CN101760644B - Leaching technique for magnesium-containing ore - Google Patents
Leaching technique for magnesium-containing ore Download PDFInfo
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- CN101760644B CN101760644B CN2008102409239A CN200810240923A CN101760644B CN 101760644 B CN101760644 B CN 101760644B CN 2008102409239 A CN2008102409239 A CN 2008102409239A CN 200810240923 A CN200810240923 A CN 200810240923A CN 101760644 B CN101760644 B CN 101760644B
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Abstract
The invention discloses a leaching technique for magnesium-containing ore, which includes the following steps that: magnesium-containing ore is mixed with sulfuric acid solution to carry out acid leaching, so that leachate containing magnesium sulfate is obtained; the leachate is purified, so that magnesium sulfate solution is obtained; the magnesium sulfate solution is depressurized, evaporated,cooled, crystallized and filtered, so that magnesium sulfate heptahydrate and mother solution containing magnesium sulfate are obtained; the mother solution is blended with aqueous ammonia to producemagnesium hydroxide precipitate; after filtration, the magnesium hydroxide precipitate and filtrate are obtained; and the filtrate is causticized by calcium hydroxide and/or calcium oxide, so that slurry containing magnesium hydroxide precipitate and calcium sulfate is obtained and ammonia is produced. According to the leaching technique for magnesium-containing ore, the metal element in the magnesium-containing ore can be recovered, and magnesium hydroxide and magnesium sulfate heptahydrate crystals can be recovered.
Description
Technical field
The present invention relates to wet method smelting process, especially relate to the extract technology of magnesium-containing ore.
Background technology
Ore smelting is traditionally undertaken by pyrometallurgical smelting process.Developed wet process smelting technique in recent years.Because hydrometallurgy can reduce the pollution to environment effectively, and can be suitable for multiple different ore deposit, therefore replace pyrometallurgical smelting just gradually.
Present wet method smelting process adopts the sulfuric acid extract technology more, the multiple metallic element that can leach in the ore to be contained.If can not reclaim, will be great waste, and some composition in the leach liquor also may damage to human body to these metallic elements.When for example magnesium-containing ore being leached, can produce the solution that contains sal epsom in a large number, because sal epsom is known as " misery " again, be the toxic substance that can cause that the people suffers from diarrhoea, and therefore country forbids containing the direct discharging of waste water of sal epsom.Traditional treatment process is that the solution that will contain sal epsom carries out heating evaporation, obtains magnesium sulfate crystals.But the shortcoming of this treatment process is the cost height, and efficient is low, need to consume a large amount of energy, and the purity of resulting magnesium sulfate crystals is low.
For example, Chinese patent CN101104521 discloses a kind of treatment process of sal epsom waste liquid, and it comprises: measure a certain amount of sal epsom waste liquid, under the mechanical stirring condition, heat condensing crystal, crystallization after drying, calcining, the primary oxidation magnesium that obtains, the flue gas of generation reclaims, and uses as system sulfuric acid; The primary oxidation magnesium that obtains is added water digestion, filtering and impurity removing, obtain magnesium hydroxide emulsion, move into emulsion in the reactor and control pressure, logical carbonic acid gas carbonization under agitation condition, after filtration, obtain magnesium bicarbonate solution, under heating and agitation condition, carry out the magnesium bicarbonate solution pyrolysis and just obtain the basic carbonate magnesium precipitate, filter at last, wash, dry and calcine, obtain activated magnesia.
Because this technology adopts evaporation-incinerating operational path, therefore, mass consumption the energy, environment caused once more polluted, and because technologies such as this process using calcinings, so to the requirement height of equipment, and then the production cost height.
Summary of the invention
Purpose of the present invention is intended to one of solve the aforementioned problems in the prior at least.
One object of the present invention is to propose a kind of leaching magnesium-containing ore that can high efficiente callback magnesium.Extract technology according to the magnesium-containing ore of the embodiment of the invention may further comprise the steps:
A) magnesium-containing ore is mixed with sulphuric acid soln carry out acidleach to obtain leaching solution containing magnesium sulfate;
B) described leach liquor is purified obtain Adlerika;
C) with the Adlerika reduction vaporization, crystallisation by cooling filters the mother liquor that obtains the magnesium sulfate heptahydrate crystal and contain sal epsom;
D) mother liquor is mixed with ammoniacal liquor, to obtain containing the slurries of magnesium hydrate precipitate and residual magnesium sulfate;
E) filter the slurries that contain magnesium hydrate precipitate and residual magnesium sulfate, obtain magnesium hydrate precipitate and filtrate respectively;
F) with calcium hydroxide and/or calcium oxide described filtrate is carried out causticization, obtain containing the slurries of magnesium hydrate precipitate and calcium sulfate, and generate ammonia.
Leaching magnesium-containing ore can reclaim the metallic element in the magnesium-containing ore according to an embodiment of the invention, reclaims magnesium hydroxide and magnesium sulfate heptahydrate crystal.Magnesium hydroxide can be used for the good fire retardant and the weighting agent of macromolecular materials such as plastics, rubber, as the flue gas desulfurization (FGD) agent, can replace caustic soda and the lime neutralizing agent as acid-bearing wastewater aspect environmental protection; As oil dope, play anticorrosion and desulfidation; Be used for the refining of electron trade, medicine, granulated sugar; Be used for lagging material and make other magnesium salts product.The magnesium sulfate heptahydrate crystal is a kind of important chemical product; therefore it can be used for industries such as process hides, fertilizer, porcelain, match, explosive, printing and dyeing, medicine; utilize the technology that from Adlerika, reclaims magnesium of this embodiment; can reduce the processing cost of wastewater treatment; and bring certain economic benefits; for the protection environment provides a kind of new technology according to embodiments of the invention with developing a circular economy, the extract technology of the magnesium-containing ore of the embodiment of the invention also has following additional technical feature simultaneously:
In one embodiment of the invention, also comprise the magnesium hydrate precipitate magnesium precipitate that is obtained calcined and obtain magnesium oxide.Can obtain the magnesium oxide end product like this.In the further embodiment of the present invention, described calcining is carried out under 600 ℃-800 ℃.The applicant finds can reach calcining effectively 600 ℃ of-800 ℃ of following calcinings, and magnesium hydrate precipitate fully is converted into magnesium oxide, improves productive rate.In further another embodiment of the present invention, before magnesium hydrate precipitate is calcined, it is washed, and washings is mixed with described filtrate.Like this, can improve magnesium hydrate precipitate is calcined the magnesian purity of acquisition, can will reclaim simultaneously, improve the rate of recovery of magnesium attached to the sal epsom on the magnesium hydrate precipitate.
In one embodiment of the invention, comprise that also the ammonia that will be generated is used for preparation and mixes employed ammoniacal liquor with Adlerika.The ammonia that causticization generated can be reclaimed and recycling like this, reduce cost, alleviate the pressure of ammonia environment.
In one embodiment of the invention, in the reaction system of sal epsom and ammoniacal liquor reaction generation magnesium hydroxide, add the magnesium hydroxide crystal seed, can change the size of crystallization crystal grain like this, to satisfy the requirement of different size magnesium products.
In one embodiment of the invention, also comprise, the described slurries that contain magnesium hydroxide and calcium sulfate are carried out pickling obtain calcium sulfate precipitation and Adlerika; The separating calcium sulphate precipitation; And the Adlerika crystallization that will isolate calcium sulfate precipitation obtains the magnesium sulfate heptahydrate crystal.Can further improve organic efficiency like this, and obtain the magnesium sulfate heptahydrate crystal magnesium in the Adlerika.In the further embodiment of the present invention, described pickling is carried out for using dilute sulphuric acid, magnesium hydrate precipitate fully and effectively can be converted into sal epsom like this.
In one embodiment of the invention, described magniferous ore is magniferous nickel sulfide ore or nickel-containing eluvial ore, and described purification comprises at least a in iron, aluminium, cobalt, nickel and the manganese of removing in the leach liquor.Thus, not only can reclaim valuable metal compositions such as iron, aluminium, cobalt, nickel and manganese, and reclaim the magnesium in the ore, both reduce pollution, again recycle resource.
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 schema of extract technology of the magnesium-containing ore of first embodiment of the invention;
Fig. 2 is the schema of extract technology of the magnesium-containing ore of second embodiment of the invention;
Fig. 3 is the schema of extract technology of the magnesium-containing ore of third embodiment of the 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.
Need to prove that the term that is adopted " calcium hydroxide and/or calcium oxide " is meant and can uses calcium oxide (unslaked lime is called slaked lime and uses after the digestion) in the present invention, also can use calcium hydroxide (white lime), also can use the mixture of the two.In actually operating, can water assimilation of quicklime using (CaO), thus obtaining milk of lime utilization, principal reaction is CaO+H
2O=Ca (OH)
2
Fig. 1 shows the schema of the extract technology of magnesium-containing ore according to an embodiment of the invention.As shown in Figure 1, at first, magnesium-containing ore mixed with sulphuric acid soln carry out acidleach to obtain leaching solution containing magnesium sulfate, the reaction of generation is as follows:
MgO+H
2SO
4＝MgSO
4+H
2O
Then, described leach liquor is purified obtain Adlerika.
Then, with the Adlerika reduction vaporization, crystallisation by cooling filters the mother liquor that obtains the magnesium sulfate heptahydrate crystal and contain sal epsom.
And then, Adlerika is mixed with ammoniacal liquor, following reaction takes place:
MgSO
4+2NH
4OH＝Mg(OH)
2↓+(NH
4)
2SO
4
Generate magnesium hydrate precipitate, to obtain containing the solution of magnesium hydrate precipitate.Generally, ammoniacal liquor does not consume the whole sal epsom in the Adlerika, has therefore obtained to contain the slurries of magnesium hydrate precipitate and residual magnesium sulfate.
Next filter the slurries that contain magnesium hydrate precipitate and residual magnesium sulfate, obtain magnesium hydrate precipitate and filtrate;
At last, use calcium hydroxide and/or calcium oxide that described filtrate is carried out causticization, following reaction take place:
(NH
4)
2SO
4+MgSO
4+2Ca(OH)
2＝2CaSO
4+Mg(OH)
2↓+2NH
3↑+2H
2O
Obtain containing the slurries of magnesium hydrate precipitate and calcium sulfate, and generate ammonia, in one embodiment of the invention, the ammonia (NH that in causticizing reaction, is generated
3) can turn back to Adlerika blended step in, can reclaim ammonia like this, the ammoniacal liquor of having regenerated has reduced cost, has alleviated the pressure of ammonia to environment.
By above-mentioned technology, can reach magnesium in the Adlerika is effectively reclaimed.
In one embodiment of the invention, in the reaction system of sal epsom and ammoniacal liquor reaction generation magnesium hydroxide, add the magnesium hydroxide crystal seed, can change the size of crystallization crystal grain like this, to satisfy the requirement of different size magnesium products.The magnesium hydrate precipitate that is obtained can directly be used as commodity selling, obtains bigger economic benefit.In addition, also can carry out deep processing to magnesium hydrate precipitate, according to shown in Figure 2, to separate the magnesium hydroxide magnesium precipitate that obtains calcine and obtain magnesium oxide.The reaction that is taken place is as follows:
Mg(OH)
2＝MgO+H
2O
In one embodiment of the invention, under 600 ℃-800 ℃ magnesium hydrate precipitate is calcined, the applicant finds can reach calcining effectively 600 ℃ of-800 ℃ of following calcinings, and magnesium hydrate precipitate fully is converted into magnesium oxide, improves productive rate.In the further embodiment of the present invention, before magnesium hydrate precipitate is calcined, it is washed, and washings is mixed with described filtrate.Like this, can improve magnesium hydrate precipitate is calcined the magnesian purity of acquisition, can will reclaim simultaneously, improve the rate of recovery of magnesium attached to the sal epsom on the magnesium hydrate precipitate.
In addition,, in another embodiment of the present invention, can carry out pickling, react as follows the slurries that contain magnesium hydroxide and calcium sulfate with reference to figure 3:
CaSO
4+Mg(OH)
2+H
2SO
4＝CaSO
4↓+MgSO
4+2H
2O
Can reach separating like this to sal epsom and calcium sulfate, after the separating calcium sulphate precipitation, obtained the higher Adlerika of purity, by Adlerika is carried out crystallization, for example can obtain the crystal of magnesium sulfate heptahydrate, further improve the organic efficiency of magnesium by reduction vaporization, the sour molten condition of control, crystallisation by cooling technology.
The sulfuric acid extract technology that is adopted among the present invention is not subjected to any restriction.For example, leaching can be leached or the leaching of oxygen enrichment high pressure for the oxygen enrichment normal pressure.Leaching process comprises magniferous nickel sulfide ore of fine grinding or for example high magnesium nickel ore concentrate of nickel-containing eluvial ore; Carry out pulp with the high magnesium nickel ore concentrate of sulphuric acid soln after to fine grinding; Concentrate after the pulp joined leach in the container, wherein leaching temperature in the container, to be controlled to be 90 ℃-100 ℃, pressure be normal pressure, and aerating oxygen leaches so that carry out the oxygen enrichment normal pressure in leaching container simultaneously.Before the leach liquor that contains sal epsom is reclaimed magnesium, leach liquor is purified.
Employed in the present invention term " purification " can be at least a in iron, aluminium, cobalt, nickel and the manganese of removing in the sulphuric leachate, but the present invention is not limited to remove mentioned component.For example, with reference to figure 6, in one embodiment of the invention, the leach liquor that the oxygen enrichment normal pressure is directly leached generation is discharged in leaching container the heavy iron container, with the temperature regulation to 75 of leach liquor ℃～80 ℃, for example 78 ℃, oxidation, neutralization also are adjusted to 3～4 with the pH value of leach liquor, thereby precipitation is tapped a blast furnace.Because the scavenging process in the sulfuric acid extract technology is that those of ordinary skills are known, gives unnecessary details no longer in detail here.
Concrete example according to the embodiment of the invention is described below.
Example 1
Table 1 contains the composition of leaching table (g/l) of sal epsom
| Mg | SO 4 2- | Al | Ni | Co | Mn | Fe |
| 26-40 | 103-160 | 0.023 | 0.004 | 0.0016 | 0.0024 | 0.002 |
Get the leach liquor vacuum-evaporation that quantitatively contains sal epsom and be concentrated to evaporation back liquid density 1.37-1.38
Cool off 20-30 ℃
Wet magnesium sulfate heptahydrate of output and mother liquor are filtered in crystallization
The dry commodity magnesium sulfate heptahydrate of producing of wet magnesium sulfate heptahydrate
Example 2
Get example 1 crystalline mother solution 500ml
Ammoniacal liquor 10-25% ammoniacal liquor
110% of ammonia vol micro-theory amount
Temperature of reaction: normal temperature～60 ℃
The adding mode: ammoniacal liquor joins in the leach liquor that contains sal epsom
Reaction times: 0.5 hour～2 hours
The filtration washing time: 1 minute～5 minutes
Magnesium hydroxide productive rate 65～80%
Magnesium hydroxide purity 〉=98%
Example 3:
Get the crystalline mother solution 500ml of example 1
Ammonia vol is 1-2 a times of theoretical amount
Temperature of reaction: normal temperature～60 ℃
The adding mode: ammoniacal liquor joins in the leach liquor that contains sal epsom
Add 0.5～3 times of magnesium hydroxide crystal seed amount
Reaction times: 0.5 hour～2 hours
Filtration time: 0.5 minute～5 minutes
The magnesium hydroxide productive rate is: 70～90%
Magnesium hydroxide purity 〉=99%
Example 4.
Get the filtered liquid and the washing lotion～500ml of example 1
Add previously prepared gypsum seed
Working concentration 5%～60% (weight percent) lime milk excessive 1.05.
The causticization time: 1 hour～2 hours
Causticization temperature: 45 ℃～105 ℃
Pickling gypsum and magnesium hydroxide
Output is filtered in PH2～5.5
Output gypsum purity 〉=95%
Mg≤0.5-1％
75-85 ℃ of output temperature, proportion 1.37-1.38 sal epsom is broad
Example 5
The ammonia steam water that contains of example 3 outputs is absorbed the ammoniacal liquor that becomes to contain ammonia 15～20% and is used to precipitate Mg (OH)
2
Example 6
80 ℃～100 ℃ dehydrations of magnesium hydroxide with example 1 or example 2
Generate anhydrous magnesium hydroxide.
Anhydrous magnesium hydroxide calcining is magnesium oxide.
Calcination time 1 hour～3 hours
600 ℃～800 ℃ of calcining temperatures
Output MgO purity 〉=99%
CaO content≤0.1%
Quality product meets lightweight MgO and active MgO specification of quality.
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 magnesium-containing ore may further comprise the steps:
A) magnesium-containing ore is mixed with sulphuric acid soln carry out acidleach to obtain leaching solution containing magnesium sulfate, wherein said described magniferous ore is magniferous nickel sulfide ore or nickel-containing eluvial ore;
B) described leach liquor is purified obtain Adlerika, wherein said purification comprises at least a in iron, aluminium, cobalt, nickel and the manganese of removing in the leach liquor;
C) with the Adlerika reduction vaporization, crystallisation by cooling filters the mother liquor that obtains the magnesium sulfate heptahydrate crystal and contain sal epsom;
D) mother liquor is mixed with ammoniacal liquor,, wherein in this step, add the magnesium hydroxide crystal seed to obtain containing the slurries of magnesium hydrate precipitate and residual magnesium sulfate;
E) filter the slurries that contain magnesium hydrate precipitate and residual magnesium sulfate, obtain magnesium hydrate precipitate and filtrate;
F) with calcium hydroxide and/or calcium oxide described filtrate is carried out causticization, obtain containing the slurries of magnesium hydrate precipitate and calcium sulfate, and generate ammonia.
2. the technology that reclaims magnesium from Adlerika according to claim 1 is characterized in that, further comprises: with step e) in the magnesium hydrate precipitate that obtained calcine and obtain magnesium oxide.
3. the technology that reclaims magnesium from Adlerika according to claim 2 is characterized in that described calcining is carried out under 600 ℃-800 ℃.
4. the technology that reclaims magnesium from Adlerika according to claim 2 is characterized in that, before the calcining magnesium hydrate precipitate it is washed, and washings is mixed with described filtrate.
5. the technology that reclaims magnesium from Adlerika according to claim 1 is characterized in that, use step F) in the ammonia preparation process D of generation) in employed ammoniacal liquor.
6. the technology that reclaims magnesium from Adlerika according to claim 1 is characterized in that, further comprises:
The described slurries that contain magnesium hydroxide and calcium sulfate are carried out pickling obtain calcium sulfate precipitation and Adlerika; And
Adlerika is turned back to step C) in handle.
7. the technology that reclaims magnesium from Adlerika according to claim 6 is characterized in that described acid is dilute sulphuric acid.
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|---|---|---|---|
| CN2008102409239A CN101760644B (en) | 2008-12-24 | 2008-12-24 | Leaching technique for magnesium-containing ore |
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|---|---|---|---|
| CN2008102409239A CN101760644B (en) | 2008-12-24 | 2008-12-24 | Leaching technique for magnesium-containing ore |
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| CN101760644B true CN101760644B (en) | 2011-08-10 |
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| CN115245738A (en) * | 2021-12-09 | 2022-10-28 | 昆明理工大学 | Method for purifying smelting flue gas and recycling magnesium resource in copper tailings by using copper tailings |
| CN114438319B (en) * | 2021-12-30 | 2023-12-08 | 云锡文山锌铟冶炼有限公司 | Method for treating calcium and magnesium in zinc hydrometallurgy process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88102284A (en) * | 1988-04-19 | 1988-12-21 | 曾宪科 | The production method of magnesium salts from dolomite with sulfuric acid wet process |
-
2008
- 2008-12-24 CN CN2008102409239A patent/CN101760644B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88102284A (en) * | 1988-04-19 | 1988-12-21 | 曾宪科 | The production method of magnesium salts from dolomite with sulfuric acid wet process |
Non-Patent Citations (1)
| Title |
|---|
| JP昭61-68324A 1986.04.08 |
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