CN106006684A - Concentration technology for producing lithium salt by sulfuric acid method - Google Patents
Concentration technology for producing lithium salt by sulfuric acid method Download PDFInfo
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- CN106006684A CN106006684A CN201610362476.9A CN201610362476A CN106006684A CN 106006684 A CN106006684 A CN 106006684A CN 201610362476 A CN201610362476 A CN 201610362476A CN 106006684 A CN106006684 A CN 106006684A
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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
- C01D15/06—Sulfates; Sulfites
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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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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a concentration technology for producing lithium salt by a sulfuric acid method. The concentration technology is used for concentrating a lithium sulfate solution prior to a lithium precipitation step and comprises the following steps of performing film concentration: performing film concentration on the lithium sulfate solution by using a concentration film of which the bore diameter is 0.1-1nm, so as to obtain a lithium sulfate concentrated solution and a permeable solution. The concentration film is used for blocking lithium ions in the lithium sulfate solution, so that redundant water is separated out, and the total content of the lithium ions in the lithium sulfate solution is increased; the purpose of concentration is achieved, and the permeable solution obtained through separation is higher in purity, and can be circularly used in a leachable extraction process of the lithium sulfate solution. Compared with evaporation concentration in the prior art, the adopted film concentration technology has the advantages of being low in energy consumption, low in production cost, high in concentration efficiency, small in treatment difficulty and small in environmental pollution.
Description
Technical field
The present invention relates to a kind of concentration technology produced for sulfuric acid process lithium salts, it is adaptable to sulfuric acid process lithium salts is raw
In product, the lithium ion before sinker technique concentrates.
Background technology
Lithium is a kind of important strategic resources material, is indispensable important former of modern high technology product
Material.The lithium resource gross reserves that China is verified occupies second place of the world, but lithium yield only accounts for whole world total output
About 5%, it is the net importer of lithium product.
Lithium carbonate is to produce secondary lithium salts and the basic material of lithium metal goods, thus becomes in lithium industry
The lithium product that consumption is maximum, other lithium products are all the downstream product of lithium carbonate on it.The life of lithium carbonate
Production. art salt lake bittern can be divided into extract according to the difference of raw material sources and Ore extracts.At present, abroad
Main employing salt lake bittern extraction process produces lithium carbonate, and China mainly uses solid mineral to extract work
Skill.Although China is also actively exploiting saline lake lithium resource, but due to the restriction of the factor such as technology, resource,
Development rate is the slowest.
Ore extract lithium mainly use the solid lithium Ore such as spodumene, lepidolite produce lithium carbonate and other
Lithium product.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, wherein sulfuric acid process is currently used main method.
And in current Production By Sulfuric Acid Process lithium carbonate production process, commonly used is all traditional evaporation and concentration
Technique.Evaporation and concentration has the disadvantages that
(1) evaporation and concentration needs steam-heating system to be evaporated lithium sulfate solution so that in solution
Moisture become gaseous state effusion, thus realize concentrate purpose.This technique determines the substantial amounts of energy and disappears
Consumption, processing cost and difficulty are bigger.
(2) this evaporating and concentrating process equipment needed thereby is more, and maintenance cost and difficulty are higher；
(3) also to environment while evaporation and concentration waste water resource, be unfavorable for enterprise can
Sustainable and healthy development.
Summary of the invention
The technical problem to be solved is to provide a kind of concentration work produced for sulfuric acid process lithium salts
Skill, this technique has that energy resource consumption is little, production cost is low, thickening efficiency is high, intractability is little, environment
Pollute little advantage, it addition, use this technique to produce the purity height of the lithium sulfate concentrated solution obtained.
The technical scheme is that a kind of for sulfuric acid process lithium salts produce
Concentration technology, the step including for the lithium sulfate solution before sinker step being carried out membrance concentration: concrete
It is that the concentration film using aperture to be 0.1-1nm carries out membrance concentration to lithium sulfate solution, obtains lithium sulfate and concentrate
Liquid and permeate.
Use having the beneficial effect that by concentrating film to the lithium ion in lithium sulfate solution of technique scheme
Intercept, unnecessary moisture is separated, improve the lithium ion content that lithium sulfate solution is total, reach
The purpose concentrated, its degree of purity of the permeate of isolated is higher, can continue cycling through and be applied to lithium sulfate
During the leaching of solution is extracted；Compared with evaporation and concentration of the prior art, the film that the present invention uses is dense
Contracting technique has that energy resource consumption is little, production cost is low, thickening efficiency is high, intractability is little, environment
Pollute little advantage.
Further, in described membrance concentration step, lithium sulfate solution in membrance concentration step described in pressure, sulfur
Acid lithium solution under conditions of pressure is 10MPa-20MPa by concentrate film.
Having the beneficial effect that of technique scheme is used to exist in the concentration application of lithium sulfate solution at present
Membrane material and hold a susceptible to plugging difficult problem, therefore membrane material can not be applied to the sector；The invention
Ground finds that the aperture by controlling to concentrate film and lithium sulfate solution, by concentrating the pressure of film, can solve this
One difficult problem, inventor was by repeatedly it is demonstrated experimentally that the technique scheme of the present invention both can ensure that sulphuric acid
Effective concentration of lithium solution, makes again concentration film that blocking is less likely to occur, and thickening efficiency is high, and concentrates film
Service life is long.
Further, in the lithium sulfate solution before membrance concentration step, lithium ion content is 20-25g/L, and film is dense
Lithium ion content in the lithium sulfate concentrated solution that contracting obtains is 40-50g/L.
Use technique scheme has the beneficial effect that guarantee lithium ion content before membrance concentration, to carry
Concentrated effect in high membrance concentration filter process and thickening efficiency, the lithium ion content that membrance concentration reaches can
Guarantee to have in sinker step preferably to apply effect.
As preferably, the concentration film used in described membrance concentration step is NF membrane or reverse osmosis membrane.
Further, lithium sulfate leachate is carried out membrane filtration before membrance concentration step: specifically use hole
Footpath is that the solid suspension in lithium sulfate leachate is intercepted, admittedly contained by the filter membrane of 1-5 μm
The amount lithium sulfate solution less than 5ppm.
Use technique scheme has the beneficial effect that employing sheet frame mistake before the existing evaporation and concentration of one side
Filter mode, its filtering accuracy is low, and the solid content that the lithium sulfate solution obtained can reach is not less than 60ppm,
So on the one hand, result in the lithium sulfate concentrated solution impurity content finally given many, affect later stage sinker and obtain
Lithium carbonate purity, on the other hand membrance concentration can be had undesirable effect by solid content height；The present invention passes through film
The lithium sulfate solution being filtrated to get, controls solid content to below 5ppm, it is ensured that lithium sulfate concentrated solution
Degree of purity, in follow-up sinker technique, due to the high purity of lithium sulfate concentrated solution, can improve
The output capacity of unit product, and it is higher pure to ensure that the solid lithium carbonate that sinker technique obtains has
Degree, makes production cost obtain the biggest reduction, and makes product quality be greatly improved.
Further, in described membrane filtration step, lithium sulfate leachate is the bar of 0.02-0.2MPa at pressure
Filter membrane is passed through under part.
Use technique scheme has the beneficial effect that by controlling pressure and membrane flux, it is ensured that right
Effective filtration of lithium sulfate leachate, and filter efficiency is high.
As preferably, the filter membrane used in described membrane filtration step is by Kynoar, polysulfones, gathers
The micro-filtration membrane that acrylonitrile, polrvinyl chloride or polypropylene material are made.
Use technique scheme has the beneficial effect that employing above-mentioned material is made micro-filtration membrane and had well
Anticorrosion effect, it is ensured that in membrane filtration processes, will cause aperture to deform because of severe corrosive, and shadow
Ring filter effect.
Further, carried out softening pre-treatment step before membrane filtration step: utilize resin to adsorb leaching alternately
Go out the calcium ions and magnesium ions in stock solution, obtain the total content lithium sulfate leachate less than 0.8g/L of calcium ions and magnesium ions.
Use having the beneficial effect that owing to calcium ions and magnesium ions content is high of technique scheme, solution can be caused to exist
Concentration process occurs supersaturation produce crystal to separate out, be attached to concentrate film surface and cause concentration film to block up
Plug, and has influence on the effect of membrance concentration, therefore carries out sofening treatment before membrance concentration, reduce calcium and magnesium from
Sub-content, to ensure during membrance concentration, will not separate out crystal, also ensure that simultaneously and sinks in follow-up
During lithium, calcium ions and magnesium ions produces calcium carbonate, magnesium carbonate and ferric carbonate with alkaline reaction, has influence on carbonic acid
The quality of lithium solid articles.
Accompanying drawing explanation
Fig. 1 is the membrance concentration system schematic 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 this
Invention, is not intended to limit the scope of the present invention.
A kind of sulfuric acid process puies forward lithium technique, comprises the following steps:
A) pretreatment: 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,
Particle diameter is less than the spodumene breeze of 80 mesh.
B) acidleach: being immersed in acid solution by pretreated spodumene breeze, the reaction condition of acidleach is:
The sulphuric acid of concentration 93%-98%, and roasting under conditions of 250-300 DEG C is added in spodumene breeze,
Obtaining acid grog, the residual acid weight/mass percentage composition controlling acid grog is 3%-6%；Carbon is added in acid grog
Acid calcium, the addition mole of calcium carbonate is 1.1 times of residual acid mole, obtains mixture, in mixture
Adding water, when the pH value of mixture is at 5.5-6.0, filter, obtaining solid content is 100000ppm
Above leaching stock solution.
C) remove impurity: step b) is obtained leaches stock solution and carries out filtering and impurity removing, obtain pure leaching stock solution.
The present invention is a kind of concentration technology produced for sulfuric acid process lithium salts, to above-mentioned sulfuric acid process step
C) the pure leaching stock solution obtained in processes, and comprises the following steps:
1) pretreatment is softened: utilize resin to adsorb the calcium ions and magnesium ions leached in stock solution alternately, obtain calcium and magnesium
The total content of the ion lithium sulfate leachate less than 0.8g/L.
2) membrane filtration: use aperture be the filter membrane of 1-5 μm be the condition of 0.02-0.2MPa at pressure
Under carry out the solid suspension in lithium sulfate leachate filtering and intercept, obtain solid content less than 5ppm, lithium
Ion concentration is the lithium sulfate solution of 20-25g/L；The filter membrane used in this step is by polyvinylidene fluoride
The micro-filtration membrane that alkene, polysulfones, polyacrylonitrile, polrvinyl chloride or polypropylene material are made.
3) membrance concentration: lithium sulfate solution by aperture is under conditions of pressure is 10MPa-20MPa
The concentration film of 0.1-1nm, obtains lithium sulfate concentrated solution and permeate, the wherein lithium in lithium sulfate concentrated solution
Ion concentration is 40-50g/L；The concentration film used in this step is NF membrane or reverse osmosis membrane.
The concentrated effect of the present invention is illustrated below by embodiment.
Embodiment 1
A kind of concentration technology produced for sulfuric acid process lithium salts, comprises the following steps:
1) pretreatment is softened: utilize resin to adsorb the calcium ions and magnesium ions leached in stock solution alternately, obtain calcium and magnesium
The lithium sulfate leachate of the total content 0.6mg/L of ion.
2) membrane filtration: by step 1) in the lithium sulfate leachate that obtains utilize the micro-filtration membrane being made up of polysulfones
Carrying out membrane filtration, micro-filtration membrane aperture is 5 μm, and lithium sulfate leachate by the pressure of micro-filtration membrane is
0.02MPa, obtain solid impurity and solid content be 4.8ppm, lithium ion content be the lithium sulfate of 20g/L
Solution；
3) membrance concentration: by step 1) in the lithium sulfate solution that obtains utilize the NF membrane being made up of polyamide
Carrying out membrance concentration, NF membrane aperture is 1nm, and lithium sulfate solution is 10MPa by the pressure of NF membrane,
Obtain lithium sulfate concentrated solution that lithium ion content is 40g/L and lithium ion content is the permeate of 0.4g/L.
Wherein, step 3) the employing membrance concentration system as shown in Figure 1 of membrance concentration concentrates, specifically
Method is as follows:
Lithium sulfate solution is pumped out in material fluid bath by low-lift pump, crosses cartridge filter, the work of cartridge filter
Be prevent outside large granular impurity enter and pollute lithium sulfate solution；
Lithium sulfate solution continues to run at circulating pump, after being pressurized to 10MPa by circulating pump, enters film group
Concentrating in part, the liquid through the NF membrane in membrane module is permeate, and NF membrane is retained down
Liquid continue cycling through flow at circulating pump pressurize, concentrate in being again introduced into membrane module, until receiving
Strength of fluid under membrane retention reaches to stop when lithium ion content is 40g/L, and now NF membrane retains down
Liquid be the lithium sulfate concentrated solution meeting production requirement.
Embodiment 2
A kind of concentration technology produced for sulfuric acid process lithium salts, comprises the following steps:
1) pretreatment is softened: utilize resin to adsorb the calcium ions and magnesium ions leached in stock solution alternately, obtain calcium and magnesium
The lithium sulfate leachate of the total content 0.52mg/L of ion.
2) membrane filtration: by step 1) in the lithium sulfate leachate that obtains utilize and to be made up of Kynoar
Micro-filtration membrane carries out membrane filtration, and micro-filtration membrane aperture is 2 μm, the lithium sulfate leachate pressure by micro-filtration membrane
For 0.1MPa, obtain solid impurity and solid content be 4ppm, lithium ion content be the lithium sulfate of 22g/L
Solution；
3) membrance concentration: by step 1) in the lithium sulfate solution that obtains utilize the NF membrane being made up of polyamide
Carrying out membrance concentration, NF membrane aperture is 1nm, and lithium sulfate solution is 15MPa by the pressure of NF membrane,
Obtain lithium sulfate concentrated solution that lithium ion content is 45g/L and lithium ion content is passing through of 0.36g/L
Liquid.
Wherein, step 3) the employing membrance concentration system as shown in Figure 1 of membrance concentration concentrates, specifically
Method is as follows:
Lithium sulfate solution is pumped out in material fluid bath by low-lift pump, crosses cartridge filter, the work of cartridge filter
Be prevent outside large granular impurity enter and pollute lithium sulfate solution；
Lithium sulfate solution continues to run at circulating pump, after being pressurized to 15MPa by circulating pump, enters film group
Concentrating in part, the liquid through the NF membrane in membrane module is permeate, and NF membrane is retained down
Liquid continue cycling through flow at circulating pump pressurize, concentrate in being again introduced into membrane module, until receiving
Strength of fluid under membrane retention reaches to stop when lithium ion content is 45g/L, and now NF membrane retains down
Liquid be the lithium sulfate concentrated solution meeting production requirement.
Embodiment 3
A kind of concentration technology produced for sulfuric acid process lithium salts, comprises the following steps:
1) pretreatment is softened: utilize resin to adsorb the calcium ions and magnesium ions leached in stock solution alternately, obtain calcium and magnesium
The lithium sulfate leachate of the total content 0.43mg/L of ion.
2) membrane filtration: by step 1) in the lithium sulfate leachate that obtains utilize by polyacrylonitrile make micro-
Filter membrane carries out membrane filtration, and micro-filtration membrane aperture is 1 μm, and lithium sulfate leachate by the pressure of micro-filtration membrane is
0.1MPa, obtain solid impurity and solid content be 3.5ppm, lithium ion content be that the lithium sulfate of 25g/L is molten
Liquid；
3) membrance concentration: by step 1) in the lithium sulfate solution that obtains utilize by receiving that cellulose acetate is made
Filter membrane carries out membrance concentration, and NF membrane aperture is 0.1nm, and lithium sulfate solution by the pressure of NF membrane is
20MPa, obtains lithium sulfate concentrated solution that lithium ion content is 50g/L and lithium ion content is 0 passes through
Liquid.
Wherein, step 3) the employing membrance concentration system as shown in Figure 1 of membrance concentration concentrates, specifically
Method is as follows:
Lithium sulfate solution is pumped out in material fluid bath by low-lift pump, crosses cartridge filter, the work of cartridge filter
Be prevent outside large granular impurity enter and pollute lithium sulfate solution；
Lithium sulfate solution continues to run at circulating pump, after being pressurized to 20MPa by circulating pump, enters film group
Concentrating in part, the liquid through the NF membrane in membrane module is permeate, and NF membrane is retained down
Liquid continue cycling through flow at circulating pump pressurize, concentrate in being again introduced into membrane module, until receiving
Strength of fluid under membrane retention reaches to stop when lithium ion content is 50g/L, and now NF membrane retains down
Liquid be the lithium sulfate concentrated solution meeting production requirement.
During at present the concentration at lithium sulfate solution is applied, due to lithium sulfate leachate lithium ion content relatively
Height, when utilizing membrane material that it is carried out high concentration concentration, also exists membrane material and holds a susceptible to plugging difficult problem, because of
Membrane material is applied to the sector by this, there is thickening efficiency low, and the membrane material life-span is short, completes a life
The product cycle is accomplished by repeatedly being replaced membrane material, the most extremely delays the production time, and becomes
This is the most at a relatively high, it is difficult to be applied to membrance concentration production process, and relative to traditional evaporation and concentration, it embodies
Advantage inconspicuous；And the present invention creatively finds that the aperture by controlling to concentrate film and lithium sulfate are molten
Liquid by concentrate film pressure, this difficult problem can be solved, inventor by repeatedly it is demonstrated experimentally that this
The bright effective concentration that both can ensure that lithium sulfate solution, makes again concentration film that blocking is less likely to occur, concentrates effect
Rate is high, and the service life concentrating film is long.Illustrate that below by way of experimental data the concentration film of the present invention exists
The stopping state of different concentration period, the change situation especially by the membrane flux under same equal pressure embodies
Stopping state, represents that below by form the film film after multiple concentration period that concentrates of different size leads to
Amount situation of change.
Following table aperture is that the NF membrane being made up of polyamide of 1nm is as concentrating the film pressure at 10MPa
The membrane flux situation of change that obtains through the experiment of multiple concentration period under power (wherein, this experiment use with
The lithium sulfate solution that in embodiment 1, composition is identical carries out membrance concentration, and before concentrating, lithium sulfate solution total amount is
10L, the area that effectively concentrates concentrating film is 0.5, the lithium ion of the lithium sulfate concentrated solution being concentrated to give
Content is 40g/L, single concentration period experience time a length of 4 hours).Complete in each production cycle
Within first 30 minutes, carry out data collection and complete the calculating of membrane flux.
When membrane flux is reduced to 2L/ .h, the concentration film more renewed, aborning, can exchange
Under concentration film be carried out after, carry out repeated application.
| Concentration period | 1 | 2 | 3 | 4 | 5 | 6 |
| Membrane flux (L/ .h) | 2.5 | 2.5 | 2.49 | 2.48 | 2.48 | 2.47 |
After in above-mentioned experiment, the pressure of first concentration period is reduced to below 10MPa, membrane flux reduces
To below 2L/ .h, after concentrating and starting 2.5 hours, by concentrate film through liquid measure start by
The fewest, after concentrating beginning 3 hours, it is calculated membrane flux through 30 minute datas collections most
It is only 0.12L/ .h, concentrates film blocking, cause cannot proceeding effectively to concentrate, the sulfur finally given
The lithium ion content of acid lithium concentrated solution is at best able to be reached for 34g/L, it is impossible to reaching lithium ion content is
The concentration requirement of 40g/L.
After in above-mentioned experiment, the pressure of first concentration period is increased to more than 20MPa, start in concentration
After 1 hour, by concentrate film through the very fast minimizing of liquid measure, collect through 30 minute datas and be calculated
Membrane flux is only 0.1L/ .h, concentrates film blocking serious, causes cannot proceeding effectively to concentrate,
The lithium ion content of the lithium sulfate concentrated solution obtained eventually is at best able to be reached for 30g/L, it is impossible to reach lithium from
Sub-content is the concentration requirement of 40g/L.
Following table aperture is that the NF membrane being made up of polyamide of 1nm is as concentrating the film pressure at 15MPa
The membrane flux situation of change that obtains through the experiment of multiple concentration period under power (wherein, this experiment use with
The lithium sulfate solution that in embodiment 2, composition is identical carries out membrance concentration, and before concentrating, lithium sulfate solution total amount is
15L, the area that effectively concentrates concentrating film is 1, and the lithium ion of the lithium sulfate concentrated solution being concentrated to give contains
Amount for 45g/L, single concentration period experience time a length of 3 hours), before each production cycle completes
Within 30 minutes, carry out data collection and complete the calculating of membrane flux.
When membrane flux is reduced to 2.1L/ .h, the concentration film more renewed, aborning, can exchange
Under concentration film be carried out after, carry out repeated application.
| Concentration period | 1 | 2 | 3 | 4 | 5 | 6 |
| Membrane flux (L/ .h) | 2.53 | 2.53 | 2.53 | 2.52 | 2.52 | 2.52 |
After in above-mentioned experiment, the pressure of first concentration period is reduced to below 10MPa, membrane flux reduces
To below 2L/ .h, after concentrating and starting 2 hours, by concentrate film through liquid measure start by
The fewest, start after 2.5 hours to concentrating, collect through 30 minute datas and be calculated membrane flux
The 0.13L/ .h that are only more, concentration film blocking, cause cannot proceeding effectively to concentrate, finally give
The lithium ion content of lithium sulfate concentrated solution is at best able to be reached for 35g/L, it is impossible to reaching lithium ion content is
The concentration requirement of 45g/L.
After in above-mentioned experiment, the pressure of first concentration period is increased to more than 20MPa, start in concentration
After 1 hour, by concentrate film through the very fast minimizing of liquid measure, collect through 30 minute datas and be calculated
Membrane flux is only 0.11L/ .h, concentrates film blocking serious, causes cannot proceeding effectively to concentrate,
The lithium ion content of the lithium sulfate concentrated solution obtained eventually is at best able to be reached for 31g/L, it is impossible to reach lithium from
Sub-content is the concentration requirement of 45g/L.
Following table aperture is that the NF membrane being made up of cellulose acetate of 0.1nm exists as concentrating film
The membrane flux situation of change obtained through the experiment of multiple concentration period under the pressure of 20MPa (wherein, should
Experiment uses the lithium sulfate solution identical with composition in embodiment 1 to carry out membrance concentration, and before concentrating, lithium sulfate is molten
Liquid total amount is 20L, and the area that effectively concentrates concentrating film is 1, the lithium sulfate concentrated solution being concentrated to give
Lithium ion content is 50g/L, single concentration period experience time a length of 8 hours), each produce week
Phase completes to carry out data collection first 30 minutes and completes the calculating of membrane flux.
When membrane flux is reduced to 1.1L/ .h, the concentration film more renewed, aborning, can exchange
Under concentration film be carried out after, carry out repeated application.
| Concentration period | 1 | 2 | 3 | 4 | 5 | 6 |
| Membrane flux (L/ .h) | 1.25 | 1.25 | 1.24 | 1.24 | 1.24 | 1.23 |
After in above-mentioned experiment, the pressure of first concentration period is reduced to below 10MPa, membrane flux reduces
To below 0.5L/ .h, after concentrating beginning 4 hours, by concentrating starting through liquid measure of film
Gradually decrease, start after 5 hours to concentrating, collect through 30 minute datas and be calculated membrane flux
The 0.12L/ .h that are only more, concentration film blocking, cause cannot proceeding effectively to concentrate, finally give
The lithium ion content of lithium sulfate concentrated solution is at best able to be reached for 30g/L, it is impossible to reaching lithium ion content is
The concentration requirement of 50g/L.
After in above-mentioned experiment, the pressure of first concentration period is increased to more than 20MPa, start in concentration
After 2 hours, by concentrate film through the very fast minimizing of liquid measure, collect through 30 minute datas and be calculated
Membrane flux is only 0.1L/ .h, concentrates film blocking serious, causes cannot proceeding effectively to concentrate,
The lithium ion content of the lithium sulfate concentrated solution obtained eventually is at best able to be reached for 28g/L, it is impossible to reach lithium from
Sub-content is the concentration requirement of 50g/L.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (8)
1. the concentration technology produced for sulfuric acid process lithium salts, it is characterised in that include for heavy
Lithium sulfate solution before lithium step carries out the step of membrance concentration: specifically using aperture is 0.1-1nm's
Concentrate film and lithium sulfate solution is carried out membrance concentration, obtain lithium sulfate concentrated solution and permeate.
The concentration technology produced for sulfuric acid process lithium salts the most according to claim 1, its feature exists
In, in described membrance concentration step, lithium sulfate solution passes through dense under conditions of pressure is 10MPa-20MPa
Contracting film.
The concentration technology produced for sulfuric acid process lithium salts the most according to claim 1, its feature exists
In, in the lithium sulfate solution before membrance concentration step, lithium ion content is 20-25g/L, and membrance concentration obtains
Lithium ion content in lithium sulfate concentrated solution is 40-50g/L.
The concentration technology produced for sulfuric acid process lithium salts the most according to claim 1, its feature exists
In, the concentration film used in described membrance concentration step is NF membrane or reverse osmosis membrane.
The concentration produced for sulfuric acid process lithium salts the most as claimed in any of claims 1 to 4
Technique, it is characterised in that before membrance concentration step, lithium sulfate leachate is carried out membrane filtration: specifically
Solid suspension in lithium sulfate leachate is intercepted by the filter membrane using aperture to be 1-5 μm,
To the solid content lithium sulfate solution less than 5ppm.
The concentration technology produced for sulfuric acid process lithium salts the most according to claim 5, its feature exists
In, in described membrane filtration step, lithium sulfate leachate passes through under conditions of pressure is 0.02-0.2MPa
Filter membrane.
The concentration technology produced for sulfuric acid process lithium salts the most according to claim 5, its feature exists
In, the filter membrane used in described membrane filtration step is by Kynoar, polysulfones, polyacrylonitrile, gathers
The micro-filtration membrane that vinyl chloride or polypropylene material are made.
The concentration technology produced for sulfuric acid process lithium salts the most according to claim 5, its feature exists
In, before membrane filtration step, carry out softening pre-treatment step: utilize resin to adsorb alternately in leaching stock solution
Calcium ions and magnesium ions, obtain the total content of the calcium ions and magnesium ions lithium sulfate leachate less than 0.8g/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107188205A (en) * | 2017-07-15 | 2017-09-22 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of acidization extracts lithium sulfate from amblygonite |
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| CN102115101A (en) * | 2011-01-05 | 2011-07-06 | 屈俊鸿 | Novel method for producing lithium carbonate and lithium hydroxide |
| CN103318925A (en) * | 2013-06-19 | 2013-09-25 | 海门容汇通用锂业有限公司 | Method for producing high-purity lithium carbonate by using lithium concentrate |
| CN103738984A (en) * | 2013-12-26 | 2014-04-23 | 江苏久吾高科技股份有限公司 | Method and device for extracting bitten lithium chloride |
| CN104310446A (en) * | 2014-10-17 | 2015-01-28 | 江苏久吾高科技股份有限公司 | Process and device for extracting battery grade lithium from brine |
| CN105540619A (en) * | 2015-08-17 | 2016-05-04 | 马培华 | Method for directly preparing battery grade lithium carbonate from salt lake brine with high magnesium-to-lithium ratio |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107188205A (en) * | 2017-07-15 | 2017-09-22 | 汕头市泛世矿产资源股份有限公司 | The technique that a kind of acidization extracts lithium sulfate from amblygonite |
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