CN219567594U - Integrated equipment for preparing co-production high-purity hydrochloric acid from lithium hydroxide - Google Patents
Integrated equipment for preparing co-production high-purity hydrochloric acid from lithium hydroxide Download PDFInfo
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- CN219567594U CN219567594U CN202320279654.7U CN202320279654U CN219567594U CN 219567594 U CN219567594 U CN 219567594U CN 202320279654 U CN202320279654 U CN 202320279654U CN 219567594 U CN219567594 U CN 219567594U
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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
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Abstract
The utility model discloses integrated equipment for preparing co-produced high-purity hydrochloric acid from lithium hydroxide, and belongs to the technical field of hydrochloric acid preparation. The device comprises a nanofiltration pretreatment unit, a divalent separation electrodialysis unit, a four-compartment bipolar membrane electrodialysis unit and a post-treatment unit; the divalent separation electrodialysis unit comprises a plurality of negative films and positive films which are arranged between a cathode and an anode, and the negative films and the positive films are alternately arranged at intervals; the water outlet of the concentrated water chamber of the divalent separation electrodialysis unit is communicated with the water inlet of the four-compartment bipolar membrane electrodialysis unit; the four-compartment bipolar membrane electrodialysis unit comprises a plurality of groups of alkaline chambers, a first acid chamber, a second acid chamber and a salt chamber which are sequentially separated by a male die, a bipolar membrane, a first negative membrane and a second negative membrane, and a water outlet of the alkaline chamber is communicated with the post-treatment unit. After lithium chloride is separated through electrodialysis, the lithium content in fresh water is less than 0.1g/L, the recycling rate is high, and the lithium chloride can be directly discharged to a salt field or used as reuse water.
Description
Technical Field
The utility model belongs to the technical field of hydrochloric acid preparation, and particularly relates to integrated equipment for preparing and co-producing high-purity hydrochloric acid by using lithium hydroxide.
Background
In the existing technology for preparing lithium hydroxide from salt lake brine, a three-compartment bipolar membrane electrodialysis process is generally adopted to convert lithium chloride in the brine after adsorption and lithium extraction and concentration to prepare a lithium hydroxide solution and a hydrochloric acid solution, but the hydrochloric acid product often contains 0.5-1 g/L of lithium ion impurities, so that the purity of the product is low.
For this reason, the advantages of different lithium extraction technologies are utilized in a coupling way, lithium, magnesium and boron in salt lake brine are separated in a green and economical way, and an integrated device for preparing co-produced high-purity hydrochloric acid from lithium hydroxide is innovatively provided.
Disclosure of Invention
The utility model aims to overcome the defects in the prior art and provides integrated equipment for preparing and co-producing high-purity hydrochloric acid by using lithium hydroxide. Specifically, the utility model provides equipment mainly based on a binary separation electrodialysis technology and a four-compartment bipolar membrane electrodialysis technology based on salt lake brine after lithium extraction by an adsorption method, and the equipment is used for preparing lithium hydroxide and co-producing high-purity hydrochloric acid.
The specific technical scheme adopted by the utility model is as follows:
the utility model provides integrated equipment for preparing co-produced high-purity hydrochloric acid by lithium hydroxide, which comprises a nanofiltration pretreatment unit, a binary separation electrodialysis unit, a four-compartment bipolar membrane electrodialysis unit and a post-treatment unit, wherein the nanofiltration pretreatment unit is connected with the bipolar membrane electrodialysis unit;
the nanofiltration pretreatment unit is internally provided with a nanofiltration membrane for removing most of calcium ions and magnesium ions in the inflow water, and the water outlet is communicated with the water inlet of a fresh water chamber of a divalent separation electrodialysis unit; the divalent separation electrodialysis unit comprises a plurality of negative films and positive films which are arranged between a cathode and an anode, wherein the negative films and the positive films are alternately arranged at intervals, the film adjacent to the anode is the negative film, and the film adjacent to the cathode is the positive film; the water outlet of the concentrated water chamber of the divalent separation electrodialysis unit is communicated with the water inlet of the salt chamber of the four-compartment bipolar membrane electrodialysis unit; the four-compartment bipolar membrane electrodialysis unit comprises a plurality of groups of alkaline chambers, a first acid chamber, a second acid chamber and a salt chamber which are sequentially separated by a male die, a bipolar membrane, a first negative membrane and a second negative membrane, and a water outlet of the alkaline chamber is communicated with the post-treatment unit; the post-treatment unit comprises an evaporation module and a centrifugal separation module which are sequentially arranged along the water flow direction.
Preferably, the nanofiltration membrane is a roll nanofiltration membrane.
Preferably, the cation membrane of the divalent separation electrodialysis is a divalent ion separation membrane.
Preferably, in the four-compartment bipolar membrane electrodialysis unit, the male die, the bipolar membrane, the first negative membrane and the second negative membrane are homogeneous membranes.
Preferably, the evaporation module is an MVR evaporator.
Preferably, an adsorption unit for extracting lithium ions is further arranged in front of the nanofiltration pretreatment unit.
Compared with the prior art, the utility model has the following beneficial effects:
1) The binary separation electrodialysis unit can realize concentration of lithium in brine, removal of boron, separation of high-valence ions such as calcium and magnesium, and can replace the traditional combined process of multistage nanofiltration calcium and magnesium removal, boron removal by resin, reverse osmosis concentration and common electrodialysis concentration, thereby realizing simplification of the process.
2) After lithium chloride is separated through electrodialysis, the lithium content in fresh water is less than 0.1g/L, the recycling rate is high, and the lithium chloride can be directly discharged to a salt field or used as reuse water.
3) Compared with the common three compartments, the four-compartment bipolar membrane electrodialysis unit is added with an anion exchange membrane, which is equivalent to adding a compartment containing hydrochloric acid solution in an acid chamber, thereby blocking migration of lithium ions and greatly improving purity of hydrochloric acid products.
Drawings
FIG. 1 is a schematic diagram of an integrated device of the present utility model;
FIG. 2 is a schematic diagram of a four compartment bipolar membrane electrodialysis unit;
FIG. 3 is a schematic diagram of a binary separation electrodialysis unit;
Detailed Description
The utility model is further illustrated and described below with reference to the drawings and detailed description. The technical features of the embodiments of the utility model can be combined correspondingly on the premise of no mutual conflict.
As shown in fig. 1, the integrated equipment for preparing co-produced high-purity hydrochloric acid by lithium hydroxide provided by the utility model comprises a nanofiltration pretreatment unit, a binary separation electrodialysis unit, a four-compartment bipolar membrane electrodialysis unit and a post-treatment unit. The structure and connection mode of each unit are specifically as follows:
the nanofiltration pretreatment unit is provided with a nanofiltration membrane for removing most of calcium ions and magnesium ions in the inflow water, and the water outlet is communicated with the water inlet of the fresh water chamber of the divalent separation electrodialysis unit. The salt lake brine is pretreated by sodium filtration, and most of calcium ions and magnesium ions in the brine are removed. In practical use, the nanofiltration membrane can be a roll nanofiltration membrane, and the retention rate of magnesium sulfate is more than 90%. An adsorption unit for extracting lithium ions can be arranged before the nanofiltration pretreatment unit, namely, firstly, salt lake brine to be treated is subjected to aluminum series adsorption to extract lithium to obtain qualified liquid, and then, the qualified liquid is subjected to pretreatment by a roll nanofiltration membrane to remove most of calcium ions and magnesium ions in the brine.
As shown in fig. 3, the divalent separation electrodialysis unit comprises a plurality of negative membranes and positive membranes which are arranged between a cathode and an anode, the negative membranes and the positive membranes are alternately arranged at intervals, the membrane adjacent to the anode is the negative membrane, the membrane adjacent to the cathode is the positive membrane, and the water outlet of the concentrated water chamber of the divalent separation electrodialysis unit is communicated with the water inlet of the salt chamber of the four-compartment bipolar membrane electrodialysis unit. In practical application, the wastewater after nanofiltration pretreatment enters a fresh water chamber of a divalent separation electrodialysis unit, pure water is introduced into a concentrated water chamber, fresh water products are obtained in the fresh water chamber after electrodialysis treatment, concentrated water products of high-lithium solution are obtained in the concentrated water chamber, and impurity ions such as calcium ions, magnesium ions, boron ions and the like are trapped in the fresh water chamber, so that deep concentration of lithium ions in brine is realized.
In practical use, the cation membrane of the divalent separation electrodialysis unit is a divalent ion separation membrane, and has special selective permeability to cations. The current density of a divalent separation electrodialysis unit is controlled to be 200-400A/square meter, the voltage is 0.3-0.5V/pair, and the operating temperature is controlled to be 20-40 ℃. The pH of the inlet water of the divalent separation electrodialysis unit is controlled to be 3-5.5. The concentration of lithium ions in the concentrated water outlet of the divalent separation electrodialysis unit is controlled to be 12-16 g/L, and the concentration of lithium ions in the fresh water outlet is controlled to be below 0.05 g/L. The retention rate of calcium and magnesium ions in the binary separation electrodialysis unit is more than 90 percent, and the retention rate of boron ions is more than 92 percent.
As shown in fig. 2, the four-compartment bipolar membrane electrodialysis unit comprises a plurality of groups of alkaline chambers, a first acid chamber, a second acid chamber and a salt chamber which are sequentially separated by a male die, a bipolar membrane, a first negative membrane and a second negative membrane, and a water outlet of the alkaline chamber is communicated with the post-treatment unit. In practical application, the concentrated water product of the binary separation electrodialysis unit is introduced into a salt chamber of the four-compartment bipolar membrane electrodialysis unit, and hydrochloric acid solution and lithium hydroxide alkali solution are obtained after electrodialysis reaction. Specifically, the hydrochloric acid solution flows out of the first acid chamber, and the lithium hydroxide alkali solution flows out of the alkali chamber.
In practical use, the four-compartment bipolar membrane electrodialysis current density is controlled to be 600-800A/square meter, the voltage is 3-4V/pair, and the operating temperature is controlled to be 30-40 ℃. The concentration of lithium hydroxide generated by the four-compartment bipolar membrane electrodialysis alkaline chamber is 2-2.5 mol/L, and the concentration of hydrochloric acid generated by the acid chamber is 2-2.5 mol/L. The lithium ion content in the hydrochloric acid solution produced by four-compartment bipolar membrane electrodialysis is less than 1mg/L, and the high-purity hydrochloric acid product is obtained. Washing and drying lithium hydroxide solution produced by four-compartment bipolar membrane electrodialysis out of a centrifuge to obtain a lithium hydroxide product with the content of more than 95.0%, and drying the lithium hydroxide product at a high temperature of 80-85 ℃ to obtain a lithium hydroxide product with the content of more than or equal to 98.0%.
The post-treatment unit comprises an evaporation module and a centrifugal separation module which are sequentially arranged along the water flow direction. In actual use, the lithium hydroxide alkali solution obtained by the four-compartment bipolar membrane electrodialysis unit is subjected to high-temperature evaporation and centrifugal separation to remove impurities, so that a battery-grade lithium hydroxide product with the content of more than or equal to 98.0% is obtained. The evaporation module may employ an MVR evaporator. The evaporation module may employ an MVR evaporator.
Examples
The embodiment utilizes the integrated equipment of the utility model to prepare the high-purity hydrochloric acid through salt lake brine, and the specific method is as follows:
removing impurities from salt lake brine after lithium extraction by an adsorption method through a nanofiltration pretreatment unit, and obtaining nanofiltration product water, wherein the removal rate of calcium and magnesium ions is 90%, lithium ions are 3-5 g/L, and boron is 1-2 g/L.
And (3) introducing hydrochloric acid into the nanofiltration water to adjust the pH value to 3, then introducing the nanofiltration water into a binary separation electrodialysis unit to concentrate and remove impurities, controlling the current density at 400A/square meter and the voltage at 0.5V/pair until the concentration of lithium ions in the obtained concentrated water is 14g/L, the concentration of fresh water lithium ions is less than 0.1g/L, and the boron removal rate and the calcium and magnesium ion removal rate of the effluent are 90%.
The four-compartment bipolar membrane electrodialysis unit comprises a salt chamber, an alkali chamber, a first acid chamber, a second acid chamber and 5% analytical pure hydrochloric acid solution. The current density is controlled at 800A/square meter, the voltage is 3.5V/pair, the salt chamber produces lithium chloride light brine, the alkali chamber produces lithium hydroxide solution with the concentration of 2.5mol/L, the first acid chamber produces high-purity hydrochloric acid solution with the concentration of 2.5mol/L, the second acid chamber produces 5% hydrochloric acid solution, the first acid chamber is the high-purity hydrochloric acid product required by the embodiment, and the lithium ion content in the product is less than 1mg/L.
And (3) feeding the lithium hydroxide-containing alkali liquor obtained in the alkali chamber into an evaporator, forcibly evaporating at 65 ℃, settling to obtain lithium hydroxide slurry, cooling to 30 ℃, and further separating by a centrifuge to obtain a lithium hydroxide product with the content of more than 95.0%.
Therefore, the utility model uses a special positive film with high selective permeability in a divalent separation electrodialysis process, can realize concentration of lithium in brine, removal of boron and separation of calcium and magnesium ions, and simplifies the process route. The advantages of different lithium extraction technologies are utilized in a coupling way, and the advantages of binary separation, electrodialysis concentration and impurity removal are realized to the maximum extent. Compared with the common three-compartment bipolar membrane, the four-compartment bipolar membrane electrodialysis has the advantages that the acid compartment is added, the introduced hydrochloric acid solution can be recycled, the migration of lithium ions is blocked, the lithium ion content in the acid compartment hydrochloric acid product is reduced, and the product purity is greatly improved.
The above embodiment is only a preferred embodiment of the present utility model, but it is not intended to limit the present utility model. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present utility model. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the utility model.
Claims (6)
1. The integrated equipment for preparing co-produced high-purity hydrochloric acid by using lithium hydroxide is characterized by comprising a nanofiltration pretreatment unit, a binary separation electrodialysis unit, a four-compartment bipolar membrane electrodialysis unit and a post-treatment unit;
the nanofiltration pretreatment unit is internally provided with a nanofiltration membrane for removing most of calcium ions and magnesium ions in the inflow water, and the water outlet is communicated with the water inlet of a fresh water chamber of a divalent separation electrodialysis unit; the divalent separation electrodialysis unit comprises a plurality of negative films and positive films which are arranged between a cathode and an anode, wherein the negative films and the positive films are alternately arranged at intervals, the film adjacent to the anode is the negative film, and the film adjacent to the cathode is the positive film; the water outlet of the concentrated water chamber of the divalent separation electrodialysis unit is communicated with the water inlet of the salt chamber of the four-compartment bipolar membrane electrodialysis unit; the four-compartment bipolar membrane electrodialysis unit comprises a plurality of groups of alkaline chambers, a first acid chamber, a second acid chamber and a salt chamber which are sequentially separated by a male die, a bipolar membrane, a first negative membrane and a second negative membrane, and a water outlet of the alkaline chamber is communicated with the post-treatment unit; the post-treatment unit comprises an evaporation module and a centrifugal separation module which are sequentially arranged along the water flow direction.
2. The integrated equipment for co-production of high purity hydrochloric acid from lithium hydroxide according to claim 1, wherein the nanofiltration membrane is a roll nanofiltration membrane.
3. The integrated apparatus for co-production of high purity hydrochloric acid from lithium hydroxide according to claim 1, wherein the cation membrane of the binary separation electrodialysis is a binary ion separation membrane.
4. The integrated apparatus for co-production of high purity hydrochloric acid according to claim 1, wherein in the four compartment bipolar membrane electrodialysis unit, the male die, the bipolar membrane, the first cathode membrane and the second cathode membrane are homogeneous membranes.
5. The integrated equipment for co-production of high purity hydrochloric acid according to claim 1, wherein the evaporation module is an MVR evaporator.
6. The integrated equipment for preparing co-produced high-purity hydrochloric acid by using lithium hydroxide according to claim 1, wherein an adsorption unit for extracting lithium ions is further arranged in front of the nanofiltration pretreatment unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202320279654.7U CN219567594U (en) | 2023-02-22 | 2023-02-22 | Integrated equipment for preparing co-production high-purity hydrochloric acid from lithium hydroxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202320279654.7U CN219567594U (en) | 2023-02-22 | 2023-02-22 | Integrated equipment for preparing co-production high-purity hydrochloric acid from lithium hydroxide |
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| CN219567594U true CN219567594U (en) | 2023-08-22 |
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| CN202320279654.7U Active CN219567594U (en) | 2023-02-22 | 2023-02-22 | Integrated equipment for preparing co-production high-purity hydrochloric acid from lithium hydroxide |
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Address after: 7/F, Building 1, Lanran Science Park, No. 17, Chujiatang Road, Cangqian Street, Yuhang District, Hangzhou City, Zhejiang Province, 310012 Patentee after: Hangzhou lanran Technology Co.,Ltd. Address before: 7/F, Building 1, Lanran Science Park, No. 17, Chujiatang Road, Cangqian Street, Yuhang District, Hangzhou City, Zhejiang Province, 310012 Patentee before: HANGZHOU LANRAN ENVIRONMENTAL TECHNOLOGY CO.,LTD. |
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