CN104338441B - Sinker mother liquor treatment process - Google Patents

Sinker mother liquor treatment process Download PDF

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CN104338441B
CN104338441B CN201410551826.7A CN201410551826A CN104338441B CN 104338441 B CN104338441 B CN 104338441B CN 201410551826 A CN201410551826 A CN 201410551826A CN 104338441 B CN104338441 B CN 104338441B
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solution
lithium
sinker
sinker mother
films
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CN104338441A (en
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韩正昌
王志磊
高亚娟
华里
马军军
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Nanjing Ge Luote Environmental Engineering Limited-Liability Co
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Nanjing Ge Luote Environmental Engineering Limited-Liability Co
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Abstract

The present invention relates to industrial lithium salts production, more particularly to lithium salts aftertreatment technology, more particularly relate to sinker mother liquor treatment process.For in current industry lithium salts production, particularly in evaporative crystallization production method, produce a large amount of mother solutions of sinker containing lithium cannot effectively utilizes problem, membrance concentration process suitable for sinker mother solution is proposed creatively, so as to obtain the high concentration lithium ion solution rich in lithium ion, it is that sinker mother solution provides the foundation as lithium salts raw materials for production.

Description

Sinker mother liquor treatment process
Technical field
The present invention relates to industrial lithium salts production, more particularly to lithium salts aftertreatment technology, more particularly relate to sink Lithium mother liquor treatment process.
Background technology
Lithium carbonate is the basic compound of lithium, is widely used in the neck such as space flight, military project, ceramics, glass, lithium battery, medicine Domain.Lithium carbonate can change into other various lithium compounds, such as lithium phosphate, lithium fluoride etc. as a kind of basic material of lithium.
Although China is also in active development saline lake lithium resource in recent years.But due to the content of magnesium in China's salt lake bittern compared with The more difficult separation of both elements of height, magnesium and lithium, also no large-scale industrialization production up till now, so China is always from lithium ore deposit Lithium salts is extracted in stone.At present, the method that lithium salts is extracted from lithium ore mainly has, Production By Sulfuric Acid Process technique, spodumene and sulphuric acid Salt mixed sintering production technology and chloridising roasting production technology, these methods are liquid phase method, by evaporative crystallization, obtain carbonic acid Lithium, yield are generally 85%.Evaporative crystallization produce lithium carbonate yield it is not high the reason for be mainly:In lithium carbonate evaporative crystallization mother solution Still contain substantial amounts of lithium, but lithium carbonate evaporative crystallization mother solution is difficult to recycle, current lithium carbonate evaporative crystallization mother solution can only be made Arrange for outer after wastewater treatment, cause the wasting of resources, lithium carbonate yield is low.
Those skilled in the art in order to improve the utilization of lithium carbonate sinker mother solution, it is tentative using its mother solution as original Material, prepare lithium phosphate, lithium fluoride etc. industry lithium salts, but due to lithium ion in unit lithium carbonate sinker mother solution content always without Method is improved, and causes to recycle high cost.
The content of the invention
During the present invention is at present industry lithium salts production, particularly in evaporative crystallization production method, generation contains lithium in a large number Sinker mother solution cannot effectively utilizes problem, creatively propose membrance concentration this enrichment method, so as to obtain rich in lithium from The high concentration lithium ion solution of son, is that sinker mother solution provides the foundation as lithium salts raw materials for production.
The invention discloses a kind of sinker mother liquor treatment process, comprises the following steps successively:
(1)In sinker mother solution, then the dilute sulfuric acid of addition mass fraction 98% is constantly monitored molten to mixed solution pH 3 ~ 7 Liquid pH simultaneously maintains mixed solution pH 3 ~ 7 by controlling sulphuric acid;
(2)By step(1)Mixed liquor after process passes sequentially through NF films, RO films, respectively the lower solution of collection membrane front end retention, And retention solution is mixed into into step again(1)Sinker mother solution;
(3)Repeat step(1)、(2), and high concentration lithium ion solution is obtained in NF films and the collection of RO films front end.
NF films mentioned here refer to NF membrane, and RO films refer to reverse osmosis membrane.
In order to protect NF films, RO films, according to existing operating guidance, it would be desirable to step(1)Sinker after process is female Liquid passes sequentially through multi-medium filtering, and activated carbon is filtered, secondary filter and ultrafiltration, so as to remove the precipitation in mother solution, float and Larger molecular organicses.After the solution of a whole set of filtering process meets upper film requirement, according still further to step(2)Carry out film process.
Wherein preferably pH is 4.5.
Used as a kind of preferred mode, we further disclose the step(1)In discharge in time the carbon dioxide for generating Gas.
Carbon dioxide is discharged reaction unit in time and can further improve step(1)Reaction efficiency, reduce anti- Between seasonable, the technology that discharge method is discharged with regard to gas in may be referred to prior art.In the present invention, it is preferred to adopt be passed through sky Carbon dioxide in mother solution is blown out by the technological means of gas by being passed through air, accelerates lithium carbonate to high-dissolvability lithium salts chemical combination The conversion of thing.
Meanwhile, we emphasize that the processing mode of above sinker mother solution is particularly preferably applied to lithium carbonate sinker mother solution, or It is lithium phosphate sinker mother solution.
Another sinker mother liquor treatment process is we also disclosed in the present invention, is comprised the following steps successively:
(1)Add alkalescence to adjust solution in sinker mother solution, pH value of solution is adjusted to 6 ~ 11;
(2)To step(1)Excessive calcium ions solution is added in solution after process, calcium fluoride precipitate is filtered to remove, Collect filtrate;
(3)By step(2)Gained filtrate removes excessive calcium ion, collects flow liquid by ion exchange resin;
(4)The flow liquid of calcium ion will be removed through RO films, the lower solution of collection membrane front end retention, and retention solution is mixed again Enter in the flow liquid of this step;
(5)It is iteratively repeated step(4), and collection obtains high concentration lithium ion solution in RO films front end;
The sinker mother solution is lithium fluoride sinker mother solution.
In order to protect RO films, according to existing operating guidance, it would be desirable to step(3)Sinker mother solution after process is successively By multi-medium filtering, activated carbon filtration, secondary filter and ultrafiltration, so as to remove the precipitation in mother solution, float and macromole Organic substance.After the solution of a whole set of filtering process meets upper film requirement, according still further to step(4)Carry out film process.
In order to further remove Natural zeolite, can suitably increase step(2)Access times, produce one-level fluorine removal, two grades The processes such as fluorine removal ....
Further, we are it is also preferred that step(4)Middle employing two-stage RO film, the flow liquid for removing calcium ion are passed sequentially through One-level RO film, two grades of RO films, and the retention solution of one-level RO film and two grades of RO films front ends is collected respectively, and will retention solution weight Newly it is mixed in flow liquid, again through one-level RO film, two grades of RO films.
Preferably, we are further disclosed the step(1)Middle regulation pH is 4.5.
We are also disclosed the alkalescence and adjust solution in sodium hydroxide solution, calcium oxide or aqua calcises simultaneously Any one, particularly preferably calcium oxide herein.
As a kind of preferred, the invention also discloses step(1)The middle pH value of solution that adjusts is to 10.5.
Further, invention additionally discloses the industrial lithium salts using aforementioned sinker mother liquor treatment process prepares liquid waste processing Method.
Further, we are also disclosed in preferably meeting in RO film backend collections during industrial lithium salts prepares method for treating waste liquid The pure water of environmental protection standard.
The present invention overcomes the technical barrier that membrane concentration method cannot be suitable in sinker mother solution application, specifically when adopting film During concentration method, as film surface ion concentration is generally 50 times into concentration of aqueous solution, therefore the lithium salts on film surface because of supersaturation And crystallize and separate out, cause film to be blocked, limit application of the embrane method in lithium salts recovery.
By the elemental lithium in membrance concentration technique efficient recovery lithium salts evaporative crystallization mother solution, the rejection of elemental lithium is reached More than 99%, the resource recycling of lithium salts sinker mother solution is realized, the yield of lithium salts preparation is improve, is reduced resource loss, Increase the benefit for enterprise.
The present invention solves lithium salts sinker mother solution because dissolubility is not high by preconditioning technique, is easily made using membrane concentration method Into the problem of stifled film, application of the membrane concentration method in the recovery of lithium salts concentrated mother liquor is realized, can be by the lithium in lithium salts sinker mother solution Constituent content lifts 5 times, can direct reuse to production technology, solve that lithium salts sinker mother solution elemental lithium content is low to be difficult to reuse A difficult problem.
Specific embodiment
With reference to specific embodiment, further the present invention will be described and explains.
Handling process of the embodiment 1 using lithium carbonate sinker solution of the present invention
Lithium carbonate sinker mother solution:Certain factory's lithium carbonate sinker mother solution, pH value is 10.04, and lithium concentration is 0.98g/L, electrical conductivity For 11.89ms/cm, water yield 100L.
(1)The concentrated sulphuric acid that mass fraction is 98% is added in lithium carbonate sinker mother solution, pH value is adjusted to 6.5,(2)Xiang Bu Suddenly(1)Air is passed through in lithium carbonate sinker mother solution after process, ventilate 0.5h.
(3)Step(2)Lithium carbonate sinker mother solution after process passes sequentially through multi-medium filtering, and activated carbon is filtered, accurate mistake Filter and ultrafiltration, remove the precipitation in mother solution, float and larger molecular organicses.The trapped fluid of ultrafiltration is back to ultrafiltration water inlet end.
(4)Step(3)Permeate after hyperfiltration treatment carries out nanofiltration, trapped fluid water outlet water yield 21L, lithium concentration 4.51g/L, PH value is 7.22, and electrical conductivity is 31.3ms/cm, and permeate water outlet water yield 75L, lithium concentration are 0.015g/L, and pH value is 5.66, electricity Conductance is 0.248ms/cm.
(5)Step(4)To production technology, trapped fluid is back to step for permeate reuse after nanofiltration process(4)Nanofiltration is entered Water end (W.E.).The permeate water outlet water yield is 61L, and pH is 5.61, and electrical conductivity is 0.017ms/cm, and lithium concentration is 0.0039g/L.
The elemental lithium response rate reaches 96.6%, and elemental lithium rejection reaches 99.7%, and elemental lithium cycles of concentration is 4.6 times.
Handling process of the embodiment 2 using lithium phosphate sinker solution of the present invention
Lithium phosphate crystalline mother solution:Certain factory's lithium phosphate crystalline mother solution, pH value is 8.71, and lithium concentration is 0.29g/L, and electrical conductivity is 10.62ms/cm, water yield 100L.
(1)The concentrated sulphuric acid that mass fraction is 98% is added in lithium phosphate sinker mother solution, pH value is adjusted to 4.5,(2)Step (1)Lithium phosphate sinker mother solution after process passes sequentially through multi-medium filtering, activated carbon filtration, secondary filter and ultrafiltration, removes female Precipitation in liquid, float and larger molecular organicses.The trapped fluid of ultrafiltration is back to ultrafiltration water inlet end.
(3)Step(2)Permeate after hyperfiltration treatment carries out nanofiltration, trapped fluid water outlet water yield 23L, lithium concentration 1.18g/L, PH value is 4.14, and electrical conductivity is 28.9ms/cm, and permeate water outlet water yield 71L, lithium concentration are 0.0016g/L, and pH value is 5.18, Electrical conductivity is 0.112ms/L.
(4)Step(3)To production technology, trapped fluid is back to step for permeate reuse after nanofiltration process(3)Nanofiltration is entered Water end (W.E.).The permeate water outlet water yield is 58L, and pH is 5.33, and electrical conductivity is 0.0028ms/cm, and lithium concentration is 0.0012g/L.
The elemental lithium response rate reaches 93.6%, and elemental lithium rejection reaches 99.76%, and elemental lithium cycles of concentration is 4.07 times.
Handling process of the embodiment 3 using lithium fluoride sinker solution of the present invention
Lithium fluoride sinker mother solution:Certain factory's lithium fluoride sinker mother solution, pH value is 3.69, and lithium concentration is 0.8205g/L, electrical conductivity For 4.05ms/cm, water yield 100L.
(1)Calcium oxide is added in lithium fluoride sinker mother solution, pH value is adjusted to 10.5;
(2)Step(1)Lithium fluoride sinker mother solution after process adds calcium chloride and removes Natural zeolite;
(3)Step(2)Lithium fluoride sinker mother solution after process carries out ion exchange resin, removes the foreign ions such as the magnesium;
(4)Step(3)Lithium fluoride sinker mother solution after process passes sequentially through multi-medium filtering, and activated carbon is filtered, accurate mistake Filter and ultrafiltration, remove the precipitation in mother solution, float and larger molecular organicses.The trapped fluid of ultrafiltration is back to ultrafiltration water inlet end;
(5)Step(4)Permeate after hyperfiltration treatment enters first-stage reverse osmosis film process, first-stage reverse osmosis trapped fluid water outlet water Amount 30L, lithium concentration 2.51g/L, pH value are 8.15, and electrical conductivity is 11.06ms/cm, the first-stage reverse osmosis permeate water outlet water yield 67L, lithium concentration are 0.0083g/L, and pH value is 6.72, and electrical conductivity is 0.257ms/cm.
(6)Step(5)First-stage reverse osmosis permeate carries out two-pass reverse osmosis, and the reuse of two-pass reverse osmosis permeate is to producing work Skill, two-pass reverse osmosis trapped fluid are back to first-stage reverse osmosis water inlet end.Two-pass reverse osmosis permeate water yield 51L, lithium concentration 0.0019g/L, pH value are 6.93, and electrical conductivity is 0.0099ms/cm.
The elemental lithium response rate reaches 91.7%, and elemental lithium rejection reaches 99.8%, and elemental lithium cycles of concentration is 3.06 times.
Embodiment 4 is by sinker mother solution directly by the experimental result of membrance concentration
4-1 lithium carbonate sinker mother solutions
Lithium carbonate sinker mother solution directly carries out nanofiltration process, after operation a period of time, reduces through flow quantity, trapped fluid stream Amount increase, intake pressure increase, after operation 1h, intake pressure exceedes the upper limit, it is impossible to continue to run with, now lithium concentration is still relatively low Level, and due to operating continuously, therefore do not meet industrialization demand.
4-2 lithium phosphate sinker mother solutions
Lithium phosphate sinker mother solution directly carries out nanofiltration process, after operation a period of time, reduces through flow quantity, trapped fluid stream Amount increase, intake pressure increase, after operation 1h, intake pressure exceedes the upper limit, it is impossible to continue to run with, now lithium concentration is still relatively low Level, and due to operating continuously, therefore do not meet industrialization demand.
4-3 lithium fluoride sinker mother solutions
Reverse-osmosis treated is directly carried out using lithium fluoride sinker mother solution, after operation a period of time, due to lithium fluoride itself it is right Film has very strong corrosivity, therefore RO films are damaged in the short time, and membrance concentration effect cannot be realized.

Claims (10)

1. sinker mother liquor treatment process, is characterized in that, comprise the following steps successively:
(1) in sinker mother solution add mass fraction 98% concentrated sulphuric acid to mixed solution pH 3~7, then constantly monitor solution PH simultaneously maintains mixed solution pH 3~7 by controlling sulphuric acid;
(2) mixed liquor after step (1) process is passed sequentially through into NF films, RO films, respectively the lower solution of collection membrane front end retention, and will Retention solution is mixed into step (1) sinker mother solution again;
(3) repeat step (1), (2), and high concentration lithium ion solution is obtained in NF films and the collection of RO films front end;The sinker is female Liquid refers to the sinker mother solution for extracting lithium salts generation by evaporative crystallization technique from lithium ore.
2. sinker mother liquor treatment process according to claim 1, is characterized in that, discharges in time and generate in the step (1) Carbon dioxide.
3. sinker mother liquor treatment process according to claim 1, is characterized in that, the sinker mother solution is that lithium carbonate sinker is female Liquid, or lithium phosphate sinker mother solution.
4. sinker mother liquor treatment process according to claim 1, is characterized in that, in the step (1), pH is 4.5.
5. sinker mother liquor treatment process, is characterized in that, comprise the following steps successively:(1) alkalescence is added to adjust molten in sinker mother solution Liquid, adjusts pH value of solution to 6~11;(2) excessive calcium ions solution is added in the solution after step (1) process, cross and filter Calcium fluoride precipitate is removed, filtrate is collected;(3) by filtrate obtained by step (2) by ion exchange resin, remove excessive calcium from Son, collects flow liquid;(4) flow liquid of calcium ion will be removed through RO films, the lower solution of collection membrane front end retention, and will retention solution weight Newly it is mixed in the flow liquid of this step;(5) step (4) is iteratively repeated, and collection obtains high concentration lithium ion solution in RO films front end; The sinker mother solution is lithium fluoride sinker mother solution.
6. sinker mother liquor treatment process according to claim 5, is characterized in that, two-stage RO film is adopted in the step (4), The flow liquid for removing calcium ion passes sequentially through one-level RO film, two grades of RO films, and collects one-level RO film and two grades of RO films front ends respectively Retention solution, and by retention solution be mixed in flow liquid again, again through one-level RO film, two grades of RO films.
7. sinker mother liquor treatment process according to claim 5, is characterized in that, it is sodium hydroxide that the alkalescence adjusts solution Any one in solution, calcium oxide solution or aqua calcises.
8. sinker mother liquor treatment process according to claim 5, is characterized in that, adjust pH value of solution to 10.5 in step (1).
9. a kind of industrial lithium salts of the sinker mother liquor treatment process in employing claim 1~8 described in any one prepares waste liquid Processing method.
10. method according to claim 9, is characterized in that, in RO film backend collection pure water.
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CN104787784B (en) * 2015-03-18 2017-06-09 江西赣锋锂业股份有限公司 It is a kind of to reclaim the method that waste material containing lithium fluoride prepares lithium salts
CN105925799A (en) * 2016-05-26 2016-09-07 四川思达能环保科技有限公司 Wet metallurgy film concentration process
CN106315629B (en) * 2016-08-30 2018-01-30 山东瑞福锂业有限公司 A kind of technique for preparing pure Lithium Carbonate using battery-level lithium carbonate sinker disposing mother liquor
CN106882822A (en) * 2017-03-15 2017-06-23 江苏容汇通用锂业股份有限公司 A kind of method that lithium is recycled into battery-level lithium carbonate in sinker mother liquor
CN107115793B (en) * 2017-05-15 2020-07-14 杭州瑞纳膜工程有限公司 Purification and concentration system and method for magnesium-containing lithium liquid
CN110104665A (en) * 2019-03-13 2019-08-09 江西赣锋锂业股份有限公司 A method of lithium carbonate is prepared using lithium fluoride waste liquid

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