CN102203307A - Method for treating nickel laterite ore - Google Patents
Method for treating nickel laterite ore Download PDFInfo
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- CN102203307A CN102203307A CN2009801438769A CN200980143876A CN102203307A CN 102203307 A CN102203307 A CN 102203307A CN 2009801438769 A CN2009801438769 A CN 2009801438769A CN 200980143876 A CN200980143876 A CN 200980143876A CN 102203307 A CN102203307 A CN 102203307A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
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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
Abstract
The invention relates to a method for processing laterite ores so that the metals contained in the laterites are turned into water-soluble form for the recovery of valuable metals, such as nickel and cobalt. Different types of nickel laterites are processed at the same time without being separated according to their iron and/or magnesium content. When laterites are pretreated with concentrated mineral acid so that the metals contained in the laterites react to form water-soluble salts, the silicates contained in the laterites are partially decomposed and postleaching liquid-solid separation becomes easier than it was previously. According to the method, the water vapour generated in the ore and acid reaction stage is utilised in ore drying and the unreacted mineral acid is recycled to the front end of the process.
Description
Invention field
The present invention relates to a kind of method of handling laterite, so that metal contained in the laterite is converted into water miscible form so that reclaim metal values, for example nickel and cobalt.Dissimilar nickel laterites can be handled simultaneously, and need not be according to their iron and/or the content of magnesium and with its separation.So that when contained metal reaction forms water-soluble salt in the laterite, silicate contained in the laterite is partly decomposed when using dense mineral acid that laterite is carried out pre-treatment, and the back leach in liquid-solid separation become and be more prone to than before this.According to this method, the water vapour that produces in the conversion zone with ore and acid is used for the drying of ore, and unreacted mineral acid is recycled to the front end of technology.
Background of invention
Disclose a kind of method in the U.S. Pat 4125588, wherein before nickel leaches, nickel laterite ores has been carried out pre-treatment with concentrated acid.This method described to laterite ore carry out drying so that the moisture content of ore less than 1%.It is the 65-100 order that dried ore powder is broken to the grain graininess scope.Ore after the pulverizing was sneaked in the concentrated acid with mass ratio in about 1: 1.By adding entry to start the metal sulfate reaction in the mixture that contains laterite and acid, the amount that adds entry accounts for the ratio of 3-40% of the quality of laterite.Metal after the sulphating leaches in the water.
U.S. Patent application US2006/0002835 has described a kind of method, and wherein laterite leached by two stages.In first stage, laterite ore mixes with the vitriol oil.Second stage, ore/acid mixture leaches then by water slurryization, so that nickel and cobalt dissolving.The feature of this method is that being used for pretreated sulfuric acid consumption is stoichiometric ratio with regard to the non-ferrous metal of ore, but not is stoichiometric ratio with regard to iron.According to embodiment 5, acid/ore deposit ratio is 0.65.A small amount of excessive acid is favourable, makes a spot of iron also dissolve, because this makes nickel and cobalt realize maximum dissolving.The leaching stage of this method can carry out under 95-105 ℃, perhaps carries out in autoclave, and the temperature maximum value is 150 ℃ in this autoclave, and pressure is equivalent to saturated vapor pressure.For improving the dissolving of cobalt, some appropriate reductant are joined leaching stage, for example sulfurous gas.Owing to use the acid that is lower than stoichiometric ratio in the initial period of leaching processing, only some laterite dissolving.This method is used to leach-and residence time of precipitate phase has to very long.The validity of this method requires the easy dissolving sapropel soil type laterite (saprolitic laterite) in the laterite to account for the overwhelming majority, thereby it is played a role in the ferric iron areas of sedimentation.
The additive method that reclaims nickel and other metal values in the prior art from laterite has very been described among the U.S. Patent application US2006/0002835 all sidedly.
Because extract technology produces very tiny and is gelatinous leaching residue under the normal pressure, this proposes special requirement for separating and wash of solid and solution, has brought very big challenge to this method.Although the process patent that much leaches based on normal pressure is arranged, does not all give enough concerns for this problem.The isolating difficulty of solid-liquid also depends on the kind of laterite on the certain degree.
Goal of the invention
The objective of the invention is to eliminate the problem that occurs in the method early, and realize that a kind of method that leaches laterite, special feature are solid and solution separating are not caused problem.The present invention also aims to by utilizing the heat that generates in the reaction and reclaiming the economy that the acid that does not consume in the reaction improves the laterite treatment process.
Summary of the invention
The present invention relates to a kind of processing nickel laterite ores to promote to reclaim nickel and cobalt and liquid-solid isolating method.According to present method,
A) be used to the laterite ore of pulverizing be carried out drying from the steam of the processing section of back,
B) dried ore is dry grinded,
C) fine ore is sent to the acid treatment mixing section that uses dense mineral acid to carry out, and wherein ore is mixed in the acid equably, and sour consumption is at least stoichiometric ratio with regard to metal contained in the ore,
D) mixture of ore and acid is dropped in environmental stress and under the temperature between the boiling point of 150 ℃ and acid the acid treatment conversion zone that carries out, thereby described acid and ore are reacted each other; The water vapour that reaction generates is recovered and circulates and is used for the drying of ore,
E) laterite ore after the acid treatment is sent to carried out acid recovery, wherein remaining unreacted acid is reclaimed by evaporation in the reaction of acid treatment mixing section, and acid subsequently is cooled and is circulated back to described mixing section,
F) laterite ore that will leave after the acid treatment of acid recovery is delivered to the metal extracting stage, and this section utilizes water to carry out.
Be that the particle diameter of the laterite ore after the pulverizing is for accounting for 90% less than 10mm according to the characteristics of method of the present invention.In the dry grinding stage, ore being milled to 90% particle diameter is favourable less than 500 μ m, and preferred 90% less than 150 μ m.
According to this method, as yet not under the temperature of big quantitative response, acid and laterite are mixed into uniform mixture in metal and acid.
In the acid treatment according to this method, this acid treatment comprises the mixing section and the conversion zone of acid and ore, and the metal in the laterite ore forms the water-soluble salt of this mineral acid.Mineral acid is following at least a: sulfuric acid, nitric acid, or hydrochloric acid, or their both mixtures at least.The concentration of mineral acid is preferably 70-98wt%.When mineral acid was sulfuric acid, conversion zone was that sulphating is handled.
Characteristics according to method of the present invention are to heat in this section front portion dropping into the acid of conversion zone and the mixture of ore.In this method, the characteristics of acid recovery section are to evaporate the laterite of unreacted acid after acid treatment.Evaporation is undertaken by the boiling point that for example laterite after the acid treatment is heated to acid under normal pressure or is used negative pressure to carry out.
According to one embodiment of the invention, the slurry that leaves the water logging section is delivered to neutralizing zone, neutralizing zone by in and slurry make iron precipitation.
According to another embodiment of the invention, the slurry that forms during water logging goes out directly is sent to ion exchange treatment, and wherein ion exchange resin is at nickel and cobalt selectively.After the ion exchange treatment, waste slurry is sent to neutralization, so that other precipitated metals.
According to the 3rd embodiment of the present invention, the slurry that forms during water logging goes out is sent to cementation (cementation) section, at this section metal values nickel and cobalt by iron powder cementation from solution.To metal values cementation with after magnetic separates, waste slurry is sent to neutralization, so that other precipitated metals.
According to the 4th embodiment of the present invention, neutralizing agent is dropped in the water extracting stage of the material after the acid treatment, make iron with the form precipitation of oxyhydroxide, and nickel and cobalt still exist with the water-soluble salt form.Neutralizing agent is preferably lime and/or milk of lime.Leach and iron precipitation stage after, with the form of oxyhydroxide, sulfide or carbonate nickel and cobalt are precipitated.
According to another embodiment of the present invention, used mineral acid is a sulfuric acid, and the material after at least some acid treatment is sent to thermal treatment, and iron sulfate is decomposed into sulfur oxide and rhombohedral iron ore in thermal treatment.Sulfur oxide is sent to sulphuric acid plant and prepares sulfuric acid, and this sulfuric acid is used for the acid treatment of laterite ore.Contain the heat treated material of leaving of rhombohedral iron ore and water-soluble metal salt and sent to water logging.
List of drawings
Fig. 1 is the schema of one embodiment of the invention, and
Fig. 2-the 5th, the schema of other embodiments of the present invention.
Detailed Description Of The Invention
According in the method for the present invention, the nickel laterite that all are dissimilar, for example limonite, saprolite ore deposit and nontronite, or their mixture, handle by dense mineral acid (70-98%) together, so that the water-soluble salt of contained metal formation mineral acid in the laterite.Even pending laterite exists with the laterite of several different types,, still do not need separated from one another with them according to method of the present invention.If contained master metal nickel, cobalt, manganese, magnesium, aluminium, chromium and iron in the laterite, wherein nickel and cobalt are mainly thought metal values.Mineral acid mainly is meant sulfuric acid, hydrochloric acid or nitric acid, or their mixture.Hereinafter for simplicity, we mention sulfuric acid, but this method is equally applicable to other mineral acids.
Equally for simplicity, used the laterite of processing of term sulphating and sulphating, but these terms do not mean that foundation method of the present invention limits the use of other acid.
Usually, liquid-solid separation has been proved to be existing problems in the normal pressure of laterite leaches.The objective of the invention is to realize a kind of method, thereby Gu make liquid/stalling characteristic good, and might make that therefore this method becomes economic method.
This technology particularly importantly, the acid and the mixing of laterite can be carried out under optimum condition.In this case, main points are that laterite is exsiccant and has enough thin particle diameter.Yet normal enriched material rugosity is enough to satisfy the degree of grinding of laterite, and in other words, this method does not need actual fine grinding.If particle diameter is thick excessively, acid can't be penetrated into laterite particulate inside, and the result generates water-soluble salt, promptly in the situation that the vitriolic sulphating is handled, will slack-off and often can't finish.On the other hand, because the solution heat of acid uses moist laterite can cause the activation of sulfation reaction, it will hinder laterite and acid mixes.
Be described by schema in accompanying drawing 1 according to method of the present invention.According to this method, laterite ore is crushed to 90% particle diameter less than 10mm.The ore of pulverizing is in dryer section 1 water vapour seasoning, and this water vapour is to produce in the sulfation reaction in subsequent reaction section 4.Dried laterite ore is sent to dry grinding section 2, and by using ball mill for example that it typically is milled to 90% particle diameter less than 500 μ m, preferred 90% less than 150 μ m there.
Dry and grind after, laterite is sent to acid treatment mixing section 3, the laterite ore and vitriol oil uniform mixing each other in suitable device wherein, described equipment for example is mixing screw, drum reactor, or the reactor of other kinds.The add-on of acid is stoichiometric ratio at least with regard to the metal in the laterite.The temperature of mixing section adjusted to preferably be lower than 100 ℃, make that the mixture that produces is non-sclerous, and be easy to further processing.Its objective is under the temperature that sulphating does not take place as yet and operate.
After mix stages, mixture is delivered to conversion zone 4, wherein at first improve technological temperature by indirect heating, the reaction between laterite and the acid after this begins to generate heat, and technology becomes autothermal to a great extent.Conversion zone is at normal pressure and carrying out under 150-300 ℃ temperature greatly.Technology just section can be for example by inside or indirect heating for example burner add heat so that required chemical reaction optimization.The technological temperature maximum can be the boiling point of acid, that is, when selecting sulfuric acid for use, working temperature is lower than 339 ℃.Laterite contains a lot of crystal water usually, in addition, for example can produce considerable water in the sulphating processing reaction, and these water evaporate in heat-processed.The water vapour that produces is recovered and is used to dry laterite, as previously mentioned.According to the method in the U.S. Pat 4125588, the treatment stage of sulphating, add entry, but, do not add water at this conversion zone according to method of the present invention.Mixing section and conversion zone are the same with afterwards extracting stage, all occur under the environmental stress, and the system that is to say is under normal pressure.To leave acid-treated material be solid and be actually powder, therefore is convenient to handle.
Use excessive acid with regard to metal contained in the laterite can improve the transformation of metal to water-soluble salt (sulphating processing), and therefore improves the recovery degree of metal.Shortcoming in this case is to have increased acid and neutral cost.The acid that reduces in the technology by the circulation of using unreacted residual acid consumes.Residual acid evaporates the laterite after acid treatment in acid recovery section 5.For example evaporate for 339 ℃ to the boiling point of acid by the laterite that adds after hot acid treatment.Another kind of mode is to use negative pressure, the boiling point lowering that makes acid.After evaporation, acid is cooled and is condensed into liquid, and is cycled back to mixing section 3.
When laterite during, can describe by the reaction equation of simplifying below for example with sulfuric acid reaction:
2FeOOH+3H
2SO
4＝＞Fe
2(SO
4)
3+4H
2O (1)
NiO+H
2SO
4＝＞NiSO
4+H
2O (2)
2CoOOH+3H
2SO
4＝＞Co
2(SO
4)
3+4H
2O (3)
Al
2O
3+3H
2SO
4＝＞Al
2(SO
4)
3+3H
2O (4)
MgO+H
2SO
4＝＞MgSO
4+H
2O (5)
M
2O+H
2SO
4＝＞M
2SO
4+H
2O(M＝Na，K) (6)
According to method of the present invention, utilize following phenomenon, according to this phenomenon, contained silicate can partial dehydration in the concentrated acid treating processes in the laterite, and generation in this phenomenon each section that also may be to carry out under the higher temperature.Simultaneously, the crystalline structure of silicate is beneficial to liquid-solid subsequently isolating mode and part takes place changes with a kind of.
According to Fig. 1, after acid treatment and acid recovery section, the solid fines that contains this sour water-soluble salt is sent to actual extracting stage 6, in this section water is delivered in the solid.The water extracting stage carries out under atmospheric condition, that is, and and under 80-105 ℃ temperature and environmental stress.The time length of this extracting stage is depended on the composition of particle diameter and laterite ore, usually between 1-2h.
The extracting stage 6 of the laterite after acid treatment, the dissolving metal of all contained sulphatings in the laterite.According to the alternatives of Fig. 1, by in neutralizing zone 7 with some suitable neutralizing agent neutralization solutions, the iron that mainly exists with trivalent separates from pregnant solution nickel salt and cobalt salt remain water miscible so that iron is precipitated.Preferred neutralizing agent is Wingdale and/or milk of lime, thereby makes the form precipitation of iron with oxyhydroxide.If wish the form precipitation of iron, can also use other known precipitation agent, for example sodium sulfate with for example jarosite.Aluminium and most chromium and iron precipitate simultaneously, thereby make them enter the leaching residue.
Water extracting stage 6 and in and after 7, carry out solids constituent from 8, use conventional separation method to make solid and liquid separation, for example concentrate and/or filter, thereby make the material of staying in the solid, for example iron and silicate are with solution separating.All dissolved metals particularly comprise the solution (PLS) of metal values, are sent to subsequently section so that this solution is done further processing, and the dissolved ion is separated effectively there, and is sent to next processing section (describing in detail in chart).As mentioned above, in the foundation processing to laterite of the present invention, the structure of silicate changes, so that solution-solids constituent is from not causing gelation and therefore being easy to carry out.The characteristics of this method are, because the character of leaching residue is compared with directly carrying out acidleach afterwards, the concentrated and washing of solution can be carried out in relative much smaller equipment.Simultaneously, with respect to currently known methods, the ratio of remaining metal values is also obviously little a lot of in the final refuse.
From solution, reclaim required metal values such as nickel and cobalt and undertaken by currently known methods, at the iron post precipitation with them with oxyhydroxide, sulfide or carbonate form precipitation, this also describes in detail in chart.In precipitation process, use common chemical, for example hydrogen sulfide, sodium pyrosulfate, lime, magnesium hydroxide or yellow soda ash.
Use lime or a kind of corresponding neutralizing agent, (scope is 9-11 usually) removes magnesium and manganese from solution under high pH value, thereby Mg and Mn are mainly precipitated with the form of oxyhydroxide.
Fig. 2 has introduced second kind of alternative embodiment, is used to handle the surplus materials that leaves water logging section 6.Initial each section of this method carries out as mentioned above.The characteristics of this alternatives are, after leaching, do not carry out liquid-solid separation, but whole slurries are delivered to ion exchange treatment 9, for example nickel and cobalt directly reclaim from slurry according to the notion that is called as " resin is in ore pulp " by ion exchange resin metal values there.After ion exchange resin absorption, resin is sent to wash-out section 10, carries out wash-out with acid or equivalent eluent there, and the elute soln that contains metal values is sent to further processing.Resin is circulated back to ion-exchange section 9.Reclaiming metal values from elute soln can for example be undertaken by sulfide precipitation or liquid-liquid extraction, is not described in detail herein.Leave the waste residue that contains iron and silicate of ion-exchange section, be sent to neutralizing zone, at neutralizing zone, iron, aluminium, manganese and magnesium etc. are precipitated out from solution.
Fig. 3 shows the third alternative embodiment of the present invention, is used to handle leaving water and leaches 6 surplus materials.Cementation section 11 by with the iron powder of suitable thickness with desirable metal values, as nickel and cobalt, cementation, thereby from the slurry that leaves extracting stage 6, reclaim them, and metal values has been stayed in the iron powder.In this case, slurry does not carry out liquid-solid separation yet before reclaiming metal values.Iron powder is for example separated from slurry by weak magnetic separator in magnetic segregation section 12.The mixture of iron powder and metal values is sent to metal values extracting stage 13, and mixture is by acidleach there, and solution is sent to subsequently processing section to reclaim nickel and cobalt.The waste residue that contains iron and silicate that produces when the cementation metal values is sent to neutralizing zone, at this iron leg, and aluminium, manganese and magnesium etc. is precipitated out from solution.
Disclosed foundation technology of the present invention also can be made amendment according to Fig. 4 among Fig. 1, wherein show, water extracting stage 6 after the acid treatment also can be used as associating extracting stage 14 to carry out, there, the laterite ore after the acid treatment can directly handle with neutralizer by the Wingdale that adds the water aequum.The precipitation of the leaching of water-soluble salt in the laterite like this,, solution neutralization and resulting iron is all carried out at same section.In this alternatives, only need a solid-liquid separation section 15, herein, the throw out and the solution separating of formed leaching residue, gypsum and iron.The PLS solution that contains nickel and cobalt is gone to processing subsequently, and for example sulfide precipitation section 16 and final solution are gone to the removal section 17 of magnesium and manganese, by neutralization metal are precipitated from solution herein.Final solution mainly is water, and it can be circulated back to extracting stage (not being shown specifically in the drawings).
Fig. 5 has disclosed another alternative embodiment of the present invention, is used for the further processing to laterite after the acid treatment.Leave mix and the material of conversion zone after acid recovery section 5 by all or part of input thermal treatment section 18, this section is carried out in drum furnace or fluid bed furnace.The heat energy required in the thermal treatment section can obtain by for example coal combustion.When used acid was sulfuric acid, the iron reaction in acid treatment section laterite generated iron sulfate, and this iron sulfate is decomposed into rhombohedral iron ore and sulfur oxide in the thermal treatment section.Sulfur oxide gas (SO
2And SO
3) being sent to sulphuric acid plant 19, the acid of producing from this sulphuric acid plant is recycled to acid treatment section 3.The material that contains rhombohedral iron ore is sent to water logging and is gone out 6, herein, and nickel, cobalt and magnesium dissolving and by above-described method recovery.Before thermolysis, free acid residual in the laterite after the acid treatment can be evaporated by the method for describing before.The advantage of this technology is that waste material is easy to handle, and reduces the consumption of acid.
Embodiment
By following examples working method is described.The laterite ore of using in the present embodiment is a nontronite, and its composition is listed in the table 1.Before experiment, dry ore, and be crushed to particle diameter 100% less than 1mm.
The composition of table 1. nickel laterite
Embodiment 1.
With ball mill the exsiccant laterite is ground to 95% particle diameter less than 105 μ m.Used acid is sulfuric acid.Sulfuric acid and laterite mix with mass ratio at mixing section at 1: 1.The 348g mixture drops into the conversion zone rotary kiln, and the central point temperature of stove is 250 ℃.Mixture is approximately 30 minutes in the residence time of stove hot-zone.The weight of rotary kiln product is 296.3g.The composition of rotary kiln product is listed in the table 2.
The composition of table 2. rotary kiln product
After handling in rotary kiln, the laterite with the 294.8g sulphating in extracting stage leaches with 1 premium on currency in the titanium reactor.Leaching experiment continues 6 hours, and slurry temperature is 80 ℃.In the leaching process, the metal content in the solid is listed in the table 3.The weight that leaches residue is 140.2g.Be listed in the table 4 to the solution metal productive rate.
Solid metal content in table 3. leaching process
Table 4. is to the solution metal productive rate
Embodiment 2
Grinding describes by the following examples for the importance of nickel productive rate in the leaching process.Use the ore that does not grind to experimentize, it has been crushed to particle diameter 100% less than 1mm.Sulfuric acid and laterite mix with mass ratio at mixing section at 1: 1.Conversion zone carries out in rotary kiln, drops into the 400g mixture in this rotary kiln.Stove central point temperature is 250 ℃.Mixture is approximately 27 minutes in the residence time of stove hot-zone.The weight of rotary kiln product is 279.1g.The one-tenth composition of rotary kiln product is listed in the table 5.
The composition of table 5. rotary kiln product
After handling in rotary kiln, the laterite in the leaching stage with the 200g sulphating leaches with 1 premium on currency in 1 liter of titanium reactor.Leaching experiment continues 6 hours, and slurry temperature is 80 ℃.The solid metal content is listed in the table 6 in the leaching process.The weight that leaches residue is 66.2g.Be listed in the table 7 to the solution metal productive rate.
Solid metal content in table 6. leaching process
Table 7. is to the solution metal productive rate
Embodiment 3
Acid and laterite mass ratio illustrate by the following examples for the importance of nickel productive rate in the leaching process.As embodiment 1, carry out in addition two experiments, difference is acid and the ratio of laterite is 0.6 and 0.8kg/kg.The acid amount that in the sulfation reaction of this processing, consumes can be after water logging goes out by volumetric soiutions in remaining acid determine.Table 8 has been listed acid and the influence of laterite ratio for the amount of metal productive rate and unreacted acid.Show in the table that when increasing the acid amount corresponding to laterite weight, the metal productive rate is obviously improved.In this case, the unreacted acid amount also increases.The result shows that for the nickel productive rate of maximum, the amount of used acid and the mass ratio of laterite should be approximately 1: 1.When the method for introducing with the present invention with sour circulation time, can realize the great amount of cost saving relevant with the acid that consumes.
Table 8. adopts different acid-laterite ratios, to solution metal productive rate and remaining acid amount
Claims (23)
1. handle nickel laterite ores to reclaim nickel and cobalt and to promote liquid-solid isolating method for one kind, it is characterized in that according to present method,
A) be used to the laterite ore of pulverizing be carried out drying (1) from the steam of the processing section of back,
B) to dried ore dry grind (2),
C) fine ore is sent to the acid treatment mixing section (3) that uses dense mineral acid, wherein ore is mixed in the acid equably, and sour consumption is at least stoichiometric ratio with regard to metal contained in the ore,
D) the acid treatment conversion zone (4) that the mixture of ore and acid is dropped in environmental stress and carries out under the temperature between the boiling point of 150 ℃ and described acid is so that described acid and ore react each other; The drying (1) that the water vapour that generates in the reaction is recovered and circulates and be used for ore,
E) laterite ore after the acid treatment is sent to carried out acid recovery (5), wherein unreacted acid is reclaimed by evaporation, and this acid subsequently is cooled and is circulated back to mixing section (3),
F) laterite ore that will leave after the acid treatment of acid recovery is delivered to metal extracting stage (6), and this section utilizes water to carry out.
2. according to the method for claim 1, the particle diameter of laterite ore that is characterised in that pulverizing is for accounting for 90% less than 10mm.
3. according to the method for claim 1, be characterised in that in the dry grinding stage (2) ore to be crushed to 90% particle diameter less than 500 μ m.
4. according to the method for claim 3, be characterised in that in the dry grinding stage (2) ore to be crushed to 90% particle diameter less than 150 μ m.
5. according to the method for claim 1, be characterised in that metal as yet not with the temperature of described acid-respons under, described acid and laterite are mixed into uniform mixture.
6. according to the method for claim 1, be characterised in that the metal in the laterite ore forms the water-soluble salt of described mineral acid in acid treatment (3,4).
7. according to the method for claim 1, be characterised in that described mineral acid is following at least a: sulfuric acid, nitric acid or hydrochloric acid, or at least two kinds mixture in these.
8. according to the method for claim 1, the concentration that is characterised in that described mineral acid is 70-98%.
9. according to the method for claim 1 and 7, be characterised in that described mineral acid is a sulfuric acid, and conversion zone (4) is that sulphating is handled.
10. according to the method for claim 1, be characterised in that and heat at the initial portion of this section dropping into the acid of conversion zone (4) and the mixture of ore.
11. more ask 1 method according to right, be characterised in that laterite to the boiling point of described acid by adding after hot acid treatment makes unreacted acid evaporation in the acid recovery section (5) under normal pressure.
12., be characterised in that and utilize negative pressure that the unreacted acid in the acid recovery section (5) is evaporated according to the method for claim 1.
13. according to the method for claim 1, be characterised in that the slurry of leaving water extracting stage (6) delivered to neutralizing zone (7), make the iron precipitation by the described slurry that neutralizes here.
14. according to the method for claim 1, be characterised in that the slurry that forms directly sent to and carry out ion exchange treatment (9) that wherein ion exchange resin is at nickel and cobalt selectively in water extracting stage (6).
15., be characterised in that and send to neutralization from the waste residue of ion exchange treatment (9) so that other precipitated metals according to the method for claim 14.
16. method according to claim 1, be characterised in that will go out the slurry that forms in (6) in water logging delivers to cementation section (11), in this section, metal values nickel and cobalt be by iron powder cementation from solution, and separate (12) by magnetic and separate from slurry.
17. according to the method for claim 16, be characterised in that metal values being carried out cementation (11) and separate (12) afterwards that described waste residue is sent to neutralization so that other precipitated metals with magnetic.
18. according to the method for claim 1, be characterised in that drop into neutralizing agent in the water extracting stage (14) of the material after acid treatment so that iron with the form precipitation of oxyhydroxide, and nickel and cobalt still are water-soluble salt.
19., be characterised in that neutralizing agent is Wingdale and/or milk of lime according to the method for claim 18.
20. according to claim 1 and 18, be characterised in that leach and iron precipitation stage (14) afterwards, with oxyhydroxide, the form of sulfide or carbonate is carried out the precipitation (16) of nickel and cobalt from solution.
21. according to the method for claim 1, the mineral acid that is characterised in that use is a sulfuric acid, and the material after at least a portion acid treatment is sent to heat-treat (18), iron sulfate is decomposed into sulfur oxide and rhombohedral iron ore in this thermal treatment.
22. according to the method for claim 21, be characterised in that sulfur oxide delivered to sulfuric acid apparatus (19) to make sulfuric acid that this sulfuric acid is used for laterite ore is carried out acid treatment.
23., be characterised in that the material of being made up of rhombohedral iron ore and water-soluble metal salt that leaves thermal treatment (18) is delivered to water logging goes out (6) according to the method for claim 21.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20080603 | 2008-11-03 | ||
| FI20080603A FI121180B (en) | 2008-11-03 | 2008-11-03 | A method for treating nickel plater ore |
| PCT/FI2009/050870 WO2010061045A1 (en) | 2008-11-03 | 2009-10-29 | Method for treating nickel laterite ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102203307A true CN102203307A (en) | 2011-09-28 |
| CN102203307B CN102203307B (en) | 2015-03-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980143876.9A Expired - Fee Related CN102203307B (en) | 2008-11-03 | 2009-10-29 | Method for treating nickel laterite ore |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2350327A4 (en) |
| CN (1) | CN102203307B (en) |
| AU (1) | AU2009321543B2 (en) |
| BR (1) | BRPI0921490A2 (en) |
| CU (1) | CU23937B1 (en) |
| EA (1) | EA018749B1 (en) |
| FI (1) | FI121180B (en) |
| WO (1) | WO2010061045A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361490A (en) * | 2012-03-30 | 2013-10-23 | 吉坤日矿日石金属株式会社 | Manufacturing method of electric lead |
| CN103917670A (en) * | 2011-11-08 | 2014-07-09 | 奥图泰有限公司 | Method for leaching a sulphidic metal concentrate |
| CN106987724A (en) * | 2017-04-08 | 2017-07-28 | 广西凤山县五福矿业发展有限公司 | A kind of method for solidifying silicon from the low molten aluminium slag of iron aluminium concentrate |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268537B (en) * | 2011-08-15 | 2013-05-29 | 广西银亿科技矿冶有限公司 | Method for extracting cobalt and nickel from laterite-nickel ore |
| CN102286661A (en) * | 2011-08-25 | 2011-12-21 | 云南锡业集团（控股）有限责任公司 | Method for direct electrolysis of laterite nickel ore by sulfuric acid leaching |
| AU2013325098B2 (en) * | 2012-09-28 | 2017-12-14 | Direct Nickel Pty Ltd | Method for the recovery of metals from nickel bearing ores and concentrates |
| FI124419B (en) * | 2013-01-29 | 2014-08-29 | Global Ecoprocess Services Oy | A method for recovering metals from oxide ores |
| JP5622061B2 (en) * | 2013-03-26 | 2014-11-12 | 住友金属鉱山株式会社 | Method for producing hematite for iron making |
| WO2015132473A1 (en) | 2014-03-06 | 2015-09-11 | Outotec (Finland) Oy | Method, arrangement and use for treating nickel ore |
| CN106987723A (en) * | 2017-04-08 | 2017-07-28 | 广西凤山县五福矿业发展有限公司 | A kind of method that aluminium is reclaimed from the low molten aluminium slag of iron aluminium concentrate |
| CN113025832B (en) * | 2021-03-02 | 2022-07-15 | 重庆大学 | Nickel extraction and CO mineralization from laterite-nickel ore2Method (2) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125588A (en) * | 1977-08-01 | 1978-11-14 | The Hanna Mining Company | Nickel and magnesia recovery from laterites by low temperature self-sulfation |
| GR63003B (en) * | 1979-06-18 | 1979-08-03 | Shipping Business Sa | Nickel and cobalt recovery from laterites by extraction with sulphuric acid under atinospheric pressure |
| US4298379A (en) * | 1980-01-31 | 1981-11-03 | The Hanna Mining Company | Production of high purity and high surface area magnesium oxide |
| ZA987217B (en) * | 1997-08-15 | 2000-02-14 | Cominco Eng Services | Chloride assisted hydrometallurgical extraction of metal from sulphide or laterite ores. |
| FI112096B (en) * | 2001-07-06 | 2003-10-31 | Omg Finland Oy | Process for the extraction of nickel and possibly cobalt by leaching from nickel-containing laterite ore |
| CN100410399C (en) * | 2004-06-28 | 2008-08-13 | 斯凯资源有限公司 | Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching |
| RU2424332C2 (en) * | 2005-11-28 | 2011-07-20 | Англо Оперейшнс Лимитед | Procedure for leaching at presence of hydrochloric acid for regeneration of valuable metal from ore |
-
2008
- 2008-11-03 FI FI20080603A patent/FI121180B/en not_active IP Right Cessation
-
2009
- 2009-10-29 EA EA201100547A patent/EA018749B1/en not_active IP Right Cessation
- 2009-10-29 AU AU2009321543A patent/AU2009321543B2/en not_active Ceased
- 2009-10-29 WO PCT/FI2009/050870 patent/WO2010061045A1/en active Application Filing
- 2009-10-29 BR BRPI0921490A patent/BRPI0921490A2/en not_active IP Right Cessation
- 2009-10-29 CN CN200980143876.9A patent/CN102203307B/en not_active Expired - Fee Related
- 2009-10-29 EP EP09828687.5A patent/EP2350327A4/en not_active Withdrawn
-
2011
- 2011-04-29 CU CU20110099A patent/CU23937B1/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917670A (en) * | 2011-11-08 | 2014-07-09 | 奥图泰有限公司 | Method for leaching a sulphidic metal concentrate |
| CN103361490A (en) * | 2012-03-30 | 2013-10-23 | 吉坤日矿日石金属株式会社 | Manufacturing method of electric lead |
| CN103361490B (en) * | 2012-03-30 | 2016-02-24 | 吉坤日矿日石金属株式会社 | The manufacture method that electricity is plumbous |
| CN106987724A (en) * | 2017-04-08 | 2017-07-28 | 广西凤山县五福矿业发展有限公司 | A kind of method for solidifying silicon from the low molten aluminium slag of iron aluminium concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0921490A2 (en) | 2016-01-19 |
| EA201100547A1 (en) | 2011-12-30 |
| FI20080603A0 (en) | 2008-11-03 |
| AU2009321543B2 (en) | 2014-09-11 |
| CN102203307B (en) | 2015-03-04 |
| EA018749B1 (en) | 2013-10-30 |
| FI20080603A (en) | 2010-05-04 |
| EP2350327A4 (en) | 2016-11-09 |
| CU23937B1 (en) | 2013-08-29 |
| AU2009321543A1 (en) | 2010-06-03 |
| WO2010061045A1 (en) | 2010-06-03 |
| EP2350327A1 (en) | 2011-08-03 |
| FI121180B (en) | 2010-08-13 |
| CU20110099A7 (en) | 2012-06-21 |
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