CN104120259A - Nickel oxide ore acid leaching solution two-step iron removal method - Google Patents
Nickel oxide ore acid leaching solution two-step iron removal method Download PDFInfo
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Abstract
The invention discloses a nickel oxide ore acid leaching solution two-step iron removal method. The method comprises the following steps: adding garnierite ore pulp into a nickel oxide ore acid leaching solution, stirring and reacting until the dissolution is completed and the pH value of the solution is more than or equal to 1.6, performing liquid-solid separation, raising the temperature of obtained liquid to 130-170 DEG C, stirring and reacting for 1-3 hours, performing liquid-solid separation, and drying a solid to obtain a hematite product; adding the garnierite ore pulp into the collected liquid for the second time, stirring and reacting until the dissolution is completed and the pH value of the solution is about 2, performing liquid-solid separation, and adding magnesium oxide and an oxidizing agent into the obtained liquid, or only adding the oxidizing agent; stirring and reacting for 0.5-4 hours, performing liquid-solid separation, and drying the solid to obtain a goethite product. By adopting the method disclosed by the invention, complete iron removal can be achieved under a relatively mild condition; hematite and goethite which can be directly sold can be obtained; meanwhile, residual acid in the acid leaching solution and acid released in the iron deposition process are recycled; loss of nickel, cobalt, aluminum and magnesium in the leaching solution can not be generated.
Description
Technical field
The present invention relates to nickel minerals smelting process, be specifically related to a kind of nickel oxide ore pickling liquor two step method for removing iron.
Background technology
Nickel oxide ore is main nickel ore resource, and acid leaching process is the common technology that nickel oxide ore is smelted, and wherein uses sulfuric acid the most common as the technique of leaching agent.Nickel oxide ore is divided into irony ore deposit and the higher large class in magnesia ore deposit two of Mg content that iron level is higher conventionally.By all containing the metal ions such as iron, nickel, cobalt, magnesium, aluminium in the resulting nickel oxide ore pickling liquor of normal pressure acidleach, high pressure acidleach or dump leaching, conventionally the iron concentration in leach liquor is higher than other concentration of metal ions, wherein in the normal pressure pickling liquor in irony ore deposit, iron concentration can be up to 30～50g/L, therefore, the first step of most of nickel oxide ore pickling liquor purification separation is deironing.
Conventional leach liquor method for removing iron mainly contains oxidation neutralisation, jarosite process, goethite process and hematite process.Oxidation neutralisation is by Fe in leach liquor with oxygenant
2+be oxidized to Fe
3+, then add alkali lye to adjust the pH value of solution, make Fe
3+with the form precipitation of ironic hydroxide, this method is easy and simple to handle, but ironic hydroxide often precipitates with colloidal form, cause solution filter difficulty, in addition, in ironic hydroxide deposition process, have other metal ion codepositions such as part or a large amount of nickel, cobalt, magnesium, aluminium, cause the loss of metal ion.Jarosite process, goethite process and hematite process all have good filtration and scourability, but jarosite is difficult to recycling, in the process of piling up and depositing, also can discharge sulfuric acid and contaminate environment, so jarosite process less use now; Hematite process and goethite process form as first-selected method for removing iron because having the advantage that can sell except iron product.
Goethite process can carry out at lower temperature (as the boiling temperature lower than solution), and iron removal energy consumption is little, and still, goethite process requires at lower acidity (if pH value is between 2～4) and lower Fe
3+concentration is carried out under (generally in 1g/L left and right).The acidity of nickel oxide ore pickling liquor is generally higher, and its pH value is mostly lower than 1, particularly normal pressure pickling liquor, and its pH value is even lower than 0, and the pH value of regulator solution just need to consume a large amount of alkaline reagentss.In addition, in nickel oxide ore pickling liquor, iron concentration is far above 1g/L, and some even reaches 50g/L, if will adopt separation of iron in goethite form, needs first with reductive agent the Fe in pickling liquor
3+be reduced to Fe
2+to maintain Fe lower in solution
3+concentration, then adds oxygenant slow oxidation Fe
2+for Fe
3+, Fe then
3+slowly be hydrolyzed to pyrrhosiderite and deposit from solution.This not only needs to consume a large amount of Oxidizing and Reducing Agents, but also has extended the time of heavy iron reaction.For the very high nickel oxide ore pickling liquor of concentration of iron, people seldom use separation of iron in goethite form.
The heavy iron processes of at present conventional rhombohedral iron ore is to carry out under the condition about 250 ℃ of left and right, pressure are 4MPa, even if the acidity of solution is very high, iron in solution also can be with the form deposition of rhombohedral iron ore, therefore iron decreasing ratio is higher, but, this method energy consumption is very high, the autoclave that also needs to use the material of high temperature high voltage resistant and high corrosion resistance to manufacture, and installation cost and operational cost are all higher.Have in recent years some patents to propose to deposit rhombohedral iron ore within the scope of 120～200 ℃, in this low temperature range, acid significantly declines to the corrosion of equipment, thereby can use low price, autoclave simple to operate, thereby reduces facility investment and maintenance cost; The acid that adds heavy iron process release can be recycled, and this will reduce acid consumption and smelting cost greatly.The patent of invention that is CN101392321A as publication number discloses a kind of method that precipitates rhombohedral iron ore within the scope of 120～200 ℃, but this method requires to add carbonaceous reducing agent to carry out microwave reducing roasting to mineral at heavy iron with before leaching, and is not suitable for the direct deironing of nickel oxide ore normal pressure pickling liquor.
In addition, within the scope of 120～200 ℃, deposit rhombohedral iron ore and generally under the condition of pH>1, carry out, similar with iron precipitation by goethite process method, adopt hematite process deironing also to need to reduce before the acidity of leach liquor.Recent domestic scholar proposed various in and the technique of residual acid in nickel oxide ore pickling liquor, some patent proposes to use in alkaline matter and the residual acid of leach liquor, as patent WO2013120131A1 adopts the acid in Wingdale or calcium carbonate and in heap leaching solution, make iron with the form deposition of pyrrhosiderite.Add in alkaline matter and leach liquor in acid can reach the object that regulates leach liquor acidity, but residual acid in leach liquor is just difficult to be recycled utilization.Some patent adopts in magnesia ore deposit and the residual acid of leach liquor, if publication number is that the patents such as CN102212684A, CN101418379A, CN102286661A, WO2001032944A1, AU2011218755A1 adopt the residual acid in magnesia nickel oxide ore and in the pickling liquor of irony nickel oxide ore, to improve the pH value of pickling liquor, but the resulting deironing product of these patents is all yellow sodium (potassium) siderotil that is difficult to recycle, be easy to cause environmental pollution.
Publication number is in the patents of invention such as CN101139656A, WO2006084335A1, WO2006029499A1, to propose to utilize higher serpentine or the vegetable mould ore deposit of Ore Leaching Mg content that in normal pressure leach liquor, in residual acid and autoclave pressure, iron precipitation generates, make iron with the form deposition of ferric oxide simultaneously, but, method described in above-mentioned patent all can not make the iron in pickling liquor remove completely, residual certain density iron still in solution, and not yet leach completely in high Mg content ore deposit.For example, in the patent of invention that publication number is CN101139656A, residual concentration of iron approaches 1.5g/L, and in the vegetable mould ore deposit adding, nickel, cobalt leaching yield are 70% and 80%, and obviously, does not dissolve completely in vegetable mould ore deposit; Publication number is that in the patent of invention of WO2006084335A1, the concentration of residual iron is lower, and in the scope of 0.3～0.8g/L, but the extraction time in vegetable mould ore deposit is very long, approaches 10 hours, and energy consumption is higher; Publication number is that in the patent of invention of WO2006029499A1, deironing rate is only 90% left and right, still has 7～10% iron not remove completely.Residual iron ion meeting interfere with subsequent Separation of nickel and cobalt process, makes Separation of nickel and cobalt decrease in efficiency, and Separation of nickel and cobalt is incomplete.In addition, publication number is the acid that the patent of invention of AU2007100902A4 proposes to add in autoclave in raw mineral materials and rhombohedral iron ore deposition process discharges, but do not illustrate leaching of ores slag kind, adopt and how to avoid impact that leached mud generates autoclave wall fouling with rhombohedral iron ore product and how separated leached mud and rhombohedral iron ore.In fact, aforesaid method still exists many technical problems to need to solve, as, how to avoid autoclave wall fouling generation and still wall fouling entrained iron sedimentation products, how to prevent the nickel cobalt loss of deposition of iron process, how to guarantee the dissolving of high Mg content ore deposit completely, how to avoid generating ferric subsulfate and the poor deposition of iron product of strainability that is difficult to processing and recycles, how completely separated deposition of iron product is with high Mg content ore deposit leached mud, how to guarantee that the iron in leach liquor removes completely, etc., for these technical barriers, above-mentioned patent does not provide effective solution.
The patent of invention that the publication number of submitting to before the applicant is CN103060549A is improved above-mentioned technique, proposed to add in batches high Mg content ore deposit in nickel oxide ore pickling liquor, the slow method of the residual acid of neutralizing acid immersion liquid progressively, the method can be controlled the dissolution rate in the pH value of pickling liquor and the sedimentation velocity of iron and high Mg content ore deposit effectively, residual acid in pickling liquor and the acid of deposition of iron process are all fully used, guaranteed that deposition of iron is complete and the dissolving of high Mg content ore deposit is complete simultaneously, the rhombohedral iron ore product obtaining is easy to filter, in product, almost there is no the loss of nickel cobalt, deposition of iron product also can be effectively separated with high Mg content ore deposit lysate.But the method requires the pH value of the add-on in high Mg content ore deposit and pickling liquor strictly to regulate and control, when the mineral composition in the pH of stoste value, iron concentration and high Mg content ore deposit changes to some extent, add-on and the joining day in high Mg content ore deposit need to be adjusted and change to production process in time, this production operation is become some is loaded down with trivial details.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency existing for existing nickel oxide ore pickling liquor iron removal, and a kind of nickel oxide ore pickling liquor two step method for removing iron are provided.The method does not need to use expensive complicated autoclave, under comparatively gentle condition, can realize removing completely of iron, and obtain can direct marketing rhombohedral iron ore and pyrrhosiderite product, the acid that simultaneously also makes residual acid in pickling liquor and deposition of iron process discharge has obtained recycling, iron removal is not added other reagent, the not loss of the nickel in leach liquor, cobalt, magnesium, aluminium.
Nickel oxide ore pickling liquor two step method for removing iron of the present invention, comprise the following steps:
(1) in nickel oxide ore pickling liquor, add noumeite ore pulp, stirring reaction to noumeite dissolves completely and makes pH value >=1.6 of solution, carries out liquid-solid separation, obtains solid A and liquid A;
(2) liquid A is warming up to 130～170 ℃, stirring reaction 1～3h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product;
(3) in liquid B, add for the second time noumeite ore pulp, stirring reaction to noumeite dissolves completely and makes the pH value of solution be slightly smaller than 2 or pH >=2, carries out liquid-solid separation, obtains solid C and liquid C;
(4) when the pH of liquid C value is slightly smaller than 2, add magnesium oxide and oxygenant, when pH >=2 of liquid C, only in liquid C, add oxygenant; Stirring reaction 0.5～4h, carries out liquid-solid separation afterwards, obtains solid D and liquid D, collects and drying solid D, obtains pyrrhosiderite product;
(5) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, combining solid A and solid C, for producing silicon product.
In the step of aforesaid method (1), described nickel oxide ore pickling liquor can be the pickling liquor of nickel oxide ore being leached to gained by existing ordinary method (as normal pressure acidleach, high pressure acidleach, dump leaching etc.).Generally, in nickel oxide ore pickling liquor, iron concentration is 3～50g/L, when iron concentration is greater than 50g/L, equally also can adopt the method for the invention to carry out deironing, when iron concentration is less than 3g/L, conventionally leach liquor is carried out adopting separation of iron in goethite form after suitably dilution.In this step, preferably after adding noumeite ore pulp, stirring reaction makes the pH value of solution reach 1.6～2.0, and this pH value scope is more conducive to the deposition of rhombohedral iron ore in step (2).
After the processing through step (2), the Fe of the overwhelming majority in liquid A
3+the form with rhombohedral iron ore deposits, Fe in separating obtained liquid B
3+concentration has been near or below 1g/L.On the other hand, after the heavy iron reaction through step (2), the acid that rhombohedral iron ore deposition discharges makes the acidity of separating obtained liquid B raise to some extent (being the reduction of pH value), more than needing further to promote the pH value to 2 of liquid B, could meet the condition of pyrrhosiderite deposition, for this reason, in step (3) to add for the second time noumeite ore pulp to come the mode of residual acid in consumable liquid B to promote the pH value of liquid B.
In the step of aforesaid method (3), in order to make step (4) pyrrhosiderite deposition be easier to carry out, preferably control the pH value of liquid C in 2～4 scope.In this step, should guarantee that the residual acid in liquid B reacts completely with the noumeite ore pulp adding for the second time, the noumeite adding for the second time dissolves completely.When noumeite dissolve completely and after liquid-solid separation the pH value of gained solution be slightly smaller than in the situation of 2 (approaching very much 2), conventionally no longer employing adds the mode of noumeite ore pulp to carry out the pH value of regulator solution, but by adding pH value that method of magnesium oxide continues regulator solution to pH >=2, now need the magnesium oxide amount that adds little, and the magnesium oxide that magnesium oxide can obtain by later separation operation returns to use, thereby substantially can not increase production cost, on the other hand, if adopting, step (3) add the mode of excessive noumeite ore pulp to come the pH value of regulator solution to its pH >=2, step (4) can add magnesium oxide, but having part noumeite dissolves not exclusively, not dissolving noumeite and leached mud completely can be present in solid C simultaneously, this has not only reduced the solubility rate of noumeite, and greatly increased the difficulty of solid C aftertreatment, and adopt in step (4), add magnesium oxide to regulate the pH value of liquid C to pH >=2, because magnesium oxide add-on is little and dissolve fast complete, thereby can not introduce solid residue, solid C also can be directly used in and reclaim silicon product, thereby greatly reduce the difficulty of solid C aftertreatment, also effectively having avoided noumeite to dissolve incomplete phenomenon occurs.Here the pH value of said solution is slightly smaller than the 2 pH values that typically refer to solution between 1.9～2.In this step, when the residual acid-respons in the noumeite ore pulp adding for the second time and liquid B makes pH >=2 of solution completely, because having met pyrrhosiderite, this pH value deposits required pH value requirement, so do not need to add again magnesium oxide to regulate the pH value of liquid C in step (4); Preferably, be control solution pH value between 2～2.2, this pH value scope had both been conducive to the deposition of pyrrhosiderite, was conducive to again reduce production costs.
In the step of aforesaid method (1), (3) and (4), stirring reaction normally carries out between the boiling temperature of solution at 40 ℃.
In the step of aforesaid method (4), magnesian add-on is pH >=2 that make liquid C, preferably makes the pH value of liquid C be controlled between 2～2.2.In this step, described oxygenant is hydrogen peroxide, oxygen or air, preferably adopts air as oxygenant.The add-on of oxygenant is same as the prior art, is generally Fe
2+0.5～2.5 times of molar weight.
In method of the present invention, described noumeite refers to the nickeliferous silicate minerals that Mg content is higher, and preferably magnesium content is within the scope of 5～25wt%; The solid content of noumeite ore pulp is 10～40wt%.
In the step of aforesaid method (5), the magnesium oxide obtaining by separation circuit can return in step (4) and use, and also can be used as direct distribution.
In the step of aforesaid method (1), when pH value >=1.6 of nickel oxide ore pickling liquor itself, omit step (1), directly carry out step (2)～(5).
Compared with prior art, the invention has the advantages that:
1, first most iron remove by rhombohedral iron ore deposition process, and remaining iron removes by pyrrhosiderite deposition process again, and this two steps have guaranteed that the iron in pickling liquor removes completely except iron processes, and iron be converted into can direct marketing rhombohedral iron ore and pyrrhosiderite product.Iron in the pickling liquor that the extract technologies such as normal pressure acidleach, high pressure acidleach and dump leaching obtain all can be used the method for the invention to remove.
While 2, utilizing the residual acid in the neutralizing acid immersion liquid of magnesia ore deposit, the deposition of iron is separated and is carried out with the dissolving in magnesia ore deposit, save the later separation operation of deposition of iron product and magnesia ore deposit lysate, avoid entrained iron sedimentation products in the generation of autoclave wall fouling and fouling completely, also avoided magnesium in solution, aluminum ion and the interference of amorphous white residue to deposition of iron process completely; By the elimination of above interference and efficient regulation and control that pH of leaching solution is carried out, avoided ferric subsulfate, yellow sodium (potassium) siderotil etc. to be easy to cause the generation of the deposition of iron product of environmental pollution and the very low deposition of iron by product of crystallization degree, made deposition of iron product kind single (only having rhombohedral iron ore and pyrrhosiderite), deposition of iron product degree of crystallinity is higher, deposition of iron speed deposition faster, iron is more thorough complete.In addition, owing to there is no the generation of ferric subsulfate and deposition of iron by product, the degree of crystallinity of deposition of iron product improves greatly, and the strainability of deposition of iron product is also improved greatly, and nickel, cobalt, magnesium, the isoionic loss of aluminium also drop to almost nil.
3, adopt the residual acid of noumeite neutralizing acid immersion liquid and the acid that rhombohedral iron ore deposition process discharges for twice, fully reclaimed the acid that nickel oxide ore acidleach process consumes, realize noumeite and leached in the situation that not consuming acid lixiviant, greatly reduced the leaching cost of sour consumption and nickel oxide ore; Compare with the patent of invention of residual acid in the neutralizing acid immersion liquid of the magnesia ore deposit of existing employing, the method for the invention had both met deposition of iron and had reacted required pH value requirement, had guaranteed that again noumeite dissolves completely.
4, the first step iron removal is that (130～170 ℃) carry out under comparatively gentle condition, does not need the autoclave that uses expensive corrosion resistance nature extremely strong; Iron removal does not need to add other reagent, and after the noumeite adding dissolves, nickel wherein, cobalt, magnesium, aluminium plasma can enter in leach liquor, and through subsequent handling extraction and application, Tie Tong wherein crosses deironing step and is converted into rhombohedral iron ore or pyrrhosiderite; Because the first step iron removal has removed most iron, when second step carries out separation of iron in goethite form, Fe in solution
3+concentration has been near or below 1g/L, does not now need to add reductive agent and can carry out deironing; The neutralizing agent magnesium oxide consumption that iron removal is added seldom even can not add, and the magnesium oxide that can prepare by later separation operation returns to use; Iron removal does not have acid solution discharge, does not produce ferric subsulfate and yellow sodium (potassium) siderotil yet, has avoided environmental pollution.Therefore, the cost of whole iron removal is lower.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of nickel oxide ore pickling liquor two step method for removing iron of the present invention.
Embodiment
With specific embodiment, the invention will be further described below, but the present invention is not limited to these embodiment.
Embodiment 1
(1) Fe in nickel oxide ore sulphuric leachate stoste
3+, Fe
2+, Ni
2+, Co
2+, Mg
2+, Al
3+concentration be respectively 30.4g/L, 0.5g/L, 1.05g/L, 0.095g/L, 4.3g/L, 1.89g/L, the pH value of stoste is 0.38, in stoste, add solid content be 30% (wt%) noumeite aqueous pulp (wherein, Fe in noumeite, Ni, Co, Mg, the content of Al is respectively 4.8%, 1.9%, and 0.04%, 24.1%, 3.7%, the add-on of noumeite ore pulp is 2.5 times of stoste volume), in 90 ℃ of stirring reaction 1h (now noumeite ore pulp dissolves completely), carry out liquid-solid separation, obtain solid A and liquid A;
(2) liquid A is warming up to 160 ℃, stirring reaction 1.5h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product;
(3) (its solid content is identical with step (1) in liquid B, to add for the second time noumeite ore pulp, the add-on of noumeite ore pulp is 0.25 times of liquid B volume), in 90 ℃ of stirring reaction 45min (the noumeite ore pulp now adding for the second time dissolves completely), carry out liquid-solid separation, obtain solid C and liquid C;
(4) in liquid C, add magnesia powder and air (wherein the concentration of magnesium oxide in liquid C is 0.1g/L, and air adds with the flow of 0.01L/min), in 80 ℃ of stirring reaction 2h, carry out liquid-solid separation, obtain solid D and liquid D, collect and drying solid D, obtain pyrrhosiderite product;
(5) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, the magnesia partly that separation circuit obtains returns to step (4) and uses; Merge and collect step (1) and step (3) gained solid A and solid C, dry, for producing silicon product.
The schema of whole technique as shown in Figure 1.
After measured, the pH value of liquid A is 1.9, Fe in liquid A
3+, Fe
2+concentration is respectively 13.3g/L and 0.58g/L; The pH value of liquid B is 1.6, Fe in liquid B
3+, Fe
2+concentration is respectively 1.03g/L and 0.52g/L; The pH value of liquid C is 2.1, Fe in liquid C
3+, Fe
2+concentration is respectively 1.45g/L and 0.74g/L; Fe in liquid D
3+concentration is 20ppm, Fe
2+do not detect.Total deironing rate is more than 99%.The main component of solid A, solid C is Si and O, and solid B and solid D are respectively rhombohedral iron ore and pyrrhosiderite, does not all detect Ni, Co, Mg, Al in solid B and solid D; The leaching yield that adopts aforesaid method to process nickel, cobalt is respectively 98%, 97%.
Embodiment 2
(1) Fe in nickel oxide ore sulphuric leachate stoste
3+, Fe
2+, Ni
2+, Co
2+, Mg
2+, Al
3+concentration be respectively 42.4g/L, 2.5g/L, 1.24g/L, 0.15g/L, 3.3g/L, 1.1g/L, the pH value of stoste is-0.03, in stoste, add solid content be 20% (wt%) noumeite aqueous pulp (wherein, Fe in noumeite, Ni, Co, Mg, the content of Al is respectively 3.2%, 1.19%, and 0.05%, 19.1%, 4.9%, the add-on of noumeite ore pulp is 3 times of stoste volume), in 100 ℃ of stirring reaction 0.5h (now noumeite ore pulp dissolves completely), carry out liquid-solid separation, obtain solid A and liquid A;
(2) liquid A is warming up to 140 ℃, stirring reaction 2h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product;
(3) (its solid content is identical with step (1) in liquid B, to add for the second time noumeite ore pulp, the add-on of noumeite ore pulp is 2 times of liquid B volume), in 100 ℃ of stirring reaction 0.5h (the noumeite ore pulp now adding for the second time dissolves completely), carry out liquid-solid separation, obtain solid C and liquid C;
(4) (wherein the concentration of magnesium oxide in liquid C is 0.2g/L in liquid C, to add magnesia powder and hydrogen peroxide, hydrogen peroxide adds with the flow of 0.05L/min), in 60 ℃ of stirring reaction 0.5h, carry out liquid-solid separation, obtain solid D and liquid D, collect and drying solid D, obtain pyrrhosiderite product;
(5) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, the magnesia partly that separation circuit obtains returns to step (4) and uses; Merge and collect step (1) and step (3) gained solid A and solid C, dry, for producing silicon product.
After measured, the pH value of liquid A is 1.9, Fe in liquid A
3+, Fe
2+concentration is respectively 14.5g/L and 0.78g/L; The pH value of liquid B is 1.4, Fe in liquid B
3+, Fe
2+concentration is respectively 1.05g/L and 0.72g/L; The pH value of liquid C is 2.0, Fe in liquid C
3+, Fe
2+concentration is respectively 1.39g/L and 0.8g/L; Fe in liquid D
3+concentration is 30ppm, Fe
2+do not detect.Total deironing rate is more than 98%.The main component of solid A, solid C is Si and O, and solid B and solid D are respectively rhombohedral iron ore and pyrrhosiderite, does not all detect Ni, Co, Mg, Al in solid B and solid D.The leaching yield that adopts aforesaid method to process nickel, cobalt is respectively 99%, 98%.
Embodiment 3
(1) Fe in nickel oxide ore sulphuric leachate stoste
3+, Fe
2+, Ni
2+, Co
2+, Mg
2+, Al
3+concentration be respectively 19.4g/L, 3.1g/L, 1.0g/L, 0.11g/L, 8.3g/L, 2.1g/L, the pH value of stoste is 0.73, in stoste, add solid content be 40% (wt%) noumeite aqueous pulp (wherein, Fe in noumeite, Ni, Co, Mg, the content of Al is respectively 1.5%, 1.09%, and 0.02%, 13.4%, 5.9%, the add-on of noumeite ore pulp is 1.5 times of stoste volume), in 60 ℃ of stirring reaction 2h (now noumeite ore pulp dissolves completely), carry out liquid-solid separation, obtain solid A and liquid A;
(2) liquid A is warming up to 130 ℃, stirring reaction 3h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product;
(3) (its solid content is identical with step (1) in liquid B, to add for the second time noumeite ore pulp, the add-on of noumeite ore pulp is 0.5 times of liquid B volume), in 40 ℃ of stirring reaction 2h (the noumeite ore pulp now adding for the second time dissolves completely), carry out liquid-solid separation, obtain solid C and liquid C;
(4) (wherein the concentration of magnesium oxide in liquid C is 0.25g/L in liquid C, to add magnesia powder and oxygen, oxygen adds with the flow of 0.01L/min), in 70 ℃ of stirring reaction 3h, carry out liquid-solid separation, obtain solid D and liquid D, collect and drying solid D, obtain pyrrhosiderite product;
(5) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, the magnesia partly that separation circuit obtains returns to step (4) and uses; Merge and collect step (1) and step (3) gained solid A and solid C, dry, for producing silicon product.
After measured, the pH value of liquid A is 2.0, Fe in liquid A
3+, Fe
2+concentration is respectively 11.3g/L and 1.2g/L; The pH value of liquid B is 1.8, Fe in liquid B
3+, Fe
2+concentration is respectively 0.97g/L and 1.09g/L; The pH value of liquid C is 2.0, Fe in liquid C
3+, Fe
2+concentration is respectively 1.09g/L and 1.28g/L; Fe in liquid D
3+concentration is 25ppm, Fe
2+do not detect.Total deironing rate is more than 96%.The main component of solid A, solid C is Si and O, and solid B and solid D are respectively rhombohedral iron ore and pyrrhosiderite, does not all detect Ni, Co, Mg, Al in solid B and solid D.The leaching yield that adopts aforesaid method to process nickel, cobalt is respectively 97%, 97%.
Embodiment 4
(1) Fe in nickel oxide ore sulphuric leachate stoste
3+, Fe
2+, Ni
2+, Co
2+, Mg
2+, Al
3+concentration be respectively 7.4g/L, 1.3g/L, 0.95g/L, 0.09g/L, 15.3g/L, 5.1g/L, the pH value of stoste is 0.83, in stoste, add solid content be 30% (wt%) noumeite aqueous pulp (wherein, Fe in noumeite, Ni, Co, Mg, the content of Al is respectively 2.4%, 1.29%, and 0.05%, 20.4%, 10.9%, the add-on of noumeite ore pulp is 1 times of stoste volume), in 70 ℃ of stirring reaction 1.5h (now noumeite ore pulp dissolves completely), carry out liquid-solid separation, obtain solid A and liquid A;
(2) liquid A is warming up to 170 ℃, stirring reaction 1h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product;
(3) (its solid content is identical with step (1) in liquid B, to add for the second time noumeite ore pulp, the add-on of noumeite ore pulp is 0.5 times of liquid B volume), in 60 ℃ of stirring reaction 1h (the noumeite ore pulp now adding for the second time dissolves completely), carry out liquid-solid separation, obtain solid C and liquid C;
(4) (wherein the concentration of magnesium oxide in liquid C is 0.25g/L in liquid C, to add magnesia powder and air, air adds with the flow of 0.015L/min), in 100 ℃ of stirring reaction 1.5h, carry out liquid-solid separation, obtain solid D and liquid D, collect and drying solid D, obtain pyrrhosiderite product;
(5) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, the magnesia partly that separation circuit obtains returns to step (4) and uses; Merge and collect step (1) and step (3) gained solid A and solid C, dry, for producing silicon product.
After measured, the pH value of liquid A is 2.0, Fe in liquid A
3+, Fe
2+concentration is respectively 5.1g/L and 1.1g/L; The pH value of liquid B is 1.7, Fe in liquid B
3+, Fe
2+concentration is respectively 0.98g/L and 0.97g/L; The pH value of liquid C is 1.95, Fe in liquid C
3+, Fe
2+concentration is respectively 0.96g/L and 1.02g/L; Fe in liquid D
3+concentration is 4ppm, Fe
2+do not detect.Total deironing rate is more than 99%.The main component of solid A, solid C is Si and O, and solid B and solid D are respectively rhombohedral iron ore and pyrrhosiderite, does not all detect Ni, Co, Mg, Al in solid B and solid D.The leaching yield that adopts aforesaid method to process nickel, cobalt is respectively 97%, 98%.
Embodiment 5
(1) Fe in nickel oxide ore sulphuric leachate stoste
3+, Fe
2+, Ni
2+, Co
2+, Mg
2+, Al
3+concentration be respectively 14.2g/L, 0.83g/L, 1.05g/L, 0.04g/L, 23.3g/L, 6.3g/L, the pH value of stoste is 1.7, stoste is warming up to 150 ℃, stirring reaction 2h, carry out liquid-solid separation, obtain solid B and liquid B, collect and drying solid B, obtain rhombohedral iron ore product;
(2) in liquid B, adding solid content is noumeite ore pulp (Fe in noumeite, Ni, the Co of 25% (wt%), Mg, the content of Al is respectively 1.94%, 1.29%, and 0.05%, 8.4%, 6.9%, the add-on of noumeite ore pulp is 1.25 times of liquid B volume), in 90 ℃ of stirring reaction 0.5h (the noumeite ore pulp now adding dissolves completely), carry out liquid-solid separation, obtain solid C and liquid C;
(3) (wherein the concentration of magnesium oxide in liquid C is 0.18g/L in liquid C, to add magnesia powder and air, air adds with the flow of 0.009L/min), in 80 ℃ of stirring reaction 1.5h, carry out liquid-solid separation, obtain solid D and liquid D, collect and drying solid D, obtain pyrrhosiderite product;
(4) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, the magnesia partly that separation circuit obtains returns to step (4) and uses; Collect step (2) gained solid C, dry, for producing silicon product.
The schema of whole technique as shown in Figure 1.
After measured, the pH value of liquid B is 1.5, Fe in liquid B
3+, Fe
2+concentration is respectively 1.39g/L and 0.71g/L; The pH value of liquid C is 2.05, Fe in liquid C
3+, Fe
2+concentration is respectively 1.16g/L and 1.82g/L; Fe in liquid D
3+concentration is 15ppm, Fe
2+do not detect.Total deironing rate is more than 99%.The main component of solid C is Si and O, and solid B and solid D are respectively rhombohedral iron ore and pyrrhosiderite, does not all detect Ni, Co, Mg, Al in solid B and solid D.The leaching yield that adopts aforesaid method to process nickel, cobalt is respectively 99%, 97%.
Embodiment 6
(1) Fe in nickel oxide ore sulphuric leachate stoste
3+, Fe
2+, Ni
2+, Co
2+, Mg
2+, Al
3+concentration be respectively 11.9g/L, 2.83g/L, 1.12g/L, 0.08g/L, 20.3g/L, 2.3g/L, the pH value of stoste is 0.92, in stoste, adding solid content is the noumeite ore pulp (Fe in noumeite of 10% (wt%), Ni, Co, Mg, the content of Al is respectively 2.4%, 1.29%, 0.05%, 20.4%, 10.9%, the add-on of noumeite ore pulp is 2 times of stoste volume), in 70 ℃ of stirring reaction 2h (now noumeite ore pulp dissolves completely), carry out liquid-solid separation, obtain solid A and liquid A;
(2) liquid A is warming up to 170 ℃, stirring reaction 1.5h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product
(3) (its solid content is identical with step (1) in liquid B, to add for the second time noumeite ore pulp, the add-on of noumeite ore pulp is 1.5 times of liquid B volume), in 90 ℃ of stirring reaction 2h (the noumeite ore pulp now adding for the second time dissolves completely), carry out liquid-solid separation, obtain solid C and liquid C;
(3) in liquid C, add the flow leaked-in air with 0.009L/min, in 85 ℃ of stirring reaction 1.5h, carry out liquid-solid separation, obtain solid D and liquid D, collect and drying solid D, obtain pyrrhosiderite product;
(4) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, the magnesia partly that separation circuit obtains returns to step (4) and uses; Merge and collect step (1) and step (3) gained solid A and solid C, dry, for producing silicon product.
After measured, the pH value of liquid A is 2.0, Fe in liquid A
3+, Fe
2+concentration is respectively 5.4g/L and 1.04g/L; The pH value of liquid B is 1.6, Fe in liquid B
3+, Fe
2+concentration is respectively 1.02g/L and 0.96g/L; The pH value of liquid C is 2.2, Fe in liquid C
3+, Fe
2+concentration is respectively 1.12g/L and 1.23g/L; Fe in liquid D
3+concentration is 6ppm, Fe
2+do not detect.Total deironing rate is more than 99%.The main component of solid A, solid C is Si and O, and solid B and solid D are respectively rhombohedral iron ore and pyrrhosiderite, does not all detect Ni, Co, Mg, Al in solid B and solid D.The leaching yield that adopts aforesaid method to process nickel, cobalt is respectively 97%, 98%.
Claims (9)
1. nickel oxide ore pickling liquor two step method for removing iron, is characterized in that comprising the following steps:
(1) in nickel oxide ore pickling liquor, add noumeite ore pulp, stirring reaction to noumeite dissolves completely and makes pH value >=1.6 of solution, carries out liquid-solid separation, obtains solid A and liquid A;
(2) liquid A is warming up to 130～170 ℃, stirring reaction 1～3h, carries out liquid-solid separation, obtains solid B and liquid B, collects and drying solid B, obtains rhombohedral iron ore product;
(3) in liquid B, add for the second time noumeite ore pulp, stirring reaction to noumeite dissolves completely and makes the pH value of solution be slightly smaller than 2 or pH >=2, carries out liquid-solid separation, obtains solid C and liquid C;
(4) when the pH of liquid C value is slightly smaller than 2, add magnesium oxide and oxygenant, when pH >=2 of liquid C, only in liquid C, add oxygenant; Stirring reaction 0.5～4h, carries out liquid-solid separation afterwards, obtains solid D and liquid D, collects and drying solid D, obtains pyrrhosiderite product;
(5) liquid D is sent into later separation operation separation nickel, cobalt, aluminium and magnesium wherein, combining solid A and solid C, for producing silicon product.
2. method according to claim 1, is characterized in that: in step (1), adding after noumeite ore pulp stirring reaction to make the pH value of solution is 1.6～2.0.
3. method according to claim 1, is characterized in that: in step (1) and (3), the solid content of described noumeite ore pulp is 10～40wt%.
4. method according to claim 1, is characterized in that: in step (3), the pH value of solution is slightly smaller than the 2 pH values that refer to solution between 1.9～2.
5. method according to claim 1, is characterized in that: in step (3), pH >=2 of solution refer to that the pH value of solution is between 2～2.2.
6. method according to claim 1, is characterized in that: in step (1), (3) and (4), stirring reaction carries out between the boiling temperature of solution at 40 ℃.
7. method according to claim 1, is characterized in that: in step (4), magnesian add-on is pH >=2 that make liquid C.
8. method according to claim 1, is characterized in that: in step (4), the add-on of oxygenant is Fe
2+0.5～2.5 times of molar weight.
9. method according to claim 1, is characterized in that: in step (1), when pH value >=1.6 of nickel oxide ore pickling liquor itself, omit step (1), directly carry out step (2)～(5).
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| AU2015207917A AU2015207917B2 (en) | 2014-07-30 | 2015-07-30 | Two-stage iron removing method for solutions obtained from acid leaching of nickel oxide ores |
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| CN104531997A (en) * | 2014-12-25 | 2015-04-22 | 广东省工业技术研究院(广州有色金属研究院) | Method for removing iron from magnesium-containing sulfuric acid leaching liquid |
| CN106673071A (en) * | 2016-12-23 | 2017-05-17 | 天津理工大学 | Method for removing iron from laterite nickel ore pickling liquid and producing iron oxide black pigment at the same time |
| CN108517407A (en) * | 2018-05-22 | 2018-09-11 | 广西银亿新材料有限公司 | A kind of method for removing iron of red soil nickel ore leaching liquid |
| CN111172392A (en) * | 2020-01-20 | 2020-05-19 | 广西赛可昱新材料科技有限公司 | Environment-friendly iron removal method without impurity in laterite-nickel ore leaching solution |
| CN111762804A (en) * | 2020-07-24 | 2020-10-13 | 眉山顺应动力电池材料有限公司 | Iron removal method for pickle liquor in acid process aluminum extraction |
| CN114314699A (en) * | 2021-12-31 | 2022-04-12 | 金川集团镍盐有限公司 | Iron removal method for nickel pill dissolving solution in chlorination system |
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| CN104120259B (en) | 2016-03-02 |
| AU2015207917B2 (en) | 2016-11-03 |
| AU2015207917A1 (en) | 2016-02-18 |
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