CN102010996A - Method for treating nickel sulfide ore biological heap leaching solution - Google Patents
Method for treating nickel sulfide ore biological heap leaching solution Download PDFInfo
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- CN102010996A CN102010996A CN2010105606325A CN201010560632A CN102010996A CN 102010996 A CN102010996 A CN 102010996A CN 2010105606325 A CN2010105606325 A CN 2010105606325A CN 201010560632 A CN201010560632 A CN 201010560632A CN 102010996 A CN102010996 A CN 102010996A
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- leaching solution
- dump leaching
- sulfide ore
- nickel sulfide
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a method for treating nickel sulfide ore biological heap leaching solution, which relates to nickel sulfide ore, in particular to a method for recovering valuable metals from high-magnesium high-iron nickel sulfide ore biological heap leaching solution. The method is characterized by comprising the following steps of: adding lime into the biological heap leaching solution for pulpifying, introducing air for oxidization reaction, oxidizing Fe<2+> in the biological heap leaching solution into Fe<3+>, hydrolyzing to generate Fe(OH)3, and performing the adsorption recovery of the valuable metals such as nickel, cobalt and copper in an ion exchange column. Normal temperature iron deposition is realized with low energy consumption; valuable metal ions in the treated heap leaching solution can be lowered to below 3ppm; and the recovery rates of the valuable metal ions are high, and both the recovery rates of the nickel and cobalt metal ions are over 99 percent. The method has low treatment cost and high economic benefit, and industrialized production is easy to realize.
Description
Technical field
A kind of treatment process of nickel sulfide ore biological dump leaching solution relates to nickel sulfide ore, reclaims the method for valuable metal in the high especially magnesium high ferro sulfuration nickel mineral dump leaching solution.
Background technology
The biological leaching also claims bacteriosmelt or microorganism to leach, and its essence is the oxidation catalysis effect by a big quasi-microorganism, makes the hydrometallurgy process of the dissolving metal in the ore.Bioleaching process be particularly suitable for handling lean ore, abandoned mine, unbalanced-ore and difficultly adopt, the dump leaching in difficult choosing, difficult smelting ore deposit and leaching on the spot, and equipment is simple, and is easy to operate, less investment, cost is low, helps the comprehensive utilization and the environment protection of resource.Therefore, at rich ore, easily handle that ore resources reduces day by day, environmental requirement improves constantly, under the condition that modern industry and development in science and technology grow with each passing day to the demand of non-ferrous metal, the biological leaching more demonstrates its unique advantages.Therefore have reason to expect that along with metallurgy, industrial microbiology, biological chemistry and development of molecular biology, biological metallurgy will become one of most important metallurgical technology of 21 century.
High magnesium low-grade nickel sulfide ore is when adopting the bacteria heap leaching method to extract valuable metal Ni, Cu etc., because of containing higher magnesium oxide in the ore deposit, therefore enter the metal of solution except Fe as major impurity, also have a large amount of magnesium also to enter in the acid leaching solution, the magnesium in the solution can reach about 40 g/L.Therefore the characteristics of high magnesium low-grade nickel sulfide ore bacteria heap leaching liquid: the one, the content of valuable metal is low especially in the leach liquor, nickel 1-3g/L wherein, copper 0.1-1g/L, cobalt 0.01-0.1g/L.The 2nd, the foreign matter content in the leach liquor is all very high, and wherein iron reaches 2-10g/L, and magnesium reaches 20-40g/L, has increased very big difficulty to solution-treated.The problem of bringing thus is that lower concentration nickel and high density magnesium may bring certain degree of difficulty to the enrichment and the solution purification of nickel because of the isolating difficulty of nickel magnesium, and these valuable metals are reclaimed fully, the amount of reagent that needs is very big, thereby makes the cost of solution-treated very high.
Owing to do not adopt the high magnesium low-grade nickel sulfide ore of bacteria heap leaching method relevant report, handle biological dump leaching solution and mainly adopt chemical precipitation method, at present as sulfurization-precipitation method, hydroxide precipitation method etc.But these methods are realizing that there is significant disadvantages in industrialized production: 1, in the suitability for industrialized production engineering, have the through engineering approaches problem of scum filtration difficulty; 2, in the suitability for industrialized production engineering, lower concentration nickel and high density magnesium may bring certain degree of difficulty to the enrichment and the solution purification of nickel because of the isolating difficulty of nickel/magnesium, and these valuable metals are reclaimed fully, the amount of reagent that needs is very big, thereby makes the cost of solution-treated very high.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, a kind of isolating difficulty of nickel/magnesium, big problem of purification difficulty that can effectively solve lower concentration nickel and the generation of high density magnesium is provided, the recovery rate of valuable metals height, reagent consumption is little, the treatment process of the nickel sulfide ore biological dump leaching solution that the cost of processing is low.
The objective of the invention is to be achieved through the following technical solutions.
A kind of treatment process of nickel sulfide ore biological dump leaching solution is characterized in that its process is biological dump leaching liquid to be added lime carry out pulp and bubbling air, carries out oxidizing reaction, makes Fe in the biological dump leaching liquid
2+Be oxidized to Fe
3+, and hydrolysis generate Fe (OH)
3After, feed ion exchange column again and carry out nickel, cobalt, copper valuable metal absorption recovery.
The treatment process of a kind of nickel sulfide ore biological dump leaching solution of the present invention is characterized in that it is solid-to-liquid ratio 10-40Kg/m that described biological dump leaching liquid (pH value 2-4.5) adds the add-on that lime carries out the lime of pulp process
3The solid-to-liquid ratio of pulp is 2-5:1.
The treatment process of a kind of nickel sulfide ore biological dump leaching solution of the present invention is characterized in that its process is that biological dump leaching liquid is added the lime pulp, bubbling air, and the feeding amount of the air when carrying out oxidizing reaction is 6-18m
3, the reaction times is 2-6h.
The treatment process of a kind of nickel sulfide ore biological dump leaching solution of the present invention, the exchange resin that it is characterized in that described ion exchange column are imido oxalic acid or aminophosphonic acid resin.
The treatment process of a kind of nickel sulfide ore biological dump leaching solution of the present invention is characterized in that the dynamic overflow mode is adopted in the processing of the saturated back of described ion exchange process absorption resin.
The treatment process of a kind of nickel sulfide ore biological dump leaching solution of the present invention, adopt lime as neutralizing agent, processing cost is low, bubbling air is as oxygenant, according to the biological dump leaching solution potential, effectively the pH value of control reactor internal reaction liquid and ventilation oxidization time make Fe in the biological dump leaching liquid under the normal temperature state
2+Be oxidized to Fe
3+, and hydrolysis generate Fe (OH)
3,The calcium sulfate co-precipitation that produces in heap leaching solution forms scum underflow liquid; The scum underflow liquid that forms behind the heavy iron of biological dump leaching solution need not to filter, and direct and resin exchanges, and has effectively avoided the through engineering approaches problem of scum filtration difficulty in the biological dump leaching solution-treated process; In the process that resin exchanges, feed an amount of air, make resin be in a kind of dynamic exchange all the time, the through engineering approaches problem that has effectively solved the poly-group of resin and stopped up from the ion-exchange column bottom; Realized that normal temperature sinks iron, energy consumption is low; Valuable metal ions in the heap leaching solution after the processing can be reduced to below the 3ppm; Valuable metal ions rate of recovery height, nickel, the cobalt metal ion rate of recovery are all more than 99%.Reclaim valuable metal ions content height in the liquid, nickel, content of copper ion can reach respectively about 50g/L, 10 g/L.Impurity ion content is low, and iron, magnesium addition ion content are respectively about 2 g/L, 3 g/L.
Method of the present invention, have processing cost low, be easy to suitability for industrialized production, have stronger economic benefit.
Description of drawings
Fig. 1 is the process flow diagram of method of the present invention.
Embodiment
A kind of treatment process of nickel sulfide ore biological dump leaching solution, the step for the treatment of processes comprises:
(1) limestone powder (granularity is less than 120 orders) is added water slurryization, wherein pulp liquid-solid ratio is 2-5:1.
(2) with the about 1m of biological dump leaching liquid
3In the input deironing pond, feed an amount of pneumatic blending, limestone powder pulp liquid is added in the deironing pond in the reactor by certain flow (60-100L/h), and the pH value of control reactor internal reaction liquid is 2-4.5 and oxidization time 2-6 hour of ventilating, and makes Fe in the biological dump leaching liquid under the normal temperature state
2+Be oxidized to Fe
3+, and hydrolysis generate Fe (OH)
3,The calcium sulfate co-precipitation that produces in heap leaching solution forms scum underflow liquid.
(3) pack in ion exchange column imido oxalic acid or aminophosphonic acid resin specific resin 20-25L after transition add suitable quantity of water, feed an amount of air 6-8 m from the ion-exchange column bottom
3The scum underflow liquid that forms behind the heavy iron of biological dump leaching solution is imported the ion exchange column from the ion-exchange column bottom by certain flow (160-200L/h), in the scum underflow liquid nickel, cobalt, copper valuable metal by resin absorption after, enter the next stage ion exchange column from the discharge of ion exchange column upper end in the scum underflow liquid, after the level Four exchange, drain in the waste liquid storage pond in the scum underflow liquid.
(4) treat in the ion exchange column that resin absorption is saturated after, the scum underflow liquid that forms behind the heavy iron of biological dump leaching solution is switched to the next stage exchange, residual scum is removed in the resin washing of adsorb after saturated, stops to ventilate in ion exchange column after the washing totally.
(5) sulfuric acid or (7%) hydrochloric acid soln of proper concn (20%) are imported the ion exchange column from the ion exchange column upper end by certain flow, collect pickle solution from the ion-exchange column bottom, the pickle solution of collecting can be used for pickling next time, after treating that valuable metal ions content and acidity meet the demands in the pickle solution, pickle solution is collected in the finished fluid storage tank.
(6) resin after the pickling is washed once more, wash qualified after, the alkaline solution of proper concn (5% sodium hydroxide) is imported the ion exchange column from the ion exchange column upper end by certain flow (60 L/h), collect alkaline wash from the ion-exchange column bottom, the alkaline wash of collecting can be used for alkali cleaning next time, treat resin make the transition fully after washing once more, the resin of washing after qualified is used for next ion-exchange.
Embodiment 1
(1) an amount of limestone powder (granularity is less than 120 orders) is added water slurryization, wherein pulp liquid-solid ratio is 3:1.
(2) with the about 1m of biological dump leaching liquid
3In the input deironing pond, feed an amount of pneumatic blending, limestone powder pulp liquid is added in the deironing pond in the reactor by certain flow (60-100L/h), and the pH value of control reactor internal reaction liquid is 2-4.5 and oxidization time 2-6 hour of ventilating, and makes Fe in the biological dump leaching liquid under the normal temperature state
2+Be oxidized to Fe
3+, and hydrolysis generate Fe (OH)
3,The calcium sulfate co-precipitation that produces in heap leaching solution forms scum underflow liquid.
Table 1 heap leaching solution is the supernatant liquor chemical ingredients behind the heavy iron of normal temperature
| Composition | pH | Ni | Co | Cu | Fe | Mg |
| Content g/L | 4.34 | 1.83 | 0.039 | 0.24 | 0.13 | 31.26 |
(3) in ion exchange column, pack into the transition after specific resin 20-25L, add suitable quantity of water, feed an amount of air from the ion-exchange column bottom, the scum underflow liquid that forms behind the heavy iron of biological dump leaching solution is imported the ion exchange column from the ion-exchange column bottom by certain flow (160-200L/h), in the scum underflow liquid nickel, cobalt, copper valuable metal by resin absorption after, enter the next stage ion exchange column from the discharge of ion exchange column upper end in the scum underflow liquid, after the level Four exchange, drain in the waste liquid storage pond in the scum underflow liquid.
(4) treat in the ion exchange column that resin absorption is saturated after, the scum underflow liquid that forms behind the heavy iron of biological dump leaching solution is switched to the next stage exchange, residual scum is removed in the resin washing of adsorb after saturated, stops to ventilate in ion exchange column after the washing totally.
(5) sulfuric acid or (7%) hydrochloric acid soln of proper concn (20%) are imported the ion exchange column from the ion exchange column upper end by certain flow, collect pickle solution from the ion-exchange column bottom, the pickle solution of collecting can be used for pickling next time, after treating that valuable metal ions content and acidity meet the demands in the pickle solution, pickle solution is collected
In the finished fluid storage tank.
Material trend in the table 2 biological dump leaching liquid treating processes
| Chemical ingredients | Ni | Co | Cu | Fe | Mg | Remarks |
| Original liquid concentration g/L | 2.02 | 0.049 | 0.46 | 9.87 | 34.68 | Get former liquid measure 1m 3 |
| Stoste metal content Kg | 2.02 | 0.049 | 0.46 | 9.87 | 34.68 | ? |
| Exchange back scum concentration g/L | 0.002 | 0.001 | 0.001 | / | 30.82 | Scum water yield 1.1m 3 |
| Residue water metal content g | 0.0135 | Do not detect | 0.0162 | / | / | ? |
| Regenerated liquid composition g/L | 50.90 | 1.23 | 11.22 | 2.43 | 3.05 | Regeneration liquid measure 39.5L |
| Resin absorption yield % | 99.53? | 99.15 | 96.34? | / | / | ? |
(6) resin after the pickling is washed once more, wash qualified after, the alkaline solution of proper concn (5% sodium hydroxide) is imported the ion exchange column from the ion exchange column upper end by certain flow (60 L/h), collect alkaline wash from the ion-exchange column bottom, the alkaline wash of collecting can be used for alkali cleaning next time, treat resin make the transition fully after washing once more, the resin of washing after qualified is used for next ion-exchange.
Embodiment 2
(1) the bacterial oxidation certain hour of earlier the dump leaching soln using being cultivated is voluntarily analyzed Fe
3+/ Fe
2+, numeric ratio is standby greater than back more than 9.
(2) with the about 1m of biological dump leaching liquid
3In the input deironing pond, feed an amount of pneumatic blending, limestone powder pulp liquid is added in the deironing pond in the reactor by certain flow (60-100L/h), and the pH value of control reactor internal reaction liquid is about 4.2 and the oxidization time 2 hours of ventilating, and makes residual F e under the normal temperature state
2+Be oxidized to Fe
3+, and hydrolysis generate Fe (OH)
3,The calcium sulfate co-precipitation that produces in heap leaching solution forms scum underflow liquid.
Table 3 heap leaching solution is the supernatant liquor chemical ingredients behind the heavy iron of normal temperature
| Composition | pH | Ni | Co | Cu | Fe | Mg |
| Content g/L | 4.30 | 1.83 | 0.039 | 0.24 | 0.08 | 31.26 |
(3) other conditions are identical with example 1.Fe concentration obviously reduces in the backwash liquor as a result.The material trend sees Table 4
Material trend in the table 4 biological dump leaching liquid treating processes
| Chemical ingredients | Ni | Co | Cu | Fe | Mg | Remarks |
| Original liquid concentration g/L | 2.02 | 0.049 | 0.46 | 9.87 | 34.68 | Get former liquid measure 1m 3 |
| Stoste metal content Kg | 2.02 | 0.049 | 0.46 | 9.87 | 34.68 | ? |
| Exchange back scum concentration g/L | 0.002 | 0.001 | 0.001 | / | 30.7 | Scum water yield 1.1m 3 |
| Residue water metal content g | 0.014 | Do not detect | 0.016 | / | / | ? |
| Regenerated liquid composition g/L | 50.50 | 1.25 | 11.5 | 1.4 | 2.95 | Regeneration liquid measure 39.5L |
| Resin absorption yield % | 99.45 | 99.15 | 96.5? | / | / | ? |
Claims (6)
1. the treatment process of a nickel sulfide ore biological dump leaching solution is characterized in that its process is biological dump leaching liquid to be added lime carry out pulp and bubbling air, carries out oxidizing reaction, makes Fe in the biological dump leaching liquid
2+Be oxidized to Fe
3+, and hydrolysis generate Fe (OH)
3After, feed ion exchange column again and carry out nickel, cobalt, copper valuable metal absorption recovery.
2. the treatment process of a kind of nickel sulfide ore biological dump leaching solution according to claim 1 is characterized in that it is solid-to-liquid ratio 10-40Kg/m that described biological dump leaching liquid (pH value 2-4.5) adds the add-on that lime carries out the lime of pulp process
3The solid-to-liquid ratio of pulp is 2-5:1.
3. the treatment process of a kind of nickel sulfide ore biological dump leaching solution according to claim 1 is characterized in that its process is that biological dump leaching liquid is added the lime pulp, bubbling air, and the feeding amount of the air when carrying out oxidizing reaction is 6-18m
3, the reaction times is 2-6h.
4. the treatment process of a kind of nickel sulfide ore biological dump leaching solution according to claim 1, the exchange resin that it is characterized in that described ion exchange column are imido oxalic acid or aminophosphonic acid resin.
5. the treatment process of a kind of nickel sulfide ore biological dump leaching solution according to claim 1 is characterized in that the dynamic overflow mode is adopted in the processing of the saturated back of described ion exchange process absorption resin.
6. the treatment process of a kind of nickel sulfide ore biological dump leaching solution according to claim 1 is characterized in that described ion exchange process, and from ion-exchange column bottom bubbling air, the feeding amount is 6-8 m
3
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965520A (en) * | 2012-12-10 | 2013-03-13 | 金川集团股份有限公司 | Method for separating and enriching copper in leachate of acid leaching sulfide mine tailing |
| CN104745813A (en) * | 2013-12-31 | 2015-07-01 | 北京有色金属研究总院 | Method for comprehensively recovering nickel and magnesium in bio-leaching process of high-magnesium low-nickel sulfide ore |
| CN108793323A (en) * | 2018-07-03 | 2018-11-13 | 江西核工业兴中新材料有限公司 | Synthesized environmental protection method handles basic cobaltous carbonate industrial wastewater Call Provision smithcraft |
| CN110563102A (en) * | 2019-09-11 | 2019-12-13 | 北京金山生态动力素制造有限公司 | Method for extracting natural mineral substances and trace elements from ores by using microorganisms |
| CN115747489A (en) * | 2022-12-06 | 2023-03-07 | 金川集团镍盐有限公司 | Method for leaching high-magnesium low-nickel sulfide ore under normal pressure |
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| CN101338367A (en) * | 2008-08-14 | 2009-01-07 | 上海西恩化工设备有限公司 | Method for enriching and purifying nickel, cobalt or copper ions |
| CN101415848A (en) * | 2006-02-02 | 2009-04-22 | 瓦利·德·利奥多斯公司 | Hybrid process using ion exchange resins in the selective recovery of nickel and cobalt from leaching effluents |
| CN101736156A (en) * | 2009-12-07 | 2010-06-16 | 中南大学 | Method for comprehensively utilizing high-iron biological copper leaching liquid |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101415848A (en) * | 2006-02-02 | 2009-04-22 | 瓦利·德·利奥多斯公司 | Hybrid process using ion exchange resins in the selective recovery of nickel and cobalt from leaching effluents |
| CN101338367A (en) * | 2008-08-14 | 2009-01-07 | 上海西恩化工设备有限公司 | Method for enriching and purifying nickel, cobalt or copper ions |
| CN101736156A (en) * | 2009-12-07 | 2010-06-16 | 中南大学 | Method for comprehensively utilizing high-iron biological copper leaching liquid |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965520A (en) * | 2012-12-10 | 2013-03-13 | 金川集团股份有限公司 | Method for separating and enriching copper in leachate of acid leaching sulfide mine tailing |
| CN104745813A (en) * | 2013-12-31 | 2015-07-01 | 北京有色金属研究总院 | Method for comprehensively recovering nickel and magnesium in bio-leaching process of high-magnesium low-nickel sulfide ore |
| CN104745813B (en) * | 2013-12-31 | 2017-02-15 | 北京有色金属研究总院 | Method for comprehensively recovering nickel and magnesium in bio-leaching process of high-magnesium low-nickel sulfide ore |
| CN108793323A (en) * | 2018-07-03 | 2018-11-13 | 江西核工业兴中新材料有限公司 | Synthesized environmental protection method handles basic cobaltous carbonate industrial wastewater Call Provision smithcraft |
| CN108793323B (en) * | 2018-07-03 | 2022-04-01 | 江西核工业兴中新材料有限公司 | Process for recovering cobalt metal by treating basic cobalt carbonate industrial wastewater by comprehensive environment-friendly method |
| CN110563102A (en) * | 2019-09-11 | 2019-12-13 | 北京金山生态动力素制造有限公司 | Method for extracting natural mineral substances and trace elements from ores by using microorganisms |
| CN115747489A (en) * | 2022-12-06 | 2023-03-07 | 金川集团镍盐有限公司 | Method for leaching high-magnesium low-nickel sulfide ore under normal pressure |
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Application publication date: 20110413 |