CN116161684A - Process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing magnesium-lithium separation device - Google Patents
Process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing magnesium-lithium separation device Download PDFInfo
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- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000926 separation method Methods 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000012267 brine Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 78
- 239000012528 membrane Substances 0.000 claims abstract description 51
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 50
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 47
- 238000000909 electrodialysis Methods 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 8
- 238000005341 cation exchange Methods 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005342 ion exchange Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 56
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 7
- 239000003011 anion exchange membrane Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 90
- 238000013375 chromatographic separation Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910019400 Mg—Li Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004891 communication Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012501 chromatography medium Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing a magnesium-lithium separation device, and belongs to the technical field of extracting lithium from salt lake brine. According to the invention, the salt lake brine with high magnesium-lithium ratio after coarse filtration of particulate matters passes through a magnesium-lithium separation device to separate magnesium and lithium, so as to obtain a hydrochloric acid solution of high-purity LiCl; pumping the obtained LiCl hydrochloric acid solution into a bipolar membrane electrodialysis refined lithium system, carrying out ion exchange and transmission through a bipolar membrane and an anion-cation exchange membrane under the action of current, and finally preparing a high-purity LiOH product, wherein the generated hydrochloric acid is recycled to a magnesium-lithium separation system, so that the process self-circulation process is realized. The continuous radial countercurrent chromatographic separation technology has the advantages of simple operation, large treatment capacity and strong friendliness of high magnesium-lithium ratio; according to the invention, the bipolar membrane electrodialysis equipment is utilized to crack water, lithium hydroxide and hydrochloric acid products can be obtained simultaneously, the purity of the obtained LiOH product is more than or equal to 95%, and the problem that gas collection is needed in the traditional electrolytic method is avoided.
Description
Technical Field
The invention relates to the technical field of extracting lithium from salt lake brine, in particular to a process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing a magnesium-lithium separation device.
Background
The application field of lithium ions is widely prevalent, and the demand for lithium resources is promoted to be increased. Salt lake lithium extraction is the most important source of lithium resources accepted. China belongs to the great country of salt lake and has rich lithium resources. The lithium-containing salt lake brine in China has the characteristics of high magnesium-lithium ratio and low lithium content, has high separation difficulty, and is urgent to solve the selective separation technology of magnesium and lithium ions.
The high magnesium-lithium ratio salt lake brine has a plurality of magnesium-lithium separation and lithium extraction technologies, and each technology has advantages and disadvantages. The extraction method is commonly used for organic solvent extraction or ionic liquid extraction, and has the problems of high cost and easy environmental pollution. The adsorption method is commonly used as an adsorbent or an ion sieve, has high adsorption capacity, and has the problems of corrosion pollution caused by acid treatment and serious dissolution loss of the adsorbent. The reaction/separation coupling method is easy to introduce other impurities. Membrane processes are commonly used for nanofiltration, electrodialysis, bipolar membranes and the like, but the methods have high pretreatment requirements, the membranes are easy to pollute, and the applicability to brine with high magnesium-lithium ratio is limited. The electrochemical method comprises an ion capturing system and a rocking chair battery system, and has the problems of high energy consumption, high electrolyte requirement and high power consumption.
Therefore, how to obtain a novel separation technology which has large processing capacity, strong high magnesium-lithium ratio tolerance, simple and stable operation and environmental friendliness is a technical problem which needs to be solved at present.
Disclosure of Invention
The invention aims to provide a process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing a magnesium-lithium separation device, which is simple to operate, high in treatment capacity, high in magnesium-lithium ratio friendliness, small in environmental pollution, and capable of greatly reducing system pressure in a radial countercurrent mode, realizing self-circulation and is an efficient magnesium-lithium continuous separation and lithium refining technology.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing a magnesium-lithium separation device, wherein the magnesium-lithium separation device comprises a separation system 5, and the separation system 5 comprises N radial flow chromatographic columns 51, and the process comprises the following steps of:
1) The salt lake brine with high magnesium-lithium ratio after coarse filtration of the particulate matters enters an M radial flow chromatographic column 51 through a feed liquid conveying pipeline 1, the feed liquid is driven by a mobile phase to be separated in the radial flow chromatographic column 51, slow component magnesium solution is collected from the lower end of the A chromatographic column along the direction of the reverse mobile phase through a slow component diversion pipeline 55, fast component lithium solution is collected from the lower end of the B chromatographic column along the direction of the forward mobile phase through a fast component diversion pipeline 56, and one cycle is completed; switching a feed liquid control valve 6 to an M+1th radial flow chromatographic column, injecting sample from the upper end of the M+1th radial flow chromatographic column, simultaneously respectively switching a radial flow chromatographic column valve along the direction of a mobile phase, collecting slow components and fast components … …, and sequentially and circularly reciprocating to realize continuous separation treatment of feed liquid; the separation system adopts the principle of a simulated moving bed;
2) Carrying out bipolar membrane electrodialysis treatment on the fast component lithium solution obtained in the step 1) to obtain a LiOH product and an HCl solution, and recycling the HCl solution as a mobile phase into the step 1);
and N is 5-8, M and A, B are independent.
Further, the magnesium-lithium separation device includes: a feed liquid conveying pipeline 1, a mobile phase conveying pipeline 2, a slow component collecting pipeline 3, a fast component collecting pipeline 4 and a separation system 5; the separation system 5 comprises N radial flow chromatographic columns 51, a circulating pump 52, N feed liquid pipelines 53, N mobile phase pipelines 54, N slow component diversion pipelines 55, N fast component diversion pipelines 56 and N connecting pipelines 57; the top of each radial flow chromatographic column 51 is communicated with the feed liquid conveying pipeline 1 through a feed liquid pipeline 53 and is communicated with the mobile phase conveying pipeline 2 through a mobile phase pipeline 54; each feed liquid pipeline 53 is provided with a feed liquid control valve 6; each mobile phase pipeline 54 is provided with a mobile phase control valve 7; the bottom of each radial flow chromatographic column 51 is communicated with the slow component collecting pipeline 3 through a slow component diversion pipeline 55 and is communicated with the fast component collecting pipeline 4 through a fast component diversion pipeline 56; each slow component diversion pipeline 55 is provided with a slow component control valve 8; each fast component diversion pipeline 56 is provided with a fast component control valve 9; the bottom of the first radial flow chromatographic column 51 is in communication with the top of the second radial flow chromatographic column 51 via a connecting line 57; the bottom of the second radial flow chromatographic column 51 is in communication with the top of the third radial flow chromatographic column 51 via a connecting line 57; … …; the bottom of the N-1 radial flow chromatographic column 51 is communicated with the top of the N radial flow chromatographic column 51 through a connecting pipeline 57; the bottom of the nth radial flow chromatographic column 51 is communicated with the top of the first radial flow chromatographic column 51 through a connecting pipeline 57; a circulation pump 52 is provided on a connecting line 57 between the bottom of the nth radial flow chromatography column 51 and the top of the first radial flow chromatography column 51.
Further, the salt lake brine with high magnesium-lithium ratio is MgCl 2 And LiCl, wherein the mass ratio of Mg to Li is more than or equal to 40.
Further, the feeding flow rate of the salt lake brine with high magnesium-lithium ratio entering the radial flow chromatographic column 51 for separation treatment through the feed liquid conveying pipeline 1 is 20-30 ml/min.
Further, a mobile phase is pumped in through the mobile phase conveying pipeline 2 to drive the feed to separate in the radial flow ion exchange chromatographic column 51, wherein the mobile phase is 0.1-1.0M HCl solution, and the circulating flow rate of the mobile phase is 30-50 ml/min.
Further, the feeding temperature of the salt lake brine with high magnesium-lithium ratio is 30-60 ℃, and the separation temperature of the radial flow ion exchange chromatographic column 51 is 50-60 ℃.
Further, the slow component is MgCl 2 And HCl in a mixture; the fast component is a mixed solution of LiCl and HCl, and the content of LiCl in the fast component is more than or equal to 95wt%.
Further, the bipolar membrane electrodialysis treatment comprises:
under the action of current, the mixed solution of LiCl and HCl makes anions pass through the anion exchange membrane and enter the HCl pool to react with H generated by the bipolar membrane + The HCl solution is obtained through the action; the cations enter LiOH pool through the cation exchange membrane to react with OH generated by the bipolar membrane - And (3) obtaining the LiOH product through the action.
Further, the bipolar membrane used in the bipolar membrane electrodialysis treatment comprises a BPM-Aquivion-Durion composite bipolar membrane.
Further, the working voltage of the bipolar membrane electrodialysis treatment is 20-40V, and the working current is 20-300A.
The invention has the beneficial effects that:
1) The invention discloses a chromatographic separation mode of a magnesium-lithium separation device, which adopts a radial countercurrent design, is a continuous radial countercurrent chromatographic separation system, belongs to a novel chromatographic separation and purification technology, and adopts the working principle of the magnesium-lithium separation device: firstly, adding a magnesium-lithium mixed solution (containing MgCl) into a feed liquid storage device 2 LiCl, HCl, wherein Mg: li is 40:1), a hydrochloric acid solution is added into a mobile phase storage device, then a magnesium-lithium mixed solution and a hydrochloric acid solution are respectively conveyed into radial flow chromatographic columns 51 through a feed liquid conveying pump and a mobile phase conveying pump, the magnesium-lithium mixed solution enters from a column head, flows towards the center in the radial flow chromatographic columns 51 under the drive of the hydrochloric acid solution, flows out from the column tail, the head and the tail of 6 radial flow chromatographic columns 51 are communicated through a connecting pipeline 57, the magnesium-lithium mixed solution is driven by a circulating pump 52 to be separated in the radial flow chromatographic columns 51 under the control of a corresponding circulating valve 571, after a proper time, a fast component (LiCl hydrochloric acid solution) reaches the bottom of the 6 th radial flow chromatographic column 51, a corresponding fast component control valve 9 below the 6 th radial flow chromatographic column 51 is opened, the fast component (LiCl hydrochloric acid solution) enters a fast component collecting pipeline 4 through a fast component guide pipe 56, and therefore high-purity LiCl hydrochloric acid solution is collected, and a slow component (MgCl) 2 To the bottom of the first radial flow chromatographic column 51), the corresponding slow component control valve 8 below the first radial flow chromatographic column 51 is opened, the slow component (MgCl 2 Solution) enters the slow component collecting pipeline 3 through the slow component guide pipe 55, thereby collecting MgCl 2 And (3) hydrochloric acid solution is switched to a next chromatographic column by a feed liquid control valve 6, sampling is carried out from the column head, and the cyclic process … … is repeated to and fro in turn, so that the efficient and continuous separation of the magnesium-lithium solution can be realized. The whole device has simple structure and convenient operation, and adopts a chromatographic separation modeThe special design of radial countercurrent has the advantages of high flow speed, low operating pressure, easy linear amplification, large sample treatment capacity and the like.
2) The simulated moving bed principle adopted by the magnesium-lithium separation device is as follows: the invention is characterized in that solid filler is fixed in chromatographic columns, a plurality of chromatographic columns are connected in series, each chromatographic column is provided with a material inlet and a material outlet, and the positions of the material inlet and the material outlet are periodically changed at set time intervals along the flowing direction of a mobile phase to simulate the countercurrent flow of a stationary phase relative to the mobile phase, thereby realizing the continuous separation of components.
3) According to the magnesium-lithium separation device, the circulating pump enables solutions in the radial flow chromatographic columns connected end to circularly flow, and the radial flow chromatographic columns are combined to form a continuous radial countercurrent chromatographic system, so that efficient and continuous countercurrent separation of brine with high magnesium-lithium ratio can be realized, lithium-containing solution with high purity can be obtained, and the treatment capacity and the yield can be increased.
4) According to the invention, a magnesium-lithium separation device and a bipolar membrane electrodialysis system are coupled, lithium is separated in a large scale by utilizing the principle of simulating a moving bed in the magnesium-lithium separation device, and the separated lithium solution is refined by utilizing electrodialysis to prepare a lithium alkali product with high purity, wherein the purity of the product is more than or equal to 95%; meanwhile, the byproduct acid (HCl solution) can be pumped to the simulated moving bed in a reflux way and used as a mobile phase, so that resources are saved.
Drawings
FIG. 1 is a process flow diagram of the invention for extracting lithium from salt lake brine with high magnesium-lithium ratio;
fig. 2 is a diagram of a magnesium-lithium separation device according to the present invention, in which: 1. a feed liquid conveying pipeline; 2. a mobile phase delivery line; 3. a slow component collection line; 4. a fast component collection pipeline; 5. a separation system; 51. a radial flow chromatographic column; 52. a circulation pump; 53. a feed liquid pipeline; 54. a mobile phase pipeline; 55. a slow component diversion pipeline; 56. a fast component diversion pipeline; 57. a connecting pipeline; 571. a flow-through valve; 6. a feed liquid control valve; 7. a mobile phase control valve; 8. a slow component control valve; 9. a fast component control valve;
fig. 3 is a radial flow ion exchange chromatography diagram, in which: 10. a liquid flow direction; 11. a chromatographic column metal sleeve; 12. a cation exchange resin filler;
FIG. 4 is a schematic diagram of a bipolar membrane electrodialysis refined lithium system;
fig. 5 is a diagram of a lithium-magnesium separation device coupled bipolar membrane electrodialysis refined lithium system extraction process.
Detailed Description
The invention provides a process for extracting lithium from salt lake brine with high magnesium-lithium ratio by utilizing a magnesium-lithium separation device, wherein the magnesium-lithium separation device comprises a separation system 5, and the separation system 5 comprises N radial flow chromatographic columns 51, and the process comprises the following steps of:
1) The salt lake brine with high magnesium-lithium ratio after coarse filtration of the particulate matters enters an M radial flow chromatographic column 51 through a feed liquid conveying pipeline 1, the feed liquid is driven by a mobile phase to be separated in the radial flow chromatographic column 51, slow component magnesium solution is collected from the lower end of the A chromatographic column along the direction of the reverse mobile phase through a slow component diversion pipeline 55, fast component lithium solution is collected from the lower end of the B chromatographic column along the direction of the forward mobile phase through a fast component diversion pipeline 56, and one cycle is completed; switching a feed liquid control valve 6 to an M+1th radial flow chromatographic column, injecting sample from the upper end of the M+1th radial flow chromatographic column, simultaneously respectively switching a radial flow chromatographic column valve along the direction of a mobile phase, collecting slow components and fast components … …, and sequentially and circularly reciprocating to realize continuous separation treatment of feed liquid; the separation system adopts the principle of a simulated moving bed;
2) Carrying out bipolar membrane electrodialysis treatment on the fast component lithium solution obtained in the step 1) to obtain a LiOH product and an HCl solution, and recycling the HCl solution as a mobile phase into the step 1);
the N is 5-8, preferably 6; the M, A, B is independently preferably < N.
In the present invention, the magnesium-lithium separation device includes: a feed liquid conveying pipeline 1, a mobile phase conveying pipeline 2, a slow component collecting pipeline 3, a fast component collecting pipeline 4 and a separation system 5; the separation system 5 comprises N radial flow chromatographic columns 51, a circulating pump 52, N feed liquid pipelines 53, N mobile phase pipelines 54, N slow component diversion pipelines 55, N fast component diversion pipelines 56 and N connecting pipelines 57; the top of each radial flow chromatographic column 51 is communicated with the feed liquid conveying pipeline 1 through a feed liquid pipeline 53 and is communicated with the mobile phase conveying pipeline 2 through a mobile phase pipeline 54; each feed liquid pipeline 53 is provided with a feed liquid control valve 6; each mobile phase pipeline 54 is provided with a mobile phase control valve 7; the bottom of each radial flow chromatographic column 51 is communicated with the slow component collecting pipeline 3 through a slow component diversion pipeline 55 and is communicated with the fast component collecting pipeline 4 through a fast component diversion pipeline 56; each slow component diversion pipeline 55 is provided with a slow component control valve 8; each fast component diversion pipeline 56 is provided with a fast component control valve 9; the bottom of the first radial flow chromatographic column 51 is in communication with the top of the second radial flow chromatographic column 51 via a connecting line 57; the bottom of the second radial flow chromatographic column 51 is in communication with the top of the third radial flow chromatographic column 51 via a connecting line 57; … …; the bottom of the N-1 radial flow chromatographic column 51 is communicated with the top of the N radial flow chromatographic column 51 through a connecting pipeline 57; the bottom of the nth radial flow chromatographic column 51 is communicated with the top of the first radial flow chromatographic column 51 through a connecting pipeline 57; a circulation pump 52 is provided on a connecting line 57 between the bottom of the nth radial flow chromatography column 51 and the top of the first radial flow chromatography column 51.
In the present invention, a flow valve 571 is provided for each connection pipe 57.
In the present invention, each radial flow chromatographic column 51 is composed of a concentric cylinder of glass and a chromatographic medium interposed therebetween, and the solution enters from the top of the radial flow chromatographic column 51 and flows centripetally from the circumference to the center of the circle and then flows out from the bottom of the radial flow chromatographic column 51.
In the present invention, the packing of each radial flow chromatography column 51 is a strong acid cation exchange resin.
In the invention, a feed end of a feed liquid conveying pipeline 1 is connected with a feed liquid conveying system; the feed liquid conveying system comprises a feed liquid conveying pump and a feed liquid storage device for storing feed liquid; the feed liquid in the feed liquid storage device is input into the feed liquid conveying pipeline 1 through a feed liquid conveying pump.
In the invention, a mobile phase conveying system is connected with the feeding end of a mobile phase conveying pipeline 2; the mobile phase conveying system comprises a mobile phase conveying pump and a mobile phase storage device for storing mobile phases; the feed liquid in the mobile phase storage device is fed into the mobile phase feed line 2 by a mobile phase feed pump.
In the invention, the discharging ends of the slow component collecting pipeline 3 and the fast component collecting pipeline 4 are connected with a fast and slow component collecting system; the fast and slow component collecting system comprises a plurality of collectors and pipelines; multiple collectors facilitate separate collection of the slow component solution and the fast component solution.
In the present invention, the mobile phase of the radial flow chromatography column 51 is hydrochloric acid solution.
In the present invention, the radial flow chromatography column 51 has a diameter of 20mm and a height of 360mm.
In the invention, the flow valve 571, the feed liquid control valve 6, the mobile phase control valve 7, the slow component control valve 8 and the fast component control valve 9 are made of peek materials.
In the present invention, the number of radial flow chromatography columns 51 is 6.
In the present invention, the type of the circulation pump 52, the feed liquid transfer pump, and the mobile phase transfer pump is one of peristaltic pump or a piston pump.
In the invention, the salt lake brine with high magnesium-lithium ratio is MgCl 2 And LiCl, wherein the mass ratio of Mg to Li is not less than 40, preferably not less than 50, and more preferably not less than 60.
In the invention, the feeding flow rate of the salt lake brine with high magnesium-lithium ratio entering the radial flow chromatographic column 51 through the feed liquid conveying pipeline 1 for separation treatment is 20-30 ml/min, preferably 22-28 ml/min, and more preferably 25ml/min.
In the present invention, a mobile phase, which is 0.1 to 1.0M HCl solution, is pumped through the mobile phase transfer line 2 at the same time as the feed to separate the feed in the radial flow ion exchange chromatography column 51, and the circulation flow rate of the mobile phase is 30 to 50ml/min, preferably 35 to 45ml/min, and more preferably 40ml/min.
In the invention, the feeding temperature of the salt lake brine with high magnesium-lithium ratio is 30-60 ℃, preferably 35-55 ℃, and more preferably 45 ℃; the separation temperature of the radial flow ion exchange chromatography column 51 is 50 to 60 ℃, preferably 55 ℃.
In the present invention, the slow component is MgCl 2 And HCl in a mixture; the fast component is a mixed solution of LiCl and HCl, and the content of LiCl in the fast component is more than or equal to 95wt percent, preferably more than or equal to 98wt percent.
In the present invention, the bipolar membrane electrodialysis treatment comprises:
under the action of current, the mixed solution of LiCl and HCl makes anions pass through the anion exchange membrane and enter the HCl pool to react with H generated by the bipolar membrane + Reacting to obtain HCl solution; the cations enter LiOH pool through the cation exchange membrane to react with OH generated by the bipolar membrane - And (3) reacting to obtain a LiOH product.
In the present invention, the bipolar membrane used in the bipolar membrane electrodialysis treatment is preferably a BPM-Aquivion-Durion composite bipolar membrane.
In the invention, the working voltage of the bipolar membrane electrodialysis treatment is 20-40V, and the working current is 20-300A; preferably, the working voltage is 25-35V, and the working current is 50-250A; more preferably, the operating voltage is 30V and the operating current is 100 to 200A.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding filtered salt lake brine with high magnesium-lithium ratio (wherein the mass ratio of Mg to Li is 40:1) into a feed liquid storage device, wherein the feed flow is 25ml/min, and the feed temperature is 50 ℃; hydrochloric acid solution with the concentration of 1.0M is added into the mobile phase storage device, and the circulation flow rate of the hydrochloric acid solution is 40ml/min.
The continuous radial countercurrent chromatographic separation operation has 18 steps, the first step is double inlet and double outlet, the mixed Mg-Li solution and hydrochloric acid solution enter the system from the upper ends of the 4 th and 1 st radial chromatographic columns, and the mixed Mg-Li solution is driven by the mobile phase to perform ion separation treatment through the radial chromatographic columns at the separation temperatureThe lower ends of column 1 and column 5 respectively collect slow component (MgCl) at 55deg.C 2 Hydrochloric acid solution) and a fast component (LiCl hydrochloric acid solution), the process lasting for 200s; the second step is circulation, wherein the magnesium-lithium mixed solution circulates in the system at the stage, namely does not enter the system and does not leave the system, and the circulation time is about 600s; the third step is single inlet and single outlet, the mobile phase is fed from the upper end of the No. 2 column, and the fast component is collected at the lower end of the No. 6 column, and the duration of the process is 10s. And then the mobile phase is switched to a No. 2 column, and all the feeding and discharging ports downwards move one column, and the magnesium-lithium solution can be effectively and continuously separated by sequentially and circularly reciprocating.
The collected high-purity fast component is pumped into a bipolar membrane electrodialysis refined lithium system, and Cl in LiCl hydrochloric acid solution is treated by current (30V, 150A) - Enters an HCl reaction tank through an anion exchange membrane and is reacted with H generated by a bipolar membrane + Reacting to obtain an HCl solution, adjusting the pH value of the HCl solution, and recycling the HCl solution to the mobile phase through a circulating pump; li (Li) + Enters a LiOH reaction tank through a cation exchange membrane and reacts with OH generated by a bipolar membrane - Reacting to obtain LiOH product, the purity of LiOH is 98%
Example 2
Adding filtered salt lake brine with high magnesium-lithium ratio (wherein the mass ratio of Mg to Li is 40:1) into a feed liquid storage device, wherein the feed flow is 30ml/min, and the feed temperature is 55 ℃; a hydrochloric acid solution with the concentration of 0.8M is added into the mobile phase storage device, and the circulation flow rate of the hydrochloric acid solution is 45ml/min.
The continuous radial countercurrent chromatographic separation operation has 18 steps, the first step is double inlet and double outlet, the mixed Mg-Li solution and hydrochloric acid solution enter the system from the upper ends of the 4 th and 1 st radial chromatographic columns, the mixed Mg-Li solution is driven by the mobile phase to perform ion separation treatment through the radial chromatographic columns, the separation temperature is 60 ℃, and the lower ends of the No. 1 column and the No. 5 column respectively collect slow components (MgCl 2 Hydrochloric acid solution) and a fast component (LiCl hydrochloric acid solution), the process lasting for 200s; the second step is circulation, wherein the magnesium-lithium mixed solution circulates in the system at the stage, namely does not enter the system and does not leave the system, and the circulation time is about 600s; the third step is single in and single outThe mobile phase was fed from the upper end of column 2 and the fast component was collected at the lower end of column 6, the duration of this process being 10s. And then the mobile phase is switched to a No. 2 column, and all the feeding and discharging ports downwards move one column, and the magnesium-lithium solution can be effectively and continuously separated by sequentially and circularly reciprocating.
The collected high-purity fast component is pumped into a bipolar membrane electrodialysis refined lithium system, and Cl in LiCl hydrochloric acid solution is treated by current (40V, 300A) - Enters an HCl reaction tank through an anion exchange membrane and is reacted with H generated by a bipolar membrane + Reacting to obtain an HCl solution, adjusting the pH value of the HCl solution, and recycling the HCl solution to the mobile phase through a circulating pump; li (Li) + Enters a LiOH reaction tank through a cation exchange membrane and reacts with OH generated by a bipolar membrane - Reacting to obtain LiOH product, the purity of LiOH is 96%
Example 3
Adding filtered salt lake brine with high magnesium-lithium ratio (wherein the mass ratio of Mg to Li is 40:1) into a feed liquid storage device, wherein the feed flow is 45ml/min, and the feed temperature is 35 ℃; a hydrochloric acid solution with the concentration of 0.5M is added into the mobile phase storage device, and the circulation flow rate of the hydrochloric acid solution is 45ml/min.
The continuous radial countercurrent chromatographic separation operation has 18 steps, the first step is double inlet and double outlet, the mixed Mg-Li solution and hydrochloric acid solution enter the system from the upper ends of the 4 th and 1 st radial chromatographic columns, the mixed Mg-Li solution is driven by the mobile phase to perform ion separation treatment through the radial chromatographic columns, the separation temperature is 40 ℃, and the lower ends of the No. 1 column and the No. 5 column respectively collect slow components (MgCl 2 Hydrochloric acid solution) and a fast component (LiCl hydrochloric acid solution), the process lasting for 200s; the second step is circulation, wherein the magnesium-lithium mixed solution circulates in the system at the stage, namely does not enter the system and does not leave the system, and the circulation time is about 600s; the third step is single inlet and single outlet, the mobile phase is fed from the upper end of the No. 2 column, and the fast component is collected at the lower end of the No. 6 column, and the duration of the process is 10s. And then the mobile phase is switched to a No. 2 column, and all the feeding and discharging ports downwards move one column, and the magnesium-lithium solution can be effectively and continuously separated by sequentially and circularly reciprocating.
Will collectThe high purity fast component is pumped into bipolar membrane electrodialysis refined lithium system, and Cl in LiCl hydrochloric acid solution is treated by current (20V, 100A) - Enters an HCl reaction tank through an anion exchange membrane and is reacted with H generated by a bipolar membrane + Reacting to obtain an HCl solution, adjusting the pH value of the HCl solution, and recycling the HCl solution to the mobile phase through a circulating pump; li (Li) + Enters a LiOH reaction tank through a cation exchange membrane and reacts with OH generated by a bipolar membrane - Reacting to obtain LiOH product with purity of 95.7%
From the above examples, the present invention provides a process for extracting lithium from salt lake brine with high magnesium-lithium ratio by using a magnesium-lithium separation device. According to the magnesium-lithium separation device designed according to the simulated moving bed principle, mg and Li in salt lake brine with high magnesium-lithium ratio are effectively separated, the content of LiCl in the obtained fast component is more than or equal to 90wt%, and then the high-purity fast component is subjected to bipolar membrane electrodialysis refined lithium system to further remove Li + The product is replaced by a recyclable LiOH product, and the purity of the obtained LiOH is more than or equal to 95 percent. According to the invention, the lithium-magnesium separation device and the bipolar membrane electrodialysis refined lithium system are coupled, so that the magnesium-lithium separation efficiency is remarkably improved, the purity of LiOH products is improved, the operation is simple, the treatment capacity is large, and the pressure of the system is greatly reduced in a radial countercurrent mode, so that the method is an efficient magnesium-lithium continuous separation technology.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. Process for extracting lithium from salt lake brine with high magnesium-lithium ratio by means of a magnesium-lithium separation device comprising a separation system (5), said separation system (5) comprising N radial flow chromatographic columns (51), characterized in that it comprises the following steps:
1) Feeding salt lake brine with high magnesium-lithium ratio after coarse filtration of particulate matters into an M-th radial flow chromatographic column (51) through a feed liquid conveying pipeline (1), separating feed liquid in the radial flow chromatographic column (51) under the drive of a mobile phase, collecting a slow component magnesium solution from the lower end of the A-th radial flow chromatographic column along the direction of a reverse mobile phase through a slow component diversion pipeline (55), and collecting a fast component lithium solution from the lower end of the B-th radial flow chromatographic column along the direction of a forward mobile phase through a fast component diversion pipeline (56), thereby completing one cycle; switching a feed liquid control valve (6) to an M+1th radial flow chromatographic column, sampling from the upper end of the M+1th radial flow chromatographic column, simultaneously switching a radial flow chromatographic column valve along the direction of a mobile phase, collecting slow components and fast components … …, and sequentially and circularly reciprocating to realize continuous separation treatment of feed liquid; the separation system adopts the principle of a simulated moving bed;
2) Carrying out bipolar membrane electrodialysis treatment on the fast component lithium solution obtained in the step 1) to obtain a LiOH product and an HCl solution, and recycling the HCl solution as a mobile phase into the step 1);
and N is 5-8, M and A, B are independent.
2. The lithium extraction process according to claim 1, wherein the magnesium-lithium separation device comprises: a feed liquid conveying pipeline (1), a mobile phase conveying pipeline (2), a slow component collecting pipeline (3), a fast component collecting pipeline (4) and a separation system (5); the separation system (5) comprises N radial flow chromatographic columns (51), a circulating pump (52), N feed liquid pipelines (53), N mobile phase pipelines (54), N slow component diversion pipelines (55), N fast component diversion pipelines (56) and N connecting pipelines (57); the top of each radial flow chromatographic column (51) is communicated with the feed liquid conveying pipeline (1) through a feed liquid pipeline (53) and is communicated with the mobile phase conveying pipeline (2) through a mobile phase pipeline (54); each feed liquid pipeline (53) is provided with a feed liquid control valve (6); each mobile phase pipeline (54) is provided with a mobile phase control valve (7); the bottom of each radial flow chromatographic column (51) is communicated with the slow component collecting pipeline (3) through a slow component diversion pipeline (55) and is communicated with the fast component collecting pipeline (4) through a fast component diversion pipeline (56); each slow component diversion pipeline (55) is provided with a slow component control valve (8); each fast component diversion pipeline (56) is provided with a fast component control valve (9); the bottom of a first radial flow chromatographic column (51) is communicated with the top of a second radial flow chromatographic column (51) through a connecting pipeline (57); the bottom of a second radial flow chromatographic column (51) is communicated with the top of a third radial flow chromatographic column (51) through a connecting pipeline (57); … …; the bottom of the N-1 radial flow chromatographic column (51) is communicated with the top of the N radial flow chromatographic column (51) through a connecting pipeline (57); the bottom of the Nth radial flow chromatographic column (51) is communicated with the top of the first radial flow chromatographic column (51) through a connecting pipeline (57); a circulating pump (52) is arranged on the connecting pipeline (57) between the bottom of the Nth radial flow chromatographic column (51) and the top of the first radial flow chromatographic column (51).
3. The process for extracting lithium according to claim 1, wherein the salt lake brine with high magnesium-lithium ratio is MgCl 2 And LiCl, wherein the mass ratio of Mg to Li is more than or equal to 40.
4. The lithium extraction process according to claim 1 or 2, wherein the feed flow rate of the salt lake brine with high magnesium-lithium ratio entering the radial flow chromatographic column (51) for separation treatment through the feed liquid conveying pipeline (1) is 20-30 ml/min.
5. The process for extracting lithium according to claim 4, wherein the mobile phase is pumped through a mobile phase conveying pipeline (2) at the same time of feeding to drive the feeding to separate in a radial flow ion exchange chromatographic column (51), the mobile phase is an HCl solution with the concentration of 0.1-1.0M, and the circulation flow rate of the mobile phase is 30-50 ml/min.
6. The process for extracting lithium according to claim 5, wherein the feeding temperature of the salt lake brine with high magnesium-lithium ratio is 30-60 ℃, and the separation temperature of the radial flow ion exchange chromatographic column (51) is 50-60 ℃.
7. The process according to claim 1, 2 or 6, wherein the slow component is MgCl 2 And HCl in a mixture; the fast component is a mixed solution of LiCl and HCl, and the content of LiCl in the fast component is more than or equal to 95wt%.
8. The process for extracting lithium of claim 7, wherein the bipolar membrane electrodialysis treatment comprises:
under the action of current, the mixed solution of LiCl and HCl makes anions pass through the anion exchange membrane and enter the HCl pool to react with H generated by the bipolar membrane + The HCl solution is obtained through the action; the cations enter LiOH pool through the cation exchange membrane to react with OH generated by the bipolar membrane - And (3) obtaining the LiOH product through the action.
9. The process for extracting lithium according to claim 1 or 8, wherein the bipolar membrane used in the bipolar membrane electrodialysis treatment comprises a BPM-Aquivion-Durion composite bipolar membrane.
10. The process for extracting lithium according to claim 9, wherein the bipolar membrane electrodialysis treatment has an operating voltage of 20 to 40V and an operating current of 20 to 300A.
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| CN108341419A (en) * | 2017-01-24 | 2018-07-31 | 马培华 | The method that battery-level lithium carbonate is directly produced from salt lake brine with high magnesium-lithium ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102049195A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Ion exchange method for solid substance containing exchangeable ions |
| CN101972558A (en) * | 2010-11-30 | 2011-02-16 | 顾雄毅 | Expanded bed chromatographic separation column used for biochemical separation process and process flow |
| CN104447909A (en) * | 2014-10-28 | 2015-03-25 | 无锡济民可信山禾药业股份有限公司 | Continuous-chromatography separating and purifying method of etimicin sulfate |
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