CN102491378B - Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine - Google Patents
Producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine Download PDFInfo
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- CN102491378B CN102491378B CN 201110358864 CN201110358864A CN102491378B CN 102491378 B CN102491378 B CN 102491378B CN 201110358864 CN201110358864 CN 201110358864 CN 201110358864 A CN201110358864 A CN 201110358864A CN 102491378 B CN102491378 B CN 102491378B
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 58
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 239000012267 brine Substances 0.000 title claims abstract description 26
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 title claims abstract description 11
- 238000002156 mixing Methods 0.000 title abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title abstract description 7
- 229910021653 sulphate ion Inorganic materials 0.000 title abstract 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000002500 ions Chemical class 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 12
- 241001131796 Botaurus stellaris Species 0.000 claims description 203
- 229910052736 halogen Inorganic materials 0.000 claims description 130
- 150000002367 halogens Chemical class 0.000 claims description 130
- 238000001704 evaporation Methods 0.000 claims description 41
- 230000008020 evaporation Effects 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 11
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 239000001095 magnesium carbonate Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 28
- 229910001425 magnesium ion Inorganic materials 0.000 description 28
- 150000003839 salts Chemical class 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 230000002269 spontaneous effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000011001 backwashing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 and winter Chemical compound 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a producing method for preparing lithium carbonate by taking carbonate type brine and sulphate type brine as raw material and by repeatedly mixing brine. Firstly carbonate type brine and sulphate type brine are mixed for performing the first brine mixing, so as to ensure that CO3<2-> ion and Mg<2+> ion in the mixed brine are completely reacted to produce basic magnesium carbonate, brine is evaporated and concentrated, and solid and liquid are separated, so that basic magnesium carbonate precipitate is removed, and lithium enrichment brine is obtained; and then the lithium enrichment brine and carbonate type brine, the lithium ion concentration of which is evaporated and concentrated to be saturated or nearly saturated, are mixed for performing second brine mixing, so that Li+ ion in the mixed brine produces lithium carbonate, solid and liquid are separated, lithium carbonate precipitate is removed, and the lithium carbonate precipitate is washed with hot water and dried, so that lithium carbonate products are obtained. Besides electricity, the method basically does not require foreign material, the investment is less, the technology is simple, the method can be applied to the mass production of lithium carbonate, the acquisition rate is high, the product quality meets the national standard, and the method is particularly suitable for the development of lithium resources of saline lake in Tibet.
Description
Technical field
The invention belongs to the chemical industry of inorganic salt field, be specifically related to a kind of production method of producing Quilonum Retard take carbonate type bittern and vitriolate type bittern as raw material with overlapping adding halogen method.
Background technology
Quilonum Retard has high value and wide market outlook, and producing at present the lithium salts method both at home and abroad from bittern has multiplely, mainly contains:
1, bittern-aluminate precipitator method;
2, organic solvent extractionprocess;
3, ion sieve method (ion-exchange, absorption) (seeing the 9th～13 page of " sea lake salt and chemical industry " the 4th phase of the 29th volume);
4, evaporative crystallization partition method;
5, the precipitator method;
6, flotation process; (see the 20th～26 page of " sea lake salt and chemical industry " the 20 volume fourth phase; The 14th～16 page of the 1st phase of the 22nd volume.The 29 volume the 4th phase 9-13 page or leaf).
7, bittern-thermal decomposition method: cooperate and use the milk of lime sulfate radical, then decompose with High Temperature Furnaces Heating Apparatus, make magnesium chloride be transformed into HCl and MgO, water logging magnesium oxide residue adds soda ash again and removes remaining magnesium ion in leach liquor, produce at last the lithium salts product.
8, the solar pond method is utilized carbonate type bittern, and spontaneous evaporation Quilonum Retard to the bittern is saturated under the normal temperature, move to again in the solar pond, utilize solar heating bittern, because Quilonum Retard is retrograde solubility, with the rising of temperature, the principle that solubleness descends is separated out Quilonum Retard in bittern.
9, the technique of utilizing the old halogen in salt lake to produce high-purity magnesium oxide and lithium salts that Chinese patent ZL200710024943.8 proposes.
Domestic salt lake resources is according to ore reserve latest survey data, and the Qinghai-Tibet Platean has 352 in salt lake, and the total area reaches 2.1465 ten thousand square kilometres, and the salt lake mainly contains carbonate type and two kinds of hydrochemical types of sulfate type.But Tibet up to the present, only have the Zha Buye salt lake through the more than ten years research of Quilonum Retard, test to be formed certain industrial scale, and the rate that obtains of Quilonum Retard is about 25%, the quality product lithium carbonate containing is 60～70%, therefore other has several salt lakes also among test, and the exploitation for the Salt Lake on Qinghai-Tibetan Plateau lithium resource provides a new approach extremely urgent.
Carbonate type contains lithium bittern in the process of extracting Quilonum Retard, the enrichment of lithium in bittern is a difficult problem, because the solubleness of Quilonum Retard is very little, and be again retrograde solubility, according to Tibetan Salt Lakes to the enrichment data of lithium in bittern, the saturated content of lithium is about 1.5g/l in the summer bittern, the saturated content of lithium is about 2.5g/l in the winter bittern, namely large in spontaneous evaporation in summer amount, when being conducive to produce, the solubleness of Quilonum Retard is little, winter severe cold season, when being unfavorable for producing, the solubleness of Quilonum Retard is large, and the solar pond that industry is generally used has been brought very large difficulty to production.
Sulfate type contains lithium bittern, in the process of extracting Quilonum Retard, although lithium energy enrichment in bittern, according to many salinization factory production datas, general lithium ion can be enriched to more than the 8g/l, and high-lithium ion can reach 12g/l, but magnesium, lithium to separate be again that salt chemical engineering is produced a difficult problem in the lithium salts for many years.
Summary of the invention
The objective of the invention is for the difficult problem of above-mentioned two types of bittern in extracting the lithium process, a kind of production method of producing Quilonum Retard take carbonate type bittern and vitriolate type bittern as raw material with overlapping adding halogen method is provided.
Purpose of the present invention can reach by following measures:
A kind of production method of producing Quilonum Retard take carbonate type bittern and vitriolate type bittern as raw material with overlapping adding halogen method comprises the steps:
1) carbonate type bittern is mixed with vitriolate type bittern carry out converting the first time halogen, the consumption of regulating two kinds of bittern makes the CO that mixes in the bittern
3 2-Ion and Mg
2+The ion complete reaction generates magnesium basic carbonate, and the bittern evaporation after converting halogen and finishing is concentrated, and solid-liquid separation is removed the basic carbonate magnesium precipitate again, obtains lithium enrichment bittern;
2) lithium enrichment bittern and evaporation concentration is saturated or mix near saturated carbonate type bittern to lithium concentration, carry out converting the second time halogen, the consumption of regulating two kinds of bittern makes the Li that mixes in the bittern
+Ion generates Quilonum Retard, and solid-liquid separation goes out the Quilonum Retard precipitation after converting halogen and finishing, and the Quilonum Retard precipitation that obtains with hot wash is also dry, obtains lithium carbonate product.
Method of the present invention further can also comprise the following step of converting for the third time halogen: convert the liquid that halogen is finished and solid-liquid separation goes out for the second time, merge with the washings after the washing Quilonum Retard precipitation, mix with vitriolate type bittern and convert for the third time halogen, the consumption of regulating two kinds of bittern makes the CO that mixes in the saltwater brine
3 2-Ion and Mg
2+The ion complete reaction generates magnesium basic carbonate;
Convert for the third time after the halogen bittern directly with convert halogen the first time and finish after bittern mix, carry out together again evaporation concentration, then solid-liquid separation is removed the basic carbonate magnesium precipitate, obtains lithium enrichment bittern to carry out the converting halogen second time;
Perhaps, convert for the third time the bittern elder generation evaporation concentration after the halogen, the bittern that obtains again with convert for the first time halogen and evaporation concentration after bittern mix, then carry out together solid-liquid separation and remove the basic carbonate magnesium precipitate, obtain lithium enrichment bittern to carry out the converting halogen second time;
Perhaps, convert for the third time the bittern elder generation evaporation concentration after the halogen, solid-liquid separation is removed the basic carbonate magnesium precipitate again, the liquid that obtains with convert for the first time the lithium enrichment bittern that halogen obtains and merge to carry out converting the second time halogen.
Method of the present invention is only by step 1) and step 2) lithium carbonate product of higher degree and yield can be obtained, but the discharge of farthest being extracted and reducing waste water for the lithium that makes in the bittern can be in step 1) and 2) process of converting for the third time halogen increased afterwards.
Carbonate type bittern of the present invention is for containing CO
3 2-Ion and Li
+The salt lake brine of ion; Described vitriolate type bittern is for containing SO
4 2-Ion, Mg
2+Ion and Li
+The salt lake brine of ion.Also might contain potassium, sodium, chlorine plasma in two kinds of bittern, concrete bittern composition is different because of different salt lakes.Vitriolate type bittern also can extend to the magnesium-containing brine of other type among the present invention.
Two kinds of bittern of the present invention can directly be converted halogen and use, also can be first that a kind of bittern prevapourising before converting halogen for the first time is concentrated, because the bittern in the most of salt lakes of salt lake brine is undersaturated, so first prevapourising is concentrated once, can reduce when converting halogen wherein a kind of operational throughput of bittern.It is concentrated to reduce water content two kinds of bittern all can certainly to be carried out prevapourising, alleviates the concentrated pressure of subsequent evaporation.Carbonate type bittern before use first prevapourising is concentrated to wherein CO
3 2-Ion reaches or is lower than saturation concentration; Vitriolate type bittern before use first prevapourising is concentrated to wherein Mg
2+Ion reaches or is lower than saturation concentration.
The purpose of converting for the first time halogen in the step 1 is in order to remove the magnesium ion in the bittern, because the magnesium basic carbonate that generates belongs to insoluble compound, can farthest remove magnesium ion and can not affect lithium ion in the bittern.Convert for the first time the consumption of two kinds of bittern in the halogen process, according to the amount of its concrete contained ion, determine to convert the halogen ratio with carbanion and the lucky complete reaction of magnesium ion in the mixing bittern.During reaction, if carbonate is excessive in the bittern, in the process of bittern evaporation enriching lithium, has Quilonum Retard and separate out, and cause the loss of lithium; If but carbonate is less, can cause in the bittern magnesium except unclean, when secondary is converted halogen, have magnesium basic carbonate and separate out, affect the quality of Quilonum Retard.
Convert in the step 1 that to carry out bittern evaporation after halogen is finished concentrated, owing to lack the ion that makes the lithium precipitation in the bittern, so lithium ion can reach largely enrichment.The content that can make lithium ion in the water after the evaporation concentration preferably makes lithium concentration reach 7.5～8.5g/l greater than 4g/l, and low moisture excessive in the bittern of can making crossed in the too high precipitation loss that easily causes lithium ion, increases subsequent production pressure.Therefore Li in the lithium enrichment bittern that obtains in the step 1
+The content of ion is preferably 7.5～8.5g/l.
For the first time converting the halogen process can carry out under 0～90 ℃, considers for saving cost and other factors (such as solubleness etc.), generally gets final product in that normal temperature (20～30 ℃) is lower.
The evaporation concentration that adopts in the step 2 is saturated or generally be 1.5～2.5g/l near the content of lithium ion in the saturated carbonate type bittern to lithium concentration, according to the difference of concrete envrionment temperature and slightly different.Convert for the second time halogen and can make the lithium ion form with Quilonum Retard in the situation of getting rid of the magnesium ion interference in lithium enrichment bittern and the saturated or near saturated bittern obtain as much as possible extracting, the lithium ion that mixes in the bittern is precipitated fully.
Convert in the halogen process for the second time, according to the ion content in two kinds of bittern, the consumption of regulating two kinds of bittern makes and mixes in the bittern and Li
+Ionic reaction generates the CO of Quilonum Retard
3 2-The molar weight of ion excessive 0～30%.The add-on that is carbanion is 100～130% of theoretical amount, determines to convert the halogen ratio.If carbanion has lacked, Quilonum Retard is separated out insufficient, affects the single line rate of recovery of lithium, and carbonate is many can not reduce the eduction rate of lithium, but carbanion is too many, causes the idling of equipment, affects equipment capacity.
Convert for the second time the Quilonum Retard precipitation that adopts hot wash to obtain after the halogen, because the solubleness of Quilonum Retard in water reduces along with the rising of temperature, so hot water can reduce the damage part that washing precipitation causes.The temperature of hot water can be regulated from 30 ℃～100 ℃, in order to take full advantage of local sun power, can adopt solar water to wash, and its temperature is generally 75～85 ℃.
For the second time converting halogen can carry out under 0～90 ℃, generally gets final product under normal temperature (20～30 ℃).A kind of scheme is to carry out under to 85 ℃ at normal temperature (20～30 ℃), particularly can under 80 ℃ or condition near 80 ℃ (such as 75 ℃～85 ℃), carry out, because the solubleness of Quilonum Retard is minimum under this temperature, can improve the eduction rate of the Quilonum Retard of this step.
Convert for the third time halogen and can make washing or extract the lithium loss that causes when incomplete and return to the extraction that circulates in the leaching process, the extraction rate reached that makes the lithium ion in the bittern to or near 100%.When converting halogen for the third time, according to the ionic concn in two kinds of bittern, it is (the same when converting halogen with the first time to determine to convert the halogen ratio in the lucky complete reaction of chemical equation carbanion and magnesium ion, but be the rate of recovery problem that has thoroughly solved lithium, and there is not trade effluent to discharge non-environmental-pollution in the whole technical process).
Convert for the third time liquid after the halogen and return the system of converting for the first time after the halogen.According to the liquid individual curing whether of converting for the third time after the halogen, can be divided into directly with convert for the first time halogen after bittern mix, concentrate first three kinds of situations of remix behind remix and the first concentrating and separating solid.Convert for the third time the evaporation concentration of the bittern after the halogen, comprise directly and convert the mixed evaporation concentration of bittern after the halogen for the first time, can make the content of lithium ion in the water greater than 4g/l, preferably make lithium concentration reach 7.5～8.5g/l, its concrete requirement with convert for the first time halogen after concentrated require identical.
Converting for the third time the halogen process can carry out under 0～90 ℃, considers for saving cost and other factors (such as solubleness etc.), generally gets final product in that normal temperature (20～30 ℃) is lower.
The invention provides a kind of salt lake carbonate type bittern and vitriolate type bittern or chloride type of utilizing and contain magnesium ion bittern, carry out in proportion converting the first time halogen according to the bittern composition, the nature constant-temperature evaporation is concentrated, for the second time convert halogen again and separate out Quilonum Retard, and separate out liquid behind the Quilonum Retard, also to return and again convert halogen in the front flow process, thereby form the overlapping production method that halogen is produced Quilonum Retard of converting.
The present invention is directed to two difficult problems of two types of bittern in extracting the lithium process, proposition is in zone with good conditionsi, the two or several places that two types of bittern are arranged are namely arranged, carrying out water body according to practical situation shifts, because the ratio that the bittern of Tibetan Salt Lakes forms or forms all is difficult to identical, even same salt lake is with the variation in season, it is also larger that it forms variation, even have the bittern type in minority salt lake to change, so when carrying out the water body transfer, need consider the amount that water body shifts, the direction that shifts, sea level elevation (preferably gravity flow) is subjected to water body to shift the storage capability in salt lake, the factors such as area of building the salt pan.Shift by dissimilar water bodys, the bittern that can realize two salt lakes or several salt lakes is prepared and is mixed, and disadvantageous factor is become favorable factor, namely utilizes the CO in the carbonate type bittern
3 2-Ion remaval falls the magnesium ion in the vitriolate type bittern, magnesium, lithium are separated, otherwise be to utilize magnesium ion in the vitriolate type bittern to get rid of carbanion in the carbonate type bittern, be conducive to the enrichment of lithium, thereby the lithium that reaches in two bittern can extract again in enrichment.
Detailed principle of the present invention is as follows:
Utilize CO in the carbonate type salt lake bittern
3 2-Mg in ion and the sulfate type salt lake bittern
2+Ar ion mixing, reaction generates the basic carbonate magnesium precipitate, removes the CO in the bittern
3 2-Ion and Mg
2+Ion, reaction equation is:
4Mg
2++4CO
3 2-+5H
2O→3MgCO
3·Mg(OH)
2·4H
2O↓+CO
2↑
Convert halogen for the first time and convert for the third time halogen according to above-mentioned principle.
CO in the recycling ortho-carbonate type lake salt bittern
3 2-Ion and convert halogen the first/three time after (remove Mg
2+Ion and CO
3 2-Ion) Li in the lithium enrichment bittern
+Ion, reaction generate the Quilonum Retard precipitation, and reaction equation is:
2Li
++CO
3 2-+H
2O→Li
2CO
3+H
2O
Overlapping definite principle of converting the halogen ratio of the present invention is:
For the first time convert halogen: be with the carbanion in the carbonate type bittern and the lucky complete reaction of the magnesium ion in the vitriolate type bittern, quality determines to convert the halogen ratio than magnesium ion: carbonate=1: 2.469-2.470 (can adopt more accurate ratio according to the different of relative molecular weight that carbonate and magnesium ion adopt).
Convert for the second time halogen, with the carbonate content in the carbonate type bittern after evaporation concentration (lithium ion approaches or reaches capacity), with convert for the first time bittern after the halogen through evaporation concentration, its lithium ion is enriched to certain content, the carbanion amount is 100～130% of theoretical amount during according to the carbonate in two kinds of bittern and lithium ion complete reaction, theoretical amount ratio is that quality determines to convert the halogen ratio than carbanion: lithium ion=4.322-5.620.
Converting for the third time halogen, is with the Mg in the vitriolate type bittern
2+Convert ion content and the second time CO in the liquid after halogen is separated out Quilonum Retard
3 2-Content, the lucky complete reaction of magnesium ion and carbanion, quality are than magnesium ion: carbonate=1: 2.469-2.470, determine to convert the halogen ratio.
Convert in the halogen process HCO in the bittern whole
3 -Ion is inoperative, can be used as foreign ion and does not consider, and facts have proved NaHCO
3(sodium bicarbonate) saturated solution and LICl saturated solution do not react under normal temperature and 80 ℃ the condition of heating, and generate without Quilonum Retard.
Bittern only loses without lithium ion except magnesium ion when carrying out mixing the first time, and its reason is that the magnesium basic carbonate that generates is insoluble compound, and the solubility product of magnesiumcarbonate is K
SP=3.5 * 10
-8, the solubility product of magnesium hydroxide is K
SP=2.0 * 10
-24, and the solubleness of Quilonum Retard is: 1.54g (0 ℃), 1.33g (20 ℃), 0.72g (100 ℃).
The solubleness of Quilonum Retard is less, the solubleness of Quilonum Retard is: 1.54g (0 ℃), (1.33g 20 ℃), (0.72g 100 ℃), so contain the carbonate type bittern of lithium, when bittern evaporation, summer, lithium ion content can reach 1.5g/l in the bittern, otherwise will separate out with the form of Quilonum Retard, and winter, lithium ion content then can reach 2.5g/l, so secondary is converted in the halogen process, evaporation concentration to lithium ion in the saturated or near saturated carbonate type bittern content of lithium ion be 1.5～2.5g/l.
In vitriolate type bittern, when magnesium ion content is higher in the bittern, just there is not carbanion; And when magnesium ion reaches certain content, have Lithium Sulphate in the bittern to separate out, if still remove the magnesium ion in this bittern, this not only without in carbanion but also the bittern without magnesium ion, so the further enrichment of the content of lithium ion is Li in the lithium enrichment bittern
+The content of ion is 7.5～8.5g/l.
Magnesium basic carbonate among the present invention refers to 3MgCO
3Mg (OH)
24H
2O or MgCO
3Mg (OH)
2
Evaporation concentration among the present invention comprises with the mode evaporation concentration of nature (such as sunshine), also comprises the evaporation concentration with Heat artificially, artificial lighting or other manual types.
Solid-liquid separation among the present invention comprises and adopts special equipment general solid or liquid separation wherein, is also included within and directly carries out precipitate and separate in salt pan or elsewhere or the facility, also comprises and adopts various filtration steps or facility to separate.
Beneficial effect of the present invention:
The present invention does not need external raw material substantially except electricity consumption, less investment, and technique is simple, can be used for extensive Quilonum Retard production, obtains the rate height, and quality product reaches national standard, is particularly suitable for the exploitation of the lithium resource of Tibetan Salt Lakes (two types of salt lakes mix layout).
The present invention is applicable to carbonate type (containing lithium) salt lake brine and any type (contains magnesium, lithium) salt lake brine converts halogen production, thereby carbonate type and sulfate type salt lake (containing lithium) bittern two difficult problems that the lithium enrichment separates with the magnesium lithium in the lithium salts leaching process have been solved, it has adaptability to raw material strong, obtain the rate height, cost is low, because production process is by solar thermal energy spontaneous evaporation bittern, but also do not need external raw material and other chemical agent, for the second time convert halogen exactly and separate out Quilonum Retard, in factory, carry out under the normal temperature, the hot water with 80 ℃ is washed in the lithium salts back washing, because consumption is little, just can satisfy with solar water, so essentially no pollution of plant produced, without the three wastes, whole production technique is simple, and how data changed during no matter how bittern formed, only need to calculate two chemical equations (reaction of the reaction of carbonate and magnesium ion and carbonate and lithium ion), general personnel can both grasp, and are easy to control, easy to operate.Industrial scale is not limit, and the investment of founding the factory is little, mainly is to build a workshop, and Quilonum Retard after the halogen sedimentation washs converting, dry, packing, storage.
The present invention does not need external raw material substantially except electricity consumption, less investment, and technique is simple, can be used for extensive Quilonum Retard production, obtains the rate height, and quality product reaches national standard, is particularly suitable for the exploitation of the lithium resource of Tibetan Salt Lakes (two types of salt lakes mix layout).
Description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Embodiment
Details are as follows in each concrete operations of the present invention:
One, according to year water body transfer amount and Hubei and Hunan Provinces sea level elevation, determine that water body shifts nominal diameter and the nominal pressure of required pipeline, and flow, the lift of required pump, too high such as lift, available multilayer relay pump device.If the bittern concentration that water body shifts is crossed low or the water yield is larger, can build first salt pan (will according to the geologic condition around the salt lake), the bittern spontaneous evaporation is concentrated into a certain concentration, carry out again water body and shift.
Two, after finishing salt pan construction and a certain type water body and transferring to the salt pan in another type water body salt lake, just can carry out the salt pan operation.
Three, carbonate type bittern, directly spontaneous evaporation is saturated to lithium ion, Li
+At 1.5～2.5g/l, for subsequent use.Carbonate type bittern and vitriolate type bittern are in processing requirement ratio (CO
3 2-And Mg
2+) convert halogen, convert bittern that halogen finishes through spontaneous evaporation enrichment method lithium ion (when lithium is enriched to the 3g/l left and right sides, will reach the saturation point of potassium ion), until (Li during the certain content of lithium ion enrichment in the bittern
+Higher, the eduction rate of Quilonum Retard is higher), stand-by.
Four, the bittern of the bittern that the carbonate type lithium ion is saturated and lithium ion enrichment carries out respectively multiple times of filtration, removes water-insoluble, in processing requirement ratio (CO
3 2-And Li
+) carry out converting halogen the second time, separate out Quilonum Retard, because solid-to-liquid ratio is too little, so need elder generation settlement separate, get Quilonum Retard slip and clear liquid.
Five, clear liquid is returned front flow process and vitriolate type bittern by processing requirement (CO
3 2-And Mg
2+) convert for the third time halogen, finish the overlapping halogen whole process of converting.
Six, with the Quilonum Retard slip, filter, countercurrent washing is more than three times, and drying again must Powdered carbonic acid lithium product.
Annotate: Powdered carbonic acid lithium is when crude product, and water content is too high, generally more than 30%, so to repeatedly wash, dry also large with heat, if when secondary is converted halogen, the crystallization rate of control Quilonum Retard, but manufacture order Oblique Crystal Quilonum Retard (commercially available prod substantially all is powdery product).This product is under front operation the same terms, owing to be crystal, the crude product water content is few, and washing times and water consumption are few.
Seven, in actual industrial production, respectively converting the halogen operation is the assay that forms according to each stage bittern, each stage of calculative determination convert the halogen ratio after, input multiple spot control industrial computer, commander respectively converts the halogen flowermeter by computer, convert the halogen operation, converting halogen flow and total amount needs accurately, to guarantee to convert the accurate of halogen ratio.
Embodiment one:
1, get Ali, Tibet A lake bittern water, density d=1.0785, (g/l) composed as follows:
K
+ Mg
2+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
2.29 0.29 43.51 0.17 1.188 2.50 364.19
When this bittern evaporation was 1.78g/l to lithium ion content, it was composed as follows:
K
+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
23.85 107.953 1.78 12.375 18.52 166.177 (g/l)
Get this bittern 50L, for subsequent use.This halogen is called A
1
2, get Ali, Tibet B lake bittern water, density d=1.1, (g/l) composed as follows:
K
+ Mg
2+ Na
+ Li
+ SO
4 2- Cl
-
3.288 12.651 32.179 0.13 4.678 86.058
With A lake bittern water A: B=94.6 in proportion: 5.4 mix convert halogen (basis of converting the halogen ratio is:
Magnesium ion: carbonate=1: 2.469, establish A=1, B=x, so (0.29+12.651x) * 2.469=2.503, get x=0.0572, A: B=1: 0.0572=94.6: 5.4), when then being evaporated to the bittern lithium ion content and being 8g/l, after solid-liquid separation, bittern consists of:
K
+ Na
+ Li
+ SO
4 2- Cl
-
41.46 90.75 8.0 16.619 206.143 g/l
Get this bittern 15L, for subsequent use.This bittern is called B
1
3, press A
1Bittern: B
1Bittern=(press A at 3.5: 1
1Carbanion excessive 10% in the bittern), get A
135 liters in bittern, B
110 liters in bittern is under agitation converted halogen, and after converting halogen and finishing, restir 4 hours stops to stir, and its supernatant liquid is removed in free setting 2 hours, and lower floor's slip is filtered, and gets filter cake and clear liquid.The carbanion amount is 100～130% of theoretical amount during according to the carbonate in two kinds of bittern and lithium ion complete reaction, and theoretical amount ratio is carbanion: lithium ion=4.3228, and convert the halogen ratio and calculate: establish A
1Be 1, B
1Be x, carbonate is in excessive 10%, and (1.78+8.0x) * 4.3228*110%=18.52 gets x=0.2643, A
1: B
1=1: 0.2643=3.78: 1, determining to convert the halogen ratio is 3.5: 1.
4, the clear liquid amount in the 3rd step is 44.6L, and it consists of:
K
+ Cl
- Na
+ SO
4 2- Li
+ CO
3 2-
27.95 171.34 107.05 12.31 1.81 8.30 g/l
5, the filter cake in the 3rd step carries out back washing through 80 ℃ of hot water of three usefulness, after the filtration, and the filter cake oven dry, the oven dry product is lithium carbonate product.
Quilonum Retard is 310g after the washing and drying, contains purely to be: 99.44%, and a single line eduction rate of lithium is 77.3% (to refer to B
1Bittern) deduct wherein three countercurrent washings loss lithium and be about 6% of finished product lithium total amount, it is 72.4% that actual single line is obtained rate.
6, clear liquid and washings mixing are converted halogen by chemical examination and B lake bittern water, be called and convert for the third time halogen, namely utilize carbanion and the reaction of the magnesium ion in the B lake bittern water in the clear liquid to generate magnesium basic carbonate, thereby remove two kinds of carbanion and magnesium ions in the bittern, converting for the third time halogen is with the Mg in the vitriolate type bittern
2+Convert ion content and the second time CO in the liquid after halogen is separated out Quilonum Retard
3 2-Content, the lucky complete reaction of magnesium ion and carbanion, magnesium ion: carbonate=1: 2.469, determine to convert the halogen ratio, method of calculation are with converting for the first time halogen.This bittern enters the bittern system after convert halogen the first time, continues evaporation concentration, obtains the bittern of lithium enrichment, participates in converting halogen for the second time, finishes the overlapping halogen of converting of whole process.
The result of laboratory test of above-mentioned test is listed in table 1.See attached list 1
Embodiment two:
Get A
1Bittern 7L gets B
1Bittern 2L is heated with stirring to 80 ℃ after the mixing, stir constant temperature for some time, and filtered while hot gets clear liquid.The clear liquid lithium ion content is 1.299g/l.Through simple material balance, B
1The single line eduction rate of bittern lithium is 83.76%, A
1The single line eduction rate of bittern lithium is 27.02%, and the Quilonum Retard that this example is separated out is crude product, gets final product to get finished product through back washing and drying again.
Annotate: the rate that always obtains of lithium: carrying secretly when other salt is separated out in the seepage that bittern produces in the salt pan spontaneous evaporation and salt pan evaporation, that the production of any salt pan is all unavoidable, usually do not affect the calculating that Workshop Production always obtains rate, if by above-mentioned routine, calculate lithium in this technique always obtain rate the time, except the production plant run, drip, leak, lithium salts is substantially all to have reclaimed.
Embodiment three:
1, get Ali, Tibet C lake bittern water, density d=1.13, (g/l) composed as follows:
K
+ Mg
2+ Ca
2+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
16.122 0.004 0.002 60.728 0.13 16.700 5.559 89.572
When this bittern evaporation was 1.78g/l to lithium ion content, it was composed as follows:
K
+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
-
49.04 107.12 1.78 15.89 75.97 197.945 (g/l)
Get this bittern 5L, for subsequent use.This halogen is called C
1
2, get Ali, Tibet D lake bittern water, density d=1.1275, (g/l) composed as follows:
K
+ Mg
2+ Ca
2+ Na
+ Li
+ SO
4 2- CO
3 2- Cl
- HCO
3 -
10.894 3.64 0.108 57.429 0.16 4.480 0.790 105.615 0.18
With A lake bittern water C: D=60.1 in proportion: 39.9 mix and convert halogen and (convert the method for calculation of halogen ratio with embodiment one, calcium ion in the bittern, magnesium ion and carbanion equivalent proportioning), when then being evaporated to the bittern lithium ion content and being 7.889g/l, after solid-liquid separation, bittern consists of:
K
+ Na
+ Li
+ SO
4 2- Cl
- HCO
3 -
49.00 107.128 7.889 15.889 197.889 10.067 g/l
Get this bittern 10L, for subsequent use.This bittern is called D
1
3, press C
1Bittern: D
1Bittern=(press C at 1: 1.8
1Carbanion excessive 10% in the bittern), get C
15 liters in bittern, D
19 liters in bittern is under agitation converted halogen, and after converting halogen and finishing, restir 4 hours stops to stir, and its supernatant liquid is removed in free setting 2 hours, and lower floor's slip is filtered, and gets filter cake and clear liquid.(the carbanion amount is 100～130% of theoretical amount during with the lithium ion complete reaction according to the carbonate in two kinds of bittern, and theoretical amount ratio is carbanion: lithium ion=4.3228, convert the calculating of halogen ratio: establish C
1Be 1, D
1Be x, carbonate is in excessive 10%, and (1.78+7.889x) * 4.3228*110%=75.97 gets x=1.8, C
1: D
1=1: 1.8, determining to convert the halogen ratio is 1: 1.8.)
4, the clear liquid amount in the 3rd step is 13.85L, and it consists of:
K
+ Cl
- Na
+ SO
4 2- Li
+ CO
3 2- HCO
3 -
48.97 197.56 106.781 15.56 1.82 6.43 g/l
5, the filter cake in the 3rd step carries out back washing through 80 ℃ of hot water of three usefulness, after the filtration, and the filter cake oven dry, the oven dry product is lithium carbonate product.
Quilonum Retard is 273g after the washing and drying, contains purely to be: 99.21%, and a single line eduction rate of lithium is 76.93% (to refer to B
1Bittern) deduct wherein three countercurrent washings loss lithium and be about 6% of finished product lithium total amount, it is 72.3% that actual single line is obtained rate.
6, clear liquid and washings mixing are converted halogen by chemical examination and D lake bittern water, be called and convert for the third time halogen, namely utilize carbanion and the reaction of the magnesium ion in the D lake bittern water in the clear liquid to generate magnesium basic carbonate, thereby remove two kinds of carbanion and magnesium ions in the bittern, this bittern enters the system after convert halogen the first time, continues evaporation concentration, obtains the bittern of lithium enrichment, participate in converting halogen for the second time, finish the overlapping halogen of converting of whole process.
The result of laboratory test of above-mentioned test is listed in table 2.See attached list 2
Subordinate list 1:
Subordinate list 2:
Claims (9)
1. a production method of producing Quilonum Retard take carbonate type bittern and vitriolate type bittern as raw material with overlapping adding halogen method is characterized in that comprising the steps:
1) carbonate type bittern is mixed with vitriolate type bittern carry out converting the first time halogen, the consumption of regulating two kinds of bittern makes the CO that mixes in the bittern
3 2-Ion and Mg
2+The ion complete reaction generates magnesium basic carbonate, and the bittern evaporation after converting halogen and finishing is concentrated, and solid-liquid separation is removed the basic carbonate magnesium precipitate again, obtains lithium enrichment bittern;
2) lithium enrichment bittern and evaporation concentration is saturated or mix near saturated carbonate type bittern to lithium concentration, carry out converting the second time halogen, the consumption of regulating two kinds of bittern makes the Li that mixes in the bittern
+Ion generates Quilonum Retard, and solid-liquid separation goes out the Quilonum Retard precipitation after converting halogen and finishing, and the Quilonum Retard precipitation that obtains with hot wash is also dry, obtains lithium carbonate product; Described evaporation concentration is saturated or be 1.5～2.5g/l near the content of lithium ion in the saturated carbonate type bittern to lithium concentration.
2. method according to claim 1, it is characterized in that converting the described second time liquid that halogen is finished and solid-liquid separation goes out, merge with the washings after the washing Quilonum Retard precipitation, mix with vitriolate type bittern and convert for the third time halogen, the consumption of regulating two kinds of bittern makes the CO that mixes in the saltwater brine
3 2-Ion and Mg
2+The ion complete reaction generates magnesium basic carbonate;
Convert for the third time after the halogen bittern directly with convert halogen the first time and finish after bittern mix, carry out together again evaporation concentration, then solid-liquid separation is removed the basic carbonate magnesium precipitate, obtains lithium enrichment bittern to carry out the converting halogen second time;
Perhaps, convert for the third time the bittern elder generation evaporation concentration after the halogen, the bittern that obtains again with convert for the first time halogen and evaporation concentration after bittern mix, then carry out together solid-liquid separation and remove the basic carbonate magnesium precipitate, obtain lithium enrichment bittern to carry out the converting halogen second time;
Perhaps, convert for the third time the bittern elder generation evaporation concentration after the halogen, solid-liquid separation is removed the basic carbonate magnesium precipitate again, the liquid that obtains with convert for the first time the lithium enrichment bittern that halogen obtains and merge to carry out converting the second time halogen.
3. method according to claim 1 and 2 is characterized in that described carbonate type bittern is for containing CO
3 2-Ion and Li
+The salt lake brine of ion; Described vitriolate type bittern is for containing SO
4 2-Ion, Mg
2+Ion and Li
+The salt lake brine of ion.
4. method according to claim 1 and 2, it is characterized in that described carbonate type bittern before use first prevapourising be concentrated to wherein CO
3 2-Ion reaches or is lower than saturation concentration; Described vitriolate type bittern before use first prevapourising is concentrated to wherein Mg
2+Ion reaches or is lower than saturation concentration.
5. method according to claim 1 and 2 is characterized in that Li in the described lithium enrichment bittern
+The content of ion is 7.5～8.5g/l.
6. method according to claim 1 is characterized in that converting in the halogen process for the second time, and the consumption of regulating two kinds of bittern makes and mixes in the bittern and Li
+Ionic reaction generates the CO of Quilonum Retard
3 2-The molar weight of ion excessive 0～30%.
7. method according to claim 1 is characterized in that step 2) in the temperature of hot water be 75～85 ℃.
8. method according to claim 2, the bittern evaporation that it is characterized in that converting for the third time after the halogen is concentrated into Li
+The content of ion reaches 7.5～8.5g/l.
9. method according to claim 1 and 2 is characterized in that converting halogen the first time or converting halogen for the second time and carry out under 0～90 ℃; Converting for the third time halogen carries out under 0～90 ℃.
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|---|---|---|---|
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| CN103787374B (en) * | 2012-10-31 | 2015-05-06 | 西藏国能矿业发展有限公司 | Method for extracting lithium carbonate from salt lake bittern |
| 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 |
| CN103482660B (en) * | 2013-09-13 | 2015-06-24 | 西藏金睿资产管理有限公司 | Method and system for preparing high-purity lithium carbonate |
| CN103708508B (en) * | 2014-01-17 | 2015-12-30 | 长沙有色冶金设计研究院有限公司 | A kind of method of producing battery-level lithium carbonate from lithium concentrate |
| CN104030322B (en) * | 2014-02-11 | 2016-03-02 | 青海锂业有限公司 | A kind ofly recycle salt lake lithium liquor and the method for by-product magnesium basic carbonate |
| CN105858693B (en) * | 2016-04-07 | 2017-09-15 | 中国科学院青海盐湖研究所 | The method that high-purity magnesium carbonate is prepared from the carbonate type bittern of plateau |
| CN105905929B (en) * | 2016-04-07 | 2017-09-15 | 中国科学院青海盐湖研究所 | The method that lithium carbonate is prepared from the carbonate type bittern of plateau |
| CN108285157A (en) * | 2018-03-23 | 2018-07-17 | 中蓝长化工程科技有限公司 | A kind of technique preparing lithium carbonate with carbonate type bittern |
| CN108358222B (en) * | 2018-04-10 | 2019-10-18 | 中蓝长化工程科技有限公司 | A kind of technique mentioning lithium from carbonate type salt lake brine |
| CN110372014B (en) | 2019-07-30 | 2020-08-21 | 中国科学院青海盐湖研究所 | Renewable magnesium removing agent and application thereof in preparation of low-magnesium lithium-rich brine |
| CN113371738A (en) * | 2020-02-25 | 2021-09-10 | 中国科学院青海盐湖研究所 | Preparation method for preparing lithium carbonate and co-producing magnesium hydroxide nanosheet by using feed liquid containing lithium and magnesium |
| CN113493216B (en) * | 2021-07-12 | 2022-09-13 | 青海锂业有限公司 | Method for preparing industrial-grade basic magnesium carbonate from salt lake brine |
| CN116040661B (en) * | 2023-01-18 | 2024-09-10 | 广东邦普循环科技有限公司 | Comprehensive utilization method of salt lake brine |
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| US5219550A (en) * | 1989-03-31 | 1993-06-15 | Cyprus Foote Mineral Company | Production of low boron lithium carbonate from lithium-containing brine |
| US7157065B2 (en) * | 1998-07-16 | 2007-01-02 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
| CN1093517C (en) * | 1999-04-20 | 2002-10-30 | 中国地质科学院盐湖与热水资源研究发展中心 | Lithium salt extraction process from carbonate type bittern |
| CN1273941A (en) * | 2000-05-31 | 2000-11-22 | 青海省地质矿产勘查院 | Process for separating Mg and Li from high-Mg Li-contained bittern |
| CN1307104C (en) * | 2003-03-21 | 2007-03-28 | 钟辉 | Magnesium sulfate hypotype salt lake brine magnesium lithium separation method |
| CN101481125B (en) * | 2009-02-13 | 2011-05-04 | 海门容汇通用锂业有限公司 | Method for cyclically using lithium deposition solution for preparing sodium carbonate solution to produce lithium carbonate |
| CN101875497B (en) * | 2010-08-18 | 2011-11-02 | 化工部长沙设计研究院 | Production process for extracting lithium from raw brine of high magnesium-lithium ratio lithium salt-containing lake |
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| CN102491378A (en) | 2012-06-13 |
| WO2013053165A1 (en) | 2013-04-18 |
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