CN101880772B - Method for recycling magnesium from magnesium-containing waste solution - Google Patents
Method for recycling magnesium from magnesium-containing waste solution Download PDFInfo
- Publication number
- CN101880772B CN101880772B CN2010101993649A CN201010199364A CN101880772B CN 101880772 B CN101880772 B CN 101880772B CN 2010101993649 A CN2010101993649 A CN 2010101993649A CN 201010199364 A CN201010199364 A CN 201010199364A CN 101880772 B CN101880772 B CN 101880772B
- Authority
- CN
- China
- Prior art keywords
- magnesium
- containing waste
- solution
- waste solution
- calcium chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling magnesium from magnesium-containing waste solution, which comprises: A) mixing magnesium-containing waste solution and calcium chloride solution for magnesium conversion, and filtering the mixed solution after magnesium conversion, thereby obtaining gypsum and magnesium chloride solution; B) settling magnesium in the magnesium chloride solution with lime milk, and filtering the mixed solution with magnesium settled after reaction, thereby obtaining magnesium hydroxide precipitate and calcium chloride solution; and C) washing and drying the magnesium hydroxide precipitate, thereby obtaining magnesium hydroxide. The method can realize the recovery of magnesium from the magnesium-containing waste solution with low-price raw materials, and can not further cause the environmental pollution.
Description
Technical field
The present invention reclaims the method for magnesium from magnesium-containing waste solution, more specifically, relate to the method that reclaims magnesium in a kind of leach liquor from hydrometallurgy.
Background technology
In field of metallurgy, acid leaching process is a kind of method of refinement valuable metal commonly used.When producing cobalt nickel or other valuable metals, adopt acid leaching process that the valuable metals such as cobalt nickel in the ore are leached usually, meanwhile also leached with impurity such as the magnesium of cobalt nickel association, manganese thereupon.Leach liquor contains a large amount of magnesium in the liquid through purifying and the removal of impurities postprecipitation goes out cobalt nickel behind the heavy cobalt nickel that obtains so subsequently, and a spot of impurity manganese etc. for example, is commonly referred to magnesium-containing waste solution.In addition, owing in acid leaching process, need to use excessive acid, so a large amount of unreacted acid that can contain in the leach liquor.In actual production, need further handle leach liquor, reclaiming the more valuable metal magnesium of content, and excessive acid is utilized again.
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 obtain primary oxidation magnesium, and the flue gas of generation reclaims as system sulfuric acid and uses; Add water digestion, filtering and impurity removing acquisition Marinco H emulsion to the primary oxidation magnesium that obtains; Move into emulsion in the reaction kettle and control pressure; Under agitation condition, feed carbonic acid gas and carry out carbonization; Obtain magnesium bicarbonate solution through filtering, under heating and agitation condition, carry out the magnesium bicarbonate solution pyrolysis and just obtain the basic carbonate magnesium precipitate; The basic carbonate magnesium precipitate that obtains is obtained activated magnesia through filtering, wash, dry and calcining.
During the magnesium of this technology in reclaiming magnesium-containing waste solution, obtain primary oxidation magnesium through the heating condensing crystal, its energy consumption is big, and the purity of resulting primary oxidation magnesium is low.And, need on the basis of preparation primary oxidation magnesium, add water digestion in order to obtain the intermediate product Marinco H, so its technical process is complicated, and consumed mass energy, environment having been caused polluted once more, production cost is high.
Summary of the invention
The present invention is intended to one of address the above problem at least, particularly solves production cost height, environmental pollution problems, and a kind of method that can from magnesium-containing waste solution, reclaim magnesium with extremely cheap raw material is provided, and can not cause once more environment and pollute.
For achieving the above object; One aspect of the present invention proposes a kind of method that from magnesium-containing waste solution, reclaims magnesium; May further comprise the steps: A) magnesium-containing waste solution is mixed transforming reactive magnesium with calcium chloride solution, reaction is filtered after finishing, and obtains plaster stone and magnesium chloride solution; B) with milk of lime said magnesium chloride solution is sunk reactive magnesium, question response filters after finishing, and obtains magnesium hydrate precipitate and rare calcium chloride solution; And C) to said magnesium hydrate precipitate wash, drying, obtain Marinco H.
The method that from magnesium-containing waste solution, reclaims magnesium according to the embodiment of the invention can also have following additional technical feature:
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, in steps A) in calcium chloride solution be saturated solution, calcium chloride use coefficient of discharge is 1.0～1.5, the reaction times is 0.5～2h.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, at step B) in calculate milk of lime with CaO concentration be 15wt%～20wt%, it is 1.0～1.3 that milk of lime uses coefficient of discharge, the reaction times is 0.5～2h.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, at step C) in to said magnesium hydrate precipitate washing 3～5 times, drying obtains Marinco H afterwards.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, further comprise: D) concentrate said rare calcium chloride solution and obtain the calcium chloride liquid concentrator, and said calcium chloride liquid concentrator returned be used for magnesium-containing waste solution is converted into magnesium chloride solution.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, at step D) in obtain the calcium chloride liquid concentrator through the said rare calcium chloride solution of heating evaporation.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, further comprise: E) said plaster stone is washed the back 120～160 ℃ of calcinings 1～5 hour, obtain the plaster of Paris.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, to said magnesium-containing waste solution impurity and purification.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, said impurity and purification comprise at least a in iron, aluminium, cobalt, nickel and the manganese of removing in the magnesium-containing waste solution.
From magnesium-containing waste solution, reclaim the method for magnesium according to an embodiment of the invention, said magnesium-containing waste solution is the sulphuric leachate in the hydrometallurgy.
Compared with prior art, the present invention has one of advantage at least:
According to the method that from magnesium-containing waste solution, reclaims magnesium of the present invention; Can from the magnesium-containing waste solution that hydrometallurgy process obtains, reclaim magnesium elements efficiently with the preparation Marinco H and as plaster stone, the plaster of Paris of auxiliary product; Whole reaction system only utilizes extremely cheap calcium chloride and milk of lime as raw material; Do not produce any waste water in the process, both solved environmental issue, realized the comprehensive utilization of resource again.The cost of entire method is relatively low and method is simple, has proposed to reclaim from magnesium-containing waste solution with tradition the diverse new method of method of magnesium.
According to the method that from magnesium-containing waste solution, reclaims magnesium of the present invention; Adopt the Adlerika of output in the hydrometallurgy process, therefore can handle the waste liquid that hydrometallurgy produces effectively, reclaimed the magnesium in the ore effectively; Increased economic benefit; Reduced the discharging of pollutent, environmental protection more helps realizing recycling economy.
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
The present invention above-mentioned and/or additional aspect and advantage from obviously with easily understanding becoming the description of embodiment, wherein below in conjunction with accompanying drawing:
Fig. 1 is the method flow diagram that from magnesium-containing waste solution, reclaims magnesium of the first embodiment of the present invention.
Fig. 2 is the method flow diagram that from magnesium-containing waste solution, reclaims magnesium of the second embodiment of the present invention.
Fig. 3 is the method flow diagram that from magnesium-containing waste solution, reclaims magnesium of the third embodiment of the present invention.
Fig. 4 is the method flow diagram that from magnesium-containing waste solution, reclaims magnesium of the fourth embodiment of the present invention.
Embodiment
To combine accompanying drawing to describe embodiments of the invention in detail below, be exemplary through 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.
In the following description; Magnesium-containing waste solution specifically is meant the sulphuric leachate behind the precipitate cobalt nickel that adopts acid leaching process to refine valuable metal such as cobalt nickel in the cobalt nickel ores and obtain; Wherein contain a large amount of unreacted sulfuric acid; And since also more in the ore with the Mg content of cobalt nickel association, more magnesium therefore also contained.In addition, also contain other impurity such as a small amount of manganese in this magnesium-containing waste solution.Yet be suitable for being not limited to the sulphuric leachate behind the precipitate cobalt nickel with the magnesium-containing waste solution that method of the present invention is handled.
The present invention mainly is through utilizing relatively low calcium chloride of cost and milk of lime from magnesium-containing waste solution, to reclaim magnesium; This method can reclaim magnesium elements efficiently with preparation Marinco H and plaster stone, plaster of Paris product from the magnesium-containing waste solution that hydrometallurgy process obtains, and the simple cost of method is low.
Obtain primary oxidation magnesium through the heating condensing crystal during magnesium of prior art in reclaiming magnesium-containing waste solution; Its energy consumption is big; And the purity of resulting primary oxidation magnesium is low; Then must behind preparation primary oxidation magnesium, add water digestion in order to obtain the intermediate product Marinco H, whole technology and consumed mass energy has caused once more environment and has polluted.In the embodiments of the invention, magnesium-containing waste solution is mixed with calcium chloride solution, question response finishes the back mixed solution is filtered, and obtains plaster stone and magnesium chloride solution; With milk of lime said magnesium chloride solution is sunk magnesium, question response finish the back to heavy magnesium after mixed solution filters, obtain magnesium hydrate precipitate and rare calcium chloride solution; And then to said magnesium hydrate precipitate wash, drying, obtain Marinco H.According to embodiments of the invention, can utilize cheap raw material, through simple technology, in the time of preparation Marinco H and plastering, reduced the discharging of pollutent, more environmental protection.
Method according to the processing magnesium-containing waste solution of the embodiment of the invention is described with reference to the accompanying drawings.
As shown in Figure 1; In the method that from magnesium-containing waste solution, reclaims magnesium according to the first embodiment of the present invention, at first get magnesium-containing waste solution, in magnesium-containing waste solution, add calcium chloride solution and transform reactive magnesium; Question response finishes the back mixed solution is filtered, and obtains plaster stone and magnesium chloride solution.Then, said magnesium chloride solution is sunk reactive magnesium with milk of lime, question response finish the back to heavy magnesium after mixed solution filters, obtain magnesium hydrate precipitate and rare calcium chloride solution.At last, to said magnesium hydrate precipitate wash, drying, obtain Marinco H.
As shown in Figure 2; From magnesium-containing waste solution, reclaiming in the method for magnesium according to a second embodiment of the present invention; After preparing Marinco H with the method identical with first embodiment; Through heating evaporation rare calcium chloride solution is concentrated, obtain the calcium chloride liquid concentrator, and it is returned the sal epsom that is used for magnesium-containing waste solution be converted into magnesium chloride.All the other steps are identical with first embodiment, for the purpose of simple, do not set forth at this.
Shown in Figure 3 is the schema of the third embodiment of the present invention.At first, prepare Marinco H with the method identical with first embodiment.After this, plaster stone is calcined, obtained plaster of Paris product.
Shown in Figure 4 is the schema of the fourth embodiment of the present invention.In this embodiment, at first magnesium-containing waste solution is carried out impurity and purification, at least a with in iron, aluminium, cobalt, nickel and the manganese of removing said magnesium-containing waste solution, magnesium-containing waste solution after being purified and slag.After this, to prepare Marinco H with embodiment 1 identical method.
Below will describe embodiments of the invention through concrete example.
For example, in the example below the present invention, use the magnesium-containing waste solution of composition as shown in table 1 below, for the calcium chloride solution that improves the use of reaction efficiency and speed of reaction is saturated calcium chloride solution.But the present invention is not limited to use saturated calcium chloride solution.
Table 1 (magnesium-containing waste solution component list (g/l))
Example 1
At first get the magnesium-containing waste solution that the 500ml Mg content is 26g/L; It is carried out impurity and purification, the calcium chloride saturated solution is added stirring reaction in the magnesium-containing waste solution, wherein calcium chloride use coefficient of discharge is 1.0; Reaction times is 1.5 hours, and the reaction after-filtration obtains plaster stone and magnesium chloride solution.Then; The milk of lime that in order to the CaO calculating concentration is 15wt% sinks magnesium to said magnesium chloride solution, and the use coefficient of discharge of milk of lime is 1.0, and the reaction times is 1 hour; After question response finishes mixed solution behind the heavy magnesium is filtered, obtain magnesium hydrate precipitate and rare calcium chloride solution.At last, said magnesium hydrate precipitate is carried out 3 washings, this after drying obtains Marinco H.
Through analyzing the content of the plaster stone of gained＞95%, the content of Marinco H＞92%.
Example 2
At first get the magnesium-containing waste solution that the 500ml Mg content is 26g/L; It is carried out impurity and purification, the calcium chloride saturated solution is added stirring reaction in the magnesium-containing waste solution, wherein calcium chloride use coefficient of discharge is 1.3; Reaction times is 0.5 hour, and the reaction after-filtration obtains plaster stone and magnesium chloride solution.Then; The milk of lime that in order to the CaO calculating concentration is 20wt% sinks magnesium to said magnesium chloride solution, and the use coefficient of discharge of milk of lime is 1.2, and the reaction times is 0.5 hour; After question response finishes mixed solution behind the heavy magnesium is filtered, obtain magnesium hydrate precipitate and rare calcium chloride solution.At last, said magnesium hydrate precipitate is carried out 3 washings, this after drying obtains Marinco H.
Through analyzing the content of the plaster stone of gained＞95%, the content of Marinco H＞92%.
Than example 1, be able to accelerate along with the consumption of calcium chloride increases speed of response, and, accelerated heavy magnesium speed because the concentration of milk of lime increases and consumption increases.
Example 3
Get rare calcium chloride solution 500ml that example 1 obtains, be heated to 85 ℃ and its volatilization is concentrated, after this be cooled to room temperature, obtain saturated calcium chloride solution and crystallization of calcium chloride.
Resulting saturated calcium chloride solution can return and be used for magnesium-containing waste solution is converted into magnesium chloride solution.
Example 4
Get the plaster stone that example 1 obtains, after its washing 3 times,, obtain the plaster of Paris 150 ℃ of calcinings 3 hours.
Gained plaster of Paris content＞94%.
Although illustrated and described embodiments of the invention and concrete example; 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 (7)
1. method that from magnesium-containing waste solution, reclaims magnesium may further comprise the steps:
A) magnesium-containing waste solution is mixed with calcium chloride solution transform reactive magnesium, reaction is filtered after finishing, and obtains plaster stone and magnesium chloride solution;
B) with milk of lime said magnesium chloride solution is sunk reactive magnesium, reaction is filtered after finishing, and obtains magnesium hydrate precipitate and rare calcium chloride solution; With
C) to said magnesium hydrate precipitate wash, drying, obtain Marinco H,
Wherein,
In steps A) in calcium chloride solution be saturated solution, it is 1.0～1.5 that calcium chloride uses coefficient of discharge, the reaction times is 0.5～2h;
At step B) in calculate milk of lime with CaO concentration be 15wt%～20wt%, it is 1.0～1.3 that milk of lime uses coefficient of discharge, the reaction times is 0.5～2h;
At step C) in to said magnesium hydrate precipitate washing 3～5 times, drying obtains Marinco H afterwards.
2. the method that from magnesium-containing waste solution, reclaims magnesium according to claim 1; It is characterized in that; Further comprise: D) concentrate said rare calcium chloride solution and obtain the calcium chloride liquid concentrator, and said calcium chloride liquid concentrator returned be used for magnesium-containing waste solution is converted into magnesium chloride solution.
3. the method that from magnesium-containing waste solution, reclaims magnesium according to claim 1 is characterized in that, at step D) in obtain the calcium chloride liquid concentrator through the said rare calcium chloride solution of heating evaporation.
4. the method that from magnesium-containing waste solution, reclaims magnesium according to claim 1 is characterized in that, further comprises: E) said plaster stone is washed the back 120～160 ℃ of calcinings 1～5 hour, obtain the plaster of Paris.
5. the method that from magnesium-containing waste solution, reclaims magnesium according to claim 1 is characterized in that, to said magnesium-containing waste solution impurity and purification.
6. the method that from magnesium-containing waste solution, reclaims magnesium according to claim 5 is characterized in that, said impurity and purification comprise at least a in iron, aluminium, cobalt, nickel and the manganese of removing in the magnesium-containing waste solution.
7. according to claim 5 or the 6 described methods that from magnesium-containing waste solution, reclaim magnesium, it is characterized in that said magnesium-containing waste solution is the sulphuric leachate in the hydrometallurgy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101993649A CN101880772B (en) | 2010-06-07 | 2010-06-07 | Method for recycling magnesium from magnesium-containing waste solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101993649A CN101880772B (en) | 2010-06-07 | 2010-06-07 | Method for recycling magnesium from magnesium-containing waste solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101880772A CN101880772A (en) | 2010-11-10 |
| CN101880772B true CN101880772B (en) | 2012-07-04 |
Family
ID=43052912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101993649A Active CN101880772B (en) | 2010-06-07 | 2010-06-07 | Method for recycling magnesium from magnesium-containing waste solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101880772B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098366B (en) * | 2017-04-25 | 2018-12-04 | 中国恩菲工程技术有限公司 | The method for handling magnesium-containing waste solution |
| CN107364879B (en) * | 2017-06-29 | 2019-11-15 | 中国恩菲工程技术有限公司 | The method of magnesium elements and calcium constituent is recycled from Adlerika |
| CN107488787B (en) * | 2017-08-10 | 2019-03-19 | 云南龙蕴科技环保股份有限公司 | A method of recycling manganese in sewage containing manganese |
| CN108754138B (en) * | 2018-05-25 | 2020-06-16 | 包头稀土研究院 | Method for circularly leaching rare earth sulfate roasted ore by magnesium chloride solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1924046A (en) * | 2006-08-25 | 2007-03-07 | 四川大学 | Method of retrieving magnesium from high magnesium phosphorus ore |
| CN101104521A (en) * | 2007-06-05 | 2008-01-16 | 昆明贵金属研究所 | Method for treating magnesium sulfate waste liquid and coproducing active magnesium chloride |
-
2010
- 2010-06-07 CN CN2010101993649A patent/CN101880772B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1924046A (en) * | 2006-08-25 | 2007-03-07 | 四川大学 | Method of retrieving magnesium from high magnesium phosphorus ore |
| CN101104521A (en) * | 2007-06-05 | 2008-01-16 | 昆明贵金属研究所 | Method for treating magnesium sulfate waste liquid and coproducing active magnesium chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101880772A (en) | 2010-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101117228A (en) | Method for extracting aluminium oxide from coal ash | |
| CN102897810B (en) | Method for producing aluminum oxide by using fly ash | |
| CN101760613B (en) | Method for leaching zinc-containing ores | |
| CN101372402A (en) | Method for preparing magnesian by calcining ammonium salt and magnesium-containing ore | |
| CN104261433A (en) | Method for producing potassium sulfate from potassium/chlorine-ion-containing solid waste | |
| CN102923742A (en) | Method for comprehensively extracting aluminum and lithium from coal ash | |
| CN103588235A (en) | Method for producing polyaluminium sulfate by using red mud slag | |
| CN102602966A (en) | Method for separating magnesium and lithium in salt lake brine and preparing lithium carbonate | |
| CN102923743A (en) | Technical method for comprehensively extracting aluminum and lithium from coal ash through acid process | |
| CN102020299A (en) | Method for producing industrial activated aluminum oxide from pulverized fuel ash | |
| CN101880772B (en) | Method for recycling magnesium from magnesium-containing waste solution | |
| CN106745128A (en) | A kind of method of aluminium lime-ash removal of impurities | |
| CN101760637B (en) | Leaching technology of magnesium-containing ore | |
| CN102502722A (en) | Preparation method of high-purity magnesium oxide | |
| CN109911909B (en) | Recovery processing method of waste sagger in preparation process of lithium cobaltate positive electrode material | |
| CN101760646A (en) | Leaching method of magnesium-containing ore | |
| CN101760614B (en) | Leaching method of nickel-containing ore | |
| CN104773748A (en) | Method for preparing low-iron polyaluminium sulfate by using aluminiferous waste sulfuric acid mother liquor | |
| CN104071954A (en) | Method of treating high-iron red mud by alkaline process for deep dealkalization and iron enrichment | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN104743586A (en) | Joint production method of alkali leaching of aluminium in Bayer red mud and aluminium oxide decomposed mother liquid evaporation for salt elimination | |
| CN104711428B (en) | Method for preparing and recovering metal in pickling sludge | |
| CN106755997A (en) | A kind of method of nickel-containing ore comprehensive utilization | |
| CN101880771A (en) | Method for recovering magnesium from magnesium-contained waste liquid | |
| CN102398913B (en) | Process for extracting metallurgical grade alumina through treatment of high alumina fly ash by using sulfuric acid method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |