CN105858693B - The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau - Google Patents
The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau Download PDFInfo
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- CN105858693B CN105858693B CN201610212584.8A CN201610212584A CN105858693B CN 105858693 B CN105858693 B CN 105858693B CN 201610212584 A CN201610212584 A CN 201610212584A CN 105858693 B CN105858693 B CN 105858693B
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- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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Abstract
The invention discloses a kind of method that high-purity magnesium carbonate is prepared in carbonate type bittern from plateau, it includes step：The first step, the original bittern A of carbonate-type is evaporated before autumn and winter, and adjusts lithium concentration so that lithium ion is separated out not in the form of mineral, and deep lake salt Tanaka is imported when lithium concentration reaches 1.2g/L~1.8g/L in bittern and continues to evaporate；Second step, when environment temperature is 15 DEG C~5 DEG C, a large amount of mirabilite hydrates are preferentially separated 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 obtain bittern B after 2.6g/L~3.5g/L, separation of solid and liquid in bittern；3rd step, 20 DEG C~60 DEG C are warming up to by bittern B, separate out carbonic acid lithium concentrate, separation of solid and liquid obtains bittern C when lithium concentration is down to 1g/L~2g/L in bittern；4th step, when environment temperature is higher than 0 DEG C, the bittern C with and high-magnesium brine mix, mixed proportion is 1.5 according to the ratio between amount of material for mixing magnesium ion and potassium ion in bittern of high-magnesium brine and bittern C compositions:1~5:1 measures, separation of solid and liquid after being aged 1~10 day after mixing, obtains high-purity carbonic acid magnesium salts ore deposit.
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 high-purity magnesium 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 nitre-potassium is analysed in evaporation-and is diluted to the main process that lithium is analysed in boron of saltouing-evaporation.And to carbonate
The exploitation in the boron-rich lithium salts lake of type, problems faced is due to the solubility properties of lithium carbonate, it is difficult to be enriched to lithium carbonate higher
Concentration, the technique of Zha Buye exploitations is the technique using freezing except nitre-evaporation enriching lithium-utilization solar pond heating analysis lithium carbonate,
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 is separated out；Solar pond is cumbersome, and the production cycle is long；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, with 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, the carbonate for causing to provide production lithium carbonate in carbonate type salt lake is not necessarily sufficient, to the steady of salt lake resources
Fixed production causes certain influence.Therefore, as far as possible merely with the element of itself in carbonate-type boron lithium salts lake, circulating life is realized
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, a kind of present invention prepares high-purity magnesium carbonate method in providing carbonate type bittern from plateau.
A kind of method that high-purity magnesium 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,
Constantly import fresh water or dilute bittern 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 the deep lake salt that depth is more than or equal to 2m
Tanaka continues to be concentrated by evaporation；
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 is preferentially separated 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 is separated out, and in the case, lithium concentration rises rapidly in bittern, and sulfate ion concentration is control using in bittern
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~
Rich lithium carbonate brine B and mirabilite ore are obtained after 3.5g/L, separation of solid and liquid；
3rd step, the rich lithium carbonate brine B that second step is obtained, which is imported, is warming up to 20 DEG C~60 DEG C, analysis in temperature elevation system
Go out carbonic acid lithium concentrate, separation of solid and liquid obtains carbonic acid lithium concentrate and bittern C when lithium concentration is down to 1g/L~2g/L in bittern；
4th step, when environment temperature be higher than 0 DEG C when, the bittern C that the 3rd step is obtained with and high-magnesium brine mix, mixing
The ratio between amount of material of magnesium ion and potassium ion is 1.5 in the mixing bittern that ratio is constituted according to high-magnesium brine and bittern C:1~
5:1 measures, separation of solid and liquid after being aged 1~10 day after mixing, obtains bittern D and high-purity carbonic acid magnesium salts ore deposit, the high purity carbon
With MgCO in sour magnesium salts ore deposit3·3H2The purity of O meters is more than 60%.
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 season be in autumn when, 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 season be in autumn when, 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, autumn is transferred to when season, when temperature starts reduction, 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 evaporate
Concentration, is evaporated in bittern lithium concentration close to importing deep lake salt field during 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 mode that intersect is imported so that bittern B and hot-air are with relative or intersecting
The form of motion carries out heat exchange, so that 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, length direction by 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 area of depth as shallow
Domain is quickly exchanged heat, is rapidly heated, and quickly separates out lithium carbonate, the width for reaching the pond body in the Wen Peng ponds as bittern B it is small and
The deep region of depth, bittern B reaches stabilization 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, 10%, first obtained are less than by the evaporation rate for limiting water in temperature elevation system
The grade for criticizing carbonic acid lithium concentrate reaches more than 90%；It is low by the evaporation rate for limiting water in temperature elevation system in 5th step
In 10%, the grade of obtained second batch carbonic acid lithium concentrate reaches more than 90%.
Preferably, bittern A adds dehydration awns in the evaporating concentration process before importing deep lake salt field in the first step
Nitre, is allowed to fully dissolving, controls evaporation rate, lithium is not separated out with mineral forms.
Compared with prior art, the present invention has advantages below：
(1) present invention based on the original bittern of carbonate-type, realized by controlling evaporation process fast enriching lithium from
The purpose of son, is not introduced into any chemical reagent, realizes cleaning, environment protection-type production, has broken away from the dependence to other resources.
(2) deep lake salt field last stage addition is entered after evaporation and concentration reaches 1.2g/L~1.8g/L to lithium concentration de-
Water saltcake, and dehydration saltcake is dissolved into bittern, and control sulfate ion concentration in bittern, it is to avoid sulfate radical is 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 is separated out, so that the whole process time shortens more than 2 months.
(3) on several key points in pilot process.The control of lithium concentration, the control of sulfate ion concentration,
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, adjusts lithium concentration, flexibly the evaporation of control Bittern of Salt Pan by adding slightly dilute bittern
Process.Lithium concentration in concentrated brine is controlled in this scope of 1.2g/L~1.8g/L, makes it in salt pan evaporation process
Not into salt, this situation is continued up into season and is transferred to autumn and winter, bittern is imported into deep lake salt Tanaka continues to be concentrated by evaporation, and works as ring
Border temperature is constantly reduced, into winter after more than 70% mirabilite hydrate in bittern is preferential is separated out from bittern so that rapid band
Go out mass crystallization water, lithium concentration rises rapidly, the concentration of control sulfate ion (is preferably when being reduced to 4g/L~7g/L
6g/L~7g/L), lithium concentration rises very rapidly up to 2.6g/L~3.5g/L in bittern, then heats up and separates out after 20 DEG C~60 DEG C
Bittern C is obtained after carbonic acid lithium concentrate, separation of solid and liquid.
Separate out carbonic acid lithium concentrate after bittern C and high-magnesium brine mix according to a certain percentage, be aged after separation of solid and liquid
Obtain high-purity carbonic acid magnesium salts ore deposit.With MgCO in the magnesium carbonate salt mine3·3H2The purity of O meters is more than 70%, by fresh water letter
Single carrying out washing treatment, directly can commercially sell.
(4) it is used as temperature elevation system by the use of solar temperature rising system or Wen Peng ponds so that bittern and hot-air quickly exchange heat, soon
Speed heating, so as to quickly separate out lithium carbonate；In addition, the present invention handles bittern using temperature elevation system, it is to avoid applied mechanical impurity
Introduce, obtained magnesium carbonate salt mine removes MgCO3·3H2Outside O, also containing part NaCl, the solubility salt such as KCl, after washing
The high-purity magnesium carbonate finally given is without extra dedoping step, directly as sale of finished goods.
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 proposes to realize using natural energy, bittern composition for Qinghai-Tibet social economy and nature feature
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 under the conditions of being also applied for similar environments
Exploitation.
The method that high-purity magnesium 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,
Constantly import fresh water or dilute bittern 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 the deep lake salt that depth is more than or equal to 2m
Tanaka continues to be concentrated by evaporation.
Original bittern A is evaporated, after enrichment method to lithium concentration 1.2g/L~1.8g/L, is importing deep lake salt field
Before, the bittern first passes through a salt pond for being stacked with dehydration saltcake, while detecting the concentration range of sulfate ion in bittern
(avoiding excessive concentration or too low).Control enters concentration 20g/L~30g/L of sulfate ion in the bittern of deep pond.It is dehydrated saltcake
Add in this step and cause bittern during dehydration saltcake is flowed through, dehydration saltcake absorbs the moisture content in bittern, gradually turns
Become mirabilite hydrate, enter while there is partially dehydrated saltcake to occur dissolving in bittern, it is high that follow-up winter freezes nitre process mirabilite hydrate
Efficiency is separated out, and takes mass crystallization water out of, rapid lifting lithium enrichment rate, so that the whole process time shortens more than 2 months.
Being dehydrated saltcake can voluntarily be given birth to for thenardite or half dehydration saltcake, these saltcake using carbonate brine processing procedure salt pan
The saltcake of production, without outsourcing.The saltcake that salt pan is voluntarily produced only need to be deposited directly on somewhere, by nature without especially handling
Weathering is dehydrated, and either dehydration or half dehydration completely, can use in this step.Saltcake adition process is dehydrated, sulfate radical is controlled
The concentration range of ion is crucial.Dehydration saltcake add can excessively cause sulfate ion increase be easily caused generation lithium sulfate answer
Salt is closed, so as to influence subsequently to be enriched with lithium ion.And it is dehydrated saltcake addition not enough, subsequently freezing nitre process, mirabilite hydrate is separated out
Rate is low to be influenceed to be concentrated by evaporation speed, delay the speed of enriching lithium process.
The above-mentioned procedure declaration that deep lake salt field is imported when lithium concentration reaches 1.2g/L~1.8g/L is as follows：First,
Verified by lot of experiments, the optium concentration of lithium ion is 1.5g/L, and actual production process lithium concentration is equal close to 1.5g/L
It is preferable condition that can obtain between preferable effect, such as 1.45g/L~1.55g/L.Secondly, in actual production process, according to
Season is different, and the height of environment temperature is, it is necessary to which the lithium concentration of control can be changed.Until season is transferred to autumn, although
It is 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 is worked as with actual
The temperature of middle bittern controls when to import deep lake salt field.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, can import deep lake salt field by lithium concentration control close to 1.2g/L, for example,
1.2g/L~1.5g/L；Season is transferred to autumn, lithium concentration control can imported into deep lake salt field close to 1.8g/L, for example,
1.5g/L~1.8g/L.No matter how environment temperature changes during the seasonal variations of plateau, and which model controls lithium concentration is
Will not separated out by lithium ion in practical operation in the form of carbonic acid lithium minerals for enclosing is defined.Dilute bittern in the first step is adopted
With the original bittern of carbonate-type, wherein lithium concentration is close to 0.16g/L；Or concentrated using from the original bittern evaporation of carbonate-type
To certain phase, wherein lithium concentration is less than 1.2g/L bittern.Dilute bittern mentioned by present patent 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 annual most of the time, 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
Influence operation, 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 be 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, import the deep lake salt Tanaka that depth is more than or equal to 2m, continue to be concentrated by evaporation.
During the stage for being dehydrated saltcake addition can be 2014.7.11~2014.11.8, the detailed process of addition can be
(but not limited to)：Will dehydration saltcake be stacked into a processing pond porch, by the original bittern of carbonate-type break through dehydration saltcake it
Enter the concentration of sulfate ion in processing pond, detection process pond afterwards, so as to control to be dehydrated the addition of saltcake, dehydration saltcake adds
Entering excessively can be so that sulfate ion, which increases, be easily caused generation lithium sulfate complex salt, so as to influence subsequently to be enriched with lithium ion.And
It is dehydrated saltcake addition not enough, is subsequently freezing nitre process, mirabilite hydrate eduction rate is low to be influenceed to be concentrated by evaporation speed, delay enrichment
The speed of lithium process.Therefore in this stage, it is crucial for how many scope to control the concentration of sulfate ion.
It is able to will be concentrated before deep lake salt field is entered according to lithium concentration in temperature Change situation and concentrated brine
Bittern imports depth and is less than or equal to 0.5m shallow lake salt Tanaka continuation evaporation and concentration, 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 reduction, 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).When season is transferred to autumn, but environment temperature it is relatively low when, bittern minimum temperature 0 DEG C with
Under, 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 evaporates dense
Contracting.Autumn is in when season, environment temperature is higher, when bittern minimum temperature is more than 5 DEG C, by lithium concentration control close
1.2g/L (1.2g/L-1.5g/L) bittern is introduced directly into deep lake salt field.
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 is preferentially separated 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 is separated out, and in the case, lithium concentration rises rapidly in bittern, and sulfate ion concentration is control using in bittern
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~
Rich lithium carbonate brine B and mirabilite ore are obtained after 3.5g/L, separation of solid and liquid.
Mirabilite ore is based on mirabilite hydrate, and 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 that lithium concentration rises in bittern
To 2.6g/L~3.5g/L, separation of solid and liquid is carried out, obtained rich lithium carbonate brine is obtained when subsequently preparing carbonic acid lithium concentrate
Lithium carbonate yield 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 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 is obtained, which is imported, is warming up to 20 DEG C~60 DEG C, analysis in temperature elevation system
Go out carbonic acid lithium concentrate, separation of solid and liquid obtains carbonic acid lithium concentrate and bittern C when lithium concentration is down to 1g/L~2g/L in bittern.
The grade of the carbonic acid lithium concentrate is more than 60%, by essence of the evaporation less than 10% for limiting water in temperature-rise period
Thin control, the grade of carbonic acid lithium concentrate can reach more than 90%.
Preferable temperature is controlled at 40 DEG C~50 DEG C, preferably close to 45 DEG C.
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
Can from top to bottom it spray in temperature elevation system, while by the side that 100 DEG C~200 DEG C of hot-air and the bittern B are opposite or intersect
Formula is imported so that bittern B and hot-air carry out heat exchange in the form of relative or intersecting motion, so that 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, carbon is constantly separated out
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%.Fresh water is added for example, entering the light bittern dilution in preceding addition part in bittern or being sprayed in temperature-rise period, also may be used
Fresh water is added in thermal insulation pool.
There is provided a Wen Peng ponds when using Wen Peng ponds as temperature elevation system, 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 region of depth as shallow is quickly exchanged heat, is rapidly heated, and quickly separate out and criticize lithium carbonate, as bittern B
The region that width is small and depth is deep of the pond body in the Wen Peng ponds is reached, bittern B reaches stabilization by abundant heat-exchange temperature, and separates out
A large amount of lithium carbonates, separation of solid and liquid obtains carbonic acid lithium concentrate when lithium concentration is down to 1g/L~2g/L in bittern.
4th step, when environment temperature be higher than 0 DEG C when, the bittern C that the 3rd step is obtained with and high-magnesium brine mix, mixing
The ratio between amount of material of magnesium ion and potassium ion is 1.5 in the mixing bittern that ratio is constituted according to high-magnesium brine and bittern C:1~
5:1 measures, separation of solid and liquid after being aged 1~10 day after mixing, obtains bittern D and high-purity carbonic acid magnesium salts ore deposit.
Chloride type bittern of the high-magnesium brine for magnesium ion content more than or equal to 10g/L, or magnesium ion content are big
In or equal to 10g/L magnesium chloride solution.
With MgCO in the magnesium carbonate salt mine of acquisition3·3H2The purity of O meters is more than 60%, and impurity is mainly NaCl and a small amount of
KCl, can remove by washing and just can commercially be sold without further refining processing, because the ore deposit is without mechanical admixture, easily
In being processed into high purity product.
Further, since the temperature elevation system that the 3rd step is used is the system of closing, avoid introducing extraneous in temperature-rise period
Mechanical admixture, therefore, final obtained magnesium carbonate salt mine passes through the simple washing process of fresh water, directly in commercial type.
Compared with prior art, the present invention has advantages below：
(1) present invention based on the original bittern of carbonate-type, realized by controlling evaporation process fast enriching lithium from
The purpose of son, is not introduced into any chemical reagent, realizes cleaning, environment protection-type production, has broken away from the dependence to other resources.
(2) deep lake salt field last stage addition is entered after evaporation and concentration reaches 1.2g/L~1.8g/L to lithium concentration de-
Water saltcake, and dehydration saltcake is dissolved into bittern, and control sulfate ion concentration in bittern, it is to avoid sulfate radical is 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 is separated out, so that the whole process time shortens more than 2 months.
(3) on several key points in pilot process.The control of lithium concentration, the control of sulfate ion concentration,
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, adjusts lithium concentration, flexibly the evaporation of control Bittern of Salt Pan by adding slightly dilute bittern
Process.Lithium concentration in concentrated brine is controlled in this scope of 1.2g/L~1.8g/L, makes it in salt pan evaporation process
Not into salt, this situation is continued up into season and is transferred to autumn and winter, bittern is imported into deep lake salt Tanaka continues to be concentrated by evaporation, season
Winter is transferred to, environment temperature is constantly reduced, more than 70% mirabilite hydrate is preferential to be separated out from bittern, so as to take a large amount of knots out of rapidly
Brilliant water, lithium concentration rises rapidly, when the concentration of control sulfate ion is reduced to 4g/L~7g/L (preferably 6g/L~
7g/L), lithium concentration rises very rapidly up to 2.6g/L~3.5g/L in bittern, then separates out lithium carbonate after 20 DEG C~60 DEG C of heating
Bittern C is obtained after concentrate, separation of solid and liquid.
Separate out carbonic acid lithium concentrate after bittern C and high-magnesium brine mix according to a certain percentage, be aged after separation of solid and liquid
Obtain high-purity carbonic acid magnesium salts ore deposit.With MgCO in the magnesium carbonate salt mine3·3H2The purity of O meters is more than 70%, after any
Handling process, directly can commercially sell, or be processed into high purity product.
(4) it is used as temperature elevation system by the use of solar temperature rising system or Wen Peng ponds so that bittern and hot-air quickly exchange heat, soon
Speed heating, so as to quickly separate out lithium carbonate；In addition, the present invention handles bittern using temperature elevation system, it is to avoid applied mechanical impurity
Introduce, the high-purity magnesium carbonate finally given passes through the simple washing process of fresh water, directly as sale of finished goods.
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
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. preparing the method for high-purity magnesium 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
Import fresh water or dilute bittern to adjust lithium concentration into evaporation and concentration 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 the deep lake salt Tanaka that depth is more than or equal to 2m
Continue to be concentrated by evaporation；
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, with temperature continue to reduce and the crystallization water precipitation, borax, sodium chloride, potassium chloride are also with aqueous salt or simple salt
Form is separated out, and in the case, lithium concentration rises rapidly in bittern, and sulfate ion concentration refers to as control using in bittern
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~
Rich lithium carbonate brine B and mirabilite ore are obtained after 3.5g/L, separation of solid and liquid；
3rd step, the rich lithium carbonate brine B that second step is obtained, which is imported, is warming up to 20 DEG C~60 DEG C in temperature elevation system, separate out carbon
Sour lithium concentrate, separation of solid and liquid obtains carbonic acid lithium concentrate and bittern C when lithium concentration is down to 1g/L~2g/L in bittern；
4th step, when environment temperature is higher than 0 DEG C, the bittern C that the 3rd step is obtained is mixed with high-magnesium brine, and mixed proportion is pressed
The ratio between amount of material of magnesium ion and potassium ion is 1.5 in the mixing bittern constituted according to high-magnesium brine and bittern C:1~5:1 counts
Amount, separation of solid and liquid after being aged 1~10 day after mixing, obtains bittern D and high-purity carbonic acid magnesium salts ore deposit, the high-purity carbonic acid magnesium salts ore deposit
In with MgCO3·3H2The purity of O meters is more than 70%.
2. the method as described in claim 1, it is characterised in that：In the first step, when lithium concentration is approached 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
It is relatively low, when bittern minimum temperature is below 0 DEG C, lithium concentration control is being imported into deep lake salt field close to 1.8g/L.
5. the method as described in claim 1, it is characterised in that：In the first step, autumn, environment temperature drop are transferred to when season
It is low relatively slow, bittern minimum temperature at 0 DEG C~5 DEG C, by lithium concentration close to 1.2g/L bittern first import depth be less than or
Shallow lake salt Tanaka equal to 0.5m continues to be concentrated by evaporation, and is evaporated in bittern lithium concentration close to importing deep lake salt during 1.8g/L
Tanaka continues to evaporate.
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 is imported so that 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, lithium carbonate is constantly separated out, 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, length direction by 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 region of depth as shallow is entered
Row quickly exchanges heat, is rapidly heated, and quickly separates out lithium carbonate, and the width for reaching the pond body in the Wen Peng ponds as bittern B is small and depth
Deep region, bittern B reaches stabilization 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 first obtained carbonic acid lithium concentrate reaches more than 90%.
10. the method as described in claim 1, it is characterised in that：Bittern A is before deep lake salt field is imported in the first step
Dehydration saltcake is added in evaporating concentration process, fully dissolving is allowed to, controls evaporation rate, lithium is not separated out with mineral forms.
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