CN105858693A - Method for preparing high-purity magnesium carbonate from plateau carbonate-type brine - Google Patents
Method for preparing high-purity magnesium carbonate from plateau carbonate-type brine Download PDFInfo
- Publication number
- CN105858693A CN105858693A CN201610212584.8A CN201610212584A CN105858693A CN 105858693 A CN105858693 A CN 105858693A CN 201610212584 A CN201610212584 A CN 201610212584A CN 105858693 A CN105858693 A CN 105858693A
- Authority
- CN
- China
- Prior art keywords
- salt
- lithium
- concentration
- brine
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Seasonings (AREA)
Abstract
The invention discloses a method for preparing high-purity magnesium carbonate from plateau carbonate-type brine. The method comprises the following steps: 1. before autumn and winter, carbonate-type original brine A is evaporated and the lithium ion concentration is regulated so that lithium ions do not precipitate in the form of minerals, and when the lithium ion concentration in the brine reaches 1.2-1.8 g/L, the brine is introduced into a deep tank salt field to continue evaporation; 2. when the ambient temperature is -15 to -5 DEG C, abundant mirabilite decahydrate preferentially precipitates, and the lithium ion concentration in the brine quickly increases; when the sulfate ion concentration drops to 4-7 g/L, the lithium ion concentration in the brine quickly increases to 2.6-3.5 g/L, and solid-liquid separation is carried out to obtain brine B; 3. the brine B is heated to 20-60 DEG C to separate out lithium carbonate concentrate, and when the lithium concentration in the brine drops to 1-2 g/L, solid-liquid separation is carried out to obtain brine C; and 4. when the ambient temperature is higher than 0 DEG C, the brine C is mixed with high-magnesium brine according to the magnesium ion:potassium ion mole ratio in the mixed brine composed of high-magnesium brine and brine C of 1.5:1-5:1, mixing is carried out, aging is carried out for 1-10 days, and solid-liquid separation is carried out to obtain the high-purity magnesium carbonate salt mine.
Description
Technical field
The present invention relates to the utilization methods of carbonate type bittern, particularly relate to a kind of from plateau carbonate-type
The method preparing high-purity magnesium carbonate in salt.
Background technology
Exploitation Tibet region salt lake resources it is difficult to chemical processing plant (CPP) cannot be built in lake region, and, away from
Remote from the place possessing industrial processes ability, therefore, can only transport after lake region obtains high-grade mineral and add
Work, its core seeks to utilize local natural environment to obtain series salt pan mineral by building salt pan.
Mainly there are carbonate-type and the big class of sulfate type two in boron-rich lithium salts lake, Tibet.Early stage, for sulfate type
The exploitation in boron-rich lithium salts lake, it is proposed that freezing analyse the main body of lithium except nitre-evaporation analysis potassium-be diluted to boron-evaporation of saltouing
Technique.And the exploitation in lithium salts lake boron-rich to carbonate-type, problems faced is the dissolubility due to lithium carbonate
Matter, it is difficult to lithium carbonate is enriched to higher concentration, the technique of Zha Buye exploitation is to utilize freezing rich except nitre-evaporation
Collection lithium-utilize solar pond intensification to analyse the technique of lithium carbonate, this technique achieves the clean production of all clear, has obtained preferably
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 Lake Jiezechaka (carbonic acid
Salt form) and the geographical position of wrong (sulfate type) Hubei and Hunan Provinces of Medulla Junci (air line distance about 70km) nearby, exploitation
Utilize carbonate-type and sulfate type two kinds boron-rich lithium salts lake bittern water coupling technique, sulfate type can be solved
Salt lake magnesium/lithium is difficult to the problem of enrichment than high, carbonate type salt lake lithium, and lithium is enriched to higher concentration, but
On the one hand, two kinds of salt lake quantity with this rare environmental condition are the most limited；On the other hand, two kinds of salt
Consume a large amount of carbonate during the coupling exploitation of lake, and produce larger amount of magnesium carbonate, cause in carbonate type salt lake
It is provided that the carbonate producing lithium carbonate is the most sufficient, the steady production of salt lake resources is caused certain impact.
Therefore, try one's best merely with the element of self in carbonate-type boron lithium salts lake, it is achieved circulating production, and break away from
Dependence to other resource, is 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 high-purity magnesium carbonate from the carbonate type bittern of plateau.
A kind of method preparing high-purity magnesium 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 environment bar
The change of part, constantly imports fresh water or dilute salt to regulate lithium concentration in evaporation and concentration salt so that
Lithium ion does not separates out with mineral forms, when in salt, lithium concentration reaches 1.2g/L～1.8g/L, by salt
Import the degree of depth deep lake salt Tanaka more than or equal to 2m and continue evaporation and concentration；
Second step, along with proceeding to winter of highlands season, when ambient temperature is-15 DEG C～-5 DEG C, in a large number
Mirabilite hydrate preferentially separates out, along with temperature continues to reduce and the precipitation of water of crystallization, Borax, sodium chloride, chlorination
Potassium also separates out with the form of aqueous salt or simple salt, and in the case, in salt, lithium concentration rises rapidly,
In salt, sulfate ion concentration is as Con trolling index, when the concentration of sulfate ion is reduced to 4g/L～7g/L
Time, in salt, lithium concentration rises very rapidly up to 2.6g/L～3.5g/L, obtains rich lithium carbonate after solid-liquid separation
Salt B and mirabilite ore；
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, separating out lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains carbonic acid
Lithium concentrate and salt C；
4th step, when ambient temperature is higher than 0 DEG C, the salt C that described 3rd step obtains and and high-magnesium brine
Mixing, mixed proportion is according to the thing of high-magnesium brine with magnesium ion in the mixing salt of salt C composition with potassium ion
The ratio of the amount of matter is that 1.5:1～5:1 measures, solid-liquid separation after being aged 1～10 day after mixing, obtains salt D
With high-purity carbonic acid magnesium salt ore deposit, with MgCO in this high-purity carbonic acid magnesium salt ore deposit3·3H2The purity of O meter is 60%
Above.
Preferably, in the described first step, when in salt, lithium concentration is close to 1.5g/L, 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 lowest temperature
When degree is more than 5 DEG C, control lithium concentration importing deep pond close to 1.2g/L (1.2g/L～1.5g/L)
Salt pan.
Preferably, in the described first step, when being in autumn, ambient temperature is relatively low in season, salt lowest temperature
When degree is below 0 DEG C, control lithium concentration importing deep pond close to 1.8g/L (1.5g/L～1.8g/L)
Salt pan.
Preferably, in the described first step, proceed to autumn when season, when temperature starts to reduce, salt lowest temperature
Spend 0 DEG C～5 DEG C, lithium concentration is first imported the degree of depth less than or equal to 0.5m at the salt close to 1.2g/L
Shallow lake salt Tanaka continue evaporation and concentration, import deep pond when being evaporated in salt lithium concentration close to 1.8g/L
Salt pan.
Preferably, the temperature elevation system that in described 3rd step, salt B imports is solar temperature rising system, at this too
Sun can comprise the following steps by temperature-rise period in temperature elevation system: by salt B in solar temperature rising system from and
Lower ejection, by the hot-air of 100 DEG C～200 DEG C and described salt B, in opposite directions or the mode that intersects imports simultaneously,
Make salt B carry out heat exchange with hot-air with the form of relative or crossing motion, thus brine temperature is rapid
Rise to 20 DEG C～60 DEG C and flow in thermal insulation pool；Described salt is incubated 2-48 hour in thermal insulation pool, no
Disconnected precipitation lithium carbonate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains lithium carbonate essence
Ore deposit.
Preferably, the temperature elevation system that in described 3rd step, salt B imports is Wen Peng pond, rises in this Wen Peng pond
Temperature process comprises the following steps: providing a Wen Peng pond, this Wen Peng pond includes cell body and closes the printing opacity of this cell body
Cover, 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,
Temperature in this Wen Peng pond is higher 20 DEG C～50 DEG C than ambient temperature；In autumn and winter season and ambient temperature-30 DEG C～0 DEG C
Time, salt B is imported described temperature canopy along the length direction in described Wen Peng pond and from the big one end of the width of cell body
Pond, described salt B carries out quick heat exchange, fast in big and depth as shallow the region of width of the cell body in this Wen Peng pond
Speed heats up, and quickly separates out lithium carbonate, and the width of the cell body arriving this Wen Peng pond as salt B is little and the degree of depth is deep
Region, salt B reaches stable through abundant heat-exchange temperature, and separates out a large amount of lithium carbonate, treats lithium in salt
When concentration is down to 1g/L～2g/L, solid-liquid separation obtains lithium carbonate concentrate.
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, obtain less than 10% by limiting the evaporation rate of the water yield in temperature elevation system
To the grade of first lithium carbonate concentrate reach more than 90%；In described 5th step, by limiting system of heating 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 reaches more than 90%.
Preferably, in the described first step, salt A adds in importing the evaporating concentration process before deep lake salt field
Dehydration Natrii Sulfas, is allowed to fully dissolve, and controls evaporation rate, makes lithium not separate out with mineral forms.
Compared with prior art, the invention have the advantages that
(1) present invention is based on the original salt of carbonate-type, realizes quick richness by controlling evaporation process
The purpose of collection lithium ion, is not introduced into any chemical reagent, it is achieved cleaning, environment protection-type produce, and have broken away from it
The dependence of its resource.
(2) after evaporation and concentration reaches 1.2g/L～1.8g/L to lithium concentration, the deep lake salt field last stage is entered
Add dehydration Natrii Sulfas, and make dehydration Natrii Sulfas be dissolved in salt, and control sulfate ion concentration in salt,
Avoiding the too much follow-up generation lithium sulfate double salt of sulfate radical, the control result of this process makes freeze nitre mistake follow-up winter
Journey mirabilite hydrate high efficiency separates out, and 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, sulfate ion concentration
Control, the control of warming temperature.When being evaporated to lithium concentration 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 ion by adding the dilutest salt
Concentration, controls the evaporation process of Bittern of Salt Pan flexibly.Lithium concentration in concentrated brine is controlled
This scope of 1.2g/L～1.8g/L so that it is do not become salt in salt pan evaporation process, continues up to season by this situation
Joint proceeds to autumn and winter, salt imports deep lake salt Tanaka and continues evaporation and concentration, when ambient temperature constantly reduces,
After entering winter, more than 70% mirabilite hydrate in salt preferentially separates out from salt, thus takes out of rapidly a large amount of
Water of crystallization, lithium concentration rises rapidly, controls the concentration of sulfate ion when being reduced to 4g/L～7g/L (
It is well 6g/L～7g/L), in salt, lithium concentration rises very rapidly up to 2.6g/L～3.5g/L, then heats up 20 DEG C
～after 60 DEG C, separate out lithium carbonate concentrate, obtain salt C after solid-liquid separation.
Separate out the salt C after lithium carbonate concentrate and high-magnesium brine mix according to a certain percentage, be aged after consolidate
Liquid isolated high-purity carbonic acid magnesium salt ore deposit.With MgCO in this magnesium carbonate salt mine3·3H2The purity of O meter is
More than 70%, through the simple carrying out washing treatment of fresh water, can the most commercially sell.
(4) utilize solar temperature rising system or Wen Peng pond as temperature elevation system so that salt and hot-air are quick
Heat exchange, it is rapidly heated, thus quickly separates out lithium carbonate；It addition, the present invention utilizes temperature elevation system to process salt,
Avoiding the introducing of applied mechanical impurity, the magnesium carbonate salt mine obtained removes MgCO3·3H2Outside O, possibly together with portion
Dividing the solubility salts such as NaCl, KCl, the high-purity magnesium carbonate finally given after washing is without additionally removing
Miscellaneous process, directly as sale of finished goods.
Detailed description of the invention
For making the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with specific embodiment,
The present invention is described in detail.Should be appreciated that specific embodiment described herein is only in order to explain this
Invention, is not intended 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 group
Become to realize the method that carbonate type salt lake produces multi mineral, for the feasibility of the method being described, to tie then tea
That blocks is utilized as example, it will be understood that this invention is applicable not only to the exploitation of Lake Jiezechaka, is also applied for tool
There is the exploitation of salt lake resources under the conditions of similar environments.
The side preparing high-purity magnesium carbonate from the carbonate type bittern of plateau of the present invention is described the most step by step
Method.
The first step, carbonate-type original salt A in the fall before, be evaporated concentrating, and according to environment bar
The change of part, constantly imports fresh water or dilute salt to regulate lithium concentration in evaporation and concentration salt so that
Lithium ion does not separates out with mineral forms, when in salt, lithium concentration reaches 1.2g/L～1.8g/L, by salt
Import the degree of depth deep lake salt Tanaka more than or equal to 2m and continue evaporation and concentration.
Original salt A is evaporated, after enrichment method to lithium concentration 1.2g/L～1.8g/L, deep importing
Before lake salt field, this salt first passes through a salt pond being stacked with dehydration Natrii Sulfas, simultaneously sulphuric acid in detection salt
The concentration range (avoiding excessive concentration or too low) of radical ion.Control to enter sulfate ion in the salt of deep pond
Concentration 20g/L～30g/L.Dehydration Natrii Sulfas adds in this step so that salt is in the process flowing through dehydration Natrii Sulfas
In, dehydration Natrii Sulfas absorbs the moisture content in salt, is gradually transformed into mirabilite hydrate, has partially dehydrated Natrii Sulfas simultaneously
Occur to dissolve and enter in salt, freeze nitre process mirabilite hydrate high efficiency follow-up winter and separate out, take mass crystallization out of
Water, promotes rapidly lithium enrichment rate, so that the whole process time shortens more than 2 months.Dehydration Natrii Sulfas
Can be thenardite or be partly dehydrated Natrii Sulfas, these Natrii Sulfas may utilize carbonate brine processing procedure salt pan voluntarily
The Natrii Sulfas produced, it is not necessary to outsourcing.The Natrii Sulfas that salt pan produces voluntarily, without processing especially, only need to be deposited directly on
Somewhere, is dehydrated through weathering, and dehydration or half dehydration, all can use in this step the most completely.De-
Water Natrii Sulfas adition process, the concentration range controlling sulfate ion is crucial.Dehydration Natrii Sulfas adds too much can be made
Sulfate ion increases and is easily caused generation lithium sulfate complex salt, thus affect follow-up enriching lithium ion.And
Dehydration Natrii Sulfas addition is inadequate, and in follow-up nitre process of freezing, mirabilite hydrate eduction rate is low can affect evaporation and concentration speed
Degree, 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
First, verifying through lot of experiments, the optium concentration of lithium ion is 1.5g/L, and actual production process lithium ion is dense
It is all preferable condition that degree all can obtain between preferable effect, such as 1.45g/L～1.55g/L close to 1.5g/L.
Secondly, in actual production process, different according to season, the height of ambient temperature, need the lithium ion controlled
Concentration can change.Until season proceeds to autumn, although be autumn, but ambient temperature is not the most stable
State, i.e. ambient temperature may be higher, it is also possible to relatively low, it should control with the temperature of salt in the middle of reality
When system imports 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 close to 1.2g/L,
Such as, 1.2g/L～1.5g/L；Season proceeds to autumn, can control lithium concentration importing close to 1.8g/L
Deep lake salt field, such as, 1.5g/L～1.8g/L.No matter during the seasonal variations of plateau, how ambient temperature changes,
Control lithium concentration be which scope will be with lithium ion in practical operation not with the form of lithium carbonate mineral
Precipitation is as the criterion.Dilute salt in the described first step uses the original salt of carbonate-type, and wherein lithium concentration connects
Nearly 0.16g/L；Or employing is concentrated to certain phase from the original bittern evaporation of carbonate-type, wherein lithium ion is dense
The degree salt less than 1.2g/L.Dilute salt mentioned by present patent application context is defined in this section dilute
Salt.
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: B2O3It is 0.1～3g/L,
Li is 0.1～2g/L, and K is 1～30g/L, and Na is 10～120g/L, and Mg is 0.01～20g/L, SO4 2-For
1～40g/L, CO3Being 1～120g/L, Br is 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 enter
Row solar evaporation.In the present embodiment, select Lake Jiezechaka lake water, owing to this lake lake water is than thin (i.e. fresh water
Content is high), for avoiding icing effect to operate, 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 gives Lake Jiezechaka Bittern of Salt Pan 2014～2015
Year on-the-spot evaporation data.
Table two Lake Jiezechaka Bittern of Salt Pan evaporation liquid phase composition
It is attached in specific experiment, sees table two, take Lake Jiezechaka Bittern of Salt Pan on February 11st, 2014
Analyzing, lithium ion initial concentration is 0.24g/L, beginning solar evaporation from this day, As time goes on,
Lithium concentration is gradually increasing along with the constantly evaporation of salt, 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 pond more than or equal to 2m
Salt Tanaka, continues evaporation and concentration.
During the stage that dehydration Natrii Sulfas adds can be 2014.7.11～2014.11.8, the detailed process of interpolation can
To be (but not limited to): dehydration Natrii Sulfas is stacked into one and processes porch, pond, by original for carbonate-type halogen
After water breaks through dehydration Natrii Sulfas, entrance processes pond, and detection processes the concentration of sulfate ion in pond, thus controls
The addition of dehydration Natrii Sulfas, dehydration Natrii Sulfas addition too much can make sulfate ion increase and be easily caused generation sulfur
Acid lithium complex salt, thus affect follow-up enriching lithium ion.And it is inadequate to be dehydrated Natrii Sulfas addition, freeze nitre follow-up
Process, mirabilite hydrate eduction rate is low can affect evaporation and concentration speed, delays the speed of enriching lithium process.Therefore
This stage, control the concentration of sulfate ion be how many scopes be crucial.
Can incite somebody to action before entering deep lake salt field according to lithium concentration in temperature Change situation and concentrated brine
Concentrated brine 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's evaporation and concentration.Depending on the annual seasonal temperature situation of change of Salt Lake Area, proceed to when season
In autumn, when temperature starts to reduce, salt minimum temperature is at 0 DEG C～5 DEG C, and lithium concentration is close to 1.2g/L (1.2
G/L～1.5g/L) salt first import the degree of depth and continue evaporation and concentration less than or equal to the shallow lake salt Tanaka of 0.5m,
Deep lake salt Tanaka is imported when being evaporated in salt lithium concentration close to 1.8g/L (1.5g/L～1.8g/L).When
Proceed to autumn season, but when ambient temperature is relatively low, lithium ion, below 0 DEG C, is contained by salt minimum temperature
Amount controls be 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).
Be in autumn when season, ambient temperature is higher, when salt minimum temperature is more than 5 DEG C, by lithium concentration
Control be introduced directly into deep lake salt field close to the salt of 1.2g/L (1.2g/L-1.5g/L).
Second step, along with proceeding to winter of highlands season, when ambient temperature is-15 DEG C～-5 DEG C, in a large number
Mirabilite hydrate preferentially separates out, along with temperature continues to reduce and the precipitation of water of crystallization, Borax, sodium chloride, chlorination
Potassium also separates out with the form of aqueous salt or simple salt, and in the case, in salt, lithium concentration rises rapidly,
In salt, sulfate ion concentration is as Con trolling index, when the concentration of sulfate ion is reduced to 4g/L～7g/L
Time, in salt, lithium concentration rises very rapidly up to 2.6g/L～3.5g/L, obtains rich lithium carbonate after solid-liquid separation
Salt B and mirabilite ore.
Mirabilite ore is based on mirabilite hydrate, and mass content accounts for 70%～more than 90%, remaining be contaminated with a small amount of Borax,
Sodium chloride, potassium chloride.
Preferably, when the concentration of sulfate ion is preferably controlled in 6g/L-7g/L, and treat lithium ion in salt
Concentration rises to 2.6g/L～3.5g/L, carries out solid-liquid separation, the rich lithium carbonate brine obtained, follow-up preparation
The lithium carbonate yield obtained when lithium carbonate concentrate can be higher.
In being attached to specifically test, as shown in Table 2, December in 2014 14 days～on January 28th, 2015 it
Between salt in lithium concentration be 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, at other it was found that, in salt lithium concentration can reach 3.9g/L.
Such rich lithium carbonate brine can obtain high-grade lithium carbonate concentrate by hyperthermic treatment.
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, separating out lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains carbon
Acid lithium concentrate and salt C.
The grade of this 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 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 halogen
Water B sprays in solar temperature rising system from top to bottom, simultaneously by the hot-air of 100 DEG C～200 DEG C with described
Salt B is in opposite directions or the mode that intersects imports so that salt B and hot-air are with the form of relative or crossing motion
Carry out heat exchange, thus brine temperature rises very rapidly up to 20 DEG C～60 DEG C and flows in thermal insulation pool；Secondly, will
Described salt is incubated 2～48 hours in thermal insulation pool, constantly separates out lithium carbonate, treats lithium concentration fall in salt
Lithium carbonate concentrate is obtained to solid-liquid separation during 1g/L～2g/L.
It is less than 10% by limiting the evaporation rate of the water yield in solar temperature rising system, the lithium carbonate concentrate obtained
Grade reaches more than 90%.Such as, before salt enters, the dilution of part light salt is added or in temperature-rise period
Spraying adds fresh 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 closing
The diffuser of this cell body, along the length direction of this cell body, the width of this cell body is gradually reduced, and this cell body
The degree of depth is gradually increased, and the temperature in this Wen Peng pond is higher 20 DEG C～50 DEG C than ambient temperature；At autumn and winter season and ring
During border temperature-30 DEG C～0 DEG C, by salt B along the length direction in described Wen Peng pond and from the width of cell body big one
End 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, it is rapidly heated, and quickly separates out batch lithium carbonate, when salt B arrives the cell body in this Wen Peng pond
The region that width 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 carbon
Acid lithium, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains lithium carbonate concentrate.
4th step, when ambient temperature is higher than 0 DEG C, the salt C that described 3rd step obtains and and high-magnesium brine
Mixing, mixed proportion is according to the thing of high-magnesium brine with magnesium ion in the mixing salt of salt C composition with potassium ion
The ratio of the amount of matter is that 1.5:1～5:1 measures, solid-liquid separation after being aged 1～10 day after mixing, obtains salt D
With high-purity carbonic acid magnesium salt ore deposit.
Described high-magnesium brine is the chloride type salt that magnesium ion content is more than or equal to 10g/L, or magnesium ion
The content magnesium chloride solution more than or equal to 10g/L.
With MgCO in the magnesium carbonate salt mine obtained3·3H2The purity of O meter is more than 60%, and impurity is predominantly
NaCl and a small amount of KCl, can remove through washing and just can commercially sell without the most refined processing,
Due to this ore deposit mechanical impurity, it is easy to be processed into high purity product.
Further, since the temperature elevation system that the 3rd step uses is the system of closing, avoid drawing in temperature-rise period
Entering the mechanical admixture in the external world, therefore, the final magnesium carbonate salt mine prepared is through the simple washing process of fresh water, directly
It is connected on commercial type.
Compared with prior art, the invention have the advantages that
(1) present invention is based on the original salt of carbonate-type, realizes quick richness by controlling evaporation process
The purpose of collection lithium ion, is not introduced into any chemical reagent, it is achieved cleaning, environment protection-type produce, and have broken away from it
The dependence of its resource.
(2) after evaporation and concentration reaches 1.2g/L～1.8g/L to lithium concentration, the deep lake salt field last stage is entered
Add dehydration Natrii Sulfas, and make dehydration Natrii Sulfas be dissolved in salt, and control sulfate ion concentration in salt,
Avoiding the too much follow-up generation lithium sulfate double salt of sulfate radical, the control result of this process makes freeze nitre mistake follow-up winter
Journey mirabilite hydrate high efficiency separates out, and 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, sulfate ion concentration
Control, the control of warming temperature.When being evaporated to lithium concentration 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 ion by adding the dilutest salt
Concentration, controls the evaporation process of Bittern of Salt Pan flexibly.Lithium concentration in concentrated brine is controlled
This scope of 1.2g/L～1.8g/L so that it is do not become salt in salt pan evaporation process, continues up to season by this situation
Joint proceeds to autumn and winter, salt imports deep lake salt Tanaka and continues evaporation and concentration, proceed to winter, environment temperature season
Degree constantly reduces, and more than 70% mirabilite hydrate preferentially separates out from salt, thus takes rapidly mass crystallization water out of,
Lithium concentration rises rapidly, controls when the concentration of sulfate ion is reduced to 4g/L～7g/L (preferably
6g/L～7g/L), in salt, lithium concentration rises very rapidly up to 2.6g/L～3.5g/L, then heats up 20 DEG C～60 DEG C
Rear precipitation lithium carbonate concentrate, obtains salt C after solid-liquid separation.
Separate out the salt C after lithium carbonate concentrate and high-magnesium brine mix according to a certain percentage, be aged after consolidate
Liquid isolated high-purity carbonic acid magnesium salt ore deposit.With MgCO in this magnesium carbonate salt mine3·3H2The purity of O meter is
More than 70%, it is not necessary to any aftertreatment technology, can the most commercially sell, or be processed into high purity product.
(4) utilize solar temperature rising system or Wen Peng pond as temperature elevation system so that salt and hot-air are quick
Heat exchange, it is rapidly heated, thus quickly separates out lithium carbonate；It addition, the present invention utilizes temperature elevation system to process salt,
Avoid the introducing of applied mechanical impurity, the high-purity magnesium carbonate finally given through the simple washing process of fresh water,
Directly as sale of finished goods.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (10)
1. the method preparing high-purity magnesium 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 environment bar
The change of part, constantly imports fresh water or dilute salt to regulate lithium concentration in evaporation and concentration salt so that
Lithium ion does not separates out with mineral forms, when in salt, lithium concentration reaches 1.2g/L～1.8g/L, by salt
Import the degree of depth deep lake salt Tanaka more than or equal to 2m and continue evaporation and concentration；
Second step, along with proceeding to winter of highlands season, when ambient temperature is-15 DEG C～-5 DEG C, in a large number
Mirabilite hydrate preferentially separates out, along with temperature continues to reduce and the precipitation of water of crystallization, Borax, sodium chloride, chlorination
Potassium also separates out with the form of aqueous salt or simple salt, and in the case, in salt, lithium concentration rises rapidly,
In salt, sulfate ion concentration is as Con trolling index, when the concentration of sulfate ion is reduced to 4g/L～7g/L
Time, in salt, lithium concentration rises very rapidly up to 2.6g/L～3.5g/L, obtains rich lithium carbonate after solid-liquid separation
Salt B and mirabilite ore；
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, separating out lithium carbonate concentrate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains carbonic acid
Lithium concentrate and salt C；
4th step, when ambient temperature is higher than 0 DEG C, the salt C that described 3rd step obtains mixes with high-magnesium brine
Closing, mixed proportion is according to the material of high-magnesium brine with magnesium ion in the mixing salt of salt C composition with potassium ion
The ratio of amount be that 1.5:1～5:1 measures, solid-liquid separation after being aged 1～10 day after mixing, obtain salt D and
High-purity carbonic acid magnesium salt ore deposit, with MgCO in this high-purity carbonic acid magnesium salt ore deposit3·3H2The purity of O meter is 70%
Above.
2. the method for claim 1, it is characterised in that: in the described first step, when in salt lithium from
When sub-concentration is close to 1.5g/L, salt is imported the described degree of depth deep lake salt Tanaka more than or equal to 2m and continues
Evaporation and concentration.
3. the method for claim 1, it is characterised in that: in the described first step, it is in the autumn when season
Ji Shi, ambient temperature is higher, when salt minimum temperature is more than 5 DEG C, controls lithium concentration close
1.2g/L imports deep lake salt field.
4. the method for claim 1, it is characterised in that: in the described first step, it is in the autumn when season
Ji Shi, ambient temperature is relatively low, when salt minimum temperature is below 0 DEG C, controls lithium concentration close
1.8g/L imports deep lake salt field.
5. the method for claim 1, it is characterised in that: in the described first step, proceed to the autumn when season
In season, ambient temperature reduces relatively slow, and salt minimum temperature is when 0 DEG C～5 DEG C, by lithium concentration close to 1.2g/L
Salt first import the degree of depth and continue evaporation and concentration less than or equal to the shallow lake salt Tanaka of 0.5m, be evaporated in salt
Import deep lake salt Tanaka when lithium concentration is close to 1.8g/L and continue evaporation.
6. the method for claim 1, it is characterised in that: the liter that in described 3rd step, salt B imports
Temperature system is solar temperature rising system, and 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 empty for the heat of 100 DEG C～200 DEG C
Gas and described salt B are in opposite directions or the mode that intersects imports so that salt B and hot-air are with relative or ship mutually
Dynamic form carries out heat exchange, thus 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 lithium ion in salt
When concentration is down to 1g/L～2g/L, solid-liquid separation obtains lithium carbonate concentrate.
7. the method for claim 1, it is characterised in that: the liter that in described 3rd step, salt B imports
Temperature system is Wen Peng pond, and 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 of this cell body
Degree direction, the width of this cell body is gradually reduced, and the degree of depth of this cell body is gradually increased, the temperature in this Wen Peng pond
Spend 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 along the length direction in described Wen Peng pond and
One end big from the width of cell body imports described Wen Peng pond, and described salt B is at the width of the cell body in this Wen Peng pond
Big and depth as shallow region carries out quick heat exchange, is rapidly heated, and quickly separates out lithium carbonate, when salt B arrives
The region that the width of the cell body reaching this Wen Peng pond is little and the degree of depth is deep, salt B reaches steady through abundant heat-exchange temperature
Fixed, and separate out a large amount of lithium carbonate, when in salt, lithium concentration is down to 1g/L～2g/L, solid-liquid separation obtains carbonic acid
Lithium concentrate.
8. the method as described in claim 1 or 6 or 7, it is characterised in that: salt B in described 3rd step
40 DEG C～50 DEG C it are warming up in temperature elevation system.
9. the method for claim 1, it is characterised in that: in described 3rd step, heated up by restriction
In system, the evaporation rate of the water yield is less than 10%, and the grade of first lithium carbonate concentrate obtained reaches more than 90%；
In described 5th step, it is less than 10% by limiting the evaporation rate of the water yield in temperature elevation system, the second batch carbon obtained
The grade of acid lithium concentrate reaches more than 90%.
10. the method for claim 1, it is characterised in that: in the described first step, salt A is importing
Evaporating concentration process before deep lake salt field adds dehydration Natrii Sulfas, is allowed to fully dissolve, control evaporation rate,
Lithium is made not separate out with mineral forms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610212584.8A CN105858693B (en) | 2016-04-07 | 2016-04-07 | The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610212584.8A CN105858693B (en) | 2016-04-07 | 2016-04-07 | The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105858693A true CN105858693A (en) | 2016-08-17 |
| CN105858693B CN105858693B (en) | 2017-09-15 |
Family
ID=56636143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610212584.8A Active CN105858693B (en) | 2016-04-07 | 2016-04-07 | The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105858693B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018085915A1 (en) * | 2016-11-08 | 2018-05-17 | Mgx Minerals Inc. | Method for the production of lithium carbonate from salt brines |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928023A (en) * | 2010-09-03 | 2010-12-29 | 山西大学 | Device and method for preparing lithium carbonate from brine by utilizing solar energy |
| CN102491378A (en) * | 2011-10-14 | 2012-06-13 | 陈兆华 | Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine |
| CN103253689A (en) * | 2012-02-17 | 2013-08-21 | 西藏国能矿业发展有限公司 | Method for extracting lithium and magnesium from salt lake brine |
| US20130272933A1 (en) * | 2010-06-28 | 2013-10-17 | Korea Resources Corporation | Method for producing high-purity lithium carbonate |
| 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 |
-
2016
- 2016-04-07 CN CN201610212584.8A patent/CN105858693B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130272933A1 (en) * | 2010-06-28 | 2013-10-17 | Korea Resources Corporation | Method for producing high-purity lithium carbonate |
| CN101928023A (en) * | 2010-09-03 | 2010-12-29 | 山西大学 | Device and method for preparing lithium carbonate from brine by utilizing solar energy |
| CN102491378A (en) * | 2011-10-14 | 2012-06-13 | 陈兆华 | Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine |
| CN103253689A (en) * | 2012-02-17 | 2013-08-21 | 西藏国能矿业发展有限公司 | Method for extracting lithium and magnesium from salt lake brine |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 王正丽等: "结则茶卡不同蒸发阶段卤水冷冻实验研究", 《天津科技大学学报》 * |
| 郝勇等: "西藏结则茶卡和龙木错盐湖卤水协同提锂研究", 《无机盐工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018085915A1 (en) * | 2016-11-08 | 2018-05-17 | Mgx Minerals Inc. | Method for the production of lithium carbonate from salt brines |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105858693B (en) | 2017-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103194622B (en) | Method for enriching boron and lithium elements in sulfate type salt lake brine | |
| CN105502440B (en) | The rough refining methd of sulfuric acid lithium salts | |
| CN105060317B (en) | A kind of method being produced high-quality potassium nitrate with ammonium nitrate double decomposition circulation process by potassium chloride | |
| CN102491378B (en) | Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine | |
| CN103058232A (en) | Method for separating carbonate from carbonate bittern containing lithium and potassium to prepare sylvinite ore and lithium carbonate concentrate | |
| CN105905929B (en) | The method that lithium carbonate is prepared from the carbonate type bittern of plateau | |
| CN108640130B (en) | Method for preparing lithium sulfate from salt lake lithium sulfate salt crude ore | |
| CN102774860B (en) | Method for preparing lithium carbonate by brine | |
| CN103553090B (en) | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy | |
| CN105858693A (en) | Method for preparing high-purity magnesium carbonate from plateau carbonate-type brine | |
| CN105858690A (en) | Method for quickly enriching lithium from plateau carbonate-type brine | |
| CN105883862B (en) | The method that lithium carbonate is prepared from the carbonate type bittern of plateau | |
| CN115159546B (en) | Method for improving evaporation efficiency of salt lake brine | |
| CN109019641B (en) | Method for separating magnesium and lithium and enriching lithium from sodium sulfate subtype salt lake brine | |
| CN103553088B (en) | Method of preparing lithium borate ores from mixed brine by utilizing natural energy | |
| CN108069443A (en) | A kind of method that potash magnesium sulphate fertilizer and potassium chloride are prepared from sulfate type salt lake brine | |
| CN105905917B (en) | The method that native borax is prepared from the carbonate type bittern of plateau | |
| CN102432042B (en) | Method for directly producing potassium nitrate end product from complex nitrate bittern | |
| CN103553065B (en) | Method for preparing boron ore from mixed brine by using natural energy | |
| CN103553087B (en) | Method of preparing lithium sulfate ores from mixed brine by utilizing natural energy | |
| CN109179455B (en) | Method for enriching lithium salt and simultaneously extracting potassium salt from carbonate type salt lake brine | |
| CN1100722C (en) | Process for precipitating B and Li in bittern at same time | |
| CN102358622B (en) | Method for producing lithium carbonate, boric acid and high purity magnesium oxide by removing magnesium from salt lake brine through salting out | |
| CN103553091B (en) | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy | |
| CN103771458A (en) | Method for preparing potassium sulfate by using boric acid production raffinate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |