CN101736150B - Leaching process for nickel-containing eluvial ores - Google Patents
Leaching process for nickel-containing eluvial ores Download PDFInfo
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- CN101736150B CN101736150B CN2008102258968A CN200810225896A CN101736150B CN 101736150 B CN101736150 B CN 101736150B CN 2008102258968 A CN2008102258968 A CN 2008102258968A CN 200810225896 A CN200810225896 A CN 200810225896A CN 101736150 B CN101736150 B CN 101736150B
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- eluvial
- eluvial ore
- ore
- nickel
- magnesium
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000002386 leaching Methods 0.000 title claims abstract description 110
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title abstract description 26
- 230000008569 process Effects 0.000 title abstract description 17
- 239000011777 magnesium Substances 0.000 claims abstract description 94
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 27
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 87
- 239000002002 slurry Substances 0.000 claims description 62
- 229940037003 alum Drugs 0.000 claims description 34
- 238000005516 engineering process Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 230000003472 neutralizing effect Effects 0.000 claims description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 6
- 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
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 62
- 229910052742 iron Inorganic materials 0.000 abstract description 32
- 239000002893 slag Substances 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract description 5
- 235000019738 Limestone Nutrition 0.000 abstract 1
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 abstract 1
- 229910052935 jarosite Inorganic materials 0.000 abstract 1
- 239000006028 limestone Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910017709 Ni Co Inorganic materials 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000080590 Niso Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910021260 NaFe Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 229910001607 magnesium mineral Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
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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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a leaching process for nickel-containing eluvial ores. The process comprises the following steps of: dividing the nickel containing eluvial ores into high-iron eluvial ores and high-magnesium eluvial ores; performing acid leaching of the high-iron eluvial ores to obtain leaching liquor of the high-iron eluvial ores; adding a jarosite precipitation agent into the leaching liquor of the high-iron eluvial ores, adding the high-magnesium eluvial ores into the leaching liquor of the high-iron eluvial ores for acid leaching so as to make ferric iron precipitated in form of iron alum and obtain the leaching liquor of the high-magnesium eluvial ores; adding an oxidant to the leaching liquor of the high-magnesium eluvial ores so as to convert a small amount of ferrous iron into ferric iron, and adding limestone so as to precipitate the ferric iron; and performing solid-liquid separation of the leaching liquor, obtained after precipitation, of the high-magnesium eluvial ores to obtain leaching slag and leaching liquid containing soluble nickel salt. By the leaching process of nickel-containing eluvial ores, provided by the invention, the iron content in the leaching liquor of the nickel containing eluvial ores is lowered, and the needed quantity of the neutral agent is also reduced.
Description
Technical field
The present invention relates to wet method smelting process, especially, the acidleach that the present invention relates to nickel-containing eluvial ore goes out technology.
Background technology
According to the nickel oxide ore geologic origin, ore bed generally is divided into limonite layer, transition layer and saprolite layer from top to bottom.Wherein the general iron content height of limonite layer, to contain magnesium low, is suitable for using the high pressure leaching-out technique to handle.Transition layer is nickeliferous and contain magnesium rising is all arranged, and is fit to use high pressure to leach or the reduction ammonia-leaching art breading.Though nickeliferous than higher in the saprolite layer, it is also very high to contain magnesium simultaneously, this ore bed generally uses thermal process smelting ferronickel or nickel sulphur.
Chinese patent application CN101001964A discloses a kind of method that is used to leach the laterite that contains limonite and saprolite.It comprises the mineral acid that adding is enough in limonite slurry and under atmospheric pressure leaches to dissolve most soluble iron.Add behind the saprolite with slurry further under being higher than the temperature of normal boiling point, be higher than under the atmospheric pressure and leach one period that is enough to leach most of nickel contained in the saprolite and is settled out most of iron in the solution.Then, reduce the pressure of slurry, and from infusion solution, reclaim nickel and/or cobalt by solvent extraction, resin-in-pulp or other ion-exchange, sulfide or precipitation of hydroxide or other recovery methods subsequently.In the method, when nickel-containing eluvial ore sulfuric acid normal pressure leached, valuable metal nickel, cobalt dissolved while under the leaching condition, impurity elements such as the iron that contains in the ore, magnesium were also leached, and except that containing a large amount of free acids, iron level is also very high in the leach liquor.Traditionally, use usually in the Wingdale and precipitate the acid of being separated out with free acid and iron, therefore not only cause consuming a large amount of sulfuric acid and Wingdale, the amount of residue is also very big.In addition, the iron level that how to reduce in the leach liquor also is a great problem that faces those skilled in the art
Summary of the invention
The present invention is intended to one of solve the aforementioned problems in the prior at least.
For this reason, one object of the present invention is to propose a kind of extract technology that reduces the nickel-containing eluvial ore of iron level in the nickel-containing eluvial ore.
Extract technology according to the nickel-containing eluvial ore of the embodiment of the invention may further comprise the steps:
Nickel-containing eluvial ore is divided into high ferro eluvial ore and high magnesium eluvial ore;
Described high ferro eluvial ore and sour the mixing are carried out acidleach, obtain high ferro eluvial ore leaching slurry;
In described high ferro eluvial ore leaching slurry, add heavy alum agent and described high magnesium eluvial ore so that high magnesium eluvial ore is carried out acidleach, and the dissolved ferric iron is settled out with the form of siderotil in the described high ferro eluvial ore leaching slurry, and obtains high magnesium eluvial ore leaching slurry; And
In described high magnesium eluvial ore leaching slurry, add oxygenant, the ferrous iron in the high magnesium eluvial ore leaching slurry is converted into ferric iron, and add first neutralizing agent ferric iron is precipitated;
To carrying out solid-liquid separation through sedimentary high magnesium eluvial ore leaching slurry to obtain leached mud and the leach liquor that contains soluble nickel salt.
Extract technology according to the nickel-containing eluvial ore of this embodiment, not only ferric iron in the high ferro eluvial ore can be come out by heavy alum reaction precipitation, and can convert a small amount of ferrous iron that is contained in the nickel-containing eluvial ore to ferric iron and be precipitated out, thereby reduce the content of iron in the leach liquor greatly.In addition, under the iron removal technology condition, as neutralizing agent, valuable component cobalt, the nickel with nickeliferous high magnesium mineral effectively leaches simultaneously with the nickeliferous high magnesium ore of part, thereby has reduced the consumption of leaching nickel-containing eluvial ore vitriolic, has saved the consumption of neutralizing agent.
In addition, the extract technology according to the nickel-containing eluvial ore of the embodiment of the invention also has following additional technical feature:
In one embodiment of the invention, described heavy alum agent is selected from and comprises Na
+, K
+Or NH
4 +Vitriol, Na
+, K
+Or NH
4 +Hydrochloride, Na
+, K
+Or NH
4 +Nitrate, Na
+, K
+Or NH
4 +Carbonate, Na
+, K
+Or NH
4 +Supercarbonate, Na
+, K
+Or NH
4 +Oxyhydroxide, and the combination group.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can improve the formation efficiency of siderotil, improve the content of nickel in the leach liquor that contains soluble nickel salt.In one embodiment of the invention, the form of described heavy alum agent with the aqueous solution joined in the described high ferro eluvial ore leaching slurry.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can further improve the formation efficiency of siderotil.
In one embodiment of the invention, described oxygenant is selected from the group by air, oxygen, superoxide, Manganse Dioxide, hypochlorite, oxymuriate, permanganate and their combination.Extract technology according to the nickel-containing eluvial ore of this embodiment can be converted into ferric iron with the ferrous iron in the high magnesium eluvial ore leaching slurry efficiently, and it is precipitated out, and has improved the production efficiency of the extract technology of nickel-containing eluvial ore.
In one embodiment of the invention, described acidleach is leached for normal pressure sulfuric acid.Extract technology according to the nickel-containing eluvial ore of this embodiment can improve the leaching efficiency of high ferro eluvial ore and high magnesium eluvial ore, and can reduce production costs.
In one embodiment of the invention, the acidleach that further comprises described high ferro eluvial ore be temperature carry out under more than or equal to 60 ℃ condition, the acidleach of described high magnesium eluvial ore is to carry out in 85 ℃～110 ℃ scope.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can further improve the leaching efficiency of high ferro eluvial ore and high magnesium eluvial ore.
In one embodiment of the invention, the form of described high ferro eluvial ore furnishing ore pulp mixed with described acid carry out acidleach, and the form of described high magnesium eluvial ore furnishing ore pulp joined in the described high ferro eluvial ore leaching slurry carry out acidleach.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can improve the leaching efficiency of high ferro eluvial ore and high magnesium eluvial ore.
In one embodiment of the invention, comprise that further described high ferro eluvial ore and high magnesium eluvial ore are worn into granularity respectively partly accounts at least 80% for being not more than 100 purposes.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can further improve the leaching efficiency of high ferro eluvial ore and high magnesium eluvial ore.
In one embodiment of the invention, before in described high ferro eluvial ore leaching slurry, adding heavy alum agent, in described high ferro eluvial ore leaching slurry, add siderotil as crystal seed.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can promote the siderotil precipitation to form bigger crystal, be convenient to follow-up separation.
In one embodiment of the invention, further comprise through the high magnesium eluvial ore leaching slurry before the solid-liquid separation behind the heavy alum adding the neutralizing agent that is selected from the group that comprises Wingdale, unslaked lime, white lime and their combination, with the residual acid in the high magnesium eluvial ore leaching slurry that neutralizes.According to the extract technology of the nickel-containing eluvial ore of this embodiment, can reduce the content of acid in the leaching slurry, be convenient to utilize leaching slurry to carry out subsequent disposal, and reduce the infringement of the acid of excessive concentration in the subsequent disposal equipment.
In one embodiment of the invention, the free acid content in the described high magnesium eluvial ore leaching slurry is 2.5g/L～10g/L.Extract technology according to the nickel-containing eluvial ore of this embodiment can guarantee that the leaching of high magnesium eluvial ore is complete, improves the leaching yield of nickel, can also guarantee that the nickel in the leaching slurry exists with the form of soluble salt simultaneously.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Fig. 1 is the synoptic diagram according to the leaching flow process of the nickel-containing eluvial ore of the embodiment of the invention;
Fig. 2 is the synoptic diagram of the leaching flow process of nickel-containing eluvial ore according to another embodiment of the present invention;
Fig. 3 is the synoptic diagram of the leaching flow process of nickel-containing eluvial ore according to another embodiment of the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, is exemplary below by the embodiment that is described with reference to the drawings, and only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Those having ordinary skill in the art will appreciate that, " high magnesium eluvial ore " is meant the nickel-containing eluvial ore that Mg content is higher, for example Mg content is usually greater than about 10% nickel-containing eluvial ore, " high ferro eluvial ore " is meant the nickel-containing eluvial ore that iron level is higher, for example, iron level is usually greater than about 8% nickel-containing eluvial ore.
Below with reference to Fig. 1 the leaching method of nickel-containing eluvial ore is according to an embodiment of the invention described.
At first, nickel-containing eluvial ore is divided into high ferro eluvial ore and high magnesium eluvial ore.Then, the high ferro eluvial ore mixed with for example sulfuric acid (with reference to figure 3) carry out acidleach, obtain high ferro eluvial ore leaching slurry, wherein the principal reaction in the leaching process is:
NiO+H
2SO
4→NiSO
4+H
2O
2FeOOH+3H
2SO
4→Fe
2(SO
4)
3+4H
2O
MgO+H
2SO
4→MgSO
4+H
2O
FeO+H
2SO
4→FeSO
4+H
2O。
Then, in high ferro eluvial ore leaching slurry, add heavy alum agent, sodium sulfate (with reference to figure 3) for example, and high magnesium eluvial ore joined in the high ferro eluvial ore leaching slurry, so that the dissolved ferric iron is settled out (promptly heavy alum removes ferric iron) with the form of siderotil in the high ferro eluvial ore leaching slurry, and obtains high magnesium eluvial ore leaching slurry; Principal reaction (precipitating alum and removing iron and high magnesium eluvial ore leach reaction) is as follows:
3Fe
2(SO4)
3+Na
2SO
4→2NaFe
3(SO4)
2(OH)
6+6H
2SO
4；
H
2SO
4+NiO→NiSO
4+H
2O
MgO+H
2SO
4→MgSO
4+H
2O
FeO+H
2SO
4→FeSO
4+H
2O。
High magnesium eluvial ore joined carry out normal pressure in the high ferro eluvial ore leaching slurry and leach, not only leached the valuable metal in the high magnesium eluvial ore, in also having played simultaneously and the acid effect in the high ferro eluvial ore leaching slurry, reduced the consumption of the required neutralizing agent of neutralizing acid thus.
Then, add oxygenant such as hydrogen peroxide (with reference to figure 3) in high magnesium eluvial ore leaching slurry, so that the dissolved oxidation of divalent becomes ferric iron in the described high magnesium eluvial ore leaching slurry, wherein the principal reaction of Fa Shenging is:
FeSO
4+H
2SO
4+H
2O
2→Fe
2(SO
4)
3+2H
2O
Then, add first neutralizing agent such as Wingdale ferric iron precipitated, wherein principal reaction:
H
2SO
4+CaCO
3→H
2O+CO
2+CaSO
4
Fe
2(SO
4)
3+3CaCO
3+3H
2O→3CO
2+2Fe(OH)
3+3CaSO
4。
High magnesium eluvial ore leaching slurry through post precipitation is carried out solid-liquid separation to obtain leached mud and the leach liquor that contains soluble nickel salt.
For pending nickel-containing eluvial ore being divided into high high ferro eluvial ore of iron content and high magnesium eluvial ore, those skilled in the art can adopt any known method with known ore preparation system the nickel-containing eluvial ore to be distinguished and separated, and for example distinguish according to the difference of the particle diameter of high ferro eluvial ore and high magnesium eluvial ore.In order to obtain leaching effect preferably, in one embodiment of the invention, high ferro eluvial ore and high magnesium eluvial ore are worn into granularity respectively partly account at least 80% for being not more than 100 purposes.If crossing to hang down, granularity may cause increasing substantially of cost.If granularity is excessive, then can cause the remarkable reduction of leaching efficiency.
In one embodiment of the invention, adopt sulfuric acid that the high ferro eluvial ore is carried out normal pressure and leach, can improve leaching efficiency like this, and, therefore can reduce production costs because sulfuric acid is to obtain easily.Adopt the vitriol oil can utilize the vitriol oil in dilution and leach institute of reaction institute liberated heat simultaneously, keep the temperature of reaction system, and do not need or reduce demand, further reduced production cost outside heating installation.In addition, owing to be that normal pressure leaches, therefore not high to the requirement of withstand voltage of equipment, reduced production cost.
In one embodiment of the invention, also contain cobalt in the nickel-containing eluvial ore, therefore, in the leaching process of high ferro eluvial ore, also can react:
CoO+H
2SO
4→NiSO
4+H
2O。
For example, in the process that the high ferro eluvial ore leaches, the temperature that leaches reaction system is controlled at more than 60 ℃, continues 1～4 hour.Can improve the leaching efficiency of valuable metal simultaneously so that leaching speed of response is improved like this.In order further to improve leaching efficiency, the content of keeping free acid in the leach liquor is 10～60g/L, can make like this in the ore that 80～95% valuable metal (nickel and the cobalt that may contain) is leached, most iron and magnesium are also leached in the ore simultaneously.
With reference to figure 2, in order further to improve leaching efficiency, in one embodiment of the invention, described high ferro eluvial ore can be modulated into ore pulp, mix with acid then, carry out acidleach to obtain high ferro eluvial ore leaching slurry.For example, the solids content that high ferro is remained in the ore pulp is 15 (weight) %～45 (weight) %, if too high solids content then can cause the viscosity height, is unfavorable for post-processed; If solid content is low excessively, can cause effective treatment capacity low excessively, and then the corresponding production cost that improved.Equally, in order further to improve leaching efficiency, also described high magnesium eluvial ore can be modulated into ore pulp, and then join in the described high ferro eluvial ore leaching slurry.
After the high ferro eluvial ore is carried out acidleach, in resulting high ferro eluvial ore leaching slurry, add heavy alum agent so that the dissolved ferric iron is settled out with the form of siderotil in the described high ferro eluvial ore leaching slurry.Heavy alum agent can be selected from and comprise Na
+, K
+Or NH
4 +Vitriol, Na
+, K
+Or NH
4 +Hydrochloride, Na
+, K
+Or NH
4 +Nitrate, Na
+, K
+Or NH
4 +Carbonate, Na
+, K
+Or NH
4 +Supercarbonate, Na
+, K
+Or NH
4 +Oxyhydroxide, and the combination group.Because these heavy alum agent all are to obtain easily, and can sink the alum reaction effectively, so can reduce production costs.Adopt the sodium sulfate that is very easy to obtain as heavy alum agent in one embodiment of the invention.The high ferro of having described above after the high ferro eluvial ore leaches leaches the heavy alum agent of adding in the ore pulp, and then adds high magnesium eluvial ore, yet the present invention is not limited to this, for example can add high magnesium eluvial ore and heavy alum agent simultaneously.
In order to improve the efficient of heavy alum reaction, the temperature that heavy alum is reacted is controlled between 85～110 ℃, and the time that heavy alum leaches is 2～6 hours.In addition, in one embodiment of the invention, the form of heavy alum agent with the aqueous solution joined in the high ferro eluvial ore leaching slurry, can promote the short mix of heavy alum agent and high ferro eluvial ore leaching slurry like this, with the heavy alum efficient of further raising.Can also add siderotil as crystal seed (NaFe for example in one embodiment of the invention
3(SO4)
2(OH)
6), to promote the growth of siderotil crystal grain, be convenient to the later stage separation.
According to foregoing heavy alum reaction as can be seen, in the process that forms siderotil, generated a large amount of acid.Usually use a large amount of Wingdales that acid is neutralized traditionally, this need consume a large amount of Wingdales.According to embodiments of the invention, adopt high magnesium eluvial ore as neutralizing agent, the acid that is discharged that neutralized on the one hand, and can utilize these acid that high magnesium eluvial ore is carried out acidleach, make the valuable metal that high magnesium remains in the ore obtain leaching, reduced the sour consumption and the consumption of Wingdale.
In one embodiment of the invention, it is to carry out in 85 ℃～110 ℃ scope that the normal pressure of high magnesium eluvial ore leaches, and can improve the speed and the efficient of leaching like this.
Owing in high magnesium eluvial ore leaching slurry, there is the ferrous iron that heavy alum reaction does not take place, in order to reduce the content of iron in the leach liquor as far as possible, in high magnesium eluvial ore leaching slurry, add oxygenant, dissolved oxidation of divalent in the high magnesium eluvial ore leaching slurry is become ferric iron, so by add first neutralizing agent for example Wingdale ferric iron is precipitated.The oxygenant of adding oxygenant can be selected from the group by air, oxygen, superoxide, Manganse Dioxide, hypochlorite, oxymuriate, permanganate and their combination in high magnesium eluvial ore leaching slurry.The oxidation capacity of these oxygenants is strong, and cost is low, therefore can oxidation of divalent be become ferric iron with low-cost high-efficiency ground.In the foregoing description, preferred air, oxygen, superoxide, this is because these oxygenants of use can be as introducing extra metal ion, for example in the leaching slurry, superoxide such as hydrogen peroxide can be used, also air or oxygen can be in reaction system, blasted.In order can fully to react, the amount that adopts oxygenant can be 0.95～1.3 times of theoretical amount.In one embodiment of the invention, the oxygenant that is adopted is selected from the group that comprises air, superoxide, Manganse Dioxide, hypochlorite, aluminate and permanganate.Can improve the efficient of oxidation like this, can reduce production costs simultaneously.First neutralizing agent is selected from the group that comprises Wingdale, unslaked lime, white lime and their combination in one embodiment of the invention, according to this embodiment, the ferric iron that can efficiently ferrous iron be transformed is precipitated out, and has improved production efficiency, can reduce production costs simultaneously.
Further in one embodiment of the invention, comprise that further the high magnesium eluvial ore leaching slurry after the heavy iron of secondary adds second neutralizing agent that is selected from the group that comprises Wingdale, unslaked lime, white lime and their combination, with the residual acid in the high magnesium eluvial ore leaching slurry that neutralizes.Can reduce the content of acid in the leaching slurry, be convenient to utilize leaching slurry to carry out subsequent disposal, and reduce the infringement of the acid of excessive concentration in the subsequent disposal equipment.In a further embodiment, free acid content in the high magnesium eluvial ore leaching slurry is 2.5g/L～10g/L, the leaching that can guarantee high magnesium eluvial ore like this is complete, the leaching that can guarantee high magnesium eluvial ore like this is complete, improve the leaching yield of nickel, can also guarantee that the nickel in the leaching slurry exists with the form of soluble salt simultaneously.
To resulting high magnesium eluvial ore leaching slurry behind the heavy iron of process secondary is carried out solid-liquid separation at last, to obtain leached mud and the leach liquor that contains soluble nickel salt.Those skilled in the art can select known method and separation known equipment according to practical situation, finish described solid-liquid separation, for example include but not limited to adopt centrifugal separation or suction method or its combination.In the resulting leach liquor that contains soluble nickel salt, the content of iron has been reduced to 0.5～10g/L after solid-liquid separation.
The present invention will be described below by concrete example.
Example 1
Get the nickel-containing eluvial ore sample, its chemical constitution following (%):
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.6 | 0.04 | 18.1 | 8.2 |
Nickel-containing eluvial ore through washing, ore grinding, screening, is obtained granularity respectively and is not more than 100 purposes and partly accounts at least 80% high magnesium eluvial ore and high ferro eluvial ore, and the chemical constitution of wherein high magnesium eluvial ore and high ferro eluvial ore is as follows:
The high ferro eluvial ore:
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.68 | 0.05 | 23.2 | 9.8 |
Magnesium eluvial ore composition:
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.58 | 0.03 | 6.4 | 20.6 |
Get 600g high ferro eluvial ore sulfuric acid normal pressure leaching condition:
Liquid/solid (weight ratio)=2.0/1
Add 98% vitriol oil: 340ml
Temperature: 94 ℃
Time: 2 hours
Leach terminal point PH:0.3
Add the heavy alum of the high magnesium eluvial ore of 150g in the ore pulp after the high ferro eluvial ore leaches and leach, processing condition are:
Temperature: 96 ℃
Time: 4 hours
Na
2SO
4：40g
Terminal point pH value 2.2
The crystal seed amount of returning 50g
Add 100% in the ore pulp after heavy alum leaches and carry out secondary place iron for granularity is not more than 200 purpose lime carbonate and blasts air, processing condition are:
Neutralizing agent: lime carbonate
Neutralizing agent add-on: 104g
2 hours reaction times
Terminal point PH:3.6
Leach the result:
High magnesium eluvial ore is leached ore pulp through suction filtration, obtain the finished product leach liquor.Leached mud process pH value is three pulping and washing of clear water of 2.5, send analysis.The leaching result is as follows:
Leach the quantity of slag: 980g
Leached mud: nickeliferous 0.26% iron content 14.4% contains magnesium 3% siliceous 15%
Leach liquor: nickeliferous 5.5g/L iron content 0.4g/l contains magnesium 42g/l
Slag meter nickel leaching yield: 79.6%
Example 2
Nickel-containing eluvial ore through washing, ore grinding, screening, is obtained granularity respectively and is not more than 100 purposes and partly accounts at least 80% high magnesium eluvial ore and high ferro eluvial ore, and its chemical constitution is as follows
The high ferro eluvial ore:
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.62 | 0.01 | 13.4 | 12.7 |
High magnesium eluvial ore:
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.33 | 0.02 | 6.3 | 19.0 |
Get 620g high ferro eluvial ore sulfuric acid normal pressure leaching condition:
Liquid/solid (weight ratio)=2.0/1
Add 98% vitriol oil: 300ml
Temperature: 94 ℃
Time: 3 hours
Leach terminal point PH:0.8
Add the heavy alum of the high magnesium eluvial ore of 180g in the ore pulp after the high ferro eluvial ore leaches and leach, processing condition are:
Temperature: 96 ℃
Time: 3 hours
Na
2SO
4：54g
Terminal point pH value 1.4
The crystal seed amount of returning 60g
Add 100% in the ore pulp after heavy alum leaches and carry out the secondary deironing for granularity is not more than 200 purpose lime carbonate and adds hydrogen peroxide, processing condition are:
Neutralizing agent: lime carbonate
Neutralizing agent add-on: 30g
1.5 hours reaction times
Terminal point pH:2.8
Leach the result:
High magnesium eluvial ore is leached ore pulp through suction filtration, obtain the finished product leach liquor.Leached mud process pH value is three pulping and washing of clear water of 2.5, send analysis.The leaching result is as follows:
Leach the quantity of slag: 691g
Leached mud: nickeliferous 0.23% iron content 13.3% contains magnesium 3% siliceous 13%
Leach liquor: nickeliferous 4.4g/l iron content 0.14g/l contains magnesium 30g/l
Slag meter nickel leaching yield: 87.4%
Example 3
Nickel-containing eluvial ore is through washing, ore grinding, screening, obtains granularity respectively and is not more than 100 purposes and partly accounts at least 80% high magnesium eluvial ore and high ferro eluvial ore, and (%) is as follows for its chemical ingredients:
The high ferro eluvial ore:
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.60 | 0.04 | 12.3 | 14.2 |
High magnesium eluvial ore:
| Element | Ni | Co | Fe | Mg |
| Content (%) | 1.54 | 0.006 | 6.1 | 19.7 |
Get 585g high ferro eluvial ore sulfuric acid normal pressure leaching condition:
Liquid/solid (weight ratio)=2.0/1
Add 98% vitriol oil: 335ml
Temperature: 94 ℃
Time: 1 hour
Leach terminal point sulfuric acid: 60g/l
Add the heavy alum of the high magnesium eluvial ore of 130g in the ore pulp after the high ferro eluvial ore leaches and leach,, processing condition are:
Temperature: 96 ℃
Time: 6 hours
KCl：60g
Terminal point pH value 1.8
The crystal seed amount of returning 60g
Add sodium hydroxide in the ore pulp after heavy alum leaches and charge into oxygen and carry out the secondary deironing, processing condition are:
Neutralizing agent: sodium hydroxide
Neutralizing agent add-on: 38g
3 hours reaction times
Terminal point pH:3.6
Leach the result:
High magnesium eluvial ore is leached ore pulp through suction filtration, obtain the finished product leach liquor.Leached mud process pH value is three pulping and washing of clear water of 2.5, send analysis.The leaching result is as follows:
Leach the quantity of slag: 717g
Leached mud: nickeliferous 0.11% iron content 11.4% contains magnesium 1% siliceous 10%
Leach liquor: nickeliferous 4.5g/L iron content 0.3g/l contains magnesium 40.5g/L
Slag meter nickel leaching yield: 91.4%
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification that scope of the present invention is by claims and be equal to and limit to these embodiment.
Claims (7)
1. the extract technology of a nickel-containing eluvial ore is characterized in that, may further comprise the steps:
Nickel-containing eluvial ore is divided into high ferro eluvial ore and high magnesium eluvial ore;
Described high ferro eluvial ore and high magnesium eluvial ore are worn into granularity respectively partly account at least 80% for being not more than 100 purposes;
Described high ferro eluvial ore and sour the mixing are carried out acidleach, obtain high ferro eluvial ore leaching slurry, wherein, the free acid content in the described high ferro eluvial ore leaching slurry is 10-60g/L;
In described high ferro eluvial ore leaching slurry, add heavy alum agent and described high magnesium eluvial ore so that high magnesium eluvial ore is carried out acidleach, and the dissolved ferric iron is settled out with the form of siderotil in the described high ferro eluvial ore leaching slurry, and obtains high magnesium eluvial ore leaching slurry; And
In described high magnesium eluvial ore leaching slurry, add oxygenant, the ferrous iron in the high magnesium eluvial ore leaching slurry is converted into ferric iron, and add first neutralizing agent ferric iron is precipitated;
To carrying out solid-liquid separation through sedimentary high magnesium eluvial ore leaching slurry to obtain leached mud and the leach liquor that contains soluble nickel salt;
High magnesium eluvial ore leaching slurry after through heavy alum before the solid-liquid separation adds the neutralizing agent that is selected from the group that comprises Wingdale, unslaked lime, white lime and their combination, with the residual acid in the high magnesium eluvial ore leaching slurry that neutralizes, the free acid content that described high magnesium eluvial ore leaches in the liquid of ore deposit is controlled to be 10g/L.
2. the extract technology of nickel-containing eluvial ore according to claim 1 is characterized in that, described heavy alum agent is selected from and comprises Na
+, K
+Or NH
4 +Vitriol, Na
+, K
+Or NH
4 +Hydrochloride, Na
+, K
+Or NH
4 +Nitrate, Na
+, K
+Or NH
4 +Carbonate, Na
+, K
+Or NH
4 +Supercarbonate, Na
+, K
+Or NH
4 +Oxyhydroxide, and the combination group.
3. the extract technology of nickel-containing eluvial ore according to claim 1 is characterized in that, described oxygenant is selected from the group by air, oxygen, superoxide, Manganse Dioxide, hypochlorite, oxymuriate, permanganate and their combination.
4. the extract technology of nickel-containing eluvial ore according to claim 1 is characterized in that, described acidleach is leached for normal pressure sulfuric acid.
5. the extract technology of nickel-containing eluvial ore according to claim 4, it is characterized in that, it is to carry out under more than or equal to 60 ℃ condition in temperature that the normal pressure of described high ferro eluvial ore leaches, and the normal pressure of described high magnesium eluvial ore to leach be to carry out in 85 ℃-110 ℃ scope.
6. the extract technology of nickel-containing eluvial ore according to claim 1, it is characterized in that, the form of described high ferro eluvial ore furnishing ore pulp mixed with described acid carry out acidleach, and the form of described high magnesium eluvial ore furnishing ore pulp joined in the described high ferro eluvial ore leaching slurry carry out acidleach.
7. the extract technology of nickel-containing eluvial ore according to claim 1 is characterized in that, adds the siderotil as crystal seed add heavy alum agent in described high ferro eluvial ore leaching slurry before in described high ferro eluvial ore leaching slurry.
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| CN111100985B (en) * | 2019-12-30 | 2021-05-18 | 荆门市格林美新材料有限公司 | A kind of comprehensive treatment method of sodium ammonium waste liquid applied to laterite nickel ore |
| CN112442604A (en) * | 2020-11-12 | 2021-03-05 | 格林美（江苏）钴业股份有限公司 | Oxidation process for ferrous iron in cobalt ore leaching solution |
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