CN102491378A - Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine - Google Patents
Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine Download PDFInfo
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- CN102491378A CN102491378A CN2011103588647A CN201110358864A CN102491378A CN 102491378 A CN102491378 A CN 102491378A CN 2011103588647 A CN2011103588647 A CN 2011103588647A CN 201110358864 A CN201110358864 A CN 201110358864A CN 102491378 A CN102491378 A CN 102491378A
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- bittern
- halogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- 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
Abstract
The invention discloses a producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine. Firstly carbonate type brine and sulphate type brine are mixed for performing the first brine mixing, so as to ensure that CO3<2-> ion and Mg<2+> ion in the mixed brine are completely reacted to produce basic magnesium carbonate, brine is evaporated and concentrated, and solid and liquid are separated, so that basic magnesium carbonate precipitate is removed, and lithium enrichment brine is obtained; and then the lithium enrichment brine and carbonate type brine, the lithium ion concentration of which is evaporated and concentrated to be saturated or nearly saturated, are mixed for performing second brine mixing, so that Li+ ion in the mixed brine produces lithium carbonate, solid and liquid are separated, lithium carbonate precipitate is removed, and the lithium carbonate precipitate is washed with hot water and dried, so that lithium carbonate products are obtained. Besides electricity, the method basically does not require foreign material, the investment is less, the technology is simple, the method can be applied to the mass production of lithium carbonate, the acquisition rate is high, the product quality meets the national standard, and the method is particularly suitable for the development of lithium resources of saline lake in Tibet.
Description
Technical field
The invention belongs to the chemical industry of inorganic salt field, being specifically related to a kind of is raw material is produced Quilonum Retard with overlapping adding halogen method working method with carbonate type bittern and vitriolate type bittern.
Background technology
Quilonum Retard has high value and vast market prospect, and from bittern, producing the lithium salts method at present both at home and abroad has multiplely, mainly contains:
1, bittern-aluminate precipitator method;
2, organic solvent extractionprocess;
3, ion sieve method (IX, absorption) (seeing the 9th～13 page of " sea lake salt and chemical industry " the 29th the 4th phase of volume);
4, evaporative crystallization partition method;
5, the precipitator method;
6, flotation process; (see the 20th～26 page of " sea lake salt and chemical industry " the 20 volume fourth phase; The 14th～16 page of the 22nd the 1st phase of volume.The 29 volume the 4th phase 9-13 page or leaf).
7, bittern-thermal decomposition method: cooperate and use the milk of lime sulfate radical, then decompose with High Temperature Furnaces Heating Apparatus, make magnesium chloride be transformed into HCl and MgO, water logging Natural manganese dioxide residue adds soda ash again and removes remaining mg ion in leach liquor, produce the lithium salts product at last.
8, the solar pond method is utilized carbonate type bittern, under the normal temperature in spontaneous evaporation to the bittern Quilonum Retard saturated; Move to again in the solar pond, utilize solar heating bittern, because Quilonum Retard is a retrograde solubility; With the rising of temperature, the principle that solubleness descends is separated out Quilonum Retard in bittern.
9, the technology of utilizing the old halogen in salt lake to produce high-purity magnesium oxide and lithium salts that Chinese patent ZL200710024943.8 proposes.
Domestic salt lake resources is according to ore reserve latest survey data, and the Qinghai-Tibet Platean has 352 in salt lake, and the total area reaches 2.1465 ten thousand square kilometres, and the salt lake mainly contains carbonate type and two kinds of hydrochemical types of sulfate-type.But Tibet up to the present; Have only the Zha Buye salt lake research of Quilonum Retard, test to be formed certain industrial scale through the more than ten years; And the rate that obtains of Quilonum Retard is about 25%; Therefore the quality product lithium carbonate containing is 60～70%, and other has several salt lakes also among test, provides a new approach extremely urgent for the exploitation of Qinghai-Tibet salt lake lithium resource.
Carbonate type contains lithium bittern in the process of extracting Quilonum Retard, and the enrichment of lithium in bittern is a difficult problem, because the solubleness of Quilonum Retard is very little; And be again retrograde solubility, to the enrichment data of lithium in bittern, the saturated content of lithium is about 1.5g/l in the summer bittern according to the salt lake, Tibet; The saturated content of lithium is about 2.5g/l in the winter bittern, and is promptly big in spontaneous evaporation in summer amount, when helping producing; The solubleness of Quilonum Retard is little, and winter severe cold season is when being unfavorable for producing; The solubleness of Quilonum Retard is big, and the solar pond that industry is generally used has been brought very big difficulty to production.
Sulfate-type contains lithium bittern, in the process of extracting Quilonum Retard, though lithium ability enrichment in bittern; According to how tame salinization factory production data; But general lithium ion enrichment is to more than the 8g/l, and high-lithium ion can reach 12g/l, but magnesium, lithium separates is again that salt chemical engineering is produced the difficult problem in the lithium salts for many years.
Summary of the invention
The objective of the invention is to the difficult problem of above-mentioned two types of bittern in extracting the lithium process, providing a kind of is raw material is produced Quilonum Retard with overlapping adding halogen method working method with carbonate type bittern and vitriolate type bittern.
The object of the invention can reach through following measure:
A kind of to be raw material with carbonate type bittern and vitriolate type bittern produce the working method of Quilonum Retard with overlapping adding halogen method, comprises the steps:
1) carbonate type bittern is mixed with vitriolate type bittern carry out converting the first time halogen, the consumption of regulating two kinds of bittern makes the CO that mixes in the bittern
3 2-Ion and Mg
2+The ion complete reaction generates magnesium basic carbonate, and the bittern evaporation of converting after halogen is accomplished concentrates, and solid-liquid separation is removed the basic carbonate magnesium precipitate again, obtains lithium enrichment bittern;
2) saturated with evaporation concentration to lithium concentration or approaching saturated carbonate type bittern mixes with lithium enrichment bittern, carries out converting the second time halogen, and the consumption of regulating two kinds of bittern makes the Li that mixes in the bittern
+Ion generates Quilonum Retard, converts halogen and accomplishes the back solid-liquid separation and go out the Quilonum Retard deposition, and Quilonum Retard deposition and drying with hot wash obtains obtain lithium carbonate product.
Method of the present invention further can also comprise the step of converting halogen as follows for the third time: convert the liquid that halogen is accomplished and solid-liquid separation goes out for the second time; Merge with the washings of washing Quilonum Retard post precipitation; Mix with vitriolate type bittern and convert halogen for the third time, the consumption of regulating two kinds of bittern makes the CO that mixes in the saltwater brine
3 2-Ion and Mg
2+The ion complete reaction generates magnesium basic carbonate;
Convert for the third time after the halogen bittern directly with convert for the first time the halogen completion after bittern mix, carry out evaporation concentration more together, solid-liquid separation is removed the basic carbonate magnesium precipitate then, obtains lithium enrichment bittern to carry out the converting halogen second time;
Perhaps, convert the bittern elder generation evaporation concentration after the halogen for the third time, the bittern that obtains again with convert for the first time halogen and evaporation concentration after bittern mix, carry out solid-liquid separation then together and remove the basic carbonate magnesium precipitate, obtain lithium enrichment bittern to carry out the converting halogen second time;
Perhaps, convert the bittern elder generation evaporation concentration after the halogen for the third time, solid-liquid separation is removed the basic carbonate magnesium precipitate again, the liquid that obtains with convert for the first time the lithium enrichment bittern that halogen obtains and merge to carry out the converting halogen second time.
Method of the present invention is only through step 1) and step 2) can obtain the lithium carbonate product of higher degree and yield; But the discharge of farthest being extracted and reducing waste water for the lithium that makes in the bittern can be in step 1) and 2) increase the process of converting halogen for the third time afterwards.
Carbonate type bittern of the present invention is for containing CO
3 2-Ion and Li
+The ionic salt lake brine; Said vitriolate type bittern is for containing SO
4 2-Ion, Mg
2+Ion and Li
+The ionic salt lake brine.In two kinds of bittern, also might contain potassium, sodium, chlorine plasma, concrete bittern composition is different because of different salt lakes.Vitriolate type bittern also can extend to the magnesium-containing brine of other type among the present invention.
Two kinds of bittern of the present invention can directly be converted halogen and use; Also can earlier a kind of bittern prevapourising before converting halogen for the first time be concentrated; Because the bittern in the most of salt lakes of salt lake brine is undersaturated,, can reduce when converting halogen wherein a kind of operational throughput of bittern so first prevapourising concentrates.Can certainly two kinds of bittern all be carried out prevapourising and concentrate, alleviate the spissated pressure of subsequent evaporation to reduce water cut.Carbonate type bittern can be concentrated to CO wherein by first before use prevapourising
3 2-Ion reaches or is lower than saturation concentration; Vitriolate type bittern can be concentrated to Mg wherein by first before use prevapourising
2+Ion reaches or is lower than saturation concentration.
The purpose of converting for the first time halogen in the step 1 is in order to remove the mg ion in the bittern, because the magnesium basic carbonate that generates belongs to insoluble compound, can farthest to remove mg ion and can not influence the lithium ion in the bittern.Convert for the first time the consumption of two kinds of bittern in the halogen process,, confirm to convert the halogen ratio with carbanion and the lucky complete reaction of mg ion in the mixing bittern according to its concrete contained ionic amount.During reaction,, in the process of bittern evaporation enriching lithium, have Quilonum Retard and separate out, and cause the loss of lithium if carbonate is excessive in the bittern; If but carbonate is less, it is clean to cause in the bittern magnesium to remove, and when secondary is converted halogen, has magnesium basic carbonate and separates out, and influences the quality of Quilonum Retard.
Convert in the step 1 and carry out bittern evaporation after halogen is accomplished and concentrate, make the sedimentary ion of lithium owing to lack in the bittern, so lithium ion can reach enrichment largely.The content that can make lithium ion in the water after the evaporation concentration preferably makes lithium concentration reach 7.5～8.5g/l greater than 4g/l, and low moisture excessive in the bittern of can making crossed in the too high deposition loss that is prone to cause lithium ion, increases subsequent production pressure.Therefore Li in the lithium enrichment bittern that obtains in the step 1
+Ionic content is preferably 7.5～8.5g/l.
For the first time converting the halogen process can carry out under 0～90 ℃, considers for saving cost and other factors (like solubleness etc.), generally gets final product down at normal temperature (20～30 ℃).
Evaporation concentration to the lithium concentration that adopts in the step 2 is saturated or generally be 1.5～2.5g/l near the content of lithium ion in the saturated carbonate type bittern, according to the difference of concrete envrionment temperature and slightly different.Convert for the second time halogen and can make the lithium ion form with Quilonum Retard under eliminating mg ion interferential situation in lithium enrichment bittern and the saturated or near saturated bittern obtain as much as possible extracting, the lithium ion that mixes in the bittern is precipitated fully.
Convert in the halogen process for the second time, according to the ion content in two kinds of bittern, the consumption of regulating two kinds of bittern makes and mixes in the bittern and Li
+Ionic reaction generates the CO of Quilonum Retard
3 2-Ionic molar weight excessive 0～30%.The add-on that is carbanion is 100～130% of a theoretical amount, confirms to convert the halogen ratio.If carbanion has lacked, Quilonum Retard is separated out insufficient, influences the single line recovery of lithium, and carbonate is many can not reduce the eduction rate of lithium, but carbanion is too many, causes the idling of equipment, influences equipment capacity.
Convert for the second time the Quilonum Retard deposition that adopts hot wash to obtain after the halogen, because the solubleness of Quilonum Retard in water reduces along with the rising of temperature, so hot water can reduce the damage part that washing precipitation causes.The temperature of hot water can be regulated from 30 ℃～100 ℃, in order to make full use of local sun power, can adopt solar water to wash, and its temperature is generally 75～85 ℃.
For the second time converting halogen can carry out under 0～90 ℃, generally gets final product down at normal temperature (20～30 ℃).A kind of scheme is to carry out under to 85 ℃ at normal temperature (20～30 ℃), particularly can under 80 ℃ or condition near 80 ℃ (as 75 ℃～85 ℃), carry out, because the solubleness of Quilonum Retard is minimum under this temperature, can improve the eduction rate of the Quilonum Retard of this step.
Convert halogen for the third time and can make washing or extract the lithium loss that causes when incomplete and return again and carry out circulation extraction in the leaching process, the extraction rate reached that makes the lithium ion in the bittern to or near 100%.When converting halogen for the third time; According to the ionic concn in two kinds of bittern; It is (the same when converting halogen with the first time to confirm to convert the halogen ratio in the lucky complete reaction of chemical equation carbanion and mg ion; But be the recovery problem that has thoroughly solved lithium, and do not have trade effluent to discharge non-environmental-pollution in the whole process flow).
Convert liquid after the halogen for the third time and return the system of converting for the first time after the halogen.According to the liquid individual curing of converting for the third time after the halogen whether, can be divided into directly with convert for the first time halogen after bittern mixes, three kinds of situation of remix behind first concentrated remix and the first concentrating and separating solid.Convert the evaporation concentration of the bittern after the halogen for the third time; Comprise directly and convert the mixed evaporation concentration of bittern after the halogen for the first time; The content that can make lithium ion in the water preferably makes lithium concentration reach 7.5～8.5g/l greater than 4g/l, its concrete requirement with convert for the first time halogen after concentrated require identical.
Converting the halogen process for the third time can carry out under 0～90 ℃, considers for saving cost and other factors (like solubleness etc.), generally gets final product down at normal temperature (20～30 ℃).
The present invention provides a kind of salt lake carbonate type bittern and vitriolate type bittern or chloride type of utilizing to contain mg ion bittern; Carry out converting the first time halogen in proportion according to the bittern composition; The nature constant-temperature evaporation concentrates, and converts halogen for the second time again and separates out Quilonum Retard, and separate out the liquid behind the Quilonum Retard; Again convert halogen in the flow process before also will returning, thereby form the overlapping working method that halogen is produced Quilonum Retard of converting.
The present invention is directed to two difficult problems of two types of bittern in extracting the lithium process, proposing just has two or several place that two types of bittern are arranged in zone with good conditionsi; Carry out water body according to practical situation and shift, because that the ratio that the bittern in salt lake, Tibet is formed or formed all is difficult to is identical, even same salt lake is with changes of seasons; It is also bigger that it forms variation, even have the bittern type in minority salt lake to change, so when carrying out the water body transfer; Need take all factors into consideration the amount that water body shifts, the direction of transfer, sea level elevation (preferably gravity flow); Receive water body to shift the storage capability in salt lake, the factors such as area of building the salt pan.Shift through dissimilar water bodys, the bittern that can realize two salt lakes or several salt lakes is prepared and is mixed, and becomes favorable factor to adverse factors, promptly utilizes the CO in the carbonate type bittern
3 2-Ion remaval falls the mg ion in the vitriolate type bittern; Make magnesium, lithium be able to separate; Otherwise be to utilize the mg ion in the vitriolate type bittern to get rid of the carbanion in the carbonate type bittern, help the enrichment of lithium, thereby the lithium that reaches in two bittern can extract again in enrichment.
Detailed principle of the present invention is following:
Utilize CO in the carbonate type salt lake brine
3 2-Mg in ion and the sulfate type salt lake bittern
2+Ion mixes, and reaction generates the basic carbonate magnesium precipitate, removes the CO in the bittern
3 2-Ion and Mg
2+Ion, reaction equation is:
4Mg
2++4CO
3 2-+5H
2O→3MgCO
3·Mg(OH)
2·4H
2O↓+CO
2↑
Convert halogen for the first time and convert halogen for the third time according to above-mentioned principle.
Utilize the CO in the ortho-carbonate type lake salt bittern again
3 2-Ion and convert halogen the first/three time after (remove Mg
2+Ion and CO
3 2-Ion) Li in the lithium enrichment bittern
+Ion, reaction generate the Quilonum Retard deposition, and reaction equation is:
2Li
++CO
3 2-+H
2O→Li
2CO
3+H
2O
The overlapping halogen determination of ratio principle of converting of the present invention is:
For the first time convert halogen: be with carbanion in the carbonate type bittern and the lucky complete reaction of the mg ion in the vitriolate type bittern; Quality confirms to convert the halogen ratio than mg ion: carbonate=1: 2.469-2.470 (the different of relative molecular weight according to carbonate and mg ion are adopted can be adopted more accurate ratio).
Convert for the second time halogen; Be with the carbonate content in the carbonate type bittern after evaporation concentration (lithium ion near or reach capacity), and convert bittern after the halogen for the first time through evaporation concentration, its lithium ion enrichment is to certain content; The carbanion amount is 100～130% of a theoretical amount during according to carbonate in two kinds of bittern and lithium ion complete reaction; Theoretical amount ratio is that quality confirms to convert the halogen ratio than carbanion: lithium ion=4.322-5.620.
Converting halogen for the third time, is with the Mg in the vitriolate type bittern
2+Convert the ion content and the second time CO in the liquid after halogen is separated out Quilonum Retard
3 2-Content, the lucky complete reaction of mg ion and carbanion, quality are than mg ion: carbonate=1: 2.469-2.470, confirm to convert the halogen ratio.
Convert in the halogen process HCO in the bittern whole
3 -Ion is inoperative, can be used as foreign ion and does not consider, and facts have proved NaHCO
3(sodium bicarbonate) saturated solution and LICl saturated solution do not react no Quilonum Retard generation under normal temperature and 80 ℃ the condition of heating.
Bittern only removes mg ion and does not have the lithium ion loss when carrying out mixing the first time, its reason is that the magnesium basic carbonate that generates is an insoluble compound, and the solubility product of magnesiumcarbonate is K
SP=3.5 * 10
-8, the solubility product of Marinco H is K
SP=2.0 * 10
-24, and the solubleness of Quilonum Retard is: 1.54g (0 ℃), 1.33g (20 ℃), 0.72g (100 ℃).
The solubleness of Quilonum Retard is less, and the solubleness of Quilonum Retard is: 1.54g (0 ℃), 1.33g (20 ℃), 0.72g (100 ℃); So contain the carbonate type bittern of lithium, when bittern evaporation, summer; Lithium ion content can reach 1.5g/l in the bittern, otherwise will separate out with the form of Quilonum Retard, and winter; Lithium ion content then can reach 2.5g/l, so secondary is converted in the halogen process, the content of lithium ion is 1.5～2.5g/l in the saturated or near saturated carbonate type bittern of evaporation concentration to lithium ion.
In vitriolate type bittern, when magnesium ion content is higher in the bittern, just there is not carbanion; And when mg ion reaches certain content, have Lithium Sulphate in the bittern to separate out, if but remove the mg ion in this bittern, this not only do not have carbanion but also do not have in the bittern of mg ion, and so the further enrichment of the content of lithium ion is Li in the lithium enrichment bittern
+Ionic content is 7.5～8.5g/l.
Magnesium basic carbonate among the present invention is meant 3MgCO
3Mg (OH)
24H
2O or MgCO
3Mg (OH)
2
Evaporation concentration among the present invention comprises with the mode evaporation concentration of nature (like sunshine), also comprises the evaporation concentration with manual work heating, artificial lighting or other manual types.
Solid-liquid separation among the present invention comprises and adopts special equipment to incite somebody to action wherein solid or liquid separation, is also included within and directly carries out precipitate and separate in salt pan or elswhere or the facility, also comprises and adopts various filtration steps or facility to separate.
Beneficial effect of the present invention:
The present invention does not need external raw material basically except that electricity consumption, less investment, and technology is simple, can be used for extensive Quilonum Retard production, obtains the rate height, and quality product reaches national standard, is particularly suitable for the exploitation of the lithium resource in salt lake, Tibet (two types of salt lakes mix layout).
What the present invention was applicable to carbonate type (containing lithium) salt lake brine and any kind (containing magnesium, lithium) salt lake brine converts halogen production, thereby has solved carbonate type and sulfate type salt lake (containing lithium) bittern lithium enrichment and isolating two difficult problems of magnesium lithium in the lithium salts leaching process, and it has adaptability to raw material strong; Obtain the rate height, cost is low, because of production process is to lean on solar thermal energy spontaneous evaporation bittern; But also do not need external raw material and other chemical agent, and convert halogen for the second time exactly and separate out Quilonum Retard, in factory, carry out under the normal temperature; The hot water with 80 ℃ is washed in the lithium salts back washing, because consumption is little, just can satisfy with solar water; So plant produced has basically no pollution, the no three wastes, whole production technology is simple; How data changed during no matter how bittern was formed, and only needed to calculate two chemical equations (reaction of the reaction of carbonate and mg ion and carbonate and lithium ion), and general personnel can both grasp; Easy to control, easy to operate.Industrial scale is not limit, and the investment of founding the factory is little, mainly is to build a workshop, and Quilonum Retard after the halogen sedimentation washs converting, dry, packing, storage.
The present invention does not need external raw material basically except that electricity consumption, less investment, and technology is simple, can be used for extensive Quilonum Retard production, obtains the rate height, and quality product reaches national standard, is particularly suitable for the exploitation of the lithium resource in salt lake, Tibet (two types of salt lakes mix layout).
Description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Embodiment
Details are as follows in each concrete operations of the present invention:
One, according to year water body transfer amount and Hubei and Hunan Provinces sea level elevation, confirm that water body shifts the nominal diameter and the nominal pressure of required pipeline, and flow, the lift of required pump, too high like lift, available multilayer relay pump device.If the bittern concentration that water body shifts is crossed low or the water yield is bigger, can build salt pan (will according to the geologic condition around the salt lake) earlier, the bittern spontaneous evaporation is concentrated into a certain concentration, carry out water body again and shift.
Two, after accomplishing salt pan construction and a certain type water body and transferring to the salt pan in another type water body salt lake, just can carry out the salt pan and operate.
Three, carbonate type bittern, directly spontaneous evaporation to lithium ion is saturated, Li
+At 1.5～2.5g/l, subsequent use.Carbonate type bittern and vitriolate type bittern are in processing requirement ratio (CO
3 2-And Mg
2+) convert halogen, convert bittern that halogen accomplishes through spontaneous evaporation enrichment method lithium ion (, will reach the saturation point of potassium ion), (Li during the certain content of lithium ion enrichment in bittern when lithium enrichment during to the 3g/l left and right sides
+High more, the eduction rate of Quilonum Retard is high more), for use.
Four, the bittern that the carbonate type lithium ion is saturated and the bittern of lithium ion enrichment carry out multiple times of filtration respectively, remove water-insoluble, in processing requirement ratio (CO
3 2-And Li
+) carry out converting halogen the second time, separate out Quilonum Retard, because solid-to-liquid ratio is too little,, get Quilonum Retard slip and clear liquid so need elder generation settlement separate.
Five, clear liquid is returned before flow process and vitriolate type bittern by processing requirement (CO
3 2-And Mg
2+) convert halogen for the third time, accomplish the overlapping halogen whole process of converting.
Six, with the Quilonum Retard slip, filter, countercurrent washing is more than three times, and warp is dry again, must Powdered carbonic acid lithium product.
Annotate: Powdered carbonic acid lithium is when bullion, and water cut is too high, generally more than 30%; So to repeatedly wash, dry also big with heat, if when secondary is converted halogen; The crystallization rate of control Quilonum Retard, but manufacture order Oblique Crystal Quilonum Retard (commercially available prod basically all is a powdery product).This product is under preceding operation the same terms, owing to be crystal, the bullion water cut is few, and washing times and water consumption are few.
Seven, in actual industrial production; Respectively converting halogen operation is the assay of forming according to each stage bittern, calculate confirm each stage convert the halogen ratio after, input multiple spot control industrial computer; Commander respectively converts the halogen flowermeter by computer; Convert the halogen operation, converting halogen flow and total amount needs accurately, to guarantee to convert the accurate of halogen ratio.
Embodiment one:
1, get the A of Ali area, Tibet lake bittern water, density d=1.0785, form (g/l) as follows:
K
+ Mg
2+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
2.29 0.29 43.51 0.17 1.188 2.50 364.19
When this bittern evaporation was 1.78g/l to lithium ion content, it was formed as follows:
K
+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
23.85 107.953 1.78 12.375 18.52 166.177 (g/l)
Get this bittern 50L, subsequent use.This halogen is called A
1
2, get the B of Ali area, Tibet lake bittern water, density d=1.1, form (g/l) as follows:
K
+ Mg
2+ Na
+ Li
+ SO
4 2- Cl
-
3.288 12.651 32.179 0.13 4.678 86.058
With A lake bittern water A: B=94.6 in proportion: 5.4 mix convert halogen (basis of converting the halogen ratio is:
Mg ion: carbonate=1: 2.469, establish A=1, B=x, (0.29+12.651x) * 2.469=2.503 so; Get x=0.0572, A: B=1: 0.0572=94.6: 5.4); When being evaporated to the bittern lithium ion content then and being 8g/l, after solid-liquid separation, bittern consists of:
K
+ Na
+ Li
+ SO
4 2- Cl
-
41.46 90.75 8.0 16.619 206.143 g/l
Get this bittern 15L, subsequent use.This bittern is called B
1
3, press A
1Bittern: B
1Bittern=(press A at 3.5: 1
1Carbanion excessive 10% in the bittern), get A
135 liters in bittern, B
110 liters in bittern is under agitation converted halogen, and after converting halogen and accomplishing, restir 4 hours stops to stir, and its supernatant liquid is removed in free setting 2 hours, lower floor's slip is filtered, filter cake and clear liquid.The carbanion amount is 100～130% of a theoretical amount during according to carbonate in two kinds of bittern and lithium ion complete reaction, and theoretical amount ratio is carbanion: lithium ion=4.3228, and convert the halogen ratio and calculate: establish A
1Be 1, B
1Be x, carbonate is in excessive 10%, (1.78+8.0x) * 4.3228*110%=18.52, x=0.2643, A
1: B
1=1: 0.2643=3.78: 1, confirming to convert the halogen ratio is 3.5: 1.
4, the clear liquid amount in the 3rd step is 44.6L, and it consists of:
K
+ Cl
- Na
+ SO
4 2- Li
+ CO
3 2-
27.95 171.34 107.05 12.31 1.81 8.30 g/l
5, the filter cake in the 3rd step carries out back washing through 80 ℃ of hot water of three usefulness, after the filtration, and the filter cake oven dry, the oven dry product is lithium carbonate product.
Quilonum Retard is 310g after the washing and drying, contains purely to be: 99.44%, and a single line eduction rate of lithium is 77.3% (to refer to B
1Bittern) deduct wherein three countercurrent washings loss lithium and be about 6% of finished product lithium total amount, it is 72.4% that actual single line is obtained rate.
6, clear liquid and washings are mixed after chemical examination is converted halogen with the B lake bittern water; Be called and convert halogen for the third time; Promptly utilize carbanion and the reaction of the mg ion in the B lake bittern water in the clear liquid to generate magnesium basic carbonate; Thereby remove two kinds of carbanion and mg ions in the bittern, converting halogen for the third time is with the Mg in the vitriolate type bittern
2+Convert the ion content and the second time CO in the liquid after halogen is separated out Quilonum Retard
3 2-Content, the lucky complete reaction of mg ion and carbanion, mg ion: carbonate=1: 2.469, confirm to convert the halogen ratio, method of calculation are with converting for the first time halogen.This bittern gets into the bittern system after convert halogen the first time, continues evaporation concentration, obtains the bittern of lithium enrichment, participates in converting for the second time halogen, accomplishes the overlapping halogen of converting of whole process.
The result of laboratory test of above-mentioned test is listed in table 1.See attached list 1
Embodiment two:
Get A
1Bittern 7L gets B
1Bittern 2L is heated with stirring to 80 ℃ after the mixing, stir constant temperature for some time, and filtered while hot gets clear liquid.The clear liquid lithium ion content is 1.299g/l.Through simple material balance, B
1The single line eduction rate of bittern lithium is 83.76%, A
1The single line eduction rate of bittern lithium is 27.02%, and the Quilonum Retard that this example is separated out is a bullion, again through back washing and drying get final product finished product.
Annotate: the rate that always obtains of lithium: carrying secretly of other salt time-like separated out in bittern seepage that spontaneous evaporation is produced in the salt pan and salt pan evaporation; Be that the production of any salt pan is all unavoidable; Usually do not influence the calculating that Workshop Production always obtains rate, if by above-mentioned routine, calculate lithium in this technology always obtain rate the time; Except that the production plant run, drip, leak, lithium salts is basically all to have reclaimed.
Embodiment three:
1, get the C of Ali area, Tibet lake bittern water, density d=1.13, form (g/l) as follows:
K
+ Mg
2+ Ca
2+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
16.122 0.004 0.002 60.728 0.13 16.700 5.559 89.572
When this bittern evaporation was 1.78g/l to lithium ion content, it was formed as follows:
K
+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
49.04 107.12 1.78 15.89 75.97 197.945 (g/l)
Get this bittern 5L, subsequent use.This halogen is called C
1
2, get the D of Ali area, Tibet lake bittern water, density d=1.1275, form (g/l) as follows:
K
+ Mg
2+ Ca
2+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
- HCO
3 -
10.894 3.64 0.108 57.429 0.16 4.480 0.790 105.615 0.18
With A lake bittern water C: D=60.1 in proportion: 39.9 mix and convert halogen (method of calculation of converting the halogen ratio are with embodiment one; Calcium ion in the bittern, mg ion and carbanion equivalent proportioning); When being evaporated to the bittern lithium ion content then and being 7.889g/l, after solid-liquid separation, bittern consists of:
K
+ Na
+ Li
+ SO
4 2- Cl
- HCO
3 -
49.00 107.128 7.889 15.889 197.889 10.067 g/l
Get this bittern 10L, subsequent use.This bittern is called D
1
3, press C
1Bittern: D
1Bittern=(press C at 1: 1.8
1Carbanion excessive 10% in the bittern), get C
15 liters in bittern, D
19 liters in bittern is under agitation converted halogen, and after converting halogen and accomplishing, restir 4 hours stops to stir, and its supernatant liquid is removed in free setting 2 hours, lower floor's slip is filtered, filter cake and clear liquid.(the carbanion amount is 100～130% of a theoretical amount during with the lithium ion complete reaction according to the carbonate in two kinds of bittern, and theoretical amount ratio is carbanion: lithium ion=4.3228, convert the calculating of halogen ratio: establish C
1Be 1, D
1Be x, carbonate is in excessive 10%, (1.78+7.889x) * 4.3228*110%=75.97, x=1.8, C
1: D
1=1: 1.8, confirming to convert the halogen ratio is 1: 1.8.)
4, the clear liquid amount in the 3rd step is 13.85L, and it consists of:
K
+ Cl
- Na
+ SO
4 2- Li
+ CO
3 2- HCO
3 -
48.97 197.56 106.781 15.56 1.82 6.43 g/l
5, the filter cake in the 3rd step carries out back washing through 80 ℃ of hot water of three usefulness, after the filtration, and the filter cake oven dry, the oven dry product is lithium carbonate product.
Quilonum Retard is 273g after the washing and drying, contains purely to be: 99.21%, and a single line eduction rate of lithium is 76.93% (to refer to B
1Bittern) deduct wherein three countercurrent washings loss lithium and be about 6% of finished product lithium total amount, it is 72.3% that actual single line is obtained rate.
6, clear liquid and washings are mixed after chemical examination is converted halogen with the D lake bittern water, be called and convert halogen for the third time, promptly utilize carbanion and the reaction of the mg ion in D lake bittern water generation magnesium basic carbonate in the clear liquid; Thereby remove two kinds of carbanion and mg ions in the bittern; This bittern gets into the system after convert halogen the first time, continues evaporation concentration, obtains the bittern of lithium enrichment; Participate in converting for the second time halogen, accomplish the overlapping halogen of converting of whole process.
The result of laboratory test of above-mentioned test is listed in table 2.See attached list 2
Subordinate list 1:
Subordinate list 2:
Claims (10)
- One kind to be raw material with carbonate type bittern and vitriolate type bittern produce the working method of Quilonum Retard with overlapping adding halogen method, it is characterized in that comprising the steps:1) carbonate type bittern is mixed with vitriolate type bittern carry out converting the first time halogen, the consumption of regulating two kinds of bittern makes the CO that mixes in the bittern 3 2-Ion and Mg 2+The ion complete reaction generates magnesium basic carbonate, and the bittern evaporation of converting after halogen is accomplished concentrates, and solid-liquid separation is removed the basic carbonate magnesium precipitate again, obtains lithium enrichment bittern;2) saturated with evaporation concentration to lithium concentration or approaching saturated carbonate type bittern mixes with lithium enrichment bittern, carries out converting the second time halogen, and the consumption of regulating two kinds of bittern makes the Li that mixes in the bittern +Ion generates Quilonum Retard, converts halogen and accomplishes the back solid-liquid separation and go out the Quilonum Retard deposition, and Quilonum Retard deposition and drying with hot wash obtains obtain lithium carbonate product.
- 2. method according to claim 1; It is characterized in that converting the said second time liquid that halogen is accomplished and solid-liquid separation goes out; Merge with the washings of washing Quilonum Retard post precipitation, mix with vitriolate type bittern and convert halogen for the third time, the consumption of regulating two kinds of bittern makes the CO that mixes in the saltwater brine 3 2-Ion and Mg 2+The ion complete reaction generates magnesium basic carbonate;Convert for the third time after the halogen bittern directly with convert for the first time the halogen completion after bittern mix, carry out evaporation concentration more together, solid-liquid separation is removed the basic carbonate magnesium precipitate then, obtains lithium enrichment bittern to carry out the converting halogen second time;Perhaps, convert the bittern elder generation evaporation concentration after the halogen for the third time, the bittern that obtains again with convert for the first time halogen and evaporation concentration after bittern mix, carry out solid-liquid separation then together and remove the basic carbonate magnesium precipitate, obtain lithium enrichment bittern to carry out the converting halogen second time;Perhaps, convert the bittern elder generation evaporation concentration after the halogen for the third time, solid-liquid separation is removed the basic carbonate magnesium precipitate again, the liquid that obtains with convert for the first time the lithium enrichment bittern that halogen obtains and merge to carry out the converting halogen second time.
- 3. method according to claim 1 and 2 is characterized in that said carbonate type bittern is for containing CO 3 2-Ion and Li +The ionic salt lake brine; Said vitriolate type bittern is for containing SO 4 2-Ion, Mg 2+Ion and Li +The ionic salt lake brine.
- 4. method according to claim 1 and 2 is characterized in that the first before use prevapourising of said carbonate type bittern is concentrated to CO wherein 3 2-Ion reaches or is lower than saturation concentration; The first before use prevapourising of said vitriolate type bittern is concentrated to Mg wherein 2+Ion reaches or is lower than saturation concentration.
- 5. method according to claim 1 and 2 is characterized in that Li in the said lithium enrichment bittern +Ionic content is 7.5～8.5g/l.
- 6. method according to claim 1 is characterized in that step 2) described in evaporation concentration to lithium concentration saturated or be 1.5～2.5g/l near the content of lithium ion in the saturated carbonate type bittern.
- 7. method according to claim 1 is characterized in that converting in the halogen process for the second time, and the consumption of regulating two kinds of bittern makes and mixes in the bittern and Li +Ionic reaction generates the CO of Quilonum Retard 3 2-Ionic molar weight excessive 0～30%.
- 8. method according to claim 1 is characterized in that step 2) in the temperature of hot water be 75～85 ℃.
- 9. method according to claim 2, the bittern evaporation that it is characterized in that converting for the third time after the halogen is concentrated into Li +Ionic content reaches 7.5～8.5g/l.
- 10. method according to claim 1 and 2 is characterized in that converting halogen the first time or converting halogen for the second time and under 0～90 ℃, carry out; Converting halogen for the third time carries out under 0～90 ℃.
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| CN103074502A (en) * | 2013-01-29 | 2013-05-01 | 中国科学院青海盐湖研究所 | Salt lake brine treatment method for separating lithium from high-magnesium-lithium-ratio salt lake brine |
| CN103482660A (en) * | 2013-09-13 | 2014-01-01 | 西藏金睿资产管理有限公司 | Method and system for preparing high-purity lithium carbonate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273941A (en) * | 2000-05-31 | 2000-11-22 | 青海省地质矿产勘查院 | Process for separating Mg and Li from high-Mg Li-contained bittern |
| US20060115396A1 (en) * | 1998-07-16 | 2006-06-01 | Boryta Daniel A | Production of lithium compounds directly from lithium containing brines |
| CN101481125A (en) * | 2009-02-13 | 2009-07-15 | 海门容汇通用锂业有限公司 | Method for cyclically using lithium deposition for preparing sodium carbonate solution to produce lithium carbonate |
| CN101875497A (en) * | 2010-08-18 | 2010-11-03 | 化工部长沙设计研究院 | Production process for extracting lithium from raw brine of high magnesium-lithium ratio lithium salt-containing lake |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219550A (en) * | 1989-03-31 | 1993-06-15 | Cyprus Foote Mineral Company | Production of low boron lithium carbonate from lithium-containing brine |
| CN1093517C (en) * | 1999-04-20 | 2002-10-30 | 中国地质科学院盐湖与热水资源研究发展中心 | Lithium salt extraction process from carbonate type bittern |
| CN1307104C (en) * | 2003-03-21 | 2007-03-28 | 钟辉 | Magnesium sulfate hypotype salt lake brine magnesium lithium separation method |
-
2011
- 2011-11-11 WO PCT/CN2011/082081 patent/WO2013053165A1/en active Application Filing
- 2011-11-11 CN CN 201110358864 patent/CN102491378B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060115396A1 (en) * | 1998-07-16 | 2006-06-01 | Boryta Daniel A | Production of lithium compounds directly from lithium containing brines |
| CN1273941A (en) * | 2000-05-31 | 2000-11-22 | 青海省地质矿产勘查院 | Process for separating Mg and Li from high-Mg Li-contained bittern |
| CN101481125A (en) * | 2009-02-13 | 2009-07-15 | 海门容汇通用锂业有限公司 | Method for cyclically using lithium deposition for preparing sodium carbonate solution to produce lithium carbonate |
| CN101875497A (en) * | 2010-08-18 | 2010-11-03 | 化工部长沙设计研究院 | Production process for extracting lithium from raw brine of high magnesium-lithium ratio lithium salt-containing lake |
Non-Patent Citations (1)
| Title |
|---|
| 刘海明等: "南美硫酸镁型硼锂盐湖综合利用技术评述", 《盐业与化工》, vol. 40, no. 3, 31 May 2011 (2011-05-31) * |
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