CN110436679A - The devices and methods therefor of lithium carbonate wash water comprehensive utilization of resources - Google Patents
The devices and methods therefor of lithium carbonate wash water comprehensive utilization of resources Download PDFInfo
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- CN110436679A CN110436679A CN201910702295.XA CN201910702295A CN110436679A CN 110436679 A CN110436679 A CN 110436679A CN 201910702295 A CN201910702295 A CN 201910702295A CN 110436679 A CN110436679 A CN 110436679A
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- Prior art keywords
- lithium carbonate
- electrodialysis
- wash water
- water
- concentrated
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Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 171
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 106
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000000909 electrodialysis Methods 0.000 claims abstract description 119
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 73
- 239000012528 membrane Substances 0.000 claims abstract description 73
- 238000005516 engineering process Methods 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 54
- 238000001223 reverse osmosis Methods 0.000 claims description 42
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 23
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 19
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 19
- 230000020477 pH reduction Effects 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000012267 brine Substances 0.000 claims description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 239000013505 freshwater Substances 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229920002472 Starch Polymers 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000000502 dialysis Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910001947 lithium oxide Inorganic materials 0.000 claims 1
- 230000003204 osmotic effect Effects 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000009938 salting Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical class [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 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 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of devices and methods therefors of lithium carbonate wash water comprehensive utilization of resources.The treatment process of existing lithium carbonate containing wash water mainly uses precipitating reagent to clean, and recycles lithium carbonate after extraction by the way of evaporative crystallization, but energy consumption is high easily causes pollution, serious waste of resources for this method, and product purity is lower.The present invention innovatively use electrodialysis-bipolar membrane electrodialysis-it is reverse osmosis-electrodialysis circulation technology, prepare lithium hydroxide and hydrochloric acid using lithium carbonate wash water as raw material, hydrochloric acid can be back to front-end-of-line, and remaining salting liquid is recyclable to be recycled, Li+Reclamation rate is greater than 95%, and alternative tradition evaporative crystallization recycles lithium carbonate technique, and reducing energy consumption reduces cost, shortens process flow.
Description
Technical field
The present invention relates to field of wastewater reclamation, especially a kind of method of lithium carbonate wash water comprehensive utilization of resources.
Background technique
Lithium is widely used in battery industry, ceramics, glass industry, aluminum i ndustry, lubricant, refrigerant, nuclear industry and photoelectricity row
The emerging application field such as industry, and lithium carbonate is product the most key in lithium salts industry one kind, is the secondary lithium salts of production and metal
The basic material of lithium can be used as raw material and prepare the high lithium salts and its compound of various added values.From the point of view of market survey statistics,
By the pulling of power battery, the demand of global lithium carbonate it is estimated by from 2017 26.5 ten thousand tons rise to the 400000 of the year two thousand twenty
Ton increases by 13.5 ten thousand tons in 3 years, and the five-year, the downstream demand amount of lithium carbonate can still keep 16% annual speedup.With
The high speed development of information industry and continually developing for lithium product, it is some it is new using field and industry to the purity of lithium carbonate product
It is required that also higher and higher.Lithium carbonate includes that industrial level lithium carbonate, battery-level lithium carbonate, medicine lithii and pure Lithium Carbonate etc. are more
Kind of different type product, purity is all 99% or more, the production attention by various countries of current battery level lithium carbonate.
Industrial production battery-level lithium carbonate using the lithium sulfate solution of lithium ore and brine output as raw material, under stiring plus
Entering temperature is 80~90 DEG C and dissolved with the EDTA and Na of polyethylene glycol2CO3Solution is stirred to react 30~60min in 85~97 DEG C,
Then it is filtered, washed, is dried to obtain Li2CO3.For the purity for guaranteeing lithium carbonate, method of purification is washed and starched at 88~92 DEG C using multistage
It is lower that multistage elution is carried out to Crude lithium Carbonate and lithium carbonate filter cake with reverse osmosis water, a large amount of lithium carbonate wash water can be generated in the process,
Wherein mainly contain Na+、Ca2+、Mg2+、Cl-, the impurity such as EDTA, since the presence of EDTA leads to wash water COD higher, direct emission
Easily cause environmental pollution.
At present in lithium carbonate wash water process field conventional processes mainly based on evaporative crystallization, recrystallization.Comparison
Publication CN107720789A, the first patent separate calcium salt magnesium salts by being passed through precipitating reagent into solution, then adjust pH=2
~4 obtain lithium hydroxide and lithium carbonate mixed solution, use the side recrystallized after obtaining lithium carbonate in last extraction solution separation
Formula obtains lithium carbonate solid.The technique often has following problems: 1) equipment energy consumption is big, easily causes pollution.Due to lithium carbonate wash water
Middle carbonic acid content is less, and carrying out concentration to lithium carbonate wash water by the way of evaporation, energy consumption is high and concentrated effect is poor, in the process can
Part lithium carbonate is lost, evaporative crystallization can discharge large quantity of exhaust gas simultaneously, pollute the environment.2) crystal habit that crystallization is formed
Difference, purity are low.3) solid slag is generated, processing cost is high, such as carries out using precipitating reagent to the calcium ions and magnesium ions in lithium carbonate wash water
Precipitating can generate a large amount of solid slags in the process, and higher using a large amount of reagent costs.
Summary of the invention
The present invention is and to provide a kind of lithium carbonate wash water comprehensive resource benefit to solve above-mentioned deficiency in the prior art
Devices and methods therefor.
The present invention is realized especially by following technical solution:
A kind of method of lithium carbonate wash water comprehensive utilization of resources, this method by electrodialysis-it is reverse osmosis-Bipolar Membrane electric osmose
The group technology of analysis handles lithium carbonate wash water.Realize that specific technical solution used by the goal of the invention is as follows:
A kind of device of lithium carbonate wash water comprehensive utilization of resources comprising the first exchange resin tower, acidification slot, electricity
Electrodialysis equipment, reverse osmosis equipment, the second exchange resin tower, bipolar membrane electrodialysis equipment and steam mechanical recompress equipment；
The water outlet connection acidification slot water inlet of first exchange resin tower, is acidified the water outlet connection electric osmose of slot
The feed liquid water inlet of desorption device, electrodialysis plant concentrated water outlet connection the second exchange resin tower water inlet, second from
The water inlet of the water outlet connection bipolar membrane electrodialysis equipment of sub-exchange resin tower, the acid solution of bipolar membrane electrodialysis equipment are salty out
The lye export connection steam mechanical of new access acidification slot water inlet, bipolar membrane electrodialysis equipment recompresses equipment water inlet；Electricity
The water outlet of electrodialysis equipment and the material liquid outlet of bipolar membrane electrodialysis equipment are all connected with reverse osmosis equipment water inlet, reverse osmosis
The concentrated water outlet of equipment accesses the feed liquid water inlet of electrodialysis plant again.
Preferably, the exhaust outlet of the acidification slot is also connected with waste gas collection device.
Preferably, the bipolar membrane electrodialysis equipment is three Room type bipolar membrane electrodialysis equipment.
Preferably, electrodialysis membrane stack is homogeneous membrane membrane stack or alloy film membrane stack in the electrodialysis plant.
Preferably, the membrane material of electrodialysis membrane stack is in PES, PVC, PE, PS, PP in the electrodialysis plant
It is one or more of.
Another object of the present invention is to provide a kind of method of lithium carbonate wash water comprehensive utilization of resources, the method packets
Include following steps:
S1, lithium carbonate wash water is pre-processed using ion exchange resin, removes Ca in wash water2+、Mg2+Equal impurity；
S2, acidification is carried out to through step S1 treated lithium carbonate wash water using acid solution, controls pH 7 hereinafter, making
Lithium carbonate is fully converted to lithium ion in wash water；
S3, the wash water after being acidified in step S2 is concentrated using electrodialytic technique；
S4, the concentrated water after electrodialysis concentration in step S3 is further cleaned using ion exchange resin, electrodialysis output
Fresh water be further concentrated using reverse osmosis technology；
S5, the concentrated water after reverse osmosis technology concentration will be used to return to electrodialysis progress secondary concentration in step S4；
S6, using bipolar membrane electrodialysis recipe step S4 ion exchange resin removal of impurities after electrodialysis concentrated water, obtain
To lithium hydroxide solution and acid solution；
S7, the remaining light salt brine of bipolar membrane electrodialysis technique are further concentrated using reverse osmosis technology；
Concentrated water in S8, step S7 after reverse osmosis concentration retrieves hydroxide according still further to step S5 and S6 circular treatment
Lithium solution and acid solution；
The recyclable importing of acid solution of S9, bipolar membrane electrodialysis technique output are acidified slot and are acidified for lithium carbonate wash water；
S10, bipolar membrane electrodialysis technique output lithium hydroxide solution using steam mechanical recompression (MVR) technology preparation
High-purity LiOH crystal.
Preferably, the lithium carbonate wash water can be the leaching for washing and starching generation from Crude lithium Carbonate or lithium carbonate filter cake multistage
Washing lotion, wherein 0.5~1.54wt% lithium carbonate is mainly contained, the Na of 0~10g/L+, the Ca of 0~50mg/L2+, 0~10mg/L's
Mg2+, the EDTA of 10~150ppm.
Preferably, the Ca in the removal lithium carbonate wash water2+、Mg2+Preprocess method can be ion-exchange,
Nanofiltration, double alkali tenderizers one or more.
Preferably, the inorganic acid of the acidification lithium carbonate wash water can be one of hydrochloric acid, nitric acid, sulfuric acid or several
Kind.
Preferably, the inorganic acid concentration of the acidification lithium carbonate wash water is 7wt.%.
Preferably, in the lithium carbonate wash water acidization, control pH=2~6,20~30 DEG C of temperature, the reaction time
For 10~30min.
Preferably, electrodialysis membrane stack used in the electrodialytic technique can be homogeneous membrane membrane stack or alloy film membrane stack
Preferably, the membrane material of the electrodialysis membrane stack is one or more of PES, PVC, PE, PS, PP.
Preferably, the content of LiCl is lower than 100ppm in 8wt% or more, COD in the electrodialysis concentration concentrated water.
Preferably, LiCl concentration is in 15g/L or more in concentrated water after the reverse osmosis concentration
Preferably, the fresh water TDS < 0.1g/L, COD < 5ppm of the reverse osmosis output.
Preferably, lithium hydroxide made from the bipolar membrane electrodialysis technology and concentration of hydrochloric acid solution are greater than 2mol/L.
Preferably, the Li of the reverse osmosis process recycling+Account for Li in lithium carbonate wash water+The 40%~60% of content.Reverse osmosis
After saturating process section recovery section lithium salts, subsequent electrodialytic recycling load can reduce, improve resource utilization, it is subsequent to obtain
The higher lithium hydroxide rate of recovery.
The present invention compared with the existing technology, has the advantages that
(1) present invention is pre-processed using ion-exchange, Ca in wash water2+、Mg2+Removal rate up to 99% or more.
Processing energy consumption when electrodialytic technique concentration lithium carbonate wash water is reduced, electrodialysis processed in units amount is increased.
(2) present invention using electrodialysis-bipolar membrane electrodialysis-it is reverse osmosis-electrodialysis group technology, pass through reverse osmosis process
Dilute LiCl solution of recycling electrodialysis and bipolar membrane electrodialysis output is simultaneously concentrated, and the concentrated water after concentration uses electrodialytic technique
Secondary concentration, secondary concentration concentrated water prepare soda acid using bipolar membrane electrodialysis technology, prepare the remaining dilute LiCl solution of soda acid again
It is concentrated using reverse osmosis technology, formation process circulation has recycled in raw material 40~60% Li+, reach the utilization rate of raw material
95% or more, it reduces resource waste；After reverse osmosis process section recovery section lithium salts, subsequent electrodialytic recycling can reduce
Load reduces equipment energy consumption, subsequent to obtain the higher lithium hydroxide rate of recovery.The concentrate of reverse osmosis output is reused for simultaneously
Bipolar membrane electrodialysis prepares soda acid, and fresh water TDS < 0.1g/L of reverse osmosis output, COD < 5ppm not can cause environmental pollution,
It can the directly elution of outlet or circulation for Crude lithium Carbonate.
(3) present invention is acidified using the recyclable lithium carbonate wash water that imports of inorganic acid solution of bipolar membrane electrodialysis technology output
Slot is acidified for wash water, is reduced reagent cost while being improved the utilization rate of resource, LiOH solution can be used steam mechanical and press again
High-purity LiOH crystal made from contracting technology technology can be used for each lithium industry, generates surcharge, promotes in Different Industries and look forward to
Cooperation between industry.
Detailed description of the invention
Fig. 1 is lithium carbonate wash water Resource comprehensive utilization device schematic diagram of the invention；
Fig. 2 is the process flow chart of lithium carbonate wash water comprehensive utilization of resources of the invention；
Fig. 3 is the schematic illustration (a) of electrodialytic technique of the present invention and the schematic illustration of bipolar membrane electrodialysis technology
(b)；
Specific embodiment
To keep the purposes, technical schemes and advantages of embodiment of the present invention clearer, below in conjunction in the present invention
The technical solution in the present invention is clearly and completely described in attached drawing, it is clear that described embodiment is the present invention one
Some embodiments, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.Therefore,
Claimed invention is not intended to limit to the detailed description of the embodiments of the present invention provided in the accompanying drawings below
Range, but it is merely representative of selected embodiment of the invention.Below by specific embodiment, in conjunction with attached drawing, to of the invention
Explanation is further described in technical solution.
As shown in Figure 1, following embodiments of the invention are realized based on lithium carbonate wash water Resource comprehensive utilization device,
The primary structure of the device includes the first exchange resin tower 1, acidification slot 2, electrodialysis plant 3, reverse osmosis equipment 4, second
Exchange resin tower 5, bipolar membrane electrodialysis equipment 6 and steam mechanical recompress equipment 7.Wherein, the first ion exchange resin
Tower 1 is used to pre-process the Ca in removal lithium carbonate wash water2+、Mg2+, preprocess method can be ion-exchange, nanofiltration, double alkali
Tenderizer.The lithium carbonate wash water being directed in the present invention can be the leaching that generation is washed and starched from Crude lithium Carbonate or lithium carbonate filter cake multistage
Washing lotion, wherein 0.5~1.54wt% lithium carbonate is mainly contained, the Na of 0~10g/L+, the Ca of 0~50mg/L2+, 0~10mg/L's
Mg2+, the EDTA of 10~150ppm.Water outlet connection acidification 2 water inlet of slot of first exchange resin tower 1, is acidified in slot 2 and sets
There is acid solution to add mouth, the inorganic acid of acidification lithium carbonate wash water can be one or more of hydrochloric acid, nitric acid, sulfuric acid.Lithium carbonate
In wash water acidization, pH=2~6 are controlled, 20~30 DEG C of temperature, the reaction time is 10~30min, and lithium carbonate is turned completely
It turns to subject to lithium ion.It is acidified the feed liquid water inlet of the water outlet connection electrodialysis plant 3 of slot 2, and since acidization can produce
Raw carbon dioxide, therefore the exhaust outlet for being acidified slot 2 is also connected with waste gas collection device 8.By taking the lithium chloride that hydrochloric acid is acidified as an example,
It is in the electrodialysis principle in electrodialysis plant 3 such as in Fig. 3 shown in (a), after LiCl solution is as feed liquid input, in diaphragm and
Ion selectivity exchange, the LiCl concentrated water after output concentration occur under the action of electric field, while still having in the feed liquid of part
LiCl does not enter concentrated water room, is exported in the form of the light salt brine containing EDTA from material liquid outlet.The concentrated water of electrodialysis plant 3 exports connection
The water inlet of second exchange resin tower 5 is further cleaned in the second exchange resin tower 5.Second ion exchange
The water inlet of the water outlet connection bipolar membrane electrodialysis equipment 6 of resin tower 5.Bipolar membrane electrodialysis equipment 6 is three Room type Bipolar Membranes
Electrodialysis plant, similarly by taking LiCl solution as an example, in (b) institute such as in Fig. 3 of the electrodialysis principle in bipolar membrane electrodialysis equipment 6
Show, after LiCl concentrated water is inputted as feed liquid, ion selectivity exchange occurs under the action of diaphragm and electric field, respectively output acid
Liquid (HCl solution) and lye (LiOH solution), while still thering is the LiCl in the feed liquid of part not enter acid solution room and lye room, with
Light salt brine form is exported from material liquid outlet.Again access is acidified 2 water inlet of slot for the acid solution outlet of bipolar membrane electrodialysis equipment 6, double
The lye export connection steam mechanical of pole membrane electrodialysis equipment 6 recompresses 7 water inlet of equipment, is made high-purity using MVR technology
LiOH crystal.The water outlet of electrodialysis plant 3 and the material liquid outlet of bipolar membrane electrodialysis equipment 6 are all connected with reverse osmosis equipment
The lithium ion in fresh water is further concentrated in 4 water inlets, and access electrodialysis is set again for the concentrated water outlet of reverse osmosis equipment 4
Standby 3 feed liquid water inlet, the concentrated water after concentration are made in bipolar membrane electrodialysis equipment 6 again by after electrodialysis, ion exchange
At acid solution and lye.
In above-mentioned electrodialysis plant 3, electrodialysis membrane stack is homogeneous membrane membrane stack or alloy film membrane stack, the membrane material of electrodialysis membrane stack
Material is one or more of PES, PVC, PE, PS, PP, can specifically be selected as needed.
Based on the device, a kind of method for lithium carbonate wash water comprehensive utilization of resources that the present invention designs, process includes
Following steps:
S1, lithium carbonate wash water is pre-processed using ion exchange resin, removes Ca in wash water2+、Mg2+Equal impurity；
S2, acidification is carried out to through step S1 treated lithium carbonate wash water using acid solution, controls pH 7 hereinafter, making
Lithium carbonate is fully converted to lithium ion in wash water；
S3, the wash water after being acidified in step S2 is concentrated using electrodialytic technique；
S4, the concentrated water after electrodialysis concentration in step S3 is further cleaned using ion exchange resin, electrodialysis output
Fresh water be further concentrated using reverse osmosis technology；
S5, the concentrated water after reverse osmosis technology concentration will be used to return to electrodialysis progress secondary concentration in step S4；
S6, using bipolar membrane electrodialysis recipe step S4 ion exchange resin removal of impurities after electrodialysis concentrated water, obtain
To lithium hydroxide solution and acid solution；
S7, the remaining light salt brine of bipolar membrane electrodialysis technique are further concentrated using reverse osmosis technology；
Concentrated water in S8, step S7 after reverse osmosis concentration is according still further to the identical mode circular treatment of step S5 and S6, again
Obtain lithium hydroxide solution and acid solution；
The recyclable importing of acid solution of S9, bipolar membrane electrodialysis technique output are acidified slot and are acidified for lithium carbonate wash water；
S10, bipolar membrane electrodialysis technique output lithium hydroxide solution using steam mechanical recompression (MVR) technology preparation
High-purity LiOH crystal.
The lithium carbonate wash water of the technological invention suitable treatment is Crude lithium Carbonate and carbonic acid in battery-level lithium carbonate purification process
The eluate of lithium filter cake.The lithium carbonate wash water in specific embodiment will be handled based on above-mentioned technique below, to show this
The particular technique effect of invention.
Embodiment 1:
Referring to attached drawing 2,10L lithium carbonate wash water lithium carbonate containing 1.2wt% in the present embodiment, the Na of 1g/L+, the Ca of 10mg/L2 +, the Mg of 1mg/L2+, the EDTA of 132ppm.A kind of method of lithium carbonate wash water comprehensive utilization of resources includes the following steps:
S1, lithium carbonate wash water is pre-processed using ion exchange resin, removes Ca in wash water2+、Mg2+Equal impurity, in advance
Ca after processing2+、Mg2+Total content < 0.33ppm；
S2, acidification is carried out to through step S1 treated lithium carbonate wash water using 7wt% hydrochloric acid, controls pH=2, instead
It answers 10min to generate to bubble-free, so that lithium carbonate in wash water is fully converted to lithium chloride, the wash water after acidification is containing 15.18g/L's
LiCl, COD 132ppm；
S3, the wash water after being acidified in step S2 being concentrated using electrodialytic technique, alloy film membrane stack is selected in electrodialysis,
LiCl of the concentrated water of electrodialysis output containing 93g/L, LiCl of the light salt brine containing 5g/L of electrodialysis output, the unit of electrodialysis concentration
Treating capacity is 2.1t material/(h platform), and processed in units energy consumption is 12.99kwh/t material；
S4, the concentrated water after electrodialysis concentration in step S3 is further cleaned using ion exchange resin, electrodialysis output
Fresh water be further concentrated using reverse osmosis technology；
S5, the LiCl concentrated water return electrodialysis progress second level that will be concentrated into 15g/L using reverse osmosis technology in step S4 are dense
Contracting；
S6, using bipolar membrane electrodialysis recipe step S4 ion exchange resin removal of impurities after electrodialysis concentrated water, obtain
To LiOH solution and HCl solution；
S7, the remaining light salt brine of bipolar membrane electrodialysis technique are further concentrated into 15g/L using reverse osmosis technology；
After electrodialysis fresh water is concentrated using reverse osmosis technology in concentrated water and step S4 in S8, step S7 after reverse osmosis concentration
The concentrated water of generation is the same, and the bipolar membrane electrodialysis technique of electrodialysis secondary concentration and S6 according still further to step S5 carries out at circulation
Reason, retrieves LiOH solution and HCl solution, concentration is respectively 1.9mol/L and 2.0mol/L, and alkaline chamber current efficiency is
55.5%；
The hydrochloric acid solution circulation importing of S9, bipolar membrane electrodialysis technique output are acidified slot and are acidified for lithium carbonate wash water.
S10, bipolar membrane electrodialysis technique output lithium hydroxide solution high-purity LiOH crystal is made using MVR technology
47.85g。
By the process, Ca in wash water2+、Mg2+Removal efficiency up to 97%, using reverse osmosis technology concentration electrodialysis and
The light salt brine of bipolar membrane electrodialysis output makes lithium ion utilization rate up to 95%.
Embodiment 2:
20L lithium carbonate wash water lithium carbonate containing 1.4wt% in the present embodiment, the Na of 1.5g/L+, the Ca of 15mg/L2+, 1.5mg/
The Mg of L2+, the EDTA of 150ppm.
Different from embodiment 1, the inorganic acid for being acidified lithium carbonate wash water is changed to sulfuric acid by the present embodiment, remaining processing lithium carbonate
The method of wash water is same as Example 1.Ca in wash water after ion exchange resin treatment2+, Mg2+Total content < 0.3ppm.Using
7wt% sulfuric acid is acidified wash water, controls pH=4, and reaction 20min to bubble-free is generated, and the wash water after acidification contains 15.3g/L
Li2SO4, COD 150ppm.Then wash water is concentrated using electrodialytic technique, the concentrated water of electrodialysis output contains 95g/L
Li2SO4, Li of the light salt brine containing 6g/L of electrodialysis output2SO4.Electrodialysis concentrated water is prepared using bipolar membrane electrodialysis technology
H2SO4With LiOH solution, concentration is respectively 2.1mol/L and 2.14mol/L, and alkaline chamber current efficiency is 60%.The hydroxide of output
High-purity LiOH crystal 102g is made using MVR technology in lithium solution.
By the process, Ca in wash water2+、Mg2+Removal efficiency up to 98%, using reverse osmosis technology concentration electrodialysis and
The light salt brine of bipolar membrane electrodialysis output makes lithium ion utilization rate up to 97%.
Embodiment 3:
50L lithium carbonate wash water lithium carbonate containing 1.5wt% in the present embodiment, the Na of 2g/L+, the Ca of 20mg/L2+, 2mg/L's
Mg2+, the EDTA of 115ppm.
Different from embodiment 1, the membrane stack that electrodialytic technique uses in the present embodiment is homogeneous membrane membrane stack, remaining processing carbonic acid
The method of lithium wash water is same as Example 1.Ca in wash water after ion exchange resin treatment2+, Mg2+Total content < 0.2ppm.Using
7wt% hydrochloric acid is acidified wash water, controls pH=5, and reaction 30min to bubble-free is generated, and the wash water after acidification contains 15.1g/L
LiCl, COD 115ppm.Then wash water is concentrated using electrodialytic technique, the concentrated water of electrodialysis output is containing 90g/L's
LiCl, LiCl of the light salt brine containing 8g/L of electrodialysis output, the processed in units amount of electrodialysis concentration are 2.7t material/(h platform),
Processed in units energy consumption is 11.32kwh/t material.Light salt brine using reverse osmosis technology is concentrated into 15g/L, and to return to electrodialysis dense
Contracting.Electrodialysis concentrated water using bipolar membrane electrodialysis technology prepare HCl and LiOH solution, concentration be respectively 1.9mol/L and
2.1mol/L, alkaline chamber current efficiency are 66%.High-purity LiOH crystal is made using MVR technology in the lithium hydroxide solution of output
251g。
By the process, Ca in wash water2+、Mg2+Removal efficiency up to 99%, using reverse osmosis technology concentration electrodialysis and
The light salt brine of bipolar membrane electrodialysis output makes lithium ion utilization rate up to 97%.
Embodiment described above is preferred version of the invention, is not intended to limit the present invention in any form,
There are also other variants and remodeling on the premise of not exceeding the technical scheme recorded in the claims.
Claims (10)
1. a kind of device of lithium carbonate wash water comprehensive utilization of resources, which is characterized in that including the first exchange resin tower
(1), slot (2), electrodialysis plant (3), reverse osmosis equipment (4), the second exchange resin tower (5), bipolar membrane electrodialysis are acidified
Equipment (6) and steam mechanical recompression equipment (7)；
Water outlet connection acidification slot (2) water inlet of first exchange resin tower (1), the water outlet of acidification slot (2) connect
Connect the feed liquid water inlet of electrodialysis plant (3), the concentrated water outlet connection the second exchange resin tower (5) of electrodialysis plant (3)
Water inlet, the second exchange resin tower (5) water outlet connection bipolar membrane electrodialysis equipment (6) water inlet, Bipolar Membrane
Again access is acidified slot (2) water inlet, the lye export of bipolar membrane electrodialysis equipment (6) for the acid solution outlet of electrodialysis plant (6)
It connects steam mechanical and recompresses equipment (7) water inlet；The water outlet and bipolar membrane electrodialysis equipment of electrodialysis plant (3)
(6) material liquid outlet is all connected with reverse osmosis equipment (4) water inlet, and the concentrated water outlet of reverse osmosis equipment (4) accesses electrodialysis again
The feed liquid water inlet of equipment (3).
2. the device of lithium carbonate wash water comprehensive utilization of resources as described in claim 1, which is characterized in that the Bipolar Membrane
Electrodialysis plant (6) is three Room type bipolar membrane electrodialysis equipment.
3. a kind of method of lithium carbonate wash water comprehensive utilization of resources, which is characterized in that described method includes following steps:
S1, lithium carbonate wash water is pre-processed using ion exchange resin, removes Ca in wash water2+、Mg2+Equal impurity；
S2, acidification is carried out to through step S1 treated lithium carbonate wash water using acid solution, controls pH 7 hereinafter, making wash water
Middle lithium carbonate is fully converted to lithium ion；
S3, the wash water after being acidified in step S2 is concentrated using electrodialytic technique；
S4, the concentrated water after electrodialysis concentration in step S3 is further cleaned using ion exchange resin, electrodialysis output it is light
Water is further concentrated using reverse osmosis technology；
S5, the concentrated water after reverse osmosis technology concentration will be used to return to electrodialysis progress secondary concentration in step S4；
S6, using bipolar membrane electrodialysis recipe step S4 ion exchange resin removal of impurities after electrodialysis concentrated water, obtain hydrogen
Lithia solution and acid solution；
S7, the remaining light salt brine of bipolar membrane electrodialysis technique are further concentrated using reverse osmosis technology；
It is molten to retrieve lithium hydroxide according still further to step S5 and S6 circular treatment for concentrated water in S8, step S7 after reverse osmosis concentration
Liquid and acid solution；
The recyclable importing of acid solution of S9, bipolar membrane electrodialysis technique output are acidified slot and are acidified for lithium carbonate wash water；
S10, bipolar membrane electrodialysis technique output lithium hydroxide solution using steam mechanical recompression (MVR) technology prepare it is high-purity
LiOH crystal.
4. a kind of method of lithium carbonate wash water comprehensive utilization of resources according to claim 3, which is characterized in that the carbon
Sour lithium wash water, which can be, washes and starches the leacheate of generation from Crude lithium Carbonate or lithium carbonate filter cake multistage, wherein mainly contain 0.5~
1.54wt% lithium carbonate, the Na of 0~10g/L+, the Ca of 0~50mg/L2+, the Mg of 0~10mg/L2+, the EDTA of 10~150ppm.
5. a kind of method of lithium carbonate wash water comprehensive utilization of resources according to claim 3, which is characterized in that described to go
Except the Ca in lithium carbonate wash water2+、Mg2+Preprocess method can be ion-exchange, nanofiltration, double alkali tenderizers one kind or
It is several.
6. a kind of method of lithium carbonate wash water comprehensive utilization of resources according to claim 3, which is characterized in that the acid
The inorganic acid for changing lithium carbonate wash water can be one or more of hydrochloric acid, nitric acid, sulfuric acid；The lithium carbonate wash water acidization
In, pH=2~6 are controlled, 20~30 DEG C of temperature, the reaction time is 10~30min.
7. a kind of method of lithium carbonate wash water comprehensive utilization of resources according to claim 3, which is characterized in that the electricity
Electrodialysis membrane stack used in osmotic technique can be homogeneous membrane membrane stack or alloy film membrane stack；The membrane material of the electrodialysis membrane stack is
One or more of PES, PVC, PE, PS, PP.
8. a kind of method of lithium carbonate wash water comprehensive utilization of resources according to claim 3, which is characterized in that the electricity
The content that LiCl in concentrated water is concentrated in dialysis is lower than 100ppm in 8wt% or more, COD.
9. a kind of method of lithium carbonate wash water comprehensive utilization of resources according to claim 3, which is characterized in that described anti-
LiCl concentration is in 15g/L or more in concentrated water after osmosis concentration；Fresh water TDS < the 0.1g/L, COD of the reverse osmosis output <
5ppm；The Li of the reverse osmosis process recycling+Account for Li in lithium carbonate wash water+The 40%~60% of content.
10. a kind of according to claim 3, method of lithium carbonate wash water comprehensive utilization of resources, which is characterized in that described double
Lithium hydroxide made from the membrane electrodialysis technology of pole and concentration of hydrochloric acid solution are greater than 2mol/L.
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