CN1274855C - Method for combined extraction of magnesium and lithium from salt lake brine - Google Patents
Method for combined extraction of magnesium and lithium from salt lake brine Download PDFInfo
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- CN1274855C CN1274855C CN 200310119202 CN200310119202A CN1274855C CN 1274855 C CN1274855 C CN 1274855C CN 200310119202 CN200310119202 CN 200310119202 CN 200310119202 A CN200310119202 A CN 200310119202A CN 1274855 C CN1274855 C CN 1274855C
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- 239000011777 magnesium Substances 0.000 title claims abstract description 88
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000012267 brine Substances 0.000 title claims abstract description 33
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 238000000605 extraction Methods 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000001556 precipitation Methods 0.000 claims abstract description 64
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 39
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000012452 mother liquor Substances 0.000 claims abstract description 23
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 21
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 20
- 239000001110 calcium chloride Substances 0.000 claims abstract description 18
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 17
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 17
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 17
- 239000004571 lime Substances 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 14
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 17
- 239000000347 magnesium hydroxide Substances 0.000 claims description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 239000008267 milk Substances 0.000 claims description 9
- 210000004080 milk Anatomy 0.000 claims description 9
- 235000013336 milk Nutrition 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 241001131796 Botaurus stellaris Species 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 238000007599 discharging Methods 0.000 claims 2
- 239000010413 mother solution Substances 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 2
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 241000347485 Silurus glanis Species 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Fertilizers (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for jointly extracting magnesium and lithium from salt lake brine, which is characterized by comprising the following steps of: the method takes salt lake brine with high concentration, particularly high magnesium-lithium ratio, as a raw material, and adopts ammonia and ammonium bicarbonate to precipitate magnesium in two sections, so as to realize effective separation and extraction of magnesium and lithium; precipitating magnesium at the first stage, adding 5-10% of seed crystals, controlling the magnesium precipitation efficiency to be 80-85% and the concentration of free ammonia to be 1.2-1.5 mol/L, precipitating magnesium at the second stage, adding ammonium bicarbonate in a solid form, reacting at normal temperature, wherein the concentration of free ammonia is lower than 0.3mol/L, and the total extraction rate of magnesium is more than 98%; the concentration of ammonium chloride in the magnesium precipitation mother liquor is high, which is beneficial to the recovery and the enrichment of lithium chloride; the method comprises the steps of converting ammonium chloride into ammonia by a lime method for recycling, evaporating ammonia mother liquor to produce calcium chloride, and producing lithium carbonate by using an enriched lithium chloride solution, wherein the extraction rate of lithium is more than 95%. The method has the advantages of good magnesium-lithium separation effect, high extraction rate, low production cost, good comprehensive benefit and no environmental pollution.
Description
The technical field is as follows:
the invention relates to the field of metallurgy, in particular to a method for jointly extracting magnesium and lithium from salt lake brine.
Background art:
for the salt lake brine with high concentration, particularly high magnesium-lithium ratio, the separation and extraction of magnesium and lithium are very difficult, so far, few literature reports on the aspect are reported, and the extraction research of magnesium and lithium is independently carried out, so the production cost is high, and the comprehensive benefit is poor. The extraction methods are now summarized as follows:
(1) the lime milk precipitation method has high requirements on the activity and purity of lime, the control range of the pH value of magnesium precipitation reaction is narrow, the method is notsuitable for high-concentration brine, and reaction products Mg (OH)2The particles are fine and difficult to filter, and the water content of the filter material is up to more than 50 percent;
(2) the carbonate precipitation method is to precipitate industrial sodium carbonate Na2CO3The following reaction is formed by adding concentrated salt lake brine:
lithium salt (Li) is extracted from lithium ore of Yingfeng in Welss lake, Chile Bokana horse and the dam chemical plant of Zhang Jia of Sichuan province in China by the method2CO3)；
(3) The ion resin exchange method utilizes artificial resin to be directly added into brine to adsorb Li, the method has low resin utilization rate, only 2-3 times of resin utilization can lose adsorption effect, and the method is not economical and has a problem in large-scale production;
(4) the organic solvent extraction method uses tributyl phosphate to extract lithium in brine, and has two problems, namely high cost and serious environmental pollution caused by organic solvent to salt lake regions;
(5) professor of Federal science and technology of Switzerland, and President J.Hsu (Jinghua) of the scientific mining and oil exploration shares of SwitzerlandThe 'evaporating pump principle' and the in-situ 'chemical reaction pool method' are used for carrying out indoor and field lithium extraction tests on the old brine discharged from the potash fertilizer plant in the Qinghai Kazaire juice salt lake in China, and certain success is achieved, but the method also has two problems, namely that magnesium is bischofite (MgCl)2·6H2O) crystal yield, the value is not high, and secondly, in the evaporation concentration process, although the relative content of lithium mixed in bischofite is not high (0.98%), the absolute content is large, so the loss of lithium is large, and the extraction rate is not high;
(6) the ammonia water precipitation method is to slowly add ammonia water with certain concentration into brine for magnesium precipitation reaction to generate Mg (OH)2High purity of product, low content of Ca, B and other impurities, and easy production of high-purity magnesite. However, the reaction raw materials of brine and ammonia water need to be diluted, the material running amount is large, the equipment productivity is low, the production cost is high, and the concentration of free ammonia in the reaction system is high, so that the environmental pollution is easily caused. If the method can solve the two problems and is applied to the separation and extraction of magnesium and lithium in salt lake brine, the method has the most development prospect.
The invention content is as follows:
the invention aims to extract magnesium and lithium by taking high-concentration salt lake brine with high magnesium-lithium ratio as a raw material and adopting two-stage magnesium precipitation. The concentration of free ammonia in the magnesium precipitation process is low, and particularly the concentration of free ammonia in the mother liquor after the two-stage magnesium precipitation is only 0.2-0.3 mol/L; the separation effect of magnesium and lithium is obvious, and the production cost is low; the production process has no environmental pollution and good comprehensive benefits.
The technical scheme of the invention is that high-concentration salt lake brine is used as a raw material, a two-stage magnesium precipitation method of ammonia and ammonium bicarbonate is adopted to separate magnesium and lithium, asalt field method byproduct ammonium chloride and concentrated lithium brine are used for producing lithium carbonate, a lime ammonia distillation method is used for converting magnesium chloride into ammonia for recycling, and a salt field method byproduct calcium chloride is characterized in that:
① the method comprises the steps of taking high-concentration salt lake brine with high magnesium-lithium ratio as a raw material, wherein the content of magnesium chloride is 400-450 g/L, and the content of lithium chloride is 0.1-0.3 mol/L;
② filtering the brine with a filter press or vacuum filtration equipment to remove solid suspended impurities in the brine for use;
③ adding reaction bottom liquid with volume half of that of bittern system into the first magnesium precipitation tank, wherein the bottom liquid is prepared by mixing 5-10 wt% of magnesium hydroxide seed crystal and deionized water;
④ adding ammonium chloride, lime and water into an ammonia distillation tank, introducing steam for heating, introducing ammonia generated by the reaction into a first-stage magnesium precipitation tank, and meanwhile, slowly adding brine into the magnesium precipitation tank under stirring for magnesium precipitation reaction, wherein the magnesium precipitation efficiency is controlled to be 80-85%, the concentration of free ammonia is 1.2-1.5 mol/L, and the magnesium precipitation reaction temperature is 50-85 ℃;
⑤ after the first stage of magnesium precipitation reaction, the reaction material is put into a settling tank, is kept stand and cooled, when the reaction material is cooled to room temperature, the supernatant is discharged, the bottom material of the sediment is filtered and washed by a centrifuge, the filtrate is merged into the discharged supernatant to obtain a first stage of magnesium precipitation mother liquor I, the concentration of magnesium chloride in the magnesium precipitation mother liquor reaches 300g/L, the free ammonia is lower than 0.3mol/L, the filtered, washed and dried magnesium hydroxide is calcined to produce magnesium oxide and magnesia, the total extraction rate of magnesium is higher than 98%, lithium chloride completely enters the magnesium precipitation mother liquor, and the separation effect of magnesium and lithium is remarkable.
⑥ adding the first-stage magnesium precipitation mother liquor I into a second-stage magnesium precipitation tank, slowly adding solid ammonium bicarbonate at room temperature, performing second-stage magnesium precipitation reaction, stirring for 1 hr after adding ammonium bicarbonate, filtering with a centrifuge, washing, and mixing the filtrate and washing liquor to obtain mother liquor II;
⑦ pouring the mother liquid II into salt pan, evaporating water naturally in the sun, separating out ammonium chloride by continuous crystallization, enriching lithium chloride, filtering and separating out ammonium chloride with centrifuge, and returning to ammonia evaporation process to obtain mother liquid III, i.e. concentrated lithium bittern after enriching lithium chloride;
⑧ mother liquor III contains LiCl200g/L or more and Mg2+Producing lithium carbonate by a carbonate precipitation method, wherein the ion content is lower than 5 g/L;
⑨ the mother liquid of lime milk after ammonia evaporation contains 50-60% calcium chloride, and is filtered by filter press to remove solid impurities, and then poured into salt pan where water is naturally evaporated in the sun, and the calcium chloride is CaCl2·6H2Separating out O crystal hydrate, drying to obtain anhydrous productCalcium chloride.
The advantages and positive effects ofthe invention are fully embodied as follows:
1. the invention takes the salt lake brine with high concentration, particularly high magnesium-lithium ratio, as the raw material, adopts two-stage magnesium precipitation to separate magnesium and lithium, and has the advantages of recycling ammonia, small material flow and high equipment productivity.
2. The magnesium hydroxide obtained by the invention has settling, filtering and washing performances, is beneficial to removing and separating impurities, and the water content of the magnesium hydroxide filter material is lower than 15%. The water content index of the magnesium hydroxide filter material obtained by other methods at home and abroad is usually between 30 and 50 percent.
3. The magnesium hydroxide obtained by the invention is in a hexagonal crystal structure and does not have colloidal property any more, so that impurities such as boron and the like are not adsorbed, and the raw materials only need to be subjected to simple filtration treatment without removing boron by other methods.
4. The concentration of the ammonium chloride in the magnesium precipitation mother liquor obtained by the method is as high as 300g/L, the ammonium chloride is easy to recover by a salt pan method, and lithium chloride is enriched at the same time; LiCl content in lithium bittern is up to more than 200g/L, and Mg2+The content is less than 5 g/L.
5. The concentration of calcium chloride in the ammonia distillation mother liquor obtained by the method is as high as 50-60%, and the calcium chloride is easy to recover by a salt pan method.
6. The concentration of free ammonia in the magnesium precipitation process is low, particularly the concentration of free ammonia in the mother liquor after the two-stage magnesium precipitation is only 0.2-0.3 mol/L, and the production process has no environmental pollution.
7. The invention can jointly extract magnesium and lithium, and has the advantages of obvious magnesium and lithium separation effect, low production cost and good comprehensive benefit.
Description of the drawings:
FIG. 1: the invention discloses a process flow diagram for jointly extracting magnesium and lithium from salt lake brine.
The specific implementation mode is as follows:
this is further illustrated below in connection with FIG. 1:
① preparing reaction base liquid
500L of deionized water is added into a first-stage magnesium precipitation tank with the volume of 2000L, and then 30kg of magnesium hydroxide is added as seed crystal to form reaction bottom liquid.
② distilling lime milk with ammonia to precipitate magnesium
Adding 600kg of water and 385kg of lime into a 2000L ammonia distillation tank, stirring to obtain lime milk, adding 580kg of solid ammonium chloride, heating by steam, and introducing ammonia generated by reaction into a first-stage magnesium precipitation tank; meanwhile, 1300kg of brine is slowly added into a first-stage magnesium precipitation tank under stirring to carry out magnesium precipitation reaction, and the temperature of the magnesium precipitation reaction is controlled to be 70 +/-7 ℃.
③ settling, filtering and washing of magnesium hydroxide
After the first-stage magnesium deposition reaction is finished, the reaction material is placed into a settling tank, standing and cooling are carried out, magnesium hydroxide is rapidly deposited, when the reaction material is cooled to room temperature, supernatant is discharged, a bottom material of the deposited material is filtered and washed by a centrifugal machine, filtrate is merged into the discharged supernatant to obtain first-stage magnesium deposition mother liquor I, the water content of the washed and filtered magnesium hydroxide is lower than 15%, and the magnesium hydroxide can be further calcined to produce magnesium oxide or magnesia after drying.
④ two-stage precipitation of magnesium from ammonium bicarbonate
And adding the first-stage magnesium precipitation mother liquor I into a second-stage magnesium precipitation tank, slowly adding 150kg of solid ammonium bicarbonate at room temperature, carrying out second-stage magnesium precipitation reaction, continuously stirring for 1 hour after the ammonium bicarbonate is added, then washing by using a centrifugal machine, filtering, and combining filtrate and washing liquor to obtain mother liquor II.
⑤ method for recovering ammonium chloride, enriching lithium chloride, and producing lithium silicate
And (3) pouring the mother liquor II into a salt pan, naturally evaporating water in the sun, continuously crystallizing and separating out ammonium chloride, continuously enriching lithium chloride, filtering and separating out the ammonium chloride by using a centrifugal machine, returning to an ammonia evaporation process, wherein the enriched lithium chloride solution contains about 200g/L of LiCl, and producing lithium carbonate by using a carbonate precipitation method.
⑥ recovery of calcium chloride by salt field method
The mother liquid after ammonia evaporation of lime milk contains 50-60% of calcium chloride, and is poured into salt pan after solid impurities are removed by a filter press, and the water content is self-absorbed under the sunThen evaporating, adding CaCl as calcium chloride2·6H2Separating out O crystal hydrate, and further drying to produce anhydrous calcium chloride.
Claims (2)
1. A method for jointly extracting magnesium and lithium from salt lake brine is characterized in that the salt lake brine with high concentration and high magnesium-lithium ratio is used as a raw material, magnesium and lithium are separated by adopting a two-stage magnesium precipitation method of ammonia and ammonium bicarbonate, a salt field method byproduct ammonium chloride and concentrated lithium brine are used for producing lithium carbonate, magnesium chloride is converted into ammonia by a lime ammonia distillation method for recycling, and a salt field method byproduct calcium chloride is used for recycling, and the method is characterized in that:
① the method comprises the steps of taking high-concentration salt lake brine with high magnesium-lithium ratio as a raw material, wherein the content of magnesium chloride is 400-450 g/L, and the content of lithium chloride is 0.1-0.3 mol/L;
② filtering the brine with a filter press or vacuum filtration equipment to remove solid suspended impurities in the brine for use;
③ adding reaction bottom liquid with volume half of that of bittern system into the first magnesium precipitation tank, wherein the bottom liquid is prepared by mixing 5-10 wt% of magnesium hydroxide seed crystal and deionized water;
④ adding ammonium chloride, lime and water into an ammonia distillation tank, introducing steam for heating, introducing ammonia generated by the reaction into a first-stage magnesium precipitation tank, and meanwhile, slowly adding brine into the magnesium precipitation tank under stirring for magnesium precipitation reaction, wherein the magnesium precipitation efficiency is controlled to be 80-85%, the concentration of free ammonia is 1.2-1.5 mol/L, and the temperature of the magnesium precipitation reaction is 50-85 ℃;
⑤ after the first-stage magnesium precipitation reaction, putting the reaction material into a settling tank, standing and cooling, discharging supernatant when cooling to room temperature, filtering and washing the bottom material of the sediment by a centrifuge, merging the filtrate into the discharged supernatant to obtain a first-stage magnesium precipitation mother solution I, and calcining the filtered, washed and dried magnesium hydroxide to produce magnesium oxide and magnesia;
⑥ adding the first-stage magnesium precipitation mother liquor I into a second-stage magnesium precipitation tank, slowly adding solid ammonium bicarbonate at room temperature, performing second-stage magnesium precipitation reaction, stirring for 1 hr after adding ammonium bicarbonate, filtering with a centrifuge, washing, and mixing the filtrate and washing liquor to obtain mother liquor II;
⑦ pouring the mother liquid II into salt pan, evaporating water naturally in the sun, separating out ammonium chloride by continuous crystallization, enriching lithium chloride, filtering and separating out ammonium chloride with centrifuge, and returning to ammonia evaporation process to obtain mother liquid III, i.e. concentrated lithium bittern after enriching lithium chloride;
⑧ mother liquor III contains LiCl200g/L or more and Mg2+Producing lithium carbonate by a carbonate precipitation method, wherein the ion content is lower than 5 g/L;
⑨ the mother liquid of lime milk after ammonia evaporation contains 50-60% calcium chloride, and is filtered by filter press to remove solid impurities, and then poured into salt pan where water is naturally evaporated in the sun, and the calcium chloride is CaCl2·6H2Separating out O crystal hydrate, and further drying to produce anhydrous calcium chloride.
2. The method for combined extraction of magnesium and lithium from salt lake brine as claimed in claim 1, wherein:
① preparing reaction base liquid
Adding 500L of deionized water into a section of magnesium precipitation tank with the volume of 2000L, and then adding 30kg of magnesium hydroxide as seed crystal to form reaction bottom liquid;
② distilling lime milk with ammonia to precipitate magnesium
Adding 600kg of water and 385kg of lime into a 2000L ammonia distillation tank, stirring to obtain lime milk, adding 580kg of solid ammonium chloride, heating by steam, and introducing ammonia generated by reaction into a first-stage magnesium precipitation tank; meanwhile, 1300kg of brine is slowly added into a first-stage magnesium precipitation tank under stirring to carry out magnesium precipitation reaction, and the temperature of the magnesium precipitation reaction is controlled to be 70 +/-7 ℃;
③ settling, filtering and washing of magnesium hydroxide
After the first-stage magnesium precipitation reaction is finished, putting the reaction material into a settling tank, standing and cooling, rapidly settling magnesium hydroxide, discharging supernatant when cooling to room temperature, filtering and washing a sedimentation base material by using a centrifugal machine, merging the filtrate into the discharged supernatant to obtain first-stage magnesium precipitation mother liquor I, and drying and then further calcining to produce magnesium oxide or magnesia, wherein the water content of the washed and filtered magnesium hydroxide is lower than 15%;
④ two-stage precipitation of magnesium from ammonium bicarbonate
Adding the first-stage magnesium precipitation mother liquor I into a second-stage magnesium precipitation tank, slowly adding 150kg of solid ammonium bicarbonate at room temperature, carrying out second-stage magnesium precipitation reaction, continuously stirring for 1 hour after the ammonium bicarbonate is added, then washing by using a centrifugal machine, filtering, and combining filtrate and washing liquor to obtain mother liquor II;
⑤ method for recovering ammonium chloride, enriching lithium chloride, and producing lithium silicate
Pouring the mother liquor II into a salt pan, naturally evaporating water in the sun, continuously crystallizing and separating out ammonium chloride, continuously enriching lithium chloride, filtering and separating out the ammonium chloride by using a centrifugal machine, returning to an ammonia evaporation process, and producing lithium carbonate by using a carbonate precipitation method, wherein the enriched lithium chloride solution contains about 200g/L LiCl;
⑥ recovery of calcium chloride by salt field method
The mother liquid after ammonia evaporation of lime milk contains 50-60% of calcium chloride, the solid impurities are removed by a filter press and then the mother liquid is poured into a salt pan, water is naturally evaporated in the sun, and the calcium chloride is CaCl2·6H2Separating out O crystal hydrate, and further drying to produce anhydrous calcium chloride.
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| CN 200310119202 CN1274855C (en) | 2003-11-20 | 2003-11-20 | Method for combined extraction of magnesium and lithium from salt lake brine |
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| CN 200310119202 CN1274855C (en) | 2003-11-20 | 2003-11-20 | Method for combined extraction of magnesium and lithium from salt lake brine |
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| CN1274855C true CN1274855C (en) | 2006-09-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11180369B2 (en) | 2019-07-30 | 2021-11-23 | Qinghai Institute Of Salt Lakes, Chinese, Academy Of Sciences | Renewable magnesium removing agent and its use in preparation of low-magnesium lithium-rich brine |
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| CN101538057B (en) * | 2009-04-24 | 2014-05-07 | 钟辉 | Method for separating magnesium from lithium and extracting lithium from brine |
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| CN102432045B (en) * | 2011-09-26 | 2013-02-13 | 江苏海龙锂业科技有限公司 | Preparation method of ultra-high purity lithium carbonate |
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| CN103253689B (en) * | 2012-02-17 | 2016-01-13 | 西藏国能矿业发展有限公司 | The method of lithium, magnesium is extracted from salt lake brine |
| CN102602966B (en) * | 2012-04-06 | 2014-01-08 | 华东理工大学 | Method for separating magnesium and lithium in salt lake brine and preparing lithium carbonate |
| FI124088B (en) | 2012-06-05 | 2014-03-14 | Outotec Oyj | Method and apparatus for preparing a pure solution containing lithium |
| CN102862997A (en) * | 2012-10-09 | 2013-01-09 | 新疆安华矿业投资有限公司 | Method for removing magnesium and sulfate ion in salt lake brine of hexahydric salt-water system |
| CN103074502B (en) * | 2013-01-29 | 2014-04-23 | 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 |
| CN106282557B (en) * | 2016-08-05 | 2018-08-28 | 四川思达能环保科技有限公司 | The method for concentration of lithium leachate |
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| CN107828960B (en) * | 2017-11-08 | 2019-04-30 | 中国科学院过程工程研究所 | The collaboration extraction system and its processing method of magnesium and lithium in a kind of salt lake bittern |
| CN108046620B (en) * | 2017-12-08 | 2019-10-22 | 中南大学 | A method of it is prepared by magnesite light burnt powder containing chrome-magnesite |
| CN109133120A (en) * | 2018-06-12 | 2019-01-04 | 国投新疆罗布泊钾盐有限责任公司 | Method for preparing high-purity magnesium oxide by using magnesium sulfate subtype salt lake brine as raw material |
| CN111204779A (en) * | 2020-03-10 | 2020-05-29 | 余荣华 | Fused salt production method for co-producing high-purity magnesium hydroxide, magnesium carbonate and nitrogen-potassium fertilizer |
| CN111268706B (en) * | 2020-03-30 | 2021-05-11 | 西部矿业股份有限公司 | Method for producing high-purity magnesium hydroxide, high-purity magnesium oxide and high-purity magnesite serial magnesium products by using salt lake brine |
| CN114890599A (en) * | 2022-05-09 | 2022-08-12 | 江苏才信通科技有限公司 | Waste water valuable resource recovery device and method |
| CN115180604A (en) * | 2022-07-11 | 2022-10-14 | 合肥国轩循环科技有限公司 | Method for simultaneously producing iron phosphate and lithium carbonate by using battery waste |
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2003
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11180369B2 (en) | 2019-07-30 | 2021-11-23 | Qinghai Institute Of Salt Lakes, Chinese, Academy Of Sciences | Renewable magnesium removing agent and its use in preparation of low-magnesium lithium-rich brine |
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