CN103397181A - Recovery process of associated metal elements in iron ore - Google Patents
Recovery process of associated metal elements in iron ore Download PDFInfo
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- CN103397181A CN103397181A CN2013103406421A CN201310340642A CN103397181A CN 103397181 A CN103397181 A CN 103397181A CN 2013103406421 A CN2013103406421 A CN 2013103406421A CN 201310340642 A CN201310340642 A CN 201310340642A CN 103397181 A CN103397181 A CN 103397181A
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Abstract
The invention relates to a recovery process of associated metal elements in iron ore, which comprises the following steps: wetting the crushed iron ore with dilute sulfuric acid; fe of moistened iron ore3+Performing ion oxidation leaching treatment, and collecting seepage liquid; when the concentration of metal ions such as copper, nickel, cobalt and the like in the seepage liquid reaches a higher level, metal recovery is needed, and the recovered residual liquid is conveyed to a liquid regulating tank; when the concentration of copper, nickel and cobalt metal ions in the seepage liquid is low, the seepage liquid directly enters a liquid regulating tank; adjusting the acidity of the seepage liquid of the liquid adjusting tank and adding the microbial culture solution, and pumping the seepage liquid into a biological oxidation reactor for Fe3+Ion regeneration; heating the regenerated seepage liquid and returning to perform Fe3+Ion oxidation leaching operation; the invention utilizes the Fe-containing3+The dilute sulfuric acid solution of ions has oxidation and dissolution effects on copper, nickel and cobalt elements accompanying the iron ore, the oxidation reaction is rapidly carried out by controlling the temperature of the higher spraying liquid, and the accompanying metal of the iron ore is dissolved and recovered in a shorter time.
Description
Technical field
The present invention relates to reclaim the method for the associated metal in iron ore, particularly the recovery process of associated metal element in a kind of iron ore.
Background technology
Tradition has the flotation beneficiation method to the recovery of associated metal element in iron ore, according to the component content of original iron ore select targetedly depressing agent, again in conjunction with concrete flotation parameters, the method that low-grade copper, zinc etc. is reclaimed.
Chinese patent literature for example, publication number is CN101906535A, open day is on December 08th, 2010, denomination of invention is the recoverying and utilizing method of low-grade lead zinc in pyrite, comprise that the pyrite Ore that the leaded zinc grade of plumbous zinc sulphur flotation separation difficulty is low is levigate, the bulk flotation of plumbous zinc sulphur, the highgrade pyrite concentrate of the leaded zinc of selected acquisition repeatedly, by the high temperature peroxide roasting in fluidizing furnace of this concentrate, flue gas is sulfuric acid processed after udst separation, slag becomes the leaded zinc slag of high ferro low sulfur type, this slag adds pelletizing caking agent and chlorizating agent to moisten mill, pelletizing processed, after the pelletizing drying, carry out the high-temp chlorination volatilization roasting, baking flue gas dust collection obtains lead and zinc concentrate, the agglomerates ore deposit is that iron content is greater than 58%, leaded zinc is less than 0.3% iron-smelting raw material.This technique is by the bulk flotation of plumbous zinc sulphur, repeatedly selected, high temperature peroxide roasting deep desulfuration, high temperature chlorination roasting takes off plumbous zinc, the plumbous zinc resource that plumbous zinc sulphur flotation separation difficulty is lost in sulfurous iron ore in a large number reclaims, when obtaining sulfuric acid, obtained qualified iron ball nodulizing, iron resources also gets the efficient use.Can obviously find out, the method is mainly to reclaim and obtain iron resources to plumbous zinc resource.
But for the Panxi Diqu vanadium titano-magnetite, aforesaid method just is not suitable for, in especially should the zone vanadium titano-magnetite, most associations have the metallic elements such as copper, nickel, cobalt, and these metallic elements mainly exist with the sulfuration phase, and rest part is composed and is stored in iron titanium oxide phase and silicate phase; Its sulfuration compound type has 33 kinds more than, but is mainly pyrite and pyrrhotite, accounts for more than 90% of sulfide total amount.
Each vanadium titano-magnetite mining area medium sulphide content content of Pan Xi is different, probably in the 1.5-2.1% scope; These sulfide relatively disperse in ore dressing process, unsuitable enrichment.Due to the difference of pyrrhotite, pyrite physico-chemical property, in ore dressing process, move towards different, the sulfide in iron ore concentrate is take pyrrhotite as main, and the sulfide in iron selection tailings is take pyrite as main.Pyrrhotite in iron ore concentrate not only is difficult for reclaiming, and also can cause the iron ore concentrate sulphur content higher.Sulfide in iron selection tailings can carry out flotation separation in selecting the titanium process, obtain a small amount of sulphur cobalt concentrate, but metal recovery rate is on the low side.
Summary of the invention
The present invention reclaims the problem difficult, that utilization ratio is low for solving the metallic elements such as association copper, nickel, cobalt in present Panxi Diqu vanadium titano-magnetite, a kind of molten novel process that reclaims associated metal element in iron ore of soaking of microorganism of utilizing is provided, the method is that the iron ore of the metallic elements such as copper, nickel, cobalt is arranged for association, at ore grinding--the technique that the metallic elements such as copper to association in ore, nickel, cobalt are carried out a biological disposal upon and reclaimed is reclaimed before iron in magnetic separation, this technique is convenient to be reclaimed, and can greatly improve the rate of recovery of associated metal.
Technical scheme of the present invention is as follows:
The recovery process of associated metal element in iron ore, is characterized in that comprising the steps:
After A, iron ore that fragmentation is good are wetting with dilute sulphuric acid, fill up anticorrosion storage bin;
B, the iron ore after processing of step A is carried out to Fe
3+Ionic oxide formation is molten soaks processing, be used to collecting percolating fluid;
C, collect in the process of the percolating fluid of step B in processing: when copper in percolating fluid, nickel, when the cobalt metal ion reaches finite concentration, percolating fluid is admitted to the metal recovery system, the raffinate that obtains after the metal recovery system is extracted metal returns to collecting tank, and the raffinate of collecting tank is transported to the tune liquid bath; When copper, nickel, cobalt concentration of metal ions in the percolating fluid of collecting were low, percolating fluid directly entered same tune liquid bath;
D, in step C, entering, adjust the percolating fluid of liquid bath first to carry out acidity adjustment, then carry out microbial culture medium and add operation;
E, the percolating fluid after step D processes is pumped in the biooxidation reactions device and carries out Fe
3+Ion regeneration; Percolating fluid after regeneration is put after being heated to 60-80 ℃ and is returned to step B and carry out iron ore Fe through auxiliary hot charging
3+Ionic oxide formation is molten soaks operation, then continues step C.
In described steps A, iron ore need be crushed to below 10mm, and is described for wetting dilution heat of sulfuric acid H
+Ionic concn is 0.01-0.5mol/L, and the consumption of dilution heat of sulfuric acid is 5% of iron ore weight.
In described step B, oxidation is molten soaks that to process be to adopt the spray mode to carry out, and spray liquid is for containing Fe
3+The dilution heat of sulfuric acid of ion, wherein Fe
3+Ionic concn is at 0.1-0.5mol/L, H
+Ionic concn is 0.01-0.5mol/L.
In described step B, the percolating fluid of collection is for containing Fe
3+The dilution heat of sulfuric acid of ion is to contain Fe
3+The dilution heat of sulfuric acid of ion is by anticorrosion storage bin, carries out with the iron ore medium sulphide content that oxidation is molten soaks reaction, and oxidation is molten soaks after reaction the percolating fluid that obtains containing copper, nickel, cobalt element.
Finite concentration described in step C is: when the concentration of nickel ion in percolating fluid or cobalt ion or cupric ion was not less than 5g/L, percolating fluid entered the metal recovery system; During less than 5g/L, percolating fluid enters the tune liquid bath when the concentration of nickel ion in percolating fluid or cobalt ion or cupric ion.
In described step D, for the reagent of acidity adjustment, be sulfuric acid, the concentration of sulfuric acid used is 1-3mol/L.
In described step D, the microbial culture medium composition that adds is: (NH
4) SO
43 g/L, MgSO
40.5 g/L, KCl 0.1 g/L, K
2HPO
40.5 g/L, Ca (NO
3)
20.01 g/L.
In described step e: the biooxidation reactions device that adopts is the reverse-flow constant temperature biochemical reaction post of iron-oxidizing bacterium after immobilization is processed, and controlling temperature is 40 ℃, and flow rate of liquid is according to reaction column height and cross-sectional area calculative determination; Described auxiliary hot charging is set to the anticorrosion water tank of temperature controllable electrically heated, heats the Fe that contains after completing
3+The dilution heat of sulfuric acid of ion is pumped to step B and sprays operation.
After in ore, copper, nickel, cobalt metal element are leached fully, finish that spray is molten soaks operation, the iron ore in anticorrosion storage bin is carried out to the clear water washing, after washing, with oscillating feeder, shed in anticorrosion storage bin iron ore and be delivered to follow-up ore grinding--magnetic concentration working.
The biological metallurgy technology is a new technology selecting the smelting field with fastest developing speed, and the microorganism that this technology is utilized has than strong oxidation iron and sulphur, can be by Fe in conjunction with the biological curing culture technique
2+The ion Quick Oxidation is Fe
3+Ion.As everyone knows, Fe
3+Ion has stronger oxidisability, can be by metallic element oxidation strippings such as the nickel in sulfide, cobalt, copper; Therefore, utilize microorganism to Fe
2+The strong oxidation characteristic of ion makes Fe in leaching solution
3+Ion is regenerated, and can realize the continous-stable stripping of the metallic element such as nickel, cobalt, copper in sulfide.
Beneficial effect of the present invention is as follows:
Utilization of the present invention contains Fe
3+The oxidation dissolution effect of the dilution heat of sulfuric acid of ion to association Cu, Ni and Co element in iron ore, by controlling higher spray liquid temperature, realize carrying out fast of oxidizing reaction, in the short period of time by the association copper in iron ore, nickel, cobalt metal element stripping recovery;
Meanwhile, reacted spray liquid is carried out to bio-oxidation and realize Fe
3+The rapid regeneration of ion, effectively reduce oxidising agent consumption, saves production cost;
In whole technical process, solution is realized closed cycle, is the friendly process of clean and effective;
The application of the method can significantly improve the association Cu, Ni and Co organic efficiency in iron ore, improves the comprehensive utilization of resources rate, increases the business economic income;
The present invention is particularly suitable in the vanadium titano-magnetite of the metallic elements such as association copper, nickel, cobalt, can effectively improve the rate of recovery, the utilization ratio of the metallic elements such as association copper, nickel, cobalt.
The accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention
Wherein, Reference numeral is: 1 exploitation obtains iron ore, 2 fragmentation procedure flow processs, and 3 dilute sulphuric acids are wetting, 4 sprinkling equipments, 5 anticorrosion storage bins, 6 collecting tanks, 7 adjust liquid bath, 8 biooxidation reactions devices, 9 auxiliary hot chargings are put, 10 metal recovery systems.
Embodiment
As shown in Figure 1, associated metal biological recovery technological principle flow process in the iron ore of content production of the present invention.
At first by known method exploitation iron ore 1, then by originally turning round and stretching out the hand technique, reclaim, its concrete operation step is as follows:
A, the iron ore that will exploit are delivered to fragmentation procedure flow process 2, in crushing circuit, iron ore are crushed to less than 10mm; Broken good iron ore is transported in the process of anticorrosion storage bin and carries out dilute sulphuric acid wetting 3, its detailed process is that iron ore is along with the final stage of belt-conveying to anticorrosion storage bin, the travelling belt top has shower nozzle constantly dilute sulphuric acid to be sprayed to the iron ore surface, and most of fine ore will be attached to the raw ore particle surface after dilute sulphuric acid is wetting or spontaneous bonding is agglomerating; Iron ore enters storage bin and stores after dilute sulphuric acid is wetting.
After anticorrosion storage bin 5 in B, steps A fills fully, will contain Fe
3+The dilution heat of sulfuric acid of ion is transported to anticorrosion storage bin, by known sprinkling equipment 4, solution is uniformly distributed in to the iron ore surface; Contain Fe
3+The dilution heat of sulfuric acid of ion penetrates into iron ore gradually by self-gravity action, under capillary action and diffusion by Fe
3+Ion, by the copper in iron ore, nickel, cobalt metal element oxidation dissolution, obtains the to be collected percolating fluid that contains copper, nickel, cobalt element after dissolving;
C, collect in the process of the percolating fluid of step B in processing: when copper in percolating fluid, nickel, when the cobalt metal ion reaches finite concentration, dissolved material gathers the conical lower portion to storage bin by the liquid seepage effect, percolating fluid is admitted to the metal recovery system, after the metal recovery system, the metal that is recycled and raffinate; The metal that reclaims can be made qualified nickel cobalt copper metal product in order to sell, and raffinate returns to collecting tank 6, and the raffinate of collecting tank 6 is transported to the tune liquid bath; When copper, nickel, cobalt concentration of metal ions in the percolating fluid of collecting were low, percolating fluid directly entered same tune liquid bath;
D, in step C, entering, adjust the percolating fluid of liquid bath first to carry out acidity adjustment, then carry out microbial culture medium and add operation;
E, the percolating fluid after step D processes is pumped in the biooxidation reactions device and carries out Fe
3+Ion regeneration; Due to Fe
3+Ion is reduced to Fe after the metallic elements such as oxidation dissolution Cu, Ni and Co
2+Ion, these are rich in Fe
2+After solion has the biooxidation reactions device 8 of iron-oxidizing bacterium by fixing cultivation, the Fe in solution
2+Ion is Fe by Quick Oxidation
3+Ion, realized Fe
3+The regeneration of ion; After regeneration, contain Fe
3+The dilution heat of sulfuric acid of ion puts through auxiliary hot charging the sprinkling equipment 4 that is heated to after 60-80 ℃ be pumped to anticorrosion storage bin 5 tops, realizes the liquid closed cycle of whole technique.
In described steps A, for wetting dilution heat of sulfuric acid H
+Ionic concn is 0.01-0.5mol/L, and the consumption of dilution heat of sulfuric acid is 5% of iron ore weight.
In described step B, the molten spray liquid of processing that soaks of oxidation is for containing Fe
3+The dilution heat of sulfuric acid of ion, wherein Fe
3+Ionic concn is at 0.1-0.5mol/L, H
+Ionic concn is 0.01-0.5mol/L.
Finite concentration described in step C is: when the concentration of nickel ion in percolating fluid or cobalt ion or cupric ion was not less than 5g/L, percolating fluid entered the metal recovery system; During less than 5g/L, percolating fluid enters the tune liquid bath when the concentration of nickel ion in percolating fluid or cobalt ion or cupric ion.
In described step D, for the reagent of acidity adjustment, be sulfuric acid, the concentration of sulfuric acid used is 3mol/L.
In described step D, the microbial culture medium composition that adds is: (NH
4) SO
43 g/L, MgSO
40.5 g/L, KCl 0.1 g/L, K
2HPO
40.5 g/L, Ca (NO
3)
20.01 g/L.
In described step e: the biooxidation reactions device that adopts is the reverse-flow constant temperature biochemical reaction post of iron-oxidizing bacterium after immobilization is processed, and controlling temperature is 40 ℃, and flow rate of liquid is according to reaction column height and cross-sectional area calculative determination; Described auxiliary hot charging is set to the anticorrosion water tank of temperature controllable electrically heated, heats the Fe that contains after completing
3+The dilution heat of sulfuric acid of ion is pumped to step B and sprays operation.
As everyone knows, iron ore selects factory that a plurality of storage bins are arranged usually, after the associated metal element recovery process in a storage bin completes, be transferred to next storage bin and carry out the associated metal recovery process, the storage bin that has completed the associated metal recovery can unload ore deposit and be transported to follow-up grinding operation after the clear water washing.So move in circles, when storage bin quantity, reserves arrange when suitable can ensure follow-up grinding operation to the ore deposit continuity, without the continuous processing that interrupts iron ore and select factory.
It should be noted that: collecting tank, adjust liquid bath, biooxidation reactions device, auxiliary hot charging is put with the metal recovery system, for each storage bin, shares, only need bottom storage bin, parallel works be set percolating fluid is drained to collecting tank.In addition, storage bin need to carry out rotproofing, to avoid causing structure erosion because sulfuric acid soaks, affects production safety.
Claims (9)
1. the recovery process of associated metal element in iron ore, is characterized in that comprising the steps:
After A, iron ore that fragmentation is good are wetting with dilute sulphuric acid, fill up anticorrosion storage bin;
B, the iron ore after processing of step A is carried out to Fe
3+Ionic oxide formation is molten soaks processing, be used to collecting percolating fluid;
C, collect in the process of the percolating fluid of step B in processing: when copper in percolating fluid, nickel, when the cobalt metal ion reaches finite concentration, percolating fluid is admitted to the metal recovery system, the raffinate that obtains after the metal recovery system is extracted metal returns to collecting tank, and the raffinate of collecting tank is transported to the tune liquid bath; When copper, nickel, cobalt concentration of metal ions in the percolating fluid of collecting were low, percolating fluid directly entered same tune liquid bath;
D, in step C, entering, adjust the percolating fluid of liquid bath first to carry out acidity adjustment, then carry out microbial culture medium and add operation;
E, the percolating fluid after step D processes is pumped in the biooxidation reactions device and carries out Fe
3+Ion regeneration; Percolating fluid after regeneration is put after being heated to 60-80 ℃ and is returned to step B and carry out iron ore Fe through auxiliary hot charging
3+Ionic oxide formation is molten soaks operation, then returns and continues step C.
2. the recovery process of associated metal element in iron ore according to claim 1, it is characterized in that: in described steps A, iron ore need be crushed to below 10mm, and is described for wetting dilution heat of sulfuric acid H
+Ionic concn is 0.01-0.5mol/L, and the consumption of dilution heat of sulfuric acid is 5% of iron ore weight.
3. the recovery process of associated metal element in iron ore according to claim 1 is characterized in that: in described step B, oxidation is molten soaks that to process be to adopt the spray mode to carry out, and spray liquid is for containing Fe
3+The dilution heat of sulfuric acid of ion, wherein Fe
3+Ionic concn is at 0.1-0.5mol/L, H
+Ionic concn is 0.01-0.5mol/L.
4. the recovery process of associated metal element according to claim 1 or 3 described iron ores, it is characterized in that: in described step B, the percolating fluid of collection is for containing Fe
3+The dilution heat of sulfuric acid of ion is to contain Fe
3+The dilution heat of sulfuric acid of ion is by anticorrosion storage bin, carries out with the iron ore medium sulphide content that oxidation is molten soaks reaction, and oxidation is molten soaks after reaction the percolating fluid that obtains containing copper, nickel, cobalt element.
5. the recovery process of associated metal element in iron ore according to claim 1, it is characterized in that: finite concentration described in step C is: when the concentration of nickel ion in percolating fluid or cobalt ion or cupric ion was not less than 5g/L, percolating fluid entered the metal recovery system; During less than 5g/L, percolating fluid enters the tune liquid bath when the concentration of nickel ion in percolating fluid or cobalt ion or cupric ion.
6. the recovery process of associated metal element in iron ore according to claim 1 is characterized in that: in described step D, for the reagent of acidity adjustment, be sulfuric acid, the concentration of sulfuric acid used is 1-3mol/L.
7. the recovery process of associated metal element according to claim 1 or 6 described iron ores, it is characterized in that: in described step D, the microbial culture medium composition that adds is: (NH
4) SO
43 g/L, MgSO
40.5 g/L, KCl 0.1 g/L, K
2HPO
40.5 g/L, Ca (NO
3)
20.01 g/L.
8. the recovery process of associated metal element in iron ore according to claim 1, it is characterized in that: the biooxidation reactions device that adopts in step e is the reverse-flow constant temperature biochemical reaction post of iron-oxidizing bacterium after immobilization is processed, controlling temperature is 40 ℃, and flow rate of liquid is according to reaction column height and cross-sectional area calculative determination; Described auxiliary hot charging is set to the anticorrosion water tank of temperature controllable electrically heated.
9. the recovery process of associated metal element according to claim 1 or 8 described iron ores, is characterized in that: heat the Fe that contains after completing
3+The dilution heat of sulfuric acid of ion is pumped to step B and sprays operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310340642.1A CN103397181B (en) | 2013-08-07 | 2013-08-07 | Recovery process of associated metal elements in iron ore |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310340642.1A CN103397181B (en) | 2013-08-07 | 2013-08-07 | Recovery process of associated metal elements in iron ore |
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| CN103397181A true CN103397181A (en) | 2013-11-20 |
| CN103397181B CN103397181B (en) | 2015-03-04 |
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ID=49560879
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Cited By (3)
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| CN107739823A (en) * | 2017-10-17 | 2018-02-27 | 辽宁石油化工大学 | A kind of method of surfactant and silver ion concerted catalysis copper cobalt sulfide ore Bioleaching |
| CN107739822A (en) * | 2017-10-17 | 2018-02-27 | 辽宁石油化工大学 | A kind of method of silver ion catalysis copper cobalt sulfide ore Bioleaching |
| CN113088715A (en) * | 2021-04-15 | 2021-07-09 | 攀钢集团攀枝花钢铁研究院有限公司 | System for realizing continuous leaching of vanadium slag |
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| CN107739822A (en) * | 2017-10-17 | 2018-02-27 | 辽宁石油化工大学 | A kind of method of silver ion catalysis copper cobalt sulfide ore Bioleaching |
| CN113088715A (en) * | 2021-04-15 | 2021-07-09 | 攀钢集团攀枝花钢铁研究院有限公司 | System for realizing continuous leaching of vanadium slag |
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|---|---|
| CN103397181B (en) | 2015-03-04 |
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