Tower equipment for extracting lithium, rubidium and cesium

Abstract

The embodiment of the present application discloses a tower device for extracting lithium, rubidium and cesium. The tower device for extracting lithium, rubidium and cesium includes a stripping tower, a pulse liquid inlet pipe and a gas control module. The stripping tower includes a tower body, a top expansion section connected to the top of the tower body, and a bottom expansion section connected to the bottom of the tower body. The top expansion section is provided with an aqueous phase liquid inlet pipe and an organic phase liquid outlet pipe, and the bottom expansion section is provided with an aqueous phase liquid outlet pipe and an organic phase liquid inlet pipe; the pulse liquid inlet pipe has a first end and a second end, and the first end of the pulse liquid inlet pipe is connected to the bottom expansion section; the gas control module is connected to the second end of the pulse liquid inlet pipe; wherein the gas control module is used to reciprocately inflate and exhaust the pulse liquid inlet pipe, so that the liquid level height in the stripping tower changes reciprocatingly, and the liquid in the stripping tower forms a pulse oscillation. By repeatedly inflating and exhausting the pulse liquid inlet pipe, the liquid in the stripping tower can form a pulse oscillation, so that the liquid in the stripping tower can be broken into small droplets to improve the efficiency of extraction.

Description

Technical Field

[0001] The present application relates to the technical field of lithium rubidium cesium extraction, and in particular to a tower device for extracting lithium rubidium cesium. Background Art

[0002] Solvent extraction is an important enrichment and separation technology in hydrometallurgy. In the related technology, a large amount of lithium leaching slag piles will be produced in the process of lithium extraction. The lithium leaching slag piles still contain a small amount of lithium remaining in the slag without being separated. Although the lithium content in the slag is low, the amount of slag is large (producing 1 ton of lithium carbonate will produce 20 to 30 tons of lithium leaching slag), and the overall lithium resources cannot be ignored. At the same time, there are rubidium and cesium resources in the lithium mica smelting slag that have not been recovered. Therefore, it is more economical to further leach valuable metals such as lithium, rubidium and cesium from the lithium smelting slag.

[0003] However, since lithium slag has the characteristics of large slag volume and low lithium rubidium and cesium content, the rubidium and cesium concentration in the leachate is low and the leachate processing volume is also large. The extraction method can effectively realize the recovery of lithium, rubidium and cesium in the leachate. Using a larger water-oil ratio in the extraction process can achieve the enrichment of lithium, rubidium and cesium in the organic phase, and the operation is simple and the cost is low.

[0004] However, the separation equipment commonly used in the industry is difficult to apply to high water-to-oil ratios. Emulsification is prone to occur under high water-to-oil ratios in the mixing and settling tank. The centrifugal extraction equipment has high maintenance costs for moving parts for large-throughput operations. The extraction tower is an important separation equipment in hydrometallurgy, in which one phase is dispersed in the form of droplets in the other phase and flows countercurrently to achieve extraction. The extraction agent is used as a dispersed phase in the tower to flow countercurrently with the lithium slag leachate by relying on the difference in density. However, the large water-to-oil ratio results in a lower organic phase flow rate in the extraction tower, low liquid holdup in the extraction tower, short residence time, and low extraction efficiency. Summary of the invention

[0005] The embodiment of the present application provides a tower device for extracting lithium, rubidium and cesium, which can improve the extraction efficiency.

[0006] In a first aspect, an embodiment of the present application provides a tower device for extracting lithium, rubidium and cesium. The tower device for extracting lithium, rubidium and cesium includes a stripping tower, a pulse liquid inlet pipe and a gas control module. The stripping tower includes a tower body, a top expansion section connected to the top of the tower body, and a bottom expansion section connected to the bottom of the tower body. The top expansion section is provided with an aqueous phase liquid inlet pipe and an organic phase liquid outlet pipe, and the bottom expansion section is provided with an aqueous phase liquid outlet pipe and an organic phase liquid inlet pipe; the pulse liquid inlet pipe has a first end and a second end, and the first end of the pulse liquid inlet pipe is connected to the bottom expansion section; the gas control module is connected to the second end of the pulse liquid inlet pipe; wherein the gas control module is used to reciprocately inflate and exhaust the pulse liquid inlet pipe, so that the liquid level height in the stripping tower changes reciprocatingly, and the liquid in the stripping tower forms a pulse oscillation.

[0007] In some exemplary embodiments, the tower equipment for extracting lithium, rubidium and cesium further includes: a ceramic foam filler, the outer peripheral wall of the ceramic foam filler abuts against the inner wall of the tower body, and the ceramic foam filler is used to crush the organic phase.

[0008] In some exemplary embodiments, the tower equipment for extracting lithium, rubidium and cesium also includes: an oleophilic tower plate, the lipophilic tower plate has a periphery in contact with the inner wall of the tower body, the oleophilic tower plate is arranged above the ceramic foam filler and is spaced apart from the ceramic foam filler, the middle of the oleophilic tower plate has an opening for oil liquid to pass through, and the oleophilic tower plate is used to gather the organic phase.

[0009] In some exemplary embodiments, the number of the ceramic foam fillers is multiple, the number of the lipophilic tower plates corresponds to the number of the ceramic foam fillers one by one, each of the ceramic foam fillers and a corresponding lipophilic tower plate form a group of internal components, and multiple groups of the internal components are spaced apart in the vertical direction.

[0010] In some exemplary embodiments, the pore density of the ceramic foam filler is greater than or equal to 10PPI and less than or equal to 100PPI, and the height of the ceramic foam filler is greater than or equal to 0.1 times the inner diameter of the tower body and less than or equal to 3 times the inner diameter of the tower body.

[0011] In some exemplary embodiments, the diameter of the opening is greater than or equal to 1 / 3 of the inner diameter of the tower body, and less than or equal to 3 / 4 of the inner diameter of the tower body.

[0012] In some exemplary embodiments, the distance between the oleophilic tower plate and the ceramic foam filler is greater than or equal to 1 / 8 of the inner diameter of the tower body, and less than or equal to 1 / 2 of the inner diameter of the tower body.

[0013] In some exemplary embodiments, the spacing between the multiple groups of internal components is greater than or equal to 1 / 4 of the inner diameter of the tower body, and less than or equal to the inner diameter of the tower body.

[0014] In some exemplary embodiments, the air control module includes a first valve and a second valve, the first valve having a third end and a fourth end, the third end of the first valve being used for air intake; the second valve having a fifth end and a sixth end, the fifth end of the second valve being connected to the fourth end of the first valve and the second end of the pulse liquid inlet pipe, and the sixth end of the second valve being used for exhaust.

[0015] In some exemplary embodiments, the tower equipment for extracting lithium, rubidium and cesium further includes an organic phase distributor, which is connected to the organic phase liquid inlet pipe and is used to disperse the organic phase.

[0016] Beneficial effect: By repeatedly inflating and exhausting the pulse liquid inlet pipe, the liquid level in the stripping tower can be repeatedly changed. When the frequency of inflation and exhaust is fast, the liquid in the stripping tower can form a pulse oscillation, so that the liquid in the stripping tower can be broken into small droplets, so that the organic phase leachate in the stripping tower is fully mixed to improve the extraction efficiency. In addition, the tower equipment for extracting lithium, rubidium and cesium in the embodiment of the present application has no moving parts, is easy to repair, and has low equipment operation and maintenance costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 This is a schematic structural diagram of a tower device for extracting lithium, rubidium and cesium in one embodiment of the present application;

[0019] Figure 2 This is a schematic diagram of the structure of the internal components in one embodiment of the present application.

[0020] Explanation of the reference numerals: 100, tower equipment for extracting lithium, rubidium and cesium; 110, stripping tower; 111, tower body; 112, top expansion section; 113, bottom expansion section; 114, aqueous phase inlet pipe; 115, organic phase outlet pipe; 116, aqueous phase outlet pipe; 117, organic phase inlet pipe; 120, pulse inlet pipe; 121, first end; 122, second end; 130, gas control module; 131, first valve; 1311, third end; 1312, fourth end; 132, second valve; 1321, fifth end; 1322, sixth end; 140, internal component; 141, ceramic foam filler; 142, lipophilic tower plate; 142a, opening; 150, organic phase distributor. DETAILED DESCRIPTION

[0021] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0022] It should be noted that all directional indications in the embodiments of the present application (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0023] In addition, the descriptions of "first", "second", etc. in this application are only for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of this application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0024] In this application, unless otherwise clearly specified and limited, the terms "connection", "fixation", etc. should be understood in a broad sense. For example, "fixation" can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0025] In addition, the technical solutions between the various embodiments of the present application can be combined with each other, but it must be based on the fact that ordinary technicians in the field can implement it. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by this application.

[0026] The purpose of the present application is to provide a pulse stripping tower with a simple equipment structure, stable operation and suitable for a large water-oil ratio.

[0027] like Figure 1 As shown, a first aspect of an embodiment of the present application provides a tower device 100 for extracting lithium, rubidium and cesium. The tower device 100 for extracting lithium, rubidium and cesium includes a stripping tower 110, a pulse liquid inlet pipe 120 and a gas control module 130.

[0028] The stripping tower 110 includes a tower body 111, a top expansion section 112 and a bottom expansion section 113, the top expansion section 112 is connected to the top of the tower body 111, and the stripping tower 110 is used to extract lithium, rubidium, and cesium ions in the leachate through an extractant, so as to further recycle and utilize. The tower body 111 is mainly used for the extraction reaction between the extractant and the leachate. The leachate in this embodiment is the leachate of solid lithium slag, the leachate is an aqueous phase, and the extractant is an organic phase. Exemplarily, the extractant can be organic phosphoric acid. The density of the aqueous phase is greater than the density of the organic phase. The aqueous phase moves downward under the action of gravity, and the organic phase moves upward under the action of buoyancy, forming a countercurrent extraction. Optionally, the flow ratio of the extractant to the leachate can be greater than or equal to 0.03 and less than or equal to 1, so that the extractant has a relatively high extraction efficiency. The liquid after the lithium, rubidium and cesium ions in the leachate are extracted is called the raffinate, and the liquid after the lithium, rubidium and cesium ions in the leachate are extracted by the extractant is called the loaded organic phase. Optionally, the aqueous phase can be used as the continuous phase and the organic phase as the dispersed phase.

[0029] The top expansion section 112 is provided with an aqueous phase inlet pipe 114 and an organic phase outlet pipe 115, wherein the aqueous phase inlet pipe 114 is used to inject the leachate, and the organic phase outlet pipe 115 is used to discharge the loaded organic phase. It can be understood that the loaded organic phase is in the form of oil, the leachate is in the form of water, and the density of the loaded organic phase is less than the density of the leachate, so the loaded organic phase will float on the upper layer of the leachate. Optionally, the height of the aqueous phase inlet pipe 114 is lower than the height of the organic phase outlet pipe 115, so that when the leachate is injected, the disturbance of the leachate to the loaded organic phase is reduced, so that the loaded organic phase flows out through the aqueous phase inlet pipe 114, while the leachate does not flow out through the aqueous phase inlet pipe 114. Optionally, the aqueous phase inlet pipe 114 and the organic phase outlet pipe 115 are respectively arranged at opposite ends of the top expansion section 112, so as to reduce the disturbance between the leachate and the loaded organic phase. In addition, the diameter of the tower body 111 is relatively small, and the flow rate of the liquid in the tower body 111 is relatively fast, while the diameter of the top expansion section 112 is relatively large, so that the flow rate of the liquid in the top expansion section 112 is relatively slow, which is conducive to the static stratification of the leachate and the loaded organic phase in the top expansion section 112. When the oil-water two-phase interface of the top expansion section 112 is established, the loaded organic phase begins to overflow from the organic phase liquid outlet pipe 115.

[0030] The bottom expansion section 113 is provided with a water phase outlet pipe 116 and an organic phase inlet pipe 117. The water phase outlet pipe 116 is used to discharge the raffinate, and the organic phase inlet pipe 117 is used to inject the extractant. It can be understood that the extractant (organic phase) is in the form of oil, the raffinate is in the form of water, and the density of the organic phase is less than the density of the raffinate, so the raffinate will sink to the lower layer of the organic phase. Optionally, the height of the water phase outlet pipe 116 is lower than the height of the organic phase inlet pipe 117, and the organic phase is injected through the organic phase inlet pipe 117, thereby reducing the disturbance of the organic phase to the raffinate when the organic phase is injected. Optionally, the water phase outlet pipe 116 and the organic phase inlet pipe 117 are respectively arranged at opposite ends of the top expansion section 112, thereby reducing the disturbance between the raffinate and the organic phase. In addition, the diameter of the tower body 111 is relatively small, and the flow rate of the liquid in the tower body 111 is relatively fast, while the diameter of the bottom expansion section 113 is relatively large, so that the flow rate of the liquid in the bottom expansion section 113 is relatively slow, which is conducive to the static stratification of the raffinate and the organic phase in the bottom expansion section 113. After the oil-water two-phase interface of the bottom expansion section 113 is established, the raffinate begins to be discharged from the water phase liquid outlet pipe 116.

[0031] The pulse liquid inlet pipe 120 has a first end 121 and a second end 122. The first end 121 of the pulse liquid inlet pipe 120 is connected to the bottom expansion section 113, and the gas control module 130 is connected to the second end 122 of the pulse liquid inlet pipe 120. The gas control module 130 is used to inflate and exhaust the pulse liquid inlet pipe 120, so as to reciprocate and change the air pressure in the pulse liquid inlet pipe 120, so that the liquid level in the stripping tower 110 changes reciprocally, thereby forming a pulse oscillation on the liquid in the stripping tower 110. Specifically, when the gas control module 130 inflates the pulse liquid inlet pipe 120, the air pressure in the pulse liquid inlet pipe 120 increases, so that the liquid in the pulse liquid inlet pipe 120 is partially pressed back into the stripping tower 110, and the liquid level in the stripping tower 110 rises. When the gas control module 130 exhausts the pulse liquid inlet pipe 120 , the gas pressure in the pulse liquid inlet pipe 120 decreases, so that the liquid in the stripping tower 110 flows back into the pulse liquid inlet pipe 120 , and the liquid level of the stripping tower 110 decreases.

[0032] The speed and frequency of the gas control module 130 for charging and exhausting can be set according to the demand. By repeatedly charging and exhausting the pulse liquid inlet pipe 120, the liquid level in the stripping tower 110 can be repeatedly changed. When the frequency of charging and exhausting is fast, the liquid in the stripping tower 110 can form a pulse oscillation, so that the liquid in the stripping tower 110 can be broken into small droplets, so that the organic phase leachate in the stripping tower 110 is fully mixed to improve the extraction efficiency. In addition, the tower equipment 100 for extracting lithium, rubidium and cesium in the embodiment of the present application has no moving parts, is easy to repair, and has low equipment operation and maintenance costs.

[0033] Optionally, there may be one or more pulse liquid inlet pipes 120. The more pulse liquid inlet pipes 120 there are, the greater the amplitude of the liquid level change in the tower body 111 is, which is beneficial to the oscillation mixing of the liquid in the tower body 111. Optionally, the height of the top of the pulse liquid inlet pipe 120 is higher than the top expansion section 112, so as to prevent the liquid in the stripping tower 110 from overflowing through the pulse liquid inlet pipe 120.

[0034] like Figure 1 As shown, in some embodiments, the tower device 100 for extracting lithium, rubidium and cesium further includes a ceramic foam filler 141, and the outer peripheral wall of the ceramic foam filler 141 abuts against the inner wall of the tower body 111. The ceramic foam filler has the characteristics of strong oleophobicity, simple preparation and high porosity. The organic phase (in the form of oil droplets) can be broken into fine oil droplets by relying on the foam filler and pulses, so that the oil droplets are dispersed more evenly. Specifically, under the action of the pulse, the liquid level in the tower body 111 will rise and fall. When the liquid level in the tower body 111 rises, the organic phase moving upward is broken under the action of the ceramic foam filler 141 and evenly dispersed in the leaching solution, thereby increasing the contact area between the organic phase and the leaching solution, and the rising speed of the fine oil droplets will slow down, thereby increasing the residence time of the organic phase in the stripping tower 110 and improving the extraction efficiency.

[0035] like Figure 1 As shown, in some embodiments, the outer diameter of the ceramic foam filler 141 is the same as the inner diameter of the tower body 111, and the ceramic foam filler 141 is close to the inner wall surface of the tower body 111, so that the organic phase must flow through the ceramic foam filler 141, thereby improving the crushing effect of the ceramic foam filler 141 on the organic phase. Exemplarily, the shape of the ceramic foam filler 141 is cylindrical.

[0036] In some embodiments, the pore density of the ceramic foam filler 141 is greater than or equal to 10PPI and less than or equal to 100PPI, where PPI (Pores Per Linear Inch) refers to the average number of pores per unit inch length. If the pore density of the ceramic foam filler 141 is less than 10PPI, the ceramic foam filler 141 has a limited effect on the crushing of the organic phase, and the degree of improvement in the contact area between the organic phase and the leachate is limited, so that the improvement in the extraction efficiency is not obvious enough. Although the pore density of the ceramic foam filler 141 is large, the crushing effect of the organic phase is better, but if the organic phase is crushed too small, emulsification is likely to occur, and the resistance through the ceramic foam filler 141 is large. According to experiments, if the pore density of the ceramic foam filler is greater than 100PPI, the organic phase is easily emulsified, and if the emulsified organic phase needs to be re-aggregated, a higher cost is required. Therefore, the pore density of the ceramic foam filler 141 of the embodiment of the present application is greater than or equal to 10PPI and less than or equal to 100PPI, so that the degree of fragmentation of the organic phase is more appropriate, which can not only improve the extraction efficiency but also make the organic phase less likely to emulsify.

[0037] In some embodiments, the height of the ceramic foam filler 141 is greater than or equal to 0.1 times the inner diameter of the tower body 111, and less than or equal to 3 times the inner diameter of the tower body 111. If the height of the ceramic foam filler 141 is less than 0.1 times the inner diameter of the tower body 111, the height of the ceramic foam filler 141 is relatively short, and the ceramic foam filler 141 is difficult to effectively crush the organic phase. If the height of the ceramic foam filler 141 is greater than 3 times the inner diameter of the tower body 111, the height of the ceramic foam filler 141 is relatively high, and the resistance of the organic phase passing through the ceramic foam filler 141 is large, and the ceramic foam filler 141 occupies too much space, so that the fusion time of the organic phase and the leachate is short, reducing the extraction efficiency. The height of the ceramic foam filler 141 of the embodiment of the present application is greater than or equal to 0.1 times the inner diameter of the tower body 111, and less than or equal to 3 times the inner diameter of the tower body 111, so that the ceramic foam filler 141 can effectively crush the organic phase, and can make the fusion time of the organic phase and the leachate appropriate, and the extraction efficiency is high.

[0038] like Figure 1 and 2 As shown, in some embodiments, the tower device 100 for extracting lithium, rubidium and cesium also includes an oleophilic tower plate 142, the periphery of the oleophilic tower plate 142 is in contact with the inner wall of the tower body 111, the oleophilic tower plate 142 is arranged above the ceramic foam filler 141 and is spaced apart from the ceramic foam filler 141, the middle part of the oleophilic tower plate 142 has an opening 142a for oil liquid to pass through, and the oleophilic tower plate 142 is used to gather oil liquid.

[0039] The plate material of the oleophilic plate 142 is selected from one or more of polytetrafluoroethylene, polyvinyl chloride, and polypropylene materials with strong lipophilicity. The oleophilic plate 142 with strong lipophilicity can make fine oil droplets adhere to the oleophilic plate 142. The oleophilic plate 142 uses a material with good lipophilicity, which can promote the coalescence of oil droplets after contacting the oleophilic plate 142, so that the fine oil droplets are coalesced into large oil droplets, and the large oil droplets flow through the openings 142a of the oleophilic plate 142 to achieve oil droplet coalescence. In addition, the oleophilic plate 142 relies on high adhesion to make more extractants (organic phase) adhere to the oleophilic plate 142, thereby increasing the content of the overall organic phase in the stripping tower 110, still having a high volume content of the organic phase under a large water-to-oil ratio, increasing the residence time of the organic phase, and having a higher extraction efficiency.

[0040] In some embodiments, the lipophilic plate 142 is tilted upward from the outer wall of the lipophilic plate 142 to the periphery of the opening 142a, so that the oil droplets can slowly move along the inclined surface of the lipophilic plate 142 to the opening 142a, and the oil droplets flow more smoothly.

[0041] In some embodiments, the lipophilic plate 142 is tilted downward from the outer wall of the lipophilic plate 142 to the periphery of the opening 142a, so that the oil droplets on the lipophilic plate 142 gather at the periphery of the lipophilic plate 142, making it difficult for the oil droplets to flow to the opening 142a, thereby extending the residence time of the organic phase and improving the extraction efficiency.

[0042] The lipophilic plate 142 of the embodiment of the present application is located above the ceramic foam filler 141. The lipophilic plate 142 and the ceramic foam filler 141 are used in combination. The hydrophobic crushing effect of the ceramic foam filler 141 on oil droplets is combined with the agglomeration effect of the lipophilic plate 142, which can effectively increase the residence time of organic matter in the tower under a large water-to-oil ratio and improve the extraction efficiency.

[0043] In some embodiments, the distance between the oleophilic plate 142 and the ceramic foam filler 141 is greater than or equal to 1 / 8 of the inner diameter of the tower body 111, and less than or equal to 1 / 2 of the inner diameter of the tower body 111, and the distance between the oleophilic plate 142 and the ceramic foam filler 141 is adapted to the variation of the liquid level in the tower body 111. If the distance between the oleophilic plate 142 and the ceramic foam filler 141 is less than 1 / 8 of the inner diameter of the tower body 111, the distance between the oleophilic plate 142 and the ceramic foam filler 141 is too close, the contact time between the small oil droplets broken by the ceramic foam filler 141 and the leaching solution is short, and the small oil droplets and the leaching solution do not have time to fully react, that is, they are adsorbed on the oleophilic plate 142, resulting in low extraction efficiency. If the distance between the lipophilic plate 142 and the ceramic foam filler 141 is greater than 1 / 2 of the inner diameter of the tower body 111, the distance between the lipophilic plate 142 and the ceramic foam filler 141 is too far, and under the action of the reciprocating pulse, the small oil droplets broken by the ceramic foam filler 141 fluctuate up and down, and are difficult to be adsorbed by the lipophilic plate 142, which easily causes the organic phase to be mixed back. In this embodiment, the distance between the lipophilic plate 142 and the ceramic foam filler 141 is greater than or equal to 1 / 8 of the inner diameter of the tower body 111, and less than or equal to 1 / 2 of the inner diameter of the tower body 111, so that the small oil droplets passing through the ceramic foam filler 141 can be attached to the plate during the rising process, preventing the reciprocating pulse from taking the oil droplets downward when the flow field is downward, preventing the organic phase from being mixed back, and also improving the flux of the organic phase, and the small oil droplets and the leaching liquid have a relatively sufficient reaction time, thereby improving the extraction efficiency.

[0044] In some embodiments, the diameter of the opening 142a of the lipophilic plate 142 is greater than or equal to 1 / 3 of the inner diameter of the tower body 111, and less than or equal to 3 / 4 of the inner diameter of the tower body 111. If the diameter of the opening 142a is less than 1 / 3 of the inner diameter of the tower body 111, the opening 142a is small, and it is difficult for the oil droplets to flow smoothly through the opening 142a. If the diameter of the opening 142a is greater than 3 / 4 of the inner diameter of the tower body 111, the opening 142a is large, and the area of ​​the lipophilic plate 142 is relatively small, and the oil droplets gather less on the lipophilic plate 142, so that the residence time of the oil droplets is short and the extraction efficiency is not high. The diameter of the opening 142a of the lipophilic tower plate 142 of the embodiment of the present application is greater than or equal to 1 / 3 of the inner diameter of the tower body 111, and less than or equal to 3 / 4 of the inner diameter of the tower body 111, so that the lipophilic tower plate 142 can not only gather a suitable number of oil droplets, but also allow the oil droplets to flow smoothly through the opening 142a.

[0045] like Figure 1 and 2 As shown, in some embodiments, there are multiple ceramic foam fillers 141, the number of lipophilic tower plates 142 corresponds to the number of ceramic foam fillers 141 one by one, each ceramic foam filler 141 and a corresponding lipophilic tower plate 142 form a group of internal components 140, and the multiple groups of internal components 140 are spaced apart in the vertical direction.

[0046] The present application adopts ceramic foam fillers 141 and lipophilic tower plates 142 as internal components 140. The fine micropores of the ceramic foam fillers 141 are combined with pulses to break large oil droplets into small oil droplets, thereby increasing the residence time of the organic phase. The small oil droplets are aggregated through the lipophilic tower plates 142. By alternating a number of ceramic foam fillers 141 and lipophilic tower plates 142, multiple breakage and aggregation of oil droplets are achieved, mass transfer is enhanced, and extraction efficiency is improved.

[0047] In some embodiments, the spacing between the multiple groups of internal components 140 is greater than or equal to 1 / 4 of the inner diameter of the tower body 111, and less than or equal to the inner diameter of the tower body 111. If the spacing between the multiple groups of internal components 140 is less than 1 / 4 of the inner diameter of the tower body 111, the spacing between the multiple groups of internal components 140 is too small, the time for the oil and the leaching liquid to mix is ​​short, and the extraction efficiency is low. If the spacing between the multiple groups of internal components 140 is greater than the inner diameter of the tower body 111, the spacing between the multiple groups of internal components 140 is too large, the number of groups of internal components 140 that can be arranged is small, and the extraction efficiency is low. In the embodiment of the present application, the spacing between the multiple groups of internal components 140 is greater than or equal to 1 / 4 of the inner diameter of the tower body 111, and less than or equal to the inner diameter of the tower body 111, so that the spacing between the multiple groups of internal components 140 is more appropriate, the mixing time of the oil and the leaching liquid is more appropriate, and the oil can be broken-coalesced multiple times to achieve mass transfer enhancement and improve extraction efficiency.

[0048] like Figure 1 As shown, in some embodiments, the air control module 130 includes a first valve 131 and a second valve 132, the first valve 131 has a third end 1311 and a fourth end 1312, the third end 1311 of the first valve 131 is used for air intake, the second valve 132 has a fifth end 1321 and a sixth end 1322, the fifth end 1321 of the second valve 132 is connected to the fourth end 1312 of the first valve 131 and the second end 122 of the pulse liquid inlet pipe 120, and the sixth end 1322 of the second valve 132 is used for exhaust. Exemplarily, the third end 1311 of the first valve 131 can be filled with compressed air, and the compressed air can be provided by an air compressor or an air storage tank, etc., which is not limited here.

[0049] First, the leachate is filled into the tower through the aqueous phase inlet pipe 114. After the tower body 111 is partially filled with the leachate, the extractant is then injected through the organic phase inlet pipe 117. The first valve 131 is opened and the second valve 132 is closed. The compressed air enters the pulse inlet pipe 120 through the first valve 131. The air pressure in the pulse inlet pipe 120 increases, thereby causing the liquid level in the pulse inlet pipe 120 to drop and the liquid level in the stripping tower 110 to rise. Then the first valve 131 is closed and the second valve 132 is opened. The compressed air in the pulse inlet pipe 120 is discharged through the second valve 132. The liquid level in the pulse inlet pipe 120 rises and the liquid level in the stripping tower 110 drops. The first valve 131 and the second valve 132 alternately change the switch state, causing the liquid level in the stripping tower 110 to rise and fall reciprocally, thereby generating pulses in the stripping tower 110. The pulse intensity can be controlled by controlling the intake pressure of the compressed air and the valve opening and closing time.

[0050] like Figure 1 As shown, in some embodiments, the tower device 100 for extracting lithium, rubidium and cesium further includes an organic phase distributor 150, which is connected to the organic phase inlet pipe 117. The organic phase distributor 150 is used to disperse the organic phase so that the organic phase is evenly distributed on the cross section of the stripping tower 110, thereby improving the extraction efficiency. The type of the organic phase distributor 150 can be a shower head type, an impact type, a pagoda type, a porous row pipe type, a porous coil type, etc.

[0051] The extraction efficiency of the tower device 100 for extracting lithium, rubidium and cesium according to the embodiment of the present application is compared with that of the extraction tower in the related art.

[0052] Embodiment 1:

[0053] A tower device 100 for extracting lithium, rubidium and cesium, using a non-borosilicate glass extraction tower with a tower diameter of DN50, internal components of 60ppi ceramic foam filler and tetrafluoroethylene tower plate, the extraction effective section height is 2m, the organic phase is composed of a kerosene solution containing 1-phenyl-1, 3-decanedione (LiX54) and tri-n-octylphosphine oxide (TOPO), the feed flow rate is 0.2L / h, the aqueous phase is a lithium slag leaching solution containing 0.2 g / L of Li+, the feed flow rate is 2L / h, and the pulse amplitude is 5 mm, frequency 0.5Hz, water as continuous phase (heavy phase), organic as dispersed phase (light phase), water phase enters from the heavy phase inlet, flows out from the heavy phase outlet, organic phase enters from the light phase inlet, flows out from the light phase outlet, after stable operation for 24h, it is measured that the volume fraction of the organic phase in the equipment in the effective section of the tower is 15%, Li+ in the water phase is <10mg / L, the extraction rate is >95%, the extraction rate meets the requirements of industrial indicators, and the present embodiment achieves a good extraction effect.

[0054] Comparative Example 1:

[0055] This comparative example uses a traditional tetrafluoro pulse baffle extraction tower without ceramic foam fillers, lipophilic plates and pulses. The same processing capacity as in Example 1 is carried out. After 24 hours of stable operation, the organic phase in the equipment is measured to account for 6% of the volume fraction of the effective section in the tower, Li+ in the water phase>100mg / L, and the extraction rate is <50%, and the extraction rate does not meet the industrial index requirements. Compared with Example 1, the lipophilicity of the tetrafluoro baffle alone has limited ability to increase the volume fraction of the organic phase in the effective section of the tower. At the same time, due to the weak crushing effect of the baffle and the low mass transfer interface area, the extraction efficiency is low, which shows that the present invention uses a combination of ceramic foam fillers and lipophilic plates to significantly increase the volume fraction and residence time of the organic phase, thereby improving the extraction efficiency.

[0056] Comparative Example 2:

[0057] This comparative example adopts a traditional tetrafluoro pulse baffle extraction tower without ceramic foam fillers, lipophilic tower plates and pulses, and is carried out with the same processing capacity as Example 1. The difference from Example 1 is that the operation adopts an organic phase as a continuous phase and an aqueous phase as a dispersed phase. After 24 hours of stable operation, it is measured that Li+ in the aqueous phase is <10 mg / L, and the extraction rate is >95%. The extraction rate meets the industrial index requirements. However, compared with Example 1, the organic phase is used as the continuous phase and the organic phase needs to fill the entire tower. During stable operation, the organic phase accounts for 80% of the volume fraction of the entire tower. Therefore, the organic volume used is (0.025)2×3.14×2×80%=3.14 L. During stable operation of Example 1, the aqueous phase fills the entire tower, and the organic phase accounts for 10% of the volume fraction of the entire tower. Therefore, the organic volume used is (0.025)2×3.14×2×10%=0.39 L. The amount of organic phase used in Example 1 is reduced by 87.6% compared with that in Comparative Example 2. Therefore, under the same extraction rate, the use of the extraction tower of the present invention can significantly reduce the amount of organic phase used, reduce production costs and reduce operational safety.

[0058] Embodiment 2:

[0059] A tower device 100 for extracting lithium, rubidium and cesium adopts a stainless steel stripping tower with a tower diameter of DN150, the effective section height of the extraction tower is 4 m, the internal component is a 50ppi ceramic foam filler, the organic phase in this embodiment is a kerosene solution containing 4-sec-butyl-2 (α-methylbenzyl) phenol (t-BAMBP), the feed flow rate is 5L / h, the aqueous phase is a lithium slag leachate containing 10mg / L of Rb+, the feed flow rate is 150L / h, the pulse amplitude is 10mm, the frequency is 0.3Hz, the aqueous phase is the continuous phase, the organic phase is the dispersed phase, the aqueous phase is imported from the heavy phase inlet and flows out from the heavy phase outlet, the organic phase is imported from the light phase inlet and flows out from the light phase outlet, after stable operation for 24h, the droplet size in the equipment is measured to be in the range of 1-0.4mm, Rb+ in the organic phase is <0.5mg / L, the extraction rate is >95%, the extraction rate meets the industrial index requirements, and the present embodiment achieves a good extraction effect.

[0060] Comparative Example 3:

[0061] The internal components of the tower in this comparative example are traditional stainless steel pulse sieve plate extraction towers, without ceramic foam fillers, lipophilic plates and pulses. The other settings are completely consistent with Example 2. After 24 hours of stable operation, the droplet size in the equipment is measured to be in the range of 1.6-0.8 mm, Rb+ in the water phase is 4 mg / L, and the stripping rate is 60%. Compared with Example 2, due to the weak crushing ability of the traditional sieve plate, the effective crushing of the droplets at a low dispersed phase flow rate cannot be achieved, thereby reducing the extraction rate, which shows that the ceramic foam filler used in the present invention is a creative setting method, so that the droplets can be fully crushed and aggregated, and the residence time is increased, so that the final extraction effect is good.

[0062] Embodiment 3:

[0063] A tower device 100 for extracting lithium, rubidium and cesium adopts a stainless steel stripping tower with a tower diameter of DN150, the effective section height of the extraction tower is 4 m, the internal component is a 50ppi ceramic foam filler, the organic phase in this embodiment is a kerosene solution containing 4-sec-butyl-2 (α-methylbenzyl) phenol (t-BAMBP), the feed flow rate is 5 L / h, the aqueous phase is a lithium slag leachate containing 9 mg / L of Cs+, the feed flow rate is 150 L / h, the pulse amplitude is 10 mm, the frequency is 0.3 Hz, the aqueous phase is the continuous phase, the organic phase is the dispersed phase, the aqueous phase is imported from the heavy phase inlet and flows out from the heavy phase outlet, the organic phase is imported from the light phase inlet and flows out from the light phase outlet, after stable operation for 24 h, the droplet size in the equipment is measured to be in the range of 1-0.4 mm, Cs+ in the organic phase is <0.45 mg / L, the extraction rate is >95%, the extraction rate meets the industrial index requirements, and the present embodiment achieves a good extraction effect.

[0064] Comparative Example 4:

[0065] The internal components of the tower in this comparative example are traditional stainless steel pulse sieve plate extraction towers without ceramic foam fillers, lipophilic plates and pulses. The other settings are exactly the same as those in Example 2. After 24 hours of stable operation, the droplet size in the equipment was measured to be in the range of 1.6-0.8 mm, the Cs+ in the aqueous phase was 3.5 mg / L, and the stripping rate was 61%. Compared with Example 3, due to the weak crushing ability of the traditional sieve plate, it is impossible to effectively crush the droplets at a low dispersed phase flow rate, thereby reducing the extraction rate. This shows that the ceramic foam filler used in the present invention is a creative setting method, which allows the droplets to be fully crushed and aggregated, and increases the residence time, so that the final extraction effect is good.

[0066] The above description is only a preferred embodiment of the present application, and does not limit the patent scope of the present application. All equivalent structural changes made based on the concept of the present application and the contents of the present application description and drawings, or direct / indirect application in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A tower device for extracting lithium, rubidium and cesium, characterized in that: include: A stripping tower, comprising a tower body, a top expansion section connected to the top of the tower body, and a bottom expansion section connected to the bottom of the tower body, wherein the top expansion section is provided with a water phase liquid inlet pipe and an organic phase liquid outlet pipe, and the bottom expansion section is provided with a water phase liquid outlet pipe and an organic phase liquid inlet pipe; A pulse liquid inlet pipe, having a first end and a second end, wherein the first end of the pulse liquid inlet pipe is connected to the bottom expansion section; an air control module, connected to the second end of the pulse liquid inlet pipe; The gas control module is used to reciprocately inflate and exhaust the pulse liquid inlet pipe, so that the liquid level in the stripping tower changes reciprocatingly, and the liquid in the stripping tower forms a pulse oscillation; The tower equipment for extracting lithium, rubidium and cesium also includes: A ceramic foam filler, the outer peripheral wall of which abuts against the inner wall of the tower body, and the ceramic foam filler is used to crush the organic phase; An oleophilic tower plate, the periphery of which is in contact with the inner wall of the tower body, the oleophilic tower plate is arranged above the ceramic foam filler and spaced apart from the ceramic foam filler, the middle of the oleophilic tower plate has an opening for oil liquid to pass through, and the oleophilic tower plate is used to gather the organic phase; The number of the ceramic foam fillers is multiple, the number of the lipophilic plates corresponds to the number of the ceramic foam fillers one by one, each ceramic foam filler and a corresponding lipophilic plate form a group of internal components, and the multiple groups of internal components are spaced apart in the vertical direction; The pore density of the ceramic foam filler is greater than or equal to 10 PPI and less than or equal to 100 PPI, and the height of the ceramic foam filler is greater than or equal to 0.1 times the inner diameter of the tower body and less than or equal to 3 times the inner diameter of the tower body; The diameter of the opening is greater than or equal to 1 / 3 of the inner diameter of the tower body, and less than or equal to 3 / 4 of the inner diameter of the tower body; The distance between the oleophilic tower plate and the ceramic foam filler is greater than or equal to 1 / 8 of the inner diameter of the tower body, and less than or equal to 1 / 2 of the inner diameter of the tower body; The spacing between the multiple groups of internal components is greater than or equal to 1 / 4 of the inner diameter of the tower body, and less than or equal to the inner diameter of the tower body.

2. The tower equipment for extracting lithium, rubidium and cesium according to claim 1, characterized in that: The gas control module comprises: A first valve, the first valve having a third end and a fourth end, the third end of the first valve being used for air intake; The second valve has a fifth end and a sixth end, the fifth end of the second valve is connected to the fourth end of the first valve and the second end of the pulse liquid inlet pipe, and the sixth end of the second valve is used for exhaust.

3. The tower equipment for extracting lithium, rubidium and cesium according to claim 1, characterized in that: The tower equipment for extracting lithium, rubidium and cesium also includes: An organic phase distributor is connected to the organic phase liquid inlet pipe and is used to disperse the organic phase.

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