CN105905929A - Method for preparing lithium carbonate from plateau carbonate bittern - Google Patents
Method for preparing lithium carbonate from plateau carbonate bittern Download PDFInfo
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/22—Treatment of water, waste water, or sewage by freezing
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Abstract
The invention provides a method for preparing lithium carbonate from plateau carbonate bittern. The method comprises the following steps: subjecting original carbonate bittern A to evaporation before autumn and winter, adjusting the concentration of lithium ions so as to allow the lithium ions not to be precipitated in the form of minerals and introducing the carbonate bittern A to a deep-pool salt field for evaporation when the concentration of lithium ions reaches 1.2 to 1.8 g/L; as considerable mirabilite decahydrate is precipitated at first when temperature is -15 to -5 DEG C and the concentration of lithium ions rapidly increases, carrying out solid-liquid separation so as to obtain bittern B when the concentration of sulfate ions decreases to 4 to 7 g/L and the concentration of lithium ions increases to 2.6 to 3.5 g/L; introducing the bittern B into a heating system for heating to 20 to 60 DEG C, allowing a first batch of lithium carbonate concentrate and bittern C to be precipitated; subjecting the bittern C to refrigeration at a temperature of -20 DEG C or below so as to realize precipitation of mixed salt I and carrying out solid-liquid separation when the concentration of sulfate ions decreases to 15 g/L or below and the concentration of lithium ions increases to 2 g/L or above so as to obtain bittern D; and continuing evaporating the bittern D, adding bittern with a carbonate ion concentration of 60 g/L or above when the concentration of lithium ions reaches 2.6 to 3.5 g/L again and carrying out heating to 20 to 60 DEG C so as to allow a second batch of lithium carbonate concentrate to be precipitated.
Description
Technical field
The present invention relates to the utilization methods of carbonate type bittern, particularly relate to a kind of from the carbonate type bittern of plateau
The method preparing lithium carbonate.
Background technology
Exploitation Tibet region salt lake resources it is difficult to chemical processing plant (CPP) cannot be built in lake region, and, distance possesses
The place of industrial processes ability is remote, therefore, can only transport processing after lake region obtains high-grade mineral, and its core seeks to profit
Series salt pan mineral are obtained by building salt pan with local natural environment.
Mainly there are carbonate-type and the big class of sulfate type two in boron-rich lithium salts lake, Tibet.Early stage, for the boron-rich lithium of sulfate type
The exploitation in salt lake, it is proposed that freezing analyse the main process of lithium except nitre-evaporation analysis potassium-be diluted to boron-evaporation of saltouing.And to carbonate
The exploitation in type boron-rich lithium salts lake, problems faced is the solubility properties due to lithium carbonate, it is difficult to be enriched to by lithium carbonate higher
Concentration, the technique of Zha Buye exploitation is to utilize freezing to analyse the technique of lithium carbonate except nitre-evaporation enriching lithium-utilize solar pond heats up,
This technique achieves the clean production of all clear, has obtained preferable lithium carbonate mineral, but in salt, lithium ion enrichment degree is relatively low, limits
The yield that lithium separates out；Solar pond complex operation, the production cycle is long；In addition to lithium, other resource is not all obtained by.By knot then
Tea card (carbonate-type) and the geographical position of wrong (sulfate type) Hubei and Hunan Provinces of Medulla Junci (air line distance about 70km) nearby, the utilization of exploitation
Carbonate-type and sulfate type two kinds boron-rich lithium salts lake bittern water coupling technique, can solve sulfate type salt lake magnesium/lithium than high, carbon
Hydrochlorate type salt lake lithium is difficult to the problem of enrichment, and lithium is enriched to higher concentration, but on the one hand, has this rare environmental condition
Two kinds of salt lake quantity the most limited；On the other hand, consume a large amount of carbonate during two kinds of salt lake coupling exploitations, and produce relatively large
Magnesium carbonate, cause carbonate type salt lake is provided that the carbonate producing lithium carbonate is the most sufficient, steady to salt lake resources
Determine production and cause certain impact.Therefore, try one's best merely with the element of self in carbonate-type boron lithium salts lake, it is achieved circulating life
Produce, and break away from the dependence to other resource, be the fabulous approach of Tibet plateau carbonate type salt lake development of resources.
Summary of the invention
To this end, the present invention provides a kind of method preparing lithium carbonate from the carbonate type bittern of plateau.
A kind of method preparing lithium carbonate from the carbonate type bittern of plateau, it includes step:
The first step, carbonate-type original salt A in the fall before, be evaporated concentrating, and according to the change of environmental condition,
In evaporation and concentration salt, constantly import fresh water or dilute salt to regulate lithium concentration so that lithium ion is not analysed with mineral forms
Go out, when lithium concentration reaches 1.2g/L～1.8g/L in salt, salt is imported the degree of depth deep lake salt more than or equal to 2m
Tanaka continues evaporation and concentration；
Second step, along with proceeding to winter of highlands season, when ambient temperature is-15 DEG C～-5 DEG C, a large amount of ten water awns
Nitre preferentially separates out, and along with temperature continues to reduce and the precipitation of water of crystallization, Borax, sodium chloride, potassium chloride are also with aqueous salt or simple
The form of salt separates out, and in the case, in salt, lithium concentration rises rapidly, and in salt, sulfate ion concentration is for controlling
Index, when the concentration of sulfate ion is reduced to 4g/L～7g/L, in salt lithium concentration rise very rapidly up to 2.6g/L～
3.5g/L, obtains rich lithium carbonate brine B and mirabilite ore after solid-liquid separation；
3rd step, the rich lithium carbonate brine B obtained by second step imports in temperature elevation system and is warming up to 20 DEG C～60 DEG C, analysis
Going out first lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains first lithium carbonate concentrate
With salt C；
4th step, by salt C below-20 DEG C at a temperature of continue freezing separate out based on sodium carbonate and the mixing of Borax
Salt I, when carbonate concentration is reduced to below 15g/L, when lithium concentration rises to more than 2g/L, carries out solid-liquid separation and is mixed
Salt I and salt D；
5th step, salt D continues evaporation, when lithium concentration reaches 2.6g/L～3.5g/L again, add carbonate from
High-carbon acid group salt more than sub-concentration 60g/L, imports in the temperature elevation system identical with temperature elevation system described in the 3rd step and is warming up to
20 DEG C～60 DEG C, separating out second batch lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains the
Two batches of lithium carbonate concentrate and salt E.
Preferably, the salt E obtained in described 5th step imports the deep lake salt Tanaka of the first step and is circulated process, according to
This mode, through abundant circular treatment, the lithium ion in carbonate-type original salt A changes into the yield of lithium carbonate concentrate and is
More than 70%.
Preferably, in the described first step, when lithium concentration is close to 1.5g/L in salt, salt is imported the described degree of depth
Deep lake salt Tanaka more than or equal to 2m continues evaporation and concentration.
Preferably, in the described first step, when being in autumn, ambient temperature is higher in season, salt minimum temperature 5 DEG C with
Time upper, controlled lithium concentration importing deep lake salt field close to 1.2g/L (1.2g/L～1.5g/L).
Preferably, in the described first step, when being in autumn, ambient temperature is relatively low in season, salt minimum temperature 0 DEG C with
Time lower, control lithium concentration importing deep lake salt field close to 1.8g/L (1.5g/L～1.8g/L).
Preferably, in the described first step, proceed to autumn when season, when temperature starts to reduce, salt minimum temperature at 0 DEG C～
5 DEG C, lithium concentration is first imported the degree of depth shallow lake salt Tanaka less than or equal to 0.5m at the salt close to 1.2g/L and continues to steam
Send out and concentrate, when being evaporated in salt lithium concentration close to 1.8g/L, import deep lake salt field.
Preferably, the temperature elevation system that in described 3rd step, salt B imports is solar temperature rising system, at this solar temperature rising
In system, temperature-rise period comprises the following steps: sprayed from top to bottom in solar temperature rising system by salt B, simultaneously by 100 DEG C
～hot-air and the described salt B of 200 DEG C in opposite directions or the mode that intersects imports so that salt B with hot-air with relative or crossing
The form of motion carries out heat exchange, thus brine temperature rises very rapidly up to 20 DEG C～60 DEG C and flows in thermal insulation pool；By described halogen
Water is incubated 2～48 hours in thermal insulation pool, constantly separates out lithium carbonate, and in salt, lithium concentration is down to during 1g/L～2g/L solid
Liquid isolated lithium carbonate concentrate.
Preferably, the temperature elevation system that in described 3rd step, salt B imports is Wen Peng pond, temperature-rise period bag in this Wen Peng pond
Including following steps: provide a Wen Peng pond, this Wen Peng pond includes cell body and closes the diffuser of this cell body, along the length side of this cell body
To, the width of this cell body is gradually reduced, and the degree of depth of this cell body is gradually increased, and the temperature in this Wen Peng pond is higher by 20 than ambient temperature
DEG C～50 DEG C；When autumn and winter season and ambient temperature-30 DEG C～0 DEG C, by salt B along the length direction in described Wen Peng pond and from pond
One end that the width of body is big imports described Wen Peng pond, and described salt B is the big and district of depth as shallow at the width of the cell body in this Wen Peng pond
Territory carries out quick heat exchange, is rapidly heated, and quickly separates out lithium carbonate, the width of the cell body arriving this Wen Peng pond as salt B little and
The region that the degree of depth is deep, salt B reaches stable through abundant heat-exchange temperature, and separates out a large amount of lithium carbonate, treats lithium concentration fall in salt
Lithium carbonate concentrate is obtained to solid-liquid separation during 1g/L～2g/L.
Preferably, in described 3rd step, salt B is warming up to 40 DEG C～50 DEG C in temperature elevation system.
Preferably, in described 3rd step, it is less than 10% by limiting the evaporation rate of the water yield in temperature elevation system, first obtained
The grade criticizing lithium carbonate concentrate reaches more than 90%；In described 5th step, low by limiting the evaporation rate of the water yield in temperature elevation system
In 10%, the grade of the second batch lithium carbonate concentrate obtained reaches more than 90%.
Preferably, in described 5th step, the preparation method of the salt of described more than carbon acid ion concentration 60g/L is: will
The salt-mixture I that 4th step obtains adds fresh water or dilute salt, and the addition of described fresh water or dilute salt is described salt-mixture I mass
50%～200%, then carry out solar evaporation, precipitated sodium chloride and potassium chloride in salt pan, be enriched with carbanion, work as carbonic acid
When ion concentration reaches more than 60g/L, solid-liquid separation obtains high-carbon acid group salt.
Compared with prior art, the invention have the advantages that
(1) present invention is based on the original salt of carbonate-type, by control evaporation process realize fast enriching lithium from
The purpose of son, the element of self in fully utilized carbonate type salt lake brine, do not additionally introduce any other reagent, it is achieved clear
Clean, environment protection-type produces, and has broken away from the dependence to other resource.
(2) after evaporation and concentration reaches 1.2g/L～1.8g/L to lithium concentration, the addition of deep lake salt field last stage is entered de-
Water Natrii Sulfas, and make dehydration Natrii Sulfas be dissolved in salt, and control sulfate ion concentration in salt, it is to avoid sulfate radical is follow-up
Producing lithium sulfate double salt, the control result of this process makes to freeze nitre process mirabilite hydrate high efficiency and separates out follow-up winter, 70%～
More than 90% Natrii Sulfas separates out, so that the whole process time shortens more than 2 months.
(3) about the several key points in pilot process.The control of lithium concentration, the control of sulfate ion concentration,
The control of warming temperature, the preparation limiting the carbonate salt of the fine processing of evaporation, more than 60g/L and addition etc..It is evaporated to
Lithium concentration is to this scope of 1.2g/L～1.8g/L, and in evaporation process, according to the situation of change of site environment temperature,
Adjust lithium concentration by adding the dilutest salt, control the evaporation process of Bittern of Salt Pan flexibly.By the lithium in concentrated brine from
Sub-concentration controls in this scope of 1.2g/L～1.8g/L so that it is does not become salt in salt pan evaporation process, this situation is continued up
Proceeding to autumn and winter to season, salt imports deep lake salt Tanaka and continues evaporation and concentration, proceed to winter season, ambient temperature constantly drops
Low, after entering winter, more than 70% mirabilite hydrate in salt preferentially separates out from salt, thus takes rapidly mass crystallization water out of,
Lithium concentration rises rapidly, and the concentration controlling sulfate ion is reduced to during 4g/L～7g/L (preferably 6g/L～7g/L),
In salt, lithium concentration rises very rapidly up to 2.6g/L～3.5g/L, obtains rich lithium carbonate brine B, salt B after solid-liquid separation
After intensification 20 DEG C～60 DEG C, separate out first lithium carbonate concentrate, after solid-liquid separation, obtain salt C.Here first carbonic acid
Lithium concentrate is through limiting the fine processing of evaporation, and grade is up to more than 90%.Salt C is through continuing cold lower temperature-20 DEG C
Freezeout goes out the salt-mixture I based on sodium carbonate and Borax, and obtains salt D, and after salt D is continued evaporation, lithium concentration is again
In the carbonate salt importing temperature elevation system of secondary 2.6g/L～3.5g/L that reach, addition more than 60g/L after intensification 20 DEG C～60 DEG C
Separate out second batch lithium carbonate concentrate, second batch lithium carbonate concentrate here through limiting the fine processing of evaporation, grade up to
More than 90%.Separating out lithium carbonate concentrate through twice, a technological process, in the original salt of carbonate, elemental lithium is with lithium carbonate shape
The yield that formula is extracted is up to more than 70%.
(4) utilize solar temperature rising system, salt B is sprayed from top to bottom, simultaneously by 100 DEG C～the hot-air of 200 DEG C
Import from bottom to top in the lower section of salt B (the most also can level or the importing that is inclined upwardly) so that salt B and hot-air phase convection current
Dynamic fully carry out heat exchange, quick heat exchange, be rapidly heated after isothermal holding, thus quickly obtain crystallization of lithium carbonate body, significantly carry
Rise the precipitation rate of lithium carbonate.It addition, by limiting in temperature elevation system, the evaporation rate of the water yield is less than 10%, and the lithium carbonate obtained is smart
The grade in ore deposit reaches more than 90%.
(5) utilize Wen Peng pond as temperature elevation system, due to the gradient-structure feature bottom Wen Peng pond so that low temperature richness lithium carbon
Hydrochlorate type salt enters quickly heat exchange behind Wen Peng pond, is rapidly heated, thus quickly obtains crystallization of lithium carbonate body, is greatly promoted carbonic acid
The precipitation rate of lithium.
(6) it is worth mentioning that: after after salt D continuation evaporation, lithium concentration reaches 2.6g/L～3.5g/L again
Add the carbonate salt of more than 60g/L import temperature elevation system heats up separate out after 20 DEG C～60 DEG C second batch lithium carbonate concentrate this
During one, the preparation of the carbonate salt of more than 60g/L adds light entirely from the salt-mixture I self-produced by this technical process
Obtain after water or the evaporation of dilute salt back dissolving, it is not necessary to additionally buy.
Detailed description of the invention
For making the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, to this
Bright it is described in detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to limit
The present invention.
The present invention is directed to Qinghai-Tibet Platean social economy and naturalness feature, propose to utilize natural energy, salt composition to realize
Carbonate type salt lake produces the method for multi mineral, for the feasibility of the method is described, is utilized as example with Lake Jiezechaka, can
To understand, this invention is applicable not only to the exploitation of Lake Jiezechaka, is also applied for having salt lake resources under the conditions of similar environments
Exploitation.
The method preparing lithium carbonate from the carbonate type bittern of plateau of the present invention is described the most step by step.
The first step, carbonate-type original salt A in the fall before, be evaporated concentrating, and according to the change of environmental condition,
In evaporation and concentration salt, constantly import fresh water or dilute salt to regulate lithium concentration so that lithium ion is not analysed with mineral forms
Go out, when lithium concentration reaches 1.2g/L～1.8g/L in salt, salt is imported the degree of depth deep lake salt more than or equal to 2m
Tanaka continues evaporation and concentration.
Original salt A is evaporated, be passed to be stacked with after enrichment method to lithium concentration 1.2g/L～1.8g/L
The salt pan of dehydration Natrii Sulfas, the simultaneously concentration range (avoiding excessive concentration or too low) of sulfate ion in detection salt.Control into
(sulfate ion concentration lower limit is how many to enter concentration 20g/L of sulfate ion in the salt of deep pond～30g/L？).
Dehydration Natrii Sulfas adds in this step so that salt is during flowing through dehydration Natrii Sulfas, and dehydration Natrii Sulfas absorbs salt
In moisture content, be gradually transformed into mirabilite hydrate, have partially dehydrated Natrii Sulfas to dissolve simultaneously and enter in salt, follow-up winter freezes nitre process
Mirabilite hydrate high efficiency separates out, and takes mass crystallization water out of, promotes rapidly lithium enrichment rate, so that the whole process time shortens
More than 2 months.Dehydration Natrii Sulfas can be thenardite or partly be dehydrated Natrii Sulfas, and these Natrii Sulfas may utilize carbonate brine processing procedure
The Natrii Sulfas that salt pan produces voluntarily, it is not necessary to outsourcing.The Natrii Sulfas that salt pan produces voluntarily, without processing especially, only need to be deposited directly on certain
Locating, be dehydrated through weathering, dehydration or half dehydration, all can use in this step the most completely.Dehydration Natrii Sulfas adition process,
The concentration range controlling sulfate ion is crucial.Dehydration Natrii Sulfas addition too much can make sulfate ion increase and be easily caused product
Raw lithium sulfate complex salt, thus affect follow-up enriching lithium ion.And it is inadequate to be dehydrated Natrii Sulfas addition, in follow-up nitre process of freezing, ten
Water Natrii Sulfas eduction rate is low can affect evaporation and concentration speed, delays the speed of enriching lithium process.
The above-mentioned procedure declaration importing deep lake salt field when lithium concentration reaches 1.2g/L～1.8g/L is as follows: first,
Optium concentration through lot of experiments card lithium ion is 1.5g/L, and actual production process lithium concentration all can obtain close to 1.5g/L
Obtaining is all preferable condition between preferable effect, such as 1.45g/L～1.55g/L.Secondly, in actual production process, according to season
Difference, the height of ambient temperature, need the lithium concentration controlled to change.Until season proceeds to autumn, although be the autumn
Season, but ambient temperature is not the most steady statue, i.e. and ambient temperature may be higher, it is also possible to relatively low, it should with halogen in the middle of reality
The temperature of water controls when to import deep lake salt field.Summary experiment law finds, proceed to autumn when season, ambient temperature is higher,
When salt minimum temperature is more than 5 DEG C, can control lithium concentration importing deep lake salt field, such as, 1.2g/ close to 1.2g/L
L～1.5g/L；Proceeding to autumn season, ambient temperature is relatively low, can control lithium concentration importing deep lake salt close to 1.8g/L
Field, such as, 1.5g/L～1.8g/L.No matter during the seasonal variations of plateau, how ambient temperature changes, and controls lithium concentration
Foundation for which scope is that lithium does not separates out with the form of lithium carbonate mineral.
Dilute salt in the described first step uses the original salt of carbonate-type, and wherein lithium concentration is close to 0.16g/L；Or
Use and be concentrated to certain phase from the original bittern evaporation of carbonate-type, wherein the lithium concentration salt less than 1.2g/L.This is specially
The profit application dilute salt mentioned by context is dilute salt defined in this section.
Highlands ambient temperature spring and summer is-10 DEG C～20 DEG C, and autumn and winter, ambient temperature was-30 DEG C～0 DEG C.
The composition of the original salt of carbonate type salt lake is as shown in following table one:
The composition of the original salt of table one carbonate type salt lake
From above-mentioned table one: carbonate type salt lake original salt A consists of: B2O3Be 0.1～3g/L, Li be 0.1～
2g/L, K are 1～30g/L, and Na is 10～120g/L, and Mg is 0.01～20g/L, SO4 2-It is 1～40g/L, CO3It is 1～120g/
L, Br are 0.01～0.50g/L, and Cl is 20～300g/L.
In the annual most of the time, original for plateau carbonate type salt lake salt can be pumped into salt pan and carry out Exposure to Sunlight
Evaporation.In the present embodiment, select Lake Jiezechaka lake water, due to this lake lake water ratio thin (i.e. fresh water content is high), for avoiding freezing
Impact operation, should avoid taking in the winter time halogen as far as possible.Therefore, in the present embodiment, take salt season at spring and summer and carry out test operation.Table
Two give Lake Jiezechaka Bittern of Salt Pan 2014～on-the-spot evaporation data in 2015.
Table two Lake Jiezechaka Bittern of Salt Pan evaporation liquid phase composition
Be attached in specific experiment, see table two, take Lake Jiezechaka Bittern of Salt Pan analysis on February 11st, 2014, lithium from
Sub-initial concentration is 0.24g/L, and beginning solar evaporation from this day, As time goes on, lithium concentration is along with salt
Constantly evaporating and be gradually increasing, during having arrived 2014.9.20～2014.11.8, lithium concentration has about risen to 1.2g/
L～1.8g/L scope, imports the degree of depth deep lake salt Tanaka more than or equal to 2m, continues evaporation and concentration.
During the stage that dehydration Natrii Sulfas adds can be 2014.7.12～2014.11.8, the detailed process of interpolation can be
(but not limited to): dehydration Natrii Sulfas is stacked into one and processes porch, pond, lithium ion is enriched to the carbon of 1.2g/L～1.8g/L
After hydrochlorate type enrichment salt breaks through dehydration Natrii Sulfas, entrance processes pond, and detection processes the concentration of sulfate ion in pond, thus controls
System dehydration Natrii Sulfas addition, dehydration Natrii Sulfas add too much can make sulfate ion increase be easily caused generation lithium sulfate be combined
Salt, thus affect follow-up enriching lithium ion.And it is inadequate to be dehydrated Natrii Sulfas addition, at follow-up nitre process of freezing, mirabilite hydrate eduction rate
Low can affect evaporation and concentration speed, delay the speed of enriching lithium process.Therefore this stage, the concentration controlling sulfate ion is many
Few scope is crucial.
According to lithium concentration in temperature Change situation and concentrated brine, will be able to concentrate before entering deep lake salt field
Salt imports the degree of depth shallow lake salt Tanaka less than or equal to 0.5m and continues evaporation and concentration, or is importing directly into deep lake salt Tanaka evaporation
Concentrate.Depending on the annual seasonal temperature situation of change of Salt Lake Area, proceed to autumn when season, when temperature starts to reduce, salt
Minimum temperature at 0 DEG C～5 DEG C, lithium concentration close to the salt of 1.2g/L (1.2g/L～1.5g/L) first import the degree of depth less than or
Shallow lake salt Tanaka equal to 0.5m continues evaporation and concentration, be evaporated in salt lithium concentration close to 1.8g/L (1.5g/L～
Deep lake salt Tanaka is imported time 1.8g/L)；Proceed to autumn when season, but when ambient temperature is relatively low, salt minimum temperature 0 DEG C with
Under, lithium ion content is introduced directly into deep lake salt Tanaka's evaporation and concentration close to the salt of 1.8g/L (1.5g/L～1.8g/L)；This season
Joint proceeds to autumn, and ambient temperature is higher, when salt minimum temperature is more than 5 DEG C, is controlled by lithium concentration close to 1.2g/L
(1.2g/L-1.5g/L) salt is introduced directly into deep lake salt field.
Second step, along with proceeding to winter of highlands season, when ambient temperature is-15 DEG C～-5 DEG C, a large amount of ten water awns
Nitre preferentially separates out, and along with temperature continues to reduce and the precipitation of water of crystallization, Borax, sodium chloride, potassium chloride are also with aqueous salt or simple
The form of salt separates out, and in the case, in salt, lithium concentration rises rapidly, and in salt, sulfate ion concentration is for controlling
Index, when the concentration of sulfate ion is reduced to 4g/L～7g/L, in salt lithium concentration rise very rapidly up to 2.6g/L～
3.5g/L, obtains rich lithium carbonate brine B and mirabilite ore after solid-liquid separation.
Mirabilite ore is based on mirabilite hydrate, and mass content accounts for 70%～more than 90%, and remaining is contaminated with a small amount of Borax, chlorination
Sodium, potassium chloride.
Preferably, when the concentration of sulfate ion is preferably controlled in 6g/L～7g/L, and treat in salt on lithium concentration
Rise to 2.6g/L～3.5g/L, carry out solid-liquid separation, the rich lithium carbonate brine obtained, follow-up obtains when preparing lithium carbonate concentrate
The lithium carbonate yield obtained can be higher.
In being attached to specifically test, as shown in Table 2, in the salt between December in 2014 14 days～28 days January in 2015
Lithium concentration is all higher than 2.6g/L and less than 3.5g/L, such as, 3.36g/L, 3.39g/L；Some is especially more than 3.5g/L,
Other it was found that, in salt lithium concentration can reach 3.9g/L.Such rich lithium carbonate brine by intensification at
Reason can obtain high-grade lithium carbonate concentrate.
3rd step, the rich lithium carbonate brine B obtained by second step imports in temperature elevation system and is warming up to 20 DEG C～60 DEG C, analysis
Going out lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains first lithium carbonate concentrate and salt
C。
The grade of this first lithium carbonate concentrate, more than 60%, is less than by limiting the evaporation of the water yield in temperature-rise period
The precise controlling of 10%, the grade of first lithium carbonate concentrate can reach more than 90%.
Preferable temperature controls at 40 DEG C～50 DEG C, preferably close to 45 DEG C.
Described temperature elevation system can be solar temperature rising system, Wen Peng pond or solar pond.
When using solar temperature rising system, the temperature-rise period of salt B comprises the following steps: first, by salt B at the sun
Temperature elevation system can be sprayed from top to bottom, in opposite directions by the hot-air of 100 DEG C～200 DEG C and described salt B or the side intersected simultaneously
Formula imports so that salt B carries out heat exchange with hot-air with the form of relative or crossing motion, thus brine temperature rises rapidly
To 20 DEG C～60 DEG C and flow in thermal insulation pool；Secondly, described salt is incubated 2～48 hours in thermal insulation pool, constantly separates out carbon
Acid lithium, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains first lithium carbonate concentrate.
It is less than 10% by limiting the evaporation rate of the water yield in solar temperature rising system, first lithium carbonate concentrate obtained
Grade reaches more than 90%.Such as, before salt enters, add the dilution of part light salt or addition of spraying in temperature-rise period is light
Water, it is possible to add fresh water in thermal insulation pool.
When using Wen Peng pond as temperature elevation system, it is provided that a Wen Peng pond, this Wen Peng pond includes cell body and closes this cell body
Diffuser, along the length direction of this cell body, the width of this cell body is gradually reduced, and the degree of depth of this cell body is gradually increased, this temperature
Temperature in canopy pond is higher 20 DEG C～50 DEG C than ambient temperature；When autumn and winter season and ambient temperature-30 DEG C～0 DEG C, by salt B edge
The length direction in described Wen Peng pond and import described Wen Peng pond from one end that the width of cell body is big, described salt B is in this Wen Peng pond
Big and depth as shallow the region of width of cell body carry out quick heat exchange, be rapidly heated, and quickly separate out batch lithium carbonate, as salt B
The region that the width of the cell body arriving this Wen Peng pond is little and the degree of depth is deep, salt B reaches stable through abundant heat-exchange temperature, and separates out
A large amount of lithium carbonate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains first lithium carbonate concentrate.
4th step, continues salt C freezing below-20 DEG C and separates out the salt-mixture I based on sodium carbonate and Borax, work as carbon
When acid group concentration is reduced to below 15g/L, when lithium concentration rises to more than 2g/L, carry out solid-liquid separation and obtain salt-mixture I and salt
D。
During Ben, the salt-mixture I obtained is mainly composed of sodium carbonate and Borax, can be used for preparing follow-up required carbonic acid
Ion concentration is at the high-carbon acid group salt of more than 60g/L, and its preparation process is: the salt-mixture I the 4th step obtained adds light
Water or dilute salt, the addition of described fresh water or dilute salt is the 50%～200% of described salt-mixture I mass, then in salt pan
Carry out solar evaporation, precipitated sodium chloride and potassium chloride, be enriched with carbanion, when carbon acid ion concentration reaches more than 60g/L
Time solid-liquid separation obtain high-carbon acid group salt.
5th step, after salt D continues evaporation, lithium concentration reaches 2.6g/L～3.5g/L again, adds above-mentioned acquisition
Carbon acid ion concentration after the high-carbon acid group salt of more than 60g/L, import (the intensification system with the 3rd step in temperature elevation system
Unite identical, or same temperature elevation system) heat up, when brine temperature rises to 20 DEG C～60 DEG C, separate out second batch lithium carbonate essence
Ore deposit, when in salt, lithium concentration is down to 1～2g/L, solid-liquid separation obtains second batch lithium carbonate concentrate and salt E.
Preferable temperature controls at 40 DEG C～50 DEG C, preferably close to 45 DEG C.
Obtaining second batch lithium carbonate concentrate, the grade of this concentrate is more than 60%.By precise controlling, i.e. limit and heat up
In system, the evaporation rate of the water yield is less than 10%, and the grade of the second batch lithium carbonate concentrate obtained can reach more than 90%.
Salt E after separating out second batch lithium carbonate concentrate imports the first step deep lake salt Tanaka and is circulated process, according to
This mode, through abundant circular treatment, the lithium ion in carbonate-type original salt A changes into the yield of lithium carbonate concentrate and is
More than 70%.
Compared with prior art, the invention have the advantages that
(1) present invention is based on the original salt of carbonate-type, by control evaporation process realize fast enriching lithium from
The purpose of son, the element of self in fully utilized carbonate type salt lake brine, do not additionally introduce any other reagent, it is achieved clear
Clean, environment protection-type produces, and has broken away from the dependence to other resource.
(2) after evaporation and concentration reaches 1.2g/L～1.8g/L to lithium concentration, the addition of deep lake salt field last stage is entered de-
Water Natrii Sulfas, and make dehydration Natrii Sulfas be dissolved in salt, and control sulfate ion concentration in salt, it is to avoid sulfate radical is follow-up
Producing lithium sulfate double salt, the control result of this process makes to freeze nitre process mirabilite hydrate high efficiency and separates out follow-up winter, 70%～
More than 90% Natrii Sulfas separates out, so that the whole process time shortens more than 2 months.
(3) about the several key points in pilot process.The control of lithium concentration, the control of sulfate ion concentration,
The control of warming temperature, the preparation limiting the carbonate salt of the fine processing of evaporation, more than 60g/L and addition etc..Work as evaporation
To lithium concentration to this scope of 1.2g/L～1.8g/L, and in evaporation process, according to the change feelings of site environment temperature
Condition, adjusts lithium concentration by adding the dilutest salt, controls the evaporation process of Bittern of Salt Pan flexibly.By the lithium in concentrated brine
Ion concentration controls in this scope of 1.2g/L～1.8g/L so that it is does not become salt in salt pan evaporation process, this situation is prolonged always
Continuing and proceed to autumn and winter in season, salt imports deep lake salt Tanaka and continues evaporation and concentration, treat to proceed to winter season, ambient temperature is not
Disconnected reduction, more than 70% mirabilite hydrate preferentially separates out from salt, thus takes rapidly mass crystallization water out of, and lithium concentration is rapid
Rising, the concentration controlling sulfate ion is reduced to during 4g/L～7g/L (preferably 6g/L～7g/L), and in salt, lithium ion is dense
Degree rises very rapidly up to 2.6g/L～3.5g/L, obtain after solid-liquid separation rich lithium carbonate brine B, salt B through intensification 20 DEG C～
Separate out first lithium carbonate concentrate after 60 DEG C, after solid-liquid separation, obtain salt C.Here first lithium carbonate concentrate is through limiting
The fine processing of evaporation, grade is up to more than 90%.Salt C separates out through continuing freezing lower temperature-20 DEG C with sodium carbonate
Be main salt-mixture I with Borax, and obtain salt D, after salt D is continued evaporation lithium concentration again reach 2.6g/L～
3.5g/L, adds in the carbonate salt importing temperature elevation system of more than 60g/L and separates out second batch carbonic acid after intensification 20 DEG C～60 DEG C
Lithium concentrate, second batch lithium carbonate concentrate here is through limiting the fine processing of evaporation, and grade is up to more than 90%.Through twice
Separate out lithium carbonate concentrate, a technological process, the yield that in the original salt of carbonate, elemental lithium extracts with lithium carbonate form up to
More than 70%.
(4) utilize solar temperature rising system, salt B is sprayed from top to bottom, simultaneously by 100 DEG C～the hot-air of 200 DEG C
Import from bottom to top in the lower section of salt B (the most also can level or the importing that is inclined upwardly) so that salt B and hot-air phase convection current
Dynamic fully carry out heat exchange, quick heat exchange, be rapidly heated after isothermal holding, thus quickly obtain crystallization of lithium carbonate body, significantly carry
Rise the precipitation rate of lithium carbonate.It addition, by limiting in temperature elevation system, the evaporation rate of the water yield is less than 10%, and the lithium carbonate obtained is smart
The grade in ore deposit reaches more than 90%.
(5) utilize Wen Peng pond as temperature elevation system, due to the gradient-structure feature bottom Wen Peng pond so that low temperature richness lithium carbon
Hydrochlorate type salt enters quickly heat exchange behind Wen Peng pond, is rapidly heated, thus quickly obtains crystallization of lithium carbonate body, is greatly promoted carbonic acid
The precipitation rate of lithium.
(6) it is worth mentioning that: after after salt D continuation evaporation, lithium concentration reaches 2.6g/L～3.5g/L again
Add the carbonate salt of more than 60g/L import temperature elevation system heats up separate out after 20 DEG C～60 DEG C second batch lithium carbonate concentrate this
During one, the preparation of the carbonate salt of more than 60g/L adds light entirely from the salt-mixture I self-produced by this technical process
Obtain after water or the evaporation of dilute salt back dissolving, it is not necessary to additionally buy.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (10)
1. the method preparing lithium carbonate from the carbonate type bittern of plateau, it includes step:
The first step, carbonate-type original salt A, before autumn and winter, is evaporated concentrating, and according to the change of environmental condition, no
Break and in evaporation and concentration salt, import fresh water or dilute salt to regulate lithium concentration so that lithium ion is not analysed with mineral forms
Go out, when lithium concentration reaches 1.2g/L～1.8g/L in salt, salt is imported the degree of depth deep lake salt more than or equal to 2m
Tanaka continue to evaporate dense go out；
Second step, along with proceeding to winter of highlands season, when ambient temperature is-15 DEG C～-5 DEG C, a large amount of mirabilite hydrates are excellent
First separating out, along with temperature continues to reduce and the precipitation of water of crystallization, Borax, sodium chloride, potassium chloride are also with aqueous salt or simple salt
Form separates out, and in the case, in salt, lithium concentration rises rapidly, and in salt, sulfate ion concentration refers to for control
Mark, when the concentration of sulfate ion is reduced to 4g/L～7g/L, in salt lithium concentration rise very rapidly up to 2.6g/L～
3.5g/L, obtains rich lithium carbonate brine B and mirabilite ore after solid-liquid separation；
3rd step, the rich lithium carbonate brine B obtained by second step imports in temperature elevation system and is warming up to 20 DEG C～60 DEG C, separates out the
A collection of lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains first lithium carbonate concentrate and halogen
Water C；
4th step, by salt C below-20 DEG C at a temperature of continue freezing and separate out based on the salt-mixture I of sodium carbonate and Borax,
When carbonate concentration is reduced to below 15g/L, when lithium concentration rises to more than 2g/L, carry out solid-liquid separation and obtain salt-mixture I
With salt D；
5th step, salt D continues evaporation, when lithium concentration reaches 2.6g/L～3.5g/L again, adds carbanion dense
The high-carbon acid group salt of degree more than 60g/L, imports in the temperature elevation system identical with temperature elevation system described in the 3rd step and is warming up to 20 DEG C
～60 DEG C, separating out second batch lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains second batch
Lithium carbonate concentrate and salt E.
2. the method for claim 1, it is characterised in that: the salt E obtained in described 5th step imports the deep of the first step
Lake salt Tanaka is circulated process, the lithium ion according to this mode, through abundant circular treatment, in carbonate-type original salt A
The flow process yield changing into lithium carbonate concentrate is more than 70%.
3. the method for claim 1, it is characterised in that: in the described first step, when being in autumn in season, ambient temperature
Higher, when salt minimum temperature is more than 5 DEG C, control lithium concentration importing deep lake salt field close to 1.2g/L.
4. the method for claim 1, it is characterised in that: in the described first step, when being in autumn in season, ambient temperature
Relatively low, when salt minimum temperature is below 0 DEG C, control lithium concentration importing deep lake salt field close to 1.8g/L.
5. the method for claim 1, it is characterised in that: in the described first step, proceeding to autumn when season, temperature starts fall
Time low, salt minimum temperature at 0 DEG C～5 DEG C, by lithium concentration the salt close to 1.2g/L first import the degree of depth less than or etc.
Shallow lake salt Tanaka in 0.5m continues evaporation and concentration, imports deep pond when being evaporated in salt lithium concentration close to 1.8g/L.
6. the method for claim 1, it is characterised in that: the temperature elevation system that in described 3rd step, salt B imports is the sun
Energy temperature elevation system, in this solar temperature rising system, temperature-rise period comprises the following steps:
Salt B is sprayed in solar temperature rising system from top to bottom, simultaneously by hot-air and the described halogen of 100 DEG C～200 DEG C
Water B is in opposite directions or crossing mode imports so that salt B carries out heat exchange with hot-air with the form of relative or crossing motion, from
And brine temperature rises very rapidly up to 20 DEG C～60 DEG C and flows in thermal insulation pool；
Described salt is incubated 2～48 hours in thermal insulation pool, constantly separates out lithium carbonate, treat that in salt, lithium concentration is down to
During 1g/L～2g/L, solid-liquid separation obtains lithium carbonate concentrate.
7. the method for claim 1, it is characterised in that: the temperature elevation system that in described 3rd step, salt B imports is temperature canopy
Pond, in this Wen Peng pond, temperature-rise period comprises the following steps:
Thering is provided a Wen Peng pond, this Wen Peng pond includes cell body and closes the diffuser of this cell body, along the length direction of this cell body, and this pond
The width of body is gradually reduced, and the degree of depth of this cell body is gradually increased, and the temperature in this Wen Peng pond is higher 20 DEG C～50 than ambient temperature
℃；
When autumn and winter season and ambient temperature-30 DEG C～0 DEG C, by salt B along the length direction in described Wen Peng pond and from cell body
One end that width is big imports described Wen Peng pond, and described salt B enters in big and depth as shallow the region of width of the cell body in this Wen Peng pond
The quick heat exchange of row, being rapidly heated, and quickly separate out lithium carbonate, the width of the cell body arriving this Wen Peng pond as salt B is little and the degree of depth
Deep region, salt B reaches stable through abundant heat-exchange temperature, and separates out a large amount of lithium carbonate, treats that in salt, lithium concentration is down to 1g/
During L～2g/L, solid-liquid separation obtains lithium carbonate concentrate.
8. the method as described in claim 1 or 6 or 7, it is characterised in that: in described 3rd step, salt B rises in temperature elevation system
Temperature is to 40 DEG C～50 DEG C.
9. the method for claim 1, it is characterised in that: in described 3rd step, by limiting the water yield in temperature elevation system
Evaporation rate is less than 10%, and the grade of first lithium carbonate concentrate obtained reaches more than 90%；In described 5th step, by limiting
In temperature elevation system, the evaporation rate of the water yield is less than 10%, and the grade of the second batch lithium carbonate concentrate obtained reaches more than 90%.
10. the method for claim 1, it is characterised in that: in described 5th step, described carbon acid ion concentration 60g/L
The preparation method of above salt is: the salt-mixture I the 4th step obtained adds fresh water or dilute salt, described fresh water or dilute salt
Addition is described salt-mixture I mass 50%～200%, then carry out solar evaporation, precipitated sodium chloride and chlorine in salt pan
Changing potassium, be enriched with carbanion, when carbon acid ion concentration reaches more than 60g/L, solid-liquid separation obtains high-carbon acid group salt.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640130A (en) * | 2018-06-26 | 2018-10-12 | 中国科学院青海盐湖研究所 | By the rough method for preparing lithium sulfate of salt lake sulfuric acid lithium salts |
| CN111470521A (en) * | 2020-05-25 | 2020-07-31 | 中国地质科学院矿产资源研究所 | Method for extracting lithium from solar cell |
| CN111620357A (en) * | 2020-03-18 | 2020-09-04 | 兰州天道提锂技术开发有限公司 | Floating type solar salt extraction lithium concentrate by matching photoelectric heating and continuous countercurrent heat exchange |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398785A (en) * | 2001-07-26 | 2003-02-26 | 陆增 | Method of extracting lithium carbonate from salt lake saline with high Mg/Li ratio |
| WO2013053165A1 (en) * | 2011-10-14 | 2013-04-18 | Chen Zhaohua | Method for production of lithium carbonate by applying multi-bittern-adding method, and using carbonate type bittern and sulfate type bittern as raw material |
| CN103086404A (en) * | 2011-11-08 | 2013-05-08 | 唐梓 | Preparation method of lithium carbonate by brine extraction with magnesium ion participating reaction |
| CN103553090A (en) * | 2013-11-15 | 2014-02-05 | 中国科学院青海盐湖研究所 | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy |
| CN103787374A (en) * | 2012-10-31 | 2014-05-14 | 西藏国能矿业发展有限公司 | Method for extracting lithium carbonate from salt lake bittern |
| CN103898341A (en) * | 2014-03-06 | 2014-07-02 | 中国科学院青海盐湖研究所 | Method for separating and extracting lithium from lithium sulfate coarse ore |
-
2016
- 2016-04-07 CN CN201610212760.8A patent/CN105905929B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398785A (en) * | 2001-07-26 | 2003-02-26 | 陆增 | Method of extracting lithium carbonate from salt lake saline with high Mg/Li ratio |
| WO2013053165A1 (en) * | 2011-10-14 | 2013-04-18 | Chen Zhaohua | Method for production of lithium carbonate by applying multi-bittern-adding method, and using carbonate type bittern and sulfate type bittern as raw material |
| CN103086404A (en) * | 2011-11-08 | 2013-05-08 | 唐梓 | Preparation method of lithium carbonate by brine extraction with magnesium ion participating reaction |
| CN103787374A (en) * | 2012-10-31 | 2014-05-14 | 西藏国能矿业发展有限公司 | Method for extracting lithium carbonate from salt lake bittern |
| CN103553090A (en) * | 2013-11-15 | 2014-02-05 | 中国科学院青海盐湖研究所 | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy |
| CN103898341A (en) * | 2014-03-06 | 2014-07-02 | 中国科学院青海盐湖研究所 | Method for separating and extracting lithium from lithium sulfate coarse ore |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640130A (en) * | 2018-06-26 | 2018-10-12 | 中国科学院青海盐湖研究所 | By the rough method for preparing lithium sulfate of salt lake sulfuric acid lithium salts |
| CN111620357A (en) * | 2020-03-18 | 2020-09-04 | 兰州天道提锂技术开发有限公司 | Floating type solar salt extraction lithium concentrate by matching photoelectric heating and continuous countercurrent heat exchange |
| CN111470521A (en) * | 2020-05-25 | 2020-07-31 | 中国地质科学院矿产资源研究所 | Method for extracting lithium from solar cell |
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