CN106745102B - A kind of preparation process of lithium carbonate - Google Patents
A kind of preparation process of lithium carbonate Download PDFInfo
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- CN106745102B CN106745102B CN201710041119.7A CN201710041119A CN106745102B CN 106745102 B CN106745102 B CN 106745102B CN 201710041119 A CN201710041119 A CN 201710041119A CN 106745102 B CN106745102 B CN 106745102B
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Abstract
The invention discloses a kind of preparation processes of lithium carbonate, include the following steps：Step S1 removal of impurities enrichment process：After salt lake bittern removal of impurities concentration, concentrate containing lithium is formed；Step S2 carbonization sinker process：The by-product washing soda Crystallization reaction solution during urea method production biruea is added into the concentrate containing lithium of step S1, when original state, the molar ratio of sodium carbonate and lithium is 1.2~1.6 in reaction solution：2, lithium carbonate precipitating is generated after reacted；Step S3 postorder treatment process：The lithium carbonate precipitating of step S2 generation is isolated, it is washed, be dried to obtain lithium carbonate product.The present invention solves the problems, such as the recycling to the material using the by-product washing soda crystal of urea method production biruea, saves its cost of transporting for long-distance.The preparation cost of lithium carbonate is also saved simultaneously, is had high economic benefit.Using preparation process of the invention, moreover it is possible to obtain the lithium carbonate product of high quality, be conducive to later period use.
Description
Technical field
The present invention relates to the technical fields that brine mentions lithium, and in particular to a kind of preparation process of lithium carbonate.
Background technique
Lithium is metal most light in nature, has high specific heat, high conductivity and chemical activity strong etc. unique physico
Characteristic is learned, there is extensive purposes.Currently, lithium metal and its compound are in glass ceramics, electrolytic aluminium, lubricating grease, air conditioner refrigerating
Sustainable growth is applied with the traditional industries field such as organic synthesis, metallurgy, medicine, chemical industry, reagent, in aluminium lithium alloy, lithium battery
Application with the civilian industries such as nuclear fusion, high-tech and military industry field is also rapidly expanded.Because of its answering in terms of lithium battery
With lithium metal is also known as " 21 century energy upstart ".
Currently, the most common method for extracting lithium from nature is that ore proposes lithium method, which refers to spodumene, lithium cloud
The solids lithium ore such as mother is raw material, production lithium carbonate and other lithium products, and spodumene is main containing one of lithium minerals, also known as α
Type spodumene, theoretical amount containing lithium are 3.75%.It includes limestone sintering process and sulfuric acid process that ore, which proposes lithium method, is based on cost and technique
The considerations of, what is now generallyd use is sulfuric acid process, and technique is when roasting α type spodumene to 1000 DEG C or so, it to be made to be changed into β
Then type spodumene mixes β type spodumene with sulfuric acid, acidified roasting generates solvable lithium sulfate, obtains sulfuric acid by leaching
Primary lithium carbonate product is made in lithium solution after purified, evaporation and concentration, sinker are dry.This method passes through more than 50 years development works
Skill is mature, but in the method, sulfuric acid can only leach β type spodumene, and cannot react with α type spodumene, therefore, need
The more loose β type spodumene of structure is converted for α type spodumene by high-temperature roasting first, therefore from the angle of reaction principle
Consider, sulfuric acid process can not be reduced and propose the cost that lithium technique is spent.And domestic lithium salts production and equipment are irregular at present,
Most enterprise's equipments fall behind, seriously polluted, are unfavorable for the extensive development of sulfuric acid process.
Lithium from Salt Lake Brine resource accounts for the 70~80% of nature lithium resource total amount, therefore, lithium is extracted from salt lake bittern
It is the main direction for proposing lithium technique now.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation processes of lithium carbonate, propose lithium method cost for solving existing ore
Height, complex process, seriously polluted problem.
To achieve the goals above, the present invention provides the following technical solutions：A kind of preparation process of lithium carbonate, feature exist
In including the following steps：
Step S1 removal of impurities enrichment process：
After salt lake bittern removal of impurities concentration, concentrate containing lithium is formed；
Step S2 carbonization sinker process：
Sodium carbonate material is added into the concentrate containing lithium and forms reaction solution, when reacting original state, the reaction solution
The molar ratio of middle sodium carbonate and lithium is 1.2~1.6：2, after reacted, lithium carbonate precipitating is generated in the reaction solution,
Wherein, the sodium carbonate material is the by-product washing soda crystal during urea method production biruea；
Step S3 postorder treatment process：
The lithium carbonate precipitating is isolated, obtains final product lithium carbonate product after washed, dry.
Preferably, the step S1 removal of impurities enrichment process includes the following steps：
Step a1：The salt lake bittern is sent into the adsorption-desorption device equipped with lithium adsorbent, by adsorbing, eluting
And desorption manipulation, lithium desorption liquid is made；
Step b1：The magnesium ion in the lithium desorption liquid is removed by cation exchange resin, removal of impurities liquid is made；
Step c1：Using reverse osmosis concentration process and process is concentrated by evaporation to removal of impurities liquid realization concentration, is formed and is contained lithium
Concentrate.
Further, the lithium concentration of the concentrate containing lithium described in step S1 is 20~25g/L.
Preferably, the sodium carbonate material in the step S2 carbonization sinker process is sodium carbonate sperm after processing, institute
The treatment process for stating sodium carbonate material includes the following steps：
Step a2：By-product washing soda during the sodium carbonate material, that is, urea method production biruea is placed
In dissolving tank, is made it dissolve completely by heating, sodium carbonate liquor is made；
Step b2：The sodium carbonate liquor is realized by millipore filter to clean, filter pressure is 0.05~0.1MPa,
Sodium carbonate sperm is made.
Specifically, the heating temperature of sodium carbonate liquor described in step a2 is 30~40 DEG C.
Preferably, step S2 be carbonized sinker process in, the stirring rate of the reaction solution during the reaction be 30~
60r/min, reaction temperature are 30~40 DEG C, and the reaction time continues 20~40min.
Preferably, step S2 is carbonized in sinker process, and when reacting original state, sodium carbonate and lithium rubs in the reaction solution
You are than being 1.4：2.
Preferably, the separate mode in step S3 postorder treatment process is heating crystallization, the heating crystallization mode
In crystal solution temperature rise to 75~85 DEG C.
Further, the liquid isolated of heating crystallization mode uses hydrochloric acid to be neutralized to pH to make after 5.5~6.5
It is played back to salt pan.
Preferably, the mode of washing in step S3 subsequent processing process is filtering and washing, and the drying mode is gas
Stream is dry and fluidized drying merges utilization.
Compared with the prior art, the preparation process of lithium carbonate of the present invention has the advantage that：Urea method production connection
By-product washing soda crystal caused by during two ureas, because containing a small amount of caustic soda and sodium chloride etc. in the by-product
Impurity is extremely limited in traditional soda ash with field, and crystal water content accounts for total material specific gravity and is in the by-product
62.93%, therefore the cost of its long-distance transport is very high.The by-product is applied in the preparation process of lithium carbonate, is solved pair
The problem of by-product washing soda recycles, and the dosage saved in the preparation of lithium carbonate to soda ash is applied,
To effectively reduce the preparation cost of lithium carbonate, have high economic benefit.Meanwhile using lithium carbonate provided by the invention
Preparation process, obtained lithium carbonate quality is high, and impurity is few, conducive to the later-stage utilization of lithium carbonate.
The preparation process process of lithium carbonate provided by the present invention is simple and easy to control, can whole-course automation carry out, be conducive to production
Stabilization is continued for.
Specific embodiment
The present invention provides many applicable creative concepts, which be can be reflected in a large number of on specific
Hereinafter.The specific embodiment described in following embodiments of the present invention is only used as a specific embodiment of the invention
Exemplary illustration, and be not meant to limit the scope of the invention.
Below with reference to specific embodiment, the invention will be further described.
The present embodiment provides a kind of preparation processes of lithium carbonate, include the following steps：
Step S1 removal of impurities enrichment process：
Step a1：Firstly, salt lake bittern is sent into the adsorption-desorption device equipped with lithium adsorbent, so that salt lake bittern
Successively by absorption, elution and desorption manipulation, lithium desorption liquid is obtained.Lithium concentration in the lithium desorption liquid is 0.4~0.6g/
L, magnesium ion concentration are 0.5~1.5g/L, and Na ion concentration is 0.3~0.5g/L, and chlorine ion concentration is 2.5~4.0g/L.
Above-mentioned absorption, elution, desorption manipulation to salt lake bittern is well known to those skilled in the art, therefore herein no longer in detail
It states, lithium adsorbent used in the present embodiment includes but is not limited to manganese systems adsorbent, aluminium system adsorbent, titanium system adsorbent and compound
Stibate adsorbent, above-mentioned adsorbent is adsorbent common on the market, and price is low.
Step b1:Above-mentioned lithium desorption liquid is set to adsorb resin by calcium and magnesium, so that the magnesium ion in lithium desorption liquid is removed, so that
Magnesium ion concentration is lower than 0.02mg/L.Above-mentioned calcium and magnesium absorption resin is one of cation exchange resin.Selected by the present embodiment
Absorption resin is faintly acid (hydroxyl) resin cation, and obtained feed liquid is the liquid that cleans.
Step c1：Removal of impurities liquid is concentrated, to improve the concentration of lithium ion.Common concentration method include the precipitation method,
Absorption method, hyperfiltration method, dialysis, the way of distillation, seasoning etc., the enrichment process in the present embodiment be preferably reverse osmosis concentration and
Evaporation and concentration combines.
Reverse osmosis also known as reverse osmosis is the UF membrane behaviour for isolating solvent from solution generally using pressure difference as motive force
Make.Reverse osmosis operation applies pressure by the high concentration feed liquid to film side, and when pressure is more than its osmotic pressure, solvent can be inverse
The direction of naturally osmotic make inverse osmosis, so that i.e. penetrating fluid, high-pressure side obtains in the solvent that is penetrated of low-pressure side of film
The solution of concentration, i.e. concentrate.The hyperfiltration used in the present embodiment includes but is not limited to that low pressure RO method, seawater are light
Change hyperfiltration, high pressure hyperfiltration and super-pressure hyperfiltration.
Removal of impurities liquid in the present embodiment is handled using hyperfiltration, obtains light salt brine in the low-pressure side of film, high-pressure side then
Obtain one section of lithium concentrate.Lithium concentration can be improved 8~12 times by one section of lithium concentrate, generally 4.0~6.0g/L.
Light salt brine obtained by hyperfiltration low-pressure side is recycled, is mentioned in lithium process for ion exchange adsorption,
Can be used as leacheate or de- analysis liquid come using, greatly reduce the water consumption of adsorption/desorption process in lithium chloride production process, from
And reduce cost.
Since the concentrated effect of hyperfiltration is unable to reach requirement of the concentrate containing lithium to lithium concentration, in the present embodiment
Concentration is further carried out to containing one section of lithium concentrate using evaporation and concentration process after reverse osmosis operation.In the present embodiment
Being concentrated by evaporation process preferably forces vacuum cycle to be concentrated by evaporation process, compared to common evaporation and concentration work in concentration process
Sequence is concentrated more efficient, and the consumption of electric power, steam and cooling water is lower, obtains containing lithium after process processing via being concentrated by evaporation
Concentrate, lithium concentration are 20~25g/L.
Since reverse osmosis concentration processing capacity is limited, and it is more to be concentrated by evaporation heat dissipation, and therefore, the present embodiment is using reverse osmosis
It concentration and is concentrated by evaporation the mode that combines removal of impurities liquid is handled, heat can be saved, can also reach to eventually forming
The requirement of lithium concentration in concentrate containing lithium.
Step S2 carbonization sinker process：
Lithium carbonate sediment, the present embodiment institute are generated by using sodium carbonate material and the reaction of concentrate containing lithium in this step
The oxide spinel sodium material used is the by-product washing soda during urea method production biruea, and urea method produces union II
The reaction of urea and technique are well known to those skilled in the art, and are first to produce hydrazine hydrate as raw material using urea, are then produced
Object hydrazine hydrate continues to produce biruea with urea reaction after processing, wherein the reaction using urea as raw material production hydrazine hydrate
Equation is as follows：
NaClO+2NaOH+H2NCONH2→N2H4·H2O+Na2CO3+NaCl
In order to which product hydrazine hydrate is separated, common processing mode be reaction product feed liquid is cooled down, thus
The washing soda crystal containing a small amount of sodium chloride is wrapped up in formation, is separated to the washing soda crystal using centrifugation.
Sodium carbonate material adopted in this step is the above-mentioned by-product washing soda isolated.In order to improve this reality
The reaction efficiency of sodium carbonate material and the concentrate containing lithium in example is applied, while improving the purity of the present embodiment final product lithium carbonate,
The present embodiment performs corresponding processing sodium carbonate material, that is, by-product washing soda and becomes sodium carbonate sperm, then makes it
With the hybrid reaction of concentrate containing lithium in step S1.
The present embodiment is as follows to the processing step of by-product washing soda：
Step a2：By-product washing soda during urea method production biruea is placed in dissolving tank, is passed through
It is heated, so that washing soda all dissolves, in order to avoid hot-spot, the present embodiment is preferably steam indirect heating
Mode.Further, the influence in order to avoid temperature to sodium carbonate liquor influences the generation of the lithium carbonate in later period and in turn in solution
In solubility, the present embodiment controlled during heating the sodium carbonate temperature of charge in dissolving tank be 30~40 DEG C.
Step b2：Sodium carbonate liquor in step a2 is realized by millipore filter to clean, filter pressure is 0.05~
0.1MPa, to remove the cotton-shaped crystal of the magnesium hydroxide in sodium carbonate liquor and mechanical admixture, so that application be made in step s 2
Sodium carbonate sperm.
Millipore filter is the general designation for the membrane filter that aperture is 0.2~1um, can filter out the 0.1um of liquid, gas
Above particle and bacterium, has that filtering accuracy is high, the rate of filtration is fast, absorption falls off less, without medium, acid-alkali-corrosive-resisting etc. is excellent
Point.Millipore filter used in the present embodiment be macromolecule engineering plastic material millipore filter, on the filter plus
The pressure of 0.05~0.1MPa of note, to be able to achieve the filtering to 0.5um crystalline solid is greater than.
To through handling obtained sodium carbonate semen sample, it is preferred to use the mode for adding calcium chloride measures in sodium carbonate sperm
Carbonate content, and make it according to the molar ratio 1.2~1.6 of sodium carbonate and lithium：2 are added in concentrate containing lithium, are reacting
In the process, reaction solution is in the excessive form of sodium carbonate, to improve the yield to lithium ion in concentrate containing lithium, and due to carbon
Sour sodium is soluble easily in water, therefore convenient for the later period to the separating treatment of sodium carbonate and lithium carbonate.It is noted that experiments verify that,
When the molar ratio of sodium carbonate and lithium is 1.4：When 2, the yield highest of lithium.
Sodium carbonate sperm and concentrate containing lithium are mixed to form reaction solution in a kettle, and are reacted as follows：Na2CO3+
2LiCl→Li2CO3+ 2NaCl, to form lithium carbonate precipitating in reaction kettle.
In addition, it is noted that above-mentioned reaction solution during reaction, control reaction solution stirring rate be 30~
60r/min, reaction temperature are 30~40 DEG C, and the reaction time continues 20~40min.
Above-mentioned response parameter is to obtain through many experiments, under above-mentioned process conditions, can make the carbonic acid in the present embodiment
Lithium rate of deposition is 95% or more, to increase the yield of lithium carbonate.
Step S3 postorder treatment process：
By the material output in step S2 reaction kettle, lithium carbonate therein is isolated.Since the solubility of lithium carbonate is with temperature
The raising of degree and become smaller, therefore the present embodiment using heating crystallization by the way of to lithium carbonate realize separate.
The material exported in reaction kettle is warming up to 75~85 DEG C as crystal solution, by crystal solution, at this time the dissolution of lithium carbonate
Degree is in 0.85g/ (100g water) left and right, to further improve the percent crystallization in massecuite of lithium carbonate, after will by way of separation of solid and liquid
It is separated.Simultaneously as most important impurity component is sodium chloride and sodium carbonate in crystal solution, crystallized by heating,
The impurity in crystal solution can be made to dissolve in the solution as much as possible, to improve the purity of crystallization of lithium carbonate body.
Solution dissolved with lithium carbonate because contain a large amount of sodium chloride, can not be separated so as to cause the lithium carbonate in solution,
So the liquid material after Crystallization Separation is adjusted to pH in after 5.5~6.5 using hydrochloric acid, it is made to be played back to salt pan i.e.
It can.
The sodium carbonate crystallization isolated is using no ion desalted water filtering and washing, to rinse out the molten of crystal surface attachment
Liquid makes crystallization pass sequentially through airstream drying tower and fluidized bed is dried later, and drying temperature control is 110~120 DEG C, from
And final product lithium carbonate product is made.
Filtering and washing refers to that, using Buchner funnel, bottle,suction and aspiration pump, the filler tube of Buchner funnel is mounted on bottle,suction
Single hole plug in and closely connect with bottle,suction, bottle,suction is connected with aspiration pump, is placed in Buchner funnel to cleaning product, on one side
Cleaning solution is filled into Buchner funnel uses suction filtration machine to reduce the pressure in bottle,suction on one side, so that the liquid in Buchner funnel
Body flows into bottle,suction along filler tube, so that the product in Buchner funnel is washed.
Using the method for pneumatic conveying drying in airstream drying tower, pneumatic conveying drying refers to the dispersion of scattered particulate solid material is outstanding
It floats in high-speed flow, a kind of method being dried under pneumatic conveying；Method of the fluidized bed using fluidized drying, stream
Change drying, which refers to blast hot-air, makes particle in fluidization in the bed for be placed with wet granular, heat is transmitted to particle from air
Heat needed for moisture evaporation is provided, thus make particle drying, since the ratio of heat transfer coefficient fixed bed under fluidization is big,
The efficiency of fluidized drying is more much greater than fixed bed drying.Using the combination of above two drying, both reduced dried
Overall heat dissipation in journey, in turn ensures the drying effect of material, while also accelerating the drying efficiency of material, so that passing through this reality
Qualified lithium carbonate product can continuously be exported by applying the drying device in example.
Via the preparation-obtained final product lithium carbonate product of the preparation process of the present embodiment lithium carbonate, through analyzing, carbon
The mass fraction of sour lithium is 99.26% or more, impurity component：Na2The mass fraction of O is 0.061~0.081%, Fe2O3Matter
Measuring the mass fraction that score is 0.0003~0.0005%, CaO is 0.040~0.082%, SO4 2-Mass fraction be 0~
0.011%, Cl-Mass fraction be 0.014~0.040%, H2The mass fraction of O is 0.040~0.120%, hydrochloric acid insoluble substance
Mass fraction be 0.001~0.003%, MgO mass fraction be 0.019~0.034%.It is computed, the present embodiment is to carbon
The yield of sour lithium is generally 70~80%.
The state quality standard of industrial lithium carbonate is：99.0% or more the mass fraction of lithium carbonate, impurity component：Na2O's
Mass fraction is 0.25% hereinafter, Fe2O3Mass fraction be 0.015% hereinafter, the mass fraction of CaO be 0.10% hereinafter,
SO4 2-Mass fraction be 0.50% hereinafter, Cl-Mass fraction be 0.020% hereinafter, H2The mass fraction of O be 0.8% with
Under, the mass fraction of hydrochloric acid insoluble substance is 0.050% hereinafter, the mass fraction of MgO is 0.025% or less.
Through comparing, industrial carbonic acid is apparently higher than using lithium carbonate product quality prepared by the preparation process in the present embodiment
The state quality standard of lithium, it is therefore, preferable using the lithium carbonate product quality obtained prepared by the present embodiment, it can be widely applied to
Industrial production.
Embodiment one
Step S1 removal of impurities enrichment process：
Step a1：Salt lake bittern is sent into the adsorption-desorption device equipped with lithium adsorbent, so that salt lake bittern successively passes through
Absorption, elution and desorption manipulation are crossed, lithium desorption liquid is obtained.Lithium concentration in the lithium desorption liquid is 0.4g/L, and magnesium ion is dense
Degree is 0.5g/L, Na ion concentration 0.3g/L, chlorine ion concentration 2.5g/L.
Step b1：Above-mentioned lithium desorption liquid is set to adsorb resin by calcium and magnesium, so that the magnesium ion in lithium desorption liquid is removed, so that
The magnesium ion concentration of lithium desorption liquid is 0.018mg/L, obtains removal of impurities liquid.
Step c1:Concentration is realized to removal of impurities liquid using reverse osmosis concentration method, obtains one section of lithium concentrate, one section of lithium concentration
Lithium concentration in liquid is that 5.0g/L continues to use evaporating and concentrating process to one section of lithium concentrate, to obtain this implementation later
Concentrate containing lithium in example, which is 20g/L.
Step S2 carbonization sinker process：
Washing soda crystal is handled first, processing step is as follows：
Step a2：By-product washing soda crystal during urea method production biruea is placed in dissolving tank,
Using steam-heated mode washing soda crystal is all dissolved, forms sodium carbonate liquor, during heating, control
Temperature of charge in dissolving tank processed is 30 DEG C.
Step b2：It realizes the sodium carbonate liquor in step a2 by millipore filter to clean, filter pressure is set as
0.05MPa can be used as lithium carbonate original to be made to remove the cotton-shaped crystal of the magnesium hydroxide in sodium carbonate liquor and mechanical admixture
The sodium carbonate sperm of material.
To sodium carbonate semen sample, the carbonate content in sodium carbonate sperm, sodium carbonate obtained by the present embodiment are measured
The concentration of sperm is 5.06mol/L.
It will contain in lithium concentrate input reaction kettle, and be 1.2 according to the molar ratio of sodium carbonate and lithium：2, the present embodiment is made
Standby sodium carbonate sperm is added in reaction kettle, hybrid reaction, and in the reaction process of reaction solution, the stirring rate of reaction solution is set
It is set to 30r/min, reaction temperature is 30 DEG C, and persistently reaction was completed after 40min altogether.This step generates lithium carbonate in a kettle
Precipitating.
Step S3 postorder treatment process：
Material in step S2 reaction kettle is transferred in crystallization kettle, material is heated, with the increase of temperature of charge, knot
Crystalline solid in brilliant kettle gradually increases, after material is warming up to 75 DEG C, to the material in crystallization kettle by the way of centrifuge separation
It is separated.
The solid material isolated carries out filtering and washing using no ion desalted water first, is then inputted pneumatic conveying drying
It is dried in tower, inputs it in fluidized bed and be dried, Two stage dryer temperature is disposed as 110 DEG C.Last object
Material is exported from fluidized bed, and natural cooling is up to final product lithium carbonate product prepared by the present embodiment.
The liquid material isolated is played back to salt pan after its pH is adjusted to 6.5 using hydrochloric acid.
In the lithium carbonate product that the present embodiment is produced, the content of lithium carbonate is 99.32%, and impurity content is as follows：Na2O
Mass fraction be 0.0804%, Fe2O3Mass fraction be 0.0004%, CaO mass fraction be 0.0436%, SO4 2-'s
Mass fraction is 0, Cl-Mass fraction be 0.024%, H2The mass fraction of O is 0.12%, the mass fraction of hydrochloric acid insoluble substance
Mass fraction for 0.002%, MgO is 0.0339%.It is computed, yield 73% of the present embodiment to lithium carbonate.
Embodiment two
Each step in the present embodiment is the same as example 1, and only in the present embodiment, sodium carbonate material uses not
It is the by-product washing soda crystal during urea method production biruea, but soda ash solution, therefore omit to by-product
Processing step a2~b2 of washing soda directly makes soda ash solution and the hybrid reaction of concentrate containing lithium.
In the lithium carbonate product that the present embodiment is produced, the mass fraction of lithium carbonate is 99.09%, and impurity content is as follows：
Na2The mass fraction of O is 0.1174%, Fe2O3Mass fraction be 0, CaO mass fraction be 0.0332, SO4 2-Quality point
Number is 0.0245, Cl-Mass fraction be 0.1313%, H2The mass fraction of O is 0.063%, the mass fraction of hydrochloric acid insoluble substance
Mass fraction for 0.040%, MgO is 0.0392%.
Embodiment three
Step S1 removal of impurities enrichment process：
Step a1：Salt lake bittern is sent into the adsorption-desorption device equipped with lithium adsorbent, so that salt lake bittern successively passes through
Absorption, elution and desorption manipulation are crossed, lithium desorption liquid is obtained.Lithium concentration in the lithium desorption liquid is 0.6g/L, and magnesium ion is dense
Degree is 1.5g/L, Na ion concentration 0.5g/L, chlorine ion concentration 4.0g/L.
Step b1：Above-mentioned lithium desorption liquid is set to adsorb resin by calcium and magnesium, so that the magnesium ion in lithium desorption liquid is removed, so that
The magnesium ion concentration of lithium desorption liquid is 0.020mg/L, obtains removal of impurities liquid.
Step c1：Concentration is realized to removal of impurities liquid using reverse osmosis concentration method, obtains one section of lithium concentrate, one section of lithium concentration
Lithium concentration in liquid is that 6.0g/L continues to use evaporating and concentrating process to one section of lithium concentrate, to obtain this implementation later
Concentrate containing lithium in example, which is 25g/L.
Step S2 carbonization sinker process：
Washing soda is handled first, processing step is as follows：
Step a2：By-product washing soda during urea method production biruea is placed in dissolving tank, is used
Steam-heated mode dissolves washing soda crystal all, forms sodium carbonate liquor, during heating, controls molten
Solving the temperature of charge in slot is 40 DEG C.
Step b2：It realizes the sodium carbonate liquor in step a2 by millipore filter to clean, filter pressure is set as
0.1MPa can be used as lithium carbonate original to be made to remove the cotton-shaped crystal of the magnesium hydroxide in sodium carbonate liquor and mechanical admixture
The sodium carbonate sperm of material.
To sodium carbonate semen sample, the carbonate content in sodium carbonate sperm, sodium carbonate obtained by the present embodiment are measured
The concentration of sperm is 5.12mol/L.
It will contain in lithium concentrate input reaction kettle, and be 1.4 according to the molar ratio of sodium carbonate and lithium：2, the present embodiment is made
Standby sodium carbonate sperm is added in reaction kettle, hybrid reaction, and in the reaction process of reaction solution, the stirring rate of reaction solution is set
It is set to 60r/min, reaction temperature is 40 DEG C, and persistently reaction was completed after 30min altogether.This step generates lithium carbonate in a kettle
Precipitating.
Step S3 postorder treatment process：
Material in step S2 reaction kettle is transferred in crystallization kettle, material is heated, with the increase of temperature of charge, knot
Crystalline solid in brilliant kettle gradually increases, after material is warming up to 85 DEG C, to the material in crystallization kettle by the way of centrifuge separation
It is separated.
The solid material isolated carries out filtering and washing using no ion desalted water first, is then inputted pneumatic conveying drying
It is dried in tower, inputs it in fluidized bed and be dried, Two stage dryer temperature is disposed as 115 DEG C.Last object
Material is exported from fluidized bed, and natural cooling is up to final product lithium carbonate product prepared by the present embodiment.
The liquid material isolated is played back to salt pan after its pH is adjusted to 6.0 using hydrochloric acid.
In the lithium carbonate product that the present embodiment is produced, the content of lithium carbonate is 99.34%, and impurity content is as follows：Na2O
Mass fraction be 0.081%, Fe2O3Mass fraction be 0.0004%, CaO mass fraction be 0.0437%, SO4 2-Matter
Measuring score is 0.011, Cl-Mass fraction be 0.04%, H2The mass fraction of O is 0.099%, the quality point of hydrochloric acid insoluble substance
The mass fraction that number is 0.001%, MgO is 0.0214%.It is computed, yield 80% of the present embodiment to lithium carbonate.
Example IV
Each step in the present embodiment is identical as embodiment three, and only in the present embodiment, sodium carbonate material uses not
It is the by-product washing soda crystal during urea method production biruea, but soda ash solution, therefore omit to by-product
Processing step a2~c2 of washing soda directly makes soda ash solution and the hybrid reaction of concentrate containing lithium.
In the lithium carbonate product that the present embodiment is produced, the mass fraction of lithium carbonate is 99.15%, and impurity content is as follows：
Na2The mass fraction of O is 0.1047%, Fe2O3Mass fraction be 0, CaO mass fraction be 0.0307, SO4 2-Quality point
Number is 0.0018, Cl-Mass fraction be 0.1027%, H2The mass fraction of O is 0.08%, the mass fraction of hydrochloric acid insoluble substance
Mass fraction for 0.042%, MgO is 0.0331%.
Embodiment five
Step S1 removal of impurities enrichment process：
Step a1：Salt lake bittern is sent into the adsorption-desorption device equipped with lithium adsorbent, so that salt lake bittern successively passes through
Absorption, elution and desorption manipulation are crossed, lithium desorption liquid is obtained.Lithium concentration in the lithium desorption liquid is 0.5g/L, and magnesium ion is dense
Degree is 1.0g/L, Na ion concentration 0.4g/L, chlorine ion concentration 3.3g/L.
Step b1：Above-mentioned lithium desorption liquid is set to adsorb resin by calcium and magnesium, so that the magnesium ion in lithium desorption liquid is removed, so that
The magnesium ion concentration of lithium desorption liquid is 0.015mg/L, obtains removal of impurities liquid.
Step c1：Concentration is realized to removal of impurities liquid using reverse osmosis concentration method, obtains one section of lithium concentrate, one section of lithium concentration
Lithium concentration in liquid is that 4.5g/L continues to use evaporating and concentrating process to one section of lithium concentrate, to obtain this implementation later
Concentrate containing lithium in example, which is 23g/L.
Step S2 carbonization sinker process：
Washing soda is handled first, processing step is as follows：
Step a2：By-product washing soda during urea method production biruea is placed in dissolving tank, is used
Steam-heated mode dissolves washing soda crystal all, forms sodium carbonate liquor, during heating, controls molten
Solving the temperature of charge in slot is 35 DEG C.
Step b2：It realizes the sodium carbonate liquor in step a2 by millipore filter to clean, filter pressure is set as
0.08MPa can be used as lithium carbonate original to be made to remove the cotton-shaped crystal of the magnesium hydroxide in sodium carbonate liquor and mechanical admixture
The sodium carbonate sperm of material.
To sodium carbonate semen sample, the carbonate content in sodium carbonate sperm, sodium carbonate obtained by the present embodiment are measured
The concentration of sperm is 5.21mol/L.
It will contain in lithium concentrate input reaction kettle, and be 1.6 according to the molar ratio of sodium carbonate and lithium：2, the present embodiment is made
Standby sodium carbonate sperm is added in reaction kettle, hybrid reaction, and in the reaction process of reaction solution, the stirring rate of reaction solution is set
It is set to 45r/min, reaction temperature is 35 DEG C, and persistently reaction was completed after 30min altogether.This step generates lithium carbonate in a kettle
Precipitating.
Step S3 postorder treatment process：
Material in step S2 reaction kettle is transferred in crystallization kettle, material is heated, with the increase of temperature of charge, knot
Crystalline solid in brilliant kettle gradually increases, after material is warming up to 80 DEG C, to the material in crystallization kettle by the way of centrifuge separation
It is separated.
The solid material isolated carries out filtering and washing using no ion desalted water first, is then inputted pneumatic conveying drying
It is dried in tower, inputs it in fluidized bed and be dried, Two stage dryer temperature is disposed as 120 DEG C.Last object
Material is exported from fluidized bed, and natural cooling is up to final product lithium carbonate product prepared by the present embodiment.
The liquid material isolated is played back to salt pan after its pH is adjusted to 6.5 using hydrochloric acid.
In the lithium carbonate product that the present embodiment is produced, the content of lithium carbonate is 99.26%, and impurity content is as follows：Na2O
Mass fraction be 0.0618%, Fe2O3Mass fraction be 0.0004%, CaO mass fraction be 0.0821%, SO4 2-'s
Mass fraction is 0, Cl-Mass fraction be 0.014%, H2The mass fraction of O is 0.04%, the mass fraction of hydrochloric acid insoluble substance
Mass fraction for 0.003%, MgO is 0.0193%.It is computed, yield 77% of the present embodiment to lithium carbonate.
Embodiment six
Each step in the present embodiment is identical as embodiment five, and only in the present embodiment, sodium carbonate material uses not
It is the by-product washing soda crystal during urea method production biruea, but soda ash solution, therefore omit to by-product
Processing step a2~c2 of washing soda directly makes soda ash solution and the hybrid reaction of concentrate containing lithium.
In the lithium carbonate product that the present embodiment is produced, the mass fraction of lithium carbonate is 99.22%, and impurity content is as follows：
Na2The mass fraction of O is 0.0788%, Fe2O3Mass fraction be 0, CaO mass fraction be 0.0339, SO4 2-Quality point
Number is 0.0081, Cl-Mass fraction be 0.0680%, H2The mass fraction of O is 0.07%, the mass fraction of hydrochloric acid insoluble substance
Mass fraction for 0.039%, MgO is 0.0399%.
Table 1 lists the mass fraction (%) of each ingredient of product lithium carbonate in one~embodiment of embodiment six.
Table 1
In table 1, embodiment one, embodiment three, embodiment fifth is that using lithium carbonate of the present invention preparation process institute
The lithium carbonate product being prepared, embodiment two, example IV and embodiment are sixth is that using soda ash solution as sodium carbonate material
Preparation-obtained lithium carbonate product.Lithium carbonate purity in lithium carbonate product each in table 1 is compared, it is known that, using this
Carbonic acid lithium content in the preparation-obtained product of preparation process of the invention lithium carbonate is apparently higher than using soda ash solution
As the carbonic acid lithium content in the preparation-obtained product of sodium carbonate material.Therefore, it can be obtained by the comparison of above-mentioned experimental result,
Quality using the obtained lithium carbonate product of the preparation process of lithium carbonate of the present invention is higher.
Why there is said effect, is with raw material of the invention using right in by-product washing soda crystal, the present invention
The processing step and reaction treatment step of washing soda are related.First, due to using soda ash solution as sodium carbonate object
Material is come when preparing lithium carbonate, soda ash is residual although being handled the magnesium chloride brought into from raw material sodium chloride in production
The micro magnesium chloride deposited will form the form of magnesium bicarbonate, and after the calcination process during soda manufacture, be converted into carbonic acid
The form of magnesium exists, and when soda ash solution to be applied to the preparation section in lithium carbonate, the magnesium carbonate contained will enter carbonic acid
In lithium finished product, and it is converted into post-processing process the form of magnesia and exists.And use lithium carbonate of the present invention
Preparation process when, by-product washing soda crystal is first handled, then just as sodium carbonate material carry out
It utilizes, due to the process in urea method production biruea, magnesium ion is existed in the form of magnesium hydroxide, and the present invention is to by-product
It in the treatment process of object washing soda, is cleaned using millipore filter to it, so as to remove washing soda crystal
A large amount of magnesium hydroxides in the sodium carbonate liquor of formation.Second, soda ash is brought into from raw material sodium chloride micro in process of production
Silicon compound can be partially converted into the sodium metasilicate hydrotrope, thus can enter in final product lithium carbonate product, and the present invention uses
Sodium carbonate material be urea method produce biruea during be in by-product washing soda existing for Crystallization, avoid silicon
The presence of element compound.Third, for soda ash during production, raw material sodium chloride can bring micro sodium sulphate into, to lead
The presence for having sulfate radical in finally formed lithium carbonate product is caused, and what the present invention directlyed adopt is in by-product existing for crystal form
Object washing soda, so that being substantially free of sulfate radical in raw material.Based on above-mentioned analysis and embodiment result obtains, this
The lithium carbonate product of high quality can be prepared in the preparation process of the invention lithium carbonate, and is significantly higher than industrial lithium carbonate matter
The national standard of amount, the utilization conducive to the later period to lithium carbonate.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and this
Field technical staff can be designed alternative embodiment without departing from the scope of the appended claims.In claim
In, any reference symbol between parentheses should not be configured to limitations on claims.Word "comprising" is not excluded for depositing
In element or step not listed in the claims.
Claims (9)
1. a kind of preparation process of lithium carbonate, which is characterized in that include the following steps：
Step S1 removal of impurities enrichment process：
After salt lake bittern removal of impurities concentration, concentrate containing lithium is formed；
Step S2 carbonization sinker process：
Sodium carbonate material is added into the concentrate containing lithium and forms reaction solution, when reacting original state, carbon in the reaction solution
The molar ratio of sour sodium and lithium is 1.2~1.6：2, after reacted, lithium carbonate precipitating is generated in the reaction solution,
Wherein, the sodium carbonate material is the by-product washing soda crystal during urea method production biruea；
Sodium carbonate material in the step S2 carbonization sinker process is sodium carbonate sperm after processing, the sodium carbonate material
Treatment process include the following steps：
Step a2：By-product washing soda during the sodium carbonate material, that is, urea method production biruea is placed on molten
It solves in slot, is made it dissolve completely by heating, sodium carbonate liquor is made；
Step b2：It realizes the sodium carbonate liquor by millipore filter to clean, filter pressure is 0.05~0.1MPa, is made
Sodium carbonate sperm；
Step S3 postorder treatment process：
The lithium carbonate precipitating is isolated, obtains final product lithium carbonate product after washed, dry.
2. the preparation process of lithium carbonate according to claim 1, which is characterized in that the step S1 removal of impurities enrichment process packet
Include following steps：
Step a1：The salt lake bittern is sent into the adsorption-desorption device equipped with lithium adsorbent, by absorption, elution and is taken off
Lithium desorption liquid is made in attached operation；
Step b1：The magnesium ion in the lithium desorption liquid is removed by cation exchange resin, removal of impurities liquid is made；
Step c1：Using reverse osmosis concentration process and process is concentrated by evaporation to removal of impurities liquid realization concentration, is formed and is concentrated containing lithium
Liquid.
3. the preparation process of lithium carbonate according to claim 1 or 2, which is characterized in that be concentrated described in step S1 containing lithium
The lithium concentration of liquid is 20~25g/L.
4. the preparation process of lithium carbonate according to claim 1, which is characterized in that sodium carbonate liquor described in step a2
Heating temperature is 30~40 DEG C.
5. the preparation process of lithium carbonate according to claim 1, which is characterized in that step S2 is carbonized in sinker process, institute
Stating the stirring rate of reaction solution during the reaction is 30~60r/min, and reaction temperature is 30~40 DEG C, and the reaction time continues 20
~40min.
6. the preparation process of lithium carbonate according to claim 1, which is characterized in that step S2 is carbonized in sinker process, instead
When answering original state, the molar ratio of sodium carbonate and lithium is 1.4 in the reaction solution：2.
7. the preparation process of lithium carbonate according to claim 1, which is characterized in that in step S3 postorder treatment process
The separate mode is heating crystallization, and the crystal solution temperature in the heating crystallization mode rises to 75~85 DEG C.
8. the preparation process of lithium carbonate according to claim 7, which is characterized in that the heating crystallization mode is isolated
Liquid use hydrochloric acid to be neutralized to pH to make it be played back to salt pan after 5.5~6.5.
9. the preparation process of lithium carbonate according to claim 1, which is characterized in that in step S3 subsequent processing process
The mode of washing is filtering and washing, and the drying mode is that pneumatic conveying drying and fluidized drying merge utilization.
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| CN107500318B (en) * | 2017-09-26 | 2019-05-10 | 马海军 | The method of lithium carbonate is extracted from aluminium oxide factory sodium aluminate solution |
| CN108217701A (en) * | 2018-04-11 | 2018-06-29 | 宜春市鼎鑫高能科技有限公司 | A kind of lithium carbonate process units |
| US11524901B2 (en) * | 2019-03-22 | 2022-12-13 | Beijing University Of Chemical Technology | Method for efficiently separating magnesium and lithium from salt lake brine and simultaneously preparing high-purity magnesium oxide and battery-grade lithium carbonate |
| CN111470521B (en) * | 2020-05-25 | 2021-08-17 | 中国地质科学院矿产资源研究所 | Method for extracting lithium from solar cell |
| CN115872421A (en) * | 2021-09-30 | 2023-03-31 | 比亚迪股份有限公司 | Method for recovering lithium from lithium-containing solution |
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