CN106011917B - The production method of high-purity hydrogen lithia - Google Patents
The production method of high-purity hydrogen lithia Download PDFInfo
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- CN106011917B CN106011917B CN201610525650.7A CN201610525650A CN106011917B CN 106011917 B CN106011917 B CN 106011917B CN 201610525650 A CN201610525650 A CN 201610525650A CN 106011917 B CN106011917 B CN 106011917B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
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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
- C01D15/02—Oxides; Hydroxides
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to a kind of production method of high-purity hydrogen lithia, its crystalline mother solution waste water after producing potassium chloride as raw material with salt lake bittern, wherein Mg/Li ratio are 200 500:1, by obtaining qualified eluent after ion sieve absorption, wash-out, eluent obtains reverse osmosis concentrated liquid after ultrafiltration membrane technique, segmented nanofiltration, external regeneration are continuously processed from the technology of friendship and reverse osmosis technology.Wherein magnesium ion content is≤30ppm, and lithium ion content is about 4 6g/L, and sodium ions content is 3 5g/L, and calcium ion content is≤5ppm, and the 30ppm of sulfate ion content 1, boron content is≤400ppm.With reverse osmosis concentrated liquid as raw material, technological process is the present invention：Super-pressure counter-infiltration it is continuous from hand over boron removal, it is continuous from hand over engaging sulphate, electrolysis with ion-exchange film, crystallization and evaporation, from handing over boron removal technology, ion-exchange membrane electrolysis, crystallization and evaporation technology, so as to obtain high-purity hydrogen lithia, and by-product boric acid and NaOH, the continuous controllable, extract yield of technical process is high, low production cost, it is easy to industrialize.
Description
Technical field
The invention belongs to salt chemical engineering field, more particularly to a kind of production method of high-purity hydrogen lithia.
Background technology
It is raw material to use the bittern after carrying potassium.Mg/Li ratio reaches 200-500 in raw material:1, washed by ion sieve absorption
Mg/Li ratio drops to 3-4 in qualified eluent after de-:1, it is continuous by hyperfiltration technique, segmented nanofiltration, external regeneration
From friendship technology, reverse osmosis technology isolate and purify after obtain reverse osmosis concentrated liquid.Wherein magnesium ion content is≤30ppm, lithium ion
Content is about 4-6g/L, and sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, potassium content≤300ppm, sulfuric acid
Radical ion content 1-30ppm, boron content is≤400ppm.In traditional handicraft, reverse osmosis concentrated liquid shines by width, adds carbon
Sour sodium sinker, is concentrated by evaporation, secondary sinker, refines and obtains lithium carbonate product, and calcium hydroxide causticization is then used again, filters carbonic acid
Calcium, calcium hydroxide, magnesium hydroxide, further refine the multi-step process such as removing calcium and magnesium, evaporative crystallization and obtain qualified Lithium hydroxide monohydrate
Product.The tediously long complexity of technical process, low lithium yield, serious waste of resources, production cost are high, lithium hydroxide poor product quality, deposit
In serious technical drawback：
A) reverse osmosis concentrated liquid after width solarization by carrying out sinker reaction, it is necessary to excessive addition sodium carbonate medicament forms lithium carbonate
Precipitation；
B) due to there are a large amount of sodium chloride in solution, the solubility of lithium carbonate increases, so that when sinker reacts in mother liquor
Lithium carbonate concentration is higher, and sinker yield is relatively low.In order to obtain sinker yield higher, it is necessary to sinker mother liquor is evaporated dense
Secondary sinker is carried out after contracting.Mix to prevent lithium carbonate saturation from separating out the sodium chloride separated out with saturation in evaporating concentration process,
Hydrochloric acid must be added to catch up with except the carbanion in sinker mother liquor, carry out being needed again when secondary sinker reacts after evaporation and concentration past molten
Sodium carbonate is added in liquid, if in order to further lift sinker yield, or even also need to carry out three sinker reactions, therefore, make
The significant wastage of sodium carbonate and salt acid treatment during into sinker；
C) sodium chloride saturation is separated out in evaporating concentration process, during centrifugation removal sodium chloride, sodium chloride crystal
Meeting entrainment mother liquor, so as to cause lithium ion yield losses；
D) lithium carbonate and calcium hydroxide carry out causticizing reaction generation calcium carbonate and lithium hydroxide, due to lithium hydroxide solubility
Relatively low, the lithium hydroxide solution of acquisition must be evaporated crystallization, expend a large amount of evaporation and concentration costs；
E) after causticizing reaction, it is necessary to separate the magnesium hydroxide carried secretly in the calcium hydroxide and calcium hydroxide of calcium carbonate and excess
Precipitation, carries lithium hydroxide solution secretly in precipitation, cause lithium ion yield losses；
Separate solid suspension after lithium hydroxide solution in still containing a large amount of calcium ions, magnesium ion and other impurities from
Son, it is necessary to use chemical precipitation method or chelating resin imurity-removal with prevent lithium hydroxide solution in evaporation process fouling and
Calcium and magnesium impurity saturation is mixed into Lithium hydroxide monohydrate product after separating out.
It can be seen that, salt lake carries lithium, produces lithium carbonate with lithium chloride, then produce hydrogen using the method for causticization by raw material of lithium carbonate
Lithia, the tediously long complexity of process route, lithium ion yield is low, raw and auxiliary material high cost, serious waste of resources, poor product quality.
In view of as above reason, it is necessary to study a kind of production method of high-purity hydrogen lithia, to solve in the prior art
One or more problems for existing.
The content of the invention
The present invention is completed in view of at least one above mentioned problem, and it is an object of the present invention to provide one kind
The production method of high-purity hydrogen lithia, with reverse osmosis concentrated liquid as raw material, wherein magnesium ion content is≤30ppm to the method,
Lithium ion content is about 4-6g/L, and sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, potassium ion≤300ppm, sulphur
Acid ion content 1-30ppm, boron content is≤500ppm, by directly using electrolysis with ion-exchange film skill after de-magging, boron removal
Art produces Lithium hydroxide monohydrate, and technological process is simple, and lithium ion yield >=99%, purity is high, low cost, chemical agent consumption
It is few, byproduct boric acid and NaOH are obtained while Lithium hydroxide monohydrate is produced, realize comprehensive utilization of resources.
The method specifically includes following steps：
A, obtain by the first concentrate of reverse osmosis concentration, wherein magnesium ion content is≤30ppm, and lithium ion content is about
It is 4-6g/L, sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, potassium ion≤300ppm, sulfate ion content
1-30ppm, boron content is≤500ppm；
B, first concentrate is carried out into boron removal using external regeneration is continuous from friendship technology, obtain the first boron removal from handing over liquid
With the first saturated resin, wherein the first boron removal from hand over liquid in boron content be less than 10ppm；
C, by the first saturated resin using NaOH regenerate hydroxyl type, obtain the first regenerated liquid and hydroxyl type tree
Fat；
D, hydroxyl type resin is used regeneration of hydrochloric acid, obtain chloride type resin and the second regenerated liquid；
E, by the first and second regenerated liquids mix, and adjust pH less than 3.0 obtain accessory substance boric acid crystal；
F, by the first boron removal from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, obtain de-magging from hand over liquid with
Second saturated resin, wherein de-magging calcium, magnesium ion total amount in liquid is handed over are less than 30ppb；
G, the second saturated resin are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
H, de-magging obtain second from handing over liquid to concentrate 2-5 times using super-pressure counter-infiltration, electrodialysis, positive infiltration or evaporator
Concentrate, lithium ion content 8-30g/L in the second concentrate, sodium ions content 6-20g/L, potassium ion≤1500ppm, calcium and magnesium from
Sub- total amount≤0.15ppm, sulfate radical and boron element total amount≤50ppm；
I, the second concentrate are electrolysed into ion-exchange membrane electrolyzer, and anode-side obtains light salt brine, chlorine；Cathode side is obtained
The mixed solution of hydrogen, lithium hydroxide and NaOH and micro potassium hydroxide；
J, part light salt brine remove sulfate radical and boron element after dechlorination, sodium sulfite are reduced using boron removal resin, and
Merge with other light salt brines and concentrated, merge with the second concentrate after concentration；
K, the chlorine and combustion of hydrogen are used to produce hydrochloric acid, or for PVC productions, or as hydrogenation reduction
Raw material；
The mixed liquor of l, the cathode side hydrogen lithia, NaOH and micro potassium hydroxide uses one-level evaporative crystallization work
Skill is evaporated crystallization, obtains the crystallization of the first high-purity of product Lithium hydroxide monohydrate and the first crystalline mother solution；
M, the first crystalline mother solution further carry out dual evaporation crystallization, the second lithium hydroxide are obtained at high operating temperatures brilliant
The first NaOH crystal is obtained under body, low-temperature condition；
N, the second lithium hydroxide crystal are because containing higher sodium ion, set is used one-level forced-circulation evaporator and tied again
It is brilliant；
O, the NaOH crystal are applied mechanically or as by-product sale as resin regeneration medicament.
According to a further aspect of the invention, the first saturated resin is meglumine base chelating resin, can specific adsorption boric acid.
According to a further aspect of the invention, the first boron removal carries out decalcification magnesium using external regeneration is continuous from friendship liquid from friendship technology,
First boron removal from handing over liquid from main from handing over column bottom charging, it is reverse by main from handing over post, after friendship liquid from main from handing over column top water outlet；It is main
From column bottom resin saturation at first is handed over, bottom saturated resin enters parsing post by Action of Gravity Field, main from friendship column top head tank
Resin is synchronously entered by Action of Gravity Field, and after resin transfer is finished, main from handing over post to recover charging, resin uses hydrochloric acid in parsing post
Regeneration Hydrogen, then use NaOH to regenerate sodium form, it is main high from friendship column top that regeneration finishes the press-in of resin compressed air
Position groove is stand-by；Main that a resin was shifted per 6-24 hours from friendship post, resin transfer time is 3-10 minutes, realizes continuously work；
Bottom resin abundant saturation when resin is shifted；Distance is main be furnished with sample tap away from column top delivery port 500-1000mm to hand over, when taking
Sample mouth discharges bottom saturated resin when having magnesium ion leakage, has 500-1000mm resin beds on sample tap as protective layer,
Ensure that magnesium ion will not leakage.
According to a further aspect of the invention, described ionic membrane is perfluorinated sulfonic acid Carboxylic Acid Ions film.
According to a further aspect of the invention, described electrolysis with ion-exchange film, the lithium hydroxide concentration of cathode side is controlled in 100g/L
Hereinafter, separated out with preventing lithium hydroxide from crystallizing.
According to a further aspect of the invention, described electrolysis with ion-exchange film, anode-side lithium concentration control 15g/L with
Under, to prevent anode-side osmotic pressure higher than cathode side, so as to cause ionic membrane to damage.
According to a further aspect of the invention, the method for being concentrated to light salt brine includes super-pressure counter-infiltration, electrodialysis, is just oozing
Saturating or evaporation.
According to a further aspect of the invention, part light salt brine is by dechlorination and adds sodium sulfite and is restored to ORP value and is less than
150mv。
According to a further aspect of the invention, cathode side hydrogen lithia, NaOH and micro potassium hydroxide mixed liquor are using more
Effect forced-circulation evaporator carries out first degree crystalline evaporation, and it is 10-30 times to be concentrated by evaporation multiple, and Lithium hydroxide monohydrate crystal is in evaporation
Crystallized in concentration process and separated out, by centrifuge separating obtained product the first Lithium hydroxide monohydrate crystal and the first crystalline mother solution.
According to a further aspect of the invention, the first crystalline mother solution carries out secondary crystallization evaporation using forced-circulation evaporator, the
One crystalline mother solution, second Lithium hydroxide monohydrate crystal structure in evaporating concentration process is separated out, and evaporation concentrated solution is in 60-90 DEG C of bar
The second Lithium hydroxide monohydrate is separated using centrifuge under part, the second crystalline mother solution is cooled to 30 DEG C of crystallization below in crystallizer,
It is centrifuged obtaining NaOH crystal and the 3rd crystalline mother solution, the 3rd crystalline mother solution returns to two grades of forced-circulation evaporators,
Continue to be concentrated by evaporation；Second Lithium hydroxide monohydrate crystal returns to one-level forced-circulation evaporator, is recrystallized, and NaOH is brilliant
Body is used as byproduct.
Compared with prior art, the beneficial effects of the present invention are：It is of the invention direct with reverse osmosis concentrated liquid as raw material, warp
Direct Electrolysis production lithium hydroxide after boron removal decalcification magnesium is crossed, not only process route is simple, lithium ion high income and product quality
Height, low production cost, chemical agent consumption is few, and comprehensive utilization of resources degree is high.
Brief description of the drawings
Fig. 1 is the production method flow chart of high-purity hydrogen lithia according to the preferred embodiment of the invention.
Specific embodiment
Preferred forms of the invention are described below by preferred embodiment, specific embodiment here is detailed
The present invention carefully is illustrated, and be should not be construed as limiting the invention, do not departing from the feelings of spirit and substance of the present invention scope
Under condition, various changes and modifications can be made, these should be all included within protection scope of the present invention.
The preferred embodiment of the present invention provides a kind of production method of high-purity hydrogen lithia.The high-purity hydrogen lithia
Production method is comprised the following steps：
A, obtain by the first concentrate of reverse osmosis concentration, wherein magnesium ion content is≤30ppm, and lithium ion content is about
It is 4-6g/L, sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, potassium ion≤300ppm, sulfate ion content
1-30ppm, boron content is≤500ppm；
B, first concentrate is carried out into boron removal using external regeneration is continuous from friendship technology, obtain the first boron removal from handing over liquid
With the first saturated resin, wherein the first boron removal from hand over liquid in boron content be less than 10ppm；
C, by the first saturated resin using NaOH regenerate hydroxyl type, obtain the first regenerated liquid and hydroxyl type tree
Fat；
D, hydroxyl type resin is used regeneration of hydrochloric acid, obtain chloride type resin and the second regenerated liquid；
E, by the first and second regenerated liquids mix, and adjust pH less than 3.0 obtain accessory substance boric acid crystal；
F, by the first boron removal from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, obtain de-magging from hand over liquid with
Second saturated resin, wherein de-magging calcium, magnesium ion total amount in liquid is handed over are less than 30ppb；
G, the second saturated resin are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
H, de-magging obtain second from handing over liquid to concentrate 2-5 times using super-pressure counter-infiltration, electrodialysis, positive infiltration or evaporator
Concentrate, lithium ion content 8-30g/L in the second concentrate, sodium ions content 6-20g/L, potassium ion≤1500ppm, calcium and magnesium from
Sub- total amount≤0.15ppm, sulfate radical and boron element total amount≤50ppm；
I, the second concentrate are electrolysed into ion-exchange membrane electrolyzer, and anode-side obtains light salt brine, chlorine；Cathode side is obtained
The mixed solution of hydrogen, lithium hydroxide and NaOH and micro potassium hydroxide；
J, part light salt brine remove sulfate radical and boron element after dechlorination, sodium sulfite are reduced using boron removal resin, and
Merge with other light salt brines and concentrated, merge with the second concentrate after concentration；
K, the chlorine and combustion of hydrogen are used to produce hydrochloric acid, or for PVC productions, or as hydrogenation reduction
Raw material；
The mixed liquor of l, the cathode side hydrogen lithia, NaOH and micro potassium hydroxide uses one-level evaporative crystallization work
Skill is evaporated crystallization, obtains the crystallization of the first high-purity of product Lithium hydroxide monohydrate and the first crystalline mother solution；
M, the first crystalline mother solution further carry out dual evaporation crystallization, the second lithium hydroxide are obtained at high operating temperatures brilliant
The first NaOH crystal is obtained under body, low-temperature condition；
N, the second lithium hydroxide crystal are because containing higher sodium ion, set is used one-level forced-circulation evaporator and tied again
It is brilliant；
O, the NaOH crystal are applied mechanically or as by-product sale as resin regeneration medicament.
According to a further aspect of the invention, the first saturated resin is meglumine base chelating resin, can specific adsorption boric acid.
Preferably, the first boron removal carries out decalcification magnesium using external regeneration is continuous from friendship liquid from friendship technology, and the first boron removal is from friendship
Liquid from main from handing over column bottom charging, it is reverse by main from handing over post, after friendship liquid from main from handing over column top water outlet；Master is from friendship column bottom tree
Fat saturation at first, bottom saturated resin enters parsing post by Action of Gravity Field, main from handing over column top head tank resin to pass through gravity
Effect is synchronous to be entered, and after resin transfer is finished, from handing over post to recover charging, resin uses regeneration of hydrochloric acid into Hydrogen to master in parsing post,
NaOH is used to regenerate sodium form again, it is main stand-by from friendship column top head tank that regeneration finishes the press-in of resin compressed air；It is main
From handing over post that a resin was shifted per 6-24 hours, resin transfer time is 3-10 minutes, realizes continuous work；At the bottom of when resin is shifted
The abundant saturation of portion's resin；Distance is main be furnished with sample tap away from column top delivery port 500-1000mm to hand over, when sample tap has magnesium ion
Bottom saturated resin is discharged during leakage, there are 500-1000mm resin beds on sample tap as protective layer, it is ensured that magnesium ion is not
Can leakage.
Preferably, described ionic membrane is perfluorinated sulfonic acid Carboxylic Acid Ions film.
Preferably, described electrolysis with ion-exchange film, the lithium hydroxide concentration of cathode side is controlled in below 100g/L, to prevent hydrogen
Lithia crystallization is separated out.
Preferably, described electrolysis with ion-exchange film, the lithium concentration of anode-side is controlled in below 15g/L, to prevent anode
Side osmotic pressure is higher than cathode side, so as to cause ionic membrane to damage.
Preferably, the method for being concentrated to light salt brine includes super-pressure counter-infiltration, electrodialysis, positive infiltration or evaporates.
Preferably, light salt brine process in part dechlorinates and adds sodium sulfite and is restored to ORP value less than 150mv.
Preferably, cathode side hydrogen lithia, NaOH and micro potassium hydroxide mixed liquor are steamed using multiple-effect forced circulation
Hair device carries out first degree crystalline evaporation, and it is 10-30 times to be concentrated by evaporation multiple, and Lithium hydroxide monohydrate crystal is tied in evaporating concentration process
Partial crystallization goes out, by centrifuge separating obtained product the first Lithium hydroxide monohydrate crystal and the first crystalline mother solution.
Preferably, the first crystalline mother solution carries out secondary crystallization evaporation using forced-circulation evaporator, and the first crystalline mother solution exists
The second Lithium hydroxide monohydrate crystal structure is separated out in evaporating concentration process, and evaporation concentrated solution is under the conditions of 60-90 DEG C using centrifugation
Machine separates the second Lithium hydroxide monohydrate, and the second crystalline mother solution is cooled to 30 DEG C of crystallization below in crystallizer, is centrifuged obtaining
NaOH crystal and the 3rd crystalline mother solution are obtained, the 3rd crystalline mother solution returns to two grades of forced-circulation evaporators, continue to be concentrated by evaporation；
Second Lithium hydroxide monohydrate crystal returns to one-level forced-circulation evaporator, is recrystallized, and NaOH crystal is used as byproduct.
Preferably, present invention also offers a kind of production method of high-purity hydrogen lithia, comprise the following steps：
A, the concentrate by reverse osmosis concentration, wherein magnesium ion content are≤30ppm, and lithium ion content is about 4-6g/
L, sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, potassium content≤300ppm, sulfate ion content 1-
30ppm, boron content is≤500ppm.
B, the reverse osmosis concentrated liquid obtained by step a is carried out into boron removal using external regeneration is continuous from friendship technology, obtain boron removal
10ppm is less than from liquid 1 and saturated resin 1, wherein boron removal boron content in liquid is handed over is handed over；
C, the saturated resin 1 for obtaining b step are regenerated using NaOH, and resin regeneration into hydroxyl type is obtained again
Raw liquid 1 and hydroxyl type resin；
D, the hydroxyl type resin obtained by step c is used regeneration of hydrochloric acid, obtain chloride type resin and regenerated liquid 2；
E, the regenerated liquid 2 obtained by the regenerated liquid 1 and Step d obtained by step c is mixed, and adjust pH and obtain secondary less than 3.0
Product boric acid crystal；
F, by the boron removal obtained by step b from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, acquisition de-magging
From liquid and saturated resin 2 is handed over, wherein de-magging calcium, magnesium ion total amount in liquid is handed over is less than 30ppb；
G, saturated resin 2 are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
De-magging obtained by h, step f concentrates 2-5 from liquid is handed over using super-pressure counter-infiltration, electrodialysis, positive infiltration or evaporator
Times, obtain concentrate, lithium ion content 8-30g/L in concentrate, sodium ions content 6-20g/L, potassium ion≤1500ppm, calcium
Magnesium ion total amount≤0.15ppm, sulfate radical and boron element total amount≤50ppm；
Concentrate obtained by i, step h, is electrolysed into ion-exchange membrane electrolyzer, and anode-side obtains light salt brine, chlorine；It is cloudy
Pole side obtains the mixed solution of hydrogen, lithium hydroxide and NaOH and micro potassium hydroxide；
Light salt brine obtained by j, step i needs to be concentrated, and method for concentration includes but is not limited to super-pressure counter-infiltration, electric osmose
Analysis, positive infiltration are evaporated, and part light salt brine using boron removal resin after dechlorination, sodium sulfite reduction by removing sulfate radical and boron unit
Element, and merge with other light salt brines and concentrated, the concentrate obtained with step h after concentration merges；
K, step i obtain chlorine can be used to produce hydrochloric acid with combustion of hydrogen, it can also be used to which PVC is produced；
L, step i obtain hydrogen can burn for producing hydrochloric acid with chlorine, also can be used as the original of hydrogenation reduction
Material；
The mixed liquor of cathode side hydrogen lithia, NaOH and micro potassium hydroxide obtained by m, step i, is steamed using one-level
Hair crystallization processes are evaporated crystallization, obtain high product purity Lithium hydroxide monohydrate and crystallize 1 and crystalline mother solution 1；
Crystalline mother solution 1 obtained by n, step m further carries out dual evaporation crystallization, and lithium hydroxide is obtained at high operating temperatures
Crystal 2, obtains NaOH crystal 1 under low-temperature condition；
The lithium hydroxide crystal 2 that o, step n are obtained is because containing higher sodium ion, set uses first degree crystalline evaporation technology
Recrystallized；
The NaOH crystal that p, step n are obtained, can apply mechanically, it is also possible to as byproduct pin as resin regeneration medicament
Sell；
Preferably, the external regeneration described in step b is continuous from friendship, and reverse osmosis concentrated liquid feeds from main from friendship column bottom, inverse
To by main from handing over post, except boron is from handing over liquid from main from handing over column top water outlet.It is main from handing over column bottom resin saturation, bottom saturation at first
Resin (saturated resin volume accounts for main from the 1/10--1/3 for handing over column volume) enters parsing post by Action of Gravity Field, main from friendship capital
Portion's head tank resin is synchronously entered by Action of Gravity Field, main to recover charging, resin in parsing post from friendship post after resin transfer is finished
Hydroxyl type is regenerated using NaOH, then again using regeneration of hydrochloric acid into chlorine type, regeneration finishes resin compressed air pressure
Become owner of stand-by from friendship column top head tank.Main that a resin was shifted per 6-24 hours from friendship post, resin transfer time is 3-10 points
Clock, is capable of achieving continuous work.Bottom resin abundant saturation when resin is shifted, distance is main from handing over column top delivery port 500-1000mm
Place is furnished with sample tap, and bottom saturated resin is discharged when sample tap has borate ion leakage, there is 500- on sample tap
1000mm resin beds are used as protective layer, it is ensured that borate ion will not leakage；
Preferably, the resin described in step b is meglumine base chelating resin, can specific adsorption boric acid；
Preferably, the accessory substance boric acid described in step e, its production capacity is that one ton of Lithium hydroxide monohydrate of every production can obtain 1 ton
Boric acid；
Preferably, the boron removal described in step f is from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, boron removal from
Hand over liquid from main from handing over column bottom charging, it is reverse by main from handing over post, after friendship liquid 1 from main from handing over column top water outlet.Master is from friendship post bottom
Portion's resin saturation at first, bottom saturated resin (saturated resin volume accounts for main from the 1/10--1/3 for handing over column volume) is made by gravity
It is main from handing over column top head tank resin synchronously to enter by Action of Gravity Field with parsing post is entered, it is main from friendship after resin transfer is finished
Post recovers charging, and resin regenerates sodium form using regeneration of hydrochloric acid into Hydrogen, then using NaOH in parsing post, and regeneration finishes tree
Fat compressed air is pressed into main stand-by from friendship column top head tank.Main that a resin was shifted per 6-24 hours from friendship post, resin turns
Shift time is 3-10 minutes, is capable of achieving continuous work.Bottom resin abundant saturation when resin is shifted；Distance is main to be gone out from friendship column top
Be furnished with sample tap at the 500-1000mm of the mouth of a river, when sample tap has magnesium ion leakage discharge bottom saturated resin, sample tap it
On have 500-1000mm resin beds as protective layer, it is ensured that magnesium ion will not leakage；
Preferably, the boron removal described in step f carries out decalcification magnesium using external regeneration is continuous from friendship liquid from friendship technology, and it is used
Resin be EDTA type chelating resins；
Preferably, the de-magging described in step h is included but is not limited to from friendship liquid method for concentration：Super-pressure counter-infiltration, electrodialysis,
Evaporation, particularly preferred super-pressure reverse osmosis process；
Preferably, the ionic membrane described in step i is perfluorinated sulfonic acid Carboxylic Acid Ions film；
Preferably, the electrolysis with ion-exchange film described in step i, the lithium hydroxide concentration of cathode side is controlled in below 100g/L, with
Prevent from lithium hydroxide from crystallizing to separate out；Preferably, the electrolysis with ion-exchange film described in step i, the lithium concentration control of anode-side exists
Below 30g/L, is preferably controlled in below 15g/L, to prevent anode-side osmotic pressure higher than cathode side, so as to cause ionic membrane to damage
It is bad；
Preferably, the electrolysis with ion-exchange film described in step i, the light salt brine that anode-side is produced needs to be concentrated, method for concentration
Including but not limited to super-pressure counter-infiltration, electrodialysis, positive infiltration or it is concentrated by evaporation；Part light salt brine is by dechlorination and adds Asia
Sodium sulphate is restored to ORP value less than 150mv, then using boron removal resin removing sulfate radical and boron element, and with other light salt brines
Merging is concentrated, and the concentrate obtained with step h after concentration merges；
Preferably, cathode side hydrogen lithia, NaOH and micro potassium hydroxide mixed liquor, are steamed using multiple-effect forced circulation
Hair device carries out first degree crystalline evaporation, and it is 10-30 times to be concentrated by evaporation multiple, and Lithium hydroxide monohydrate crystal is tied in evaporating concentration process
Partial crystallization goes out, by centrifuge separating obtained product Lithium hydroxide monohydrate crystal 1 and crystalline mother solution 1, the yield of Lithium hydroxide monohydrate
>=99%；
Preferably, the crystalline mother solution 1 that step m is obtained, secondary crystallization evaporation is carried out using forced-circulation evaporator, and crystallization is female
Liquid 1 in evaporating concentration process Lithium hydroxide monohydrate crystal 2 crystallization separate out, evaporation concentrated solution under the conditions of 60-90 DEG C use from
Scheming separates Lithium hydroxide monohydrate 2, and crystalline mother solution 2 is cooled to 30 DEG C of crystallization below in crystallizer, is centrifuged obtaining hydrogen
Oxidation sodium crystal and crystalline mother solution 3, crystalline mother solution 3 return to two grades of forced-circulation evaporators, continue to be concentrated by evaporation；One water hydroxide
Crystalline lithium 2 returns to one-level forced-circulation evaporator recrystallization, and NaOH crystal is used as byproduct.
Preferably, present invention also offers a kind of production method of high-purity hydrogen lithia, reverse osmosis concentrated liquid is taken, wherein
Magnesium ion content is 30ppm, and lithium ion content is about 5g/L, and sodium ions content is 4g/L, and calcium ion content is 5ppm, potassium ion
Content 200ppm, sulfate ion content 30ppm, boron content 400ppm, are processed using following steps：
It is a, reverse osmosis concentrated liquid is continuous from the technology of friendship using external regeneration, and taken off using meglumine base chelating resin
Boron, obtains boron removal from liquid 1 and saturated resin 1 is handed over, and wherein boron removal boron content in liquid is handed over is 5ppm；
B, the saturated resin 1 for obtaining a steps are regenerated using NaOH, and resin regeneration into hydroxyl type is obtained again
Raw liquid 1 and hydroxyl type resin；
C, the hydroxyl type resin obtained by b step is used regeneration of hydrochloric acid, obtain chloride type resin and regenerated liquid 2；
D, the regenerated liquid 2 obtained by the regenerated liquid 1 and Step d obtained by b step is mixed, and adjust pH3.0 and obtain accessory substance
Boric acid crystal, often producing 10 tons of lithium hydroxides can obtain 1 ton of boric acid；
E, by the boron removal obtained by step a from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, acquisition de-magging
From liquid and saturated resin 2 is handed over, wherein de-magging calcium, magnesium ion total amount in liquid is handed over is 28ppb；
F, saturated resin 2 are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
De-magging obtained by g, step e concentrates 3.5 times from liquid is handed over using evaporator, obtains concentrate, lithium ion in concentrate
Content 17.5g/L, sodium ions content 14g/L, potassium ion 70ppm, calcium ions and magnesium ions total amount 0.1ppm, sulfate ion 1ppm, boron
Acid ion 8ppm；
Concentrate obtained by h, step g, using perfluorinated sulfonic acid Carboxylic Acid Ions film, is electrolysed, anode-side acquisition light salt brine,
Chlorine；Cathode side obtains the mixed solution of hydrogen, lithium hydroxide and NaOH and micro potassium hydroxide；Anode-side control lithium from
Sub- concentration is 12g/L, cathode side control lithium hydroxide concentration 80g/L；
Light salt brine obtained by i, step h, part light salt brine by dechlorination, addition sodium sulfite reduction, control ORP value be-
100mv, removes sulfate radical and boron element, and merge with other light salt brines using electrodialysis concentration, after concentration using boron removal resin
The concentrate obtained with step g merges；
J, step h obtain chlorine can be used to produce hydrochloric acid with combustion of hydrogen, it can also be used to which PVC is produced；
K, step h obtain hydrogen can burn for producing hydrochloric acid with chlorine, also can be used as the original of hydrogenation reduction
Material；
The mixed liquor of cathode side hydrogen lithia, NaOH and micro potassium hydroxide obtained by l, step h is strong using multiple-effect
Circulating evaporator processed carries out first degree crystalline evaporation, and it is 15 times to be concentrated by evaporation multiple, and Lithium hydroxide monohydrate crystal had been concentrated by evaporation
Crystallized in journey and separated out, by centrifuge separating obtained product Lithium hydroxide monohydrate crystal 1 and crystalline mother solution 1, Lithium hydroxide monohydrate
Yield is 99.1%；
The crystalline mother solution 1 that m, step l are obtained, secondary crystallization evaporation is carried out using forced-circulation evaporator, and crystalline mother solution 1 exists
The crystallization of Lithium hydroxide monohydrate crystal 2 is separated out in evaporating concentration process, and evaporation concentrated solution is separated under the conditions of 80 DEG C using centrifuge
Lithium hydroxide monohydrate 2, crystalline mother solution 2 is cooled to 25 DEG C of crystallizations in crystallizer, be centrifuged obtain NaOH crystal and
Crystalline mother solution 3, crystalline mother solution 3 returns to two grades of forced-circulation evaporators, continues to be concentrated by evaporation；Lithium hydroxide monohydrate crystal 2 is returned
One-level forced-circulation evaporator is recrystallized, and NaOH crystal is used as byproduct；
The lithium hydroxide crystal 2 that n, step m are obtained is because containing higher sodium ion, set uses first degree crystalline evaporation technology
Recrystallized；
The NaOH crystal that step n is obtained, can apply mechanically, it is also possible to as byproduct pin as resin regeneration medicament
Sell.
Preferably, present invention also offers a kind of production method of high-purity hydrogen lithia, reverse osmosis concentrated liquid is taken, wherein
Magnesium ion content is 20ppm, and lithium ion content is about 6g/L, and sodium ions content is 5g/L, and calcium ion content is 3ppm, potassium ion
Content 250ppm, sulfate ion content 20ppm, boron content 450ppm, are processed using following steps：
It is a, reverse osmosis concentrated liquid is continuous from the technology of friendship using external regeneration, and taken off using meglumine base chelating resin
Boron, obtains boron removal from liquid 1 and saturated resin 1 is handed over, and wherein boron removal boron content in liquid is handed over is 6ppm；
B, the saturated resin 1 for obtaining a steps are regenerated using NaOH, and resin regeneration into hydroxyl type is obtained again
Raw liquid 1 and hydroxyl type resin；
C, the hydroxyl type resin obtained by b step is used regeneration of hydrochloric acid, obtain chloride type resin and regenerated liquid 2；
D, the regenerated liquid 2 obtained by the regenerated liquid 1 and Step d obtained by b step is mixed, and adjust pH2.8 and obtain accessory substance
Boric acid crystal, often producing 10 tons of lithium hydroxides can obtain 1 ton of boric acid；
E, by the boron removal obtained by step a from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, acquisition de-magging
From liquid and saturated resin 2 is handed over, wherein de-magging calcium, magnesium ion total amount in liquid is handed over is 30ppb；
F, saturated resin 2 are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
De-magging obtained by g, step e concentrates 2 times from liquid is handed over using electrodialysis, obtains concentrate, and lithium ion contains in concentrate
Measure 12g/L, sodium ions content 10g/L, potassium ion 500ppm, calcium ions and magnesium ions total amount 0.06ppm, sulfate ion 1ppm, boric acid
Radical ion 6ppm；
Concentrate obtained by h, step g, using perfluorinated sulfonic acid Carboxylic Acid Ions film, is electrolysed, anode-side acquisition light salt brine,
Chlorine；Cathode side obtains the mixed solution of hydrogen, lithium hydroxide and NaOH and micro potassium hydroxide；Anode-side control lithium from
Sub- concentration is 8g/L, cathode side control lithium hydroxide concentration 90g/L；
Light salt brine obtained by i, step h, part light salt brine by dechlorination, addition sodium sulfite reduction, control ORP value be-
150mv, using boron removal resin remove sulfate radical and boron element, and merges with other light salt brines using be concentrated by evaporation, after concentration and
The concentrate that step g is obtained merges；
J, step h obtain chlorine can be used to produce hydrochloric acid with combustion of hydrogen, it can also be used to which PVC is produced；
K, step h obtain hydrogen can burn for producing hydrochloric acid with chlorine, also can be used as the original of hydrogenation reduction
Material；
The mixed liquor of cathode side hydrogen lithia, NaOH and micro potassium hydroxide obtained by l, step h is strong using multiple-effect
Circulating evaporator processed carries out first degree crystalline evaporation, and it is 12 times to be concentrated by evaporation multiple, and Lithium hydroxide monohydrate crystal had been concentrated by evaporation
Crystallized in journey and separated out, by centrifuge separating obtained product Lithium hydroxide monohydrate crystal 1 and crystalline mother solution 1, Lithium hydroxide monohydrate
Yield is 99.2%；
The crystalline mother solution 1 that m, step l are obtained, secondary crystallization evaporation is carried out using forced-circulation evaporator, and crystalline mother solution 1 exists
The crystallization of Lithium hydroxide monohydrate crystal 2 is separated out in evaporating concentration process, and evaporation concentrated solution is separated under the conditions of 75 DEG C using centrifuge
Lithium hydroxide monohydrate 2, crystalline mother solution 2 is cooled to 28 DEG C of crystallizations in crystallizer, be centrifuged obtain NaOH crystal and
Crystalline mother solution 3, crystalline mother solution 3 returns to two grades of forced-circulation evaporators, continues to be concentrated by evaporation；Lithium hydroxide monohydrate crystal 2 is returned
One-level forced-circulation evaporator is recrystallized, and NaOH crystal is used as byproduct；
The lithium hydroxide crystal 2 that n, step m are obtained is because containing higher sodium ion, set uses first degree crystalline evaporation technology
Recrystallized；
The NaOH crystal that step n is obtained, can apply mechanically, it is also possible to as byproduct pin as resin regeneration medicament
Sell.
Preferably, present invention also offers a kind of production method of high-purity hydrogen lithia, reverse osmosis concentrated liquid is taken, wherein
Magnesium ion content is 15ppm, and lithium ion content is about 4.8g/L, and sodium ions content is 3.9g/L, and calcium ion content is 4ppm, potassium
Ion concentration 300ppm, sulfate ion content 10ppm, boron content 350ppm, are processed using following steps：
It is a, reverse osmosis concentrated liquid is continuous from the technology of friendship using external regeneration, and taken off using meglumine base chelating resin
Boron, obtains boron removal from liquid 1 and saturated resin 1 is handed over, and wherein boron removal boron content in liquid is handed over is 4ppm；
B, the saturated resin 1 for obtaining a steps are regenerated using NaOH, and resin regeneration into hydroxyl type is obtained again
Raw liquid 1 and hydroxyl type resin；
C, the hydroxyl type resin obtained by b step is used regeneration of hydrochloric acid, obtain chloride type resin and regenerated liquid 2；
D, the regenerated liquid 2 obtained by the regenerated liquid 1 and Step d obtained by b step is mixed, and adjust pH2.7 and obtain accessory substance
Boric acid crystal, often producing 10 tons of lithium hydroxides can obtain 1 ton of boric acid；
E, by the boron removal obtained by step a from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, acquisition de-magging
From liquid and saturated resin 2 is handed over, wherein de-magging calcium, magnesium ion total amount in liquid is handed over is 30ppb；
F, saturated resin 2 are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
De-magging obtained by g, step e using 2.5 times of super-pressure reverse osmosis concentration, obtains concentrate, in concentrate from handing over liquid
Lithium ion content 12g/L, sodium ions content 10g/L, potassium ion 750ppm, calcium ions and magnesium ions total amount 0.08ppm, sulfate ion
1ppm, borate ion 6ppm；
Concentrate obtained by h, step g, using perfluorinated sulfonic acid Carboxylic Acid Ions film, is electrolysed, anode-side acquisition light salt brine,
Chlorine；Cathode side obtains the mixed solution of hydrogen, lithium hydroxide and NaOH and micro potassium hydroxide；Anode-side control lithium from
Sub- concentration is 9g/L, cathode side control lithium hydroxide concentration 100g/L；
Light salt brine obtained by i, step h, part light salt brine controls the ORP value to be by dechlorination, addition sodium sulfite reduction
0mv, using boron removal resin remove sulfate radical and boron element, and merges with other light salt brines using electrodialysis concentration, after concentration and
The concentrate that step g is obtained merges；
J, step h obtain chlorine can be used to produce hydrochloric acid with combustion of hydrogen, it can also be used to which PVC is produced；
K, step h obtain hydrogen can burn for producing hydrochloric acid with chlorine, also can be used as the original of hydrogenation reduction
Material；
The mixed liquor of cathode side hydrogen lithia, NaOH and micro potassium hydroxide obtained by l, step h is strong using multiple-effect
Circulating evaporator processed carries out first degree crystalline evaporation, and it is 20 times to be concentrated by evaporation multiple, and Lithium hydroxide monohydrate crystal had been concentrated by evaporation
Crystallized in journey and separated out, by centrifuge separating obtained product Lithium hydroxide monohydrate crystal 1 and crystalline mother solution 1, Lithium hydroxide monohydrate
Yield is 99.3%
The crystalline mother solution 1 that m, step l are obtained, secondary crystallization evaporation is carried out using forced-circulation evaporator, and crystalline mother solution 1 exists
The crystallization of Lithium hydroxide monohydrate crystal 2 is separated out in evaporating concentration process, and evaporation concentrated solution is separated under the conditions of 70 DEG C using centrifuge
Lithium hydroxide monohydrate 2, crystalline mother solution 2 is cooled to 30 DEG C of crystallizations in crystallizer, be centrifuged obtain NaOH crystal and
Crystalline mother solution 3, crystalline mother solution 3 returns to two grades of forced-circulation evaporators, continues to be concentrated by evaporation；Lithium hydroxide monohydrate crystal 2 is returned
One-level forced-circulation evaporator is recrystallized, and NaOH crystal is used as byproduct.
The lithium hydroxide crystal 2 that n, step m are obtained is because containing higher sodium ion, set uses first degree crystalline evaporation technology
Recrystallized；
The NaOH crystal that step n is obtained, can apply mechanically, it is also possible to as byproduct pin as resin regeneration medicament
Sell.
Preferably, the present invention is crystalline mother solution waste water after raw material produces potassium chloride with salt lake bittern, and wherein Mg/Li ratio is
200-500:1, by obtaining qualified eluent after ion sieve absorption, wash-out, eluent is by ultrafiltration membrane technique, segmented nanofiltration
Technology, external regeneration continuously after the technology of friendship and reverse osmosis technology treatment, obtain reverse osmosis concentrated liquid.Wherein magnesium ion content is
≤ 30ppm, lithium ion content is about 4-6g/L, and sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, sulfate ion
Content 1-30ppm, boron content is≤400ppm.With reverse osmosis concentrated liquid as raw material, technological process is the present invention：Super-pressure
Counter-infiltration (or electrodialysis, evaporation and concentration) it is continuous from hand over boron removal, it is continuous from hand over engaging sulphate, electrolysis with ion-exchange film, crystallization and evaporation, from
Boron removal technology, ion-exchange membrane electrolysis, crystallization and evaporation technology are handed over, so that high-purity hydrogen lithia is obtained, and by-product boric acid and hydrogen
Sodium oxide molybdena, the continuous controllable, extract yield of technical process is high, low production cost, it is easy to industrialize.
In sum, the beneficial effects of the present invention are：It is of the invention direct with reverse osmosis concentrated liquid as raw material, by boron removal
Direct Electrolysis production lithium hydroxide after decalcification magnesium, not only process route is simple, lithium ion high income and product quality is high, production
Low cost, chemical agent consumption is few, and comprehensive utilization of resources degree is high.
The invention is not restricted to above-mentioned specific embodiment.It is understood that not departing from spirit and substance of the present invention model
In the case of enclosing, various changes and modifications can be made, these should be all included within protection scope of the present invention.
Claims (7)
1. a kind of production method of high-purity hydrogen lithia, it is characterised in that comprise the following steps：
A, with salt lake bittern as raw material production potassium chloride after crystalline mother solution waste water, wherein Mg/Li ratio be 200-500:1, by from
Qualified eluent is obtained after the absorption of son sieve, wash-out, eluent connects by ultrafiltration membrane technique, segmented nanofiltration, external regeneration
Continue after friendship technology and reverse osmosis technology treatment, obtain by the first concentrate of reverse osmosis concentration, wherein magnesium ion content is
≤ 30ppm, lithium ion content is 4-6g/L, and sodium ions content is 3-5g/L, and calcium ion content is≤5ppm, potassium ion≤
300ppm, sulfate ion content 1-30ppm, boron content are≤500ppm；
B, first concentrate is carried out into boron removal using external regeneration is continuous from friendship technology, obtain the first boron removal from handing over liquid and the
One saturated resin, wherein the first boron removal boron content in liquid is handed over is less than 10ppm；
C, by the first saturated resin using NaOH regenerate hydroxyl type, obtain the first regenerated liquid and hydroxyl type resin；
D, hydroxyl type resin is used regeneration of hydrochloric acid, obtain chloride type resin and the second regenerated liquid；
E, by the first and second regenerated liquids mix, and adjust pH less than 3.0 obtain accessory substance boric acid crystal；
F, by the first boron removal from handing over the liquid to carry out decalcification magnesium from friendship technology using external regeneration is continuous, obtain de-magging from friendship liquid and second
Saturated resin, wherein de-magging calcium, magnesium ion total amount in liquid is handed over are less than 30ppb；
G, the second saturated resin are into Hydrogen and then standby using NaOH regeneration sodium form using regeneration of hydrochloric acid；
H, de-magging obtain second and concentrate from handing over liquid to concentrate 2-5 times using super-pressure counter-infiltration, electrodialysis, positive infiltration or evaporator
Liquid, lithium ion content 8-30g/L in the second concentrate, sodium ions content 6-20g/L, potassium ion≤1500ppm, calcium ions and magnesium ions are total
Amount≤0.15ppm, sulfate radical and boron element total amount≤50ppm；
I, the second concentrate are electrolysed into ion-exchange membrane electrolyzer, and anode-side obtains light salt brine, chlorine；Cathode side obtains hydrogen
The mixed solution of gas, lithium hydroxide and NaOH and micro potassium hydroxide；
J, part light salt brine are by dechlorinating, sodium sulfite uses boron removal resin removing sulfate radical and boron element after reducing, and and its
The merging of its light salt brine is concentrated, and is merged with the second concentrate after concentration；
K, the chlorine and combustion of hydrogen are used to produce hydrochloric acid, or for PVC productions, or as the original of hydrogenation reduction
Material；
The mixed liquor of l, the cathode side hydrogen lithia, NaOH and micro potassium hydroxide is existed using one-level evaporative crystallization technique
Crystallization is evaporated in one-level forced-circulation evaporator, the crystallization of the first high-purity of product Lithium hydroxide monohydrate and the first crystallization is obtained
Mother liquor；
M, the first crystalline mother solution carry out dual evaporation crystallization using two grades of forced-circulation evaporators, and the first crystalline mother solution is evaporating dense
The second Lithium hydroxide monohydrate crystal structure is separated out in compression process, and evaporation concentrated solution is separated under the conditions of 60-90 DEG C using centrifuge
Second Lithium hydroxide monohydrate, obtains the second crystalline mother solution, and the second crystalline mother solution is cooled to 30 DEG C of crystallization below in crystallizer, passes through
Centrifugation obtains NaOH crystal and the 3rd crystalline mother solution, and the 3rd crystalline mother solution returns to two grades of forced-circulation evaporators, after
It is continuous to be concentrated by evaporation；
N, the second Lithium hydroxide monohydrate crystal are because containing higher sodium ion, set is used one-level forced-circulation evaporator and tied again
It is brilliant；
O, the NaOH crystal are applied mechanically or as by-product sale as resin regeneration medicament；
Wherein, first boron removal is from handing over the liquid to carry out decalcification magnesium from friendship technology and be specially using external regeneration is continuous：First boron removal
From handing over liquid from main from handing over column bottom charging, it is reverse by main from handing over post, after friendship liquid from main from handing over column top water outlet；Master is from friendship post bottom
Portion's resin saturation at first, bottom saturated resin enters parsing post by Action of Gravity Field, main from handing over column top head tank resin to pass through
Action of Gravity Field synchronously enters, and after resin transfer is finished, main from handing over post to recover charging, resin uses regeneration of hydrochloric acid Cheng Qing in parsing post
Type, then use NaOH to regenerate sodium form, it is main stand-by from friendship column top head tank that regeneration finishes the press-in of resin compressed air；
Main that a resin was shifted per 6-24 hours from friendship post, resin transfer time is 3-10 minutes, realizes continuously work；When resin is shifted
The abundant saturation of bottom resin；Distance is main be furnished with sample tap away from column top delivery port 500-1000mm to hand over, when sample tap have magnesium from
Bottom saturated resin is discharged during sub- leakage, there are 500-1000mm resin beds on sample tap as protective layer, it is ensured that magnesium ion
Will not leakage.
2. method according to claim 1, it is characterised in that the first saturated resin is meglumine base chelating resin, can be special
Property absorption boric acid.
3. method according to claim 2, it is characterised in that described ionic membrane is perfluorinated sulfonic acid Carboxylic Acid Ions film.
4. method according to claim 2, it is characterised in that described electrolysis, the lithium hydroxide concentration control of cathode side exists
Below 100g/L, is separated out with preventing lithium hydroxide from crystallizing.
5. the method according to claim any one of 3-4, it is characterised in that described electrolysis, the lithium concentration of anode-side
Control, in below 15g/L, is higher than cathode side to prevent anode-side osmotic pressure, so as to cause ionic membrane to damage.
6. the method according to claim any one of 3-4, it is characterised in that the method concentrated to light salt brine includes super
High pressure counter-infiltration, electrodialysis, positive infiltration are evaporated.
7. method according to claim 6, it is characterised in that part light salt brine simultaneously adds sodium sulfite reduction by dechlorination
150mv is less than to ORP value.
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| CN106430256B (en) * | 2016-10-28 | 2017-08-08 | 荆门市格林美新材料有限公司 | Lithium hydroxide preparation system |
| CN106495188B (en) * | 2016-10-28 | 2017-08-08 | 荆门市格林美新材料有限公司 | Lithium hydroxide preparation system |
| CN106946275B (en) * | 2017-03-06 | 2019-04-05 | 青海锂业有限公司 | The method for directly producing battery-stage monohydrate lithium hydroxide using salt lake richness lithium brine |
| CN108660476B (en) * | 2017-08-10 | 2019-04-02 | 青海盐湖工业股份有限公司 | A kind of new process of salt lake bittern production high-purity hydrogen lithia |
| CN107720786A (en) * | 2017-10-18 | 2018-02-23 | 中国科学院青海盐湖研究所 | A kind of LITHIUM BATTERY lithium hydroxide preparation method based on UF membrane coupled method |
| CN110817904B (en) * | 2018-08-14 | 2021-07-20 | 比亚迪股份有限公司 | Lithium hydroxide monohydrate, preparation method and application thereof, lithium ion battery anode material and lithium ion battery |
| CN109207730B (en) * | 2018-09-19 | 2020-03-10 | 中国科学院青海盐湖研究所 | Method and system for recovering lithium from waste lithium iron phosphate batteries |
| CN109264737B (en) * | 2018-11-14 | 2019-07-16 | 启迪清源（北京）科技有限公司 | Recycling lithium and the method for producing high-purity boric acid or borax |
| KR102600507B1 (en) | 2018-12-21 | 2023-11-09 | 맹그로브 워터 테크놀로지스 리미티드 | Li recovery processes and onsite chemical production for li recovery processes |
| CN110065958B (en) * | 2019-03-27 | 2022-03-18 | 浙江工业大学 | Method for preparing lithium hydroxide by treating salt lake brine through integrated selective electrodialysis and selective bipolar membrane electrodialysis |
| CN110029354B (en) * | 2019-05-08 | 2020-10-13 | 蓝星(北京)化工机械有限公司 | Method for preparing battery-grade lithium hydroxide by direct electrolysis of lithium chloride |
| CN110453092A (en) * | 2019-08-22 | 2019-11-15 | 四川思达能环保科技有限公司 | Lithium salt solution treatment process |
| RU2713360C2 (en) * | 2019-09-25 | 2020-02-04 | Общество с ограниченной ответственностью "Экостар-Наутех" | Method of producing lithium hydroxide monohydrate from brines |
| CN112777616A (en) * | 2021-01-30 | 2021-05-11 | 四川思达能环保科技有限公司 | Impurity removal process for lithium hydroxide heavy solution |
| CN113998713A (en) * | 2021-09-07 | 2022-02-01 | 内蒙古博源工程有限责任公司 | System for preparing sodium carbonate and baking soda and by-producing boric acid and ferric hydroxide by natural alkali liquor |
| CN113998714A (en) * | 2021-11-24 | 2022-02-01 | 四川顺应动力电池材料有限公司 | Method for producing battery-grade lithium hydroxide |
| EP4186997A1 (en) | 2021-11-26 | 2023-05-31 | K-UTEC AG Salt Technologies | Preparation of lithium hydroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102016123A (en) * | 2008-04-22 | 2011-04-13 | 凯米涛弗特公司 | Method of making high purity lithium hydroxide and hydrochloric acid |
| CN103924258A (en) * | 2014-04-28 | 2014-07-16 | 中国科学院青海盐湖研究所 | Method for preparing lithium hydroxide through electrolysis of salt lake brine |
| CN105177288A (en) * | 2015-10-28 | 2015-12-23 | 中国科学院青海盐湖研究所 | Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio |
-
2016
- 2016-07-06 CN CN201610525650.7A patent/CN106011917B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102016123A (en) * | 2008-04-22 | 2011-04-13 | 凯米涛弗特公司 | Method of making high purity lithium hydroxide and hydrochloric acid |
| CN103924258A (en) * | 2014-04-28 | 2014-07-16 | 中国科学院青海盐湖研究所 | Method for preparing lithium hydroxide through electrolysis of salt lake brine |
| CN105177288A (en) * | 2015-10-28 | 2015-12-23 | 中国科学院青海盐湖研究所 | Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio |
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