CN109354046A - A method of lithium carbonate is prepared using dirty mother liquor is steamed - Google Patents
A method of lithium carbonate is prepared using dirty mother liquor is steamed Download PDFInfo
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- CN109354046A CN109354046A CN201811322212.6A CN201811322212A CN109354046A CN 109354046 A CN109354046 A CN 109354046A CN 201811322212 A CN201811322212 A CN 201811322212A CN 109354046 A CN109354046 A CN 109354046A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- 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
Abstract
The invention belongs to the technical field of lithium carbonate preparation more particularly to a kind of methods for preparing lithium carbonate using dirty mother liquor is steamed, comprising: (1) will steam dirty mother liquor and carry out high-temperature calcination；(2) calcined product is leached, using obtaining the solution a containing lithium after filter；(3) the solution a containing lithium is mixed to primary removal of impurities with saturated aqueous sodium carbonate, clear liquid b is obtained by filtration；(4) clear liquid b is subjected to initial concentration；(5) solution c is mixed to the secondary removal of impurities of progress with soluble carbonate salt solid and obtains clear liquid d；(6) clear liquid d is mixed with acid solution and carries out acidity adjustment acquisition solution e；The solution e is carried out second again to be concentrated, obtains solution f；(7) solution f is reacted with carbonating reagent, lithium carbonate is made；Wherein steaming dirty mother liquor is " a step acid extracting " coal ash for manufacturing in aluminium oxide, remaining the steamings dirt mother liquor of evaporative crystallization process.The method of the present invention is direct from the dirty mother liquor of remaining steaming, quickly prepares lithium carbonate, highly efficient, quick.
Description
Technical field
The invention belongs to the technical field of lithium carbonate preparation more particularly to a kind of sides that lithium carbonate is prepared using the dirty mother liquor of steaming
Method.
Background technique
Lithium is the most light metallic element of nature, and very active alkali metal element.In metallurgical industry, lithium is utilized
Deoxidier, desulfurizing agent can be served as with the property of the element reactions such as O, N, S, Cl, lithium.In addition, with battery technology, atom
The continuous development of energy industry, is continuously increased the demand of lithium, and therefore, lithium is referred to as " new energy metal ".
Currently, the primary raw material for extracting lithium is lithium ore and brine containing lithium.It is higher that lithium needs are extracted directly from ore
The methods of high-temperature roasting and high pressure acidleach, not only condition is harsh for these methods, and there are energy consumption height, equipment requirement height etc. to ask
Topic.The content of magnesium in brine, calcium, boron impurity is primarily limited to from the prior art technology for mentioning lithium in brine, because in the brine of part
Magnesium, lithium content are relatively high, increase the extraction difficulty of lithium, so that production procedure complicates.
With the continuous development of China's power industry, the discharge amount of flyash is sharply increased.China's flyash in 2009
Discharge amount is up to 3.75 hundred million tons, brings a series of environmental problems.The coal mine in the quasi- area Ge Er belongs to based on " high alumina, rich gallium "
One of four big open coal mines.Contain Al in flyash2O3、SiO2、Fe2O3、TiO2、CaO、MgO、Li2O etc..The type flyash
By " a step acid extracting " technique, the metallurgical-grade aluminum oxide quality that purity reaches 98.6% or more can be produced.The technique is main
It include: the processes such as salt Ore Leaching, sedimentation, resin removal of impurities, evaporative crystallization and roasting.And in this process, the material containing lithium can be
It steams and is enriched in dirty mother liquor, content can reach 0.2~0.6g/L；Preferable condition is provided for the extraction and exploitation of elemental lithium.Before
Phase, applicant have applied for a patent about the method for producing lithium carbonate from flyash, patent No. CN103101935
A.But this application documents be " a step acid extracting " coal ash for manufacturing for aluminium oxide after, refined crystalline aluminium chloride liquid is evaporated crystallization
The mother liquor generated after process, the mother liquor is to further realizing the extraction of lithium carbonate, it is also necessary to carry out repeatedly purifying to mention to it
The content of high wherein lithium, process and trivial operations.
To sum up, steaming dirt how more convenient, that effectively comprehensive utilization flyash is generated by " a step acid extracting " technique
Mother liquor is the direction studied from now on and emphasis.
Summary of the invention
It is an object of the present invention to be extracted for existing utilization " a step acid extracting " coal ash for manufacturing for the product after aluminium oxide
Lithium carbonate there are the problem of, a kind of method preparing lithium carbonate using dirty mother liquor is steamed is provided, " a step acid extracting " flyash is utilized
Prepare the dirty mother liquor of remaining steaming after aluminium oxide directly, quickly prepare lithium carbonate, this method is highly efficient, quick, it is easier to realize
Industrialization.
To achieve the goals above, the present invention provides a kind of method for preparing lithium carbonate using dirty mother liquor is steamed, including as follows
Step:
(1) it will steam at dirty mother liquor is 300~600 DEG C in temperature and calcine, calcined product is made；
(2) calcined product is leached in leachate, using obtaining the solution a containing lithium after filter；Wherein, the leaching
Liquid is selected from water or weakly acidic aqueous solution out；The mass ratio of the calcined product and leachate is 1:(1-15)；
(3) after the solution a by described containing lithium is mixed with aqueous sodium carbonate, and the pH value for adjusting mixed solution is 7~10,
Clear liquid b is obtained by filtration；
(4) after the clear liquid b being carried out initial concentration, solution c is obtained；Wherein, in the solution c lithium content be 1~
5g/L；
(5) after the pH value for mixing the solution c with soluble carbonate salt solid, and adjusting mixed solution is 9~12, mistake
Filter obtains clear liquid d；
(6) the clear liquid d is mixed with acid solution, the acidity of mixed solution is adjusted, make its pH value 5~8
Afterwards, solution e is obtained；The solution e is carried out second after being concentrated again, obtains solution f；Wherein, in the solution f lithium content
For 9~14g/L；
(7) the solution f is mixed with carbonating reagent and is reacted, can be prepared by the lithium carbonate；
Wherein, the dirty mother liquor of the steaming is that for " a step acid extracting " coal ash for manufacturing in aluminium oxide, evaporative crystallization process is remaining
Steam dirty mother liquor." a step acid extracting " coal ash for manufacturing discloses in numerous patents document for aluminium oxide method, for example, patent document
CN201110103722.6、CN200810051317.2、CN201110103785.1、CN200810051316.8、
CN201110103861.9 etc..
The method provided according to the present invention, it is preferable that in step (1), the dirty mother liquor of the steaming is 0.1~0.6g/L of lithium content
Saturation liquor alumini chloridi.
Preferably, in step (1), the calcining is selected from Spray calcination or dinectly bruning, more preferably Spray calcination.
It is highly preferred that the temperature of the calcining is 400~500 DEG C.
The method provided according to the present invention, it is preferable that in step (2), calcined product described in step (2) and leachate
Mass ratio is 1:(5-10).
Preferably, leachate described in step (2) is weakly acidic aqueous solution；In the present invention, the weakly acidic aqueous solution refers to pH
For 3.0~7.0 aqueous solution；The weakly acidic aqueous solution is described " a step acid extracting " coal ash for manufacturing for two in alumina technology
Secondary evaporation condensed water, for example, double evaporation-cooling condensed water of " a step acid extracting " coal ash for manufacturing for aluminium oxide pilot plant；Its (H containing acid+) concentration be 0.0005~0.005mol/L.The endpoint pH of acquired solution is 2~5 after the process of the leaching, for example,
Endpoint pH is 3 or 4；
Preferably, the temperature of leaching described in step (2) is 70-100 DEG C, more preferably 80-90 DEG C；The time of leaching is
1-4h, more preferably 2-3h；The number of leaching is 3 times or more, more preferably 3-5 times.
The method provided according to the present invention, it is preferable that in step (3), the concentration of the aqueous sodium carbonate is 1~
3mol/L, more preferably 1~2mol/L.
Preferably, after the pH value that mixed solution is adjusted in step (3) is 7~9, clear liquid b is obtained by filtration.Lead in step (3)
The pH value of mixed solution is overregulated, main purpose is the aluminium ion removed in solution, Al3+It is in pH=8, i.e., precipitable complete；
In addition, this step can be understood as the additional amount of control lye.In the aqueous solution not chemically reacted, there is only regulation solution
When pH value, base amount can be regulated and controled with pH value；When there is precipitation reaction generation, it is also necessary to calculate progress precipitation reaction and additionally consume
Base amount.
Step (4) can first use acid solution (such as the hydrochloric acid of 36wt% before the clear liquid b is carried out initial concentration
Solution) to adjust pH value be 6.0, its object is to dissolve the carbonate deposition retained in clear liquid b, discharge lithium ion.
The method provided according to the present invention, it is preferable that in step (5), the soluble carbonate salt solid be selected from sodium carbonate,
Potassium carbonate or ammonium carbonate, more preferably sodium carbonate.
Preferably, after the pH value that mixed solution is adjusted in step (5) is 10~11.5, clear liquid d is obtained by filtration.Step (5)
In by adjust mixed solution pH value, main purpose is that calcium ion therein is completely removed in this pH value range.In addition,
This step can be understood as determining sodium carbonate solid dosage by theoretical calculation, can also control soluble carbon by endpoint pH
The additional amount of hydrochlorate solid.
The method provided according to the present invention, it is preferable that in step (6), the acidity of mixed solution is adjusted, makes its pH
After value is 6.0~7.5, solution e is obtained；In the clear liquid d that step (5) is obtained by filtration, still there is carbonic acid that is undissolved, penetrating strainer
Salt precipitating, wherein can be mingled with part lithium ion, the purpose that the acidity of mixed solution is adjusted in step (6) is to dissolve the portion
The carbonate deposition divided.Wherein the dosage of acid solution can be obtained by the pH value of regulation.
Preferably, acid solution described in step (6) be inorganic acid solution, the inorganic acid solution be selected from hydrochloric acid solution,
Sulfuric acid solution or nitric acid solution, preferably hydrochloric acid solution；The mass fraction is 35-40wt%, more preferably 36-
36.5wt%.
The method provided according to the present invention, it is preferable that in step (4), the content of lithium is 1~2g/L in the solution c；Step
Suddenly in (6), the content of lithium is 10~12g/L in the solution f.
The method provided according to the present invention, it is preferable that in step (7), the carbonating reagent is selected from carbon dioxide, carbonic acid
Sodium solid or carbonic acid saturated aqueous solution of sodium；Wherein the dosage of sodium carbonate can first calculate theoretical addition amount, and in operation adition process
In slightly excess.
Preferably, it is 90-100 DEG C that the process conditions of step (7) described reaction, which include: reaction temperature, reaction time 1-2
Hour.
In the present invention, step (7) after reaction, obtained product be Crude lithium Carbonate product, can by repeatedly washing,
The purification process such as drying obtain the lithium carbonate product of high-purity.In the purification process of Crude lithium Carbonate, such as it can be secondary wash
It washs, washing the water that uses for the secondary water boiled or can boil soft water.
The present invention is direct using the dirty mother liquor of steaming remaining in evaporative crystallization process, quickly prepares lithium carbonate, eliminates to work
It is highly efficient, quick for the purified treatment of the mother liquor of raw material.Absorption or the co-precipitation of aluminium lithium etc. are directlyed adopt compared to by mother liquor
Mode prepares lithium carbonate precipitating, and the method for the present invention can be separated aluminium lithium by high-temperature calcination, solves conventional chlorinating aluminium and chlorine
Change the difficult problem of lithium separation, avoids conventional addition sodium hydroxide and be initially formed aluminium lithium precipitating, then brought through operations such as calcining, water loggings
Problem at high cost；It is highly efficient, quick by way of dirty mother liquor prepares lithium carbonate product from steaming Spray calcination, reduce alkali
Liquid precipitate process has saved lye cost；And the reaction time greatly shortens, it is easier to realize industrialization.
Compared with the existing technology, technical solution of the present invention bring beneficial effect is:
(1) from the evaporative crystallization process of flyash " a step acid extracting " aluminium oxide extraction process, remaining steaming dirt is female
Liquid directly prepares lithium carbonate precipitating, can not only turn waste into wealth, but also can simplify preparation section and behaviour with high efficiency extraction lithium carbonate
Make；
(2) in the preferred embodiment, can make to steam dirt by the way of Spray calcination (temperature is controlled at 300-600 DEG C)
Aluminium chloride in mother liquor is completely converted into aluminium oxide, and then separates aluminium oxide in leaching process in the solution more with lithium chloride
Conveniently, separating effect is preferable；
(3) it is difficult to leach lithium chloride in the leaching process of lithium ion, when extraction temperature is low, cost liter when extraction temperature is high
It is high；Therefore, in the preferred embodiment, extraction temperature, extraction time, leach between number effective to cooperate be that lithium ion can be with
The guarantee that success is leached；By mechanical stirring in leaching process, aluminium can be achieved with by simple filtration, lithium separates；
(4) the method for the present invention is combined by Spray calcination with the removal of impurities of solution twice, solves conventional chlorinating aluminium and chlorination
The difficult problem of lithium separation avoids conventional addition sodium hydroxide and is initially formed aluminium lithium precipitating, then brings into through operations such as calcining, water loggings
This high problem；Lye precipitation process is decreased, lye cost has been saved；And the reaction time greatly shortens, it is easier to real
Now industrialize.
Detailed description of the invention
Fig. 1 is the process flow steamed dirty mother liquor in a kind of example of the invention and prepare lithium carbonate.
Specific embodiment
In order to technical characteristic and content of the invention is understood in detail, it is described in more detail below of the invention excellent
Select embodiment.Although describing the preferred embodiment of the present invention in embodiment, however, it is to be appreciated that can be in a variety of manners
Realize the present invention without that should be limited by the embodiments set forth herein.
As shown in Figure 1, including following step using the method that dirty mother liquor prepares lithium carbonate is steamed in a kind of example of the invention
It is rapid:
(1) it will steam at dirty mother liquor is 300~600 DEG C in temperature and calcine, calcined product is made；
(2) calcined product is leached in leachate, using obtaining the solution a containing lithium after filter；Wherein, the leaching
Liquid is selected from water or weakly acidic aqueous solution out；The mass ratio of the calcined product and leachate is 1:(1-15)；
(3) after the solution a by described containing lithium is mixed with aqueous sodium carbonate, and the pH value for adjusting mixed solution is 7~10,
Clear liquid b is obtained by filtration；
(4) after the clear liquid b being carried out initial concentration, solution c is obtained；Wherein, the content of lithium ion is in the solution c
1~5g/L；
(5) after the pH value for mixing the solution c with soluble carbonate salt solid, and adjusting mixed solution is 9~12, mistake
Filter obtains clear liquid d；
(6) the clear liquid d is mixed with acid solution, the acidity of mixed solution is adjusted, make its pH value 5~8
Afterwards, solution e is obtained；The solution e is carried out second after being concentrated again, obtains solution f；Wherein, lithium ion in the solution f
Content is 9~14g/L；
(7) the solution f is mixed with carbonating reagent and is reacted, can be prepared by the lithium carbonate；
Wherein, the dirty mother liquor of the steaming is " a step acid extracting " coal ash for manufacturing in alumina technology, and evaporative crystallization process is surplus
Remaining steaming dirt mother liquor.
In some examples of the invention, step (1) the saturation aluminium chloride for steaming dirty mother liquor and being 0.1~0.6g/L of lithium content
Solution.Before being roasted into calcining furnace, steaming dirt mother liquor composition used for example can be with are as follows: 0.36g/L lithium ion,
0.255g/L magnesium ion, 0.01g/L calcium ion, 0.0035g/L titanium ion, 91g/L aluminium ion.In the present invention, the steaming dirt is female
The content (g/L) of lithium is equivalent to the mass concentration for steaming lithium ion in dirty mother liquor in liquid.
In the preferred embodiment, in step (1), the calcining is selected from Spray calcination or dinectly bruning, preferably sprays
Mist calcining.Products therefrom is the alkali metal oxide and its esters based on aluminium oxide after Spray calcination.Preferably, the calcining
Temperature be 400~500 DEG C, for example, 450 DEG C or 480 DEG C.By Spray calcination, realizes aluminium chloride and turn to aluminium oxide
Become, this is premise and the preparation stage for carrying out the separation of aluminium lithium.The advantage of Spray calcination be so that calcining sample granularity is thinner so that
With fine porosity, for leaching process advantageously.
In the preferred embodiment, the mass ratio of calcined product described in step (2) and leachate is 1:(5-10), such as
Mass ratio is 1:6,1:8 or 1:9；In view of the leaching degree of lithium ion, in order to soak lithium ion in the step
Out completely, need to control the amount ratio of calcined product and leachate.It, can using pure water or weakly acidic aqueous solution as leachate
Promote the dissolution of lithium ion in solid；It is opposite that strong acid is selected then aluminium oxide to be caused to become aluminium chloride, lithium ion can be adsorbed, causes to soak
Extracting rate decline.
Preferably, leachate described in step (2) be weakly acidic aqueous solution or deionized water, pH value 3-7, for example,
4,5 or 6.In some instances, the weakly acidic aqueous solution can be described " a step acid extracting " coal ash for manufacturing for alumina technology
In double evaporation-cooling condensed water, for example, wherein contain micro HCl.(the H containing acid in double evaporation-cooling condensed water+) concentration is
0.0005~0.005mol/L.In step (2), the endpoint pH of acquired solution is 2~5 after the process of the leaching, example
Such as, after leaching process the endpoint pH of acquired solution 2.5,3,4；The pH value of solution a because of gained containing lithium is in acidity, meeting
There is aluminum ions precipitation；Therefore, rear extended meeting is further increased except aluminium process (i.e. secondary removal of impurities).
The temperature of leaching described in step (2) is 70-100 DEG C, such as 75 DEG C, 85 DEG C or 95 DEG C, preferably 80-90
℃；The time of leaching is 1-4h, such as 2.5h, 3.5h, preferably 2-3h.Extraction temperature of the invention is committed step, is leached
Temperature is low, is difficult to leach lithium chloride, and the used time also can be elongated, needs to carry out mechanical stirring in leaching process, is just able to achieve aluminium lithium point
From.
In the step, the leaching in order to guarantee lithium ion is complete, and lithium ion, which is carried out, repeatedly to be leached, and preferably 3-5 times leaching makes
Its leaching rate reaches 95% or more.
In some instances, the concentration of step (3) described aqueous sodium carbonate is 1~3mol/L, preferably 1~2mol/
L, for example, 1.5mol/L.
Preferably, the pH value of mixed solution is adjusted in step (3) as clear liquid is obtained by filtration behind 7~9 (such as 8.0,8.5)
b.The purpose of step is to clean for the first time, addition saturated aqueous sodium carbonate is can in resulting lithium chloride solution after removing is leached
The aluminium chloride that can contain.
In some examples, step (4) carry out initial concentration before, can first the acidity to the clear liquid b for example, by
Mass fraction is that 35-40wt% hydrochloric acid solution is adjusted, and after making its pH value 6.0~7.5, then carries out the behaviour of initial concentration
Make.
In some instances, step (5) the soluble carbonate salt solid is selected from sodium carbonate, potassium carbonate or ammonium carbonate,
Preferably sodium carbonate；The step is second of removal of impurities, and the purpose that soluble carbonate salt is added is to remove and mention in lithium solution
Calcium and magnesium ion, and removed with calcium carbonate, magnesium carbonate precipitation form.
Preferably, the pH value of mixed solution is adjusted as clear liquid d is obtained by filtration behind 10~11.5 (for example, 10.5,11.0).
In some instances, the acidity of mixed solution is adjusted in step (6), after making its pH value 6.0~7.5, obtains
Obtain solution e；The purpose that mixed solution carries out acidification is to dissolve crystals of sodium carbonate, is prevented because of local concentration of sodium carbonate mistake
It is high and crystals of sodium carbonate coated lithium ion precipitating occur and the phenomenon that generating impurity occur and prevent from precipitating lithium ion,
And the situation for causing solution lithium ion to lose.
Preferably, the acid solution be inorganic acid solution, the inorganic acid solution be selected from hydrochloric acid solution, sulfuric acid solution or
Nitric acid solution, preferably hydrochloric acid solution；The mass fraction of the acid solution is 35-40wt%, preferably 36-36.5wt%.
In the preferred embodiment, in step (4), the content of lithium is 1~2g/L in the solution c after initial concentration；
The purpose of initial concentration is to prepare for second of removal of impurities.In step (6), lithium in the solution f after second of concentration
Content is 10~12g/L.The purpose of second of concentration is to improve the concentration of lithium ion, prepare for lithium carbonate precipitating preparation.
In the present invention, the mode of initial concentration and second concentration has very much, such as enamel reaction still heating can be used, temperature for 80~
100 DEG C of realizations.
In some instances, step (7) carbonating reagent is selected from carbon dioxide, sodium carbonate solid or sodium carbonate saturation
Solution.
Preferably, it is 90-100 DEG C that the process conditions of step (7) described reaction, which include: reaction temperature, reaction time 1-2
Hour.It is preferred that the purpose of reaction process condition is to reduce the solubility of lithium carbonate, prevent final product from losing.
In the present invention, after reaction, obtained product is Crude lithium Carbonate product to step (7), need by repeatedly washing,
The purification process such as drying could obtain the lithium carbonate product of high-purity.In the purification process of Crude lithium Carbonate, such as it can be secondary
Washing, washing the water that uses for the secondary water boiled or can boil soft water.The process purified to Crude lithium Carbonate is removal
The impurity such as soluble carbonate.
Raw material sources:
Development in science and technology Co., Ltd, CAS 1310-73-2 are recovered in sodium hydroxide (AR), Tianjin；
Sodium carbonate (GR), Shanghai traditional Chinese medicines, CAS 497-19-8；
Steaming dirty mother liquor is remaining mother liquor of the flyash through salting-out crystallization process in " a step acid extracting " technique, it includes it is each
Ingredient and its content are shown in Table 1.
Table 1 steams dirty mother liquor composition and its content
Embodiment 1
(1) it is spray-dried to steam dirty mother liquor, obtains the product of roasting based on white alumina, which mainly wraps
It includes: the chlorination of the lithium chloride of 3wt%, the aluminium oxide of 82wt%, the magnesia of 3.3wt%, the potassium chloride of 3.7wt%, 4.7wt%
The calcium chloride and other impurities of sodium and 0.8wt%；The temperature of the roasting is 450 DEG C；
(2) by the product of roasting by 2 leachings, infusion solution is the double evaporation-cooling condensation prepared in alumina technology
Water, H therein+Concentration is 0.005mol/L, and the endpoint pH of acquired solution is adjusted to 3.0 after the process of leaching；Through 80
DEG C water bath with thermostatic control mechanical stirring, extraction time are after 3.0 hours, and filtering obtains solution a of the clarification containing lithium；The leaching rate of lithium ion
It is 95%；Wherein, the mass ratio of product of roasting and leachate is 1:10；
(3) aqueous sodium carbonate of 2.0mol/L is added in the solution a in gained containing lithium, the pH value for adjusting mixed solution is
After 8.0, filtering precipitating obtains clear liquid b；
(4) it is 6.0 with the salt acid for adjusting pH value of 36.5wt% by gained clear liquid b, and is heated to 90 using enamel reaction still
It DEG C is concentrated for the first time, obtains solution c, the content of the Li ion in solution c is 1.5g/L；
(5) sodium carbonate solid is added in acquired solution c and precipitates calcium and magnesium ion, after making its pH value 11.50, filtering is obtained
Obtain clear liquid d；
(6) the clear liquid d is mixed with the hydrochloric acid solution of 36wt%, the acidity of mixed solution is adjusted, its pH is made
After value is 7.0, solution e is obtained；Solution e is carried out second again to be concentrated, until the content for obtaining lithium ion in solution f is 12g/L；
(7) under 95 DEG C of constant temperatures, carbonating reagent saturated aqueous sodium carbonate is added in solution f and reacts to carbonic acid
Lithium precipitating is complete；Products therefrom is filtered, is dried, and the purity for obtaining lithium carbonate reaches 94.1%；The lithium ion rate of recovery is
86.4%.
Embodiment 2
The step of preparing the method and technique of lithium carbonate from the dirty mother liquor of steaming (1) such as embodiment 1；
(2) by the product of roasting by 3 leachings, leachate is the double evaporation-cooling condensed water prepared in alumina technology,
H therein+Concentration is 0.005mol/L, and the endpoint pH of acquired solution is adjusted to 4.0 after the process of leaching, through 85 DEG C of perseverances
Tepidarium mechanical stirring and filter progress, extraction time are to obtain solution a of the clarification containing lithium after 3.5 hours；The leaching of lithium ion
Rate is 98%；Wherein, the mass ratio of product of roasting and leachate is 1:15；
(3) aqueous sodium carbonate of 2.0mol/L is added in the solution a in gained containing lithium, the pH value for adjusting mixed solution is
After 8.0, filtering precipitating obtains clear liquid b；
(4) it is 7.0 with the salt acid for adjusting pH value of 36wt% by gained clear liquid b, and is heated to 90 DEG C using enamel reaction still
The content for carrying out the Li ion being concentrated into solution c for the first time is 1.5g/L；
(5) sodium carbonate solid is added in acquired solution c and precipitates calcium and magnesium ion, after making its pH value 12.50, filtering is obtained
Obtain clear liquid d；
(6) by the mixed in hydrochloric acid of the clear liquid d and 36wt%, the acidity of mixed solution is adjusted, makes its pH value
After 7.0, solution e is obtained；Solution e is carried out second again to be concentrated, until the content for obtaining lithium ion in solution f is 12g/L；
(7) under 95 DEG C of constant temperatures, carbonating reagent saturated aqueous sodium carbonate is added in solution f and reacts to carbonic acid
Lithium precipitating is complete；Products therefrom is filtered, is dried, and the purity for obtaining lithium carbonate reaches 96.5%；The lithium ion rate of recovery is
95.1%.
Embodiment 3
(1) it is spray-dried to steam dirty mother liquor, obtains the product of roasting based on white alumina, which mainly wraps
Include the chlorination of the lithium chloride of 3wt%, the aluminium oxide of 82wt%, the magnesia of 3.3wt%, the potassium chloride of 3.7wt%, 4.7wt%
The calcium chloride and other impurities of sodium and 0.8wt%；The temperature of the roasting is 430 DEG C；
(2) by the product of roasting by 3 leachings, leachate is double evaporation-cooling condensed water, H therein+Concentration is
0.005mol/L, the endpoint pH of acquired solution is adjusted to 2.5 after the process of leaching, through 90 DEG C of water bath with thermostatic control mechanical stirrings
With filtering etc. processes, extraction time be 4.0 hours after, obtain clarification the solution a containing lithium；The leaching rate of lithium ion is 98.6%；
Wherein, the mass ratio of product of roasting and leachate is 1:15；
(3) aqueous sodium carbonate of 2.0mol/L is added in the solution a in gained containing lithium, the pH value for adjusting mixed solution is
After 8.0, filtering precipitating obtains clear liquid b；
(4) by gained clear liquid b with 36% salt acid for adjusting pH value be 7.0, and using enamel reaction still be heated to 90 DEG C into
The content that row is concentrated into the Li ion in solution c for the first time is 1.5g/L；
(5) sodium carbonate solid is added in acquired solution c and precipitates calcium and magnesium ion, after making its pH value 12.50, filtering is obtained
Obtain clear liquid d；
(6) by the mixed in hydrochloric acid of the clear liquid d and 36wt%, the acidity of mixed solution is adjusted, makes its pH value
After 7.0, solution e is obtained；Solution e is carried out second again to be concentrated, until the content for obtaining lithium ion in solution f is 16g/L；
(7) under 100 DEG C of constant temperatures, addition saturated aqueous sodium carbonate, which is reacted to lithium carbonate, in solution f has been precipitated
Entirely；Products therefrom is filtered, is dried；It is washed 2~3 times with boiling soft water again, obtains lithium carbonate purity and reach 99.6%；Lithium ion
The rate of recovery 92.0%.
Comparative example 1
(1) lithium ion in evaporation mother liquor is separated using the aluminium lithium precipitation method；Pass through the sodium hydroxide of 4.0mol/L
Solution precipitating steams aluminium, lithium ion in dirty mother liquor；Solution ph is controlled 5.6, it is ensured that aluminium hydroxide unformed hydrogen
Aluminium oxide composition；The result shows that: the problems such as lithium ion rate of deposition reaches 90%, but there are filtration difficulties；Then by roasting
(400 DEG C), obtain product of roasting；
(2) by product of roasting by 1 leaching, infusion solution is secondary softened water, pH value 7.0；The calcining produces
The mass ratio of object and leachate is 1:10；Through being leached 3.0 hours under the conditions of 85 DEG C；
It (filters, be concentrated, carbonating precipitating step using step (3) (4) (5) (6) (7) same as Example 1 later
Suddenly after), the ult rec of lithium ion reaches 82%；Lithium carbonate purity reaches 92.4%.
Comparative example 2
(1) lithium ion in evaporation mother liquor is separated using the aluminium lithium precipitation method；It is total by sodium hydroxide and calcium oxide
With precipitation of aluminium lithium ion；Solution ph is controlled 5.6, and the rate of deposition of lithium ion can also reach 90% at this time；Filtration problem has
Some improvement obtain product of roasting then by roasting (400 DEG C)；
(2) by product of roasting by 1 leaching, infusion solution is secondary softened water, pH value 7.0；The calcining produces
The mass ratio of object and leachate is 1:10；Through being leached 3.0 hours under the conditions of 85 DEG C；
It (filters, be concentrated, carbonating precipitating step using step (3) (4) (5) (6) (7) same as Example 1 later
Suddenly after), the ult rec of lithium ion is 85%, and lithium carbonate purity reaches 96%.
Using conventional lithium chloride and aluminium chloride separation in comparative example 1-2, although final lithium carbonate purity obtained and reality
It is close to apply product purity made from example, but can have that filtration difficulty, the lithium rate of recovery is low, alkali is at high cost, economy is bad etc. asks
Topic.And the present invention is combined by Spray calcination with solution removal of impurities, solves the problems, such as that conventional chlorinating aluminium separates hardly possible with lithium chloride,
Not only obtained lithium carbonate purity is very high, but also may be implemented that the separation of aluminium lithium is more convenient, separating effect is preferable.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of method for preparing lithium carbonate using dirty mother liquor is steamed, which comprises the steps of:
(1) it will steam at dirty mother liquor is 300~600 DEG C in temperature and calcine, calcined product is made；
(2) calcined product is leached in leachate, using obtaining the solution a containing lithium after filter；Wherein, the leachate
Selected from water or weakly acidic aqueous solution；The mass ratio of the calcined product and leachate is 1:(1-15)；
(3) after the solution a by described containing lithium is mixed with aqueous sodium carbonate, and the pH value for adjusting mixed solution is 7~10, filtering
Obtain clear liquid b；
(4) after the clear liquid b being carried out initial concentration, solution c is obtained；Wherein, the content of lithium is 1~5g/L in the solution c；
(5) it after the pH value for mixing the solution c with soluble carbonate salt solid, and adjusting mixed solution is 9~12, filters
To clear liquid d；
(6) the clear liquid d is mixed with acid solution, the acidity of mixed solution is adjusted, after making its pH value 5~8, obtained
Obtain solution e；The solution e is carried out second after being concentrated again, obtains solution f；Wherein, in the solution f lithium content be 9~
14g/L；
(7) the solution f is mixed with carbonating reagent and is reacted, can be prepared by the lithium carbonate；
Wherein, the dirty mother liquor of the steaming is " a step acid extracting " coal ash for manufacturing in aluminium oxide, and the remaining steaming of evaporative crystallization process is dirty
Mother liquor.
2. the method according to claim 1, wherein in step (1), the dirty mother liquor of the steaming be lithium content 0.1~
The saturation liquor alumini chloridi of 0.6g/L.
3. method according to claim 1 or 2, which is characterized in that in step (1), the calcining selected from Spray calcination or
Person's dinectly bruning, preferably Spray calcination；
Preferably, the temperature of the calcining is 400~500 DEG C.
4. the method according to claim 1, wherein in step (2), the quality of the calcined product and leachate
Than for 1:(5-10)；
Preferably, the leachate is weakly acidic aqueous solution, and the weakly acidic aqueous solution is the standby oxidation of " a step acid extracting " coal ash for manufacturing
Double evaporation-cooling condensed water in aluminium technique is 0.0005~0.005mol/L containing acid concentration.
5. the temperature of the leaching is 70-100 DEG C the method according to claim 1, wherein in step (2),
Preferably 80-90 DEG C；The time of leaching is 1-4h, preferably 2-3h；The number of leaching is 3 times or more, preferably 3-5 times.
6. the method according to claim 1, wherein the concentration of the aqueous sodium carbonate is 1 in step (3)
~3mol/L, preferably 1~2mol/L；
After the pH value for adjusting mixed solution is 7~9, clear liquid b is obtained by filtration.
7. according to the method described in claim 6, it is characterized in that, the soluble carbonate salt solid is selected from carbon in step (5)
Sour sodium, potassium carbonate or ammonium carbonate, preferably sodium carbonate；
After the pH value for adjusting mixed solution is 10~11.5, clear liquid d is obtained by filtration.
8. the method according to claim 1, wherein the acidity of mixed solution is adjusted in step (6),
After making its pH value 6.0~7.5, solution e is obtained；The acid solution is inorganic acid solution, and the inorganic acid solution is selected from salt
Acid solution, sulfuric acid solution or nitric acid solution, preferably hydrochloric acid solution；The mass fraction of the acid solution is 35-40wt%.
9. method according to claim 1 to 8, which is characterized in that in step (4), lithium in the solution c
Content is 1~2g/L；In step (6), the content of lithium is 10~12g/L in the solution f.
10. method according to claim 1 to 8, which is characterized in that in step (7), the carbonating reagent
Selected from carbon dioxide, sodium carbonate solid or carbonic acid saturated aqueous solution of sodium；
Preferably, it is 90-100 DEG C that the process conditions of reaction described in step (7), which include: reaction temperature, and the reaction time is that 1-2 is small
When.
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