CN119082452B

CN119082452B - Tower type equipment for extracting lithium rubidium cesium

Info

Publication number: CN119082452B
Application number: CN202411587382.2A
Authority: CN
Inventors: 王勇; 谭博仁; 许东兵; 常朝
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2024-11-08
Filing date: 2024-11-08
Publication date: 2025-02-11
Anticipated expiration: 2044-11-08
Also published as: CN119082452A

Abstract

The embodiment of the application discloses tower equipment for extracting lithium, rubidium and cesium, which comprises a stripping tower, a pulse liquid inlet pipe and an air control module, wherein the stripping tower comprises a tower body, a top expansion section communicated with the top of the tower body and a bottom expansion section communicated with 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, the bottom expansion section is provided with the aqueous phase liquid outlet pipe and the organic phase liquid inlet pipe, the pulse liquid inlet pipe is provided with a first end and a second end, the first end of the pulse liquid inlet pipe is communicated with the bottom expansion section, the air control module is communicated with the second end of the pulse liquid inlet pipe, and the air control module is used for reciprocally inflating and deflating the pulse liquid inlet pipe so as to enable the liquid level in the stripping tower to reciprocally change, and the liquid in the stripping tower forms pulse oscillation. By repeatedly inflating and exhausting the pulse liquid inlet pipe, the liquid in the stripping tower can form pulse oscillation, so that the liquid in the stripping tower can be broken into small liquid drops, and the extraction efficiency is improved.

Description

Tower type equipment for extracting lithium rubidium cesium

Technical Field

The application relates to the technical field of extraction of lithium, rubidium and cesium, in particular to tower equipment for extracting lithium, rubidium and cesium.

Background

The solvent extraction is an important enrichment and separation technology in hydrometallurgy, in the related technology, a large amount of lithium leaching slag pile is generated in the lithium extraction process, a small amount of lithium still exists in the lithium leaching slag pile and is not separated, the content of lithium in the slag is low, the slag quantity is large (20-30 tons of lithium leaching slag can be produced when 1 ton of lithium carbonate is produced), the total lithium resources are not negligible, meanwhile, rubidium cesium resources are not recovered in the lepidolite smelting slag, and therefore, valuable metals such as lithium rubidium cesium and the like are further leached from the lithium smelting slag, and the economic efficiency is high.

However, the lithium slag has the characteristics of large slag quantity and low content of lithium, rubidium and cesium, the concentration of rubidium and cesium in the leaching solution is low, the treatment capacity of the leaching solution is also high, the recovery of lithium, rubidium and cesium in the leaching solution can be effectively realized by adopting an extraction method, and compared with the use of larger water and oil in the extraction process, the enrichment of lithium, rubidium and cesium in an organic phase can be realized, the operation is simple, and the cost is low.

However, the separation equipment commonly used in the industry is difficult to be suitable for high-water oil, the emulsification phenomenon is easy to occur under the condition that the mixer-settler is large in comparison, and the maintenance cost of the centrifugal extraction equipment for large-flux operation moving parts is high. The extraction tower is an important separation device in hydrometallurgy, wherein one phase is dispersed in the other phase in the form of liquid drops to realize extraction by countercurrent flow, and the extractant serving as a dispersed phase and the lithium slag leaching liquid in the tower can realize extraction by countercurrent flow with different densities. However, the larger water-oil ratio makes the flow of the organic phase in the extraction tower lower, the liquid holdup in the extraction tower is low, the residence time is short, and the extraction efficiency is low.

Disclosure of Invention

The embodiment of the application provides tower equipment for extracting lithium, rubidium and cesium, which can improve the extraction efficiency.

In a first aspect, an embodiment of the application provides tower equipment for extracting lithium, rubidium and cesium, which comprises a stripping tower, a pulse liquid inlet pipe and a gas control module, wherein the stripping tower comprises a tower body, a top expansion section communicated with the top of the tower body and a bottom expansion section communicated with 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, 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 is provided with a first end and a second end, the first end of the pulse liquid inlet pipe is communicated with the bottom expansion section, the gas control module is communicated with the second end of the pulse liquid inlet pipe, and the gas control module is used for reciprocally inflating and deflating the pulse liquid inlet pipe so as to enable the liquid level in the stripping tower to reciprocally change, and the liquid in the stripping tower forms pulse oscillation.

In some exemplary embodiments, the tower apparatus for extracting lithium rubidium cesium further comprises a ceramic foam packing, an outer peripheral wall of the ceramic foam packing abutting an inner wall of the tower body, the ceramic foam packing for breaking up the organic phase.

In some exemplary embodiments, the tower device for extracting lithium, rubidium and cesium further comprises an oleophilic tower plate, wherein the periphery of the oleophilic tower plate is abutted against the inner wall of the tower body, the oleophilic tower plate is arranged above the ceramic foam filler and is arranged at intervals with the ceramic foam filler, an opening for oil supply liquid to pass through is formed in the middle of the oleophilic tower plate, and the oleophilic tower plate is used for gathering organic phases.

In some exemplary embodiments, the number of the ceramic foam fillers is a plurality, the number of the oleophilic trays corresponds to the number of the ceramic foam fillers one by one, each ceramic foam filler and a corresponding oleophilic tray are a group of inner members, and a plurality of groups of inner members are arranged at intervals along the vertical direction.

In some exemplary embodiments, the ceramic foam filler has a pore density of greater than or equal to 10PPI and less than or equal to 100PPI, and a height of greater than or equal to 0.1 times and less than or equal to 3 times the inner diameter of the column.

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

In some exemplary embodiments, the distance between the oleophilic trays and the ceramic foam packing is greater than or equal to 1/8 of the column inner diameter and less than or equal to 1/2 of the column inner diameter.

In some exemplary embodiments, the spacing between the sets of internals is greater than or equal to 1/4 of the inner diameter of the tower and less than or equal to the inner diameter of the tower.

In some exemplary embodiments, the gas control module includes a first valve having a third end and a fourth end, the third end of the first valve for gas intake, and a second valve having a fifth end and a sixth end, the fifth end of the second valve in communication with both the fourth end of the first valve and the second end of the pulse feed tube, the sixth end of the second valve for gas discharge.

In some exemplary embodiments, the tower apparatus for extracting lithium rubidium cesium further comprises an organic phase distributor in communication with the organic phase feed pipe, the organic phase distributor for dispersing an organic phase.

The liquid level in the stripping tower can be repeatedly changed by repeatedly inflating and exhausting the pulse liquid inlet pipe, and when the frequency of inflating and exhausting is faster, the liquid in the stripping tower can form pulse oscillation, so that the liquid in the stripping tower can be broken into small liquid drops, and the organic phase leaching liquid in the stripping tower is fully mixed, so that the extraction efficiency is improved. In addition, the tower type equipment for extracting lithium, rubidium and cesium has no moving parts, is easy to overhaul and has low equipment operation and maintenance cost.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a schematic structural diagram of a tower apparatus for extracting lithium, rubidium and cesium in one embodiment of the present application;

Fig. 2 is a schematic structural view of an inner member in an embodiment of the present application.

The reference numerals indicate tower equipment for extracting lithium, rubidium and cesium, 110, a stripping tower, 111, a tower body, 112, a top expansion section, 113, a bottom expansion section, 114, an aqueous phase liquid inlet pipe, 115, an organic phase liquid outlet pipe, 116, an aqueous phase liquid outlet pipe, 117, an organic phase liquid inlet pipe, 120, a pulse liquid inlet pipe, 121, a first end, 122, a second end, 130, a gas control module, 131, a first valve, 1311, a third end, 1312, a fourth end, 132, a second valve, 1321, a fifth end, 1322, a sixth end, 140, an inner member, 141, ceramic foam filler, 142, an oleophilic tower plate, 142a, an opening, 150 and an organic phase distributor.

Detailed Description

The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.

It should be noted that all directional indicators (such as up, down, left, right, front, and rear are used in the embodiments of the present application) are merely for explaining the relative positional relationship, movement conditions, and the like between the components in a certain specific posture (as shown in the drawings), and if the specific posture is changed, the directional indicators are changed accordingly.

Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.

In the present application, unless explicitly specified and limited otherwise, the terms "connected," "fixed," and the like are to be construed broadly, and for example, "fixed" may be fixedly connected, detachably connected, or integrally formed, mechanically connected, electrically connected, directly connected, indirectly connected via an intervening medium, or in communication between two elements or in an interaction relationship between two elements, unless otherwise explicitly specified. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.

In addition, the technical solutions of the embodiments of the present application may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present application.

The application aims to provide a pulse back extraction tower which has a simple equipment structure and stable operation and is suitable for a large water-oil ratio.

As shown in fig. 1, a first aspect of the present application provides a tower apparatus 100 for extracting lithium, rubidium and cesium, where the tower apparatus 100 for extracting lithium, rubidium and cesium includes a stripping tower 110, a pulse liquid inlet pipe 120 and a gas control module 130.

The stripping tower 110 comprises a tower body 111, a top expansion section 112 and a bottom expansion section 113, wherein the top expansion section 112 is communicated with the top of the tower body 111, and the stripping tower 110 is used for extracting lithium, rubidium and cesium ions in the leaching solution through an extractant, so that further recycling is performed. The tower 111 is mainly used for an extraction reaction between an extractant and a leaching solution, wherein the leaching solution in the embodiment is a leaching solution of solid lithium slag, the leaching solution is a water phase, the extractant is an organic phase, and the extractant can be organic phosphoric acid. The density of the water phase is greater than that of the organic phase, the water phase moves downwards under the action of gravity, and the organic phase moves upwards under the action of buoyancy, so that countercurrent extraction is formed. Alternatively, the flow ratio of extractant to leachate may be greater than or equal to 0.03 and less than or equal to 1, thereby providing a relatively high extraction efficiency for the extractant. The liquid in the leaching solution after lithium, rubidium and cesium ions are extracted is called raffinate, and the liquid in the leaching solution after lithium, rubidium and cesium ions are extracted by the extractant is called loaded organic phase. Alternatively, an aqueous phase may be used as the continuous phase and an organic phase as the dispersed phase.

The top expansion section 112 is provided with an aqueous phase feed pipe 114 and an organic phase discharge pipe 115, the aqueous phase feed pipe 114 being used for injecting the leachate and the organic phase discharge pipe 115 being used for discharging the loaded organic phase. It will be appreciated that the loaded organic phase is in the form of an oil and the leach solution is in the form of water, the density of the loaded organic phase being less than that of the leach solution, and thus the loaded organic phase will float to the upper layer of the leach solution. Optionally, the height of the aqueous phase feed pipe 114 is lower than the height of the organic phase drain 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 feed pipe 114, but the leachate does not flow out through the aqueous phase feed pipe 114. Optionally, an aqueous phase feed pipe 114 and an organic phase discharge pipe 115 are provided at opposite ends of the top expanded section 112, respectively, to reduce turbulence between the leachate and the loaded organic phase. In addition, the diameter of the tower 111 is relatively small, the flow rate of the liquid in the tower 111 is relatively fast, and 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, and the standing delamination of the leaching liquid in the top expansion section 112 and the loaded organic phase is facilitated. After the oil-water two-phase interface of the top expansion section 112 is established, the organic phase overflow pipe 115 starts to overflow the loaded organic phase.

The bottom expansion 113 is provided with an aqueous phase outlet 116 and an organic phase inlet 117, the aqueous phase outlet 116 being used for discharging the raffinate and the organic phase inlet 117 being used for injecting the extractant. It will be appreciated that the extractant (organic phase) is in the form of an oil and the raffinate is in the form of an aqueous liquid, the density of the organic phase being less than that of the raffinate, and thus the raffinate will settle in the lower layers of the organic phase. Optionally, the height of the aqueous 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, so that disturbance of the organic phase relative to the raffinate is reduced when the organic phase is injected. Optionally, an aqueous phase effluent pipe 116 and an organic phase feed pipe 117 are disposed at opposite ends of the top expanded section 112, respectively, to reduce turbulence between the raffinate and the organic phase. In addition, the diameter of the column 111 is relatively small, the flow rate of the liquid in the column 111 is relatively fast, and 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, and the rest layering of the raffinate and the organic phase in the bottom expansion section 113 is facilitated. After the oil-water two-phase interface of the bottom expansion section 113 is established, the raffinate begins to be discharged from the aqueous phase outlet pipe 116.

The impulse fluid intake tube 120 has a first end 121 and a second end 122, the first end 121 of the impulse fluid intake tube 120 is in communication with the bottom expansion section 113, and the air control module 130 is in communication with the second end 122 of the impulse fluid intake tube 120. The air control module 130 is used for inflating and deflating the pulse liquid inlet pipe 120 to reciprocally change the air pressure in the pulse liquid inlet pipe 120, so that the liquid level in the stripping tower 110 reciprocally changes, and a pulse oscillation is formed on the liquid in the stripping tower 110. Specifically, when the air 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 of the stripping tower 110 increases. When the air control module 130 exhausts the pulse liquid inlet pipe 120, the air pressure in the pulse liquid inlet pipe 120 is reduced, 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 is reduced.

The speed and frequency of the aeration and the exhaustion of the air control module 130 can be set according to the requirements, the liquid level in the stripping tower 110 can be repeatedly changed by repeatedly aerating and exhausting the pulse liquid inlet pipe 120, and when the frequency of the aeration and the exhaustion is faster, the liquid in the stripping tower 110 can form pulse oscillation, so that the liquid in the stripping tower 110 can be broken into small liquid drops, and the organic phase leaching liquid in the stripping tower 110 is fully mixed, so that the extraction efficiency is improved. In addition, the tower type equipment 100 for extracting lithium, rubidium and cesium has no moving parts, is easy to overhaul and has low equipment operation and maintenance cost.

Alternatively, the number of the pulse liquid inlet pipes 120 may be one or more, and the greater the number of the pulse liquid inlet pipes 120, the greater the liquid level variation amplitude in the tower 111, so as to facilitate the vibration mixing of the liquid in the tower 111. Optionally, the top of the pulse feed 120 is higher than the top expansion section 112, thereby avoiding overflow of liquid in the stripper 110 through the pulse feed 120.

As shown in fig. 1, in some embodiments, the tower apparatus 100 for extracting lithium rubidium cesium further includes a ceramic foam packing 141, and an outer peripheral wall of the ceramic foam packing 141 abuts an inner wall of the tower body 111. The ceramic foam filler has the characteristics of strong oleophobic property, simple preparation and high porosity, and the organic phase (in the shape of oil drops) can be broken into small oil drops by virtue of the foam filler and the pulse, so that the oil drops are dispersed more uniformly. Specifically, under the action of the pulse, the liquid level of the liquid in the tower body 111 will rise and fall, when the liquid level of the liquid in the tower body 111 rises, the organic phase moving upwards is broken under the action of the ceramic foam filler 141 and uniformly dispersed in the leaching solution, so that the contact area of the organic phase and the leaching solution is increased, and the rising speed of fine oil drops will be slowed down, so that the residence time of the organic phase in the stripping tower 110 is increased, and the extraction efficiency is improved.

As shown in fig. 1, 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 closely attached to the inner wall surface of the tower body 111, so that the organic phase inevitably flows through the ceramic foam filler 141, and the crushing effect of the ceramic foam filler 141 on the organic phase is improved. Illustratively, the ceramic foam filler 141 is cylindrical in shape.

In some embodiments, the ceramic foam filler 141 has a pore density of greater than or equal to 10PPI and less than or equal to 100PPI, PPI (Pores PER LINEAR INCH) referring to the average pore number per inch of length. If the pore density of the ceramic foam filler 141 is less than 10PPI, the crushing effect of the ceramic foam filler 141 on the organic phase is wired, and the improvement degree of the contact area of the organic phase with the leachate is limited, so that the improvement of the extraction efficiency is not obvious enough. Although the ceramic foam filler 141 has a high pore density to provide a good crushing effect of the organic phase, if the organic phase is crushed too little, an emulsification phenomenon is easily generated and resistance through the ceramic foam filler 141 is large. Through experiments, if the pore density of the porcelain foam filler is greater than 100PPI, the organic phase is easily emulsified, and if the emulsified organic phase needs to be re-aggregated, higher cost is required. Therefore, the pore density of the ceramic foam filler 141 according to the embodiment of the present application is greater than or equal to 10PPI and less than or equal to 100PPI, so that the crushing degree of the organic phase is relatively suitable, and not only can the extraction efficiency be improved, but also the organic phase is not easy to be emulsified.

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 111 and less than or equal to 3 times the inner diameter of the tower 111. If the height of the ceramic foam filler 141 is 0.1 times smaller than the inner diameter of Yu Dati 111, the height of the ceramic foam filler 141 is relatively short, 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, the resistance of the organic phase to the ceramic foam filler 141 is high, and the ceramic foam filler 141 occupies too much space, so that the fusion time of the organic phase and the leaching liquid is less, and the extraction efficiency is reduced. The height of the ceramic foam filler 141 is greater than or equal to 0.1 time of the inner diameter of the tower body 111 and less than or equal to 3 times of the inner diameter of the tower body 111, so that the ceramic foam filler 141 can effectively crush an organic phase, the fusion time of the organic phase and the leaching liquid is proper, and the extraction efficiency is high.

As shown in fig. 1 and 2, in some embodiments, the tower apparatus 100 for extracting lithium, rubidium and cesium further includes an oleophilic tray 142, the perimeter of the oleophilic tray 142 is abutted against the inner wall of the tower body 111, the oleophilic tray 142 is disposed above the ceramic foam filler 141 and is spaced from the ceramic foam filler 141, an opening 142a for passing oil is formed in the middle of the oleophilic tray 142, and the oleophilic tray 142 is used for collecting oil.

The plate of the lipophilic column plate 142 is made of one or more of polytetrafluoroethylene, polyvinyl chloride and polypropylene materials with high lipophilicity, the lipophilic column plate 142 with high lipophilicity can enable tiny oil drops to adhere to the lipophilic column plate 142, the lipophilic column plate 142 is made of materials with high lipophilicity, coalescence of the oil drops after the oil drops are contacted with the lipophilic column plate 142 can be promoted, so that the tiny oil drops are coalesced into large oil drops, and the large oil drops flow through the openings 142a of the lipophilic column plate 142, so that oil drop coalescence is achieved. In addition, the lipophilic tower plate 142 can adhere more extractant (organic phase) to the lipophilic tower plate 142 by virtue of high adhesion, so that the content of the whole organic phase in the stripping tower 110 is improved, the volume content of the organic phase is still higher under the condition of high water-oil ratio, the residence time of the organic phase is prolonged, and the extraction efficiency is higher.

In some embodiments, from the outer peripheral wall of the lipophilic tray 142 to the periphery of the opening 142a, the lipophilic tray 142 is disposed obliquely upward, so that the oil droplets can slowly move to the opening 142a along the oblique surface of the lipophilic tray 142, and the oil droplets flow smoothly.

In some embodiments, from the outer peripheral wall of the lipophilic tray 142 to the periphery of the opening 142a, the lipophilic tray 142 is inclined downward, so that oil droplets on the lipophilic tray 142 are gathered on the periphery of the lipophilic tray 142, and thus the oil droplets are difficult to flow to the opening 142a, the residence time of the organic phase is prolonged, and the extraction efficiency is improved.

According to the embodiment of the application, the oleophylic tray 142 is positioned above the ceramic foam filler 141, the oleophylic tray 142 and the ceramic foam filler 141 are combined, and the hydrophobic breaking effect of the ceramic foam filler 141 on oil drops is combined with the coalescence effect of the oleophylic tray 142, so that the residence time of the organic substances in the tower under the condition of large water oil can be effectively improved, and the extraction efficiency is improved.

In some embodiments, the distance between the oleophilic tray 142 and the ceramic foam filler 141 is greater than or equal to 1/8 of the inner diameter of the column 111 and less than or equal to 1/2 of the inner diameter of the column 111, and the distance between the oleophilic tray 142 and the ceramic foam filler 141 is adapted to the variation range of the liquid level in the column 111. If the distance between the lipophilic tower plate 142 and the ceramic foam filler 141 is smaller than 1/8 of the inner diameter of Yu Dati a, the distance between the lipophilic tower plate 142 and the ceramic foam filler 141 is too short, the contact time between the small oil drops broken by the ceramic foam filler 141 and the leaching liquid is shorter, and the small oil drops and the leaching liquid do not react sufficiently, namely are adsorbed on the lipophilic tower plate 142, so that the extraction efficiency is lower. If the distance between the lipophilic column plate 142 and the ceramic foam filler 141 is greater than 1/2 of the inner diameter of the column 111, the distance between the lipophilic column plate 142 and the ceramic foam filler 141 is too far, and under the action of reciprocating pulse, the small oil drops broken by the ceramic foam filler 141 undulate up and down, are difficult to be adsorbed by the lipophilic column plate 142, and the back mixing of the organic phase is easy to be caused. In this embodiment, the distance between the oleophilic tower 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 drops passing through the ceramic foam filler 141 can be attached to the tower plate in the ascending process, the oil drops are prevented from being taken away downwards when the reciprocating pulse is downwards in the flow field, the flux of the organic phase can be improved by preventing the back mixing of the organic phase, and the small oil drops and the leaching liquid have more sufficient reaction time, so that the extraction efficiency can be improved.

In some embodiments, the diameter of the openings 142a of the oleophilic tray 142 is greater than or equal to 1/3 of the inner diameter of the column 111 and less than or equal to 3/4 of the inner diameter of the column 111. If the diameter of the opening 142a is smaller than 1/3 of the inner diameter of Yu Dati a, the opening 142a is smaller, and it is difficult for oil droplets to smoothly flow through the opening 142 a. If the diameter of the opening 142a is greater than 3/4 of the inner diameter of the tower 111, the opening 142a is larger, the area of the lipophilic tray 142 is relatively smaller, and oil droplets are less accumulated on the lipophilic tray 142, so that the residence time of the oil droplets is shorter and the extraction efficiency is not high. The diameter of the opening 142a of the lipophilic column plate 142 in the embodiment of the present application is greater than or equal to 1/3 of the inner diameter of the column body 111 and less than or equal to 3/4 of the inner diameter of the column body 111, so that the lipophilic column plate 142 can not only collect a proper amount of oil drops, but also enable the oil drops to smoothly flow through the opening 142 a.

As shown in fig. 1 and 2, in some embodiments, the number of ceramic foam fillers 141 is plural, the number of oleophilic trays 142 corresponds to the number of ceramic foam fillers 141 one by one, each ceramic foam filler 141 and a corresponding oleophilic tray 142 are a set of inner members 140, and the plurality of sets of inner members 140 are arranged at intervals in the vertical direction.

The application adopts ceramic foam filler 141 and oleophilic tower plate 142 as inner member 140, and combines tiny micropores of ceramic foam filler 141 with pulses to break large oil drops into tiny oil drops, enhance the residence time of organic phase, realize coalescence of small oil drops by oleophilic tower plate 142, realize multiple breaking-coalescence of oil drops by alternately arranging a plurality of ceramic foam fillers 141 and oleophilic tower plates 142, realize mass transfer strengthening, and promote extraction efficiency.

In some embodiments, the spacing between sets of internals 140 is greater than or equal to 1/4 of the inner diameter of tower 111 and less than or equal to the inner diameter of tower 111. If the interval between the inner members 140 is smaller than 1/4 of the inner diameter Yu Dati, the interval between the inner members 140 is too small, the mixing time of the oil and the leaching liquid is less, and the extraction efficiency is lower. If the intervals between the inner members 140 are larger than the inner diameter of the tower 111, the intervals between the inner members 140 are too large, the number of the inner members 140 can be arranged is small, and the extraction efficiency is low. The interval between the multiple groups of inner members 140 is larger than or equal to 1/4 of the inner diameter of the tower body 111 and smaller than or equal to the inner diameter of the tower body 111, so that the interval between the multiple groups of inner members 140 is proper, the mixing time of oil liquid and leaching liquid is proper, the oil liquid can be crushed and coalesced for multiple times, mass transfer reinforcement is realized, and extraction efficiency is improved.

As shown in fig. 1, in some embodiments, the gas 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 gas 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 communicated with both the fourth end 1312 of the first valve 131 and the second end 122 of the pulse inlet pipe 120, and the sixth end 1322 of the second valve 132 is used for gas exhaust. For example, the third end 1311 of the first valve 131 may be flushed with compressed air, which may be provided by an air compressor or an air tank, etc., without limitation.

Firstly, the water phase liquid inlet pipe 114 fills the leaching liquid into the tower, after the tower body 111 is partially filled with the leaching liquid, the organic phase liquid inlet pipe 117 is used for injecting the extracting agent, the first valve 131 is opened, the second valve 132 is closed, the compressed air enters the pulse liquid inlet pipe 120 through the first valve 131, the air pressure in the pulse liquid inlet pipe 120 is increased, so that the liquid level in the pulse liquid inlet pipe 120 is reduced, and the liquid level in the stripping tower 110 is increased. Then the first valve 131 is closed and the second valve 132 is opened, the compressed air in the pulse liquid inlet pipe 120 is discharged through the second valve 132, the liquid level in the pulse liquid inlet pipe 120 rises, and the liquid level in the stripping tower 110 falls. The first valve 131 and the second valve 132 alternately change the on-off state, so that the liquid level in the stripping tower 110 rises and falls, and then pulses are generated in the stripping tower 110, and the pulse intensity can be controlled by controlling the inlet pressure of the compressed air and the valve opening and closing time.

As shown in fig. 1, in some embodiments, the tower apparatus 100 for extracting lithium, rubidium and cesium further includes an organic phase distributor 150, where the organic phase distributor 150 is in communication with the organic phase feed pipe 117, and the organic phase distributor 150 is configured to disperse the organic phase so that the organic phase is uniformly distributed over the cross section of the stripping tower 110, thereby improving the extraction efficiency. The organic phase distributor 150 may be of the type of showerhead, impact, pagoda, porous calandria, porous coiled, etc.

The tower apparatus 100 for extracting lithium rubidium cesium according to the embodiment of the present application is compared with the extraction efficiency of the extraction tower of the related art.

Example 1:

A tower device 100 for extracting lithium rubidium cesium adopts a non-borosilicate glass extraction tower with a tower diameter DN50, wherein the inner member is a 60ppi ceramic foam filler and a tetrafluoro tower plate, the height of an effective extraction section is 2m, an organic phase is a kerosene solution containing 1-phenyl-1, 3-decanedione (LiX 54) and tri-n-octyl phosphine oxide (TOPO), the feeding flow is 0.2L/h, an aqueous phase is a lithium slag leaching solution, the feeding flow is 2L/h, the pulse amplitude is 5mm, the frequency is 0.5Hz, water is used as a continuous phase (heavy phase), the organic phase is a dispersed phase (light phase), the aqueous phase flows out from a heavy phase inlet, the organic phase flows out from a light phase inlet, the light phase outlet flows out, after 24h of stable operation, the volume fraction of the effective section in the device is 15%, the Li+ <10mg/L in the aqueous phase is measured, the extraction rate is more than 95%, and the extraction rate meets the industrial index requirements.

Comparative example 1:

The comparative example adopts a traditional tetrafluoro pulse baffle extraction tower, has no ceramic foam filler, lipophilic tower plates and pulses, is carried out according to the same treatment capacity of the embodiment 1, and after stable operation for 24 hours, the volume fraction of an organic phase in the equipment accounting for the effective section in the tower is measured to be 6 percent, the Li < + >100mg/L in a water phase, the extraction rate is less than 50 percent, and the extraction rate can not meet the industrial index requirement. Compared with the embodiment 1, the capacity of improving the volume fraction of the effective section of the organic phase in the tower is limited only by the lipophilicity of the tetrafluoro baffle plate, and meanwhile, the extraction efficiency is low due to the weak crushing effect of the baffle plate and low mass transfer interface area, so that the invention is proved to obviously improve the volume fraction and the residence time of the organic phase by adopting the combination mode of ceramic foam filler and the oleophilic tower plate, thereby improving the extraction efficiency.

Comparative example 2:

The comparative example adopts a traditional tetrafluoro pulse baffle extraction tower, no ceramic foam filler, lipophilic tower plate and pulse, and the same treatment capacity is carried out according to the embodiment 1, and is different from the embodiment 1, the operation adopts the organic phase as a continuous phase, the aqueous phase is a dispersed phase, after the stable operation is carried out for 24 hours, li < + > <10 mg/L in the aqueous phase is measured, the extraction rate is >95%, the extraction rate meets the industrial index requirement, but compared with the embodiment 1, the organic phase is adopted as the continuous phase, the organic phase occupies 80% of the total tower volume during the stable operation, the organic phase (0.025) is adopted to fill the total tower, the organic phase (0.14) is 2 multiplied by 3.14 multiplied by 80% = 3.14L, the organic phase (0.025) is adopted to fill the total tower volume fraction 10%, the organic phase (0.025) is adopted to fill the total tower volume fraction 2 multiplied by 3.14 multiplied by 10% = 0.39L, the organic phase consumption of the embodiment 1 is reduced by 87.6% compared with the comparative example 2, and the organic phase consumption can be obviously reduced under the same extraction rate, and the production cost and the operation is safe.

Example 2:

A tower device 100 for extracting lithium, rubidium and cesium adopts a stainless steel back extraction tower with a tower diameter of DN150, the height of the effective section of the extraction tower is 4m, an inner member is 50ppi ceramic foam filler, the organic phase of the embodiment is kerosene solution containing 4-sec-butyl-2 (alpha-methylbenzyl) phenol (t-BAMBP), the feeding flow is 5L/h, the water phase is lithium slag leaching liquid, rb+ containing 10mg/L is carried out, the feeding flow is 150L/h, the pulse amplitude is 10mm, the frequency is 0.3 Hz, the water phase is a continuous phase, the organic phase is a dispersed phase, the water phase flows out from a heavy phase inlet, flows out from a heavy phase outlet, the organic phase enters from a light phase inlet, flows out from a light phase outlet, after stable operation is carried out for 24 h, the measured droplet size range in the device is 1-0.4mm, rb+ <0.5 mg/L in the organic phase, the extraction rate is more than 95%, and the embodiment meets the industrial index requirements.

Comparative example 3:

The internal components of the tower of the comparative example are a traditional stainless steel pulse sieve plate extraction tower, no ceramic foam filler, lipophilic tower plates and pulses are adopted, other setting modes are completely consistent with those of the embodiment 2, after the stable operation is carried out for 24 h, the size range of liquid drops in the equipment is measured to be 1.6-0.8mm, rb+ in water phase is 4 mg/L, and the back extraction rate is 60%. Compared with the embodiment 2, the traditional sieve plate has weaker breaking capacity, and can not realize effective breaking of the liquid drops under the low flow velocity of the dispersed phase, so that the extraction rate is reduced, and the ceramic foam filler adopted by the invention is an creative setting mode, so that the liquid drops can be fully broken and coalesced, and the residence time is increased, and the final extraction effect is good.

Example 3:

A tower device 100 for extracting lithium rubidium cesium adopts a stainless steel back extraction tower with a tower diameter DN150, the height of the effective section of the extraction tower is 4m, an inner member is 50ppi ceramic foam filler, the organic phase of the embodiment is kerosene solution containing 4-sec-butyl-2 (alpha-methylbenzyl) phenol (t-BAMBP), the feeding flow is 5L/h, the water phase is lithium slag leaching solution, the Cs+ containing 9mg/L is 150L/h, the pulse amplitude is 10mm, the frequency is 0.3 Hz, the water phase is continuous phase, the organic phase is dispersed phase, the water phase flows out from a heavy phase inlet, flows out from a heavy phase outlet, the organic phase flows out from a light phase inlet, and after stable operation is carried out at 24h, the measured droplet size range in the device is 1-0.4mm, the Cs+ in the organic phase is <0.45 mg/L, the extraction rate is more than 95%, and the extraction rate meets the industrial index requirements.

Comparative example 4:

The internal components of the tower of the comparative example are a traditional stainless steel pulse sieve plate extraction tower, no ceramic foam filler, lipophilic tower plates and pulses are adopted, other setting modes are completely consistent with those of the embodiment 2, after the stable operation is carried out for 24h hours, the size range of liquid drops in the equipment is measured to be 1.6-0.8mm, cs+ in water phase is 3.5mg/L, and the back extraction rate is 61%. Compared with the embodiment 3, the traditional sieve plate has weaker breaking capacity, and can not realize effective breaking of the liquid drops under the low flow velocity of the dispersed phase, so that the extraction rate is reduced, and the ceramic foam filler adopted by the invention is an creative setting mode, so that the liquid drops can be fully broken and coalesced, and the residence time is increased, and the final extraction effect is good. ‌ A

The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the application, and all equivalent structural changes made by the specification and drawings of the present application or direct/indirect application in other related technical fields are included in the scope of the present application.

Claims

1. A tower device for extracting lithium, rubidium and cesium, characterized in that it comprises:

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 further comprises:

An organic phase distributor is connected to the organic phase liquid inlet pipe and is used to disperse the organic phase.