CN109336138A - The separation method of potassium sodium in a kind of mixed sulfate containing potassium and sodium - Google Patents
The separation method of potassium sodium in a kind of mixed sulfate containing potassium and sodium Download PDFInfo
- Publication number
- CN109336138A CN109336138A CN201811573941.9A CN201811573941A CN109336138A CN 109336138 A CN109336138 A CN 109336138A CN 201811573941 A CN201811573941 A CN 201811573941A CN 109336138 A CN109336138 A CN 109336138A
- Authority
- CN
- China
- Prior art keywords
- sodium
- potassium
- mixed
- sulfate
- obtains
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a kind of separation method of potassium sodium in mixed sulfate containing potassium and sodium, the method mixes ferric sulfate with mixed sulfate, so that potassium therein is converted into autunezite, and then realizes the separation of potassium and sodium；Sulfuric acid nak response in the separation process in ferric sulfate and mixed sulfate generates the autunezite of indissoluble, and sodium sulphate does not participate in reaction, the autunezite and sodium sulphate of generation pass through solid-liquor separation, to realize the separation of potassium sodium in the mixed sulfate containing potassium and sodium, the purity > 95% for the autunezite that separation method of the present invention obtains, the purity > 92% of sodium sulphate.
Description
Technical field
The present invention relates to potassium sodium in the separation field of potassium sodium in mixed salt more particularly to a kind of mixed sulfate containing potassium and sodium
Separation method.
Background technique
The production process of many enterprises of chemical industry can generate a large amount of abraum salt, residue, with many kinds of, ingredient is multiple
Miscellaneous, the features such as source is a variety of, poisonous and harmful substance content is high, processing cost is high, environmental hazard is big.If such abraum salt is directly arranged
Soil Surrounding will be destroyed by putting, and increase water body salt content.Nacl had both been important industrial chemicals and national strategy money
Source recycles chemical industry by-product abraum salt as the raw material of industry or other research and development purposes, can not only eliminate the pollution to environment,
Resource can also be made full use of to realize by-product recycling and circular economy.Therefore, abraum salt has been processed into urgent problem to be solved.
Sylvite, sodium salt are all soluble salts, what they always coexisted in nature.The separation of chemical industry sodium potassium
It is mainly realized using the two different solubility at different temperatures, with production and expanding economy, with common
Recrystallization method is difficult to realize being kept completely separate for sodium potassium.
The separating extraction device and separating and extracting process of a kind of sodium and potassium are disclosed in CN102448885A, using multistage cold
But it crystallizes and absorbs the mode that combines, Isolating chlorinated potassium and sodium bicarbonate with conversion, the patent is applied to containing sodium, potassium, chlorine
Mixed solution, and process is longer, energy consumption is larger.
CN103555969A discloses a kind of new method of potassium sodium separation, using t-BAMBP dimethylbenzene system to potassium carbonate,
The sodium hydroxide solution of sodium carbonate is extracted, separating potassium sodium, and this method generates a large amount of raffinate, cleaning solution, and containing big
The organic matter of amount, environmental hazard are big.
CN107188201A discloses a kind of separation system and sodium salt and sylvite separation method, the separation system include according to
Secondary connected Crystallization Separation equipment, heat preservation settlement equipment, cooling crystallizing equipment and centrifugation apparatus；The heat preservation settlement equipment is equipped with
Feeding inlet, the first discharge port and the second discharge port, the feeding inlet and first discharge port with the Crystallization Separation equipment
It is connected, second discharge port is connected with the cooling crystallizing equipment.The separation system can be by the sodium salt and sylvite in solution
It is precipitated, and the crystals of sodium salt and sylvite crystal being separated from each other.The sodium salt and sylvite separation method use above-mentioned separation
System handles the waste water containing sodium salt and sylvite, the crystals of sodium salt and sylvite crystal that can be separated from each other, this side
The process of case is complicated, and separative efficiency is insufficient.
Although above-mentioned document discloses the method for potassium sodium in some mixed salts of the separation containing potassium and sodium, but still there is separation
Therefore the problem of process is complicated for operation, low separation efficiency develops a kind of simple process, cost is relatively low, products obtained therefrom purity is high
New potassium-sodium separation method still has a very important significance.
Summary of the invention
The purpose of the present invention is to provide a kind of separation method of potassium sodium in mixed sulfate containing potassium and sodium, the methods
Ferric sulfate is mixed with mixed sulfate, so that potassium therein is converted into autunezite, and then realizes the separation of potassium and sodium；It is described
Sulfuric acid nak response in separation process in ferric sulfate and mixed sulfate generates the autunezite of indissoluble, and sodium sulphate is not participated in
Reaction, the autunezite and sodium sulphate of generation are by solid-liquor separation, to realize potassium sodium in the mixed sulfate containing potassium and sodium
Separation, the purity > 95% for the autunezite that separation method of the present invention obtains, the purity > 92% of sodium sulphate.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
The present invention provides a kind of separation method of potassium sodium in mixed sulfate containing potassium and sodium, the method is by ferric sulfate
It is mixed with mixed sulfate, so that potassium therein is converted into autunezite, and then realizes the separation of potassium and sodium.
Mixed sulfate of the present invention containing potassium and sodium refers to that industrial processes or sewage disposal process generate
The salt-mixture containing sodium sulphate and potassium sulfate, and in the salt-mixture, the mass percentage of sodium sulphate and potassium sulfate >=
90% (illustratively including 90%, 92%, 95%, 97% or 99% etc.), to ensure that the purity of product.
Potassium of the present invention, sodium respectively represent potassium element and sodium element.
The method of the invention converts autunezite for the potassium in the mixed sulfate containing potassium and sodium using ferric sulfate and sinks
It forms sediment, and sodium salt still keeps dissolved state, and the separation of potassium sodium in the mixed sulfate containing potassium and sodium is realized by solid-liquor separation, and
Guarantee the separative efficiency of potassium.
Preferably, the molar ratio of the ferric sulfate and potassium is (1-8): 1, such as 1:1,2:1,3:1,4:1,5:1,6:1,7:
1 or 8:1 etc., preferably (3-6): 1.
The present invention uses the molar ratio relationship of above-mentioned ferric sulfate and potassium, and ensure that in heating reaction process will contain potassium and sodium
Mixed sulfate in the potassium of 95% or more (illustratively include 95%, 96%, 98%, 99% or 99.9% etc.) be converted into Huang
The purity > 95% of krausite and isolated autunezite, the purity > 92% of sodium sulphate.
Preferably, it the described method comprises the following steps:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, is dissolved by heating to obtain mixed solution；
(2) pH for the mixed solution that sulfuric acid regulating step (1) obtains is added, heating reaction, solid-liquor separation obtains Huang later
Krausite and filtrate；
(3) pH for the filtrate that alkali regulating step (2) obtain is added, solid-liquor separation obtains iron hydroxide and sodium salt solution, from
And realize the separation of potassium and sodium.
Preferably, the concentration of the mixed sulfate containing potassium and sodium is 10-400g/L, example in step (1) described mixed solution
Such as 10g/L, 30g/L, 50g/L, 100g/L, 150g/L, 200g/L, 250g/L, 300g/L, 350g/L or 400g/L；It is preferred that
For 50-200g/L.
Preferably, the temperature of step (1) described heating for dissolving is 20-100 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., preferably 50-100 DEG C.
Preferably, the pH of step (2) described mixed solution be 1-3, such as 1,1.2,1.5,1.8,2,2.2,2.5,2.8 or
3 etc., preferably 1.2-2.
It is 1-3 that the present invention, which controls sulfuric acid and adjusts the pH of mixed solution, is conducive to improve point of potassium sodium in sulfate mixed liquor
From efficiency, the potassium conversion of (illustratively including 95%, 98%, 99% or 99.9% etc.) 95% or more in mixed sulfate is controlled
For precipitation as jarosite, further increase the purity of autunezite and sodium sulphate.
The reaction equation that potassium of the present invention reacts generation precipitation as jarosite with ferric sulfate is as follows:
K2SO4+3Fe2(SO4)3+12H2O→2K2Fe6(SO4)4(OH)12+6H2SO4；
By reaction equation it can be seen that reaction process generates autunezite and sulfuric acid, therefore after reaction under the pH of solution
Drop.
Preferably, the temperature of step (2) the heating reaction is 50-100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70
DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc., preferably 70-90 DEG C.
Preferably, step (2) it is described heating reaction time be 0.5-10h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h,
7h, 8h, 9h or 10h etc., preferably 1-8h.
It preferably, further include stirring during step (2) the heating reaction.
Preferably, the rate of the stirring be 50-500r/min, such as 50r/min, 100r/min, 150r/min,
200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min or 500r/min, preferably 100-
300r/min。
Preferably, step (3) described alkali includes sodium hydroxide.
Preferably, pH >=3 of step (3) described filtrate, such as 3,4,5 or 6 etc., preferably 3-4.
Step (3) of the present invention controls pH >=3 of filtrate by the way that alkali is added, so that excessive ferric sulphate precipitate generates hydrogen
Iron oxide, realizes the recycling of molysite, while ensure that the purity of sodium sulphate recycling.
Preferably, the method also includes obtaining ferric sulfate in the iron hydroxide for obtaining sulfuric acid addition step (3), and will
In ferric sulfate return step (1).
Excessive ferric sulfate is realized its separation with sodium sulphate by sodium hydroxide pellets by the present invention, molten with sulfuric acid later
Solution obtains ferric sulfate, and recycling in return step (1), to improve the utilization rate of ferric sulfate.
Preferably, the method also includes step (3) the sodium salt solution evaporative crystallization is obtained sodium sulphate.
Preferably, in the condensed water return step (1) of the evaporative crystallization.
The present invention will be used to dissolve mixed sulfate and sulphur containing potassium and sodium in the condensed water return step (1) of evaporative crystallization
Sour iron realizes recycling for water, reduces separation costs.
As currently preferred technical solution, the described method comprises the following steps:
(I) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, heat under conditions of 20-100 DEG C molten
Solution obtains mixed solution；The molar ratio of the ferric sulfate and potassium is (1-8): 1, the mix sulphur containing potassium and sodium in the mixed solution
The concentration of hydrochlorate is 10-400g/L；
(II) pH that the mixed solution that sulfuric acid regulating step (I) obtains is added is 1-3, is heated under the conditions of 50-100 DEG C anti-
0.5-10h is answered, further includes stirring during heating reaction, the rate of stirring is 50-500r/min, and solid-liquor separation obtains later
Autunezite and filtrate；
(III) be added pH >=3 of filtrate that sodium hydroxide regulating step (II) obtains, solid-liquor separation obtain iron hydroxide and
Sodium salt solution；
(IV) sulfuric acid dissolution is added in the iron hydroxide that step (III) obtains and obtains ferric sulfate, gained ferric sulfate returns to step
Suddenly in (I)；
(V) sodium salt solution that step (III) obtains is evaporated crystallization and obtains sodium sulphate, the condensed water of evaporative crystallization returns
It returns in step (I).
Compared with the existing technology, the invention has the following advantages:
(1) the method for the invention converts yellow potassium iron for the potassium in the mixed sulfate containing potassium and sodium using ferric sulfate
Alum, while sodium sulphate remains at dissolved state, to realize potassium in the mixed sulfate containing potassium and sodium by solid-liquor separation
The separation of sodium, while the purity > 95% of isolated autunezite, the purity > 92% of sodium sulphate；
(2) the excessive ferric sulfate being added in the separation process of the method for the invention is dissolved by alkaline chemical precipitation and acid adding
The step of, it realizes the recycling of ferric sulfate, reduces costs；
(3) separation process of the method for the invention is easy to operate, it is not necessary that organic solvent is added.
Detailed description of the invention
Fig. 1 is the work of the separation method of potassium sodium in mixed sulfate containing potassium and sodium described in the specific embodiment of the invention
Skill flow chart.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
In mixed sulfate of the present invention containing potassium and sodium the separation method of potassium sodium process flow chart as shown in Figure 1,
Itself specifically includes the following steps:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, is dissolved by heating to obtain mixed solution；
(2) pH for the mixed solution that sulfuric acid regulating step (1) obtains is added, heats hybrid reaction, solid-liquor separation obtains later
To autunezite and filtrate；
(3) pH for the filtrate that alkali regulating step (2) obtain is added, solid-liquor separation obtains iron hydroxide and sodium salt solution；
(4) sulfuric acid dissolution is added in the iron hydroxide that step (3) obtains and obtains ferric sulfate, gained ferric sulfate return step
(1) in；
(5) sodium salt solution that step (3) obtains is evaporated crystallization and obtains sodium sulphate, the condensed water of evaporative crystallization returns
In step (1).
Example 1-12 below is all made of above-mentioned process flow.
Embodiment 1
The separation method of potassium sodium in mixed sulfate containing potassium and sodium:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, dissolve by heating under conditions of 50 DEG C
To mixed solution；The molar ratio of the ferric sulfate and potassium is 3:1, the mixed sulfate concentration containing potassium and sodium of the mixed solution
For 200g/L；
(2) pH that the mixed solution that sulfuric acid regulating step (1) obtains is added is 1, and heating reaction 8h, adds under the conditions of 50 DEG C
It further include stirring during thermal response, the rate of stirring is 100r/min, and solid-liquor separation obtains autunezite and filtrate later；
(3) pH that the filtrate that sodium hydroxide regulating step (2) obtain is added is 3, and solid-liquor separation obtains iron hydroxide and sulphur
Acid sodium solution；
(4) sulfuric acid dissolution is added in the iron hydroxide that step (3) obtains and obtains ferric sulfate, gained ferric sulfate return step
(1) in；
(5) sodium salt solution that step (3) obtains is evaporated crystallization and obtains sodium sulphate, the evaporation condensed water of evaporative crystallization
In return step (1).
In mixed sulfate containing potassium and sodium described in the present embodiment, the content of potassium sulfate is 5wt%, gained autunezite
Purity is 98%, and the purity of sodium sulphate is 95%, meets III class Grade A index of industrial sulphuric acid sodium.
Embodiment 2
The separation method of potassium sodium in mixed sulfate containing potassium and sodium:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, dissolve by heating under conditions of 20 DEG C
To mixed solution；The molar ratio of the ferric sulfate and potassium is 1:1, and the mixed sulfate containing potassium and sodium is dense in the mixed solution
Degree is 50g/L；
(2) pH that the mixed solution that sulfuric acid regulating step (1) obtains is added is 3, and heating reaction 1h, adds under the conditions of 70 DEG C
It further include stirring during thermal response, the rate of stirring is 300r/min, and solid-liquor separation obtains autunezite and filtrate later；
(3) pH that the filtrate that sodium hydroxide regulating step (2) obtain is added is 4, and solid-liquor separation obtains iron hydroxide and sodium
Salting liquid；
(4) sulfuric acid dissolution is added in the iron hydroxide that step (3) obtains and obtains ferric sulfate, gained ferric sulfate return step
(1) in；
(5) sodium salt solution that step (3) obtains is evaporated crystallization and obtains sodium sulphate, the evaporation condensed water of evaporative crystallization
In return step (1).
In mixed sulfate containing potassium and sodium described in the present embodiment, the content of potassium sulfate is 10wt%, gained Huang potassium iron
Alum purity is 95.8%, and the purity of sodium sulphate is 92.7%, meets III class qualified product index of industrial sulphuric acid sodium.
Embodiment 3
The separation method of potassium sodium in mixed sulfate containing potassium and sodium:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, is dissolved by heating under conditions of 100 DEG C
Obtain mixed solution；The molar ratio of the ferric sulfate and potassium is 6:1, the mixed sulfate containing potassium and sodium in the mixed solution
Concentration is 400g/L；
(2) pH that the mixed solution that sulfuric acid regulating step (1) obtains is added is 2, and reaction is heated under the conditions of 100 DEG C
0.5h further includes stirring during heating reaction, and the rate of stirring is 500r/min, and solid-liquor separation obtains autunezite later
And filtrate；
(3) it is 3.5 that the pH of filtrate that sodium hydroxide regulating step (2) obtain, which is added, solid-liquor separation obtain iron hydroxide and
Sodium salt solution；
(4) sulfuric acid dissolution is added in the iron hydroxide that step (3) obtains and obtains ferric sulfate, gained ferric sulfate return step
(1) in；
(5) sodium salt solution that step (3) obtains is evaporated crystallization and obtains sodium sulphate, the evaporation condensed water of evaporative crystallization
In return step (1).
In mixed sulfate containing potassium and sodium described in the present embodiment, the content of potassium sulfate is 20wt%, gained Huang potassium iron
Alum purity is 97.74%, and the purity of sodium sulphate is 97.45%, meets II class qualified product index of industrial sulphuric acid sodium.
Embodiment 4
The separation method of potassium sodium in mixed sulfate containing potassium and sodium:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, is dissolved by heating under conditions of 100 DEG C
Obtain mixed solution；The molar ratio of the ferric sulfate and potassium is 8:1, the mixed sulfate containing potassium and sodium in the mixed solution
Concentration is 10g/L；
(2) pH that the mixed solution that sulfuric acid regulating step (1) obtains is added is 1.2, and reaction is heated under the conditions of 70 DEG C
10h further includes stirring during heating reaction, and the rate of stirring is 50r/min, later solid-liquor separation obtain autunezite and
Filtrate；
(3) pH that the filtrate that sodium hydroxide regulating step (2) obtain is added is 3, and solid-liquor separation obtains iron hydroxide and sodium
Salting liquid；
(4) sulfuric acid dissolution is added in the iron hydroxide that step (3) obtains and obtains ferric sulfate, gained ferric sulfate return step
(1) in；
(5) sodium salt solution that step (3) obtains is evaporated crystallization and obtains sodium sulphate, the evaporation condensed water of evaporative crystallization
In return step (1).
In mixed sulfate containing potassium and sodium described in the present embodiment, the content of potassium sulfate is 30wt%, gained Huang potassium iron
Alum purity is 95.33%, and the purity of sodium sulphate is 98.62%, meets II class Grade A index of industrial sulphuric acid sodium.
Embodiment 5
The separation method of potassium sodium in mixed sulfate containing potassium and sodium:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, is dissolved by heating under conditions of 100 DEG C
Obtain mixed solution；The molar ratio of the ferric sulfate and potassium is 8:1, the mixed sulfate containing potassium and sodium in the mixed solution
Concentration is 300g/L；
(2) pH that the mixed solution that sulfuric acid regulating step (1) obtains is added is 1.5, heating reaction 6h under the conditions of 95 DEG C,
It further include stirring during heating reaction, the rate of stirring is 200r/min, and solid-liquor separation obtains autunezite and filter later
Liquid；
(3) it is 3.2 that the pH of filtrate that sodium hydroxide regulating step (2) obtain, which is added, solid-liquor separation obtain iron hydroxide and
Sodium salt solution；
(4) sulfuric acid dissolution is added in the iron hydroxide that step (3) obtains and obtains ferric sulfate, gained ferric sulfate return step
(1) in；
(5) sodium salt solution that step (3) obtains is evaporated crystallization and obtains sodium sulphate, the evaporation condensed water of evaporative crystallization
In return step (1).
In mixed sulfate containing potassium and sodium described in the present embodiment, the content of potassium sulfate is 8wt%, gained autunezite
Purity is 97.25%, and the purity of sodium sulphate is 98.17%, meets II class Grade A index of industrial sulphuric acid sodium.
Embodiment 6
The molar ratio of the ferric sulfate and potassium in embodiment 1 is replaced with 6:1 by 3:1 by the present embodiment；Other conditions with
Embodiment 1 is compared to identical.
Autunezite purity obtained by the present embodiment is 98.77%, and the purity of sodium sulphate is 97.23%, meets industrial sulphuric acid
II class qualified product index index of sodium.
Embodiment 7
The molar ratio of the ferric sulfate and potassium in embodiment 1 is replaced with 8:1 by 3:1 by the present embodiment；Other conditions with
Embodiment 1 is compared to identical.
Autunezite purity obtained by the present embodiment is 96.52%, and the purity of sodium sulphate is 96.27%, meets industrial sulphuric acid
III class Grade A index of sodium.
Embodiment 8
The molar ratio of the ferric sulfate and potassium in embodiment 1 is replaced with 1:1 by 3:1 by the present embodiment；Other conditions with
Embodiment 1 is compared to identical.
Autunezite purity obtained by the present embodiment is 96.33%, and the purity of sodium sulphate is 93.59%, meets industrial sulphuric acid
III class qualified product index of sodium.
Embodiment 9
The pH of step (2) in embodiment 1 is replaced with 3 by 1 by the present embodiment, other conditions complete phase compared with Example 1
Together.
Autunezite purity obtained by the present embodiment is 97.11%, and the purity of sodium sulphate is 96.86%, meets industrial sulphuric acid
III class Grade A index index of sodium.
Embodiment 10
The pH of step (2) in embodiment 1 is replaced with 1.2 by 1 by the present embodiment, and other conditions are complete compared with Example 1
It is identical.
Autunezite purity obtained by the present embodiment is 98.06%, and the purity of sodium sulphate is 95.79%, meets industrial sulphuric acid
III class Grade A index index of sodium.
Embodiment 11
The pH of step (2) in embodiment 1 is replaced with 2 by 1 by the present embodiment, other conditions complete phase compared with Example 1
Together.
Autunezite purity obtained by the present embodiment is 98.16%, and the purity of sodium sulphate is 96.88%, meets industrial sulphuric acid
III class Grade A index index of sodium.
Embodiment 12
The pH of step (2) in embodiment 1 is replaced with 4 by 1 by this comparative example, and the pH that filtrate is adjusted in step (3) is 4,
His condition is identical compared with Example 1.
Autunezite purity obtained by the present embodiment is 96.2%, and the purity of sodium sulphate is 93.3%, meets industrial sulphuric acid sodium
III class qualified product index.
Comparative example 1
The pH of step (2) in embodiment 1 is replaced with 0.5 by 1 by this comparative example, and other conditions are complete compared with Example 1
It is identical.
Autunezite purity obtained by the present embodiment is 32.55%, and the purity of sodium sulphate is 64.32%.
It can be seen that the autunezite purity > isolated using separation method of the present invention by embodiment 1-12
95%, the purity > 92% of sodium sulphate；Comparative example 1,6-8 can be seen that when the molar ratio of the ferric sulfate and potassium is (1-
8): when 1, the purity of isolated autunezite and sodium sulphate is higher, and the molar ratio of optimal ferric sulfate and potassium is (3-
6): 1, comparative example 1,9-12 and comparative example 1 it can be seen that when step (2) pH be 1-3 when, isolated autunezite with
The purity of sodium sulphate is higher, and the Optimal pH of step (2) is 1.2-2, as step (2) pH > 3, isolated yellow potassium iron
The purity of alum and sodium sulphate decreases, as the pH < 1 of step (2), isolated autunezite and sodium sulphate it is pure
It spends lower.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (9)
1. the separation method of potassium sodium in a kind of mixed sulfate containing potassium and sodium, which is characterized in that the method by ferric sulfate with
Mixed sulfate mixing so that potassium therein is converted into autunezite, and then realizes the separation of potassium and sodium.
2. the method as described in claim 1, which is characterized in that the molar ratio of the ferric sulfate and potassium is (1-8): 1, preferably
(3-6): 1.
3. method according to claim 1 or 2, which is characterized in that the described method comprises the following steps:
(1) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, is dissolved by heating to obtain mixed solution；
(2) pH for the mixed solution that sulfuric acid regulating step (1) obtains is added, heating reaction, solid-liquor separation obtains yellow potassium iron later
Alum and filtrate；
(3) pH for the filtrate that alkali regulating step (2) obtain is added, solid-liquor separation obtains iron hydroxide and sodium salt solution, thus real
The separation of existing potassium and sodium.
4. method as claimed in claim 3, which is characterized in that the mix sulphur containing potassium and sodium in step (1) described mixed solution
The concentration of hydrochlorate is 10-400g/L, preferably 50-200g/L；
Preferably, the temperature of step (1) described heating for dissolving is 20-100 DEG C, preferably 50-100 DEG C.
5. the method as claimed in claim 3 or 4, which is characterized in that the pH of step (2) described mixed solution is 1-3, preferably
1.2-2；
Preferably, the temperature of step (2) the heating reaction is 50-100 DEG C, preferably 70-90 DEG C；
Preferably, the time of step (2) the heating reaction is 0.5-10h, preferably 1-8h；
It preferably, further include stirring during step (2) the heating reaction；
Preferably, the rate of the stirring is 50-500r/min, preferably 100-300r/min.
6. such as the described in any item methods of claim 3-5, which is characterized in that step (3) described alkali includes sodium hydroxide；
Preferably, pH >=3 of step (3) described filtrate, preferably 3-4.
7. such as the described in any item methods of claim 3-6, which is characterized in that the method also includes step is added in sulfuric acid
(3) ferric sulfate is obtained in the iron hydroxide obtained, and will be in ferric sulfate return step (1).
8. such as the described in any item methods of claim 3-7, which is characterized in that the method also includes by step (3) sodium
Salting liquid evaporative crystallization obtains sodium sulphate；
Preferably, in the condensed water return step (1) of the evaporative crystallization.
9. the method according to claim 1, which is characterized in that the described method comprises the following steps:
(I) mixed sulfate, ferric sulfate and water containing potassium and sodium are mixed, carries out dissolving by heating under conditions of 20-100 DEG C
To mixed solution；The molar ratio of the ferric sulfate and potassium is (1-8): 1, the mixed sulfate containing potassium and sodium in the mixed solution
Concentration be 10-400g/L；
(II) pH that the mixed solution that sulfuric acid regulating step (I) is obtained is added is 1-3, and reaction is heated under the conditions of 50-100 DEG C
0.5-10h further includes stirring during heating reaction, and the rate of stirring is 50-500r/min, and solid-liquor separation obtains Huang later
Krausite and filtrate；
(III) pH >=3 for the filtrate that sodium hydroxide regulating step (II) is obtained are added, solid-liquor separation obtains iron hydroxide and sodium salt
Solution；
(IV) sulfuric acid dissolution is added in the iron hydroxide that step (III) obtains and obtains ferric sulfate, gained ferric sulfate return step
(I) in；
(V) sodium salt solution that step (III) obtains is evaporated crystallization and obtains sodium sulphate, the condensed water of evaporative crystallization returns to step
Suddenly in (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811573941.9A CN109336138B (en) | 2018-12-21 | 2018-12-21 | Method for separating potassium and sodium in mixed sulfate containing potassium and sodium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811573941.9A CN109336138B (en) | 2018-12-21 | 2018-12-21 | Method for separating potassium and sodium in mixed sulfate containing potassium and sodium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109336138A true CN109336138A (en) | 2019-02-15 |
| CN109336138B CN109336138B (en) | 2020-11-10 |
Family
ID=65303132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811573941.9A Active CN109336138B (en) | 2018-12-21 | 2018-12-21 | Method for separating potassium and sodium in mixed sulfate containing potassium and sodium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109336138B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387374A (en) * | 2021-06-28 | 2021-09-14 | 四川能投鼎盛锂业有限公司 | Potassium removing process of ore lithium extraction production system |
| CN113880119A (en) * | 2021-12-09 | 2022-01-04 | 中国科学院过程工程研究所 | Method for preparing potassium sulfate from potassium chloride |
| CN114634257A (en) * | 2022-03-04 | 2022-06-17 | 太原碧蓝水利工程设计股份有限公司 | Method for treating acidic mine water and hydroxyl potassium ferric sulfate synthesized by acidic mine water |
| RU2800950C1 (en) * | 2022-07-22 | 2023-08-01 | Общество с ограниченной ответственностью "ДЖИЭСЭМ КЕМИКЭЛ" | Method for continuous production of purified potassium sulphate and sodium sulphate and device for continuous purification of potassium sulphate and sodium sulphate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4305914A (en) * | 1977-05-09 | 1981-12-15 | Electrolytic Zinc Company | Process for precipitating iron as jarosite with a low non-ferrous metal content |
| FI96841C (en) * | 1993-12-30 | 1996-09-10 | Kemira Oy | Process for preparing useful three-iron iron compounds |
| CN101343695A (en) * | 2008-08-20 | 2009-01-14 | 攀钢集团研究院有限公司 | Method for reducing content of kalium and sodium in vanadium solvent extraction circulation liquid |
| CN103112901B (en) * | 2013-03-02 | 2014-08-20 | 湘潭大学 | Method for reducing contents of calcium ions, magnesium ions, potassium ions and sodium ions in manganese sulfate |
-
2018
- 2018-12-21 CN CN201811573941.9A patent/CN109336138B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4305914A (en) * | 1977-05-09 | 1981-12-15 | Electrolytic Zinc Company | Process for precipitating iron as jarosite with a low non-ferrous metal content |
| FI96841C (en) * | 1993-12-30 | 1996-09-10 | Kemira Oy | Process for preparing useful three-iron iron compounds |
| CN101343695A (en) * | 2008-08-20 | 2009-01-14 | 攀钢集团研究院有限公司 | Method for reducing content of kalium and sodium in vanadium solvent extraction circulation liquid |
| CN103112901B (en) * | 2013-03-02 | 2014-08-20 | 湘潭大学 | Method for reducing contents of calcium ions, magnesium ions, potassium ions and sodium ions in manganese sulfate |
Non-Patent Citations (3)
| Title |
|---|
| ZHIWU LEI ET AL.: "Potassium fixation and the separation from sodium through the formation of K-alunite by using activated aluminum hydroxide", 《SEPARATION SCIENCE AND TECHNOLOGY》 * |
| 严忠庆等: "《废合金钢制取化工冶金产品过程》", 31 January 1983 * |
| 王长秋等: "黄钾铁矾的形成条件研究及其环境意义", 《岩石矿物学杂志》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387374A (en) * | 2021-06-28 | 2021-09-14 | 四川能投鼎盛锂业有限公司 | Potassium removing process of ore lithium extraction production system |
| CN113880119A (en) * | 2021-12-09 | 2022-01-04 | 中国科学院过程工程研究所 | Method for preparing potassium sulfate from potassium chloride |
| CN114634257A (en) * | 2022-03-04 | 2022-06-17 | 太原碧蓝水利工程设计股份有限公司 | Method for treating acidic mine water and hydroxyl potassium ferric sulfate synthesized by acidic mine water |
| RU2800950C1 (en) * | 2022-07-22 | 2023-08-01 | Общество с ограниченной ответственностью "ДЖИЭСЭМ КЕМИКЭЛ" | Method for continuous production of purified potassium sulphate and sodium sulphate and device for continuous purification of potassium sulphate and sodium sulphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109336138B (en) | 2020-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106910959B (en) | Method for selectively recovering lithium from lithium iron phosphate waste | |
| CN104302791B (en) | Method for processing red mud | |
| CN102276099B (en) | Comprehensive treatment method of waste water from laterite-nickel ore wet smelting | |
| CN109336138A (en) | The separation method of potassium sodium in a kind of mixed sulfate containing potassium and sodium | |
| Xing et al. | Clean and efficient process for the extraction of rubidium from granitic rubidium ore | |
| CN103922416A (en) | Method for separating and recovering iron from red mud | |
| CN101586185A (en) | The method of Separation and Recovery arsenic and iron from biological oxidation solution of sulfide ore | |
| CN101760641A (en) | Technology for recovering magnesium from magnesium sulfate solution | |
| CN103663505B (en) | Method for treating potassium feldspar according to sub-molten salt method to prepare potassium carbonate | |
| CN102583458A (en) | Method for extracting basic magnesium carbonate, iron hydroxide and calcium sulfate from serpentine under normal temperature and pressure | |
| CN101760637B (en) | Leaching technology of magnesium-containing ore | |
| CN102628105B (en) | Method for comprehensively recycling and using baric waste slag in refined aluminum production process | |
| CN108486379B (en) | The efficient separation method of arsenic and alkali in a kind of arsenic alkaline slag | |
| CN104291362B (en) | A kind of method utilizing the solid waste containing potassium, chloride ion to produce potassium carbonate | |
| CN103757259B (en) | A kind of chemical waste sulfuric acid, waste hydrochloric acid combine the method for each element of process red soil nickel ore synthetical recovery | |
| CN101723431B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN116199377A (en) | Incineration fly ash resource utilization method for quality control of washing waste salt | |
| CN103274434B (en) | The method of magnesium ion is reclaimed from Adlerika | |
| CN102345016B (en) | Method for recovering arsenic and heavy metals from contaminated acid generated by metallurgical off-gas | |
| CN108585057A (en) | A method of arsenic and alkali in arsenic alkaline slag are detached based on ultra-fine ferric hydroxide colloid | |
| CN107739042B (en) | The method that high-purity magnesium sulfate is prepared by magnesium sulfate waste | |
| CN101760644B (en) | Leaching technique for magnesium-containing ore | |
| CN102943174A (en) | Method for preparing nickel sulfide concentrate through titanium dioxide waste acids | |
| US20240067522A1 (en) | Resource utilization method of crude sodium sulfate | |
| CN108950225A (en) | A method of zinc oxide is produced using electrolytic zinc acid system leached mud |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |