CN103204523B - Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit - Google Patents
Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit Download PDFInfo
- Publication number
- CN103204523B CN103204523B CN201310124579.8A CN201310124579A CN103204523B CN 103204523 B CN103204523 B CN 103204523B CN 201310124579 A CN201310124579 A CN 201310124579A CN 103204523 B CN103204523 B CN 103204523B
- Authority
- CN
- China
- Prior art keywords
- bittern
- lithium
- liquid separation
- boron
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 48
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 30
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 30
- 239000012267 brine Substances 0.000 title claims abstract description 22
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 170
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 103
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052796 boron Inorganic materials 0.000 claims abstract description 89
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 75
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 55
- 239000011777 magnesium Substances 0.000 claims abstract description 54
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000001704 evaporation Methods 0.000 claims abstract description 44
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 42
- 230000008020 evaporation Effects 0.000 claims abstract description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011435 rock Substances 0.000 claims abstract description 19
- 230000008014 freezing Effects 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001103 potassium chloride Substances 0.000 claims abstract description 14
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 11
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 9
- -1 carnallitite Chemical compound 0.000 claims abstract description 7
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 15
- 230000008676 import Effects 0.000 claims description 8
- 230000002269 spontaneous effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 239000013505 freshwater Substances 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 description 30
- 229910052700 potassium Inorganic materials 0.000 description 17
- 229960002337 magnesium chloride Drugs 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 14
- 229940091250 magnesium supplement Drugs 0.000 description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QYHKLBKLFBZGAI-UHFFFAOYSA-N boron magnesium Chemical compound [B].[Mg] QYHKLBKLFBZGAI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- NKEPWRHODHQIRS-UHFFFAOYSA-N lithium;sulfuric acid;hydrate Chemical compound [Li].O.OS(O)(=O)=O NKEPWRHODHQIRS-UHFFFAOYSA-N 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001932 seasonal effect Effects 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BBCJOIRLESMVQK-UHFFFAOYSA-M Cl[Li].[Na] Chemical compound Cl[Li].[Na] BBCJOIRLESMVQK-UHFFFAOYSA-M 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Seasonings (AREA)
Abstract
A kind of plateau sulfate type salt lake making from brine that utilizes is for the method in lithium salts ore deposit, it comprises step: sulfate type salt lake brine is evaporated to sodium-chlor state of saturation, freezing precipitation saltcake in the winter time, carries out solid-liquid separation when the content of sulfate ion is 1g/L ~ 7g/L in control bittern; Bittern after separating out saltcake is evaporated precipitated sodium chloride in spring and summer; Separate out sylvite, carnallitite, epsom salt to the bittern evaporation after precipitated sodium chloride, control to carry out solid-liquid separation after lithium concentration is more than or equal to 6g/L in bittern, the bittern after solid-liquid separation is the bittern of high content of magnesium chloride; The bittern of high content of magnesium chloride and saltcake hybrid reaction are separated out sodium salt and magnesium salts, controls to carry out solid-liquid separation when Mg/Li ratio is less than or equal to 8:1 in solution, obtain boron-rich lithium bittern; Boron-rich lithium bittern and water are reacted and separates out boron rock, after solid-liquid separation, obtain rich lithium bittern; Rich lithium bittern is imported evaporation in lithium salts pond and separate out lithium salts ore deposit.
Description
Technical field
The present invention relates to the exploitation technique of salt lake brine, especially relate to a kind of plateau sulfate type salt lake making from brine that utilizes for the method in lithium salts ore deposit.
Background technology
Have the lithium of the title of " energy upstart " of 21 century be nature the gentliest, the most active metallic element, be a kind of new forms of energy raw material.Occurring in nature lithium resource is mainly present in granitic pegmatite-type mineral deposit, salt lake brine, seawater and GEOTHERMAL WATER.
China is one of country that saline lake lithium resource is the abundantest in the world, the Qinghai-Tibet Platean of China has the salt lake of One's name is legion.Wherein salt lake, Chaidamu of Qinghai Province is as Cha Er Han Salt Lake, large bavin dawn salt lake, eastern West Taijinar Salt Lake, a Li Ping salt lake, small Si Kule salt lake etc., through the great amount of investment of country's decades, Infrastructure is as better in conditions such as highway, railway, electric power, water resourcess, develop or possess exploit condition, wherein Cha Er Han Salt Lake has become the maximum Salt Lake Potash production base of China.In the exploitation in these salt lakes, people attempt the comprehensive utilization realizing the resources such as potassium, lithium, boron, magnesium, sodium by persistence, some technology successfully realizes industrialness trial production, but what really realize large-scale commercial production only has potash fertilizer, the production of sodium salt, magnesium salts series product begins to take shape, but the production of boron, lithium is still difficult.
The envrionment conditions of Salt Lake Area, plateau is relatively more severe, and have a strong impact on the exploitation of salt lake brine, major cause is: height above sea level, the general height above sea level of such as Tibetan Salt Lakes is in 4000 ~ 5000m scope, and high person reaches more than 5000m, and physical environment is extremely severe, ecotope is very fragile, and environmental requirement is high; Have inconvenient traffic, such as salt lake, Tibet region transportation condition extreme difference, away from national highway, what condition was best also only has sandstone road to arrive, and away from produce market consumption area, haul distance is the shortest also 2000km, and major part is at more than 3000km; Infrastructure is substantially blank, away from electrical network, does not build the condition of large-scale factory, and circumference several hundred kilometers does not have chemical enterprise and can supply the off-set facility of utilization.But it is long that Salt Lake Area, plateau has the sunshine duration, year temperature difference and day and night temperature large, drought, the favourable natural condition such as wind is large, the present invention is intended to the natural energy resource making full use of Salt Lake Area, plateau, realizes the concentration and separation of elemental lithium in the vitriolate type bittern of plateau.
Summary of the invention
For this reason, the invention provides a kind of plateau sulfate type salt lake making from brine that utilizes for the method in lithium salts ore deposit, make full use of the natural natural condition in Salt Lake Area, energy-saving and environmental protection are pollution-free.
Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit, it comprises step:
The first step, by original for sulfate type salt lake bittern evaporation to sodium-chlor state of saturation, under the temperature environment in plateau winter, when the temperature of bittern is-30 DEG C ~ 0 DEG C, carry out freezing precipitation saltcake, when the content of sulfate ion is 1g/L ~ 7g/L in control bittern, carry out solid-liquid separation;
Second step, by the bittern after precipitation saltcake under the temperature environment of plateau spring and summer, evaporating precipitated sodium chloride when the temperature of bittern is 0 DEG C ~ 40 DEG C, carrying out solid-liquid separation when starting to separate out sylvite;
3rd step, carries out spontaneous evaporation to the bittern after precipitated sodium chloride and separates out sylvite, carnallitite, epsom salt successively, controls to carry out solid-liquid separation after lithium concentration is more than or equal to 6g/L in bittern, and the bittern after solid-liquid separation is the bittern of high content of magnesium chloride;
4th step, separates out sodium salt and magnesium salts by the bittern of described high content of magnesium chloride and saltcake hybrid reaction, controls to carry out solid-liquid separation when Mg/Li ratio is less than or equal to 8:1 in solution, obtains boron-rich lithium bittern;
5th step, when described boron-rich lithium bittern evaporation is reached preset value to the content of boron or elemental lithium and water or original bittern hybrid reaction, separate out boron rock, the solid-liquid separation when starting to separate out lithium salts, obtains rich lithium bittern after solid-liquid separation;
6th step, import in lithium salts pond by described rich lithium bittern, lithium salts ore deposit is separated out in evaporation.
Alternatively, the consisting of of the original bittern of described plateau sulfate type salt lake: B
2o
3be 0.1 ~ 3g/L, Li be 0.1 ~ 2g/L, K be 1 ~ 25g/L, Na be 10 ~ 120g/L, Mg be 10 ~ 120g/L, SO
4 2-be 1 ~ 40g/L, Br be 0.01 ~ 0.50g/L, Cl be 90 ~ 300g/L.
Alternatively, in the described the first step, under the temperature environment in plateau winter, the temperature of bittern is carry out freezing precipitation saltcake under the condition of-30 DEG C ~-20 DEG C, and in the bittern after solid-liquid separation, the content of sulfate ion reduces more than 90%.
Alternatively, the saltcake in described 4th step adopts the saltcake of the freezing precipitation of the first step.
Alternatively, in described 4th step, the bittern of high content of magnesium chloride and the temperature of saltcake hybrid reaction control at-5 DEG C ~ 40 DEG C.
Alternatively, in described 5th step, described in be evaporated to lithium or boron content reach the boron-rich lithium bittern of preset value and the volume ratio of fresh water or original bittern is 50% ~ 500%.
Alternatively, in the 5th step, when the boron-rich lithium bittern evaporation the 4th step obtained is 6g/L ~ 15g/L to lithium concentration and described fresh water or original bittern hybrid reaction.
Alternatively, in the 5th step, by described boron-rich lithium bittern evaporation to B
2o
3when the concentration of boron of meter is more than or equal to 20g/L and described water or original bittern hybrid reaction.
Alternatively, in described 6th step, by natural intensification-method of evaporation by lithium with Li
2sO
4h
2the form crystallization of O.
Alternatively, under the temperature environment of-10 DEG C ~ 50 DEG C, obtain Li by rich lithium bittern described in natural intensification-method of evaporation process
2sO
4h
2o purity is the lithium salts ore deposit of more than 30%.
Compared with prior art, the present invention has the following advantages:
First, in the whole technical process of the present invention, utilize the temperature condition that Salt Lake Area is natural, enrichment process is carried out to useful element in the vitriolate type bittern of natural salt lake, without the need to additionally adding chemical substance, environment friendly and pollution-free, and greatly reduce production cost.
Secondly, in the step of freezing precipitation saltcake in the winter time, the content of conscious control sulfate ion, that is, control sulfate concentration in bittern and, within the scope of 1g/L ~ 7g/L, potassium element in bittern efficiently removed.
Thirdly, remove coexisting of boron in the bittern after potassium, lithium and a large amount of magnesium, utilize present method process product saltcake to return in the bittern converting high content of magnesium chloride and remove magnesium, reduce the Mg/Li ratio example in bittern, particularly, control below Mg/Li ratio 8:1, to the enrichment of boron, lithium, there is keying action.
Again, in the step of removing boron, utilize water or original bittern and boron-rich reason bittern hybrid reaction, utilize acidization relative to prior art, environment friendly and pollution-free, and the boron rock of high purity more than 90% can be obtained.
Finally, by the step of above-mentioned a series of removal potassium, magnesium, boron, in bittern, elemental lithium obtains high-grade enrichment, obtains rich lithium bittern, and then evaporation obtains lithium salts ore deposit.
Embodiment
For making object of the present invention, technical scheme and advantage clearly understand, below in conjunction with specific embodiment, the present invention is described in detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The present invention utilizes plateau sulfate type salt lake making from brine to be specifically described below step by step for the method in lithium salts ore deposit:
The first step: original for plateau sulfate type salt lake bittern is imported pre-drying pool and evaporates, the content of sodium ion in bittern and sulfate ion is regulated by the flooding quantity controlling bittern, make the concentration of sodium ion in bittern to sodium-chlor state of saturation, and the concentration of sulfate ion is 5g/L ~ 25g/L.
The present invention's sulfate type salt lake brine used can be arbitrary plateau type sulfate type salt lake brine, and such as Qinghai-Tibet Platean, plateau, Andean etc., as long as the composition of sulfate type salt lake brine used meets the composition described in following table one.
Table one
The original bittern come from plateau sulfate type salt lake contains a small amount of calcium constituent usually, therefore first can carry out deliming process, and import in gypsum pond by original bittern, spontaneous evaporation, makes the calcium constituent in original bittern separate out with gypsum form.So-called spontaneous evaporation, refer to this evaporative process substantially not by temperature conditions, the height of temperature only affects the length of evaporation time, does not affect evaporation results.The gypsum of separating out can build salt pan by local use.Certainly, also can additionally arrange gypsum pond, in pre-drying pool, bittern evaporation process will separate out calcium, and in the present embodiment, pre-drying pool has deliming function concurrently.
Import in pre-drying pool by through the bittern after Calcium treatment, carry out spontaneous evaporation, precipitated sodium chloride, the bittern controlling to come in salt lake regulates the concentration of sodium ion in pre-drying pool to be in sodium-chlor state of saturation at the flooding quantity of pre-drying pool, sulfate ion in this evaporative process bittern obtains enrichment, when the concentration of bittern sulfate ion reaches this scope of 5g/L ~ 25g/L, the bittern of sodium-chlor state of saturation is now imported first and freezes nitre pond, freezing treatment is carried out under the temperature environment in plateau winter, separate out saltcake, solid-liquid separation is carried out when the concentration of sulfate ion is 1g/L ~ 7g/L in control solution, bittern after solid-liquid separation enters next step, solid saltcake is deposited in first and freezes in nitre pond, gained saltcake can be used as reaction raw materials in subsequent technique.
The bittern of above-mentioned sodium-chlor state of saturation be usually placed on carry out in-30 DEG C ~ 0 DEG C temperature range freezing, just saltcake can be separated out, and under the temperature environment in Salt Lake Area, plateau winter, the temperature of bittern meets this condition, therefore, the winter temperature condition that the technical program utilizes highlands natural, carries out process implementing on the spot, so not only environmental protection but also reduce production cost.
Measure the content that first freezes sulfate ion in the bittern in nitre pond, when in bittern, sulfate ion content is reduced within the scope of 1g/L ~ 7g/L, the process that saltcake is separated out can terminate.In addition, detect the solid phase composition of separating out, this freezes in nitre process, outside separating out apart from a small amount of sodium-chlor, in bittern, other beneficial elements (such as potassium, magnesium, boron, lithium etc.) are not separated out, the saltcake obtained like this and the mixture of sodium-chlor, the two is easy to be separated, thus obtains follow-up recycled saltcake.
Due to winter temperature condition will be utilized to carry out freezing precipitation saltcake, therefore the technique such as the deliming of bittern, the concentration of adjustment sodium ion completes before need arriving in the winter time, and preferably makes the concentration of sulfate ion in bittern control as 5g/L ~ 25g/L.
Under differing temps, the amount of freezing precipitation saltcake is different, that is, the degree that reduces in bittern of sulfate radical is different, and when within the scope of brine temperature-30 DEG C ~-20 DEG C, in bittern, sulfate radical reduces and reaches more than 90%.
For freezing precipitation saltcake, the embodiment of freezing precipitation saltcake under below providing differing temps.Get me
The western sulfate type salt lake brine of state, solarization consists of Na to the bittern of sodium-chlor saturation stage
+7.25%, K
+1.31%, Mg
2+0.47%, Li
+0.019%, Cl
-12.55%, SO
4 2-1.68%, B
2o
30.10%, consist of Na at-20 DEG C of freezing rear bittern
+6.97%, K
+1.32%, Mg
2+0.49%, Li
+0.021%, Cl
-13.30%, SO
4 2-0.168%, B
2o
30.105%, more than 90% SO can be removed
4 2-; After this bittern is freezing at-9 DEG C, bittern consists of Na
+7.04%, K
+1.32%, Mg
2+0.48%, Li
+0.02%, Cl
-13.11%, SO
4 2-0.535%, B
2o
30.10%, freezingly remove 78%SO
4 2-.
Second step, evaporating precipitated sodium chloride by the bittern after separating out saltcake, carrying out solid-liquid separation when starting to separate out sylvite under the temperature environment of plateau spring and summer.Bittern after solid-liquid separation enters next step, and solid is stayed in sodium salt pond.Under the temperature environment of 0 DEG C ~ 40 DEG C, spontaneous evaporation just can precipitated sodium chloride usually to separate out the bittern after saltcake, spring and summer seasonal temperature (the Salt Lake Area, plateau of Salt Lake Area, plateau, spring and summer, solar term temperature was general at 0 DEG C ~ about 25 DEG C, but brine temperature can be high, usually at 0 DEG C ~ 40 DEG C) meet this condition, in the present embodiment, temperature condition spring and summer utilizing highlands natural, carries out process implementing on the spot.
Be specially: at the end of winter, the bittern of separating out after saltcake imported in sodium salt pond, proceeds to the spring and summer stage when season, utilize the temperature condition in spring and summer stage, make bittern fully evaporate precipitated sodium chloride.Detect the composition of separating out solid phase, when sylvite starts to separate out, carry out solid-liquid separation, the bittern of precipitated sodium chloride is imported next step.
3rd step, carries out spontaneous evaporation to the bittern after precipitated sodium chloride and separates out sylvite, carnallitite, epsom salt successively, controls to carry out solid-liquid separation after lithium concentration is more than or equal to 6g/L in bittern, and the bittern after solid-liquid separation is the bittern of high content of magnesium chloride.
(1) sylvite and carnallitite is separated out.
Bittern after precipitated sodium chloride in 3rd step is imported in sylvite pond, evaporates, separate out sylvite, that is, the mixing salt of Repone K and sodium-chlor.It is very large that Repone K varies with temperature changes in solubility, and sodium-chlor to vary with temperature solubleness substantially constant, therefore, sylvite can mix with water, utilize the temperature difference, Evaporation preparation Repone K.Secondly, the bittern of separating out after sylvite being imported in carnallitite pond, proceeds evaporation and separate out carnallitite (being mixed with sodium-chlor), when starting have bischofite to separate out in precipitation solid phase, carrying out solid-liquid separation.
(2) epsom salt is separated out.
The bittern of separating out sylvite and carnallitite is imported epsom salt pond, evaporation process separates out epsom salt, control to carry out solid-liquid separation after lithium concentration is more than or equal to 6g/L in solution, bittern after solid-liquid separation is the bittern of high content of magnesium chloride, enter next step, solid imports second and freezes (or nitre pond is frozen as second in this epsom salt pond) in nitre pond.
4th step, the bittern of described high content of magnesium chloride and saltcake hybrid reaction are separated out sodium salt and magnesium salts, control to carry out solid-liquid separation when Mg/Li ratio is less than or equal to 8:1 in solution, obtain boron-rich lithium bittern and enter next step after solid-liquid separation, solid imports described second and freezes in nitre pond.
Be specially: arrange demagging pond, the mirabilite ore frozen first in nitre pond directly puts into demagging pond, or the mirabilite ore mixing water frozen first in nitre pond is formed in saltcake aqueous solution importing demagging pond.The bittern of high content of magnesium chloride is imported demagging pond and mirabilite ore or saltcake aqueous solution react, separate out sodium salt and magnesium salts, control to carry out solid-liquid separation when Mg/Li ratio reaches preset value in solution, thus obtain boron-rich lithium bittern.
In bittern by the high content of magnesium chloride after the first step to the 5th step process, main beneficial element is lithium, boron, and two kinds of main components and a large amount of magnesium coexist.The existence of a large amount of magnesium, make the concentration and separation of lithium very difficulty: 1. high Mg/Li ratio is the great crucial problem that salt lake brine carries lithium, due to the high similarity of lithium magnesium character, and be separated the relatively less lithium of content from a large amount of containing magnesium solution, technical difficulty is quite large, and cost is high.Found through experiments, when extracting lithium from sulfate type salt lake brine, Mg/Li ratio value has certain economic feasibility at below 8:1, and this ratio is lower, and economy is better.Experiment finds, the boron-rich lithium bittern obtained when Mg/Li ratio value is at below 8:1, and the lithium ore deposit grade finally obtained is more than 20%; The boron-rich lithium bittern obtained when Mg/Li ratio value is at below 6:1, the lithium ore deposit grade finally obtained is more than 30%.The practical situation needs that industry is concrete can be considered, select suitable Mg/Li ratio to carry out the preparation of boron-rich lithium bittern.And in the boron-rich lithium salts lake bittern water of sulfate type, Mg/Li ratio value generally at decades of times to hundreds of times, reach as high as thousands of times., therefore, this stage reduces Mg/Li ratio, and for the boron-rich lithium bittern of preparation, the final lithium that extracts has great importance.2. under the existence of a large amount of chlorion, magnesium mainly with poly hydration ionic species exist, this hydrated ion due to hydration levels very high, large quantity of moisture is fixed by magnesium, cause evaporation to be the devil.3. under high magnesium ion exists, due to the reduction of vaporator rate and the increase of brine viscosities, make bittern not yet reach expection enrichment degree and just enter algid stage in winter, the change of temperature, lithium and boron dispersion in bittern are separated out, is unfavorable for the enrichment of beneficial element.
Therefore, need a large amount of magnesium to remove, main purpose has two: 1. significantly reduce Mg/Li ratio in bittern, the relative concentration of lithium is increased substantially, and reduces the tooling cost that follow-up lithium extracts; 2., after magnesium ion and chlorion enter solid phase in a large number, brine viscosities reduces, and velocity of evaporation increases substantially, and solid phase separation performance is greatly improved, and lithium carries reduction secretly.
Utilize the bittern of high content of magnesium chloride and saltcake hybrid reaction in the present invention, separate out sodium salt and magnesium salts, control to carry out solid-liquid separation when Mg/Li ratio is less than or equal to 8:1 in solution, thus obtain the solution of boron-rich elemental lithium.In the present invention, the saltcake that the first step is separated out can be returned in the bittern converted and be applied to high content of magnesium chloride and react, make full use of the product of technological process.Saltcake returns to be converted demagging principle and is:
Na
2sO
410H
2o (s)+MgCl
2====MgSO
47H
2o (s)+2NaCl (s) (formula 1)
Na
2sO
4(aq)+MgCl
2====MgSO
47H
2o (s)+2NaCl (s) (formula 2)
2Na
2sO
4(aq)+MgCl
2====Na
2sO
4mgSO
43H
2o (s)+2NaCl (s) (formula 3)
Above-mentioned reaction saltcake used can be solid saltcake or the saltcake aqueous solution.
Temperature of reaction preferably controls at-5 DEG C ~ 40 DEG C, and temperature is too high, then the lithium ion with certain enrichment degree can be separated out with the form of the moisture salt of Lithium Sulphate, and cause Lithium Sulphate grade not high, it is unfavorable to bring to aftertreatment.It is best that the bittern of the present invention's height content of magnesium chloride when repeatedly repetition test finds at-5 DEG C ~ 40 DEG C and saltcake fully can react demagging effect.
Return for saltcake and convert demagging, below provide embodiment: the old halogen (bittern of high content of magnesium chloride) after the first step of learning from else's experience to the 5th step process, principal element consists of: Na
+0.50%, K
+0.50%, Mg
2+6.93%, Li
+0.58%, Cl
-20.95%, SO
4 2-3.49%, B
2o
31.72%, add a certain amount of saltcake aqueous solution, it consists of: Na
+3.88%, K
+0%, Mg
2+0.048%, Li
+0%, Cl
-0.42%, SO
4 2-7.93%, B
2o
30%, now Mg in system
2+: SO
4 2-amount ratio be about 1:1.Solid-liquid separation after salt is separated out in a large number, liquid phase consists of: Na
+1.19%, K
+0.70%, Mg
2+5.09%, Li
+0.85%, Cl
-14.86%, SO
4 2-7.72%, B
2o
32.16%, Mg/Li ratio reduces to 5.99 by 11.86.This old halogen adds and consists of Na
+11.59%, K
+0%, Mg
2+0.02%, Li
+0%, Cl
-0.50%, SO
4 2-7.93%, B
2o
3the saltcake solid of 0%, makes Mg in system
2+: SO
4 2-amount ratio be about 1:0.75, solid-liquid separation after for some time, liquid phase consists of: Na
+0.74%, K
+0.82%, Mg
2+5.23%, Li
+0.94%, Cl
-14.33%, SO
4 2-8.70%, B
2o
32.40%, Mg/Li ratio reduces to 5.54 by 11.86.
In addition, second freezes in nitre pond and mainly contains epsom salt, sodium-chlor, carries the solution of lithium and boron secretly, epsom salt in this pond and sodium-chlor are under physical environment, under effect with seasonal temperature change, rainwater and supplementary part fresh water etc., transform, generate saltcake and magnesium chloride, in the winter time through cryogenic freezing, separate out saltcake, this saltcake and first freezes that the saltcake in nitre pond is the same can be utilized in this technique demagging step.
5th step, when described boron-rich lithium bittern evaporation is reached preset value to the content of boron or elemental lithium and water react and separate out boron rock, the solid-liquid separation when starting to separate out lithium salts, obtain rich lithium bittern after solid-liquid separation.
The boron rock pond holding water or original bittern (original bittern is the bittern come from plateau sulfate type salt lake) is provided, boron-rich lithium bittern evaporation is imported when the content of boron or elemental lithium reaches preset value boron rock pond and described water or original bittern hybrid reaction, separate out boron rock, solid-liquid separation is carried out when starting to separate out lithium salts, bittern after solid-liquid separation enters next step, and solid is stayed in boron rock pond.
When evaporating boron-rich lithium bittern here, taking the content of lithium or boron as the index of evaporation degree, is because with B
2o
3the boron concentration of meter meets boron rock and separates out condition when being more than or equal to 20g/L, the eduction rate of boron is more than 80%, and boron rock purity is more than 90%.And when lithium concentration in bittern reaches 6g/L ~ 15g/L with B
2o
3the concentration of the boron of meter is satisfied is more than or equal to this content condition of 20g/L, therefore, in actual evaporation technique, can control the content of lithium or the arbitrary element of boron.In the present embodiment, owing to considering the preparation in follow-up lithium salts ore deposit, therefore in this step with the content of elemental lithium for index, namely boron rock pond and described fresh water or original bittern hybrid reaction is imported when boron-rich lithium bittern evaporation reaches 6g/L ~ 15g/L to lithium concentration, solid-liquid separation is carried out when starting to separate out lithium salts, solid is boron rock, and liquid is the bittern of enriching lithium element.
Be specially: boron rock pond is set, wherein put into the water of predetermined amount or original bittern.Boron-rich lithium bittern through control be evaporated to lithium concentration about 6g/L ~ 15g/L (now in bittern with B
2o
3the boron concentration of meter is more than or equal to 20g/L) import in boron rock pond and mix with water or original bittern, wherein, in boron rock pond, the volume of water or original bittern is be evaporated to 50% ~ 500% times that lithium concentration is the volume of the boron-rich lithium bittern of about 6g/L ~ 15g/L, that is, above-mentioned water or original bittern are 50% ~ 500% with the volume ratio being evaporated to boron or lithium content and reaching the boron-rich lithium bittern of aforementioned predetermined extent.Described boron-rich lithium bittern and the abundant hybrid reaction of water, the poly Borate anion in solution and water is made to react the borate that depolymerization is low polymerization degree, both boratory Metastable zone had been destroyed, again reduce boratory solubleness, a large amount of borate is separated out from solution with the form of the storehouse water of low solubility (many water) szaibelyite or pinnoite.This step, the eduction rate of boron is more than 80%, and boron rock purity is more than 90%.Before lithium salts is separated out, carry out solid-liquid separation, the rich lithium bittern after solid-liquid separation enters next step, and solids bulk is in boron rock pond.
6th step, import in lithium salts pond by described rich lithium bittern, lithium salts ore deposit is separated out in evaporation.
Separate out in the bittern behind boron magnesium ore deposit, due to the eutectoid of magnesium boron and with mass crystallization water, the further enrichment of lithium and Mg/Li ratio reduce, and be actually Lithium Sulphate, lithium chloride, magnesium sulfate, magnesium chloride coexist, according to Mg in solution
2+, Li
+//SO
4 2-, Cl
-– H
2how warm facies relationship in O system, by natural intensification-method of evaporation by lithium with a water salt (Li
2sO
4h
2o) form crystallization, obtains the sulfuric acid lithium salts of higher degree.Separate out Li
2sO
4h
2the purity of O, more than 30%, transports other places to and is processed into desired product.
Separate out Li
2sO
4h
2bittern after O is got back in demagging pond, and after certain number of times that circulates, when the enrichment of element such as the bromine in bittern are to normality, evaporate to dryness, transports processing.
Separate out lithium salts ore deposit for this step, provide following examples.Test one: the bittern after the first step of learning from else's experience to the 7th step process, principal element consists of: Na
+0.74%, K
+0.72%, Mg
2+5.82%, Li
+1.10%, Cl
-19.44%, SO
4 2-3.33%, B
2o
30.50%, after-10 DEG C time, lithium salts is separated out in spontaneous evaporation, liquid phase consists of: K
+0.20%, Mg
2+7.57%, Li
+0.72%, Cl
-24.26%, SO
4 2-0.37%, B
2o
30.74%, solid phase consists of K
+2.13%, Mg
2+6.04%, Li
+3.31%, Cl
-25.00%, SO
4 2-18.97%, B
2o
30.36%, through Discriminating materials and chemical analysis, prove that solid is mainly sulfuric acid monohydrate lithium, carnallitite, magnesium chloride hexahydrate, lithium ore deposit purity is with Li
2sO
4h
2o meter reaches 30.49%.
Experiment two: the bittern after the first step of learning from else's experience to the 7th step process, principal element consists of: K
+1.05%, Mg
2+5.64%, Li
+0.79%, Cl
-17.51%, SO
4 2-5.74%, B
2o
31.11%, this bittern solar day according under be naturally warmed up to 40 DEG C to 50 DEG C evaporations analyse lithium after liquid phase consist of: K
+0.23%, Mg
2+7.50%, Li
+0.50%, Cl
-21.09%, SO
4 2-4.00%, B
2o
31.57%, solid phase consists of K
+3.68%, Mg
2+3.28%, Li
+3.73%, Cl
-26.74%, SO
4 2-27.42%, B
2o
30.35%, through Discriminating materials and chemical analysis, prove that solid is mainly sulfuric acid monohydrate lithium, carnallitite, magnesium chloride hexahydrate, sodium-chlor, lithium ore deposit purity is with Li
2sO
4h
2o meter reaches 34.38%.
Compared with prior art, the present invention has the following advantages:
First, in the whole technical process of the present invention, utilize the temperature condition that Salt Lake Area is natural, enrichment process is carried out to useful element in the vitriolate type bittern of natural salt lake, without the need to additionally adding chemical substance, environment friendly and pollution-free, and greatly reduce production cost.
Secondly, in the step of freezing precipitation saltcake in the winter time, the content of conscious control sulfate ion, that is, control sulfate concentration in bittern and, within the scope of 1g/L ~ 7g/L, potassium element in bittern efficiently removed.
Thirdly, remove coexisting of boron in the bittern after potassium, lithium and a large amount of magnesium, utilize present method process product saltcake to return in the bittern converting high content of magnesium chloride and remove magnesium, reduce the Mg/Li ratio example in bittern, particularly, control below Mg/Li ratio 8:1, to the enrichment of boron, lithium, there is keying action.
Again, in the step of removing boron, utilize water or original bittern and boron-rich reason bittern hybrid reaction, utilize acidization relative to prior art, environment friendly and pollution-free, and the boron rock of high purity more than 90% can be obtained.
Finally, by the step of above-mentioned a series of removal potassium, magnesium, boron, in bittern, elemental lithium obtains high-grade enrichment, obtains rich lithium bittern, and then evaporation obtains lithium salts ore deposit.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit, it comprises step:
The first step, original for plateau sulfate type salt lake bittern is imported pre-drying pool evaporate, the content of sodium ion in bittern and sulfate ion is regulated by the flooding quantity controlling bittern, by original for sulfate type salt lake bittern evaporation to sodium-chlor state of saturation and the concentration of sulfate ion is 5g/L ~ 25g/L, under the temperature environment in plateau winter, carry out freezing precipitation saltcake when the temperature of bittern is-30 DEG C ~ 0 DEG C, when the content of sulfate ion is 1g/L ~ 7g/L in control bittern, carry out solid-liquid separation;
Second step, by the bittern after precipitation saltcake under the temperature environment of plateau spring and summer, evaporating precipitated sodium chloride when the temperature of bittern is 0 DEG C ~ 40 DEG C, carrying out solid-liquid separation when starting to separate out sylvite;
3rd step, carries out spontaneous evaporation to the bittern after precipitated sodium chloride and separates out sylvite, carnallitite, epsom salt successively, controls to carry out solid-liquid separation after lithium concentration is more than or equal to 6g/L in bittern, obtains the bittern of high content of magnesium chloride after solid-liquid separation;
4th step, separates out sodium salt and magnesium salts by the bittern of described high content of magnesium chloride and saltcake hybrid reaction, controls to carry out solid-liquid separation when Mg/Li ratio is less than or equal to 8:1 in solution, obtains boron-rich lithium bittern;
5th step, when being 6g/L ~ 15g/L by described boron-rich lithium bittern evaporation to lithium concentration or with B
2o
3when the concentration of boron of meter is more than or equal to 20g/L and water or original bittern hybrid reaction, the volume ratio of described boron-rich lithium bittern and fresh water or original bittern is 50% ~ 500%, separate out boron rock, the solid-liquid separation when starting to separate out lithium salts, obtains rich lithium bittern after solid-liquid separation;
6th step, import in lithium salts pond by described rich lithium bittern, lithium salts ore deposit is separated out in evaporation.
2. the method for claim 1, is characterized in that: consisting of of the original bittern of described plateau sulfate type salt lake: B
2o
3be 0.1 ~ 3g/L, Li be 0.1 ~ 2g/L, K be 1 ~ 25g/L, Na be 10 ~ 120g/L, Mg be 10 ~ 120g/L, SO
4 2-be 1 ~ 40g/L, Br be 0.01 ~ 0.50g/L, Cl be 90 ~ 300g/L.
3. the method for claim 1, it is characterized in that: in the described the first step, under the temperature environment in plateau winter, the temperature of bittern is carry out freezing precipitation saltcake under the condition of-30 DEG C ~-20 DEG C, and in the bittern after solid-liquid separation, the content of sulfate ion reduces more than 90%.
4. the method for claim 1, is characterized in that: the saltcake in described 4th step adopts the saltcake of the freezing precipitation of the first step.
5. the method for claim 1, is characterized in that: in described 4th step, the bittern of high content of magnesium chloride and the temperature of saltcake hybrid reaction control at-5 DEG C ~ 40 DEG C.
6. the method for claim 1, is characterized in that: in described 6th step, by natural intensification-method of evaporation by lithium with Li
2sO
4h
2the form crystallization of O.
7. method as claimed in claim 6, is characterized in that: under the temperature environment of-10 DEG C ~ 50 DEG C, obtains Li by rich lithium bittern described in natural intensification-method of evaporation process
2sO
4h
2o purity is the lithium salts ore deposit of more than 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310124579.8A CN103204523B (en) | 2012-10-18 | 2013-04-11 | Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103971925A CN102910652A (en) | 2012-10-18 | 2012-10-18 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN201210397192.5 | 2012-10-18 | ||
| CN2012103971925 | 2012-10-18 | ||
| CN201310124579.8A CN103204523B (en) | 2012-10-18 | 2013-04-11 | Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103204523A CN103204523A (en) | 2013-07-17 |
| CN103204523B true CN103204523B (en) | 2015-09-16 |
Family
ID=47609263
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103971925A Pending CN102910652A (en) | 2012-10-18 | 2012-10-18 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN201310124971.2A Expired - Fee Related CN103224244B (en) | 2012-10-18 | 2013-04-11 | Method for enriching and separating beneficial elements in sulfate type salt lake brine by using nature energy |
| CN201310125330.9A Expired - Fee Related CN103194622B (en) | 2012-10-18 | 2013-04-11 | Method for enriching boron and lithium elements in sulfate type salt lake brine |
| CN2013101251159A Pending CN103204512A (en) | 2012-10-18 | 2013-04-11 | Method for preparing boron rock from plateau sulfate type salt lake brine |
| CN201310124579.8A Expired - Fee Related CN103204523B (en) | 2012-10-18 | 2013-04-11 | Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit |
| CN201310128794.5A Expired - Fee Related CN103204520B (en) | 2012-10-18 | 2013-04-11 | Method for preparing single-form potassic salt ore from plateau sulfate type salt lake brine |
Family Applications Before (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103971925A Pending CN102910652A (en) | 2012-10-18 | 2012-10-18 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN201310124971.2A Expired - Fee Related CN103224244B (en) | 2012-10-18 | 2013-04-11 | Method for enriching and separating beneficial elements in sulfate type salt lake brine by using nature energy |
| CN201310125330.9A Expired - Fee Related CN103194622B (en) | 2012-10-18 | 2013-04-11 | Method for enriching boron and lithium elements in sulfate type salt lake brine |
| CN2013101251159A Pending CN103204512A (en) | 2012-10-18 | 2013-04-11 | Method for preparing boron rock from plateau sulfate type salt lake brine |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310128794.5A Expired - Fee Related CN103204520B (en) | 2012-10-18 | 2013-04-11 | Method for preparing single-form potassic salt ore from plateau sulfate type salt lake brine |
Country Status (1)
| Country | Link |
|---|---|
| CN (6) | CN102910652A (en) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910652A (en) * | 2012-10-18 | 2013-02-06 | 中国科学院青海盐湖研究所 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
| CN103387244B (en) * | 2013-07-29 | 2015-02-18 | 中国科学院青海盐湖研究所 | Method for enriching lithium in carbonate type salt lake brine |
| CN103508472A (en) * | 2013-10-08 | 2014-01-15 | 中国科学院青海盐湖研究所 | Method for enriching lithium and removing calcium in oil filed water by utilizing evaporating-freezing principle |
| CN103553091B (en) * | 2013-11-15 | 2015-04-29 | 中国科学院青海盐湖研究所 | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy |
| CN103553065B (en) * | 2013-11-15 | 2015-04-01 | 中国科学院青海盐湖研究所 | Method for preparing boron ore from mixed brine by using natural energy |
| CN103553090B (en) * | 2013-11-15 | 2015-03-18 | 中国科学院青海盐湖研究所 | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy |
| CN103553088B (en) * | 2013-11-15 | 2015-06-17 | 中国科学院青海盐湖研究所 | Method of preparing lithium borate ores from mixed brine by utilizing natural energy |
| CN103539161B (en) * | 2013-11-15 | 2015-05-20 | 中国科学院青海盐湖研究所 | Method for preparing sylvite ore from mixed brine by use of natural energy |
| CN103572071B (en) * | 2013-11-15 | 2016-03-02 | 中国科学院青海盐湖研究所 | A kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio |
| CN103553092B (en) * | 2013-11-15 | 2015-04-01 | 中国科学院青海盐湖研究所 | Method for preparing carnallite ore from mixed brine by using natural energy |
| CN103553087B (en) * | 2013-11-15 | 2015-06-17 | 中国科学院青海盐湖研究所 | Method of preparing lithium sulfate ores from mixed brine by utilizing natural energy |
| CN103588227B (en) * | 2013-11-21 | 2015-11-18 | 化工部长沙设计研究院 | The production technique of nitre evaporation de-magging converted by the old halogen in a kind of salt lake |
| CN105366694B (en) * | 2014-08-13 | 2016-10-05 | 南风化工集团股份有限公司 | The method that the deep pond of a kind of salt lake bittern stores |
| CN105502440B (en) * | 2015-12-04 | 2019-03-26 | 中国科学院青海盐湖研究所 | The rough refining methd of sulfuric acid lithium salts |
| CN106219643A (en) * | 2016-07-22 | 2016-12-14 | 中国科学院青海盐湖研究所 | A kind of concentration cycles utilizes the method for industry high-salt wastewater |
| CN108069443A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院青海盐湖研究所 | A kind of method that potash magnesium sulphate fertilizer and potassium chloride are prepared from sulfate type salt lake brine |
| CN108069442A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院青海盐湖研究所 | One kind prepares potassium sulfate method from sulfate type salt lake brine |
| CN108069444A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院青海盐湖研究所 | A kind of method of comprehensive utilization of sulfate type bittern |
| CN108069441A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院青海盐湖研究所 | A kind of method that carnallite is prepared using intercrystalline bittern |
| CN107399751A (en) * | 2016-12-13 | 2017-11-28 | 地矿集团格尔木盐湖资源开发有限公司 | A kind of production technology of strontium salt |
| CN107814398B (en) * | 2017-11-28 | 2019-12-06 | 中国科学院青海盐湖研究所 | Preparation method of magnesium sulfate heptahydrate |
| CN108217693B (en) * | 2017-12-27 | 2021-03-23 | 地矿集团格尔木盐湖资源开发有限公司 | Salt field technology for separating components by using temperature difference |
| CN108640130B (en) * | 2018-06-26 | 2020-07-24 | 中国科学院青海盐湖研究所 | Method for preparing lithium sulfate from salt lake lithium sulfate salt crude ore |
| CN108726538B (en) * | 2018-07-04 | 2020-08-11 | 中国科学院青海盐湖研究所 | Method for directly preparing low-sodium salt by using sulfate type salt lake brine |
| CN109019641B (en) * | 2018-10-12 | 2020-12-11 | 中国科学院青海盐湖研究所 | Method for separating magnesium and lithium and enriching lithium from sodium sulfate subtype salt lake brine |
| CN109292801B (en) * | 2018-12-05 | 2021-03-23 | 中国科学院青海盐湖研究所 | Preparation method of food-grade magnesium chloride |
| CN109607654A (en) * | 2019-01-31 | 2019-04-12 | 内蒙古科技大学 | Device, method and the application of strong brine low temperature crystallization desalination |
| CN112079362A (en) * | 2019-06-14 | 2020-12-15 | 中国科学院青海盐湖研究所 | Preparation method of polyboromagnesite |
| CN110194471B (en) * | 2019-06-19 | 2020-11-06 | 中国科学院青海盐湖研究所 | Method for desulfurizing sodium sulfate subtype salt lake brine and enriching lithium |
| CN110713195A (en) * | 2019-11-27 | 2020-01-21 | 青海民族大学 | Method for improving production efficiency of chloride type salt pan and chloride type salt pan product |
| CN111072041B (en) * | 2019-12-24 | 2021-12-28 | 燕山大学 | Method for rapidly preparing two-dimensional boron alkene |
| CN111704148A (en) * | 2020-05-27 | 2020-09-25 | 王新磊 | Production method of raw salt |
| CN112142076B (en) * | 2020-09-08 | 2022-06-24 | 中国科学院青海盐湖研究所 | Method for extracting lithium from brine by adsorption method |
| CN112047412A (en) * | 2020-09-27 | 2020-12-08 | 长沙紫宸科技开发有限公司 | Seawater atomization cyclone desalination equipment system and method |
| CN112349354B (en) * | 2020-11-05 | 2024-03-15 | 青海省柴达木综合地质矿产勘查院 | Brine and brine simulation salt preparation method |
| CN112479237A (en) * | 2020-12-08 | 2021-03-12 | 华东理工大学 | Method for preparing anhydrous magnesium carbonate by directly utilizing salt lake brine |
| CN114059989B (en) * | 2021-11-09 | 2024-04-26 | 青海省柴达木综合地质矿产勘查院 | Solution mining method of low-grade solid potassium salt ore |
| CN114014340A (en) * | 2021-11-19 | 2022-02-08 | 广东邦普循环科技有限公司 | Method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio |
| CN115465874B (en) * | 2022-11-15 | 2023-03-07 | 山西大学 | Device and method for preparing micron-sized crystalline magnesium sulfate hollow tube |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287163A (en) * | 1979-05-29 | 1981-09-01 | Saline Processors, Inc. | Process for recovering lithium from brine by salting out lithium sulfate monohydrate |
| CN1249272A (en) * | 1998-09-25 | 2000-04-05 | 青海省柴达木综合地质勘查大队 | Process for precipitating B and Li in bittern at same time |
| CN1270927A (en) * | 1999-04-20 | 2000-10-25 | 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 |
| CN1335262A (en) * | 2001-09-07 | 2002-02-13 | 中信国安锂业科技有限责任公司 | Lithium carbonate preparing process from salt lake bittern with high Mg/Li ratio |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852044A (en) * | 1969-11-13 | 1974-12-03 | Great Salt Lake Minerals | Recovery of substantially potassium-free hydrated magnesium chloride from contaminated aqueous solutions |
| CN1037835C (en) * | 1993-07-23 | 1998-03-25 | 大连理工大学化工学院 | Separating method for boric acid and magnesium sulfate mixed solution |
| CN1039112C (en) * | 1995-03-03 | 1998-07-15 | 大连理工大学 | Comprehensive utilization method for decomposition of B-Mg-Fe ore with sulfuric acid |
| CN1613826A (en) * | 2004-10-13 | 2005-05-11 | 张仲轩 | Method for preparing carnallite from magnesium sulfate subtype potassium-containing brine |
| CN101157460B (en) * | 2007-08-28 | 2010-09-01 | 中国科学院青海盐湖研究所 | Method for preparing potassium chloride by employing sulfate type salt lake potassium-containing brine |
| JP2011006275A (en) * | 2009-06-25 | 2011-01-13 | Kobelco Eco-Solutions Co Ltd | Method and apparatus for producing lithium carbonate |
| CN101698488B (en) * | 2009-11-04 | 2012-03-21 | 中国科学院青海盐湖研究所 | Method for preparing lithium carbonate by using salt lake brine with high magnesium-to-lithium ratio |
| CN102442687B (en) * | 2010-10-13 | 2014-04-30 | 云南省化工研究院 | Method for preparing potassium chloride from solid potassic salt ore through rotating decomposition and positive flotation |
| CN102259899B (en) * | 2011-05-04 | 2013-08-07 | 中国科学院青海盐湖研究所 | Method for enriching micro elements in saturate magnesium chloride brine by recycling potassium chloride |
| CN102653407B (en) * | 2012-05-03 | 2014-06-04 | 中国科学院青海盐湖研究所 | Method for preparing potassium chloride from sulfate type salt lake brine |
| CN102730723B (en) * | 2012-07-17 | 2014-02-26 | 中国科学院青海盐湖研究所 | High-concentration salt pan enriching method of Li<+> in sulfate type salt lake brine |
| CN102910652A (en) * | 2012-10-18 | 2013-02-06 | 中国科学院青海盐湖研究所 | Clean production process of plateau sulfate type boron-lithium salt lake brine |
-
2012
- 2012-10-18 CN CN2012103971925A patent/CN102910652A/en active Pending
-
2013
- 2013-04-11 CN CN201310124971.2A patent/CN103224244B/en not_active Expired - Fee Related
- 2013-04-11 CN CN201310125330.9A patent/CN103194622B/en not_active Expired - Fee Related
- 2013-04-11 CN CN2013101251159A patent/CN103204512A/en active Pending
- 2013-04-11 CN CN201310124579.8A patent/CN103204523B/en not_active Expired - Fee Related
- 2013-04-11 CN CN201310128794.5A patent/CN103204520B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287163A (en) * | 1979-05-29 | 1981-09-01 | Saline Processors, Inc. | Process for recovering lithium from brine by salting out lithium sulfate monohydrate |
| CN1249272A (en) * | 1998-09-25 | 2000-04-05 | 青海省柴达木综合地质勘查大队 | Process for precipitating B and Li in bittern at same time |
| CN1270927A (en) * | 1999-04-20 | 2000-10-25 | 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 |
| CN1335262A (en) * | 2001-09-07 | 2002-02-13 | 中信国安锂业科技有限责任公司 | Lithium carbonate preparing process from salt lake bittern with high Mg/Li ratio |
Non-Patent Citations (3)
| Title |
|---|
| "含硼老卤添加芒硝卤水继续富集的控制";张柏顺等;《盐湖研究》;20060630;第14卷(第2期);第26-34页 * |
| "含硼资源开发的有关相化学研究进展";孟令宗等;《世界科技研究与发展》;20080229;第30卷(第1期);第16-20页 * |
| "盐卤硼酸盐化学 IV.浓缩盐卤中析出的新硼酸盐固相";高世扬等;《无机化学》;19860331;第2卷(第1期);第40-52页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103194622A (en) | 2013-07-10 |
| CN103204512A (en) | 2013-07-17 |
| CN103224244B (en) | 2015-03-11 |
| CN103204520A (en) | 2013-07-17 |
| CN103204520B (en) | 2015-03-18 |
| CN103194622B (en) | 2014-10-15 |
| CN103224244A (en) | 2013-07-31 |
| CN102910652A (en) | 2013-02-06 |
| CN103204523A (en) | 2013-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103204523B (en) | Utilize plateau sulfate type salt lake making from brine for the method in lithium salts ore deposit | |
| CN105502440B (en) | The rough refining methd of sulfuric acid lithium salts | |
| CN105152191A (en) | Method for preparing lithium carbonate through salt lake brine with high ratio of magnesium to lithium | |
| CN114014340A (en) | Method for removing calcium and enriching lithium from salt lake brine with high calcium-lithium ratio | |
| CN108640130B (en) | Method for preparing lithium sulfate from salt lake lithium sulfate salt crude ore | |
| GB2619191A (en) | Process for mineralization from evaporation and brine mixing of calcium chloride-type lithium-containing salt like brine | |
| CN100478278C (en) | Preparation method of lithium carbonate by using brine of oil field | |
| CN103553090B (en) | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy | |
| CN103553088B (en) | Method of preparing lithium borate ores from mixed brine by utilizing natural energy | |
| CN103553087B (en) | Method of preparing lithium sulfate ores from mixed brine by utilizing natural energy | |
| CN103553065B (en) | Method for preparing boron ore from mixed brine by using natural energy | |
| CN104291359A (en) | Mining method of solid potash ores | |
| CN103539161B (en) | Method for preparing sylvite ore from mixed brine by use of natural energy | |
| CN103553091B (en) | Method for extracting Mg, K, B and Li from mixed brine by utilizing natural energy | |
| CN1100722C (en) | Process for precipitating B and Li in bittern at same time | |
| CN104477941B (en) | A kind of method utilizing potassium mixed salt cryogenic freezing to produce carnallite | |
| CN104030323B (en) | Beach, the salt pan solarization method that a kind of salt lake lithium liquor is recycled | |
| CN103086404A (en) | Preparation method of lithium carbonate by brine extraction with magnesium ion participating reaction | |
| CN103553092B (en) | Method for preparing carnallite ore from mixed brine by using natural energy | |
| CN102730723B (en) | High-concentration salt pan enriching method of Li<+> in sulfate type salt lake brine | |
| CN110713195A (en) | Method for improving production efficiency of chloride type salt pan and chloride type salt pan product | |
| CN108069444A (en) | A kind of method of comprehensive utilization of sulfate type bittern | |
| CN104192878B (en) | A kind of method preparing carnallitite raw material from solid kalium mine | |
| CN103508472A (en) | Method for enriching lithium and removing calcium in oil filed water by utilizing evaporating-freezing principle | |
| CN103588227B (en) | The production technique of nitre evaporation de-magging converted by the old halogen in a kind of salt lake |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 810008, Xinning Road, Xining, Qinghai, 18 Co-patentee after: Tibet Ali lithium source Mining Development Co.,Ltd. Patentee after: QINGHAI INSTITUTE OF SALT LAKES, CHINESE ACADEMY OF SCIENCES Address before: 810008, Xinning Road, Xining, Qinghai, 18 Co-patentee before: Tibet Ali Xusheng Salt Lake Resources Development Co.,Ltd. Patentee before: QINGHAI INSTITUTE OF SALT LAKES, CHINESE ACADEMY OF SCIENCES |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150916 |