CN106756023A - The method that depth separates calcium and magnesium impurity in manganese sulfate - Google Patents
The method that depth separates calcium and magnesium impurity in manganese sulfate Download PDFInfo
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- CN106756023A CN106756023A CN201611219130.XA CN201611219130A CN106756023A CN 106756023 A CN106756023 A CN 106756023A CN 201611219130 A CN201611219130 A CN 201611219130A CN 106756023 A CN106756023 A CN 106756023A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
Abstract
A kind of method that depth separates calcium and magnesium impurity in manganese sulfate, comprises the following steps：Manganese sulfate containing calcium and magnesium impurity is soluble in water, obtain the manganese sulfate solution containing calcium and magnesium impurity；Manganese sulfate solution containing calcium and magnesium impurity is mixed and heated with soluble fluoride salt dissolving, the heavy agent of rush, cooling and aging obtains manganese sulfate filtrate to form calcirm-fluoride and fluorination magnesium precipitate, filtering；Manganese sulfate filtrate is extracted using organic extraction agent solution, extract containing manganese is obtained；Manganese extract will be contained to be stripped using sulfuric acid solution, manganese sulfate strip liquor will be obtained；Manganese sulfate strip liquor is adjusted into pH value to 4.5~6.5, evaporation obtains the mass content of calcium constituent no more than 20ppm, the manganese sulfate of the mass content no more than 10ppm of magnesium elements.Rationally, reaction condition is easily controllable, and equipment investment is few, and product yield is high, with huge practical value for the method process is simple.Thoroughly, wherein the mass content of calcium constituent is no more than 20ppm to the removal of impurities of calcium and magnesium impurity in the manganese sulfate for obtaining, and the mass content of magnesium elements is no more than 10ppm.
Description
Technical field
The present invention relates to non-ferrous metal technical field, more particularly to a kind of depth separates the side of calcium and magnesium impurity in manganese sulfate
Method.
Background technology
The purposes of manganese widely, is related to the every aspect of human being's production life.With scientific and technical constantly progressive, sulfuric acid
Manganese salt based on manganese, its consumption and purposes constantly expand；It is increasingly exhausted with high-grade promoter manganese, conventional ion exchanges,
The production technologies such as evaporating, concentrating and crystallizing, chemical precipitation and extraction have been difficult to meet the production needs of high-purity sulphuric acid manganese product.
At present, most heavy metal ion can be removed well in the sulphuric leachate of manganese ore, however calcium and magnesium therein from
Son purification is but very difficult, the difficulty for causing high-purity sulphuric acid manganese product to prepare.And the clean-up effect of calcium and magnesium can directly determine sulfuric acid
Whether manganese product can reach the quality requirement of other manganese sulfate products such as heavy-duty battery raw material.So research and development depth point
The method of calcium and magnesium impurity shows important especially in manganese sulfate.
The content of the invention
Based on this, it is necessary to provide a kind of high income, calcium and magnesium impurities removing efficiency depth high and separate calcium and magnesium impurity in manganese sulfate
Method.
A kind of method that depth separates calcium and magnesium impurity in manganese sulfate, comprises the following steps：
Manganese sulfate containing calcium and magnesium impurity is soluble in water, obtain the manganese sulfate solution containing calcium and magnesium impurity；
The manganese sulfate solution containing calcium and magnesium impurity is mixed and heated with soluble fluoride salt dissolving, the heavy agent of rush, is cooled down, it is old
Change, to form calcirm-fluoride and fluorination magnesium precipitate, filtering, obtain manganese sulfate filtrate；
The manganese sulfate filtrate is extracted using organic extraction agent solution, extract containing manganese is obtained；
The extract containing manganese is stripped using sulfuric acid solution, manganese sulfate strip liquor is obtained；
The manganese sulfate strip liquor is adjusted into pH value to 4.5~6.5, evaporation, the mass content for obtaining calcium constituent is no more than
20ppm, the manganese sulfate of the mass content no more than 10ppm of magnesium elements.
The method that above-mentioned depth separates calcium and magnesium impurity in manganese sulfate, rationally, reaction condition is easily controllable, equipment for process is simple
Small investment, product yield is high, with huge practical value.Thoroughly, wherein calcium is first for the removal of impurities of calcium and magnesium impurity in the manganese sulfate for obtaining
The mass content of element is no more than 20ppm, and the mass content of magnesium elements is no more than 10ppm.
Wherein in one embodiment, the matter of calcium magnesium element total amount and water in the manganese sulfate solution containing calcium and magnesium impurity
Amount volume ratio is 1g/ (1.3~2.6) L.
Wherein in one embodiment, the soluble fluoride salt dissolving is at least one in sodium fluoride and potassium fluoride, described
Soluble fluoride salt dissolving is 6~10 with the mass ratio of calcium magnesium element total amount in the manganese sulfate solution containing calcium and magnesium impurity:1.
Wherein in one embodiment, the heavy agent of rush is at least one in barium fluoride, calcium sulfate and barium sulfate, described
It is 4~13 to promote heavy agent with the mass ratio of calcium magnesium element total amount in the manganese sulfate solution containing calcium and magnesium impurity:1.
Wherein in one embodiment, the condition of the heating is 95~100 DEG C of 1~2h of heating, the time of the ageing
It is 4~8h.
Wherein in one embodiment, the organic extraction agent solution is the mixed liquor of organic extractant and kerosene, described
Organic extractant is di (isooctyl) phosphate, isooctyl phosphoric acid di-isooctyl, di alkyl phosphonic acid and di-(2-ethylhexyl)phosphoric acid ester
In at least one.
Wherein in one embodiment, the volume of organic extractant and the kerosene described in the organic extraction agent solution
Than being 15~35:65~85.
Wherein in one embodiment, the organic extractant is the organic extractant by NaOH solution saponification, soap
Rate is 50%~70%.
Wherein in one embodiment, the organic extraction agent solution is 1~3 with the volume ratio of the manganese sulfate filtrate:
1。
Wherein in one embodiment, the concentration of the sulfuric acid solution is 0.5~2mol/L；The extract containing manganese and institute
The volume ratio for stating sulfuric acid solution is 1:1~2.
Brief description of the drawings
Fig. 1 be an embodiment depth separate manganese sulfate in calcium and magnesium impurity method flow chart.
Specific embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing
Give preferred embodiment of the invention.But, the present invention can be realized in many different forms, however it is not limited to herein
Described embodiment.On the contrary, the purpose for providing these embodiments is to make the understanding to the disclosure more saturating
It is thorough comprehensive.
Fig. 1 is referred to, the depth of one embodiment of the invention separates the method for calcium and magnesium impurity in manganese sulfate, including following step
Suddenly.
Step S1：Manganese sulfate containing calcium and magnesium impurity is soluble in water, obtain the manganese sulfate solution containing calcium and magnesium impurity.
Preferably, calcium magnesium element total amount is with the mass volume ratio of water in the manganese sulfate solution containing calcium and magnesium impurity
1g/ (1.3~2.6) L.When the content of calcium and magnesium impurity in the manganese sulfate containing calcium and magnesium impurity is, it is known that directly press calcium magnesium element total amount
Mass volume ratio with water is 1g/ (1.3~2.6) L dissolvings, obtains the manganese sulfate solution containing calcium and magnesium impurity.When containing calcium and magnesium
The content of calcium and magnesium impurity is unknown in the manganese sulfate of impurity, and calcium and magnesium impurity content point is first carried out to the manganese sulfate containing calcium and magnesium impurity
Analysis, obtains the content of calcium and magnesium impurity.
Preferably, heating for dissolving can be also used in step S1, the temperature of heating for dissolving is 90~100 DEG C.
Step S2：Manganese sulfate solution containing calcium and magnesium impurity is mixed and heated with soluble fluoride salt dissolving, the heavy agent of rush, it is cold
But, to form calcirm-fluoride and fluorination magnesium precipitate, ageing, filtering, manganese sulfate filtrate is obtained.
Step S2 promotes calcium ions and magnesium ions to form calcirm-fluoride and fluorination magnesium precipitate respectively with fluorine ion using soluble fluoride salt dissolving,
So that most of calcium and magnesium impurity enriched obtains the sulfuric acid of preliminary sedimentation deliming magnesium addition in precipitation, and then by filtering
Manganese filtrate.Because the amount of wherein calcium ions and magnesium ions is relatively fewer, the heavy agent of rush is added to make a small amount of calcirm-fluoride for just having generated and fluorination
Magnesium can comparatively fast be precipitated with heavy agent is promoted, and then improve the separative efficiency of settling velocity and calcium ions and magnesium ions.
Preferably, soluble fluoride salt dissolving is at least one in sodium fluoride and potassium fluoride.Preferably, soluble fluoride salt dissolving with
The mass ratio of calcium magnesium element total amount is 6~10 in the manganese sulfate solution containing calcium and magnesium impurity:1.
Preferably, it is at least one in barium fluoride, calcium sulfate and barium sulfate to promote heavy agent.Preferably, promote heavy agent with it is described
The mass ratio of calcium magnesium element total amount is 4~13 in manganese sulfate solution containing calcium and magnesium impurity:1.
Preferably, the condition of heating is 95~100 DEG C of 1~2h of heating.Because the solubility of the fluoride salts such as sodium fluoride is limited,
Solution is set to reach pre- boiling state using being heated to 95~100 DEG C, it is ensured that the fluoride salt such as calcium ions and magnesium ions and sodium fluoride possesses fully
Temperature and time needed for reaction, and then ensure the efficiency of separating calcium and magnesium.
Preferably, the time of ageing is 4~8h.Ageing can ensure the CaF of generation2And MgF2Sediment is promoting the work of heavy agent
With the lower time with precipitation enough, so as to efficiently separate calcium and magnesium impurity.
Step S3：Manganese sulfate filtrate is extracted using organic extraction agent solution, extract containing manganese is obtained.
Step S3 continues abstraction impurity removal to the manganese sulfate filtrate of preliminary sedimentation deliming magnesium addition, so as to by most of manganese ion
It is extracted into organic phase, most calcium and magnesium impurity is stayed in raffinate.
Preferably, organic extraction agent solution is the mixed liquor of organic extractant and kerosene, and organic extractant is that di(2-ethylhexyl)phosphate is different
Monooctyl ester (P204), isooctyl phosphoric acid di-isooctyl (P507), di alkyl phosphonic acid (Cyanex272) and di-(2-ethylhexyl)phosphoric acid
At least one in ester.It is furthermore preferred that organic extraction agent solution is the mixed liquor of di-(2-ethylhexyl)phosphoric acid ester and kerosene.More
Preferably, the volume ratio of organic extractant and kerosene is 15~35 in organic extraction agent solution:65~85.
It is furthermore preferred that organic extractant is the organic extractant by NaOH solution saponification, saponification rate is 50%~
70%, the molar concentration of NaOH solution used by saponification is 8~12mol/L.
Saponification be in order to control the scope of the pH value of organic extractant, and then be conducive to manganese ion and calcium ions and magnesium ions point
From.Saponification rate is more than 70%, then organic extractant pH value is higher, and calcium and magnesium manganese ion is extracted by organic extractant simultaneously, is not reached
Separate the purpose of manganese and calcium ions and magnesium ions；Saponification rate is less than 50%, then organic extractant pH value is relatively low, although calcium ions and magnesium ions are all difficult
Extracted by organic extractant, but manganese ion extraction yield also degradation, and then cause the yield of manganese sulfate product seriously relatively low,
Causing production cost increases.
Specifically, step S3 is specially to mix manganese sulfate filtrate and organic extraction agent solution extract, stratification,
Isolated organic phase, i.e. extract containing manganese.Specifically, step S3 uses single-stage extraction.
It is furthermore preferred that organic extraction agent solution is 1~3 with the volume ratio of manganese sulfate filtrate:1；Extraction is stirred in step S3
Time is 20~30min；The time of static layering is 30~40min after stirring extraction, so that manganese element in the raffinate
Concentration is 1~2g/L.
Because organic extraction agent solution preferentially extracts Mn ions, then also there is extraction to Ca, Mg ion, in order that calcium and magnesium
Ion depth separate, it is to avoid calcium ions and magnesium ions simultaneously extract cannot ion so that influence manganese sulfate product quality, it is necessary to control
The concentration of manganese element is 1~2g/L in raffinate processed.
By control the volume ratio of manganese sulfate filtrate and organic extraction agent solution during extraction, extraction and static layering when
Between, so control manganese element in raffinate concentration be 1~2g/L.Manganese sulfate filtrate is small with the volume ratio of organic extraction agent solution
In 1：1, then the manganese for being remained in extraction raffinate causes the yield of manganese ion relatively low more than 2g/L；Manganese sulfate filtrate and organic extraction
The volume ratio of agent solution is more than 1：3, then the manganese for being remained in raffinate is less than 1g/L, causes part calcium ions and magnesium ions to be also extracted to
In machine phase, the purpose of depth separating calcium and magnesium is not reached, influence the quality of manganese sulfate product.
Wherein in one embodiment, step is included after step s 3 and also before step S 4, will be described containing manganese extraction
Take liquid ion.Preferably, water and the volume ratio containing manganese extract are 3~1:1.It is furthermore preferred that the number of times of ion is 3
~4 times.The purpose of washing of adding water is to wash away the impurity such as calcium, magnesium, fluorine, the sodium carried secretly in organic extract.If washing time
Number is inadequate, then can cause that impurity is higher, and then influences the product quality of manganese sulfate.
Specifically, the ion of extract containing manganese is specially：Manganese extract will be contained and water will mix washing, it is quiet
Layering is put, organic phase is obtained.Preferably, the time of agitator treating is 30~40min, and the time of static layering is after agitator treating
35~45min.
Step S4：Manganese extract will be contained to be stripped using sulfuric acid solution, manganese sulfate strip liquor will be obtained.
Preferably, the concentration of sulfuric acid solution is 0.5~2mol/L.Preferably, the volume of extract containing manganese and sulfuric acid solution
Than being 1:1~2.Preferably, the number of times of back extraction is 1~2 time.
Specifically, manganese extract will be contained in step S4 be stripped using sulfuric acid solution, the step of obtain manganese sulfate strip liquor
Manganese extract will specially be contained and sulfuric acid solution will mix back extraction, stratification, the back extraction of isolated water phase, i.e. manganese sulfate
Liquid.Preferably, the time of the stirring back extraction is 20~30min, and the time of stratification is 30 after the stirring back extraction
~40min.
Step S5：Manganese sulfate strip liquor is adjusted into pH value to 4.5~6.5, evaporation, the mass content for obtaining calcium constituent does not surpass
Cross 20ppm, the manganese sulfate of the mass content no more than 10ppm of magnesium elements.
Preferably, the reagent used by regulation pH is manganese carbonate.Manganese sulfate strip liquor due to containing sulfuric acid solution, its acidity value
It is higher, the manganese carbonate regulation pH value of alkalescence is added, new impurity will not be introduced, while control ph is conducive to sulphur to 4.5~6.5
The evaporative crystallization of sour manganese.The manganese sulfate for obtaining is manganese sulfate monohydrate.
Thoroughly, wherein the mass content of calcium constituent is no more than 20ppm, magnesium elements to the removal of impurities of calcium and magnesium impurity in the manganese sulfate for obtaining
Mass content be no more than 10ppm.
The method that above-mentioned depth separates calcium and magnesium impurity in manganese sulfate, rationally, reaction condition is easily controllable, equipment for process is simple
Small investment, product yield is high, with huge practical value.Specifically, the high income of manganese sulfate is up to 93%.
It is below specific embodiment.
Embodiment 1
The manganese sulfate raw material that 100g is contained into calcium and magnesium impurity is added in 600mL water, and is heated to 100 DEG C of stirring and dissolvings,
Obtain the manganese sulfate solution containing calcium and magnesium impurity.The mass content of Ca elements is in manganese sulfate raw material containing calcium and magnesium impurity
The mass content of 0.12%, Mg element is 0.11%, and the mass content of manganese sulfate is 88.65%.
The above-mentioned manganese sulfate solution containing calcium and magnesium impurity is mixed and heated to 1.38g sodium fluorides solid, 3g barium fluorides
100 DEG C are stirred 2 hours, are cooled to room temperature, are aged 8 hours, and filtering obtains manganese sulfate filtrate.
By manganese sulfate filtrate and organic extraction agent solution by volume 1:1 mixing carries out single-stage extraction, stirring extraction
30min, stratification 40min, obtain extract containing manganese.Wherein organic extraction agent solution be di-(2-ethylhexyl)phosphoric acid ester and
Kerosene mixture, the wherein volume ratio of di-(2-ethylhexyl)phosphoric acid ester and kerosene are 15:85.And di-(2-ethylhexyl)phosphoric acid
The saponification rate 70% of ester, the molar concentration of the NaOH solution used by saponification is 12mol/L.
By water and extract containing manganese by volume 1:1 stirring mixing carries out washing impurity-removing 40min, stratification 45min, point
From the extract containing manganese for obtaining organic phase, washing lotion is abandoned.Washing 4 times.
Extract containing manganese and 2mol/L sulfuric acid solutions after by ion by volume 1:1 stirring mixing is stripped
30min, stratification 40min, the manganese sulfate strip liquor of isolated water phase；Back extraction number of times is 2 times.Manganese sulfate strip liquor is adjusted
Section pH to 6.5, evaporation, crystallization obtains manganese sulfate crystal, and its purity is 99.2%.
Embodiment 2
The manganese sulfate raw material containing calcium and magnesium impurity used by embodiment 2 is same as Example 1.100g is contained into calcium and magnesium impurity
Manganese sulfate raw material be added in 300mL water, and be heated to 90 DEG C of stirring and dissolvings, obtain the manganese sulfate containing calcium and magnesium impurity molten
Liquid.
The above-mentioned manganese sulfate solution containing calcium and magnesium impurity and 2.3g sodium fluorides solid, 1g calcium sulfate are mixed and heated to 95
DEG C stirring 1 hour, is cooled to room temperature, is aged 4 hours, and filtering obtains manganese sulfate filtrate.
By manganese sulfate filtrate and organic extraction agent solution by volume 1:3 mixing carry out single-stage extraction, stirring extraction
20min, stratification 30min, obtain extract containing manganese.Wherein organic extraction agent solution is that di (isooctyl) phosphate and kerosene mix
The volume ratio of thing, wherein di (isooctyl) phosphate and kerosene is 35:65.And the saponification rate 50% of di (isooctyl) phosphate, used by saponification
NaOH solution molar concentration be 8mol/L.
By water and extract containing manganese by volume 3:1 stirring mixing carries out washing impurity-removing 30min, stratification 35min, point
From the extract containing manganese for obtaining organic phase, washing lotion is abandoned.Washing 3 times.
Extract containing manganese and 0.5mol/L sulfuric acid solutions after by ion by volume 1:2 stirring mixing are stripped
Take 20min, stratification 30min, the manganese sulfate strip liquor of isolated water phase；Back extraction number of times is 1 time.By manganese sulfate strip liquor
Regulation pH to 4.5, evaporation, crystallization obtains manganese sulfate crystal.
Embodiment 3
The manganese sulfate raw material containing calcium and magnesium impurity used by embodiment 3 is same as Example 1.100g is contained into calcium and magnesium impurity
Manganese sulfate raw material (raw material is same as Example 1) be added in 300mL water, and be heated to 95 DEG C of stirring and dissolvings, contained
The manganese sulfate solution of calcium and magnesium impurity.
The above-mentioned manganese sulfate solution containing calcium and magnesium impurity is mixed and heated to 1.84g potassium fluorides solid, 2g barium sulfate
98 DEG C are stirred 1.5 hours, are cooled to room temperature, are aged 6 hours, and filtering obtains manganese sulfate filtrate.
By manganese sulfate filtrate and organic extraction agent solution by volume 1:2 mixing carry out single-stage extraction, stirring extraction
25min, stratification 35min, obtain extract containing manganese.Wherein organic extraction agent solution is isooctyl phosphoric acid di-isooctyl and coal
Oil mixture, the wherein volume ratio of isooctyl phosphoric acid di-isooctyl and kerosene are 25:75.And the soap of isooctyl phosphoric acid di-isooctyl
Rate 60%, the molar concentration of the NaOH solution used by saponification is 10mol/L.
By water and extract containing manganese by volume 2:1 stirring mixing carries out washing impurity-removing 35min, stratification 40min, point
From the extract containing manganese for obtaining organic phase, washing lotion is abandoned.Washing 4 times.
Extract containing manganese and 1.2mol/L sulfuric acid solutions after by ion by volume 1:1.5 stirring mixing are carried out instead
Extraction 25min, stratification 35min, the manganese sulfate strip liquor of isolated water phase；Back extraction number of times is 2 times.Manganese sulfate is stripped
Liquid adjusts pH to 5.5, and evaporation, crystallization obtains manganese sulfate crystal.
Comparative example 1
Raw material and operating procedure with embodiment 1 is essentially identical, and difference is：The quality of sodium fluoride solid is
1.15g, the quality of barium fluoride is 0.5g.
Comparative example 2
Raw material and operating procedure with embodiment 1 is essentially identical, and difference is：By manganese sulfate filtrate and organic extraction
Agent solution by volume 1:4 mixing carry out single-stage extraction, and stirring extraction 40min, stratification 20min obtain extract containing manganese.
Wherein the volume ratio of di-(2-ethylhexyl)phosphoric acid ester and kerosene is 45:55.And the saponification rate of di-(2-ethylhexyl)phosphoric acid ester
80%, the molar concentration of the NaOH solution used by saponification is 13mol/L.
Comparative example 3
Raw material and operating procedure with embodiment 1 is essentially identical, and difference is：By manganese sulfate filtrate and organic extraction
Agent solution by volume 1:0.5 mixing carries out single-stage extraction, and stirring extraction 100min, stratification 20min obtain being extracted containing manganese
Liquid.Wherein the volume ratio of di-(2-ethylhexyl)phosphoric acid ester and kerosene is 10:90.And the saponification of di-(2-ethylhexyl)phosphoric acid ester
Rate 40%, the molar concentration of NaOH solution used by saponification is 6mol/L.
The manganese sulfate that embodiment 1~3 and comparative example 1~3 are obtained is carried out into elementary analysis, the analysis result for obtaining such as table
1.As shown in Table 1, the high income of the manganese sulfate of embodiment 1~3 is up to 93%, and in the manganese sulfate for obtaining calcium constituent mass content not
More than 0.002% (i.e. 20ppm), the mass content of magnesium elements is no more than 0.001% (i.e. 10ppm).The yield of comparative example 1 is relatively low,
And calcium ions and magnesium ions mass content is higher.Yield is higher in comparative example 2, but its calcium ions and magnesium ions mass content is too high.In comparative example 3
Calcium ions and magnesium ions mass content is relatively low, but its yield is too low.
Table 1
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of method that depth separates calcium and magnesium impurity in manganese sulfate, it is characterised in that comprise the following steps：
Manganese sulfate containing calcium and magnesium impurity is soluble in water, obtain the manganese sulfate solution containing calcium and magnesium impurity；
The manganese sulfate solution containing calcium and magnesium impurity is mixed and heated with soluble fluoride salt dissolving, the heavy agent of rush, is cooled down, ageing,
To form calcirm-fluoride and fluorination magnesium precipitate, filtering, manganese sulfate filtrate is obtained；
The manganese sulfate filtrate is extracted using organic extraction agent solution, extract containing manganese is obtained；
The extract containing manganese is stripped using sulfuric acid solution, manganese sulfate strip liquor is obtained；
The manganese sulfate strip liquor is adjusted into pH value to 4.5~6.5, evaporation, the mass content for obtaining calcium constituent is no more than
20ppm, the manganese sulfate of the mass content no more than 10ppm of magnesium elements.
2. the method that depth as claimed in claim 1 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that described to contain calcium and magnesium
Calcium magnesium element total amount and the mass volume ratio of water are 1g/ (1.3~2.6) L in the manganese sulfate solution of impurity.
3. the method that depth as claimed in claim 1 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the soluble fluoride
Salt dissolving is at least one in sodium fluoride and potassium fluoride, and the soluble fluoride salt dissolving is molten with the manganese sulfate containing calcium and magnesium impurity
The mass ratio of calcium magnesium element total amount is 6~10 in liquid:1.
4. the method that depth as claimed in claim 1 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the heavy agent of the rush is
In at least one in barium fluoride, calcium sulfate and barium sulfate, the heavy agent of the rush and the manganese sulfate solution containing calcium and magnesium impurity
The mass ratio of calcium magnesium element total amount is 4~13:1.
5. the method that depth as claimed in claim 1 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the bar of the heating
Part is 95~100 DEG C of 1~2h of heating, and the time of the ageing is 4~8h.
6. the method that depth as claimed in claim 1 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the organic extraction
Agent solution is the mixed liquor of organic extractant and kerosene, and the organic extractant is di (isooctyl) phosphate, isooctyl phosphoric acid two is different
At least one in monooctyl ester, di alkyl phosphonic acid and di-(2-ethylhexyl)phosphoric acid ester.
7. the method that depth as claimed in claim 6 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the organic extraction
The volume ratio of organic extractant described in agent solution and the kerosene is 15~35:65~85.
8. the method that depth as claimed in claim 6 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the organic extraction
Agent is the organic extractant by NaOH solution saponification, and saponification rate is 50%~70%.
9. the method that depth as claimed in claim 6 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that the organic extraction
Agent solution is 1~3 with the volume ratio of the manganese sulfate filtrate:1.
10. the method that the depth as described in any one of claim 1~9 separates calcium and magnesium impurity in manganese sulfate, it is characterised in that institute
The concentration for stating sulfuric acid solution is 0.5~2mol/L；The extract containing manganese is 1 with the volume ratio of the sulfuric acid solution:1~2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111170368A (en) * | 2020-02-27 | 2020-05-19 | 中国恩菲工程技术有限公司 | Treatment system and treatment method for reducing content of impurities in soluble manganese sulfate solution |
| CN111187906A (en) * | 2020-02-18 | 2020-05-22 | 中国恩菲工程技术有限公司 | Method for purifying manganese sulfate solution |
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| CN112795773A (en) * | 2020-12-18 | 2021-05-14 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
| CN115159579A (en) * | 2022-08-01 | 2022-10-11 | 贵州金瑞新材料有限责任公司 | Method for deeply separating calcium and magnesium impurities in manganese sulfate |
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