CN102874849B - Method for producing anhydrous lithium chloride special for electrolyzing by using lithium recovered from lithium-containing pharmaceutical waste water - Google Patents
Method for producing anhydrous lithium chloride special for electrolyzing by using lithium recovered from lithium-containing pharmaceutical waste water Download PDFInfo
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- CN102874849B CN102874849B CN201210334501.4A CN201210334501A CN102874849B CN 102874849 B CN102874849 B CN 102874849B CN 201210334501 A CN201210334501 A CN 201210334501A CN 102874849 B CN102874849 B CN 102874849B
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Abstract
The invention discloses a method for producing anhydrous lithium chloride special for electrolyzing lithium by using lithium recovered from lithium-containing pharmaceutical waste water. The method comprises the following steps of: (a) preparing materials and removing impurities; (b) initially removing organic matters; (c) performing microelectrolysis and deeply removing the organic matters; (d) concentrating to separate sodium out; (e) evaporating and crystallizing; (f) performing centrifugal separation; (g) drying; and (h) cooling and packaging. By the method, the anhydrous lithium chloride special for producing and electrolyzing the lithium can be directly obtained by using the lithium recovered from the lithium-containing pharmaceutical waste water, so that the product impurity is more than 99 percent, the content of the sodium is less than 0.25 percent, and the whiteness of the products is high.
Description
Technical field
The present invention relates to the preparation method of the special-purpose Lithium chloride (anhydrous) of electrolysis, particularly relate to from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water.
Background technology
Much medicine intermediate producer adopts metallic lithium at present, butyllithium or other organolithium compounds are made the catalyzer of medicine intermediate reaction, as made Catalyst Production efavirenz of metallic lithium, during the medicine intermediates such as gemfibrozil, after building-up reactions completes, the lithium containing catalyst composition that circulation is not reclaimed completely enters pharmacy waste water treatment system, in this pharmacy waste water except containing lithium chloride, also contain residual ethyl trichloroacetate, Diisopropylamine, the organism such as tetrahydrofuran (THF), sodium salt, calcium salt, the impurity such as vitriol, if this pharmacy waste water directly outer row causes severe contamination to environment, also wasted lithium resource simultaneously, how effectively to process containing lithium pharmacy waste water, reclaiming lithium resource is a urgent problem.
Patent of invention (CN1211546A) disclose a kind of synthesis of alkyl lithium compound containing lithium method for treating waste liquid, will be containing lithium waste liquid after oily water separation, with hydrochloric acid, regulate for twice after pH value and filtration, by every mole of lithium, add the sodium carbonate of 1 ~ 1.03 mole, at the temperature of 90 ~ 95 ℃, reaction makes lithium carbonate product, then through centrifuge dehydration, and again take hydrochloric acid, to transform Quilonum Retard be lithium chloride solution, finally by centrifuge dripping, obtain lithium chloride products.The method can not directly be prepared the special-purpose Lithium chloride (anhydrous) of electrolysis from contain lithium waste liquid, but be converted into Quilonum Retard through SPC-D sinker, through hcl acidifying, be converted into Lithium chloride (anhydrous) again, increased Lithium chloride (anhydrous) production cost, this lithium chloride products is not removed clean organism in addition, can not be directly used in the special-purpose lithium chloride of electrolysis production metallic lithium.
Patent of invention (200410046996.6) discloses a kind of utilization and containing lithium waste liquid, has produced the method for Lithium chloride (anhydrous), contain lithium waste liquid through oil trap oil removal, waste water is received to stoste test tank, in sending into after metering and still, with technical hydrochloric acid, regulate pH to 11 ~ 12, the consumption of technical hydrochloric acid is according to OH in wastewater flow rate and waste water
-concentration determine, the Fe that technical hydrochloric acid is brought into
3+in alkaline environment, form precipitation, simultaneously in and in still, add precipitation agent BaCl
2, ammonium oxalate makes in solution the Ca of trace
2+and SO4
2-ion precipitation is separated out, BaCl
2consumption according to SO4 in waste water
2-amount determine; Feed liquid enters tundish after filter pocket filters, with analyzing hydrochloric acid adjust pH to 6 ~ 8; With volume pump, feed liquid drying device nozzle is sent into spray-dryer, by the warm airs of 150 ℃ ~ 300 ℃, material is dried and obtains lithium chloride particle.This patent has realized from lithium waste liquid directly prepares Lithium chloride (anhydrous), but this method is not except sodium process, sodium in lithium waste liquid (1.5% ~ 3%) all enters into product, product purity is not high, affect follow-up electrolytic metal lithium quality, simultaneously in electrolytic process due to the high potential safety hazard that exists of sodium content in raw material.
Above two patents all adopt nature phase-splitting that organism is separated with lithium chloride solution, but this method can not be completely by organism and solution separating, in the finished product, still there is more organism, cause product appearance poor, while carrying out electrolysis during as electrolysis raw material, electrolyzer easily catches fire, there is potential safety hazard, meanwhile, electrolytic metal lithium is of poor quality, can not reach and be directly used in the specification of quality that the special-purpose Lithium chloride (anhydrous) of metallic lithium is produced in fused salt electrolysis.
Summary of the invention
The present invention completes in order to solve deficiency of the prior art, the object of this invention is to provide directly from reclaim the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, product purity high (>99%), sodium content low (<0.25%), the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis that reclaims from containing lithium pharmacy waste water that product whiteness is good.
Of the present invention from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, comprise following technical process:
A, batching removal of impurities: by pumping in batching kettle containing lithium pharmacy waste water of metering, with pH to 11 ~ 12 of lithium hydroxide solution regulator solution, stirring reaction 15 ~ 30 minutes, the Mg in precipitation waste liquid
2+, Fe
3+plasma, measures containing SO in lithium pharmacy waste water
4 2-mass percent concentration and Ca
2+mass percent concentration, add according to SO
4 2-mass percent concentration and Ca
2+mass percent concentration and the BaCl that obtains of calculation formula metering
2with ammonium oxalate stirring reaction 15 ~ 30 minutes, remove the Ca in solution
2+and SO
4 2-, then through press filtration, remove solid precipitation;
B, just except organic: in the filtrate obtaining toward step a, add hydrochloric acid, adjust pH to 7 ~ 8, add Powdered Activated Carbon in solution quality 1 ‰ ratios, heat up and are controlled at 50 ~ 80 ℃, stir 40 ~ 90 minutes, obtain clear solution after press filtration;
C, micro-electrolysis degree of depth are except organic: will be through step b just except organic solution removes organic device (the micro-electrolysis tower 10m of imperial AT&M by micro-electrolysis
3/ h) carry out degree of depth organic matter removal, obtain purer lithium chloride stoste;
D, the concentrated sodium of analysing: the lithium chloride stoste evaporation concentration that step c is obtained to the density of solution is 1.29～1.31g/cm
3, be then cooled to 60 ℃ of following stirrings and analyse above sodium in 30 minutes, after press filtration, obtain the clean liquid of lithium chloride;
E, evaporative crystallization: the clean liquid of lithium chloride that steps d is obtained carries out evaporating, concentrating and crystallizing;
F, centrifugation: the magma that step e is obtained carries out centrifugation, obtain water content and be 2～5% lithium chloride solid, and mother liquor is back to d step cycle;
G, dry: the wet lithium chloride solid of step f acquisition is dried at 220～250 ℃ of temperature, obtains the special-purpose Lithium chloride (anhydrous) of electrolysis of water content≤0.25%;
H, cooling packing: will be cooled to below 40 ℃ through the special-purpose Lithium chloride (anhydrous) of the dried electrolysis of step g, and then be packaged to be the special-purpose Lithium chloride (anhydrous) product of electrolysis.
The method that reclaims the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis from containing lithium pharmacy waste water of the present invention can also be:
BaCl in described step a
2amount according to described containing SO in lithium pharmacy waste water
4 2-amount determine, calculation formula is: M
baCl2=ρ
waste water* V
waste water* SO
4 2-% * 208/96, wherein ρ
waste waterfor the density containing lithium pharmacy waste water, unit is Kg/m
3; V
waste waterfor the volume containing lithium pharmacy waste water, unit is m
3; SO
4 2-% is for containing SO in lithium pharmacy waste water
4 2-mass percent concentration; 208 is BaCl
2molecular weight; 96 is SO
4 2-molecular weight; M
baCl2for the BaCl adding
2quality, unit is Kg; The amount of described step a mesoxalic acid ammonium is according to the Ca containing in lithium pharmacy waste water
2+amount determine, calculation formula is: M
(NH4) 2C2O4=ρ
waste water* V
waste water* Ca
2+% * 124/40, wherein, ρ
waste waterfor the density containing lithium pharmacy waste water, unit is Kg/m
3; V
useless waterfor the volume containing lithium pharmacy waste water, unit is m
3; Ca
2+% is Ca
2+mass percent concentration; 124 is (NH4)
2c
2o
4molecular weight; 40 is Ca
2+nucleidic mass, M
(NH4) 2C2O4for the quality that adds ammonium oxalate calculating, unit is Kg.
In described steps d, with the titanium of built-in refrigerating unit, analyse sodium groove and analyse sodium.
In described steps d, with the titanium of built-in refrigerating unit, analyse sodium groove and analyse sodium.
In described step f, the P40 pusher centrifuge that use can realize continuously feeding centrifugation carries out centrifugation.
In described step g, h, use can realize that dry, the cooling tray dryer machine carrying out continuously in same equipment is dried and be cooling.
Of the present invention from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is by after above-mentioned steps, in terms of existing technologies, its advantage having is that cost is low because the step adopting is fairly simple, facility investment is few, realized directly from high containing producing purity lithium pharmacy waste water, the special-purpose Lithium chloride (anhydrous) product of electrolysis that sodium content is low, avoids contaminate environment, reclaim lithium resource simultaneously, avoid the wasting of resources.
Accompanying drawing explanation
Fig. 1 the present invention is from reclaiming the process flow sheet of the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water.
Embodiment
Fig. 1 below in conjunction with accompanying drawing is described in further detail from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water of the present invention.
The method that reclaims the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis from containing lithium pharmacy waste water of the present invention, please refer to Fig. 1, comprises following technical process:
A, batching removal of impurities: by pumping in batching kettle containing lithium pharmacy waste water of metering, with pH to 11 ~ 12 of lithium hydroxide solution regulator solution, stirring reaction 15 ~ 30 minutes, the Mg in precipitation waste liquid
2+, Fe
3+plasma, measures containing SO in lithium pharmacy waste water
4 2-mass percent concentration and Ca
2+mass percent concentration, add according to SO
4 2-mass percent concentration and Ca
2+mass percent concentration and the BaCl that obtains of calculation formula metering
2with ammonium oxalate stirring reaction 15 ~ 30 minutes, remove the Ca in solution
2+and SO
4 2-, then through press filtration, remove solid precipitation;
B, just except organic: in the filtrate obtaining toward step a, add hydrochloric acid, adjust pH to 7 ~ 8, add Powdered Activated Carbon in solution quality 1 ‰ ratios, heat up and are controlled at 50 ~ 80 ℃, stir 40 ~ 90 minutes, obtain clear solution after press filtration;
C, micro-electrolysis degree of depth are except organic: will just except organic solution removes organic device by micro-electrolysis, carry out degree of depth organic matter removal through step b, and obtain purer lithium chloride stoste; Micro-electrolysis tower that concrete micro-electrolysis can Shi Long Mtekvision Co., Ltd. except organic device be sold, specification can be processing power 10m
3/ h.Micro-electrolysis tower is like this before all for the treatment of sewage.
D, the concentrated sodium of analysing: the lithium chloride stoste evaporation concentration that step c is obtained to the density of solution is 1.29～1.31g/cm
3, be then cooled to 60 ℃ of following stirrings and analyse above sodium in 30 minutes, after press filtration, obtain the clean liquid of lithium chloride;
E, evaporative crystallization: the clean liquid of lithium chloride that steps d is obtained carries out evaporating, concentrating and crystallizing;
F, centrifugation: the magma that step e is obtained carries out centrifugation, obtain water content and be 2～5% lithium chloride solid, and mother liquor is back to d step cycle;
G, dry: the wet lithium chloride solid of step f acquisition is dried at 220～250 ℃ of temperature, obtains the special-purpose Lithium chloride (anhydrous) of electrolysis of water content≤0.25%;
H, cooling packing: will be cooled to below 40 ℃ through the special-purpose Lithium chloride (anhydrous) of the dried electrolysis of step g, and then be packaged to be the special-purpose Lithium chloride (anhydrous) product of electrolysis.
Of the present invention from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is by after above-mentioned steps, in terms of existing technologies, its advantage having is that cost is low because the step adopting is fairly simple, facility investment is few, realized directly from high containing producing purity lithium pharmacy waste water, the special-purpose Lithium chloride (anhydrous) product of electrolysis that sodium content is low, avoids contaminate environment, reclaim lithium resource simultaneously, avoid the wasting of resources.
Of the present invention from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, on the basis of previous technique scheme, can also be:
BaCl in described step a
2amount according to described containing SO in lithium pharmacy waste water
4 2-amount determine, according to chemical equation: BaCl
2+ SO
4 2-=BaSO
4+ Cl
-, calculation formula is: M
baCl2=ρ
waste water* V
waste water* SO
4 2-% * 208/96, wherein ρ
waste waterfor the density containing lithium pharmacy waste water, unit is Kg/m
3; V
waste waterfor the volume containing lithium pharmacy waste water, unit is m
3; SO
4 2-% is for containing SO in lithium pharmacy waste water
4 2-mass percent concentration; 208 is BaCl
2molecular weight; 96 is SO
4 2-molecular weight; M
baCl2for the BaC adding
l2 quality, unit is Kg; The amount of described step a mesoxalic acid ammonium is according to the Ca containing in lithium pharmacy waste water
2+amount determine, according to chemical equation: Ca
2++ C
2o
4 2-=CaC
2o
4, calculation formula is: M
(NH4) 2C2O4=ρ
waste water* V
waste water* Ca
2+% * 124/40, wherein, ρ
useless scorchingfor the density containing lithium pharmacy waste water, unit is Kg/m
3; V
waste waterfor the volume containing lithium pharmacy waste water, unit is m
3; Ca
2+% is Ca
2+mass percent concentration; 124 is (NH4)
2c
2o
4molecular weight; 40 is Ca
2+nucleidic mass, M
(NH4) 2C2O4for the quality that adds ammonium oxalate calculating, unit is Kg.Add so the quantitative BaCl calculating by formula
2and ammonium oxalate, make containing the SO in lithium pharmacy waste water
4 2-and Ca
2+be completely removed, and there is no unnecessary Ba
2+and C
2o
4 2-residual, the purity of the special-purpose Lithium chloride (anhydrous) of electrolysis finally obtaining is higher.In addition, can also be in described steps d, with the titanium of built-in refrigerating unit, analyse sodium groove and analyse sodium.Analyse like this sodium better effects if, in final product, sodium content is lower.Can also be in described step f, the P40 pusher centrifuge that use can realize continuously feeding centrifugation carries out centrifugation.Can be the P40 pusher centrifuge that Hangzhou Qing Ji company limited sells, like this, can realize continuously feeding, guarantee the production efficiency of the special-purpose Lithium chloride (anhydrous) of production electrolysis.In addition, can also be in described step g, h, use can realize that dry, the cooling tray dryer machine carrying out continuously in same equipment is dried and be cooling.Such advantage is to be dried with cooling to carry out simultaneously, enhances productivity.
Embodiment 1:
A, batching removal of impurities: by 7.6m
3containing lithium pharmacy waste water, (measure containing Ca by analysis
2+% is 0.02%, SO4
2-% is 0.07%, i.e. Ca
2+quality percentage composition be 0.02%, SO4
2-quality percentage composition be 0.07%, solution density 1070Kg/m now
3) pump in batching kettle, with the pH to 12 of lithium hydroxide solution regulator solution, stirring reaction 30 minutes, the Mg in precipitation waste liquid
2+, Fe
3+plasma, then adds the BaCl of 12.3Kg
2with 5.0Kg ammonium oxalate stirring reaction 30 minutes, remove the Ca in solution
2+and SO
4 2-, through press filtration, remove solid precipitation;
B, just except organic: in the filtrate obtaining toward step a, add hydrochloric acid, the pH value to 8 of regulator solution, adds 8.1Kg Powdered Activated Carbon, heats up and is controlled at 80 ℃, stirs 90 minutes, obtains clear solution after press filtration;
C, micro-electrolysis degree of depth are except organic: will be through step b just except organic solution removes organic device (micro-electrolysis tower 10m that imperial Mtekvision Co., Ltd. sells by micro-electrolysis
3/ h) carry out the degree of depth except organic, obtain purer 8m
3lithium chloride stoste;
D, the concentrated sodium of analysing: lithium chloride stoste evaporation concentration to the solution density that step c is obtained is 1.31g/cm
3, be then cooled to 25 ℃, stir and analyse sodium in 50 minutes, after press filtration, obtain 2.6m
3the clean liquid of lithium chloride;
E, evaporative crystallization: the clean liquid of lithium chloride that steps d is obtained carries out evaporating, concentrating and crystallizing;
F, centrifugation: the magma that step h is obtained carries out centrifugation, obtain water content and be 3.3% 520Kg lithium chloride solid, and mother liquor is back to d step cycle;
G, dry: the wet lithium chloride solid that step f is obtained is dried at 250 ℃, obtains water content and is 0.19% the special-purpose Lithium chloride (anhydrous) of 501Kg electrolysis;
H, cooling packing: will be cooled to 25 ℃ through the special-purpose Lithium chloride (anhydrous) of the dried electrolysis of step g, and then be packaged to be the special-purpose Lithium chloride (anhydrous) product of 500Kg electrolysis;
Embodiment 2:
A, batching removal of impurities: by 7.5m
3containing lithium waste liquid, (measure containing Ca by analysis
2+% is 0.03%, SO4
2-% is 0.1%, and now the density of solution is 1090Kg/m
3) pump in batching kettle, with the pH to 11 of lithium hydroxide solution regulator solution, stirring reaction 15 minutes, the Mg in precipitation waste liquid
2+, Fe
3+plasma, then adds 17.7Kg BaCl
2with 7.6Kg ammonium oxalate stirring reaction 15 minutes, remove the Ca in solution
2+and SO
4 2-, through press filtration, remove solid precipitation;
B, just except organic: in the filtrate obtaining toward step a, add hydrochloric acid, the pH value to 7 of regulator solution, adds 8.2Kg Powdered Activated Carbon, heats up and is controlled at 50 ℃, stirs 40 minutes, obtains clear solution after press filtration;
C, micro-electrolysis degree of depth are except organic: will be through step b just except organic solution removes organic device (micro-electrolysis tower 10m that imperial Mtekvision Co., Ltd. sells by micro-electrolysis
3/ h) carry out the degree of depth except organic, obtain purer 8.1m
3lithium chloride stoste;
D, the concentrated sodium of analysing: the lithium chloride stoste evaporation concentration that step c is obtained to the density of solution is 1.29g/cm
3, be then cooled to 40 ℃, stir and analyse sodium in 35 minutes, after press filtration, obtain 2.72m
3the clean liquid of lithium chloride;
E, evaporative crystallization: the clean liquid of lithium chloride that steps d is obtained carries out evaporating, concentrating and crystallizing;
F, centrifugation: the magma that step h is obtained carries out centrifugation, obtain water content and be 4.2% 526Kg lithium chloride solid, and mother liquor is back to d circulation.
G, dry: the wet lithium chloride solid that step f is obtained is dried at 220 ℃, obtains water content and is 0.23% the special-purpose Lithium chloride (anhydrous) of 503Kg electrolysis;
H, cooling packing: will be cooled to 35 ℃ through the special-purpose Lithium chloride (anhydrous) of the dried electrolysis of step g, and then be packaged to be the special-purpose Lithium chloride (anhydrous) product of 503Kg electrolysis;
Embodiment 3:
A, batching removal of impurities: by 7.5m
3containing lithium pharmacy waste water, (measure containing Ca by analysis
2+% is 0.04%, SO4
2-% is 0.13%, and now the density of solution is 1080Kg/m
3) pump in batching kettle, the pH to 10.5 with lithium hydroxide solution regulator solution, reacts 25 minutes, the Mg in precipitation waste water
2+, Fe
3+plasma, then adds 22.8Kg BaCl
2with 10Kg ammonium oxalate reaction 25 minutes, remove the Ca in waste water
2+and SO
4 2-, through press filtration, remove solid precipitation;
B, just except organic: in the filtrate obtaining toward step a, add hydrochloric acid, the pH value to 7.5 of regulator solution, adds 8.1Kg Powdered Activated Carbon, heats up and is controlled at 65 ℃, stirs 65 minutes, obtains clear solution after press filtration;
C, micro-electrolysis degree of depth are except organic: will be through step b just except organic solution removes organic device (micro-electrolysis tower 10m that imperial Mtekvision Co., Ltd. sells by micro-electrolysis
3/ h) carry out the degree of depth except organic, obtain purer 7.95m
3lithium chloride stoste;
D, the concentrated sodium of analysing: the lithium chloride stoste evaporation concentration that step C is obtained to the density of solution is 1.3(g/cm
3), be then cooled to 30 ℃, stir and analyse sodium in 45 minutes, after press filtration, obtain 2.65m
3the clean liquid of lithium chloride;
E, evaporative crystallization: the clean liquid of lithium chloride that steps d is obtained carries out evaporating, concentrating and crystallizing;
F, centrifugation: the magma that step h is obtained carries out centrifugation, obtain water content and be 4.6% 531Kg lithium chloride solid, and mother liquor is back to d step cycle;
G, dry: the wet lithium chloride solid that step f is obtained is dried at 235 ℃, obtains water content and is 0.21% the special-purpose Lithium chloride (anhydrous) of 502Kg electrolysis;
H, cooling packing: will be cooled to 30 ℃ through the special-purpose Lithium chloride (anhydrous) of the dried electrolysis of step g, and then be packaged to be the special-purpose Lithium chloride (anhydrous) product of 502Kg electrolysis;
The lithium chloride products that above-described embodiment is obtained detects, and obtains technical indicator as follows:
As can be seen from the above table by preparation method of the present invention, can direct preparation of high-purity degree, the special-purpose Lithium chloride (anhydrous) of the low electrolysis containing sodium, quality product meets the requirement of national standard (GB/T 10575-2007) LiCl-1.
Above-mentionedly only several specific embodiments in the present invention are illustrated; but can not be as protection scope of the present invention; every equivalence variation of having done according to the design spirit in the present invention or modification or equal proportion zoom in or out etc., all should think and fall into protection scope of the present invention.
Claims (5)
1. from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is characterized in that: comprise following technical process:
A, batching removal of impurities: by pumping in batching kettle containing lithium pharmacy waste water of metering, with pH to 11～12 of lithium hydroxide solution regulator solution, stirring reaction 15～30 minutes, the Mg in precipitation waste liquid
2+, Fe
3+plasma, measures containing SO in lithium pharmacy waste water
4 2-mass percent concentration and Ca
2+mass percent concentration, add according to SO
4 2-mass percent concentration and Ca
2+mass percent concentration and the BaCl that obtains of calculation formula metering
2with ammonium oxalate stirring reaction 15～30 minutes, remove the Ca in solution
2+and SO
4 2-, then through press filtration, remove solid precipitation;
B, just except organic: in the filtrate obtaining toward step a, add hydrochloric acid, adjust pH to 7～8, add Powdered Activated Carbon in solution quality 1 ‰ ratios, heat up and are controlled at 50～80 ℃, stir 40～90 minutes, obtain clear solution after press filtration;
C, micro-electrolysis degree of depth are except organic: will just except organic solution removes organic device by micro-electrolysis, carry out degree of depth organic matter removal through step b, and obtain purer lithium chloride stoste;
D, the concentrated sodium of analysing: the lithium chloride stoste evaporation concentration that step c is obtained to the density of solution is 1.29～1.31g/cm
3, be then cooled to 60 ℃ of following stirrings and analyse above sodium in 30 minutes, after press filtration, obtain the clean liquid of lithium chloride;
E, evaporative crystallization: the clean liquid of lithium chloride that steps d is obtained carries out evaporating, concentrating and crystallizing;
F, centrifugation: the magma that step e is obtained carries out centrifugation, obtain water content and be 2～5% lithium chloride solid, and mother liquor is back to d step cycle;
G, dry: the wet lithium chloride solid of step f acquisition is dried at 220～250 ℃ of temperature, obtains the special-purpose Lithium chloride (anhydrous) of electrolysis of water content≤0.25%;
H, cooling packing: will be cooled to below 40 ℃ through the special-purpose Lithium chloride (anhydrous) of the dried electrolysis of step g, and then be packaged to be the special-purpose Lithium chloride (anhydrous) product of electrolysis.
2. according to claim 1 from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is characterized in that: BaCl in described step a
2amount according to described containing SO in lithium pharmacy waste water
4 2-amount determine, calculation formula is: M
baCl2=ρ
waste water* V
waste water* SO
4 2-% * 208/96, wherein ρ
waste waterfor the density containing lithium pharmacy waste water, unit is Kg/m
3; V
waste waterfor the volume containing lithium pharmacy waste water, unit is m
3; SO
4 2-% is for containing SO in lithium pharmacy waste water
4 2-mass percent concentration; 208 is BaCl
2molecular weight; 96 is the atomic mass sum that the atomic mass of a S atom adds four Sauerstoffatoms; M
baCl2for the BaCl adding
2quality, unit is Kg; The amount of described step a mesoxalic acid ammonium is according to the Ca containing in lithium pharmacy waste water
2+amount determine, calculation formula is: M
(NH4) 2C2O4=ρ
waste water* V
waste water* Ca
2+% * 124/40, wherein, ρ
waste waterfor the density containing lithium pharmacy waste water, unit is Kg/m
3; V
waste waterfor the volume containing lithium pharmacy waste water, unit is m
3; Ca
2+% is Ca
2+mass percent concentration; 124 is (NH
4)
2c
2o
4molecular weight; 40 is the atomic mass of calcium atom, M
(NH4) 2C2O4for the quality that adds ammonium oxalate calculating, unit is Kg.
3. according to claim 2 from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is characterized in that: in described steps d, with the titanium of built-in refrigerating unit, analyse sodium groove and analyse sodium.
4. according to claim 2 from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is characterized in that: in described step f, the P40 pusher centrifuge that use can realize continuously feeding centrifugation carries out centrifugation.
5. according to claim 2 from reclaim the method for the special-purpose Lithium chloride (anhydrous) of lithium production electrolysis containing lithium pharmacy waste water, it is characterized in that: in described step g, h, use can realize that dry, the cooling tray dryer machine carrying out continuously in same equipment is dried and be cooling.
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|---|---|---|---|
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| CN105836767B (en) * | 2016-04-22 | 2017-10-31 | 天齐锂业股份有限公司 | A kind of method for preparing anhydrous Lithium chloride using waste liquid containing lithium |
| CN108002410B (en) * | 2016-10-31 | 2019-10-18 | 湖南金源新材料股份有限公司 | Lithium is recycled from low content extraction tail water and extracts the circulation utilization method of tail water |
| CN112408437B (en) * | 2020-11-19 | 2023-03-28 | 江西天新药业股份有限公司 | Method for recovering lithium salt |
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| US6921522B2 (en) * | 1998-07-16 | 2005-07-26 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
| CN1559902A (en) * | 2004-02-26 | 2005-01-05 | 东北大学 | Purification process of removing impurity sodium from lithium chloride |
| CN1781847A (en) * | 2004-11-24 | 2006-06-07 | 中国石化集团巴陵石油化工有限责任公司 | Process for producing lithium chloride using waste liquid containing lithium |
| US8309043B2 (en) * | 2010-12-06 | 2012-11-13 | Fmc Corporation | Recovery of Li values from sodium saturate brine |
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