CN103964474B - The recovery method of lithium in a kind of triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor - Google Patents
The recovery method of lithium in a kind of triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor Download PDFInfo
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- CN103964474B CN103964474B CN201410216658.6A CN201410216658A CN103964474B CN 103964474 B CN103964474 B CN 103964474B CN 201410216658 A CN201410216658 A CN 201410216658A CN 103964474 B CN103964474 B CN 103964474B
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- lithium
- mother liquor
- quilonum retard
- triphane
- sulfuric acid
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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 62
- 239000012452 mother liquor Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 15
- 235000021355 Stearic acid Nutrition 0.000 claims description 13
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000008117 stearic acid Substances 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 235000017550 sodium carbonate Nutrition 0.000 description 12
- 238000001914 filtration Methods 0.000 description 8
- 229910001947 lithium oxide Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000002000 scavenging effect Effects 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000276489 Merlangius merlangus Species 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Fats And Perfumes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses the recovery method of lithium in a kind of triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor, recovery method for solving prior art lithium in Quilonum Retard mother liquor produces seconds Quilonum Retard, first grade Quilonum Retard yield is low, the soluble impurity (SO in mother liquor
4 2-, K
+, Cl
-) retrieval system affects the problem of product quality.The present invention mainly comprises the concentrated of Quilonum Retard mother liquor; Reaction generates and is separated lithium stearate, and reaction is produced Lithium Sulphate and Lithium Sulphate is sent into Lithium Sulphate liquid storage groove.The invention solves the recovery of lithium and the problem of product quality in Quilonum Retard mother liquor, both improve the yield of first grade Quilonum Retard, and prevented again soluble impurity (SO
4 2-, K
+, Cl
-) retrieval system, ensure that the quality of product.
Description
Technical field
The invention belongs to ore deposit method and produce Quilonum Retard technical field, be specifically related to the recovery method of lithium in a kind of triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor.
Background technology
Current ore deposit method is produced in Quilonum Retard technique, the process such as mainly comprise roasting, ball milling, acidifying, leaching, filtration, Gou Hua, freezing, evaporation and crystallisation by cooling is separated.
Such as application number be 201310243237.8 patent of invention disclose a kind of method of lithium concentrate production pure Lithium Carbonate, the method comprises the steps:
(1) sour grog step is prepared: lithium concentrate is first processed into roasting material through 1000-1150 DEG C of calcining transformations in rotary kiln, roasting material is cooled to after 80-145 DEG C through cooler and carries out being milled to ball mill the sieving rate that 200 orders are greater than 80%, and then roasting material is mixed through worm conveyor with the vitriol oil of 18-22% mass parts, and be warming up to 250-280 DEG C of constant temperature 20-and within 30 minutes, arrive to obtain sour grog, the remaining sulfuric acid mass percentage controlling sour grog is 3-6%;
(2) prepare adjusting slurry step: in surge tank, add 4 cubes of slag washing waters, 100-130kg coarse whiting, stirs, more slowly add 2800-3000Kg acid grog, obtain adjusting slurry;
(3) prepare Lithium Sulphate leach liquor step: pH is adjusted to 5-6 by adjusting slurry Paris white or sour grog, then carry out filtering and washing with filter, obtain Lithium Sulphate leach liquor and slag washing water;
(4) Lithium Sulphate scavenging solution step is prepared: in Lithium Sulphate leach liquor, add quality than sodium carbonate: sodium hydroxide=1: the sodium carbonate of 1 and sodium hydroxide mixing solutions regulate the pH to 9.5-11.5 of lithium sulfate solution, then carry out filtration to it and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue;
(5) prepare Lithium Sulphate and complete liquid step: it is 55-60g/L that Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then carry out filtration and obtain Lithium Sulphate and complete liquid;
(6) prepare sodium carbonate solution step: sodium carbonate is dissolved in (Quilonum Retard stirs washing lotion) water of condensation, with sodium hydroxide also through insulation Chen Hua, obtain sodium carbonate solution after filtration, the concentration of sodium carbonate of sodium carbonate solution is 280-300g/L;
(7) elementary sinker reactions steps: sodium carbonate solution is transferred in sinker reactor, open and stir, then sodium carbonate solution is warming up to 95-98 DEG C, and keep temperature slowly to add Lithium Sulphate completing liquid, control the excessive 10%-15% of sodium carbonate, Lithium Sulphate completes after liquid adds and carries out centrifugation and washing, obtains Quilonum Retard and Quilonum Retard mother liquor.
(8) analyse mother liquid of sodium preparation process: Quilonum Retard mother liquor is neutralized to pH4.5-5 with sulfuric acid in a heated condition, through evaporation concentration, after isolating anhydrous sodium sulphate, obtain and analyse mother liquid of sodium, control to analyse mother liquid of sodium Li
2o concentration is at 25-30g/L
(9) stirring of Quilonum Retard is washed: Quilonum Retard enters in reactor, adds water of condensation, stir and wash Quilonum Retard by 1:4 solid-to-liquid ratio, washs to obtain Quilonum Retard through solid-liquid separation, and obtains stirring washing lotion, stirs washing lotion Lithium Oxide 98min concentration and controls as Li2O≤4g/L; Stir washing lotion be recycling in preparation sodium carbonate solution and size mixing leaching Lithium Sulphate for sour grog on a small quantity;
(10) pure Lithium Carbonate preparation process: top grade Quilonum Retard is joined in pure water and passes into carbon dioxide solubility and become lithia water, and the content controlling Lithium Oxide 98min in lithia water is 14-19g/L, then filter, filtrate is transferred in high-purity sinker still, open and stir and be warmed up to 90-98 DEG C, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate; Carbonization mother liquor carries out recycle and continues on for carbonization and dissolve top grade Quilonum Retard and become lithia water after cooling, and the content controlling Lithium Oxide 98min in lithia water is 14-19g/L, be warming up to after filtering 90-98 DEG C separate out precipitation and solid-liquid separation, washing obtain 99.99% pure Lithium Carbonate, obtain carbonization mother liquor equally; Carbonization mother liquor after several times recycle is used as the bath water of top grade Quilonum Retard.
Li in sinker mother liquor
2the mass concentration of O is that (to about 7 g/L the lithium in mother liquor exist with Quilonum Retard form, and this area all adopts with Li
2o measures), there are two kinds for the recovery method of lithium in sinker mother liquor at present:
One, mother liquor sulfuric acid is neutralized, removing CO
3 2-, evaporation concentration, by Li
2o is concentrated into about 30g/L, carries out secondary sinker, obtains seconds Quilonum Retard.
Two, mother liquor is analysed sodium through freezing, after fractional crystallization sodium sulfate, mother liquor retrieval system joins alkali, and alkalization deliming, to utilize the CO in system
3 2-.
But the seconds Quilonum Retard poor quality that first method produces, reduce the yield of first grade Quilonum Retard simultaneously.
Although second method avoids the generation of seconds Quilonum Retard, due to the soluble impurity (SO in mother liquor
4 2-, K
+, Cl
-) whole retrieval system, the storage effect of impurity is inevitable, can affect product quality.
Summary of the invention
The present invention in order to the recovery method solving prior art lithium in Quilonum Retard mother liquor produce seconds Quilonum Retard, first grade Quilonum Retard yield is low, the soluble impurity (SO in mother liquor
4 2-, K
+, Cl
-) retrieval system affects the problem of product quality, and the recovery method of lithium in a kind of triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor is provided, solve the recovery of lithium and the problem of product quality in Quilonum Retard mother liquor, both improve the yield of first grade Quilonum Retard, and prevented again soluble impurity (SO
4 2-, K
+, Cl
-) retrieval system, ensure that the quality of product.
The present invention is for solving the problems of the technologies described above, and the technical scheme of employing is:
A recovery method for lithium in triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor, is characterized in that, comprise the following steps:
(1) the Quilonum Retard mother liquor after sinker is concentrated, as the Li in mother liquor
2after the mass concentration of O reaches 20-25g/L, (in mother liquor, lithium exists with Quilonum Retard form, and this area adopts Li
2o measures), mother liquor is sent in reactor;
(2) according to Li
2the amount of O, adds stearic acid and sodium hydroxide and stirs; Be not less than the water-fast lithium stearate of reaction generation under 90 ° of C; Stop stirring and leave standstill, lithium stearate floats on liquid level gradually completely;
Reaction mechanism: NaOH+CH
3(CH
2)
16cOOH=CH
3(CH
2)
16cONa+H
2o
Li
++ (CH
2)
16CONa=(CH
2)
16COLi + Na
+
Due to CH
3(CH
2)
16cOLi is completely water insoluble, and lighter than water, floats on the water surface, so after stopping stirring, lithium stearate just floats on the water surface completely, directly just liquid phase and solid phase is separated;
(3) due to after lithium stearate is separated with mother liquor, directly discharged from bottom valve by mother liquor, lithium stearate is stayed in reactor, directly adds water and washs, discharge washing water after washing.(lithium stearate still rests in reactor)
(4) add hot water and the vitriol oil again pH value to be adjusted to 4-5 and to carry out reaction and generate Lithium Sulphate and water-fast stearic acid; After having reacted, stop stirring, then because stearic acid is water insoluble, bubble through the water column, directly lower part liquid and lithium sulfate solution are discharged;
Reaction mechanism:
H
2SO
4+ 2 CH
3(CH
2)
16COLi = 2CH
3(CH
2)
16COOH + Li
2SO
4
(5) directly to adding after pH value is adjusted to 7-8 by sodium hydroxide in reactor, the liquid in reactor is sent into the Lithium Sulphate liquid storage groove of system.
Further, in described step (2), the temperature of reactor is controlled more than 95 DEG C.
Further, the time of stirring in described step (2) is more than 30 minutes, leaves standstill more than 10 minutes again after stirring.
Further, the mother liquor in described step (3) is discharged from the bottom valve of reactor.
Further, described bottom valve is equipped with screen cloth.
Compared with prior art, the present invention has following beneficial effect:
Lithium in Quilonum Retard mother liquor after sinker of the present invention is all reclaimed, and with the form retrieval system of Lithium Sulphate, the soluble impurity (SO in mother liquor
4 2-, K
+, Cl
-) be all discharged, prevent soluble impurity retrieval system on the impact of product quality.To solve in existing technique the recovery of lithium and the problem of product quality in Quilonum Retard mother liquor, both improve the yield of first grade Quilonum Retard, and prevented again soluble impurity (SO
4 2-, K
+, Cl
-) impact that retrieval system causes, ensure that the quality of product.First grade Quilonum Retard total recovery of the present invention is increased to more than 95%.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and described embodiment is only the present invention's part embodiment, is not whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments used obtained under creative work prerequisite, belongs to protection scope of the present invention.
Sulfuric acid process is the production method that domestic and international triphane extraction lithium salts generally adopts, and the ultimate principle of this technique is that sulfuric acid and β-triphane, at 250 ~ 300 DEG C, replacement(metathesis)reaction occurs, and generates Li
2sO
4.Reactional equation is as follows:
β-Li
2O·Al
2O
3·4SiO
2+H
2SO
4→ Li
2SO
4+H
2O·Al
2O
3·4SiO
2
Production By Sulfuric Acid Process Quilonum Retard mainly comprises the following steps:
By lithium concentrate in rotary kiln 1050-1100 DEG C carry out conversion roasting, roasting after material be called roasting material; Roasting material through ball mill fine grinding, carry out acidizing fired 250-300 DEG C of nitration mixture (be mixed into 18-22% amount the vitriol oil), the material after acidizing fired is called sour grog; With leaching (neutralizing with coarse whiting), filtering separation (comprising leached mud washing) in acid grog water, obtain 25-30 g/L leach liquors; Leach liquor, through heating, adds NaOH and Na
2cO
3purification and impurity removal, filtering separation obtain scavenging solution, scavenging solution through evaporation concentration, obtained liquid, complete liquid Li
2o concentration is 60g/L, in a kettle. under heating condition, completes liquid and adds the carrying out sinker through the soda ash solution purified, obtaining first grade Quilonum Retard of 300g/L excess coefficient 12-15.
The recovery method of lithium in triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor of the present invention, comprises the following steps:
(1) the Quilonum Retard mother liquor after sinker is concentrated, as the Li in mother liquor
2after the mass concentration of O reaches 20-25g/L, (in mother liquor, lithium exists with Quilonum Retard form, and this area adopts Li
2o measures), mother liquor is sent in reactor;
(2) according to Li
2the amount of O, adds stearic acid and sodium hydroxide and stirs; Be not less than the water-fast lithium stearate of reaction generation under 90 ° of C; Stop stirring and leave standstill, lithium stearate floats on liquid level gradually completely;
Reaction mechanism: NaOH+CH
3(CH
2)
16cOOH=CH
3(CH
2)
16cONa+H
2o
Li
++ (CH
2)
16CONa=(CH
2)
16COLi + Na
+
Due to CH
3(CH
2)
16cOLi is completely water insoluble, and lighter than water, floats on the water surface, so after reaction can being stirred stopping, lithium stearate just floats on the water surface completely, directly just liquid phase and solid phase is separated;
(3) due to after lithium stearate is separated with mother liquor, directly discharged from bottom valve by mother liquor, lithium stearate is stayed in reactor, directly adds water and washs, discharge washing water after washing.(lithium stearate still rests in reactor);
(4) add hot water and the vitriol oil again pH value to be adjusted to 4-5 and to carry out reaction and generate Lithium Sulphate and water-fast stearic acid; After having reacted, stop stirring, then because stearic acid is water insoluble, bubble through the water column, directly lower part liquid and lithium sulfate solution are discharged;
Reaction mechanism:
H
2SO
4+ 2 CH
3(CH
2)
16COLi = 2CH
3(CH
2)
16COOH + Li
2SO
4
(5) directly to adding after pH value is adjusted to 7-8 by sodium hydroxide in reactor, the liquid in reactor is sent into the Lithium Sulphate liquid storage groove of system.(add-on of sodium hydroxide is only limitted to by pH regulator to 7-8, adds membership and makes stearic acid generate sodium stearate, although can not impact system, can have influence on being separated of liquid phase and lithium stearate) therefore the add-on of sodium hydroxide is only limitted to adjust ph.
The temperature of reactor controls more than 95 DEG C in (2) by described step.
The time of stirring in described step (2) is more than 30 minutes, leaves standstill more than 10 minutes again after stirring.
Mother liquor in described step (3) is discharged from the bottom valve of reactor.
Lithium in Quilonum Retard mother liquor after sinker of the present invention is all reclaimed, and with the form retrieval system of Lithium Sulphate, the soluble impurity (SO in mother liquor
4 2-, K
+, Cl
-) be all discharged, prevent soluble impurity retrieval system on the impact of product quality.To solve in existing technique the recovery of lithium and the problem of product quality in Quilonum Retard mother liquor, both improve the yield of first grade Quilonum Retard, and prevented again soluble impurity (SO
4 2-, K
+, Cl
-) impact that retrieval system causes, ensure that the quality of product.First grade Quilonum Retard total recovery of the present invention is increased to more than 95%.
Embodiment one
Adopt 2 m
3enamel reaction still gets 1 m
3quilonum Retard concentrated mother liquor, Li
2o concentration is 25g/L, injection heating reactor, drops into stearic acid (stearic acid acid number is by 207) 476kg, after stearic acid melts, add the sodium hydroxide 87.5L of liquid caustic soda 50% sodium hydroxide 133.8kg or 50%, control temperature of reaction and be greater than 95 degree, stir 30 minutes, leave standstill 10 minutes; Treating that lithium stearate is bubbled through the water column completely, discharge whole liquid phase from the bottom valve of reactor, in order to prevent lithium stearate to be discharged, one deck screen cloth can be added on bottom valve, close bottom valve; Heating water 1 m
3, stir and wash 10 minutes, discharge washing water after leaving standstill to wash water storage tank, close bottom valve; Add hot water 1m again
3, add vitriol oil 50L, and continue to add sulfuric acid to pH value to 3-4, stir 20-30 minute completely transparent to stearic acid, stop stir, leave standstill, add sodium hydroxide regulate PH to 7-8, exhaust the fluid into lithium sulfate solution storage tank.To solve in existing technique the recovery of lithium and the problem of product quality in Quilonum Retard mother liquor, both improve the yield of first grade Quilonum Retard, and prevented again soluble impurity (SO
4 2-, K
+, Cl
-) impact that retrieval system causes, ensure that the quality of product.First grade Quilonum Retard total recovery of the present invention is increased to more than 95%.
Claims (4)
1. the recovery method of lithium in triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor, is characterized in that, comprise the following steps:
(1) the Quilonum Retard mother liquor after sinker is concentrated, as the Li in mother liquor
2after the mass concentration of O reaches 20-25g/L, mother liquor is sent in reactor;
(2) according to Li
2the amount of O, adds stearic acid and sodium hydroxide and stirs; The temperature of reactor controls generating water-fast lithium stearate for more than 95 DEG C reactions;
(3) after isolating mother liquor, lithium stearate is washed, after washing, discharge washing water, then add hot water and the vitriol oil and pH value is adjusted to 4-5 and carries out reaction and generate Lithium Sulphate and water-fast stearic acid;
(4) add after pH value is adjusted to 7-8 by sodium hydroxide in reactor, the liquid in reactor is sent into the Lithium Sulphate liquid storage groove of system.
2. the recovery method of lithium in triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor according to claim 1, is characterized in that, the time of stirring in described step (2) is more than 30 minutes, leaves standstill more than 10 minutes again after stirring.
3. the recovery method of lithium in triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor according to claim 2, it is characterized in that, the mother liquor in described step (3) is discharged from the bottom valve of reactor.
4. the recovery method of lithium in triphane Production By Sulfuric Acid Process Quilonum Retard process mother liquor according to claim 3, it is characterized in that, described bottom valve is equipped with screen cloth.
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| CN107857283B (en) * | 2017-12-13 | 2019-11-22 | 清华大学 | A method for preparing battery-grade lithium carbonate based on selective solid-solid separation technology |
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| CN101481125B (en) * | 2009-02-13 | 2011-05-04 | 海门容汇通用锂业有限公司 | The method for recirculating the heavy lithium mother liquor for the production of lithium carbonate with sodium carbonate solution |
| CN102249471B (en) * | 2011-05-12 | 2012-10-17 | 江西赣锋锂业股份有限公司 | A kind of battery grade lithium carbonate mother liquor processing method |
| US9677152B2 (en) * | 2012-02-10 | 2017-06-13 | Sumitomo Metal Mining Co., Ltd. | Method for recovering lithium |
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2014
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