CN105836766A - Method for removing boron ions in high lithium solution - Google Patents
Method for removing boron ions in high lithium solution Download PDFInfo
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- CN105836766A CN105836766A CN201610155905.5A CN201610155905A CN105836766A CN 105836766 A CN105836766 A CN 105836766A CN 201610155905 A CN201610155905 A CN 201610155905A CN 105836766 A CN105836766 A CN 105836766A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 72
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 boron ions Chemical class 0.000 title abstract description 46
- 238000001179 sorption measurement Methods 0.000 claims abstract description 187
- 238000011069 regeneration method Methods 0.000 claims abstract description 60
- 230000008929 regeneration Effects 0.000 claims abstract description 59
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 95
- 239000007788 liquid Substances 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 25
- 239000003480 eluent Substances 0.000 claims description 19
- 238000010521 absorption reaction Methods 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 11
- 239000003456 ion exchange resin Substances 0.000 claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000007423 decrease Effects 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 35
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 150000003839 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 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- 241001131796 Botaurus stellaris Species 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052642 spodumene Inorganic materials 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for removing boron ions in a high lithium solution. The method is based on an apparatus for removing boron ions in the high lithium solution. According to the apparatus, adsorption columns successively rotate from one module to another one by one under the driving of a rotating disk, so cyclic operation of adsorption, desorption, regeneration and readsorption is finished. The method maximally utilizes adsorption efficiency of the adsorption columns by controlling the number of adsorption columns in each module and the flow of each fluid flowing through the adsorption columns in each module, so it is guaranteed that the concentration of boron ions in the high lithium solution decreases to no more than 0.1 ppm; thus, requirements on the high lithium solution used as battery-grade and high-purity lithium salt products are met.
Description
Technical field
The invention belongs to Separation & Purification technical field prepared by inorganic material, specifically, relate to a kind of de-
Method except the boron ion in high lithium solution.
Background technology
Whole world lithium resource mainly includes lithium Ore (predominantly spodumene, lepidolite) and the lake bittern water Han lithium salts.
At present, lithium salts product mainly extracts from containing lithium salts lake bittern water, therefore containing substantial amounts of boron in lithium salts lake bittern water
Ion can inevitably enter in lithium salts product, causes in lithium salts product the content of boron ion all more than 30
Ppm (i.e. 30mg/L).Therefore, the above-mentioned lithium salts product prepared normally only reaches technical grade.
Usually, during preparing lithium salts product, typically firstly the need of preparing high lithium solution, i.e.
When preparing the lithium salts products such as lithium chloride, lithium carbonate, lithium sulfate, crystallize in final step, precipitate, convert
Step before the lithium ion solution of high concentration that obtained, as preparing lithium bicarbonate, described
In high lithium solution, the concentration of lithium ion can reach 8g/L～10g/L, and for prepare lithium chloride, Lithium hydrate,
For lithium sulfate etc., the concentration of the lithium ion in its most corresponding high lithium solution will be higher, the fullest
With；Test shows: only when in described high lithium solution, the content of boron ion is less than 0.1ppm, crystallized,
Precipitation, convert obtain lithium chloride, lithium carbonate, the content of boron ion could not in the lithium salts product such as lithium sulfate
More than 15ppm, it is thus possible to fully meet LITHIUM BATTERY and the requirement of high purity lithium product salt.
Between selecting ion exchange technique due to the ion exchange resin absorption property to lithium ion and boron ion
Difference, can separate boron ion from high lithium solution, thus become one and prepare high purity lithium product salt
Main method.When using selection ion exchange technique to prepare high purity lithium product salt at present, general employing is fixing
Bed carries out ion exchange, but the method still has a shortcomings: as low in ion exchange resin utilization ratio, make
Consumption is big, and acid, alkali consume big, and water loss is big, and the waste liquid of generation is many, thus causes cost high, meanwhile,
Mother solution amount is caused to increase owing to the concentration of high lithium solution can reduce due to dilution；It addition, equipment is huge, logical
Crossing frequent switch valve and carry out intermittently operated, automaticity is low；Product liquid quality is unstable.Therefore, have
Necessary searching is a kind of can improve the utilization rate of ion exchange resin, the raising removal efficiency of boron ion, automatization
Degree is high and the method that can run continuously is to remove the boron ion in high lithium solution.
Summary of the invention
For solving the problem that above-mentioned prior art exists, the invention provides a kind of boron removed in high lithium solution
The method of ion, the method is based on a kind of operation of circulation continuously realizing absorption-eluting-regeneration-adsorb again
Equipment, the concentration of the boron ion in high lithium solution not only can be down to below requirement, also can be saved by described method
The consumption of eluent, regenerated liquid etc..
In order to reach foregoing invention purpose, present invention employs following technical scheme:
A kind of method of boron ion removed in high lithium solution, described method includes step: A, by some absorption
Post is arranged on rotating disk, and in described some adsorption columns filling for adsorbing boron ion in high lithium solution
Ion exchange resin；Wherein, described high lithium solution refers to the lithium obtained during preparing lithium salts product
Ion concentration is not less than the mixed aqueous solution of 8g/L；B, it is separately operable adsorption module, eluting module, regeneration
Module；It is positioned at the adsorption column within described adsorption module and is adsorbed described boron ion by described high lithium solution, and
Obtain product feed liquid；The described boron ion being positioned in the adsorption column of described eluting inside modules absorption is eluted liquid
Eluting；It is positioned at the adsorption column within described regeneration module and is reproduced liquid regeneration, and regain the described boron of absorption
The ability of ion；Wherein, described high lithium solution flows through the flow being positioned at the adsorption column within described adsorption module
For 100mL/min～120mL/min, described eluent flows through the adsorption column being positioned at described eluting inside modules
Flow is 8mL/min～10mL/min, and described regenerated liquid flows through the adsorption column being positioned within described regeneration module
Flow be 8mL/min～10mL/min；C, after the scheduled time, rotate described rotating disk, described some adsorption columns
Pass sequentially through described adsorption module, eluting module, regeneration module；D, it is alternately repeated described step B and step
C。
Further, in described step B, also include being separately operable and be located in described adsorption module and described
Water liftout module between eluting module and being located between described regeneration module and described adsorption module
Material top water module；It is positioned in the adsorption column of described water liftout inside modules the described high lithium solution being detained described
Liftout use water displacement in water liftout module, is positioned in the adsorption column of described material top water inside modules the water being detained
Divide and replaced by described product feed liquid；Wherein, described liftout water flows through and is positioned at described water liftout inside modules
The flow of adsorption column is 5mL/min～6mL/min, and described product feed liquid flows through and is positioned at described material top water module
The flow of the adsorption column in portion is 5mL/min～6mL/min.
Further, in described step B, it is positioned at described eluting mould when described eluent flows through from the bottom to top
After adsorption column in block, the eluting water being positioned in described eluting module flow through from the bottom to top be positioned at described in wash
Adsorption column in demoulding block；When described regenerated liquid flows through the adsorption column being positioned in described regeneration module from the bottom to top
After, the regeneration water being positioned in described regeneration module flows through the absorption being positioned in described regeneration module from the bottom to top
Post；Wherein, described eluting water flows through the flow of the adsorption column being positioned at described eluting inside modules is 30
ML/min～32mL/min, described regeneration water flows through the flow being positioned at the adsorption column within described regeneration module
For 80mL/min～90mL/min.
Further, the described scheduled time is 50min～55min.
Further, described eluent be mass percent be the aqueous hydrochloric acid solution of 7%～8%, described regenerated liquid
For the sodium hydrate aqueous solution that mass percent is 6%～7%.
Beneficial effects of the present invention:
(1) circulate operation continuously according to what the equipment of the present invention achieved absorption-eluting-regeneration-adsorb again, inhale
Attached module, eluting module, the inside of regeneration module are assigned with adsorption column, it is achieved thereby that many adsorption columns
Continuous Cycle Automation remove the boron ion in high lithium solution；
(2) the method according to the invention is by the number of the adsorption column in the above-mentioned each module of reasonable distribution, respectively flow
The size of amount, has maximally utilised the adsorption efficiency of adsorption column, it is ensured that boron in the product feed liquid of acquisition
The content of ion is down to below requirement, thus can meet as LITHIUM BATTERY and the requirement of high purity lithium product salt.
Accompanying drawing explanation
By combining the following description that accompanying drawing is carried out, above and other aspect of embodiments of the invention, feature
Will become clearer from advantage, in accompanying drawing:
Fig. 1 is that the equipment removing the boron ion in high lithium solution according to an embodiment of the invention is in deployed condition
Under structural representation；
Fig. 2 is process chart according to an embodiment of the invention.
Detailed description of the invention
Hereinafter, with reference to the accompanying drawings to describe embodiments of the invention in detail.However, it is possible to it is different with many
Form implements the present invention, and the present invention should not be construed as limited to the specific embodiment that illustrates here.
On the contrary, it is provided that these embodiments are to explain the principle of the present invention and actual application thereof, so that this area
Others skilled in the art it will be appreciated that various embodiments of the present invention and be suitable for the various of specific intended application and repair
Change.In the accompanying drawings, for the sake of clarity, the shape and size of element, and identical label can be exaggerated
Same or analogous element will be used to indicate all the time.
Although it will be appreciated that and term " first ", " second " etc. here can being used to describe various element,
But these elements should not be limited by these terms.These terms are only used for an element and another yuan
Part makes a distinction.
A kind of method that embodiment of the invention discloses that boron ion removed in high lithium solution, the method based on
The equipment of a kind of boron ion removed in high lithium solution, is first described described equipment.
Fig. 1 is that the equipment of a kind of boron ion removed in high lithium solution is launching
Structural representation under state.
With reference to Fig. 1, include according to the equipment of the boron ion removed in high lithium solution of the present embodiment: rotating disk 1,
The some adsorption columns 2 arranged in the form of a ring that are connected on described rotating disk 1 and be arranged in order and arrange in the form of a ring
Adsorption module 3, water liftout module 4, eluting module 5, regeneration module 6, material top water module 7；Namely
Saying, in the apparatus, material top water module 7 is the most adjacent with adsorption module 3.Rotating disk 1 can drive adsorption column 2
Rotate, so that adsorption column 2 passes sequentially through described adsorption module 3, water liftout module 4, eluting mould
Block 5, regeneration module 6, material top water module 7；When described adsorption column 2 turns to adsorption module 3 inside,
Adsorption column 2 is by adsorbing boron ion in described high lithium solution, to obtain product feed liquid；When adsorption column 2 turns to
When water liftout module 4 is internal, the high lithium solution being detained in adsorption column 2 is replaced by liftout water；When adsorption column 2
Turn to eluting module 5 internal time, adsorption column 2 through elution to remove boron ion；When adsorption column 2
When turning to regeneration module 6 inside, adsorption column 2 regenerates to regain the energy of absorption boron ion through regenerated liquid
Power；When adsorption column 2 turns to water module 7 inside, material top, the moisture being detained in adsorption column 2 is by described product
Product feed liquid is replaced.
Specifically, in adsorption column 2, be filled with ion exchange resin, the boron that can be used for adsorbing in high lithium solution from
Son, to obtain product feed liquid；Wherein, described high lithium solution refers to during preparing lithium salts product,
The lithium concentration obtained before finally precipitating operation is not less than the mixed aqueous solution of 8g/L.As in preparation
During lithium bicarbonate, in described initial feed liquid, lithium concentration is about 8g/L～10g/L, and for preparation
Lithium chloride, in the most described initial feed liquid, lithium concentration is about 10g/L～30g/L, and other such as prepare hydroxide
Lithium or lithium sulfate etc., wherein the concentration of lithium ion is all close to saturated.
Adsorption module 3 includes the first feed liquid case 31 for storing described high lithium solution, for storing described product
Second feed liquid case 32 of product feed liquid.
In the present embodiment, in adsorption column 2, the nonionic adsorption resin of filling is sodium-ion type adsorbent resin, can
Use R-ONa+Representing, after the boron ion in it has adsorbed high lithium solution, it is changed into R-OB3+Type.When
So, in adsorption column 2 nonionic adsorption resin of filling can also is that other arbitrarily can be used as adsorbing boron ion from
Sub-exchange resin, repeats the most one by one.
Water liftout module 4 includes for storage except the first water tank 41 of material water.What deserves to be explained is, work as position
After the adsorption column 2 within adsorption module 3 turns to water liftout module 4, these adsorption columns 2 can be carried secretly
Part high lithium solution, needs water flowing from the bottom to top so that this part height lithium solution is discharged adsorption column 2, i.e. produces secondary
Feed liquid, and the water being now passed through is described liftout water.Preferably, in order to reduce the waste of feed liquid, can
Described secondary feed liquid is incorporated in the first feed liquid case 31.
Eluting module 5 includes the 3rd feed liquid case 51 for storing eluent, for storing the of eluting waste liquid
Four feed liquid casees 52 and for storing the second water tank 53 of eluting water.
In the present embodiment, described eluent be mass percent be the aqueous hydrochloric acid solution of 7%～8%.
Specifically, first, when being positioned in the adsorption column 2 within water liftout module 3 the high lithium solution quilt being detained
After liftout water is replaced, it is internal that these adsorption columns 2 turn to eluting module 5 with rotating disk 1；It is positioned at
Eluent in three feed liquid casees 51 flows through the adsorption column 2 being positioned within eluting module 5 the most from the bottom to top, to it
In R-OB3+The ion exchange resin of type carries out eluting, is changed into R-OH+Type, simultaneously produce comprise boron from
The eluting waste liquid of son, and enter in the 4th feed liquid case 52；Then, these adsorption columns 2 continue with rotating disk 1 to
Front rotation, the eluting water being positioned in the second water tank 53 flows through the warp being positioned within eluting module 5 from the bottom to top
Cross the adsorption column 2 of elution, to clean the eluent of the excess wherein carried secretly, and produce secondary eluent.
Regeneration module 6 include the 5th feed liquid case 61 for storing, regenerating liquid, for storing, regenerating waste liquid
Six feed liquid casees 62 and the three-tank 63 for storing, regenerating water.
In the present embodiment, described regenerated liquid be mass percent be the sodium hydrate aqueous solution of 6%～7%.
Specifically, first, clean through described eluting water when the adsorption column 2 being positioned in described eluting module 5
After, these adsorption columns 2 are rotated further to regeneration module 6 internal with rotating disk 1；It is positioned in the 5th feed liquid case 61
Regenerated liquid flow through the adsorption column 2 being positioned within regeneration module 6 the most from the bottom to top, to R-OH therein+Type
Ion exchange resin carries out Regeneration Treatment, is again changed into R-ONa+Type, produces regeneration liquid waste, side by side simultaneously
Enter in the 6th feed liquid case 62；Then, these adsorption columns 2 continue to rotate forward with rotating disk 1, are positioned at the 3rd water
Regeneration water in case 63 flows through the adsorption column through regenerated liquid regeneration being positioned within regeneration module 6 from the bottom to top
2, to clean the excess regeneration alkali liquor wherein carried secretly, and produce secondary recycling liquid.
Water module 7 one end, material top connects described second feed liquid case 32.What deserves to be explained is, when being positioned at regeneration mould
After the internal adsorption column 2 of block 6 turns to material top water module 7, these adsorption columns 2 can be used in entrainment portions regeneration
Water, need to be passed through product feed liquid from the bottom to top by this partial regeneration water discharge adsorption column 2, i.e. to produce waste water.
Preferably, in order to reduce waste, described waste water can be incorporated in the second water tank 53 for containing eluting water
And/or in the three-tank 63 containing regeneration water.When being positioned at the adsorption column 2 within the water module 7 of material top
After the regeneration water of middle delay is excluded, these adsorption columns 2 continue to turn to described absorption with rotating disk 1
Module 3 is internal.So, a complete absorption-water liftout-eluting-regeneration-material top water-adsorb again is i.e. completed
Circulation operation, and adsorption column 2 during whole without take out, can realize recycling.
More specifically, with reference to shown in Fig. 2, in the present embodiment, it is positioned at the absorption within adsorption module 3
Post 2 has four, is denoted as adsorption column a, adsorption column b, adsorption column c and adsorption column d respectively；Wherein, absorption
Post a and adsorption column b is in parallel, adsorption column c and adsorption column d is in parallel, connects the most again；It is to say, absorption
Post a and adsorption column c connects with after adsorption column b and adsorption column d parallel connection respectively again；So, described high lithium solution
First flow through adsorption column c and adsorption column d, then flow through adsorption column a and adsorption column b, arrive the second feed liquid case
In 32.
In the present embodiment, being positioned at the adsorption column 2 within eluting module 5 has four, be denoted as respectively adsorption column e,
Adsorption column f, adsorption column g and adsorption column h；Wherein, adsorption column e and adsorption column f is in series；So, institute
Stating eluent and flow through adsorption column f and adsorption column e successively, produced eluting waste liquid arrives the 4th feed liquid case 52；
And adsorption column g and adsorption column h is in series；So, described eluting water can flow through successively adsorption column h and
Adsorption column g, and produce secondary eluent.Preferably, described secondary eluent may be incorporated in adsorption column e.
In the present embodiment, being positioned at the adsorption column 2 within regeneration module 6 has five, be denoted as respectively adsorption column i,
Adsorption column j, adsorption column k, adsorption column l and adsorption column m；Wherein, adsorption column i and adsorption column j is in series；
So, described regenerated liquid flows through adsorption column j and adsorption column i successively, and produced regeneration liquid waste arrives the 6th material
Liquid case 62；And adsorption column k, adsorption column l and adsorption column m are sequentially connected in series；So, described regeneration water is i.e.
Adsorption column m, adsorption column l and adsorption column k can be flowed through successively, and produce secondary recycling liquid.Preferably, described
Secondary recycling liquid may be incorporated in adsorption column i.
In the present embodiment, it is positioned at the adsorption column 2 within water liftout module 4 and is positioned at material top water module 7
The adsorption column 2 in portion is one.
It is to say, in above process, five corresponding inside modules are all placed with some adsorption columns 2, i.e.
A total of 15 of adsorption column 2 in the present embodiment；Certainly, the present invention is not restricted to this, usually, for
Ensure in each module, adsorption column 2 all can adsorb/and water liftout/eluting/regeneration/material top water is complete,
Controlling its total amount should be less than ten.And every adsorption column 2 all can be washed along adsorption module 3-liftout module 4-
The path of demoulding block 5-regeneration module 6-material top water module 7-adsorption module 3 rotates, so, i.e. the most successively
Continuously the boron ion in high lithium solution can be adsorbed, thus obtain qualified product feed liquid.
Preferably, in the present embodiment, the equipment of the boron ion in described removing high lithium solution also includes and institute
State the fixed disk 8 that rotating disk 1 is oppositely arranged；There is on described rotating disk 1 some first holes 11, described fixed disk 8
On there are some second holes 81 being oppositely arranged with some first holes 11, the first hole 11 and the second hole 81 are one by one
Relatively, for respectively by or to first feed liquid case the 31, second feed liquid case the 32, first water tank the 41, the 3rd feed liquid
Case the 51, the 4th feed liquid case the 52, second water tank the 53, the 5th feed liquid case the 61, the 6th feed liquid case the 62, the 3rd water
Case 63 transmits high lithium solution, product feed liquid, liftout water, eluent, eluting waste liquid, eluting water,
The liquid such as regenerated liquid, regeneration liquid waste, regeneration water.
The method that below will be described in detail the boron ion removed in high lithium solution based on the said equipment, the method
Comprise the steps:
In step, some adsorption columns 2 are installed on the turntable 1, and in described some adsorption columns 2
Filling is for adsorbing the ion exchange resin of the boron ion in high lithium solution.
In the present embodiment, each adsorption column 2 loads the ion exchange resin of 260mL～320mL.
In stepb, adsorption module 3, water liftout module 4, eluting module 5, regeneration module it are separately operable
6 and material top water module 7.
Specifically, in adsorption module 3, first-class with 100mL/min～120mL/min of high lithium solution
Amount flows through the adsorption column 2 being positioned within adsorption module 3, and adsorbs boron ion from high lithium solution, and obtains product
Product feed liquid.
In water liftout module 4, it is positioned at except material water flows through with the second flow of 5mL/min～6mL/min
Adsorption column 2 within water liftout module 4, and the high lithium solution replacement that will be detained.
In eluting module 5, first eluent flows through with the 3rd flow of 8mL/min～10mL/min and is positioned at
Adsorption column 2 within eluting module 5, and the boron ion elution of absorption in adsorption column 2 is fallen；Then eluting is used
Water flow through with the 4th flow of 30mL/min～32mL/min be positioned within eluting module 5 and through eluting
The adsorption column 2 of liquid eluting.
In regeneration module 6, first regenerated liquid flows through with the 5th flow of 8mL/min～10mL/min and is positioned at
Adsorption column 2 within regeneration module 6, and carry out regenerating by adsorption column 2 and regain the energy of absorption boron ion
Power；Then regeneration water flows through with the 6th flow of 80mL/min～90mL/min and is positioned at regeneration module 6
Portion and through regenerated liquid regeneration adsorption column 2.
In the water module 7 of material top, product feed liquid flows through with the 7th flow of 5mL/min～6mL/min and is positioned at
Material top adsorption column 2 within water module 7, and the regeneration water of delay is replaced.
Preferably, after described eluting water flows through the adsorption column 2 being positioned within described eluting module 5, need
The secondary eluent discharged is carried out the mensuration of pH, so that the pH of secondary eluent remains 6～7；Therewith
Similar, after described regeneration water flows through the adsorption column 2 being positioned within described regeneration module 6, it is right to need
The secondary recycling liquid discharged carries out the mensuration of pH, so that the pH of secondary recycling liquid remains 8～9.
In step C, after 50min～55min, rotating disk 1 drives some adsorption columns 2 to rotate, described some
Adsorption column 2 passes sequentially through adsorption module 3, water liftout module 4, eluting module 5, regeneration module 6 and material top
Water module 7.
What deserves to be explained is, rotating disk 1 often rotates once, and described some adsorption columns 2 rotate the most forward a position
Put；It is to say, in the present embodiment, rotating disk 1 often rotates once, and adsorption column a turns to forward absorption
The position that post b is original, adsorption column b turns to the most forward the position that adsorption column c is original, the like.
In step D, be alternately repeated described step B and step C, i.e. achieve the absorption of adsorption column 2-
The circulation operation of water liftout-eluting-regeneration-material top water-adsorb again.
The method of boron ion that will be described by specific embodiment in above-mentioned removing high lithium solution below.
Experiment comprises experiment one～experiment four.Wherein, the initial feed liquid that experiment one～experiment four are used is
Containing 8g/L～9g/L lithium ion and the mixed aqueous solution containing about 15ppm～30ppm boron ion.De-
Except the result of boron ion is as shown in table 1.
Table 1 experiment condition and experimental result contrast table
In Table 1, the unit of described first flow～the 7th flow is mL/min；Described boron ion is initial
Amount represents the content of the boron ion in high lithium solution, and described boron ion product content represents the boron in product feed liquid
The content of ion, its unit is ppm.
As it can be seen from table 1 the concentration of the boron ion in high lithium solution is all down to 0.1ppm's in different experiments
Below requirement so that the product feed liquid obtained through absorption can be used as preparing LITHIUM BATTERY and high purity lithium product salt.When
So, according to described in the method for the boron ion removed in high lithium solution of the present invention and first flow～the 7th stream
The parameters such as the number of amount and adsorption column 2 are not limited to described in above-described embodiment, usually, and flow
The number of size and adsorption column 2 all can be according to the quantity of the ion exchange resin of filling in every adsorption column 2
And the concentration of the boron ion in high lithium solution is adjusted.As when the content overproof of boron ion in product feed liquid,
Then can be positioned at the number of adsorption column 2 within adsorption module 3 by increase or the numerical value of reduction first flow comes
It is adjusted.As when the pH value of test secondary eluent exceeds standard (less than 6), being then positioned at by increase
The number of the adsorption column 2 for being passed through eluting water within eluting module 5 or the numerical value of reduction the 4th flow
It is adjusted.Certainly, on the basis of above-mentioned each index can reach, take the fewest adsorption column 2
Number, the biggest flow number, to improve the adsorption efficiency of adsorption column 2 as far as possible；Meanwhile, also can save
The consumption of eluent, regenerated liquid, water etc..
Although illustrate and describing the present invention with reference to specific embodiment, but those skilled in the art will
Understand: in the case of without departing from the spirit and scope of the present invention limited by claim and equivalent thereof,
The various changes in form and details can be carried out at this.
Claims (5)
1. the method for the boron ion removed in high lithium solution, it is characterised in that described method includes step:
A, some adsorption columns are arranged on rotating disk, and filling is used for adsorbing high lithium in described some adsorption columns
The ion exchange resin of the boron ion in solution；Wherein, described high lithium solution refers to preparing lithium salts product
Lithium concentration obtained in process is not less than the mixed aqueous solution of 8g/L；
B, it is separately operable adsorption module, eluting module, regeneration module；It is positioned at the suction within described adsorption module
Attached column is adsorbed described boron ion by described high lithium solution, and obtains product feed liquid；It is positioned at described eluting module
In internal adsorption column, the described boron ion of absorption is eluted liquid eluting；It is positioned at the suction within described regeneration module
Attached column is reproduced liquid regeneration, and regains the ability adsorbing described boron ion；Wherein, described high lithium solution
Flow through that to be positioned at the flow of the adsorption column within described adsorption module be 100mL/min～120mL/min, described in wash
De-liquid stream is 8mL/min～10mL/min through being positioned at the flow of the adsorption column of described eluting inside modules, described
Regenerated liquid flows through that to be positioned at the flow of the adsorption column within described regeneration module be 8mL/min～10mL/min；
C, rotating described rotating disk after the scheduled time, described some adsorption columns pass sequentially through described adsorption module, wash
Demoulding block, regeneration module；
D, it is alternately repeated described step B and step C.
Method the most according to claim 1, it is characterised in that in described step B, also includes point
The water liftout module that Yun Hang not be located between described adsorption module and described eluting module and be located in institute
State the material top water module between regeneration module and described adsorption module；It is positioned at the suction of described water liftout inside modules
The described high lithium solution being detained in attached column is replaced by the liftout water in described water liftout module, is positioned at described material
The moisture being detained in the adsorption column of top water inside modules is replaced by described product feed liquid；Wherein, described liftout is used
It is 5mL/min～6mL/min that water flows through the flow of the adsorption column being positioned at described water liftout inside modules, described product
It is 5mL/min～6mL/min that product feed liquid flows through the flow of the adsorption column being positioned at described material top water inside modules.
Method the most according to claim 2, it is characterised in that in described step B, washes when described
After de-liquid flows through the adsorption column being positioned in described eluting module from the bottom to top, it is positioned in described eluting module
Eluting water flows through the adsorption column being positioned in described eluting module from the bottom to top；When described regenerated liquid from the bottom to top
After flowing through the adsorption column being positioned in described regeneration module, the regeneration water being positioned in described regeneration module by down to
On flow through the adsorption column being positioned in described regeneration module；Wherein, described eluting water flows through and is positioned at described eluting
The flow of the adsorption column of inside modules is 30mL/min～32mL/min, described regeneration water flow through be positioned at described
The flow of the adsorption column within regeneration module is 80mL/min～90mL/min.
4. according to the arbitrary described method of claim 1-3, it is characterised in that the described scheduled time is 50
Min～55min.
Method the most according to claim 4, it is characterised in that described eluent is that mass percent is
The aqueous hydrochloric acid solution of 7%～8%, described regenerated liquid be mass percent be the sodium hydrate aqueous solution of 6%～7%.
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| CN106629975A (en) * | 2016-12-27 | 2017-05-10 | 南京慧城水处理设备有限公司 | Method used for removing trace boron in desalination seawater with boron selective chelating resin |
| CN111041201A (en) * | 2019-12-30 | 2020-04-21 | 西安蓝晓科技新材料股份有限公司 | A new method for extracting lithium from salt lake brine |
| WO2021147573A1 (en) * | 2020-01-23 | 2021-07-29 | 西安蓝晓科技新材料股份有限公司 | New method for extracting metal nickel from laterite nickel ore leaching liquor |
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