CN101723431B - Method for recovering magnesium from magnesium sulfate solution - Google Patents
Method for recovering magnesium from magnesium sulfate solution Download PDFInfo
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- CN101723431B CN101723431B CN2008102236916A CN200810223691A CN101723431B CN 101723431 B CN101723431 B CN 101723431B CN 2008102236916 A CN2008102236916 A CN 2008102236916A CN 200810223691 A CN200810223691 A CN 200810223691A CN 101723431 B CN101723431 B CN 101723431B
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- adlerika
- magnesium
- calcium sulfate
- calcium
- marinco
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Abstract
The invention provides a method for recovering magnesium from a magnesium sulfate solution, which comprises the following steps of: (A) mixing calcium oxide and/or calcium hydroxide with calcium sulphate which is used as seed crystal; (B) mixing the magnesium sulfate solution with the mixture of the calcium oxide and/or the calcium hydroxide and the calcium sulphate to generate calcium sulphate precipitation and magnesium hydroxide precipitation; and (C) separating the calcium sulphate and the magnesium hydroxide. By recovering the magnesium hydroxide from the magnesium sulfate solution, the invention can recover the magnesium from the magnesium sulfate solution in a low-cost and low-pollution mode so as to achieve resource recycle.
Description
Technical field
The present invention relates to reclaim the method for magnesium, concrete, relate to the method that from Adlerika, reclaims magnesium.
Background technology
At present, in many industrial circles, often produce the waste liquid that contains magnesium in a large number.For example, in hydrometallurgy process, ore being carried out acidleach goes out to produce the solution that contains sal epsom in a large number.Because sal epsom is known as " misery " again, is the toxic substance that can cause that the people suffers from diarrhoea, therefore country forbids containing the direct discharging of waste water of sal epsom.
Traditional treatment process is that the solution that contains sal epsom is carried out heating evaporation, obtains magnesium sulfate crystals.But it is high that the shortcoming of this treatment process is a cost, 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; Add water digestion to the primary oxidation magnesium that obtains, filtering and impurity removing obtains Marinco H emulsion; Move into emulsion in the minute-pressure reaction kettle and control pressure, logical carbonic acid gas carbonization under agitation condition is through filtering; 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 has been caused pollution once more, and because methods such as this process using calcining are therefore high to the requirement of equipment; And then production cost is high, is inappropriate for large-scale industrial application.
Summary of the invention
The object of the invention is intended to one of solve the aforementioned problems in the prior at least.
For this reason, one object of the present invention is to propose a kind of method that from Adlerika, reclaims magnesium that can improve organic efficiency.
The method that from Adlerika, reclaims magnesium according to the embodiment of the invention may further comprise the steps:
A) quicklime and/or calcium hydroxide are mixed with calcium sulfate as crystal seed,
B) mixture of Adlerika with quicklime and/or calcium hydroxide and calcium sulfate mixed, to generate calcium sulfate precipitation and magnesium hydrate precipitate; And
C) separating calcium sulphate and Marinco H.
The method that from Adlerika, reclaims magnesium according to the embodiment of the invention; Owing in the reaction system of sal epsom and quicklime and/or calcium hydroxide, there is calcium sulfate as crystal seed; The granularity of the calcium sulfate that generates in can the augmenting response process; Thereby can utilize the granularity of calcium sulfate precipitation and the difference of Marinco H granularity, follow-up separating calcium sulphate at an easy rate and magnesium hydrate precipitate, and can improve the recovery and the purity of magnesium hydrate precipitate.Therefore, the present invention can reclaim magnesium with low-cost, oligosaprobic mode from Adlerika, reach the recycling of resource.
In one embodiment of the invention, Adlerika is mixed with the mixture of quicklime and/or calcium hydroxide and calcium sulfate comprise Adlerika is added in take part in Taoism quicklime and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed.Contriver of the present invention finds; Through Adlerika being joined in quicklime and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed; For example splash into wherein; Can further improve the granularity of the calcium sulfate precipitation of reaction efficiency and generation, thus more separate easily calcium sulfate and Marinco H.
Said Adlerika is the leach liquor that contains magnesium and the leaching of metal concentrate sulfuric acid.Owing in containing the leaching of magnesium concentrate sulfuric acid, can produce the solution of a large amount of sulfur acid magnesium, the effect of therefore low-cost recovery magnesium technology in the industrial application that concentrate sulfuric acid leaches is better.In the further embodiment of the present invention, said Adlerika is the solution of leach liquor through obtaining after purifying, and has so not only obtained the metal ingredient in the ore effectively, and can reclaim the magnesium in the waste liquid that leaches as sulfuric acid.Purification comprises at least a metal of removing in the leach liquor, and for example iron, copper, cobalt, nickel, chromium thus, not only can reclaim iron, copper, cobalt, nickel, the medium composition of chromium, and reclaim the magnesium in the ore, have both reduced pollution, again recycle resource.
In one embodiment of the invention; Calcium sulfate as crystal seed prepares through alkali-metal vitriol and quicklime and/or calcium hydroxide reaction; The resulting like this calcium sulfate as crystal seed can make the calcium sulfate in the Adlerika be attached on it more easily; Generate the deposition of larger particle, thereby separate with precipitated magnesium hydroxide more easily.In further embodiment, said alkali-metal vitriol is sodium sulfate, can save cost like this.
In one embodiment of the invention; As the calcium sulfate of crystal seed be through Adlerika and quicklime and/or calcium hydroxide reaction obtain calcium sulfate with Marinco H, separating calcium sulphate and Marinco H, then the calcium sulfate after separating is washed and drying after obtain; Can save alkali-metal vitriol like this, save cost.
In one embodiment of the invention, further comprise isolated Marinco H is washed and/or drying, can improve the magnesian purity of institute's separation of hydrogen like this, and be convenient to prolonged preservation.
In one embodiment of the invention; Further comprise with separating the Marinco H that obtains and make the magnesium goods, for example can be used to prepare fertilizer, also can be used to make artificial board; Can utilize further Marinco H like this, improve the economic value added that reclaims Marinco H.
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 through practice of the present invention.
Description of drawings
Fig. 1 is the schema of the method for magnesium that from Adlerika, reclaims of first embodiment of the invention;
Fig. 2 is the schema of the method for magnesium that from Adlerika, reclaims of second embodiment of the invention;
Fig. 3 is the schema of the method for magnesium that from Adlerika, reclaims of third embodiment of the invention;
Fig. 4 is the schema of the method for magnesium that from Adlerika, reclaims of fourth embodiment of the invention.
Fig. 5 is the schema of the method for magnesium that from Adlerika, reclaims of fifth embodiment of the invention.
Embodiment
Describe embodiments of the invention below in detail, the example of said embodiment is shown in the drawings, is exemplary through the embodiment that is described with reference to the drawings below, 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 in the present invention " quicklime and/or calcium hydroxide " is meant and can uses quicklime (unslaked lime) also can use calcium hydroxide (white lime), also can add the mixture of the two.In actually operating, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H
2O=Ca (OH)
2, the mixture of milk of lime as quicklime and calcium hydroxide used.
Fig. 1 shows the schema according to the method for magnesium that from Adlerika, reclaims of first embodiment of the invention.According to shown in Figure 1, at first quicklime and/or calcium hydroxide are mixed with calcium sulfate as crystal seed.Then in resulting mixture, add Adlerika, to generate calcium sulfate precipitation and magnesium hydrate precipitate, its reaction that mainly takes place is:
MgSO
4+Ca(OH)
2＝CaSO
4+Mg(OH)
2，
Last separating calcium sulphate and Marinco H.
As stated, sal epsom in the Adlerika and calcium hydroxide reaction generate calcium sulfate precipitation and magnesium hydrate precipitate.Yet the particle of calcium sulfate precipitation and magnesium hydrate precipitate is all very little, and the granularity difference is smaller, and more specifically, calcium sulfate precipitation is a crystalline form, and Marinco H is a gel, and Marinco H is coated on the calcium sulfate, so the two is difficult to separate.In addition, when sal epsom and calcium hydroxide reacted, the formation of magnesium hydrate precipitate had limited the further increase of calcium sulfate granularity, thereby has further increased separating difficulty.
According to embodiments of the invention; In the reaction system that sal epsom and calcium hydroxide react, contain calcium sulfate as crystal seed, therefore, when sal epsom and calcium hydroxide react; Formed calcium sulfate precipitation can be formed on the crystal seed; Thereby the granularity of calcium sulfate precipitation can further increase, and promptly forms the calcium sulfate precipitation of volume particle size, is convenient to separating between follow-up calcium sulfate and the magnesium hydrate precipitate thus.
The source of the employed in the present invention calcium sulfate as crystal seed is not restricted; Both can be the ready-made calcium sulfate of buying from market; Also can be the calcium sulfate that obtains through independent chemical reaction, the product calcium sulfate that also can be in this technology to be generated.
In addition; In actually operating; At first Adlerika is added take part in Taoism quicklime and/or calcium hydroxide and as the mixing of the calcium sulfate of crystal seed; Then Adlerika is added and for example splash in the said mixture, can further improve the granularity of calcium sulfate precipitation of efficient and the generation of reaction like this.
With reference to figure 2, in one embodiment of the invention, be to use calcium sulfate precipitation that alkali-metal vitriol and quicklime and/or calcium hydroxide reaction generated in that to separate the back resulting as the calcium sulfate of crystal seed.The contriver finds that the calcium sulfate that uses this method to obtain can obviously increase the granularity of the calcium sulfate precipitation of generation as crystal seed.In addition, in a further embodiment, employed alkali-metal vitriol is sodium sulfate; Because the cost of sodium sulfate is low; And the sodium hydroxide that is generated is solvable and can reuse, and therefore when can being convenient to separation of hydrogen sodium oxide and calcium sulfate, has also reduced cost.
With reference to figure 4; In one embodiment of the invention; As the calcium sulfate of crystal seed is to obtain calcium sulfate with Marinco H, separating calcium sulphate and Marinco H, then the calcium sulfate after separating is carried out obtaining after the classification washing through Adlerika and quicklime and/or calcium hydroxide reaction; Do not need extra independent preparation calcium sulfate crystal seed like this and saved alkali-metal vitriol, therefore further saved to produce and produced this.For example; Can in the part of sulfuric acid magnesium solution, add a certain amount of quicklime and/or calcium hydroxide earlier; Obtain calcium sulfate and magnesium hydrate precipitate, from this reaction system, isolate calcium sulfate and Marinco H then, and the calcium sulfate precipitation that obtains is washed the calcium sulfate that obtains as crystal seed.
In addition, as stated, at the beginning of technological process, also can be earlier in Adlerika, add the calcium sulfate enough as crystal seed from market, then through reaction, separate the calcium sulfate that obtains and just can be used as after the crystal seed of use.
In an embodiment of the present invention, quicklime and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, both can use quicklime (unslaked lime), also can use calcium hydroxide (white lime), also can use the mixture of the two.Concrete, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H
2O=Ca (OH)
2More specifically, unslaked lime adds less water to be made its heating, aquation, is paste, and after thermopositive reaction finished basically, thin up was sized mixing, and under the situation of time permission, can prolong digestion time.When using commercial lime, except that prolonging digestion time, also need sieve, to remove unreacted residue.It will be appreciated by those skilled in the art that; Quicklime and/or calcium hydroxide are mixed with calcium sulfate as crystal seed; Both promptly can milk of lime be joined in the calcium sulfate Adlerika as crystal seed, also can the calcium sulfate Adlerika as crystal seed be joined in the milk of lime.In one embodiment of the invention; Be that milk of lime is joined in the calcium sulfate Adlerika as crystal seed; The contriver finds to adopt this method can improve the efficient at follow-up sal epsom and calcium hydroxide reaction, further facilitates later separation Marinco H and calcium sulfate.
Milk of lime is mixed with Adlerika, and stir, thereby sal epsom and milk of lime react, and have generated throw out calcium sulfate and Marinco H, principal reaction is MgSO
4+ Ca (OH)
2=Mg (OH)
2↓+CaSO
4↓.
Because it is big that the granularity of the size ratio Marinco H of calcium sulfate is wanted, and owing to added the calcium sulfate crystal seed, compare with not adding crystal seed, the granulometric facies of calcium sulfate can further increase for the granularity of Marinco H.Therefore can be different according to two kinds of sedimentary particle sizes, easily calcium sulfate is separated with Marinco H.
In addition, in one embodiment of the invention, in order to obtain the higher Marinco H of purity, and prolonged preservation, isolated Marinco H is washed and/or dry.Washings can adopt deionized water, can prevent that like this Marinco H suspension from flocculating.
With reference to figure 5, in one embodiment of the invention, separate the Marinco H that obtains and to be used to prepare the magnesium goods.For example, in a specific embodiment of the present invention, separate the Marinco H that obtains, therefore can be used for fertiliser containing magnesium, also can be used to make artificial board as farm crop because it contains high-load magnesium.
With reference to figure 4, in one embodiment of the invention, as previously mentioned, the calcium sulfate that separation is obtained can be used as crystal seed and turns back in the reaction system after removing the impurity (like Marinco H) on surface through washing.In addition, resulting calcium sulfate can also be used to prepare sulfuric acid and cement.
The source of Adlerika does not receive any restriction in the present invention, as long as contain sal epsom in its solution.With reference to figure 3, in one embodiment of the invention, Adlerika is the leach liquor that contains magnesium and the leaching of metal concentrate sulfuric acid.Using at present sulfuric acid that ore is carried out that acidleach goes out is that development is very fast at present, uses very wide wet process smelting technique, and the sulfate waste liquid that is still produced also becomes the factor that environment is made a very bad impression.Traditionally, the solution that contains sal epsom not only is untreated as waste liquid, and magnesium wherein abandons as waste liquid.Consider that mining industry can produce the waste liquid of several tons even tens of tons every day, therefore use treatment process of the present invention can obtain extraordinary economic benefit, greatly reduce production cost.
In further embodiment of the present invention, employed Adlerika is a sulphuric leachate through the solution that obtains after purifying, and promptly reclaims other compositions in (removals) leach liquor earlier, and then reclaims the interior magnesium that exists with the sal epsom form of waste liquid.For example, " purification " can be at least a metal of removing in the sulphuric leachate, for example iron, copper, cobalt, nickel and chromium, but the present invention is not limited to remove mentioned component.
In one embodiment of the invention, employed sulphuric acid soln be to the sulphuric leachate of high magnesium low-grade nickel minerals (laterite, nickel sulfide concentrate) through deironing, reclaim the solution that obtains after copper, nickel, the cobalt process.Particularly, the method for purification is with milk of lime the pH value of solution to be transferred to 7.5-8 under 60-80 ℃, feeds pressurized air, with the Fe of small amount of residual
2+Oxidation, hydrolytic precipitation.Further adjust pH value to 9.2, under this pH value, heavy metal ion etc. all can be reduced to 10-5mM.Obtain containing the MgSO of small amount of calcium after the filtration
4Solution contains Mg10-20g/L.
Although illustrated and described embodiments of the invention; For those of ordinary skill in the art; Be appreciated that under the situation that does not break away from principle of the present invention and spirit and can carry out multiple variation, modification, replacement and modification that scope of the present invention is accompanying claims and be equal to and limit to these embodiment.
Claims (8)
1. method that from Adlerika, reclaims magnesium may further comprise the steps:
A) quicklime and/or calcium hydroxide are mixed with calcium sulfate as crystal seed,
B) mixture of Adlerika with quicklime and/or calcium hydroxide and calcium sulfate mixed, to generate calcium sulfate precipitation and magnesium hydrate precipitate; And
C) separating calcium sulphate and Marinco H,
Wherein, Adlerika mixed with the mixture of quicklime and/or calcium hydroxide and calcium sulfate comprise Adlerika splashed in quicklime and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed,
Said Adlerika is the leach liquor that contains magnesium and the leaching of metal concentrate sulfuric acid.
2. the method that from Adlerika, reclaims magnesium according to claim 1 is characterized in that, said Adlerika is the solution of said leach liquor through obtaining after purifying.
3. the method that from Adlerika, reclaims magnesium according to claim 2 is characterized in that said purification comprises at least a metal of removing in the leach liquor.
4. the method that from Adlerika, reclaims magnesium according to claim 1 is characterized in that, prepares through alkali-metal vitriol and quicklime and/or calcium hydroxide reaction as the calcium sulfate of crystal seed.
5. the method that from Adlerika, reclaims magnesium according to claim 4 is characterized in that said alkali-metal vitriol is sodium sulfate.
6. the method that from Adlerika, reclaims magnesium according to claim 1; It is characterized in that, as the calcium sulfate of crystal seed be through Adlerika and quicklime and/or calcium hydroxide reaction obtain calcium sulfate with Marinco H, separating calcium sulphate and Marinco H, then the calcium sulfate after separating is washed and drying after obtain.
7. the method that from Adlerika, reclaims magnesium according to claim 1 is characterized in that, further comprises isolated Marinco H is washed and drying.
8. the method that from Adlerika, reclaims magnesium according to claim 1 is characterized in that, further comprises with separating the Marinco H that obtains making the magnesium goods.
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| CN2008102236916A CN101723431B (en) | 2008-10-07 | 2008-10-07 | Method for recovering magnesium from magnesium sulfate solution |
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| CN2008102236916A CN101723431B (en) | 2008-10-07 | 2008-10-07 | Method for recovering magnesium from magnesium sulfate solution |
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| CN101723431B true CN101723431B (en) | 2012-03-14 |
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| CN102275958B (en) * | 2011-07-29 | 2013-02-06 | 武汉工程大学 | Method for preparing magnesium hydroxide utilizing magnesium sulfate as raw material |
| CN102351221B (en) * | 2011-07-29 | 2013-05-01 | 武汉工程大学 | Method for preparing magnesium hydroxide from acid-dissolved magnesium ion-containing raw materials |
| CN103950957A (en) * | 2014-04-22 | 2014-07-30 | 彭振超 | Process method for preparing magnesium hydroxide from magnesium sulfate |
| CN106282553B (en) * | 2015-05-26 | 2019-05-31 | 有研稀土新材料股份有限公司 | The smelting separation method of Rare Earth Mine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016175A (en) * | 2006-02-12 | 2007-08-15 | 山东滨化集团有限责任公司 | Method of eliminating magnesium sulfate from magnesium sulfate containing waste water solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016175A (en) * | 2006-02-12 | 2007-08-15 | 山东滨化集团有限责任公司 | Method of eliminating magnesium sulfate from magnesium sulfate containing waste water solution |
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| JP昭61-68324A 1986.04.08 |
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