CN115537581A - Combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device and use method thereof - Google Patents
Combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device and use method thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 111
- 239000012267 brine Substances 0.000 title claims abstract description 104
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 104
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000000605 extraction Methods 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 140
- 238000001728 nano-filtration Methods 0.000 claims abstract description 93
- 238000004821 distillation Methods 0.000 claims abstract description 73
- 239000012530 fluid Substances 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 45
- 230000000149 penetrating effect Effects 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 31
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 239000000498 cooling water Substances 0.000 claims abstract description 16
- 239000012466 permeate Substances 0.000 claims abstract description 14
- 239000012141 concentrate Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 13
- 239000012982 microporous membrane Substances 0.000 claims description 13
- 230000003075 superhydrophobic effect Effects 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 230000004907 flux Effects 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000000523 sample Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 239000012612 commercial material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
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- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 102000015863 Nuclear Factor 90 Proteins Human genes 0.000 description 2
- 108010010424 Nuclear Factor 90 Proteins Proteins 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
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Abstract
The invention discloses a combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device and a use method thereof. The ultrasonic-nanofiltration-membrane distillation combined device comprises an ultrasonic-nanofiltration combined system, an ultrasonic-membrane distillation combined system, a raw material liquid tank, a cooler, a cooling tank, a permeate liquid tank, a concentrate liquid tank, an electronic balance and conductivity measuring equipment. In the process, the raw material liquid is subjected to the ultrasonic enhanced nanofiltration effect in an ultrasonic-nanofiltration combined system to obtain a concentrated solution and a penetrating fluid; and the moisture of the penetrating fluid is in the form of water vapor and is led into a cooling tank by cooling water at the cold side end of the ultrasonic-membrane distillation combined system for circulation, and lithium is enriched at the hot side end. The invention firstly adopts an ultrasonic combined enhanced nanofiltration separation process and a membrane distillation enrichment process, and aims at solving the problems of difficult lithium resource collection, low yield, environmental pollution and the like, so as to achieve the purpose of effectively separating and purifying the salt lake brine with high magnesium-lithium ratio and realize high-efficiency lithium resource production.
Description
Technical Field
The invention belongs to the technical field of lithium extraction from salt lake brine, further belongs to the technical field of combined strengthening of lithium extraction from salt lake brine with a high magnesium-lithium ratio, and particularly relates to a combined strengthening device for lithium extraction from salt lake brine with a high magnesium-lithium ratio and a use method thereof.
Background
According to data, the total amount of lithium resources is found to be 510 ten thousand tons at present in China, wherein the salt lake type lithium resources account for 69 percent of lithium reserves and 87 percent of basic reserves and become a main source for extracting lithium. Through comparative analysis on the components of valuable brine in the world, the salt lake brine in China mostly belongs to a chloride type and a magnesium sulfate subtype, and has the characteristics of high magnesium-lithium ratio and low lithium content.
With the high-speed development of economy, the continuous promotion of urbanization and industrialization processes in China, on one hand, the demand of lithium is rapidly increased, on the other hand, the industrial pollution is increasingly serious, and in addition, the current situation of brine in China is combined, the contradiction of lithium resource shortage is aggravated. Therefore, the salt lake brine with high magnesium-lithium ratio is treated, the utilization rate of lithium resources is improved, and the sustainable development strategy of China is facilitated.
At present, the realization of magnesium-lithium separation and lithium enrichment is an important process for treating salt lake brine. Among them, nanofiltration and membrane distillation are emerging lithium extraction technologies in membrane separation processes. The membrane surface of the nanofiltration technology has the combined effect of south-south resistance, steric hindrance and dielectric, monovalent/multivalent ions are effectively screened, and the separation of ions with different valence states in brine is realized under the condition of not introducing other solvents. The membrane distillation technology is used for separating a solution containing non-volatile solutes through a super-hydrophobic membrane, so that 100% of brine can be trapped to allow water vapor to achieve the purpose of concentration, and the technology is favorable for enriching lithium in the brine.
According to the research at home and abroad, when the nanofiltration membrane is used for separating salt lake brine with high magnesium-lithium ratio, a concentration polarization layer is easy to generate on the membrane surface, so that membrane hole blockage and membrane pollution are caused, the separation efficiency is reduced, and the recovery ratio of lithium is influenced; although the membrane distillation has a better application prospect in the aspect of replacing the traditional membrane concentration, the problems of low flux, slow water gasification, easy crystallization of the membrane surface after long-time operation and the like exist, the membrane distillation effect is seriously influenced, and the enrichment efficiency is reduced.
Therefore, when the nanofiltration membrane is used for separating salt lake brine with high magnesium-lithium ratio, a concentration polarization layer is easily generated on the membrane surface, membrane hole blockage and membrane pollution are caused, the separation efficiency is reduced, and the recovery ratio of lithium is influenced; although the membrane distillation has a good application prospect in the aspect of replacing the traditional membrane concentration, the technical defects that the flux is low, the water gasification is slow, the surface of a membrane is easy to crystallize after long-time operation and the like exist, the membrane distillation effect is seriously influenced, and the enrichment efficiency is reduced are solved.
Disclosure of Invention
The invention aims to provide a combined strengthening device for extracting lithium from salt lake brine with high magnesium-lithium ratio;
the second purpose of the invention is to provide a use method of the combined strengthening high magnesium-lithium ratio salt lake brine lithium extraction device;
the first object of the present invention is achieved by: the device consists of an ultrasonic nanofiltration combined system and an ultrasonic membrane distillation combined system;
the ultrasonic nanofiltration combined system is formed by connecting a raw material tank, a first pressure pump, an inlet flowmeter, an inlet pressure gauge, a nanofiltration assembly, an outlet pressure gauge, a first outlet control valve, a concentrated liquid tank, an electronic balance, conductivity measurement equipment, a first ultrasonic control panel and a first ultrasonic generator;
the ultrasonic membrane distillation combined system is formed by connecting a enrichment liquid tank, a second outlet control valve, a thermometer, a membrane distillation assembly, a second pressure pump, a cooling system, a thermometer, conductivity measuring equipment, an electronic balance, a second ultrasonic control panel and a second ultrasonic generator in sequence.
The second object of the present invention is achieved by: the method comprises the following steps:
feeding the proportioned raw material brine into a raw material barrel, pumping the proportioned raw material brine into a high-pressure side of an ultrasonic nanofiltration combined system by a first pressure pump, applying pressure on two sides of a nanofiltration membrane to form a pressure difference, and starting ultrasonic waves;
a large amount of lithium ions and partial water in the raw material brine are transferred from a high-pressure side to a low-pressure side through a nanofiltration membrane under the action of ultrasonic cavitation to form a lithium-rich penetrating fluid, a valve penetrating fluid is opened to enter a penetrating fluid tank, mass difference is obtained through an electronic balance, penetrating flux is calculated, and the conductivity change of the brine is monitored in real time in a conductivity measuring device;
the solution remaining on the high pressure side becomes a lithium-depleted concentrate rich in magnesium, borate, sulfate and other ions; pumping the lithium-rich penetrating fluid into the high-pressure side of the ultrasonic membrane distillation combined system through a second pressure pump, forming pressure difference on two sides of the super-hydrophobic membrane, and starting ultrasonic waves;
monitoring temperature change in real time from a thermometer and regulating and controlling in time, evaporating partial water of the lithium-rich penetrating fluid into water vapor under the action of energy of ultrasonic waves, transferring the water vapor from the high-pressure side to the low-pressure side of the hydrophobic membrane, condensing the water vapor by cooling water, then bringing the condensed water into a cooling tank for circulation, calculating flux through mass difference of an electronic balance, and monitoring conductivity change in real time by using conductivity measuring equipment;
enriching lithium in the rest solution at a high pressure side, opening a second outlet control valve to collect the enriched solution into an enriched solution tank or closing a valve to return to a raw material tank for circulation; opening an outlet control valve, and obtaining penetrating fluid from a penetrating fluid tank or obtaining enriched liquid from an enriched fluid tank to measure the content of each ion in the brine;
the lithium-containing brine comprises chlorinated salt lake brine, sulfuric acid salt lake brine and lithium-containing old brine obtained by extracting potassium from the chlorinated salt lake brine and then evaporating; mg in salt lake brine 2+ With Li + The mass ratio of (1) to (180) is 40 + The concentration is 5.3X 10 -3 ～8.5×10 -3 g/L；
The pressure difference applied to the two sides of the membrane in the ultrasonic nanofiltration combined system and the ultrasonic membrane distillation system is 2-5 bar; the temperature of the lithium-containing raw material brine of the ultrasonic nanofiltration combined system is 0-20 ℃, and the pH value is 5.5-8; the ultrasonic power is adjusted to 35khz, the temperature is adjusted to 80 ℃, the temperature of the ultrasonic-membrane distillation combined system is controlled to be 60-80 ℃, and the pH value is 5.5-8;
the nanofiltration membrane is a monovalent ion selective nanofiltration membrane, and the material is selected from at least one of cellulose acetate and derivatives thereof, aromatic polyamide, polyimide and sulfonated polyfurfuryl; the membrane distillation is a hydrophobic microporous membrane, and the commonly used commercial material is at least one selected from polyvinylidene fluoride, polytetrafluoroethylene, polypropylene and polyvinyl chloride.
The method is more suitable for extracting lithium from the salt lake brine with high magnesium-lithium ratio by adopting a novel reaction/separation coupling technology. The device comprises three parts of a nanofiltration technology which is coupled and driven by pressure, a membrane distillation technology which is driven by vapor pressure difference and an ultrasonic technology which generates cavitation. The ultrasonic technology is used as auxiliary mass transfer equipment for extracting lithium in salt lake: in an ultrasonic-nanofiltration combined system, the micro-jet flow generated by ultrasonic technology can weaken the concentration polarization phenomenon, reduce membrane pollution and achieve the aim of effectively strengthening the magnesium-lithium separation in the nanofiltration process; in the ultrasonic-membrane distillation combined system, ultrasonic waves enhance ion diffusion and increase water vapor generation by strengthening mass transfer and heat transfer processes between membrane interfaces, so that the aim of lithium enrichment in the membrane distillation process is fulfilled, and the lithium resource recovery efficiency is improved. That is to say, the device and the using method thereof have the advantages of simple and reasonable process flow, reliable operation and low energy consumption.
Drawings
FIG. 1 is a schematic structural diagram of a combined reinforced high Mg/Li ratio lithium extraction device for salt lake brine according to the present invention;
FIG. 2 is a schematic cross-sectional view of a nanofiltration module of an ultrasonic-nanofiltration combined system of a combined enhanced lithium extraction device for salt lake brine with high Mg/Li ratio according to the present invention;
FIG. 3 is a schematic cross-sectional view of a membrane distillation assembly of an ultrasonic-membrane distillation combined system of a combined enhanced high Mg/Li ratio salt lake brine lithium extraction device according to the present invention;
FIG. 4 is a schematic flow chart of a method for using the combined enhanced high magnesium-lithium ratio salt lake brine lithium extraction device of the present invention;
in the figure: 1-a raw material tank, 2-a pressure pump, 201-a first pressure pump; 202-a second pressure pump; 3-ultrasonic operation warning lamp, 4-power adjusting knob, 5-ultrasonic power button, 6-temperature display instrument, 7-inlet flowmeter, 8-inlet pressure gauge, 9-ultrasonic-membrane distillation combined system, 10-outlet control valve, 101-first outlet control valve; 102-a second outlet control valve; 11-concentrated liquid tank, 12-electronic balance, 13-conductivity measuring equipment, 14-cavity, 15-cooler, 16-ultrasonic-nanofiltration combined system, 17-thermometer, 18-cooling tank, 19-concentrated liquid tank, 20-concentrated liquid outlet, 21-vapor condensate outlet, 22-penetrating liquid inlet, 23-super-hydrophobic microporous membrane, 24-cooling water inlet, 25-concentrated liquid outlet, 26-penetrating liquid outlet, 27-raw material liquid inlet, 28-nanofiltration membrane, 29-heat insulation layer, 30-exhaust outlet, 31-magnetron, 32-cooling water fluid domain cavity, 33-concentrated liquid fluid domain cavity, 34-penetrating liquid fluid domain cavity, 35-concentrated liquid fluid domain cavity, 36-ultrasonic probe, 37-amplitude transformer, 38-transducer and 39-outlet pressure gauge.
Detailed Description
The invention is further illustrated in the following figures and examples in order to provide the person skilled in the art with a detailed understanding of the invention, without restricting it in any way. Any variations or modifications made in accordance with the teachings of the present invention are intended to be within the scope of the present invention.
The invention is further elucidated below with reference to the drawing.
As shown in fig. 1-3, the invention provides a combined enhanced high magnesium-lithium ratio salt lake brine lithium extraction device, which consists of an ultrasonic nanofiltration combined system and an ultrasonic membrane distillation combined system;
the ultrasonic nanofiltration combined system is formed by connecting a raw material tank, a first pressure pump, an inlet flowmeter, an inlet pressure gauge, a nanofiltration component, an outlet pressure gauge, a first outlet control valve, a concentrated liquid tank, an electronic balance, conductivity measuring equipment, a first ultrasonic control panel and a first ultrasonic generator;
the ultrasonic membrane distillation combined system is formed by connecting a enrichment liquid tank, a second outlet control valve, a thermometer, a membrane distillation assembly, a second pressure pump, a cooling system, a thermometer, conductivity measuring equipment, an electronic balance, a second ultrasonic control panel and a second ultrasonic generator in sequence.
The nanofiltration component consists of a nanofiltration membrane in the middle, a penetrating fluid domain cavity, a concentrated solution fluid domain cavity, a penetrating fluid outlet, a raw material liquid inlet and a concentrated solution outlet;
the penetrating fluid domain cavity is positioned at the upper part of the nanofiltration membrane; the concentrated solution fluid domain cavity is positioned at the lower part of the nanofiltration membrane.
The membrane distillation assembly consists of a super-hydrophobic microporous membrane in the middle, an enriched liquid fluid domain cavity, a cooling water inlet, a steam condensate outlet, a penetrating fluid inlet and an enriched liquid outlet;
the enrichment liquid fluid domain cavity is positioned on the upper part of the super-hydrophobic microporous membrane; the cooling water fluid domain cavity is positioned at the lower part of the super-hydrophobic microporous membrane.
The cooling system is composed of a cooling tank and a cooler which are connected with at least two sides of the ultrasonic membrane distillation combined system.
The first ultrasonic control panel and the second ultrasonic control panel have the same structure; the first ultrasonic generator and the second ultrasonic generator have the same structure.
The surface of the first ultrasonic control panel or the surface of the second ultrasonic control panel are respectively provided with an ultrasonic power supply button, a temperature display instrument, a power adjusting knob and an ultrasonic operation warning lamp.
The first ultrasonic generator or the second ultrasonic generator is formed by connecting an energy converter, an amplitude transformer and an ultrasonic probe in sequence.
A first ultrasonic reaction cavity is arranged in the ultrasonic nanofiltration combined system; the ultrasonic membrane distillation combined system is provided with a second ultrasonic reaction cavity;
the first ultrasonic reaction cavity and the second ultrasonic reaction cavity have the same structure.
The first ultrasonic reaction cavity or the second ultrasonic reaction cavity consists of a cavity, an air outlet, a heat insulation layer and a magnetron; the heat insulation layer is located inside the cavity, the magnetrons are uniformly distributed outside the cavity, and the air outlet penetrates through the inside of the magnetrons.
In order to achieve the purpose of the scheme of the invention, as shown in fig. 4, a method for using a combined enhanced high magnesium-lithium ratio salt lake brine lithium extraction device is also provided, and the method comprises the following steps:
feeding the proportioned raw material brine into a raw material barrel, pumping the proportioned raw material brine into a high-pressure side of an ultrasonic nanofiltration combined system by a first pressure pump, applying pressure on two sides of a nanofiltration membrane to form a pressure difference, and starting ultrasonic waves;
a large amount of lithium ions and part of water in the raw material brine are transferred from a high-pressure side to a low-pressure side through a nanofiltration membrane under the action of ultrasonic cavitation to form a lithium-rich penetrating fluid, the penetrating fluid enters a penetrating fluid tank by opening a valve, the penetrating fluid is subjected to mass difference calculation and penetrates through a flux, and the conductivity change of the brine is monitored in real time in a conductivity measuring device;
the solution remaining on the high pressure side becomes a lithium-depleted concentrate rich in magnesium, borate, sulfate and other ions; pumping the lithium-rich penetrating fluid into the high-pressure side of the ultrasonic membrane distillation combined system through a second pressure pump, forming pressure difference on two sides of the super-hydrophobic membrane, and starting ultrasonic waves;
monitoring temperature change in real time from a thermometer and regulating and controlling in time, evaporating partial water of the lithium-rich penetrating fluid into water vapor under the action of energy of ultrasonic waves, transferring the water vapor from the high-pressure side to the low-pressure side of the hydrophobic membrane, condensing the water vapor by cooling water, then bringing the condensed water into a cooling tank for circulation, calculating flux through mass difference of an electronic balance, and monitoring conductivity change in real time by using conductivity measuring equipment;
enriching lithium in the rest solution at a high pressure side, opening a second outlet control valve to collect the enriched solution into an enriched solution tank or closing a valve to return to a raw material tank for circulation; opening an outlet control valve, and obtaining penetrating fluid from a penetrating fluid tank or obtaining enriched fluid from an enriched fluid tank to measure the content of each ion in the brine;
the lithium-containing brine comprises chlorinated salt lake brine, sulfate salt lake brine and lithium-containing old brine obtained by extracting potassium from the chlorinated salt lake brine and then evaporating; mg in salt lake brine 2+ With Li + The mass ratio of (1) to (180) is 40 + The concentration is 5.3X 10 -3 ～8.5×10 -3 g/L；
The pressure difference applied to the two sides of the membrane in the ultrasonic nanofiltration combined system and the ultrasonic membrane distillation system is 2-5 bar; the temperature of the lithium-containing raw material brine of the ultrasonic nanofiltration combined system is 0-20 ℃, and the pH value is 5.5-8; the ultrasonic power is adjusted to 35khz, the temperature is adjusted to 80 ℃, the temperature of the ultrasonic-membrane distillation combined system is controlled to be 60-80 ℃, and the pH value is 5.5-8;
the nanofiltration membrane is a monovalent ion selective nanofiltration membrane, and the material is selected from at least one of cellulose acetate and derivatives thereof, aromatic polyamide, polyimide and sulfonated polyaluminium sulfate; the membrane distillation is a hydrophobic microporous membrane, and the commonly used commercial material is at least one selected from polyvinylidene fluoride, polytetrafluoroethylene, polypropylene and polyvinyl chloride.
Specifically, in the embodiment of the invention, an ultrasonic-nanofiltration-membrane distillation combined enhanced device for extracting lithium from salt lake brine with high magnesium-lithium ratio and a use method thereof comprise an ultrasonic-nanofiltration combined system 16 and an ultrasonic-membrane distillation combined system 9, wherein the ultrasonic-nanofiltration combined system mainly comprises a nanofiltration component, a raw material tank 1, a first pressure pump 201, an inlet flowmeter 7, an inlet pressure gauge 8, an outlet pressure gauge 39, a first outlet control valve 101, a concentrated liquid tank 11, an electronic balance 12, a conductivity measuring device 13, an ultrasonic control panel and an ultrasonic generator, and the nanofiltration component comprises a nanofiltration membrane 28, a permeate fluid domain cavity 34, a concentrated liquid fluid domain cavity 33, a permeate outlet 26, a raw material liquid inlet 27 and a concentrated liquid outlet 25 in the middle of the component. The ultrasonic control panel comprises an ultrasonic power supply button 5, a temperature display instrument 6, a power adjusting knob 4 and an ultrasonic operation warning lamp 3 which are arranged on the surface, the ultrasonic reaction cavity comprises a cavity 14, an air outlet 30, a heat insulation layer 29 and a magnetron 31, the heat insulation layer is positioned in the cavity, the magnetron is uniformly distributed outside the cavity, and the air outlet penetrates through the inside of the magnetron and is arranged on the cavity; the ultrasonic generator is sequentially connected with the transducer 38, the amplitude transformer 37 and the ultrasonic probe 36; the ultrasonic-membrane distillation combined system mainly comprises a membrane distillation assembly, an enrichment liquid tank 19, a second pressure pump 202, a thermometer 17, a second outlet control valve 102, a cooling system, an electronic balance 12, a conductivity measuring device 13, an ultrasonic control panel and an ultrasonic generator, wherein the membrane distillation assembly comprises a super-hydrophobic microporous membrane 23 in the middle of the assembly, an enrichment liquid fluid domain cavity 35, a cooling water fluid domain cavity 32, a cooling water inlet 24, a water vapor condensate outlet 21, a penetrating fluid inlet 22 and an enrichment liquid outlet 20, the cooling system comprises a cooling tank 18 and a cooler 15, and the ultrasonic control panel and the ultrasonic generator of the ultrasonic-membrane distillation combined system are the same as those of the ultrasonic control panel and the ultrasonic generator of the ultrasonic-nanofiltration combined system.
The ultrasonic-nanofiltration combined system 16 is connected with a penetrating fluid inlet and outlet pipeline interface of the ultrasonic-membrane distillation combined system 9 in a series connection mode; the pipeline interfaces on the surface of the magnetron 31 are connected in series.
Namely, the invention provides a device for enhancing the lithium extraction of salt lake brine with high magnesium-lithium ratio by combining ultrasonic-nanofiltration-membrane distillation. The device adopts unconventional metallurgy strengthening means (ultrasonic metallurgy) to strengthen the magnesium-lithium separation in the nanofiltration process and the lithium enrichment in the membrane distillation process so as to achieve the aim of quickly and efficiently extracting lithium, and has the characteristics of simple process flow, reliable operation, low energy consumption, good quality of prepared final products, namely lithium carbonate and lithium chloride, lower cost and environmental friendliness.
An ultrasonic-nanofiltration-membrane distillation combined enhanced device for extracting lithium from salt lake brine with a high magnesium-lithium ratio comprises an ultrasonic-nanofiltration combined system 16 and an ultrasonic-membrane distillation combined system 9, wherein the ultrasonic-nanofiltration combined system mainly comprises a nanofiltration component, a raw material tank 1, a first pressure pump 201, an inlet flowmeter 7, an inlet pressure gauge 8, an outlet pressure gauge 39, a first outlet control valve 101, a concentrated liquid tank 11, an electronic balance 12, a conductivity measurement device 13, an ultrasonic control panel and an ultrasonic generator, and the nanofiltration component comprises a nanofiltration membrane 28 in the middle of the component, a permeate fluid domain cavity 34, a concentrated liquid domain cavity 33, a permeate outlet 26, a raw material liquid inlet 27 and a concentrated liquid outlet 25. The ultrasonic control panel comprises an ultrasonic power supply button 5, a temperature display instrument 6, a power adjusting knob 4 and an ultrasonic operation warning lamp 3 which are arranged on the surface, the ultrasonic reaction cavity comprises a cavity 14, an air outlet 30, a heat insulation layer 29 and a magnetron 31, the heat insulation layer 29 is positioned in the cavity, the magnetron is uniformly distributed outside the cavity, and the air outlet penetrates through the inside of the magnetron and is arranged on the cavity; the ultrasonic generator comprises a transducer 38, a horn 37 and an ultrasonic probe 36; the ultrasonic-membrane distillation combined system mainly comprises a membrane distillation assembly, an enrichment liquid tank 19, a second pressure pump 202, a thermometer 17, a second outlet control valve 102, a cooling system, a conductivity measuring device 13, an electronic balance 12, an ultrasonic control panel and an ultrasonic generator, wherein the membrane distillation assembly comprises a super-hydrophobic microporous membrane 23 in the middle of the assembly, an enrichment liquid fluid domain cavity 35, a cooling water fluid domain cavity 32, a cooling water inlet 24, a water vapor condensate outlet 21, a penetrating fluid inlet 22 and an enrichment liquid outlet 20, the cooling system comprises a cooling tank 18 and a cooler 15, and the ultrasonic control panel and the ultrasonic generator of the ultrasonic-membrane distillation combined system are the same as those of the ultrasonic control panel and the ultrasonic generator of the ultrasonic-nanofiltration combined system.
The ultrasonic-nanofiltration combined system 16 is connected with the pipeline interface of the penetrating fluid inlet and outlet of the ultrasonic-membrane distillation combined system 9 in a series connection mode, and the pipeline interface on the surface of the magnetron 31 is connected in a series connection mode.
The application method of the ultrasonic-nanofiltration-membrane distillation combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device comprises the following steps: the proportioned raw material brine is sent into a raw material barrel 1, is pumped into the high-pressure side of an ultrasonic-nanofiltration combined system 9 by a pressure pump 2, pressure is applied to the two sides of a nanofiltration membrane 28 to form a pressure difference, and ultrasonic waves are started. A large amount of lithium ions and part of water in raw material brine are transferred from a high-pressure side to a low-pressure side through a nanofiltration membrane under the action of ultrasonic cavitation to form lithium-rich permeate, the valve permeate is opened and enters a permeate tank 11, the mass difference is obtained through an electronic balance 12, the permeate flux is calculated, and the conductivity change of the brine is monitored in real time in a conductivity measuring device 13. The solution remaining on the high pressure side becomes a lithium-depleted concentrate rich in magnesium, borate, sulfate, and other ions. The lithium-rich penetrating fluid is pumped into the high-pressure side of the ultrasonic-membrane distillation combined system 16 through a pressure pump, a pressure difference is formed between two sides of the super-hydrophobic membrane 23, ultrasonic waves are started, and temperature change is monitored in real time from the thermometer 17 and is regulated and controlled in time. Part of the lithium-rich penetrating fluid water is evaporated into water vapor under the action of the energy of ultrasonic waves, the water vapor is transferred from the high-pressure side to the low-pressure side of the hydrophobic membrane, the water vapor is condensed by cooling water and then is brought into a cooling tank 18 for circulation, the flux is calculated through the mass difference of an electronic balance 12, and the change of the conductivity is monitored in real time by a conductivity measuring device 13. The remaining part of the solution is enriched in lithium on the high pressure side, and the outlet control valve 10 is opened to collect the enriched liquid into the enriched liquid tank 19 or closed to circulate back to the raw material tank 1. The outlet control valve is opened, and the permeate liquid is taken from the permeate liquid tank 11 and the enriched liquid is taken from the enriched liquid tank 19 to measure the content of each ion in the brine.
The lithium-containing brine comprises chlorinated salt lake brine, sulfuric acid salt lake brine and lithium-containing old brine obtained by extracting potassium from the chlorinated salt lake brine and then evaporating; mg in salt lake brine 2+ With Li + The mass ratio of (1) to (180) is 40 + The concentration is 5.3X 10 -3 ～8.5×10 -3 g/L。
The pressure difference applied to two sides of the membrane in the ultrasonic-nanofiltration combined system and the ultrasonic-membrane distillation system is 2-5 bar; the temperature of the lithium-containing raw material brine of the ultrasonic-nanofiltration combined system is 0-20 ℃, and the pH value is 5.5-8; the ultrasonic power is adjusted to 35khz, the temperature is adjusted to 80 ℃, the temperature of the ultrasonic-membrane distillation combined system is controlled to be 60-80 ℃, and the pH value is 5.5-8.
The nanofiltration membrane is a monovalent ion selective nanofiltration membrane, and the material is selected from at least one of cellulose acetate and derivatives thereof, aromatic polyamide, polyimide and sulfonated polyfurfuryl; the membrane distillation is a hydrophobic microporous membrane, and the commonly used commercial material is at least one selected from polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polypropylene (PP) and polyvinyl chloride (PVC).
By adopting the ultrasonic-nanofiltration-membrane distillation combined lithium extraction technology, the method greatly improves the enrichment degree of lithium and ensures the yield of lithium.
The ultrasonic-nanofiltration combined separation technology provided by the method can also efficiently intercept divalent metal ions existing in brine.
The invention relates to a device for enhancing lithium extraction from salt lake brine with high magnesium-lithium ratio by combining ultrasonic, nanofiltration and membrane distillation and a using method thereof. The ultrasonic-nanofiltration-membrane distillation combined device comprises an ultrasonic-nanofiltration combined system, an ultrasonic-membrane distillation combined system, a raw material liquid tank, a cooler, a cooling tank, a permeating liquid tank, a concentrated liquid tank, an electronic balance and conductivity measuring equipment. In the process, the raw material liquid is subjected to the ultrasonic enhanced nanofiltration effect in an ultrasonic-nanofiltration combined system to obtain a concentrated solution and a penetrating fluid; the moisture of the penetrating fluid is taken into a cooling tank by cooling water for circulation at the cold side end of the ultrasonic-membrane distillation combined system in the form of water vapor, and lithium is enriched at the hot side end. The invention firstly adopts an ultrasonic combined enhanced nanofiltration separation process and a membrane distillation enrichment process, and aims at solving the problems of difficult lithium resource collection, low yield, environmental pollution and the like, so as to achieve the purpose of effectively separating and purifying the salt lake brine with high magnesium-lithium ratio and realize high-efficiency lithium resource production.
The first embodiment is as follows:
this example illustrates the separation effect of a nanofiltration device.
Under the premise of not adding ultrasonic action, a NF90 nanofiltration membrane is used for separating the salt lake brine, and the effective membrane area of the membrane is 24cm 2 . The nano filter is composed of a membrane component, a raw water pump, a high-pressure pump, a raw water tank, a water production tank and the like. Lithium is contained by 5.31X 10 -3 g/L, magnesium 225X 10 -3 g/L, 5.69X 10 of calcium -3 g/L and chlorine 115X 10 -3 And (3) pumping raw material brine with the concentration of g/L and the pH =5.5 into a raw water tank, and separating the raw material brine at the temperature of 18-20 ℃ and under the pressure difference of 5 bar. The separation operation is intermittent circulation operation, namely, concentrated solution at an outlet returns to a stock solution tank for circulation. After 3 hours sampling analysis, the composition of each feed liquid is shown in table 1:
TABLE 1 concentration of each feed liquid composition after separation in the nanofiltration device
It can be seen that the retention rate of magnesium ions is more than 85% after the separation by the nanofiltration method, the mass ratio of magnesium to lithium is reduced from 42.37 in the raw material brine to 4.16 in the produced water, and the ratio is suitable for refining the obtained lithium-rich brine by an alkaline method and preparing lithium carbonate. Apparent separation coefficient of magnesium and lithium of the process is
. Therefore, the nanofiltration method has high-efficiency removal effect on divalent ions in the brine, and is beneficial to refining the lithium-rich brine.
The meanings and formulae for the parameters are explained below:
film pair Mg 2+ With Li + Apparent separation coefficient of (2):
；
wherein subscripts C and P represent a concentrate and a product obtained by nanofiltration, respectively.
The second embodiment:
this example illustrates the separation effect of the combined ultrasound-nanofiltration.
Under the premise of adding ultrasonic action, a NF90 nanofiltration membrane is used for separating the salt lake brine, and the effective membrane area of the membrane is 24cm 2 The ultrasound was adjusted to 35khz. The nano filter is composed of a membrane component, an ultrasonic device, a raw water pump, a high-pressure pump, a raw water tank, a water production tank and the like. Lithium is 5.31 x 10 -3 g/L, magnesium 225X 10 -3 g/L, 5.69X 10 of calcium -3 g/L and chlorine 115X 10 -3 And (3) pumping raw material brine with the concentration of g/L and the pH =5.5 into a raw water tank, and separating the raw material brine at the temperature of 18-20 ℃ and under the pressure difference of 5 bar. The separation operation is intermittent circulation operation, namely, concentrated solution at an outlet returns to a stock solution tank for circulation. After 3 hours sampling analysis, the composition of each feed liquid is shown in table 2:
TABLE 2 composition concentration of each feed liquid after separation in ultrasonic-nanofiltration combination system
It can be seen that, compared with the first embodiment, the magnesium content in the produced water is greatly reduced through the combined action of the ultrasonic and nanofiltration, the lithium content is enriched, and simultaneously, the divalent ions are almost completely intercepted; the retention rate of magnesium ions reaches more than 90 percent, and the mass ratio of magnesium to lithium is reduced from 42.37 in raw material brine to 3.78 in produced water. Apparent separation coefficient of magnesium and lithium of the process is
. Therefore, the method enhances the diffusion performance of the membrane to ions in brine and improves the utilization rate of raw materials.
Example three:
this example illustrates the enrichment effect of the combined ultrasound-membrane distillation.
Under the action of ultrasonic wave, super-hydrophobicThe membrane is used for enriching the salt lake brine, and the effective membrane area of the membrane is 20cm 2 And heating the first-stage enrichment liquid in a heater to 40-60 ℃. The ultrasonic sound was adjusted to 35khz and the temperature was adjusted to 80 ℃. The nano filter consists of a membrane component, an ultrasonic device, a raw water pump, a high-pressure pump, a cooling tank, a heater, a water production tank and the like. Lithium is added to 9.5X 10 -3 g/L, magnesium 20.43X 10 -3 g/L, calcium 0.28X 10 -3 g/L and chlorine 84.56X 10 -3 And g/L and pH =6 of the primary enrichment solution is added into the combined assembly, and the secondary enrichment is carried out on the primary enrichment solution under the pressure difference of 5 bar. After 3 hours sampling analysis, the composition of each feed was as shown in table 3:
TABLE 3 composition concentration of each feed liquid after enrichment by ultrasonic-membrane distillation combined system
In conclusion, compared with the first and second embodiments, the brine solution enriched by the combined action of ultrasonic and membrane distillation carries away the water vapor in the primary enrichment solution, so that the lithium ions are concentrated to a greater extent, the concentration of the lithium ions is increased to be 3.5 times of the original concentration, and the content of lithium in the primary enrichment solution is increased, so that the concentration and the relative content of the lithium-rich product solution are more suitable for alkaline refining and lithium carbonate preparation.
Claims (10)
1. A combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device is characterized in that the device consists of an ultrasonic nanofiltration combined system and an ultrasonic membrane distillation combined system;
the ultrasonic nanofiltration combined system is formed by connecting a raw material tank, a first pressure pump, an inlet flowmeter, an inlet pressure gauge, a nanofiltration component, an outlet pressure gauge, a first outlet control valve, a concentrated liquid tank, an electronic balance, conductivity measuring equipment, a first ultrasonic control panel and a first ultrasonic generator;
the ultrasonic membrane distillation combined system is formed by connecting a enrichment liquid tank, a second outlet control valve, a thermometer, a membrane distillation assembly, a second pressure pump, a cooling system, a thermometer, conductivity measuring equipment, an electronic balance, a second ultrasonic control panel and a second ultrasonic generator in sequence.
2. The combined enhanced high magnesium-lithium ratio lithium extraction device from salt lake brine as claimed in claim 1, wherein the nanofiltration component comprises a nanofiltration membrane at the middle part, a permeate fluid domain cavity, a concentrate fluid domain cavity, a permeate outlet, a raw material liquid inlet and a concentrate outlet;
the penetrating fluid domain cavity is positioned at the upper part of the nanofiltration membrane; the concentrated solution fluid domain cavity is positioned at the lower part of the nanofiltration membrane.
3. The combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device as claimed in claim 1, wherein the membrane distillation assembly is composed of a super-hydrophobic microporous membrane in the middle, a concentrated solution fluid domain cavity, a cooling water inlet, a water vapor condensate outlet, a permeate inlet and a concentrated solution outlet;
the enrichment liquid fluid domain cavity is positioned on the upper part of the super-hydrophobic microporous membrane; the cooling water fluid domain cavity is positioned at the lower part of the super-hydrophobic microporous membrane.
4. The combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device as claimed in claim 1, wherein the cooling system is composed of a cooling tank and a cooler connected with at least two sides of the ultrasonic membrane distillation combined system.
5. The combined reinforced high-magnesium-lithium ratio salt lake brine lithium extraction device as claimed in claim 1, wherein the first ultrasonic control panel and the second ultrasonic control panel have the same structure; the first ultrasonic generator and the second ultrasonic generator have the same structure.
6. The combined reinforced high magnesium-lithium ratio salt lake brine lithium extraction device as claimed in claim 1 or 5, wherein the first ultrasonic control panel or the second ultrasonic control panel is provided with an ultrasonic power button, a temperature display instrument, a power adjustment knob and an ultrasonic operation warning lamp on the surface respectively.
7. The combined enhanced high-magnesium-lithium ratio salt lake brine lithium extraction device as claimed in claim 1 or 5, wherein the first ultrasonic generator or the second ultrasonic generator is composed of a transducer, an amplitude transformer and an ultrasonic probe which are connected in sequence.
8. The combined enhanced high magnesium-lithium ratio lithium extraction device from salt lake brine as claimed in claim 1, wherein a first ultrasonic reaction cavity is arranged in the ultrasonic nanofiltration combined system; the ultrasonic membrane distillation combined system is provided with a second ultrasonic reaction cavity;
the first ultrasonic reaction cavity and the second ultrasonic reaction cavity are identical in structure.
9. The combined reinforced high-magnesium-lithium ratio salt lake brine lithium extraction device as claimed in claim 1, wherein the first ultrasonic reaction cavity or the second ultrasonic reaction cavity is composed of a cavity, an air outlet, an insulating layer and a magnetron; the heat insulation layer is located inside the cavity, the magnetrons are uniformly distributed outside the cavity, and the air outlet penetrates through the insides of the magnetrons.
10. The use method of the combined enhanced high magnesium lithium ratio salt lake brine lithium extraction device according to any one of claims 1 to 9, wherein the method comprises the following steps:
feeding the proportioned raw material brine into a raw material barrel, pumping the proportioned raw material brine into a high-pressure side of an ultrasonic nanofiltration combined system by a first pressure pump, applying pressure on two sides of a nanofiltration membrane to form a pressure difference, and starting ultrasonic waves;
a large amount of lithium ions and part of water in the raw material brine are transferred from a high-pressure side to a low-pressure side through a nanofiltration membrane under the action of ultrasonic cavitation to form a lithium-rich penetrating fluid, the penetrating fluid enters a penetrating fluid tank by opening a valve, the penetrating fluid is subjected to mass difference calculation and penetrates through a flux, and the conductivity change of the brine is monitored in real time in a conductivity measuring device;
the solution remaining on the high pressure side becomes a lithium-depleted concentrate rich in magnesium, borate, sulfate and other ions; pumping the lithium-rich penetrating fluid into the high-pressure side of the ultrasonic membrane distillation combined system through a second pressure pump, forming pressure difference on two sides of the super-hydrophobic membrane, and starting ultrasonic waves;
monitoring temperature change in real time from a thermometer and regulating and controlling in time, evaporating partial water of the lithium-rich penetrating fluid into water vapor under the action of energy of ultrasonic waves, transferring the water vapor from the high-pressure side to the low-pressure side of the hydrophobic membrane, condensing the water vapor by cooling water, then bringing the condensed water into a cooling tank for circulation, calculating flux through mass difference of an electronic balance, and monitoring conductivity change in real time by using conductivity measuring equipment;
enriching lithium in the rest solution at a high pressure side, opening a second outlet control valve to collect the enriched solution into an enriched solution tank or closing a valve to return to a raw material tank for circulation; opening an outlet control valve, and obtaining penetrating fluid from a penetrating fluid tank or obtaining enriched liquid from an enriched fluid tank to measure the content of each ion in the brine;
the lithium-containing brine comprises chlorinated salt lake brine, sulfuric acid salt lake brine and lithium-containing old brine obtained by extracting potassium from the chlorinated salt lake brine and then evaporating; mg in salt lake brine 2+ With Li + The mass ratio of (1) to (180) is 40 + The concentration is 5.3X 10 -3 ～8.5×10 -3 g/L；
The pressure difference applied to the two sides of the membrane in the ultrasonic nanofiltration combined system and the ultrasonic membrane distillation system is 2-5 bar; the temperature of the lithium-containing raw material brine of the ultrasonic nanofiltration combined system is 0-20 ℃, and the pH value is 5.5-8; the ultrasonic power is adjusted to 35khz, the temperature is adjusted to 80 ℃, the temperature of the ultrasonic-membrane distillation combined system is controlled to be 60-80 ℃, and the pH value is 5.5-8;
the nanofiltration membrane is a monovalent ion selective nanofiltration membrane, and the material is selected from at least one of cellulose acetate and derivatives thereof, aromatic polyamide, polyimide and sulfonated polyfurfuryl; the membrane distillation is a hydrophobic microporous membrane, and the commonly used commercial material is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, polypropylene and polyvinyl chloride.
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