A method for separating and purifying rubidium and cesium using a pulsed extraction column

Abstract

The present invention relates to a method for separating and purifying rubidium and cesium using a pulsed extraction column. By operating multiple three-way valves in the same pipeline for the equipment used in this method and combining with the setting of specific method parameters, multiple pulsed treatments can be carried out with a single compressed gas, thereby reducing the volume of compressed air or compressed inert gas required for pulsed input and greatly reducing the production energy consumption.

Description

Technical Field

[0001] The present invention belongs to the technical field of extraction in chemical separation, and particularly relates to an extraction tower, an extraction method and uses for rubidium and cesium extraction, and particularly relates to a method for separating and purifying rubidium and cesium by using a pulsed extraction tower. Background Art

[0002] The solvent extraction method is one of the main industrial methods for extracting and separating rubidium and cesium. The commonly used industrial extractant is 4-tert-butyl-2-(α-methylbenzyl)phenol (i.e., t-BAMBP). Through the different distribution coefficients of rubidium, cesium and other impurity ions in the extractant and the aqueous phase, the separation and purification of rubidium and cesium are achieved successively through the extraction, washing and stripping sections in a mixer-settler extraction tank. However, the mixer-settler has a large amount of hold-up liquid and the cost of the extractant t-BAMBP is high, resulting in a high investment cost of the extractant for the rubidium and cesium extraction process. At the same time, the mixer-settler is a single-stage extraction device. For a rubidium and cesium system with a high requirement for the number of separation stages, a large number of devices are required, and the equipment operation and maintenance cost is high.

[0003] An extraction tower is a differential countercurrent extraction device. A single device can have multiple theoretical stages. Applying the extraction tower to rubidium and cesium extraction can significantly reduce the number of equipment and the amount of extractant hold-up liquid. Pulsing is the most commonly used means of introducing energy into the extraction tower. By intermittently introducing and exhausting compressed air, vibration is formed in the liquid in the extraction tower, which can significantly improve the mixing and mass transfer performance of the liquid-liquid two phases. In order to obtain more theoretical stages, the height of the extraction tower is usually about 10 - 20 m. The pulsed device relying on air pressure as the power requires a large volume of compressed air for each introduction and exhaust. In the rubidium and cesium process, pulsed energy needs to be introduced into the extraction towers in the extraction, washing and stripping sections, resulting in a high load on the air compressor. Especially in the industrial application of a pulsed extraction tower with a large tower diameter, there is extremely high energy consumption. Chinese Patent Publication No. CN101829435A discloses a pulsed baffle extraction device, which realizes efficient mass transfer between two phases by using high-pressure gas as the power to generate vortices in the two-phase fluid. However, since the pulsed gas flow used only serves for extraction, the load on the air compressor is high and the energy consumption is large. Summary of the Invention

[0004] In view of the above technical problems, the object of the present invention is to provide a method for separating and purifying rubidium and cesium with a simple equipment structure, stable operation, large flooding load, and energy consumption saving. A pulsed extraction column is used to replace the mixer-settler used in the existing rubidium and cesium extraction, washing, and stripping processes. Starting from the pressure gradient of the extraction column, a combined pulsed extraction column is proposed. The high-pressure gas discharged during the pulsed exhaust stage of the first-stage extraction column is used as the compressed gas input during the pulsed ventilation stage of the second-stage extraction column, and the high-pressure gas discharged during the pulsed exhaust stage of the second-stage extraction column is used as the compressed gas input during the pulsed ventilation stage of the third-stage extraction column. There is only one exhaust port for the three-stage extraction column, reducing the management of volatile organic compound (VOC) gas emissions, improving the utilization rate of compressed air, and reducing the process energy consumption.

[0005] It is achieved by the following technical means:

[0006] A method for separating and purifying rubidium and cesium using a pulsed extraction column, and the method uses a pulsed extraction column device.

[0007] The pulsed extraction column device includes an extraction column component, a washing column component, a stripping column component, and a pulse component.

[0008] The extraction column component includes an extraction column body, extraction column internals, an organic phase clarification section of the extraction column, an aqueous phase clarification section of the extraction column, an organic phase inlet of the extraction column, an aqueous phase inlet of the extraction column, an organic phase outlet of the extraction column, and an aqueous phase outlet of the extraction column; the organic phase clarification section of the extraction column, the extraction column body, and the aqueous phase clarification section of the extraction column are arranged in a through manner from top to bottom. The diameter or effective diameter of the organic phase clarification section of the extraction column and the aqueous phase clarification section of the extraction column is greater than the diameter or effective diameter of the extraction column body. The extraction column internals are densely arranged in the extraction column body. The organic phase inlet of the extraction column and the aqueous phase outlet of the extraction column are respectively opened on the side wall of the aqueous phase clarification section of the extraction column, and the aqueous phase inlet of the extraction column and the organic phase outlet of the extraction column are respectively opened on the side wall of the organic phase clarification section of the extraction column.

[0009] The washing column component includes a washing column body, washing column internals, an organic phase clarification section of the washing column, an aqueous phase clarification section of the washing column, an organic phase inlet of the washing column, an aqueous phase inlet of the washing column, an organic phase outlet of the washing column, and an aqueous phase outlet of the washing column; the organic phase clarification section of the washing column, the washing column body, and the aqueous phase clarification section of the washing column are arranged in a through manner from top to bottom. The diameter or effective diameter of the organic phase clarification section of the washing column and the aqueous phase clarification section of the washing column is greater than the diameter or effective diameter of the washing column body. The washing column internals are densely arranged in the washing column body. The organic phase inlet of the washing column and the aqueous phase outlet of the washing column are respectively opened on the side wall of the aqueous phase clarification section of the washing column, and the aqueous phase inlet of the washing column and the organic phase outlet of the washing column are respectively opened on the side wall of the organic phase clarification section of the washing column.

[0010] The stripping column component includes a stripping column body, internal components of the stripping column, an organic phase clarification section of the stripping column, an aqueous phase clarification section of the stripping column, an organic phase inlet of the stripping column, an aqueous phase inlet of the stripping column, an organic phase outlet of the stripping column, and an aqueous phase outlet of the stripping column; the organic phase clarification section of the stripping column, the stripping column body, and the aqueous phase clarification section of the stripping column are arranged in through connection from top to bottom, the diameter or effective diameter of the organic phase clarification section of the stripping column and the aqueous phase clarification section of the stripping column is greater than the diameter or effective diameter of the stripping column body, the internal components of the stripping column are densely arranged in the stripping column body, the organic phase inlet of the stripping column and the aqueous phase outlet of the stripping column are respectively opened on the side wall of the aqueous phase clarification section of the stripping column, and the aqueous phase inlet of the stripping column and the organic phase outlet of the stripping column are respectively opened on the side wall of the organic phase clarification section of the stripping column.

[0011] The pulse assembly includes a pulse main pipe, an extraction column pulse three-way valve, a scrubbing column three-way valve, a stripping column three-way valve, an extraction column pulse leg, a scrubbing column pulse leg, and a stripping column pulse leg; the extraction column pulse three-way valve, the scrubbing column three-way valve, and the stripping column three-way valve are sequentially arranged on the pulse main pipe, the inlet end of the pulse main pipe is the compressed air inlet end, and the outlet end of the pulse main pipe is the gas discharge end; the top end of the extraction column pulse leg is communicated with the side communication end of the extraction column pulse three-way valve, the bottom end of the extraction column pulse leg is communicated with the aqueous phase clarification section of the extraction column, the top end of the scrubbing column pulse leg is communicated with the side communication end of the scrubbing column pulse three-way valve, the bottom end of the scrubbing column pulse leg is communicated with the aqueous phase clarification section of the scrubbing column, the top end of the stripping column pulse leg is communicated with the side communication end of the stripping column pulse three-way valve, and the bottom end of the stripping column pulse leg is communicated with the aqueous phase clarification section of the stripping column.

[0012] Preferably, the pulse assembly further includes a pressure gauge, and the pressure gauge is respectively arranged in front of the extraction column pulse three-way valve, the scrubbing column three-way valve, or the stripping column three-way valve on the pulse main pipe.

[0013] Preferably, the internal components of the extraction column are baffle plates, the internal components of the scrubbing column are sieve plates, and the internal components of the stripping column are sieve plates.

[0014] Preferably, the inlet ends of the extraction column pulse three-way valve, the scrubbing column three-way valve, and the stripping column three-way valve are all communicated with the pulse main pipe in the direction close to the compressed air inlet end, and the straight outlet ends are all communicated with the pulse main pipe in the direction close to the gas discharge end.

[0015] Preferably, transfer tanks are provided between the organic phase outlet of the extraction column and the organic phase inlet of the scrubbing column, and between the organic phase outlet of the scrubbing column and the organic phase inlet of the stripping column.

[0016] Preferably, the diameters of the pulse legs of the extraction column, washing column, and stripping column are 1 / 3 to 1 / 5 of the diameters of the extraction column body, washing column body, and stripping column body, respectively, and the heights of the tops of the pulse legs of the extraction column, washing column, and stripping column are 0.5 to 2 m higher than the tops of the organic phase clarification sections of the extraction column, washing column, and stripping column, respectively.

[0017] Preferably, according to different internal components in the column body, the pulse column can be divided into a pulsed baffle extraction column, a pulsed sieve plate extraction column, and a pulsed packing extraction column.

[0018] Preferably, the method includes the following steps:

[0019] (1) The initial organic phase is discharged into the extraction column body through the organic phase inlet of the extraction column, and the aqueous raw material containing rubidium and cesium is discharged into the extraction column body through the aqueous phase inlet of the extraction column. The organic phase and the aqueous phase contact countercurrently by gravity and density difference and carry out an extraction reaction in the internal components of the extraction column body. The flow rate of the materials is such that the ratio of the initial organic phase to the aqueous raw material containing rubidium and cesium is maintained at (10 - 2):(0.9 - 1.1). The raffinate after extraction is discharged through the aqueous phase outlet of the extraction column, and the organic phase loaded with rubidium and cesium is discharged through the organic phase outlet of the extraction column and enters the organic phase inlet of the washing column after passing through the transfer tank.

[0020] (2) The organic phase loaded with rubidium and cesium obtained in step (1) is discharged into the washing column body through the organic phase inlet of the washing column, and pure water is discharged into the washing column body through the aqueous phase inlet of the washing column. The organic phase and the aqueous phase contact countercurrently by gravity and density difference and carry out washing in the internal components of the washing column body. The flow rate of the materials is such that the ratio of the organic phase loaded with rubidium and cesium to pure water is maintained at (20 - 6):(0.9 - 1.1). The aqueous phase after washing is discharged through the aqueous phase outlet of the washing column, and the organic phase loaded with rubidium and cesium after washing is discharged through the organic phase outlet of the washing column and enters the organic phase inlet of the stripping column after passing through the transfer tank.

[0021] (3) The organic phase loaded with rubidium and cesium after washing in step (2) is discharged into the stripping column body through the organic phase inlet of the stripping column. One or both of dilute hydrochloric acid or dilute sulfuric acid solutions with an acidity of 0.01 - 2 mol / L are used as the stripping aqueous phase and are discharged into the stripping column body through the aqueous phase inlet of the stripping column. The organic phase and the aqueous phase contact countercurrently by gravity and density difference and carry out stripping treatment in the internal components of the stripping column body. The flow rate of the materials is such that the ratio of the organic phase loaded with rubidium and cesium to the stripping aqueous phase is maintained at (20 - 2):(0.9 - 1.1).

[0022] (4) After the countercurrent flow in steps (1) to (3) stabilizes, compressed gas is introduced through the inlet end of the pulse main pipe, and the extraction tower pulse three-way valve, the scrubbing tower three-way valve, and the stripping tower three-way valve are started, and the first pulse mode and the second pulse mode are carried out in sequence. The first pulse mode is that the inlet end of the extraction tower pulse three-way valve is connected to the side connection end of the extraction tower pulse three-way valve and the direct outlet end of the extraction tower pulse three-way valve is closed, while the inlet end of the scrubbing tower pulse three-way valve is closed, and the side connection end of the scrubbing tower pulse three-way valve is connected to the direct outlet end of the scrubbing tower pulse three-way valve. At the same time, the inlet end of the stripping tower pulse three-way valve is connected to the side connection end of the stripping tower pulse three-way valve and the direct outlet end of the stripping tower pulse three-way valve is closed. The second pulse mode is that the inlet end of the extraction tower pulse three-way valve is closed, the side connection end of the extraction tower pulse three-way valve is connected to the direct outlet end of the extraction tower pulse three-way valve, while the inlet end of the scrubbing tower pulse three-way valve is connected to the side connection end of the scrubbing tower pulse three-way valve, and the direct outlet end of the scrubbing tower pulse three-way valve is closed. At the same time, the inlet end of the stripping tower pulse three-way valve is closed, and the side connection end of the stripping tower pulse three-way valve is connected to the direct outlet end of the stripping tower pulse three-way valve.

[0023] (5) Repeat the first pulse mode and the second pulse mode in sequence multiple times, and the duration of each first pulse mode is 0.5 - 5 s, and the duration of each second pulse mode is 0.5 - 5 s. The stripped aqueous phase is discharged through the stripping tower aqueous phase outlet to obtain the product for extracting and separating rubidium and cesium. The blank organic phase after stripping is discharged through the stripping tower organic phase outlet and enters the subsequent production process.

[0024] Preferably, the lowest pressure in the extraction tower body is higher than the highest pressure in the scrubbing tower body, and the lowest pressure in the scrubbing tower body is higher than the highest pressure in the stripping tower body.

[0025] Preferably, the initial organic phase in step (1) is a mixed solution of t-BAMBP and a diluent mixed in a volume ratio of (5 - 30):(95 - 70). The diluent is one or a combination of more of sulfonated kerosene, xylene, diethylbenzene, or cyclohexane. The aqueous phase raw material containing rubidium and cesium is an aqueous phase raw material containing rubidium and / or cesium and containing lithium and / or potassium.

[0026] Through step (1), rubidium and / or cesium in the aqueous phase raw material are extracted into the organic phase to achieve separation from lithium and / or potassium. Further, through step (2), the remaining lithium and / or potassium are washed away to achieve purification. Then, through step (3), stripping is carried out.

[0027] Preferably, the compressed gas in step (4) is compressed air or compressed inert gas; the extraction tower pulse three-way valve, the scrubbing tower three-way valve, and the stripping tower three-way valve are electric control valves or pneumatic control valves, which connect the respective side communication ends to the straight outlet ends in the case of power failure or gas cut-off, and connect the respective inlet ends to the side communication ends in the case of power-on or gas supply.

[0028] Preferably, the straight outlet end of the stripping tower pulse three-way valve of the last stage is connected to the exhaust gas duct or the external atmosphere.

[0029] The pressure gauge is used to detect the change value of the pressure in the pulse leg during the intake stage and the exhaust stage.

[0030] The technical effects of the present invention are as follows:

[0031] In the process of using the pulsed tower for the separation and purification of rubidium and cesium, the present invention replaces the mixer-settler or other forms of extraction equipment with a specific multi-stage pulsed tower, realizes the extraction separation of rubidium and cesium and subsequent processes (washing, stripping, and extractant recovery), and adopts a group of pulsed coupling devices, reducing the volume of compressed air or compressed inert gas required for pulsed input, thereby reducing the production energy consumption.

[0032] By setting three three-way valves and cooperating with the setting of three pulse legs, the present invention uses the characteristic that a single extraction tower has more theoretical stages to replace the traditional mixer-settler without changing the rubidium and cesium extraction process, saves the usage amount of the extractant, and reduces the engineering investment cost and the extractant post-treatment cost. And by cleverly using the pressure gradient in the extraction tower, the entry of a single compressed air or compressed inert gas can cause pulses in multiple extraction towers, reducing the usage amount of compressed air and saving a large amount of energy, meeting the requirements of sustainable development.

[0033] The device used in the method of the present invention, through the setting of three tower bodies and the specific setting of the specific cooperation mode, realizes the characteristics of low hold-up volume, small floor area, and low extractant investment cost; small power consumption, energy saving, etc. And since no power components are set in this device, the equipment operation and maintenance cost is low and the overhaul is easy; and because the enhanced extraction is carried out by means of gas pulses, the technical effects of low noise and little or no impact on the surrounding environment are achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is a schematic structural diagram of the pulsed extraction tower device provided by the specific embodiment of the present invention.

[0035] Figure 2 Schematic diagram of the combined switch of each three-way valve provided by the specific embodiment of the present invention.

[0036] Wherein: 1 - extraction tower body; 2 - scrubbing tower body; 3 - back-extraction tower body; 4 - extraction tower pulse three-way valve; 5 - scrubbing tower three-way valve; 6 - back-extraction tower three-way valve; 7 - extraction tower pulse leg; 71 - scrubbing tower pulse leg; 72 - back-extraction tower pulse leg; 8 - extraction tower internals; 9 - extraction tower organic phase inlet; 10 - extraction tower aqueous phase inlet; 11 - extraction tower organic phase outlet; 12 - extraction tower aqueous phase outlet; 13 - scrubbing tower organic phase inlet; 14 - scrubbing tower aqueous phase inlet; 15 - scrubbing tower organic phase outlet; 16 - scrubbing tower aqueous phase outlet; 17 - back-extraction tower organic phase inlet; 18 - back-extraction tower aqueous phase inlet; 19 - back-extraction tower organic phase outlet; 20 - back-extraction tower aqueous phase outlet; 21 - extraction tower organic phase clarification section; 211 - scrubbing tower organic phase clarification section; 212 - back-extraction tower organic phase clarification section; 22 - extraction tower aqueous phase clarification section; 221 - scrubbing tower aqueous phase clarification section; 222 - back-extraction tower aqueous phase clarification section; 23 - compressed gas inlet end; 231 - gas discharge end; 24 - pressure gauge; 25 - side connection end of the extraction tower pulse three-way valve; 26 - inlet end of the extraction tower pulse three-way valve; 27 - straight outlet end of the extraction tower pulse three-way valve. Detailed implementation mode

[0037] The process technical solution of the present invention will be further described below by combining examples and drawings. In the detailed implementation mode, unless otherwise stated, each feature is only an example of a series of equivalent or similar features. It is only for helping to understand the present invention. Those skilled in the art should understand that the said examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0038] As Figure 1 shown, this implementation mode provides a combined pulse extraction tower, which includes three tower body related components: an extraction tower component, a scrubbing tower component, a back-extraction tower component and a pulse component.

[0039] The extraction tower component includes an extraction tower body, extraction tower internals, an extraction tower organic phase clarification section, an extraction tower aqueous phase clarification section, an extraction tower organic phase inlet, an extraction tower aqueous phase inlet, an extraction tower organic phase outlet and an extraction tower aqueous phase outlet; the extraction tower organic phase clarification section, the extraction tower body and the extraction tower aqueous phase clarification section are arranged in through connection from top to bottom, the diameter or effective diameter of the extraction tower organic phase clarification section and the extraction tower aqueous phase clarification section is larger than the diameter or effective diameter of the extraction tower body, the extraction tower internals are closely arranged in the extraction tower body, the extraction tower organic phase inlet and the extraction tower aqueous phase outlet are respectively opened on the side wall of the extraction tower aqueous phase clarification section, and the extraction tower aqueous phase inlet and the extraction tower organic phase outlet are respectively opened on the side wall of the extraction tower organic phase clarification section.

[0040] The scrubbing tower component includes a scrubbing tower body, internal components of the scrubbing tower, an organic phase clarification section of the scrubbing tower, an aqueous phase clarification section of the scrubbing tower, an organic phase inlet of the scrubbing tower, an aqueous phase inlet of the scrubbing tower, an organic phase outlet of the scrubbing tower, and an aqueous phase outlet of the scrubbing tower; the organic phase clarification section of the scrubbing tower, the scrubbing tower body, and the aqueous phase clarification section of the scrubbing tower are arranged in a vertically penetrating manner from top to bottom, the diameter or effective diameter of the organic phase clarification section of the scrubbing tower and the aqueous phase clarification section of the scrubbing tower is greater than the diameter or effective diameter of the scrubbing tower body, the internal components of the scrubbing tower are densely arranged in the scrubbing tower body, the organic phase inlet of the scrubbing tower and the aqueous phase outlet of the scrubbing tower are respectively opened on the side wall of the aqueous phase clarification section of the scrubbing tower, and the aqueous phase inlet of the scrubbing tower and the organic phase outlet of the scrubbing tower are respectively opened on the side wall of the organic phase clarification section of the scrubbing tower.

[0041] The stripping tower component includes a stripping tower body, internal components of the stripping tower, an organic phase clarification section of the stripping tower, an aqueous phase clarification section of the stripping tower, an organic phase inlet of the stripping tower, an aqueous phase inlet of the stripping tower, an organic phase outlet of the stripping tower, and an aqueous phase outlet of the stripping tower; the organic phase clarification section of the stripping tower, the stripping tower body, and the aqueous phase clarification section of the stripping tower are arranged in a vertically penetrating manner from top to bottom, the diameter of the organic phase clarification section of the stripping tower and the aqueous phase clarification section of the stripping tower is greater than the diameter of the stripping tower body (the tower body, the organic phase clarification section, and the aqueous phase clarification section of the stripping tower in this embodiment are all cylindrical), the internal components of the stripping tower are densely arranged in the stripping tower body, the organic phase inlet of the stripping tower and the aqueous phase outlet of the stripping tower are respectively opened on the side wall of the aqueous phase clarification section of the stripping tower, and the aqueous phase inlet of the stripping tower and the organic phase outlet of the stripping tower are respectively opened on the side wall of the organic phase clarification section of the stripping tower.

[0042] The pulse assembly includes a main pulse pipe, an extraction tower pulse three-way valve, a scrubbing tower three-way valve, a stripping tower three-way valve, an extraction tower pulse leg, a scrubbing tower pulse leg, and a stripping tower pulse leg; the extraction tower pulse three-way valve, the scrubbing tower three-way valve, and the stripping tower three-way valve are sequentially arranged on the main pulse pipe, the inlet end of the main pulse pipe is the compressed gas inlet end, and the outlet end of the main pulse pipe is the gas discharge end; the top end of the extraction tower pulse leg is connected to the side communication end of the extraction tower pulse three-way valve, the bottom end of the extraction tower pulse leg is connected to the aqueous phase clarification section of the extraction tower, the top end of the scrubbing tower pulse leg is connected to the side communication end of the scrubbing tower pulse three-way valve, the bottom end of the scrubbing tower pulse leg is connected to the aqueous phase clarification section of the scrubbing tower, the top end of the stripping tower pulse leg is connected to the side communication end of the stripping tower pulse three-way valve, and the bottom end of the stripping tower pulse leg is connected to the aqueous phase clarification section of the stripping tower.

[0043] The tower body 1 is an extraction tower, which is used to extract an aqueous raw material containing rubidium and cesium. The initial organic phase is discharged into the extraction tower body through the organic phase inlet of the extraction tower, and the aqueous raw material containing rubidium and cesium is discharged into the extraction tower body through the aqueous phase inlet of the extraction tower. The organic phase and the aqueous phase are in countercurrent contact with each other by gravity and density difference in the internal components of the extraction tower body for extraction reaction. The flow rate of the material is such that the ratio of the initial organic phase to the aqueous raw material containing rubidium and cesium is maintained at (10-2): (0.9-1.1). The raffinate after extraction is discharged through the aqueous phase outlet of the extraction tower, and the organic phase loaded with rubidium and cesium is discharged through the organic phase outlet of the extraction tower and enters the organic phase inlet of the washing tower after passing through the transfer tank.

[0044] The tower body 2 is a washing tower, which is used to wash away impurities in the loaded organic phase. The organic phase loaded with rubidium and cesium obtained in step (1) is discharged into the washing tower body through the organic phase inlet of the washing tower, and pure water is discharged into the washing tower body through the water phase inlet of the washing tower. The organic phase and the water phase are contacted with each other in countercurrent by gravity and density difference and washed in the internal components of the washing tower body. The flow rate of the material is such that the ratio of the organic phase loaded with rubidium and cesium to pure water is maintained at (20-6): (0.9-1.1). The washed water phase is discharged through the water phase outlet of the washing tower, and the washed organic phase loaded with rubidium and cesium is discharged through the organic phase outlet of the washing tower and enters the organic phase inlet of the stripping tower after passing through the transfer tank.

[0045] The tower body 3 is a stripping tower, which is used to strip the rubidium and cesium in the organic phase into the water phase. The organic phase loaded with rubidium and cesium after washing in the above step is discharged into the stripping tower body through the organic phase inlet of the stripping tower. One or both of dilute hydrochloric acid or dilute sulfuric acid solution with an acidity of 0.01-2 mol / L are used as the stripping water phase and are discharged into the stripping tower body through the water phase inlet of the stripping tower. The organic phase and the water phase are in countercurrent contact by gravity and density difference in the internal components of the stripping tower body for stripping treatment. The flow rate of the material keeps the ratio of the organic phase loaded with rubidium and cesium to the stripping water phase at (20-2): (0.9-1.1). The water phase after stripping is discharged through the water phase outlet of the stripping tower to obtain the product of extracting and separating rubidium and cesium. The blank organic phase after stripping is discharged through the organic phase outlet of the stripping tower to enter the subsequent production process.

[0046] After the continuous countercurrent flow of the aqueous phase and the organic phase in the tower bodies 1, 2, and 3 is stable, the three-way valves 4, 5, and 6 of the tower body air intake and exhaust devices are started, the air intake end of the extraction tower pulse three-way valve 4 is connected to the compressed air, and the exhaust end of the stripping tower three-way valve 6 is connected to the atmosphere or the exhaust duct.

[0047] Each three-way valve is switched in an L-shaped manner, which is divided into the inlet end 26 of the three-way valve being connected to the side communication end 25 connected to the pulse leg or the straight outlet end 27 of the three-way valve exhaust being connected to the side communication end 25. For the convenience of describing the following process, when the inlet end of each three-way valve is connected to the side communication end, it is described as the air inlet end is open, and when the straight outlet end of the three-way valve is connected to the side communication end, it is described as the air inlet end is closed.

[0048] The combined switching modes of each three-way valve are as follows Figure 2 (a), Figure 2 (b), and Figure 2 (c), alternating as shown. When the inlet end of the extraction tower pulse three-way valve 4 is open, the inlet end of the scrubbing tower three-way valve 5 is closed, and the inlet end of the stripping tower three-way valve 6 is open. When the inlet end of the extraction tower pulse three-way valve 4 is closed, the inlet end of the scrubbing tower three-way valve 5 is open, and the inlet end of the stripping tower three-way valve 6 is closed. According to this combination, the three three-way valves cycle between open and closed states. The opening and closing times of the three-way valves are controlled by a relay or timer. The opening time of the air inlet end is adjustable within 0.5 - 5 s, and the closing time of the air inlet end is also adjustable within 0.5 - 5 s. The process by which each three-way valve forms a pulse on the tower body through the above combination is as follows

[0049] As Figure 2 (a) shows, when the inlet end of the extraction tower pulse three-way valve 4 is open and the inlet end communicates with the side connection end, compressed air enters the inside of the extraction tower pulse leg. The entry of high-pressure air causes the liquid level inside the pulse leg to drop, and the liquid is squeezed into the extraction tower body 1, causing the liquid level inside the extraction tower body 1 to rise. As Figure 2 (b) shows, when the inlet end of the extraction tower pulse three-way valve 4 is closed and the direct outlet end communicates with the side connection end, the inlet end of the scrubbing tower three-way valve 5 is open. At this time, the gas in the extraction tower pulse leg is connected to the gas in the scrubbing tower pulse leg. The air pressure in the extraction tower pulse leg is higher than the pressure in the scrubbing tower pulse leg. The pressure difference causes the compressed air in the extraction tower pulse leg to enter the scrubbing tower pulse leg. The liquid level in the extraction tower body drops, and the liquid level in the scrubbing tower body rises. As Figure 2 (c) shows, when the inlet end of the scrubbing tower three-way valve 5 is closed and the direct outlet end communicates with the side connection end, the inlet end of the stripping tower three-way valve 6 is open. At this time, the gas in the scrubbing tower pulse leg is connected to the gas in the stripping tower pulse leg. The air pressure in the scrubbing tower pulse leg is higher than the pressure in the stripping tower pulse leg. The pressure difference causes the compressed air in the scrubbing tower pulse leg to enter the stripping tower pulse leg. The liquid level in the scrubbing tower body drops, and the liquid level in the stripping tower body rises. When the inlet end of the stripping tower three-way valve 6 is closed next time and the direct outlet end is connected to the atmosphere or the waste gas exhaust pipe, the compressed air is discharged

[0050] In the above process, the compressed air entering from the inlet end of the extraction tower pulse three-way valve 4, through the sequential cooperation of the extraction tower pulse three-way valve 4, the scrubbing tower three-way valve 5, and the stripping tower three-way valve 6, first enters the extraction tower pulse leg of No. 1 and then is discharged into the scrubbing tower pulse leg, and then is discharged from the scrubbing tower pulse leg through the stripping tower pulse leg, and finally is discharged through the exhaust end of the stripping tower three-way valve 6. During the process of the compressed air entering and discharging from the pulse leg, the liquid level in the tower body rises and falls to form a pulse. The entry of a single portion of compressed air can cause the liquid levels in 1, 2, and 3 tower bodies to form pulses in sequence, greatly reducing the total volume of compressed air required to form a pulse

[0051] During the above process, the compressed air flows relying on the pressure difference inside the extraction tower body 1, the washing tower body 2, and the stripping tower body 3. Therefore, the pressure relationship between the tower bodies is: the lowest pressure of the extraction tower body 1 is higher than the highest pressure of the washing tower body 2, P 1,低 >P 2,高 , the lowest pressure of the washing tower body 2 is higher than the highest pressure of the stripping tower body 3, P 2,低 >P 3,高 . Therefore, the use of the pulse combination device requires a sufficiently large pressure difference range. Generally, the height of an industrial extraction tower is usually 15 - 25m, which has a sufficient pressure difference to allow the use of the pulse combination device.

[0052] Example 1

[0053] Based on the above specific implementation method, in this example, the extraction tower combination device of this example is applied to the extraction process of rubidium and cesium at 15m 3 / h (in this example, it is the separation and purification of rubidium from lithium and potassium, and in other examples, it can be the separation and purification of cesium from lithium and potassium or other forms). The diameter of the extraction tower is set to 1m, the height of the tower body is 20m, and the diameters of the organic phase clarification section and the aqueous phase clarification section are both 1.5m, and the height of each is 2m. This example sets the tower body height of 20m with 5 theoretical stages. The pulse high amplitude in this example is set to 40mm, and the intake and exhaust cycle time of the main pulse pipe is 8s.

[0054] Taking the aqueous phase as the continuous phase and the organic phase as the dispersed phase, the volume of the organic phase required to fill the entire tower is:

[0055]

[0056] Among them, the "upper enlarged section volume" is the volume of the organic phase clarification section, and the volume of the organic phase used for each theoretical stage is:

[0057] Comparative Example 1

[0058] This comparative example uses a mixer-settler to achieve the above technical process objectives. It is also an extraction process of rubidium and cesium at 15m 3 / h. The volume of the mixing chamber of the mixer-settler used is 1.3m 3 , and the volume of the clarification chamber is 5.22m 3 . The amount of organic phase used for each stage is:

[0059]

[0060] By comparing Example 1 and Comparative Example 1, comparing the extraction tower and the mixer-settler, the reduction in the amount of organic phase used for each stage is:

[0061]

[0062] It can be seen that under the same throughput, applying the extraction column of the present invention to the extraction and separation of rubidium and cesium will save 49.2% of the organic phase usage. Moreover, the larger the throughput, the more volume of the organic phase can be saved, and the effect of saving the investment cost of the extractant is more obvious.

[0063] Comparative Example 2

[0064] In this comparative example, instead of using a pulse main pipe and three three-way valves, the pulse treatment is carried out separately by the pulse method. The same settings as in Example 1 are used, with the high pulse amplitude being 40 mm and the intake and exhaust cycle time being 8 s. At this time, the intake volume of a single column in one pulse cycle is:

[0065]

[0066] According to this intake volume, the intake volume required for a single extraction column per minute is:

[0067] V 总 = 60÷8×0.126 = 0.95 m 3 ;

[0068] According to this intake volume, with the maximum working pressure of 0.8 MPa and the flow rate of 0.54 - 1.72 m 3 of the air compressor, the power is about 8 KW. For 3 extraction columns, a 24 KW air compressor needs to be configured.

[0069] However, in Example 1, the combined device of the present invention is used to form pulses for 3 columns simultaneously, and only one 8 KW air compressor is required. Compared with this comparative example, the energy consumption is saved by 16 KW.

[0070] Calculated based on working 300 days a year and 24 hours a day, the annual electricity savings can be:

[0071] W = (24 - 8) KW×24 h×300 = 115200 KW·h.

[0072] It can be seen that the energy that can be saved by the present invention is huge, and for pulse columns with a larger tower diameter, the effect is more obvious.

[0073] According to the above specific embodiments and the pulsed combined extraction column of Example 1, compared with the common rubidium and cesium extraction equipment, the mixer-settler of Comparative Example 1, compare the electricity consumption that can be saved by using the pulsed combined extraction column:

[0074] The above extraction column combination is a three-stage pulsed extraction column. The 20 m tower body height has 5 theoretical stages, and three 20 m tower body heights can have 15 theoretical stages. Using the pulsed combined device of the above specific embodiments and Example 1 of the present invention, only one 8 KW air compressor is required to provide pulsed power. The volume of the mixing chamber of the mixer-settler in Comparative Example 1 is 1.3 m3 , stirring motor speed is 60rpm, the motor power required for each extraction equilibrium stage is 1.5KW, the total motor power of 15 stages is 22.5KW, the power is calculated based on 300 working days per year and 24 hours per day, the power that can be saved each year is:

[0075] W=(22.5-8)KW×24h×300=104400KW·h.

[0076] It can be seen that the energy that can be saved by the present invention is enormous, and the effect is more obvious for more extraction stages and higher processing volumes.

[0077] The technical principle of the present invention is described above in conjunction with specific embodiments. These descriptions are only for explaining the principle of the present invention and cannot be interpreted as limiting the scope of protection of the present invention in any way. Based on the explanations herein, those skilled in the art can associate other specific implementations of the present invention without paying creative labor, and these methods will fall within the scope of protection of the present invention.

Claims

1. A method for separating and purifying rubidium and cesium using a pulsed extraction column, characterized in that, the method uses a pulsed extraction column device; The pulsed extraction column device includes an extraction column component, a washing column component, a stripping column component and a pulse component; The extraction column component includes an extraction column body, internal components of the extraction column, an organic phase clarification section of the extraction column, an aqueous phase clarification section of the extraction column, an organic phase inlet of the extraction column, an aqueous phase inlet of the extraction column, an organic phase outlet of the extraction column and an aqueous phase outlet of the extraction column; the organic phase clarification section of the extraction column, the extraction column body and the aqueous phase clarification section of the extraction column are arranged in through connection from top to bottom, the diameter or effective diameter of the organic phase clarification section of the extraction column and the aqueous phase clarification section of the extraction column is greater than the diameter or effective diameter of the extraction column body, the internal components of the extraction column are densely arranged in the extraction column body, the organic phase inlet of the extraction column and the aqueous phase outlet of the extraction column are respectively opened on the side wall of the aqueous phase clarification section of the extraction column, and the aqueous phase inlet of the extraction column and the organic phase outlet of the extraction column are respectively opened on the side wall of the organic phase clarification section of the extraction column; The washing column component includes a washing column body, internal components of the washing column, an organic phase clarification section of the washing column, an aqueous phase clarification section of the washing column, an organic phase inlet of the washing column, an aqueous phase inlet of the washing column, an organic phase outlet of the washing column and an aqueous phase outlet of the washing column; the organic phase clarification section of the washing column, the washing column body and the aqueous phase clarification section of the washing column are arranged in through connection from top to bottom, the diameter or effective diameter of the organic phase clarification section of the washing column and the aqueous phase clarification section of the washing column is greater than the diameter or effective diameter of the washing column body, the internal components of the washing column are densely arranged in the washing column body, the organic phase inlet of the washing column and the aqueous phase outlet of the washing column are respectively opened on the side wall of the aqueous phase clarification section of the washing column, and the aqueous phase inlet of the washing column and the organic phase outlet of the washing column are respectively opened on the side wall of the organic phase clarification section of the washing column; The stripping column component includes a stripping column body, internal components of the stripping column, an organic phase clarification section of the stripping column, an aqueous phase clarification section of the stripping column, an organic phase inlet of the stripping column, an aqueous phase inlet of the stripping column, an organic phase outlet of the stripping column and an aqueous phase outlet of the stripping column; the organic phase clarification section of the stripping column, the stripping column body and the aqueous phase clarification section of the stripping column are arranged in through connection from top to bottom, the diameter or effective diameter of the organic phase clarification section of the stripping column and the aqueous phase clarification section of the stripping column is greater than the diameter or effective diameter of the stripping column body, the internal components of the stripping column are densely arranged in the stripping column body, the organic phase inlet of the stripping column and the aqueous phase outlet of the stripping column are respectively opened on the side wall of the aqueous phase clarification section of the stripping column, and the aqueous phase inlet of the stripping column and the organic phase outlet of the stripping column are respectively opened on the side wall of the organic phase clarification section of the stripping column; The pulse component includes a pulse main pipe, a pulsed three-way valve for the extraction column, a three-way valve for the washing column, a three-way valve for the stripping column, a pulsed leg for the extraction column, a pulsed leg for the washing column and a pulsed leg for the stripping column; The extraction tower pulse three-way valve, the washing tower three-way valve and the stripping tower three-way valve are sequentially arranged on the pulse main pipe. The inlet end of the pulse main pipe is the compressed air inlet end, and the outlet end of the pulse main pipe is the gas discharge end; the top of the extraction tower pulse leg is connected to the side connection end of the extraction tower pulse three-way valve, and the bottom of the extraction tower pulse leg is connected to the aqueous phase clarification section of the extraction tower. The top of the washing tower pulse leg is connected to the side connection end of the washing tower three-way valve, and the bottom of the washing tower pulse leg is connected to the aqueous phase clarification section of the washing tower. The top of the stripping tower pulse leg is connected to the side connection end of the stripping tower three-way valve, and the bottom of the stripping tower pulse leg is connected to the aqueous phase clarification section of the stripping tower; The pulse assembly sequentially performs the first pulse mode and the second pulse mode. The first pulse mode is that the inlet end of the extraction tower pulse three-way valve is connected to the side connection end of the extraction tower pulse three-way valve and the direct outlet end of the extraction tower pulse three-way valve is closed. At the same time, the inlet end of the washing tower three-way valve is closed, and the side connection end of the washing tower three-way valve is connected to the direct outlet end of the washing tower three-way valve. At the same time, the inlet end of the stripping tower three-way valve is connected to the side connection end of the stripping tower three-way valve and the direct outlet end of the stripping tower three-way valve is closed; The second pulse mode is that the inlet end of the extraction tower pulse three-way valve is closed, the side connection end of the extraction tower pulse three-way valve is connected to the direct outlet end of the extraction tower pulse three-way valve. At the same time, the inlet end of the washing tower three-way valve is connected to the side connection end of the washing tower three-way valve, and the direct outlet end of the washing tower three-way valve is closed. At the same time, the inlet end of the stripping tower three-way valve is closed, and the side connection end of the stripping tower three-way valve is connected to the direct outlet end of the stripping tower three-way valve.

2. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 1, characterized in that, the pulse assembly further includes a pressure gauge, and the pressure gauge is respectively arranged in front of the extraction tower pulse three-way valve, the washing tower three-way valve or the stripping tower three-way valve on the pulse main pipe.

3. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 1, characterized in that, the internal component of the extraction tower is a baffle plate, the internal component of the washing tower is a sieve plate, and the internal component of the stripping tower is a sieve plate.

4. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 1, characterized in that, the inlet ends of the extraction tower pulse three-way valve, the washing tower three-way valve and the stripping tower three-way valve are all connected to the pulse main pipe in the direction close to the compressed air inlet end, and the direct outlet ends are all connected to the pulse main pipe in the direction close to the gas discharge end.

5. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 1, characterized in that, transfer tanks are arranged between the organic phase outlet of the extraction tower and the organic phase inlet of the washing tower, and between the organic phase outlet of the washing tower and the organic phase inlet of the stripping tower.

6. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 1, characterized in that, The diameters of the pulse legs of the extraction column, washing column, and stripping column are respectively 1 / 3 to 1 / 5 of the diameters of the extraction column body, washing column body, and stripping column body, and the heights of the tops of the pulse legs of the extraction column, washing column, and stripping column are respectively 0.5 to 2 m higher than the tops of the organic phase clarification sections of the extraction column, washing column, and stripping column.

7. The method for separating and purifying rubidium and cesium using a pulsed extraction column according to any one of claims 1 to 6, characterized in that, the method comprises the following steps: (1) Discharge the initial organic phase into the extraction column body through the organic phase inlet of the extraction column, and discharge the aqueous raw material containing rubidium and cesium into the extraction column body through the aqueous phase inlet of the extraction column. The organic phase and the aqueous phase are in countercurrent contact by gravity and density difference to carry out an extraction reaction in the internal components of the extraction column body. The flow rate of the materials is such that the ratio of the initial organic phase to the aqueous raw material containing rubidium and cesium is maintained at (10 to 2):(0.9 to 1.1). The raffinate after extraction is discharged through the aqueous phase outlet of the extraction column, and the organic phase loaded with rubidium and cesium is discharged through the organic phase outlet of the extraction column and enters the organic phase inlet of the washing column after passing through the transfer tank; (2) Discharge the organic phase loaded with rubidium and cesium obtained in step (1) into the washing column body through the organic phase inlet of the washing column, and discharge pure water into the washing column body through the aqueous phase inlet of the washing column. The organic phase and the aqueous phase are in countercurrent contact by gravity and density difference to carry out washing in the internal components of the washing column body. The flow rate of the materials is such that the ratio of the organic phase loaded with rubidium and cesium to pure water is maintained at (20 to 6):(0.9 to 1.1). The aqueous phase after washing is discharged through the aqueous phase outlet of the washing column, and the organic phase loaded with rubidium and cesium after washing is discharged through the organic phase outlet of the washing column and enters the organic phase inlet of the stripping column after passing through the transfer tank; (3) Discharge the organic phase loaded with rubidium and cesium after washing in step (2) into the stripping column body through the organic phase inlet of the stripping column, and use one or both of dilute hydrochloric acid or dilute sulfuric acid solutions with an acidity of 0.01 to 2 mol / L as the stripping aqueous phase, and discharge it into the stripping column body through the aqueous phase inlet of the stripping column. The organic phase and the aqueous phase are in countercurrent contact by gravity and density difference to carry out a stripping treatment in the internal components of the stripping column body. The flow rate of the materials is such that the ratio of the organic phase loaded with rubidium and cesium to the stripping aqueous phase is maintained at (20 to 2):(0.9 to 1.1); After the countercurrent flow in steps (1) to (3) stabilizes, compressed gas is introduced through the inlet end of the pulse main pipe, and the extraction tower pulse three-way valve, the scrubbing tower three-way valve, and the stripping tower three-way valve are started, and the first pulse mode and the second pulse mode are carried out in sequence. In the first pulse mode, the inlet end of the extraction tower pulse three-way valve is connected to the side connection end of the extraction tower pulse three-way valve, and the direct outlet end of the extraction tower pulse three-way valve is closed. At the same time, the inlet end of the scrubbing tower three-way valve is closed, and the side connection end of the scrubbing tower three-way valve is connected to the direct outlet end of the scrubbing tower three-way valve. At the same time, the inlet end of the stripping tower three-way valve is connected to the side connection end of the stripping tower three-way valve, and the direct outlet end of the stripping tower three-way valve is closed. In the second pulse mode, the inlet end of the extraction tower pulse three-way valve is closed, the side connection end of the extraction tower pulse three-way valve is connected to the direct outlet end of the extraction tower pulse three-way valve. At the same time, the inlet end of the scrubbing tower three-way valve is connected to the side connection end of the scrubbing tower three-way valve, and the direct outlet end of the scrubbing tower three-way valve is closed. At the same time, the inlet end of the stripping tower three-way valve is closed, and the side connection end of the stripping tower three-way valve is connected to the direct outlet end of the stripping tower three-way valve. (5) Repeat the first pulse mode and the second pulse mode in sequence for multiple times. The duration of each first pulse mode is 0.5 - 5 s, and the duration of each second pulse mode is 0.5 - 5 s. The stripped aqueous phase is discharged through the aqueous phase outlet of the stripping tower to obtain the product for extracting and separating rubidium and cesium. The blank organic phase after stripping is discharged through the organic phase outlet of the stripping tower and enters the subsequent production process.

8. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 7, characterized in that, the lowest pressure in the extraction tower body is higher than the highest pressure in the scrubbing tower body, and the lowest pressure in the scrubbing tower body is higher than the highest pressure in the stripping tower body.

9. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 7, characterized in that, the initial organic phase in step (1) is a mixed solution of t-BAMBP and a diluent mixed in a volume ratio of (5 - 30):(95 - 70). The diluent is one or a combination of more of sulfonated kerosene, xylene, diethylbenzene, or cyclohexane. The aqueous phase raw material containing rubidium and cesium is an aqueous phase raw material containing rubidium and / or cesium and containing lithium and / or potassium.

10. The method for separating and purifying rubidium and cesium using a pulsed extraction tower according to claim 7, characterized in that, the compressed gas in step (4) is compressed air or compressed inert gas. The extraction tower pulse three-way valve, the scrubbing tower three-way valve, and the stripping tower three-way valve are electric control valves or pneumatic control valves. In the case of power failure or gas cut-off, their respective side connection ends are connected to the direct outlet ends, and in the case of power-on or gas supply, their respective inlet ends are connected to the side connection ends.

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