground sample, drying at room temperature for 24h in a dryer, removing 80% of water, heating at 150 ℃ in a muffle furnace for 2h, quantitatively putting the heated sample into a conical flask, adding distilled water, and leaching at normal temperature and normal pressure in a water bath oscillator for 30min, wherein Ni and Cu are leached into distilled water, and Fe is NaFe3(SO4)2(OH)6The precipitate is separated. The measured leaching rates are respectively as follows: 99.49% of Ni, 99.65% of Cu and 0% of Fe.
Example 3:
the main component of a test sample of the main component of a copper nickel sulfide ore is chalcopyrite (CuFeS)2) Pyrite (FeS)2) Violarite (FeNi)2S4). The contents of Ni, Cu and Fe were 4.72%, 4.40% and 26.55%, respectively. 100mL of 0.3mol/L sodium chlorite solution is prepared and put into a conical flask, 1g of ore sample is put into the solution to form a reaction system, and oxygen is ensuredThe agent is in excess. And (3) placing the reaction system in a water bath oscillator (250rpm) and oscillating at normal temperature and normal pressure for 10min to complete the reaction, wherein Ni and Cu are leached into distilled water, leaching residues are precipitates of Fe, and Fe is directly separated from Ni and Cu. The measured leaching rates are respectively as follows: 99.99% of Ni, 99.80% of Cu and 0% of Fe.
FIG. 2 is an XRD spectrum of the leached residue after the reaction in the present example, which shows that the main component of the leached residue is ferroferric oxide (Fe)3O4)。
The dilute sodium chlorite solution has excellent leaching effect on the copper-nickel sulfide ore, can realize the complete leaching of copper and nickel elements and the fixation of iron element by leaching for 10min at normal temperature and normal pressure, the iron element is completely fixed in insoluble ferroferric oxide, and in addition, the sodium chlorite is prepared into the dilute solution, and can also avoid harmful gas ClO generated in the reaction process as much as possible2Into the air.
Example 4:
the main component of a copper nickel sulfide ore is nickel pyrite ((Ni, Fe)9S8) Chalcopyrite (CuFeS)2) Pyrite (FeS)2). The contents of Ni, Cu and Fe in the sample were 4.97%, 4.73% and 30.24%, respectively. 100ml of 0.3mol/L sodium chlorite solution is prepared and put into a conical flask, and 1.5g of ore sample is put into the solution to form a reaction system, so that the excessive amount of oxidant is ensured. And (3) placing the reaction system in a water bath oscillator (250rpm) and oscillating at normal temperature and normal pressure for 20min to complete the reaction, wherein Ni and Cu are leached into distilled water, and Fe is separated in a ferroferric oxide precipitate form. The measured leaching rates are respectively as follows: 99.79% of Ni, 99.36% of Cu and 0% of Fe.
Claims (9)
1. A method for leaching copper and nickel and separating iron from a copper-nickel sulfide ore is characterized in that an oxidant, namely oxychloride, is added into the copper-nickel sulfide ore to leach out copper and nickel, and iron is precipitated.
2. The method for copper-nickel leaching and iron separation of a copper-nickel sulfide ore according to claim 1, wherein the oxychloride as the oxidant is sodium chlorate, and the method comprises the following steps:
(1) mixing copper nickel sulfide ore, sodium chlorate and distilled water and ball milling;
(2) drying the ball-milled sample in the step (1) at room temperature to 60-80% of dehydration;
(3) heating the dried sample in the step (2) for reaction;
(4) putting the sample reacted in the step (3) into distilled water, leaching copper and nickel, dissolving the sample in the distilled water, and forming precipitate NaFe by iron3(SO4)2(OH)6。
3. The method for leaching copper and nickel and separating iron from copper and nickel sulfide ore according to claim 2, wherein the mass ratio of copper and nickel sulfide ore to distilled water in the step (1) is 1: (1-1.5); the mass ratio of the copper nickel sulfide ore to the sodium chlorate is 1: (0.85-1.30).
4. The method for copper-nickel leaching and iron separation of copper-nickel sulfide ore according to claim 2, wherein the ball milling conditions in the step (1) are as follows: the rotation speed is 200-400 rpm, and the time is 50-100 min.
5. The method for copper-nickel leaching and iron separation of a copper-nickel sulfide ore according to claim 2, wherein the heating reaction conditions in the step (3) are as follows: the temperature is 100-400 ℃, and the time is 100-150 min.
6. The method for leaching copper and nickel and separating iron from copper-nickel sulfide ore according to claim 2, wherein the leaching time in the step (4) is 20-40 min; the leaching process selects ultrasonic, oscillation or stirring modes.
7. The method for copper-nickel leaching and iron separation of a copper-nickel sulfide ore according to claim 1, wherein the oxychloride as the oxidant is sodium chlorite, and the specific steps are as follows:
(1) preparing a sodium chlorite solution with the concentration of 0.1-0.5 mol/L;
(2) and (2) mixing and reacting the copper-nickel sulfide ore with the sodium chlorite solution prepared in the step (1) at normal temperature, leaching copper and nickel into an aqueous solution after the reaction is finished, and forming precipitated ferroferric oxide by iron.
8. The method for leaching copper and nickel and separating iron from copper and nickel sulfide ore according to claim 7, wherein the mass ratio of the copper and nickel sulfide ore to the sodium chlorite is 1 (1.35-4.45).
9. The method for leaching copper and nickel and separating iron from copper-nickel sulfide ore according to claim 7, wherein the reaction time in the step (2) is 10-30 min; the reaction process selects ultrasonic wave, oscillation or stirring mode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910814901.7A CN112442591B (en) | 2019-08-30 | 2019-08-30 | Copper-nickel leaching and iron separation method for copper-nickel sulfide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910814901.7A CN112442591B (en) | 2019-08-30 | 2019-08-30 | Copper-nickel leaching and iron separation method for copper-nickel sulfide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112442591A true CN112442591A (en) | 2021-03-05 |
| CN112442591B CN112442591B (en) | 2023-10-20 |
Family
ID=74733748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910814901.7A Active CN112442591B (en) | 2019-08-30 | 2019-08-30 | Copper-nickel leaching and iron separation method for copper-nickel sulfide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112442591B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114934193A (en) * | 2022-05-24 | 2022-08-23 | 浙江伽能环境工程有限责任公司 | Method for enhancing normal-pressure acid leaching efficiency of nickel anode mud desulfurization slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050118081A1 (en) * | 2003-09-30 | 2005-06-02 | Jaguar Nickel Inc. | Process for the recovery of value metals from base metal sulfide ores |
| CN101760611A (en) * | 2010-01-30 | 2010-06-30 | 中南大学 | Method for wet-method oxidative decomposition of metal sulfide ores |
| CN102703693A (en) * | 2012-05-22 | 2012-10-03 | 北京大学 | Method for enriching and recovering metal nickel, copper and cobalt from tailings of copper and nickel mines |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| CN108060301A (en) * | 2017-12-05 | 2018-05-22 | 北京科技大学 | A kind of method that rubidium and by-product active calcium silicate are extracted in the ore from rubidium |
-
2019
- 2019-08-30 CN CN201910814901.7A patent/CN112442591B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050118081A1 (en) * | 2003-09-30 | 2005-06-02 | Jaguar Nickel Inc. | Process for the recovery of value metals from base metal sulfide ores |
| CN101760611A (en) * | 2010-01-30 | 2010-06-30 | 中南大学 | Method for wet-method oxidative decomposition of metal sulfide ores |
| CN102703693A (en) * | 2012-05-22 | 2012-10-03 | 北京大学 | Method for enriching and recovering metal nickel, copper and cobalt from tailings of copper and nickel mines |
| CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
| CN108060301A (en) * | 2017-12-05 | 2018-05-22 | 北京科技大学 | A kind of method that rubidium and by-product active calcium silicate are extracted in the ore from rubidium |
Non-Patent Citations (1)
| Title |
|---|
| 中国冶金百科全书总编辑委员会《有色金属冶金》卷编辑委员会, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114934193A (en) * | 2022-05-24 | 2022-08-23 | 浙江伽能环境工程有限责任公司 | Method for enhancing normal-pressure acid leaching efficiency of nickel anode mud desulfurization slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112442591B (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022134749A1 (en) | Method for recovering lithium in lithium iron phosphate waste and application thereof | |
| CN112410556B (en) | Method for recovering waste lithium iron phosphate powder | |
| CN101817553B (en) | Method for treating arsenic-containing smoke dust | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN104762466A (en) | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore | |
| CN107445209A (en) | Remove the method that manganous dithionate prepares saturation manganese sulfate slurries and manganese sulfate in pyrolusite pulp leachate | |
| CN107746957A (en) | A kind of method that rare precious metal is reclaimed in the copper leached solution from copper anode mud | |
| CN104261473B (en) | A kind of preparation method of Vanadium Pentoxide in FLAKES | |
| GB2621039A (en) | Harmless treatment method for recovering sulfur, rhenium, and arsenic from arsenic sulfide slag | |
| CN112442591B (en) | Copper-nickel leaching and iron separation method for copper-nickel sulfide ore | |
| CN114229875A (en) | Comprehensive recovery method of waste sodium ion battery | |
| CN107058750A (en) | Germanic Bellamya aeruginosa comprehensive recycling process | |
| CN111926196B (en) | Method for recovering zinc from smelting waste residues | |
| CN105838908A (en) | Efficient and clean molybdenum smelting method | |
| CN101328540B (en) | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue | |
| CN106882839B (en) | Method for comprehensively utilizing titanium white waste acid | |
| CN108063295B (en) | Method for extracting lithium from slag generated by pyrogenic recovery of lithium battery | |
| CN108913892A (en) | A method of the comprehensively recovering valuable metal from the pickle liquor of cupric | |
| CN106480319A (en) | A kind of method of the immersion cleaning treatment hydrogen containing tail gas synthetical recovery antimony of alkali containing antimony | |
| CN113981239A (en) | Process for leaching kalin type gold ore by composite chloride salt | |
| CN103572041A (en) | Wet deep dearsenification method for high-arsenic iron ores | |
| BRPI0905473A2 (en) | physicochemical process for the recovery of metals contained in steel industry waste | |
| CN85107329B (en) | Chlorination-hydrolyzation process for making antimony white from antimony sulfide ore | |
| CN112777642A (en) | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag | |
| CN107381646B (en) | The method for preparing mangano-manganic oxide using acid-soluble manganese ore recycled based on sulphur, ammonia |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |