CN106064824A - A kind of production technology of sulfuric acid process lithium salts - Google Patents
A kind of production technology of sulfuric acid process lithium salts Download PDFInfo
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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
Abstract
The production technology of a kind of sulfuric acid process lithium salts, comprises the following steps: 1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate；2) lithium sulfate leachate is carried out remove impurity process, obtain the leachate containing lithium processed through remove impurity；3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, obtain filtrate and solid impurity；4) membrance concentration: by step 3) filtrate that obtains utilizes NF membrane or reverse osmosis membrane to carry out membrance concentration, obtains permeate and concentrated solution；Will transmit through liquid and return Water circulation system；5) sinker: by step 4) concentrated solution that obtains carries out sinker process, and separate, obtain lithium carbonate precipitation；6) lithium carbonate precipitation is carried out separating, washing, is dried, prepare finished product.The advantage such as the production technology of sulfuric acid process lithium salts of the present invention has that energy resource consumption is little, low cost, intractability are little, saving time, efficiency are high and pollution-free.
Description
Technical field
The present invention relates to lithium salts production technical field, particularly relate to a kind of purification produced for sulfuric acid process lithium salts and concentrate work
Skill.
Background technology
Lithium is a kind of important strategic resources material, is the indispensable important source material of modern high technology product.China
The lithium resource gross reserves verified occupies second place of the world, but lithium yield only accounts for about the 5% of whole world total output, is only entering of lithium product
Mouth state.
Lithium carbonate is to produce secondary lithium salts and the basic material of lithium metal goods, thus it is maximum to become consumption in lithium industry
Lithium product, other lithium products are all the downstream product of lithium carbonate on it.The production technology of lithium carbonate is according to raw material sources
Difference can be divided into salt lake bittern to extract and Ore extracts.At present, external main employing salt lake bittern extraction process produces carbonic acid
Lithium, China mainly uses solid mineral extraction process.Although China is also actively exploiting saline lake lithium resource, but due to technology,
The restriction of the factors such as resource, development rate is the slowest.
Ore extracts lithium and mainly uses the solid lithium Ore such as spodumene, lepidolite to produce lithium carbonate and other lithium products.
Extracting the with a long history of lithium resource from Ore, technology is the most ripe, and main production has lime sinter process and sulfuric acid process, its
Middle sulfuric acid process is currently used main method.As it is shown in figure 1, in remove impurity laggard row plate-and-frame filtration and evaporation and concentration, the most again
Carry out the subsequent operations such as sinker, finally prepare finished product.
Evaporation and concentration needs steam-heating system to be evaporated lithium sulfate solution so that the moisture in solution becomes gaseous state
Effusion, thus realize the purpose concentrated.This technique has that energy resource consumption is big, processing cost and difficulty is relatively big, cost is high, consumption
Time, efficiency is low, seriously polluted.
Use plate-and-frame filtration mode more filtration after remove impurity, owing to filter cloth aperture is big, cause its precision to reduce so that Queen Lu
In feed liquid, solid content is higher, and then operation does not use effective means to carry out solid impurity interception so that product quality is relatively low；
This evaporating and concentrating process equipment needed thereby is more, and maintenance cost and difficulty are higher.
Also to environment while evaporation and concentration waste water resource, it is unfavorable for the Sustainable Healthy Development of enterprise.
Summary of the invention
The technical problem to be solved is to provide the production technology of a kind of sulfuric acid process lithium salts, has energy resource consumption
Little, low cost, intractability are little, save the advantages such as time, efficiency are high and pollution-free.
The technical scheme is that
The production technology of a kind of sulfuric acid process lithium salts, comprises the following steps:
1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate；
2) lithium sulfate leachate is carried out remove impurity process, obtain the leachate containing lithium processed through remove impurity；
3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, obtain
Filtrate and solid impurity；
4) membrance concentration: by step 3) filtrate that obtains utilizes NF membrane or reverse osmosis membrane to carry out membrance concentration, obtains permeate
And concentrated solution；Will transmit through liquid and return Water circulation system；
5) sinker: by step 4) concentrated solution that obtains carries out sinker process, and separate, obtain lithium carbonate precipitation；
6) lithium carbonate precipitation is carried out separating, washing, is dried, prepare finished product.
Inventor, in years of researches, finds that evaporation and concentration has that energy resource consumption is big, processing cost is relatively big with difficulty, becomes
This height, time-consuming, the problems such as efficiency is low, seriously polluted.Propose first and membrane filtration and membrance concentration are used for the production of sulfuric acid process lithium salts
In technique.And be arranged between impurity removal process and sinker technique, lithium sulfate solution is carried out deep purifying and concentration, there is raising
The advantages such as product quality, energy-saving and cost-reducing, reduction processing cost.
By membrane filtration, the float in solution is intercepted, it is achieved solid-liquid separation；Float is produced during acidleach, as
Fruit is not got rid of, and can affect product quality and subsequent treatment process difficulty and cost；And due to the physicochemical characteristic of float,
(for the filter press) problem easily produce filtering material blocking, frequently changing；Utilize micro-filtration membrane by solution
Float intercept, it is achieved solid-liquid separation, there is the advantage that precision is high, intercepting efficiency is high.
By membrance concentration, lithium concentration is improved to saturation, it is achieved feed liquid concentrates；What membrance concentration produced simultaneously is saturating
Cross liquid and return Water circulation system, can recycle, there is the advantage such as environmental protection, using water wisely, significantly reduce cost.
Compared with evaporation and concentration of the prior art, the membrane filtration of present invention employing and membrance concentration are with the use of having yield
The advantages such as height, purity are high, energy resource consumption is little, low cost, intractability are little, save the time, efficiency is high, pollution-free.
The purification concentration technology of the present invention purification be applicable to lithium salts production process and concentration, lithium salts can be carbon
Acid lithium, it is also possible to Lithium hydrate or other compounds containing lithium etc..
On the basis of technique scheme, the present invention can also do following improvement.
Further, in step 3) in, the aperture of membrane filtration is 1-5 μm.
Above-mentioned further scheme is used to provide the benefit that: the filter effect of the float in raising solution further, real
Existing solid-liquid separation, it is to avoid the impact on later product.If aperture is too small, filtering accuracy improves but flux reduces；If hole
Footpath is excessive, and flux raises but filtering accuracy reduces.
Further, in step 3) in, the temperature of membrane filtration is 0-100 DEG C.
Above-mentioned further scheme is used to provide the benefit that: the filter effect of the float in raising solution further, real
Existing solid-liquid separation, it is to avoid the impact on later product.If temperature is too high, the dissolubility of the composition of solution is produced impact.
Further, in step 3) in, the pressure of membrane filtration is 0.02-0.2MPa.
Above-mentioned further scheme is used to provide the benefit that: the filter effect of the float in raising solution further, real
Existing solid-liquid separation, it is to avoid the impact on later product.If hypotony, filtering accuracy improves but flux reduces；If pressure
Power is too high, and flux increases but filtering accuracy reduces, and meanwhile, is easily damaged film, affects the service life of film, increases and produce into
This.
Further, step 4) in, during membrance concentration, conditional parameter scope is: lithium sulfate solution is enriched to lithium content is
The concentrated solution of 40-50g/L.
Above-mentioned further scheme is used to provide the benefit that: to be easy to the carrying out of late stage process.
Further, step 4) in, when using NF membrane to carry out membrance concentration, temperature is 0-40 DEG C, and pressure is 10-20Mpa, cuts
The molecular weight staying material is more than 100.
Use above-mentioned further scheme to provide the benefit that: by the setting of above-mentioned parameter, on the one hand can ensure that concentration
Final concentration, on the one hand can ensure that flux, thickening efficiency is high.
Further, step 1) in, pretreatment method particularly includes: take spodumene concentrate, to lithium brightness at 1100-1200 DEG C
Stone concentrate roasting 0.5-2 hour, then cool to 80-145 DEG C, obtain spodumene calcining；Spodumene calcining is carried out ore grinding,
Particle diameter is less than the spodumene breeze of 80 mesh.
Above-mentioned further scheme is used to provide the benefit that: by pretreatment, beneficially the carrying out of late phase reaction.
Further, step 1) in, the reaction condition of acidleach is: add the sulfur of concentration 93%-98% in spodumene breeze
Acid, and roasting under conditions of 250-300 DEG C, obtain acid grog, and the residual acid weight/mass percentage composition controlling acid grog is 3%-
6%；Adding calcium carbonate in acid grog, the addition mole of calcium carbonate is 1.1 times of residual acid mole, obtains mixture, to mixed
Adding water in compound, when the pH value of mixture is at 5.5-6.0, filter, the lithium sulfate obtaining solid content more than 10% leaches
Liquid.
Above-mentioned further scheme is used to provide the benefit that: to control reaction condition and the consumption of each raw material by strict, protect
Prepared by the success of card lithium sulfate leachate.
Further, step 2) in, use the method adjusting pH that lithium sulfate leachate carries out remove impurity process, precipitated calcium magnesium salt.
Above-mentioned further scheme is used to provide the benefit that:
Calcium ions and magnesium ions in lithium sulfate leachate is formed precipitation, it is to avoid the impact on late stage process.
Further, step 5) in, sinker method particularly includes: in concentrated solution, add soda saturated solution, make lithium carbonate
Precipitation, filters and separates lithium carbonate precipitation.
Use above-mentioned further scheme to provide the benefit that: to improve the effect of sinker, improve the yield of lithium salts.
Further, step 6) in, separating, washing method particularly includes: hot wash lithium carbonate, the temperature of hot water is 40-90
℃。
Above-mentioned further scheme is used to provide the benefit that: to improve clean result.
The present invention does not has special strict restriction for the membrane material during membrane filtration and membrance concentration.All can be from city
Sell acquisition or be prepared by conventional method.
Micro-filtration membrane is divided into inoranic membrane and organic high molecular layer according to filmogen, and inoranic membrane is divided into again ceramic membrane, metal film
And intermetallic compound porous material, organic high molecular layer is divided into again natural macromolecule membrane and synthetic polymeric membrane；According to film
Form is divided into again Flat Membrane, tubular membrane, rolled film and hollow-fibre membrane；According to masking principle, the preparation method of polymeric membrane is divided
For leaching (dry-wet method), stretching hole forming method, phase inversion, thermic phase method, dip coating, irradiation method, surface chemical modification method,
Nuclear track method, power formation method etc., the preparation method of inoranic membrane mainly has sol-gel process, sintering process, chemical precipitation method etc..
Applying and wider should belong to organic polymer hollow-fibre membrane, main micro-filtration membrane kind has Kynoar
(PVDF), polysulfones (PSF), polyacrylonitrile (PAN), polrvinyl chloride (PVC), polypropylene (PP) etc..
The material of NF membrane is macromolecular material, mainly polyamide (PA), polyvinyl alcohol (PvA), SPSF
(sPS), sulfonated polyether sulfone (sPEs), cellulose acetate (cA) and derivant thereof etc..
Common reverse osmosis membrane materials has two big class, i.e. cellulose acetate membrane component and composite membrane elements.
(1) cellulose acetate membrane component
General cellulose generates triacetate fiber through esterification, then through secondary be hydrolyzed into mixing one, two, triacetate fiber.
The salt rejection rate affecting film is that acetyl content height then salt rejection rate is high with the most important factor of aquifer yield, but aquifer yield is few.
Cellulose acetate membrane weakness substantially is, passage in time, and ester functional groups will hydrolyze, simultaneously salt rejection rate by
Gradually declining and flow increase, along with the reinforcement of hydrolysis, film is more vulnerable to microbiological attack, and film itself also will lose it simultaneously
Function and integrity.
(2) composite membrane element
The main support structure of composite membrane is the polyester non-woven after being calendered machine calendering, and its surface is without loose fiber also
And hard smooth, due to polyester non-woven the most irregularly and the most loose, it is not suitable as the bottom of salt barrier layer, thus
Being cast on non-woven fabric surface by micropore engineering plastics polysulfones, the hole on polysulfones layer surface controls at about 15nm, and barrier layer is adopted
With the aromatic polyamides of high-crosslinking-degree, thickness is about at 0.2um.High-crosslinking-degree aromatic polyamides is gathered by benzene three acyl chlorides and phenylenediamine
Conjunction forms.
Accompanying drawing explanation
Fig. 1 is the production technological process of the sulfuric acid process lithium salts described in prior art
Fig. 2 is the production technological process of sulfuric acid process lithium salts of the present invention.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
Non-for limiting the scope of the present invention.
As in figure 2 it is shown, the production technology of sulfuric acid process lithium salts includes: acidleach, remove impurity, membrane filtration, membrance concentration, sinker, separation
Wash, be dried, prepare finished product.Concrete operations are as follows.
1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate.
Pretreatment method particularly includes: take spodumene concentrate, to spodumene concentrate roasting 0.5-2 at 1100-1200 DEG C
Hour, then cool to 80-145 DEG C, obtain spodumene calcining；Spodumene calcining is carried out ore grinding, obtains particle diameter less than 80 purposes
Spodumene breeze.
The reaction condition of acidleach is: add the sulphuric acid of concentration 93%-98% in spodumene breeze, and at 250-300 DEG C
Under conditions of roasting, obtain acid grog, control acid grog residual acid weight/mass percentage composition be 3%-6%；Add in acid grog
Calcium carbonate, the addition mole of calcium carbonate is 1.1 times of residual acid mole, obtains mixture, adds water in mixture, works as mixture
PH value when 5.5-6.0, filter, obtain the lithium sulfate leachate of solid content more than 10%.
2) use tune pH method (pH regulator is 11-12) to carry out remove impurity process lithium sulfate leachate, obtain processing through remove impurity
The leachate containing lithium.
3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, film mistake
The aperture of filter is 1-5 μm, and the temperature of membrane filtration is 0-100 DEG C, and the pressure of membrane filtration is 0.02-0.2Mpa, obtains filtrate with solid
Body impurity.
4) membrance concentration: by step 3) filtrate that obtains utilizes NF membrane or reverse osmosis membrane to carry out membrance concentration, obtains permeate
With concentrated solution (lithium sulfate solution is enriched to the concentrated solution that lithium content is 50g/L), will transmit through liquid and return Water circulation system.
5) sinker: to step 4) concentrated solution that obtains adds soda saturated solution, make lithium carbonate precipitate, filtration separation of carbon
Acid lithium precipitation.
6) lithium carbonate precipitation being utilized hot wash lithium carbonate, the temperature of hot water is 40-90 DEG C, separates, and is dried, prepares into
Product lithium carbonate.
The material of the micro-filtration membrane of the membrane filtration in the embodiment of the present invention is ceramic membrane or intermetallic compound porous material, especially
It uses the filter effect of intermetallic compound porous material more preferable, due in the leachate that produces after acidleach process, and filterability
Can difference easily block, by intermetallic compound porous material and arrange suitable filtercondition and can ensure that long-time stable is transported
Row, good filtration effect.
The material of the membrance concentration in the embodiment of the present invention is macromolecular material.
It is specifically introduced below by some specific embodiments.
Embodiment 1
The production technology of sulfuric acid process lithium salts comprises the following steps:
1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate.
Pretreatment method particularly includes: take spodumene concentrate, to spodumene concentrate roasting 0.5 hour at 1100 DEG C, then
Cool to 80 DEG C, obtain spodumene calcining；Spodumene calcining is carried out ore grinding, obtains the particle diameter spodumene breeze less than 80 mesh.
The reaction condition of acidleach is: add the sulphuric acid of concentration 93%-98% in spodumene breeze, and at the bar of 250 DEG C
Roasting under part, obtains acid grog, and the residual acid weight/mass percentage composition controlling acid grog is 3%；Calcium carbonate, carbon is added in acid grog
The addition mole of acid calcium is 1.1 times of residual acid mole, obtains mixture, adds water in mixture, when the pH value of mixture exists
When 5.5, filter, obtain the lithium sulfate leachate of solid content more than 10%.
2) method (pH regulator is 11) using tune pH carries out remove impurity process, precipitated calcium magnesium salt to lithium sulfate leachate, obtains
To the leachate containing lithium processed through remove impurity.
3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, film mistake
The aperture of filter is 1 μm, and the temperature of membrane filtration is 0 DEG C, and the pressure of membrane filtration is 0.02Mpa, obtains filtrate and solid impurity.
4) membrance concentration: by step 3) filtrate that obtains utilizes NF membrane to carry out membrance concentration, and obtain permeate and concentrated solution (will
Lithium sulfate solution is enriched to the concentrated solution that lithium content is 50g/L), when using NF membrane to carry out membrance concentration, temperature is 0 DEG C, pressure
For 10Mpa, the molecular weight retaining material is 100, will transmit through liquid and returns Water circulation system.
5) sinker: to step 4) concentrated solution that obtains adds soda saturated solution, make lithium carbonate precipitate, filtration separation of carbon
Acid lithium precipitation.
6) lithium carbonate precipitation being utilized hot wash lithium carbonate, the temperature of hot water is 40 DEG C, separates, and is dried, and prepares finished product
Lithium carbonate.
Embodiment 2
The production technology of sulfuric acid process lithium salts comprises the following steps:
1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate.
Pretreatment method particularly includes: take spodumene concentrate, to spodumene concentrate roasting 2 hours at 1200 DEG C colder
But it is cooled to 145 DEG C, obtains spodumene calcining；Spodumene calcining is carried out ore grinding, obtains the particle diameter spodumene breeze less than 80 mesh.
The reaction condition of acidleach is: adds the sulphuric acid of concentration 98% in spodumene breeze, and roasts under conditions of 300 DEG C
Burning, obtain acid grog, the residual acid weight/mass percentage composition controlling acid grog is 6%；Calcium carbonate is added in acid grog, calcium carbonate
Addition mole is 1.1 times of residual acid mole, obtains mixture, adds water in mixture, when the pH value of mixture is 6.0,
Filter, obtain the lithium sulfate leachate of solid content more than 10%.
2) method (pH regulator is 11) using tune pH carries out remove impurity process, precipitated calcium magnesium salt to lithium sulfate leachate, obtains
To the leachate containing lithium processed through remove impurity.
3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, film mistake
The aperture of filter is 5 μm, and the temperature of membrane filtration is 100 DEG C, and the pressure of membrane filtration is 0.2Mpa, obtains filtrate and solid impurity.
4) membrance concentration: by step 3) filtrate that obtains utilizes reverse osmosis membrane to carry out membrance concentration, obtains permeate and concentrated solution
(lithium sulfate solution is enriched to the concentrated solution that lithium content is 40g/L), when using NF membrane to carry out membrance concentration, temperature is 40 DEG C,
Pressure is 20Mpa, and the molecular weight retaining material is 300, will transmit through liquid and returns Water circulation system.
5) sinker: to step 4) concentrated solution that obtains adds soda saturated solution, make lithium carbonate precipitate, filtration separation of carbon
Acid lithium precipitation.
7) lithium carbonate precipitation being utilized hot wash lithium carbonate, the temperature of hot water is 90 DEG C, separates, and is dried, and prepares finished product
Lithium carbonate.
Embodiment 3
The production technology of sulfuric acid process lithium salts comprises the following steps:
1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate.
Pretreatment method particularly includes: take spodumene concentrate, to spodumene concentrate roasting 1 hour at 1150 DEG C colder
But it is cooled to 120 DEG C, obtains spodumene calcining；Spodumene calcining is carried out ore grinding, obtains the particle diameter spodumene breeze less than 80 mesh.
The reaction condition of acidleach is: adds the sulphuric acid of concentration 95% in spodumene breeze, and roasts under conditions of 280 DEG C
Burning, obtain acid grog, the residual acid weight/mass percentage composition controlling acid grog is 5%；Calcium carbonate is added in acid grog, calcium carbonate
Addition mole is 1.1 times of residual acid mole, obtains mixture, adds water in mixture, when the pH value of mixture is 5.8,
Filter, obtain the lithium sulfate leachate of solid content more than 10%.
2) method (pH regulator is 11) using tune pH carries out remove impurity process, precipitated calcium magnesium salt to lithium sulfate leachate, obtains
To the leachate containing lithium processed through remove impurity.
3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, film mistake
The aperture of filter is 2 μm, and the temperature of membrane filtration is 50 DEG C, and the pressure of membrane filtration is 0.1Mpa, obtains filtrate and solid impurity.
4) membrance concentration: by step 3) filtrate that obtains utilizes NF membrane to carry out membrance concentration, and obtain permeate and concentrated solution (will
Lithium sulfate solution is enriched to the concentrated solution that lithium content is 45g/L), when using NF membrane to carry out membrance concentration, temperature is 20 DEG C, pressure
For 15Mpa, the molecular weight retaining material is 200, will transmit through liquid and returns Water circulation system.
5) sinker: to step 4) concentrated solution that obtains adds soda saturated solution, make lithium carbonate precipitate, filtration separation of carbon
Acid lithium precipitation.
6) lithium carbonate precipitation being utilized hot wash lithium carbonate, the temperature of hot water is 60 DEG C, separates, and is dried, and prepares finished product
Lithium carbonate.
Inventor has the most also carried out the Adjustment Tests in membrane filtration aperture, and concrete operations are: on the basis of embodiment 1
Adjusting the aperture of membrane filtration, other parameter and step are constant.Result of the test such as table 1.
Experimental result according to table 1, it can be seen that aperture is the least, the granule interception rate of solid is the highest, when aperture is 0.1-
Time between 5 microns, solid particle interception rate all can reach more than 90%, and especially aperture is between 0.1-1 micron, solid particle
Interception rate all can reach 99.9%.But, inventor finds under study for action, and aperture is between 0.1-1 micron, and flux is the lowest,
Filtration time is longer and easily blocks filter opening, makes the yield decline of the finished product lithium carbonate prepared, cost raise.Therefore, comprehensively examine
After worry, by the aperture of membrane filtration between 1-5 micron, can ensure that solid particle interception rate is effective, flux is good, finished product simultaneously
The yield of lithium carbonate is high, the purity of finished product lithium carbonate is high.
Table 1
| The aperture (micron) of membrane filtration | Solid particle interception rate | Membrane Filtration Flux (m3/h.㎡) |
| 0.1 | 99.9% | 0.2 |
| 0.5 | 99.9% | 0.3 |
| 1 (i.e. embodiment 1) | 99.9% | 0.6 |
| 3 | 95% | 0.7 |
| 5 | 92% | 0.8 |
| 7 | 88% | 0.85 |
| 10 | 86% | 0.9 |
| 15 | 82.5% | 1.0 |
| 18 | 81% | 1.1 |
| 20 | 78% | 1.2 |
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. the production technology of a sulfuric acid process lithium salts, it is characterised in that comprise the following steps:
1) acidleach: pretreated spodumene breeze is immersed in sulfuric acid solution, obtains lithium sulfate leachate；
2) lithium sulfate leachate is carried out remove impurity process, obtain the leachate containing lithium processed through remove impurity；
3) membrane filtration: by step 2) through remove impurity process the leachate containing lithium utilize micro-filtration membrane to carry out membrane filtration, obtain filtrate
And solid impurity；
4) membrance concentration: by step 3) filtrate that obtains utilizes NF membrane or reverse osmosis membrane to carry out membrance concentration, obtains permeate and dense
Contracting liquid；Will transmit through liquid and return Water circulation system；
5) sinker: by step 4) concentrated solution that obtains carries out sinker process, and separate, obtain lithium carbonate precipitation；
6) lithium carbonate precipitation is carried out separating, washing, is dried, prepare finished product.
The production technology of a kind of sulfuric acid process lithium salts, it is characterised in that in step 3) in, membrane filtration
Aperture be 1-5 μm.
The production technology of a kind of sulfuric acid process lithium salts, it is characterised in that in step 3) in, membrane filtration
Temperature be 0-100 DEG C.
The production technology of a kind of sulfuric acid process lithium salts, it is characterised in that in step 3) in, membrane filtration
Pressure be 0.02-0.2MPa.
5. according to the production technology of sulfuric acid process lithium salts a kind of described in any one of claim 1-4, it is characterised in that step 4) in,
During membrance concentration, conditional parameter scope is: lithium sulfate solution is enriched to the concentrated solution that lithium content is 40-50g/L.
6. according to the production technology of sulfuric acid process lithium salts a kind of described in any one of claim 1-4, it is characterised in that step 4) in,
When using NF membrane to carry out membrance concentration, temperature is 0-40 DEG C, and pressure is 10-20Mpa, and the molecular weight retaining material is more than 100.
7. according to the production technology of sulfuric acid process lithium salts a kind of described in any one of claim 1-4, it is characterised in that step 1) in,
Pretreatment method particularly includes: take spodumene concentrate, to spodumene concentrate roasting 0.5-2 hour at 1100-1200 DEG C colder
But it is cooled to 80-145 DEG C, obtains spodumene calcining；Spodumene calcining is carried out ore grinding, obtains the particle diameter spodumene ore deposit less than 80 mesh
Powder；The reaction condition of acidleach is: add the sulphuric acid of concentration 93%-98% in spodumene breeze, and the condition of 250-300 DEG C
Lower roasting, obtains acid grog, and the residual acid weight/mass percentage composition controlling acid grog is 3%-6%；Calcium carbonate is added in acid grog,
The addition mole of calcium carbonate is 1.1 times of residual acid mole, obtains mixture, adds water in mixture, when the pH value of mixture
When 5.5-6.0, filter, obtain the lithium sulfate leachate of solid content more than 10%.
8. according to the production technology of sulfuric acid process lithium salts a kind of described in any one of claim 1-4, it is characterised in that step 2) in,
Use the method adjusting pH that lithium sulfate leachate carries out remove impurity process, precipitated calcium magnesium salt.
9. according to the production technology of sulfuric acid process lithium salts a kind of described in any one of claim 1-4, it is characterised in that step 5) in,
Sinker method particularly includes: in concentrated solution, add soda saturated solution, make lithium carbonate precipitate, filter and separate lithium carbonate precipitation.
10. according to the production technology of sulfuric acid process lithium salts a kind of described in any one of claim 1-4, it is characterised in that step 6) in,
Separating, washing method particularly includes: hot wash lithium carbonate, the temperature of hot water is 40-90 DEG C.
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| CN108640131A (en) * | 2018-04-28 | 2018-10-12 | 四川思达能环保科技有限公司 | Lithium ore prepares the method and system of lithium carbonate |
| CN111377465A (en) * | 2020-03-23 | 2020-07-07 | 中国科学院青海盐湖研究所 | Method for preparing battery-grade lithium carbonate by using lepidolite |
| CN112624159A (en) * | 2020-12-22 | 2021-04-09 | 成都大川锂电科技有限公司 | Method for extracting spodumene by adopting sulfuric acid nano atomization process |
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| CN113735143A (en) * | 2021-09-27 | 2021-12-03 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity lithium carbonate by directly carbonizing lithium hydroxide |
| CN114032388A (en) * | 2021-09-17 | 2022-02-11 | 江西金德锂新能源科技有限公司 | Process for extracting metal salt from lepidolite raw material |
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| CN108165767A (en) * | 2017-12-28 | 2018-06-15 | 中国地质科学院矿产综合利用研究所 | Method for jointly leaching spodumene based on microwave and pressure field |
| CN108640131A (en) * | 2018-04-28 | 2018-10-12 | 四川思达能环保科技有限公司 | Lithium ore prepares the method and system of lithium carbonate |
| CN111377465A (en) * | 2020-03-23 | 2020-07-07 | 中国科学院青海盐湖研究所 | Method for preparing battery-grade lithium carbonate by using lepidolite |
| CN112624159A (en) * | 2020-12-22 | 2021-04-09 | 成都大川锂电科技有限公司 | Method for extracting spodumene by adopting sulfuric acid nano atomization process |
| CN112624159B (en) * | 2020-12-22 | 2023-05-02 | 成都大川锂电科技有限公司 | Method for extracting spodumene by adopting sulfuric acid nano atomization process |
| CN112694106A (en) * | 2020-12-31 | 2021-04-23 | 四川思达能环保科技有限公司 | Concentration treatment method for lithium bicarbonate solution |
| CN114032388A (en) * | 2021-09-17 | 2022-02-11 | 江西金德锂新能源科技有限公司 | Process for extracting metal salt from lepidolite raw material |
| CN114032388B (en) * | 2021-09-17 | 2023-08-22 | 江西金德锂新能源科技有限公司 | Process for extracting metal salt from lepidolite raw material |
| CN113735143A (en) * | 2021-09-27 | 2021-12-03 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity lithium carbonate by directly carbonizing lithium hydroxide |
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