CN209759047U - Device for preparing lithium hydroxide by using high magnesium-lithium ratio old brine solution bipolar membrane electrodialysis method - Google Patents
Device for preparing lithium hydroxide by using high magnesium-lithium ratio old brine solution bipolar membrane electrodialysis method Download PDFInfo
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- CN209759047U CN209759047U CN201920163045.9U CN201920163045U CN209759047U CN 209759047 U CN209759047 U CN 209759047U CN 201920163045 U CN201920163045 U CN 201920163045U CN 209759047 U CN209759047 U CN 209759047U
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Abstract
The utility model relates to a lithium hydroxide preparation and purification technical field specifically are a device of lithium hydroxide is prepared to high magnesium lithium ratio old bittern solution bipolar membrane electrodialysis method, wash the device including mellow wine, mellow wine washes the device and connects and add mellow wine device, mellow wine washes the solution output of device and connects the electrodialysis device, the purification device is connected to the solution output of electrodialysis device, CO 2 intake pipe is connected to the purification device, the solution output of purification device is connected and is received the membrane device, receive the output of membrane device and connect bipolar membrane electrodialysis ware, bipolar membrane electrodialysis ware connects CO 2 outlet duct, the CO 2 intake pipe of purification device is connected to CO 2 outlet duct, the utility model overcomes the shortcoming of current technology, provide an investment cost is low, and is efficient, the purification device of salt lake lithium that economic nature is good.
Description
The patent application claims the priority of Chinese utility model patent application with application number of '201821530742.5', entitled 'device for preparing lithium hydroxide by bipolar membrane electrodialysis of high magnesium-lithium ratio old brine solution', and application date of '2018.9.18'.
Technical Field
the utility model relates to a lithium hydroxide preparation and purification technical field specifically are a device of lithium hydroxide is prepared to high magnesium lithium ratio old bittern solution bipolar membrane electrodialysis method.
Background
Lithium hydroxide is white powder, is one of the most important lithium salts, is widely applied to industries such as chemical raw materials, chemical reagents, lithium ion batteries, petroleum, metallurgy, glass, ceramics and the like, and is also an important raw material in national defense industry, atomic energy industry and aerospace industry. At present, lithium hydroxide is mainly used for producing lithium-based lubricating grease, electrolyte of an alkaline storage battery and absorption liquid of a lithium bromide refrigerator, and can also be used as a raw material for producing other lithium salt products. Lithium batteries are mostly adopted in electric automobiles and other electric tools, and lithium hydroxide is a key raw material for preparing lithium ion batteries. Lithium and its compounds are widely used in industrial sectors and high and new technology industries, and are known as "energy metals promoting world progress".
Because the process for extracting lithium from salt lake brine is simpler than that of extracting lithium from ore, the production cost is low, and the resource is rich, the process for extracting lithium from brine does not occupy the leading position of the lithium extraction industry in the last century, and the lithium extraction is mainly performed in the salt lake.
At present, the method for preparing lithium hydroxide by taking brine as a raw material mainly comprises a lithium carbonate causticizing method, an ionic membrane electrolysis method, an aluminate precipitation method, a calcining method and the like.
The preparation process of the lithium carbonate causticization method is a main industrial preparation method, adopts sodium carbonate causticization solution, has high impurity content and is not suitable for battery-grade application.
The method for preparing LiOH by the brine ion-exchange membrane electrolysis method and the ion-exchange membrane electrolysis method has the advantages of high recovery rate (nearly 100%), no secondary pollution, high purity of the prepared product (99%) and the like. However, the method has very high requirements on the content of impurity ions in the refined brine and high lithium content in the brine. In addition, the ionic membrane is expensive and difficult to maintain, and the production cost for preparing Li0H is relatively increased.
the calcining method has the advantages that the lithium, magnesium and other resources can be comprehensively utilized, and the required chemical raw materials are less; impurities such as boron, magnesium and the like can be removed by calcining, and the purity of the lithium hydroxide is improved. The disadvantages are that magnesium causes complex process flow, severe corrosion of equipment, large amount of evaporated water and high energy consumption.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is to overcome prior art's defect, provide a device of high magnesium lithium ratio old bittern solution bipolar membrane electrodialysis legal system preparation lithium hydroxide.
In order to solve the technical problem, the utility model provides a following technical scheme:
The utility model provides a device of lithium hydroxide is prepared to old bittern solution bipolar membrane electrodialysis method of high magnesium lithium ratio, wash the device including the mellow wine, the mellow wine is washed the device and is connected with the mellow wine device, the solution output end that the mellow wine washed the device is connected the electrodialysis device, the purification device is connected to the solution output end of electrodialysis device, CO2 intake pipe is connected to the purification device, the solution output end of purification device connects and receives the membrane device, receive the output connection bipolar membrane electrodialysis ware of membrane device, bipolar membrane electrodialysis ware connects CO 2 outlet duct, CO 2 outlet duct connects the CO 2 intake pipe of purification device.
an acid adding device is arranged between the nanofiltration membrane device and the bipolar membrane electrodialyzer.
A multi-chamber pool is arranged in the bipolar membrane electrodialyzer, and at least two compartments are arranged in the multi-chamber pool.
The alcohol adding device is used for adding alcohol, and the alcohol can be linear alkane alcohol containing C1/C5.
The alcohol added by the alcohol adding device is selected from one of methanol, ethanol or propanol.
The electrodialysis device is a monovalent ion selective membrane electrodialysis device.
the utility model discloses a theory of operation and working process as follows:
1. Washing precipitated magnesium with alcohol to prepare a medium magnesium-lithium ratio salt solution:
Mg in domestic old brine: the Li ratio is very high and can reach a ratio of 20: magnesium salts are precipitated in an alcohol washing device by adding alcohol to high magnesium to lithium ratio bittern while lithium remains in the aqueous alcohol solution, and alcohols which can be used include C1/C5 straight chain alkane alcohols such as methanol, ethanol, propanol, etc., wherein ethanol is most effective and 90% of magnesium salts can be removed.
2. Purifying the concentrated lithium salt by electrodialysis to obtain a solution with a low magnesium-lithium ratio:
The alcohol aqueous solution after alcohol precipitation can directly enter an electrodialysis device of a monovalent ion selective membrane to remove most of the residual magnesium, and the selectivity is about 90%.
3. And (3) introducing the salt lake solution with high lithium-magnesium ratio into a purification device by utilizing CO 2 to purify the lithium solution:
The solution subjected to the electrodialysis for removing magnesium enters a purification device, a magnesium carbonate and lithium carbonate salt solution can be formed by adding CO 2 into the purification device, a solution with high lithium content is formed by utilizing the characteristic that the solubility of the magnesium carbonate in water is lower than that of lithium carbonate in water, for example, the magnesium-lithium ratio is improved to about 1: 2, and the optimal condition for precipitating magnesium is that when the stirring time is 20min and n (CO 3 2- )/n (Mg) is 0.91, the removal rate of magnesium ions can reach 98%, the magnesium carbonate is precipitated and removed, and most of lithium ions are remained in the solution.
4. Precipitating magnesium carbonate, feeding the filtered lithium-rich solution into a nanofiltration membrane device, separating out multivalent ions, particularly divalent magnesium ions and carbonate ions through the nanofiltration membrane device, and concentrating the lithium-rich solution, wherein the reasonable lithium carbonate concentration is 0.5-1, 3 percent and the optimal concentration is 1 percent because the solubility of the lithium carbonate in water is not large.
5. Lithium hydroxide is prepared from lithium solution by a bipolar membrane electrodialyzer, while the by-product acid:
The concentrated and purified lithium carbonate solution can directly enter a bipolar membrane electrodialyzer to prepare lithium hydroxide; the concentrated and purified lithium carbonate solution can also be neutralized by strong acid to obtain lithium salt, and then the lithium salt enters a bipolar membrane electrodialyzer to prepare lithium hydroxide.
The utility model discloses a bipolar membrane electrodialysis method can go on in the multi-chambered pond of two compartments at least, when the lithium salt dissociation forms weak acid, use two-chambered structure bipolar membrane electrodialyzer, adopt bipolar membrane and cation exchange membrane to pair this moment, if the lithium carbonate salt belongs to weak acid salt, produce lithium hydroxide through two-chambered structure, the carbonic acid that obtains simultaneously can decompose into CO 2, do not have other accessory substances and pollutant, accessory substance CO 2 can let in the solution of high magnesium-lithium ratio, utilize the characteristics that the water solubility is little at magnesium carbonate, form magnesium carbonate sediment, filter the precipitation separation, obtain the solution that is rich in the lithium salt, then make magnesium carbonate content fall to below 1ppm through nanofiltration technique, the enrichment lithium carbonate is to 1% content.
Most often three-chamber structures are more common. When the lithium salt is dissociated to form strong acid, a bipolar membrane electrodialyzer with a three-chamber structure is used, the bipolar membrane is matched with an anion-cation exchange membrane, the lithium salt solution is added into a feeding chamber, under the action of an electric field, lithium ions enter the bipolar membrane chamber through the anode membrane and are combined with hydroxide ions separated by the bipolar membrane to form lithium hydroxide, and acid radical ions can be chloride ions and nitrate radical ions, and the sulfate radical ions enter the other chamber of the bipolar membrane through the cathode membrane and are combined with the hydrogen ions to form corresponding acid.
The utility model discloses the beneficial effect who reaches is:
the utility model overcomes the shortcoming of current technology, provides a purification device of salt lake lithium that investment cost is low, and is efficient, and economic nature is good. Additionally, the utility model discloses utilized bipolar membrane electrodialysis device, can directly obtain high-purity lithium hydroxide through the lithium salt, avoided the impurity height of caustic soda method, the complicated shortcoming of purification process, can obtain the higher lithium hydroxide product of purity.
drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention, and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of a first embodiment of the present invention;
fig. 2 is a schematic structural diagram of a second embodiment of the present invention.
In the figure: 1. an alcohol washing device; 2. an electrodialysis unit; 3. a purification device; 4. a nanofiltration membrane device; 5. bipolar membrane electrodialysers; 6. an alcohol adding device; 7. a CO2 air inlet pipe; 8. and (4) an acid adding device.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are presented herein only to illustrate and explain the present invention, and not to limit the present invention.
The first embodiment is as follows:
As shown in figure 1, the device for preparing lithium hydroxide by using the bipolar membrane electrodialysis method for the old brine solution with the high magnesium-lithium ratio comprises an alcohol washing device 1, wherein the alcohol washing device 1 is connected with an alcohol adding device 6, the solution output end of the alcohol washing device 1 is connected with an electrodialysis device 2, the solution output end of the electrodialysis device 2 is connected with a purification device 3, the purification device 3 is connected with a CO 2 air inlet pipe 7, the solution output end of the purification device 3 is connected with a nanofiltration membrane device 4, the output end of the nanofiltration membrane device 4 is connected with a bipolar membrane electrodialysis device 5, the bipolar membrane electrodialysis device 5 is connected with a CO 2 air outlet pipe, and the CO 2 air outlet pipe is connected with a CO 2 air.
A multi-chamber pool is arranged in the bipolar membrane electrodialyzer 5, and at least two compartments are arranged in the multi-chamber pool.
The alcohol adding device 6 is used for adding alcohol, and the alcohol can be linear alkane alcohol containing C1/C5.
The alcohol added by the alcohol adding device 6 is selected from one of methanol, ethanol or propanol, and ethanol is preferred.
The electrodialysis device 2 is a monovalent ion selective membrane electrodialysis device.
The utility model discloses a theory of operation and working process as follows:
1. Washing the precipitated magnesium with alcohol in an alcohol washing device 1 to prepare a medium magnesium-lithium ratio salt solution,
Mg in domestic old brine: the Li ratio is very high and can reach a ratio of 20: precipitation of magnesium salts by addition of alcohol to a high magnesium to lithium ratio old halide, while lithium remains in the hydroalcoholic solution. Alcohols that can be used include C1/C5 linear alkane alcohols such as methanol, ethanol, propanol, etc., where ethanol is most effective and 90% of the magnesium salts can be removed.
2. Purifying and concentrating lithium salt by using an electrodialysis device 2 to obtain solution with low magnesium-lithium ratio,
The alcohol aqueous solution after alcohol precipitation can directly enter an electrodialysis device 2 of a monovalent ion selective membrane to remove most of the residual magnesium, and the selectivity is about 90 percent.
3. the purification device 3 utilizes CO 2 to purify lithium solution from salt lake solution with high lithium-magnesium ratio:
The solution after the magnesium is removed by electrodialysis enters a purification device 3, a magnesium carbonate and lithium carbonate salt solution can be formed by adding CO 2, a solution with high lithium content is formed by utilizing the characteristics that the magnesium carbonate has low solubility in water and the lithium carbonate has high solubility in water, for example, the magnesium-lithium ratio is improved to about 1: 2, the optimal condition of magnesium precipitation is that when the stirring time is 20min and n (CO 3 2- )/n (Mg) is 0.91, the removal rate of magnesium ions can reach 98%, and most of lithium ions are remained in the solution after the magnesium carbonate precipitation is removed.
4. Precipitating magnesium carbonate, passing the filtered lithium-rich solution through a nanofiltration membrane device 4, separating out multivalent ions, particularly divalent magnesium ions and carbonate ions, and concentrating the lithium-rich solution. Since lithium carbonate has a low solubility in water, a reasonable lithium carbonate concentration is between 0.5 and 1, 3%, and the optimum concentration is 1%.
5. The lithium solution is passed through a bipolar membrane electrodialyzer 5 to prepare lithium hydroxide while the by-product acid:
the lithium carbonate solution concentrated and purified by the nanofiltration membrane device 4 can directly enter a bipolar membrane electrodialyzer 5 to prepare lithium hydroxide.
When lithium salt is dissociated to form strong acid, a bipolar membrane electrodialysis method with a three-chamber structure is used, the bipolar membrane is matched with an anion-cation exchange membrane, the anion-cation exchange membrane uses an alkali-resistant type anode membrane and an acid-resistant cathode membrane, lithium salt solution is added into a feeding chamber, under the action of an electric field, lithium ions enter the bipolar membrane chamber through the anode membrane and are combined with hydroxide ions separated from the bipolar membrane to form lithium hydroxide, carbonate ions enter the other chamber of the bipolar membrane through the cathode membrane and are combined with hydrogen ions to form corresponding carbonic acid, and the carbonic acid is subsequently decomposed to generate CO 2.
Example two
As shown in fig. 2, this embodiment is substantially the same as the first embodiment, except that an acid adding device 8 is disposed between the nanofiltration membrane device 4 and the bipolar membrane electrodialyzer 5, and a certain amount of 0.50% LiCl is added into the acid adding device 8. The concentrated and purified lithium carbonate solution is neutralized by strong acid to obtain lithium salt, and then the lithium salt enters a bipolar membrane electrodialyzer 5 to prepare lithium hydroxide.
EXAMPLE III
this example is substantially the same as the first example, except that the bipolar membrane electrodialyzer 5 is provided with a multi-compartment cell comprising two compartments, the two-compartment structure is provided with two sets of cation exchange membranes and a bipolar membrane, and the cation exchange membranes are alkaline-blocking type cation membranes.
Claims (6)
1. The utility model provides a device of lithium hydroxide is prepared to old bittern solution bipolar membrane electrodialysis legal system of high magnesium lithium ratio, a serial communication port, including the mellow wine device of washing, the mellow wine is washed the device and is connected with the mellow wine device, the mellow wine is washed the solution output of device and is connected the electrodialysis device, the purification device is connected to the solution output of electrodialysis device, CO 2 intake pipe is connected to the purification device, the solution output of purification device is connected and is received the membrane device, receive the output connection bipolar membrane electrodialyzer of membrane device, bipolar membrane electrodialyzer connects CO 2 outlet duct, CO 2 outlet duct connects the CO 2 intake pipe of purification device.
2. The device for preparing lithium hydroxide by the bipolar membrane electrodialysis method for the old halogen solution with high magnesium-lithium ratio according to claim 1, wherein an acid adding device is arranged between the nanofiltration membrane device and the bipolar membrane electrodialysis device.
3. The device for preparing lithium hydroxide by the bipolar membrane electrodialysis of the high magnesium-lithium ratio old halogen solution according to claim 1 or 2, wherein a multi-chamber cell is arranged in the bipolar membrane electrodialysis device, and at least two compartments are arranged in the multi-chamber cell.
4. The device for preparing lithium hydroxide by the bipolar membrane electrodialysis of the high magnesium-lithium ratio old halogen solution as claimed in claim 1 or 2, wherein the alcohol adding device is used for adding alcohol, and the alcohol can be linear alkane alcohol comprising C1/C5.
5. The device for preparing lithium hydroxide by the bipolar membrane electrodialysis method for the old halogen solution with the high magnesium-lithium ratio according to claim 4, wherein the alcohol added by the alcohol adding device is selected from one of methanol, ethanol or propanol.
6. the bipolar membrane electrodialysis device for preparing lithium hydroxide from the high magnesium-lithium ratio old halogen solution according to claim 1 or 2, wherein the electrodialysis device is a monovalent ion selective membrane electrodialysis device.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821530742 | 2018-09-18 | ||
| CN2018215307425 | 2018-09-18 |
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| CN209759047U true CN209759047U (en) | 2019-12-10 |
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| CN201920163045.9U Expired - Fee Related CN209759047U (en) | 2018-09-18 | 2019-01-30 | Device for preparing lithium hydroxide by using high magnesium-lithium ratio old brine solution bipolar membrane electrodialysis method |
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