CN105883862B - The method that lithium carbonate is prepared from the carbonate type bittern of plateau - Google Patents
The method that lithium carbonate is prepared from the carbonate type bittern of plateau Download PDFInfo
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Abstract
The invention discloses a kind of method that lithium carbonate is prepared in carbonate type bittern from plateau, it includes step:The first step, the original bittern A of carbonate-type are evaporated concentration, and adjust lithium concentration before autumn and winter so that lithium ion is not separated out with mineral forms, when lithium concentration reaches 1.2g/L~1.8g/L in bittern, is imported deep lake salt Tanaka and is continued to be concentrated by evaporation;Second step, when environment temperature is 15 DEG C~5 DEG C, a large amount of mirabilite hydrates preferentially separate out, lithium concentration rises rapidly in bittern, when the concentration of sulfate ion is reduced to 4g/L~7g/L, lithium concentration rises very rapidly up to 2.6g/L~3.5g/L in bittern, and rich lithium carbonate brine B is obtained after separation of solid and liquid;3rd step, bittern B is imported in temperature elevation system and is warming up to 20 DEG C~60 DEG C, separate out carbonic acid lithium concentrate.
Description
Technical field
The present invention relates to the utilization methods of carbonate type bittern, more particularly to one kind is from the carbonate type bittern of plateau
The method for preparing lithium carbonate.
Background technology
Tibet region salt lake resources are developed most it is difficult to chemical processing plant (CPP) can not be built in lake region, moreover, distance possesses
Industrial processes ability it is local remote, therefore, can only lake region obtain high-grade mineral after transport processing, its core seeks to profit
Serial salt pan mineral are obtained by building salt pan with local natural environment.
Mainly there are carbonate-type and the major class of sulfate type two in the boron-rich lithium salts lake in Tibet.Early stage, for the boron-rich lithium of sulfate type
The exploitation in salt lake, it is proposed that freezing removes the main process that nitre-potassium is analysed in evaporation-is diluted to boron of saltouing-evaporation analysis lithium.And to carbonate
The exploitation in the boron-rich lithium salts lake of type, problems faced are due to the solubility properties of lithium carbonate, it is difficult to are enriched to lithium carbonate higher
Concentration, Zha Buye exploitation technique be using freezing except nitre-evaporation enriching lithium-using solar pond heating analysis lithium carbonate technique,
The technique realizes full clean manufacturing, has obtained preferable carbonic acid lithium minerals, but lithium ion enrichment degree is relatively low in bittern, limitation
The yield that lithium separates out;Solar pond is cumbersome, production cycle length;Other resources are not utilized in addition to lithium.By knot then
The geographical position in tea card (carbonate-type) and wrong (sulfate type) Hubei and Hunan Provinces of dragon wood (air line distance about 70km) nearby, the utilization of exploitation
Carbonate-type and the boron-rich lithium salts lake bittern water coupling technique of two kinds of sulfate type, can solve sulfate type salt lake magnesium/lithium than high, carbon
The problem of hydrochlorate type salt lake lithium is difficult to be enriched with, and lithium is enriched to higher concentration, but on the one hand, there is this rare environmental condition
Two kinds of salt lake quantity it is limited after all;On the other hand, a large amount of carbonates are consumed during two kinds of salt lake coupling exploitations, and produced relatively large
Magnesium carbonate, it is not necessarily sufficient to cause to provide the carbonate of production lithium carbonate in carbonate type salt lake, to the steady of salt lake resources
Fixed production causes necessarily to influence.Therefore, circulating life is realized merely with the element of itself in carbonate-type boron lithium salts lake as far as possible
Production, and the dependence to other resources is broken away from, it is the fabulous approach of Tibet plateau carbonate type salt lake development of resources.
The content of the invention
Therefore, the present invention provides a kind of method that lithium carbonate is prepared in carbonate type bittern from plateau.
A kind of method that lithium carbonate is prepared in carbonate type bittern from plateau, it includes step:
The first step, the original bittern A of carbonate-type in the fall before, be evaporated concentration, and according to the change of environmental condition,
Fresh water or dilute bittern constantly are imported to adjust lithium concentration into evaporation and concentration bittern so that lithium ion is not analysed with mineral forms
Go out, when lithium concentration reaches 1.2g/L~1.8g/L in bittern, bittern is imported into deep lake salt of the depth more than or equal to 2m
Tanaka continues to be concentrated by evaporation, and the bittern first passes through a salt pond for being stacked with dehydration saltcake during bittern to be imported to deep pond,
Control enters concentration 20g/L~30g/L of sulfate ion in deep pond bittern;
Second step, as season is transferred to the winter of highlands, when environment temperature is -15 DEG C~-5 DEG C, a large amount of ten water awns
Nitre preferentially separates out, and as temperature continues to reduce the precipitation with the crystallization water, borax, sodium chloride, potassium chloride are also with aqueous salt or simple
The form of salt separates out, and in the case, lithium concentration rises rapidly in bittern, using sulfate ion concentration in bittern as control
Index, when the concentration of sulfate ion is reduced to 4g/L~7g/L, in bittern lithium concentration rise very rapidly up to 2.6g/L~
3.5g/L, obtain after separation of solid and liquid rich lithium carbonate brine B and mirabilite ore (based on mirabilite hydrate, mass content accounts for 70%~
More than 90%, remaining is contaminated with a small amount of borax, sodium chloride, potassium chloride);
3rd step, the rich lithium carbonate brine B that second step obtains is imported in temperature elevation system and is warming up to 20 DEG C~60 DEG C, analysis
Go out carbonic acid lithium concentrate, the grade of the carbonic acid lithium concentrate is more than 60%.
Preferably, the dehydration saltcake in the first step is that the mirabilite hydrate that freezing and crystallizing separates out is dehydrated to obtain by weathering
Thenardite or partially dehydrated saltcake.
Preferably, in the first step, when lithium concentration is close to 1.5g/L in bittern, bittern is imported into the depth
Deep lake salt Tanaka more than or equal to 2m continues to be concentrated by evaporation.
Preferably, in the first step, when being in autumn in season, environment temperature is higher, bittern minimum temperature 5 DEG C with
When upper, lithium concentration control was being imported into deep lake salt field close to 1.2g/L (1.2g/L~1.5g/L).
Preferably, in the first step, when being in autumn in season, environment temperature is relatively low, bittern minimum temperature 0 DEG C with
When lower, lithium concentration control is being imported into deep lake salt field close to 1.8g/L (1.5g/L~1.8g/L).
Preferably, in the first step, when season is transferred to autumn, and temperature starts to reduce, bittern minimum temperature 0 DEG C~
5 DEG C, lithium concentration is first imported into shallow lake salt Tanaka of the depth less than or equal to 0.5m in the bittern close to 1.2g/L and continues to steam
Hair concentration, deep pond is imported when being evaporated in bittern lithium concentration close to 1.8g/L.
Preferably, the temperature elevation system that bittern B is imported in the 3rd step is solar temperature rising system, in the solar temperature rising
Temperature-rise period comprises the following steps in system:Bittern B is sprayed from top to bottom in solar temperature rising system, while by 100 DEG C
~200 DEG C of hot-air and the bittern B are opposite or the mode that intersects imports so that bittern B and hot-air are with relative or intersecting
The form of motion carries out heat exchange, so as to which brine temperature rises very rapidly up to 20 DEG C~60 DEG C and flowed into thermal insulation pool;By the halogen
Water is incubated 2~48 hours in thermal insulation pool, constantly separates out lithium carbonate, consolidates when lithium concentration in bittern is down to 1g/L~2g/L
The isolated carbonic acid lithium concentrate of liquid.
Preferably, the temperature elevation system that bittern B is imported in the 3rd step is Wen Peng ponds, the temperature-rise period bag in the Wen Peng ponds
Include following steps:A Wen Peng ponds are provided, the Wen Peng ponds include pond body and close the diffuser of the pond body, along the length side of the pond body
To the width of the pond body is gradually reduced, and the depth of the pond body gradually increases, and the temperature in the Wen Peng ponds is higher than ambient temperature by 20
DEG C~50 DEG C;In autumn and winter and -30 DEG C of environment temperature~0 DEG C, by length directions of the bittern B along the Wen Peng ponds and from pond
The big one end of the width of body imports the Wen Peng ponds, and the width of pond bodies of the bittern B in the Wen Peng ponds is big and the area of depth as shallow
Domain is quickly exchanged heat, is rapidly heated, and quickly separates out lithium carbonate, when bittern B reach the pond body in the Wen Peng ponds width it is small and
The deep region of depth, bittern B reaches stable by abundant heat-exchange temperature, and separates out a large amount of lithium carbonates, treats that lithium concentration drops in bittern
Carbonic acid lithium concentrate is obtained to separation of solid and liquid during 1g/L~2g/L.
Preferably, bittern B is warming up to 40 DEG C~50 DEG C in temperature elevation system in the 3rd step.
Preferably, in the 3rd step, it is less than 10% by the evaporation rate for limiting water in temperature elevation system, obtained carbonic acid
The grade of lithium concentrate reaches more than 90%.
Compared with prior art, the present invention has advantages below:
(1) present invention based on the original bittern of carbonate-type, by control evaporation process realize fast enriching lithium from
The purpose of son, the element of itself in carbonate type salt lake brine is fully utilized, does not additionally introduce other reagents, realize cleaning, ring
Guarantor's formula produces, and has broken away from the dependence to other resources.
(2) it is de- to enter the addition of deep lake salt field last stage after evaporation and concentration reaches 1.2g/L~1.8g/L to lithium concentration
Water saltcake, and dehydration saltcake is dissolved into bittern, and sulfate ion concentration in bittern is controlled, avoid sulfate radical excessively follow-up
Lithium sulfate double salt is produced, the control result of the process causes follow-up winter to freeze nitre process mirabilite hydrate high efficiency and separate out, 70%~
More than 90% saltcake separates out, so that the whole process time shortens more than 2 months.
(3) key point controlled on lithium concentration in pilot process.Be evaporated to lithium concentration to 1.2g/L~
This scope of 1.8g/L, and in evaporation process, according to the situation of change of site environment temperature, adjusted by adding slightly dilute bittern
Lithium concentration, flexibly control the evaporation process of Bittern of Salt Pan.By in concentrated brine lithium concentration control 1.2g/L~
This scope of 1.8g/L, make it in salt pan evaporation process not into salt, this situation continued up into season is transferred to autumn and winter, by halogen
Water, which imports deep lake salt Tanaka, to be continued to be concentrated by evaporation, when environment temperature constantly reduces, into winter after in bittern more than 70% ten
Water saltcake preferentially separates out from bittern, so as to take mass crystallization water out of rapidly, as temperature continues to reduce the precipitation with the crystallization water,
Borax, sodium chloride, potassium chloride etc. are also separated out in the form of aqueous salt or simple salt, due to lithium ion in the precipitation bittern of these salt
Concentration rises rapidly, when controlling the concentration of sulfate ion to be reduced to 4g/L~7g/L (preferably 6g/L~7g/L), in bittern
Lithium concentration rises very rapidly up to 2.6g/L~3.5g/L, and rich lithium carbonate brine is obtained after separation of solid and liquid, the rich lithium carbonate
Bittern prepares high-grade carbonic acid lithium concentrate after can be used for heating or heating.Here, the concentration of sulfate ion is preferably controlled in
During 6g/L~7g/L, and treat that lithium concentration rises to 2.6g/L~3.5g/L in bittern, carries out separation of solid and liquid, obtained rich lithium
Carbonate brine, subsequently preparing the lithium carbonate yield obtained when carbonic acid lithium concentrate can be higher.
(4) solar temperature rising system is utilized, bittern B is sprayed from top to bottom, while by 100 DEG C~200 DEG C of hot-air
Imported from bottom to top in bittern B lower section (certainly also can horizontal or importings that be inclined upwardly) so that bittern B and the relative stream of hot-air
It is dynamic fully to carry out heat exchange, quickly exchange heat, be rapidly heated after isothermal holding, so as to quickly obtain crystallization of lithium carbonate body, carry significantly
Rise the precipitation rate of lithium carbonate.In addition, it is less than 10% by the evaporation rate for limiting water in temperature elevation system, obtained lithium carbonate essence
The grade of ore deposit reaches more than 90%.
(5) by the use of Wen Peng ponds as temperature elevation system, due to the gradient-structure feature in warm canopy bottom of pond portion so that low temperature richness lithium carbon
Hydrochlorate type bittern quickly exchanges heat after entering Wen Peng ponds, is rapidly heated, and so as to quickly obtain crystallization of lithium carbonate body, greatly promotes carbonic acid
The precipitation rate of lithium.
Embodiment
For the objects, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, to this hair
It is bright to be described in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit
The present invention.
The present invention is directed to Qinghai-Tibet social economy and nature feature, proposes to realize using natural energy, bittern composition
The method that carbonate type salt lake produces multi mineral, to illustrate the feasibility of this method, example is utilized as with Lake Jiezechaka, can
To understand, the invention is applicable not only to the exploitation of Lake Jiezechaka, the salt lake resources for being also applied for having under the conditions of similar environments
Exploitation.
The method that lithium carbonate is prepared from the carbonate type bittern of plateau of the present invention is described step by step below.
The first step, the original bittern A of carbonate-type in the fall before, be evaporated concentration, and according to the change of environmental condition,
Fresh water or dilute bittern constantly are imported to adjust lithium concentration into evaporation and concentration bittern so that lithium ion is not analysed with mineral forms
Go out, when lithium concentration reaches 1.2g/L~1.8g/L in bittern, bittern is imported into deep lake salt of the depth more than or equal to 2m
Tanaka continues to be concentrated by evaporation, and the bittern first passes through a salt pond for being stacked with dehydration saltcake during bittern to be imported to deep pond,
Control enters concentration 20g/L~30g/L of sulfate ion in deep pond bittern, and constantly to deep lake salt field in the evaporation process
It is middle to import fresh water or dilute bittern to adjust lithium concentration so that lithium ion is not separated out with mineral forms.
Original bittern A is evaporated, can be passed to be stacked with the salt pan for being dehydrated saltcake after concentration process, detects simultaneously
The concentration of sulfate ion in bittern, (avoiding excessive concentration or too low).Dehydration saltcake adds so that bittern exists in this step
During flowing through dehydration saltcake, dehydration saltcake absorbs the moisture content in bittern, is gradually transformed into mirabilite hydrate, while has part de-
The dissolving of water saltcake enters in bittern, and follow-up winter freezes nitre process mirabilite hydrate high efficiency and separated out, and takes mass crystallization water out of, carries rapidly
Lithium enrichment rate is risen, so that the whole process time shortens more than 2 months.It can be ten that freezing and crystallizing separates out to be dehydrated saltcake
Water saltcake is dehydrated obtained thenardite or partially dehydrated saltcake after weathering.These saltcake can utilize carbonate brine to handle
The saltcake that process salt pan voluntarily produces, without outsourcing.The saltcake that salt pan voluntarily produces need to be only deposited directly on without especially handling
Somewhere, it is dehydrated, either dehydration or partially dehydrated completely, is can use in this step by weathering.Saltcake is dehydrated to add
Process, the concentration range for controlling sulfate ion are crucial.Dehydration saltcake, which adds, excessively can cause sulfate ion to increase easily
Cause to produce lithium sulfate complex salt, so as to influence subsequently to be enriched with lithium ion.And it is inadequate to be dehydrated saltcake addition, subsequently freezing nitre mistake
Journey, mirabilite hydrate eduction rate is low to be influenceed to be concentrated by evaporation speed, delay the speed of enriching lithium process.
It is above-mentioned deep lake salt field is imported when lithium concentration reaches 1.2g/L~1.8g/L procedure declaration it is as follows:First,
Optium concentration by lot of experiments checking lithium ion is 1.5g/L, and actual production process lithium concentration is close to 1.5g/L
Preferable effect is obtained, such as is preferable condition between 1.45g/L~1.55g/L.Secondly, in actual production process, according to season
Section is different, and the height of environment temperature is, it is necessary to which the lithium concentration of control can change.Until season is transferred to autumn, although
Autumn, but environment temperature is not perhaps stable state, i.e. and environment temperature may be higher, it is also possible to relatively low, it should among reality
When the temperature of bittern imports deep lake salt field to control.Experiment law is summarized to find, when season is transferred to autumn, environment temperature compared with
Height, when bittern minimum temperature is more than 5 DEG C, lithium concentration can be controlled and import deep lake salt field close to 1.2g/L, for example,
1.2g/L~1.5g/L;Autumn is transferred to when season, environment temperature is relatively low, can control lithium concentration and be imported close to 1.8g/L
Deep lake salt field, for example, 1.5g/L~1.8g/L.No matter how environment temperature changes during the seasonal variations of plateau, control lithium from
Sub- concentration is that lithium separates out not in the form of carbonic acid lithium minerals for the foundation of which scope.
Dilute bittern in the first step uses the original bittern of carbonate-type, and wherein lithium concentration is close to 0.16g/L;Or
Certain phase is concentrated to using from the original bittern evaporation of carbonate-type, wherein lithium concentration is less than 1.2g/L bittern.This is specially
Dilute bittern mentioned by profit application context is dilute bittern defined in this section.
Highlands spring and summer environment temperature is -10 DEG C~20 DEG C, and autumn and winter environment temperature is -30 DEG C~0 DEG C.
The composition of the original bittern of carbonate type salt lake is as shown in following table one:
The composition of the original bittern of the carbonate type salt lake of table one
From above-mentioned table one:The original bittern A of carbonate type salt lake composition is:B2O3For 0.1~3g/L, Li is 0.1~
2g/L, K are 1~30g/L, and Na is 10~120g/L, and Mg is 0.01~20g/L, SO4 2-For 1~40g/L, CO3For 1~120g/
L, Br are 0.01~0.50g/L, and Cl is 20~300g/L.
In the most of the time of whole year, carbonate type salt lake original bittern in plateau can be pumped into salt pan and carry out Exposure to Sunlight
Evaporation.In the present embodiment, from Lake Jiezechaka lake water, because the lake lake water is than thin (i.e. fresh water content is high), to avoid freezing
Operation is influenceed, should try one's best and avoid taking halogen in the winter time.Therefore, in the present embodiment, bittern is taken to carry out test operation in spring and summer season.Table
Two give Lake Jiezechaka Bittern of Salt Pan 2014~2015 years scene evaporation data.
The Lake Jiezechaka Bittern of Salt Pan of table two evaporation liquid phase composition
Be attached in specific experiment, referring to table two, take within 2 11st, 2014 Lake Jiezechaka Bittern of Salt Pan analyze, lithium from
Sub- initial concentration is 0.24g/L, since this day solar evaporation, over time, lithium concentration is with bittern
Constantly evaporate and be gradually increasing, during 2014.9.20~2014.11.8 has been arrived, lithium concentration has about risen to 1.2g/
L~1.8g/L scopes, the deep lake salt Tanaka that depth is more than or equal to 2m is imported, continues to be concentrated by evaporation.
During the stage for being dehydrated saltcake addition can be 2014.-7.12~2014.11.8, the detailed process of addition can be with
It is (but not limited to):Dehydration saltcake is stacked into a processing pond porch, by lithium concentration 1.2g/L~1.8g/L scopes
Enriched carbonate type bittern break through dehydration saltcake after enter processing pond, the concentration of sulfate ion in detection process pond, from
And the addition of dehydration saltcake is controlled, dehydration saltcake, which adds, can excessively cause sulfate ion increases easily to cause to produce lithium sulfate
Complex salt, so as to influence subsequently to be enriched with lithium ion.And it is inadequate to be dehydrated saltcake addition, subsequently freezing nitre process, mirabilite hydrate analysis
Extracting rate is low to be influenceed to be concentrated by evaporation speed, delay the speed of enriching lithium process.Therefore this stage, the concentration of sulfate ion is controlled
It is crucial for how many scope.
According to lithium concentration in temperature Change situation and concentrated brine, be able to will be concentrated before deep lake salt field is entered
Bittern, which imports shallow lake salt Tanaka of the depth less than or equal to 0.5m, to be continued to be concentrated by evaporation, or is importing directly into deep lake salt Tanaka evaporation
Concentration.Depending on the annual seasonal temperature situation of change in Salt Lake Area, autumn is transferred to when season, when temperature starts to reduce, bittern
Minimum temperature at 0 DEG C -5 DEG C, lithium concentration close to 1.2g/L (1.2g/L~1.5g/L) bittern first import depth be less than or
Shallow lake salt Tanaka equal to 0.5m continues to be concentrated by evaporation, be evaporated in bittern lithium concentration close to 1.8g/L (1.5g/L~
Deep lake salt Tanaka is imported when 1.8g/L);
Autumn is transferred to when season, but when environment temperature is relatively low, bittern minimum temperature is below 0 DEG C, by lithium ion content
Control is introduced directly into deep lake salt Tanaka in the bittern close to 1.8g/L (1.5g/L~1.8g/L) and is concentrated by evaporation.
Autumn is in when season, environment temperature is higher, and when bittern minimum temperature is more than 5 DEG C, lithium concentration is controlled
Deep lake salt field is introduced directly into the bittern close to 1.2g/L (1.2g/L~1.5g/L).
Second step, as season is transferred to the winter of highlands, when environment temperature is -15 DEG C~-5 DEG C, a large amount of ten water awns
Nitre preferentially separates out, and as temperature continues to reduce the precipitation with the crystallization water, borax, sodium chloride, potassium chloride are also with aqueous salt or simple
The form of salt separates out, and in the case, lithium concentration rises rapidly in bittern, using sulfate ion concentration in bittern as control
Index, when the concentration of sulfate ion is reduced to 4g/L~7g/L, in bittern lithium concentration rise very rapidly up to 2.6g/L~
3.5g/L, rich lithium carbonate brine B and mirabilite ore are obtained after separation of solid and liquid.
For mirabilite ore based on mirabilite hydrate, mass content accounts for more than 70%~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 bittern on lithium concentration
2.6g/L~3.5g/L is risen to, separation of solid and liquid is carried out, obtained rich lithium carbonate brine, is obtained when subsequently preparing carbonic acid lithium concentrate
The lithium carbonate yield obtained can be higher.
It is attached in specific experiment, as shown in Table 2, in the bittern between December 14~28 days January in 2015 in 2014
Lithium concentration is all higher than 2.6g/L and is less than 3.5g/L, for example, 3.36g/L, 3.39g/L;Some be even more more than 3.5g/L,
Other are it was found that, lithium concentration can reach 3.9g/L in bittern.Such rich lithium carbonate brine by heating at
Reason can obtain high-grade carbonic acid lithium concentrate.
3rd step, the rich lithium carbonate brine B that second step obtains is imported in temperature elevation system and is warming up to 20 DEG C~60 DEG C, analysis
Go out carbonic acid lithium concentrate, the grade of the carbonic acid lithium concentrate is more than 60%.Preferable temperature is controlled at 40 DEG C~50 DEG C, preferably close to 45
℃。
The temperature elevation system can be solar temperature rising system, Wen Peng ponds or solar pond.
When using solar temperature rising system, bittern B temperature-rise period comprises the following steps:First, by bittern B in the sun
It can spray from top to bottom in temperature elevation system, while side that is 100 DEG C~200 DEG C of hot-air and the bittern B is opposite or intersecting
Formula imports so that bittern B and hot-air carry out heat exchange in the form of relative or intersecting motion, so as to which brine temperature rises rapidly
To 20 DEG C~60 DEG C and flow into thermal insulation pool;Secondly, the bittern is incubated 2~48 hours in thermal insulation pool, constantly separates out carbon
Sour lithium, separation of solid and liquid obtains carbonic acid lithium concentrate when lithium concentration is down to 1g/L~2g/L in bittern.
It is less than 10% by the evaporation rate for limiting water in solar temperature rising system, the grade of obtained carbonic acid lithium concentrate reaches
To more than 90%.Such as added before bittern enters part light bittern dilution or in temperature-rise period spraying add fresh water, also can be
Fresh water is added in thermal insulation pool.
When using Wen Peng ponds as temperature elevation system, there is provided a Wen Peng ponds, the Wen Peng ponds include pond body and close the pond body
Diffuser, along the length direction of the pond body, the width of the pond body is gradually reduced, and the depth of the pond body gradually increases, the temperature
Temperature in canopy pond is higher than ambient temperature 20 DEG C~50 DEG C;In autumn and winter and -30 DEG C of environment temperature~0 DEG C, by bittern B edges
The length direction in the Wen Peng ponds and the Wen Peng ponds are imported from the big one end of the width of pond body, the bittern B is in the Wen Peng ponds
Pond body width it is big and the region of depth as shallow is quickly exchanged heat, is rapidly heated, and lithium carbonate is quickly separated out, when bittern B is arrived
The region that width up to the pond body in the Wen Peng ponds is small and depth is deep, bittern B reach stable by abundant heat-exchange temperature, and separate out big
Lithium carbonate is measured, separation of solid and liquid obtains carbonic acid lithium concentrate when lithium concentration is down to 1g/L~2g/L in bittern.
Compared with prior art, the present invention has advantages below:
(1) present invention based on the original bittern of carbonate-type, by control evaporation process realize fast enriching lithium from
The purpose of son, the element of itself in carbonate type salt lake brine is fully utilized, does not additionally introduce any other reagent, realize clear
Clean, environment protection-type production, has broken away from the dependence to other resources.
(2) it is de- to enter the addition of deep lake salt field last stage after evaporation and concentration reaches 1.2g/L~1.8g/L to lithium concentration
Water saltcake, and dehydration saltcake is dissolved into bittern, and sulfate ion concentration in bittern is controlled, avoid sulfate radical excessively follow-up
Lithium sulfate double salt is produced, the control result of the process causes follow-up winter to freeze nitre process mirabilite hydrate high efficiency and separate out, 70%~
More than 90% saltcake separates out, so that the whole process time shortens more than 2 months.
(3) key point controlled on lithium concentration in pilot process.When be evaporated to lithium concentration to 1.2g/L~
This scope of 1.8g/L, and in evaporation process, according to the situation of change of site environment temperature, adjusted by adding slightly dilute bittern
Lithium concentration, flexibly control the evaporation process of Bittern of Salt Pan.By in concentrated brine lithium concentration control 1.2g/L~
This scope of 1.8g/L, make it in salt pan evaporation process not into salt, this situation continued up into season is transferred to autumn and winter, by halogen
Water, which imports deep lake salt Tanaka, to be continued to be concentrated by evaporation, and environment temperature constantly reduces, and more than 70% water saltcake preferentially separates out from bittern,
So as to take mass crystallization water out of rapidly, as temperature continues to reduce the precipitation, borax, sodium chloride, potassium chloride etc. with the crystallization water
Separated out in the form of aqueous salt or simple salt, because lithium concentration rises rapidly in the precipitation bittern of these salt, control sulfuric acid
When the concentration of radical ion is reduced to 4g/L~7g/L (preferably 6g/L~7g/L), lithium concentration rises very rapidly up in bittern
2.6g/L~3.5g/L, rich lithium carbonate brine is obtained after separation of solid and liquid, the rich lithium carbonate brine can be used for heating or heating up
After prepare high-grade carbonic acid lithium concentrate.Here, when the concentration of sulfate ion is preferably controlled in 6g/L~7g/L, and bittern is treated
Middle lithium concentration rises to 2.6g/L~3.5g/L, carries out separation of solid and liquid, obtained rich lithium carbonate brine, subsequently prepares carbon
The lithium carbonate yield obtained when sour lithium concentrate can be higher.
(4) solar temperature rising system is utilized, bittern B is sprayed from top to bottom, while by 100 DEG C~200 DEG C of hot-air
Imported from bottom to top in bittern B lower section (certainly also can horizontal or importings that be inclined upwardly) so that bittern B and the relative stream of hot-air
It is dynamic fully to carry out heat exchange, quickly exchange heat, be rapidly heated after isothermal holding, so as to quickly obtain crystallization of lithium carbonate body, carry significantly
Rise the precipitation rate of lithium carbonate.In addition, it is less than 10% by the evaporation rate for limiting water in temperature elevation system, obtained lithium carbonate essence
The grade of ore deposit reaches more than 90%.
(5) by the use of Wen Peng ponds as temperature elevation system, due to the gradient-structure feature in warm canopy bottom of pond portion so that low temperature richness lithium carbon
Hydrochlorate type bittern quickly exchanges heat after entering Wen Peng ponds, is rapidly heated, and so as to quickly obtain crystallization of lithium carbonate body, greatly promotes carbonic acid
The precipitation rate of lithium.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (9)
1. preparing the method for lithium carbonate in a kind of carbonate type bittern from plateau, it includes step:
The first step, the original bittern A of carbonate-type in the fall before, be evaporated concentration, and according to the change of environmental condition, constantly
Fresh water or dilute bittern are imported to adjust lithium concentration to being concentrated by evaporation in bittern so that lithium ion is not separated out with mineral forms,
When lithium concentration reaches 1.2g/L~1.8g/L in bittern, bittern is imported into deep lake salt Tanaka of the depth more than or equal to 2m
Continuing to be concentrated by evaporation, the bittern first passes through a salt pond for being stacked with dehydration saltcake during bittern to be imported to deep lake salt field,
Control enters concentration 20g/L~30g/L of sulfate ion in deep pond Bittern of Salt Pan;
Second step, as season is transferred to the winter of highlands, when environment temperature is -15 DEG C~-5 DEG C, a large amount of mirabilite hydrates are excellent
First separate out, as temperature continues to reduce and the precipitation of the crystallization water, borax, sodium chloride, potassium chloride are also with aqueous salt or simple salt
Form separates out, and in the case, lithium concentration rises rapidly in bittern, is referred to using sulfate ion concentration in bittern as control
Mark, when the concentration of sulfate ion is reduced to 4g/L~7g/L, in bittern lithium concentration rise very rapidly up to 2.6g/L~
3.5g/L, rich lithium carbonate brine B and mirabilite ore are obtained after separation of solid and liquid;
3rd step, the rich lithium carbonate brine B that second step obtains is imported in temperature elevation system and is warming up to 20 DEG C~60 DEG C, separates out carbon
Sour lithium concentrate, the grade of the carbonic acid lithium concentrate is more than 60%.
2. the method as described in claim 1, it is characterised in that:In the first step, when lithium concentration approaches in bittern
During 1.5g/L, bittern is imported into deep lake salt Tanaka of the depth more than or equal to 2m and continues to be concentrated by evaporation.
3. the method as described in claim 1, it is characterised in that:In the first step, when being in autumn in season, environment temperature
It is higher, when bittern minimum temperature is more than 5 DEG C, lithium concentration control is being imported into deep lake salt field close to 1.2g/L.
4. the method as described in claim 1, it is characterised in that:In the first step, when being in autumn in season, environment temperature
Relatively low, bittern minimum temperature is importing deep lake salt field below 0 DEG C, by lithium concentration control close to 1.8g/L.
5. the method as described in claim 1, it is characterised in that:In the first step, autumn is transferred to when season, temperature starts to drop
Low, bittern minimum temperature first imports depth in the bittern close to 1.2g/L at 0 DEG C~5 DEG C, by lithium concentration and is less than or equal to
0.5m shallow lake salt Tanaka continues to be concentrated by evaporation, and deep pond is imported when being evaporated in bittern lithium concentration close to 1.8g/L.
6. the method as described in claim 1, it is characterised in that:The temperature elevation system that bittern B is imported in 3rd step is the sun
Energy temperature elevation system, temperature-rise period comprises the following steps in the solar temperature rising system:
Bittern B is sprayed from top to bottom in solar temperature rising system, while by 100 DEG C~200 DEG C of hot-air and the halogen
Mode opposite or intersecting water B imports so that and bittern B and hot-air carry out heat exchange in the form of relative or intersecting motion, from
And brine temperature rises very rapidly up to 20 DEG C~60 DEG C and flowed into thermal insulation pool;
The bittern is incubated 2~48 hours in thermal insulation pool, constantly separates out lithium carbonate, treats that lithium concentration is down in bittern
Separation of solid and liquid obtains carbonic acid lithium concentrate during 1g/L~2g/L.
7. the method as described in claim 1, it is characterised in that:The temperature elevation system that bittern B is imported in 3rd step is warm canopy
Pond, temperature-rise period comprises the following steps in the Wen Peng ponds:
A Wen Peng ponds are provided, the Wen Peng ponds include pond body and close the diffuser of the pond body, along the length direction of the pond body, the pond
The width of body is gradually reduced, and the depth of the pond body gradually increases, and the temperature in the Wen Peng ponds is higher than ambient temperature by 20 DEG C~50
℃;
In autumn and winter and -30 DEG C of environment temperature~0 DEG C, by length directions of the bittern B along the Wen Peng ponds and from pond body
The big one end of width imports the Wen Peng ponds, and the width of pond bodies of the bittern B in the Wen Peng ponds is big and the region of depth as shallow is entered
Row quickly exchanges heat, is rapidly heated, and quickly separates out lithium carbonate, when bittern B reach the pond body in the Wen Peng ponds width is small and depth
Deep region, bittern B reaches stable by abundant heat-exchange temperature, and separates out a large amount of lithium carbonates, treats that lithium concentration is down to 1g/ in bittern
Separation of solid and liquid obtains carbonic acid lithium concentrate during L~2g/L.
8. the method as described in claim 1 or 6 or 7, it is characterised in that:Bittern B rises in temperature elevation system in 3rd step
Temperature is to 40 DEG C~50 DEG C.
9. the method as described in claim 1, it is characterised in that:In 3rd step, by limiting water in temperature elevation system
Evaporation rate is less than 10%, and the grade of obtained carbonic acid lithium concentrate reaches more than 90%.
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