An apparatus and method for organic saponification in hydrometallurgy

Abstract

The present application belongs to the technical field of hydrometallurgy, and particularly relates to a device and method for organic saponification in hydrometallurgy, which simultaneously applies pulse fluid technology and ultrasonic technology to organic saponification in hydrometallurgy. The pulse fluid utilizes an external mechanical field to strengthen the reaction process. The circulating heat preservation water transmits ultrasonic waves to the reaction process to strengthen mass transfer and mixing, and has good mixing effect and mass and heat transfer characteristics. The control is simple and accurate, and the pulse fluid technology is particularly suitable for multiphase reactions and has a very significant effect on strengthening transmission. Through efficient mixing and precise control of the pulse fluid technology, the amount of saponification solution used in the hydrometallurgy process can be significantly saved, the saponification efficiency of the extractant is improved, ammonia loss and environmental hazards caused by ammonia volatilization in the process are avoided, and precise control of process parameters and fully automatic control of multi-stage continuous extraction are realized.

Description

Technical Field

[0001] This invention belongs to the field of hydrometallurgical technology, specifically a device and method for organic saponification in hydrometallurgical processes. Background Technology

[0002] Acidic organophosphorus extractants, such as bis(2-ethylhexyl)phosphate (P204), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507), and bis(2,4,4-trimethylpentyl)phosphonic acid (Cyanex 272), are widely used extractants in hydrometallurgical extraction processes. They are extensively applied in the separation of nickel, cobalt, and rare earth elements, as well as in the separation of rare and dispersed elements (Ga). 3 + In 3+ Enrichment of elements such as Fe and impurity elements 3+ Al 3+ Ca 2+ Mn 2+ Zn 2+ ,Sc 3+ Deep purification of (etc.).

[0003] The reaction process of acidic organophosphorus extractants with metal ions can be described as a bonding process in which acid radical anions and metal ions form neutral extractable compounds. As the solvent extraction reaction proceeds, the H+ in the feed solution... + The content of [acid] gradually increases, leading to a decrease in the extraction efficiency of the target metal ions. To mitigate the negative impact of aqueous phase pH changes on the extraction performance of acidic organophosphorus extractants, an industrial pre-saponification process is typically added before the extraction step. This involves neutralizing the acidic organophosphorus extractant with an alkaline substance (NaOH, NH4OH, Ca(OH)2, etc.) beforehand to reduce the amount of H2 produced during the extraction process. + The quantity is adjusted to balance the acidity of the feed solution in the later stages of extraction. Currently, in order to meet environmental protection requirements, relevant companies are using ammonia soap technology to reduce the generation of high-salinity wastewater.

[0004] Industrial pre-saponification is usually carried out in an extraction tank. The multi-stage countercurrent saponification process is also relatively mature in actual production. However, due to the open tank, the water seal cannot completely prevent the ammonia odor from escaping, and it is not conducive to the precise control of the temperature in each tank. When the two phases are mixed, the mechanical stirring efficiency of the stirring chamber is low, the oil and water contact is not sufficient, and the accidental errors caused by manual operation result in the saponification rate no longer meeting the requirements. Summary of the Invention

[0005] To address the problems existing in the prior art, the main objective of this invention is to propose an apparatus and method for organic saponification in hydrometallurgical processes.

[0006] According to one aspect of the present invention, the present invention provides the following technical solution:

[0007] An apparatus for organic saponification in hydrometallurgical processes is a tower-type packed bed pulsed fluid reactor, comprising:

[0008] Pulse fluid generator, light phase inlet section, heavy phase inlet section, filling section, light phase outlet section, heavy phase outlet section, and circulating water ultrasonic heating device;

[0009] The pulsed fluid generator is located at the bottom of the equipment, generating a periodic external mechanical force field and transmitting it to the fluid inside the equipment, causing it to form tiny microspheres, thereby enhancing mass transfer and improving contact efficiency. The filling section is located in the middle of the equipment and is filled with packing material in a random packing manner. The light phase inlet section is located below the filling section and has a light phase inlet. The heavy phase inlet section is located above the filling section and has a heavy phase inlet. The heavy phase outlet section is located at the bottom of the equipment and has a heavy phase outlet. The light phase outlet section is located at the top of the equipment and has a light phase outlet. A heat exchange jacket is connected to the outside of the filling section, and the heat exchange jacket is connected to the circulating water ultrasonic heating device through a pipeline.

[0010] The heavy phase enters the equipment through the heavy phase inlet, passes through the filling section from top to bottom, and is extracted from the heavy phase outlet section at the bottom of the equipment as a continuous phase medium. The light phase enters the equipment through the light phase inlet, passes through the filling section from bottom to top, and under the action of the pulse fluid generator, it undergoes continuous two-phase exchange and phase separation with the continuous phase, and finally overflows from the light phase outlet section at the top of the equipment.

[0011] As a preferred embodiment of the equipment for organic saponification in hydrometallurgy according to the present invention, the light phase inlet is connected to a light phase storage container, and a light phase feed flow pump is provided on the connecting pipe; the heavy phase inlet is connected to a heavy phase storage container, and a heavy phase feed flow pump is provided on the connecting pipe; a heavy phase outlet flow valve is provided at the heavy phase outlet.

[0012] As a preferred embodiment of the equipment for organic saponification in hydrometallurgy as described in this invention, the light phase outlet section and the heavy phase outlet section are further provided with observation holes for observing the interface between the two phases.

[0013] As a preferred embodiment of the device for organic saponification in hydrometallurgy according to the present invention, the pulse fluid generating device is a diaphragm oscillating pump.

[0014] To solve the above-mentioned technical problems, according to another aspect of the present invention, the present invention provides the following technical solution:

[0015] A method for organic saponification in hydrometallurgical processes includes the following steps:

[0016] S1. Introduce pure water (heavy phase) into the equipment through the heavy phase inlet to form a continuous phase. After the pure water flows out from the heavy phase outlet, adjust the heavy phase feed flow pump to obtain a stable heavy phase feed flow rate.

[0017] S2. After the heavy phase feed flow rate stabilizes, the extraction organic phase (light phase) is introduced into the equipment through the light phase inlet using a flow pump to form a dispersed phase. When the light phase flows out from the light phase outlet, the light phase feed flow pump is adjusted to obtain a stable light phase feed flow rate.

[0018] S3. When the light phase feed flow rate is stable, adjust the heavy phase outlet flow valve and observe the interface between the two phases through the observation hole. When the phase interface position remains stable, a stable heavy phase discharge flow rate is obtained.

[0019] S4. Replace the heavy phase with saponified liquid from pure water and introduce it into the equipment through the heavy phase inlet. Maintain the previous heavy phase flow rate and observe the interface between the two phases through the observation hole until the interface position is stable.

[0020] S5. Turn on the pulse fluid generator and adjust the oscillation frequency and amplitude; at the same time, turn on the circulating water ultrasonic heating device, monitor the liquid temperature inside the equipment in real time, so that the temperature inside the equipment is kept stable, and adjust the ultrasonic frequency to enhance the full mixing and mass transfer between the light phase and the heavy phase.

[0021] S6. Real-time monitoring of the saponification rate of the light phase effluent and the OH content in the heavy phase effluent. - Concentration, saponification rate of light phase effluent and OH in heavy phase effluent - When the concentration is stable, it can be considered that the mass transfer between the two phases in the equipment has reached equilibrium, and the heavy phase at this time is the fully saponified organic phase.

[0022] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, in step S1, the pure water (heavy phase) comes from an ultrapure water system.

[0023] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, in step S2, the extracted organic phase is a mixture of acidic phosphine extractant and solvent oil, wherein the proportion of acidic phosphine extractant is 5~50 vol%, and the proportion of solvent oil is 50~95 vol%; the acidic phosphine extractant is one of di(2-ethylhexyl) phosphate (P204), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507), or di(2,4,4-trimethylpentyl)phosphonic acid (Cyanex 272); and the solvent oil is industrial kerosene.

[0024] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, in step S2, when the light phase feed flow rate is stable, the ratio of the heavy phase feed flow rate to the light phase feed flow rate is 1:(3~9).

[0025] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, in step S4, the saponification liquid is an alkaline aqueous solution, preferably ammonia or sodium hydroxide solution, with the ammonia concentration being 1.0~8.0 mol / L and the sodium hydroxide solution concentration being 0.5~3.0 mol / L.

[0026] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, in step S5, the pulse fluid generator can enable the two phases in the equipment to obtain different oscillation frequencies and amplitudes, with a frequency of 0.25~1.0Hz and an amplitude of 1~5cm.

[0027] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, in step S5, the temperature of the circulating water is 40~50℃; and the ultrasonic frequency of the ultrasonic heating device for the circulating water is 20~40kHz.

[0028] As a preferred embodiment of the method for organic saponification in hydrometallurgy according to the present invention, wherein: in step S6, the saponification rate of the qualified light phase effluent is 60-80%; the OH content in the qualified heavy phase effluent is... - The concentration of OH is not higher than 0.2 mol / L. Preferably, the OH in the saponified heavy phase effluent is... - The concentration of OH is not higher than 0.1 mol / L. Further preferred, the OH in the saponified heavy phase effluent should not exceed 0.1 mol / L. - The concentration is not higher than 0.05 mol / L.

[0029] The beneficial effects of this invention are as follows:

[0030] This invention provides an apparatus and method for organic saponification in hydrometallurgical processes. It simultaneously applies pulsed fluid technology and ultrasonic technology to organic saponification in hydrometallurgical processes. The pulsed fluid utilizes an external mechanical force field to enhance the reaction process, while the ultrasonic waves, conducted through circulating insulated water, enhance mass transfer and mixing. This results in excellent mixing, mass transfer, and heat transfer characteristics, with simple and precise control. It is particularly suitable for multiphase reactions, showing significant effects in enhancing mass transfer. Through the efficient phase mixing and precise control of pulsed fluid technology, the amount of saponification liquid used in the hydrometallurgical process can be significantly reduced, the saponification efficiency of the extractant can be improved, and ammonia loss and environmental hazards caused by ammonia volatilization can be avoided. Simultaneously, it achieves precise control of process parameters and fully automated control of multi-stage continuous extraction. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0032] Figure 1 This is a schematic diagram of the equipment used in the hydrometallurgical process for organic saponification according to the present invention.

[0033] Among them, 1-pulse fluid generator, 2-light phase inlet section, 3-heavy phase inlet section, 4-filling section, 5-light phase outlet section, 6-heavy phase outlet section, 7-light phase storage container, 8-heavy phase storage container, 9-ultrapure water machine, 10-circulating water ultrasonic heating device, 11-light phase effluent container, 12-heavy phase effluent container.

[0034] The effects, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0035] The technical solutions described below in conjunction with the embodiments will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] This invention provides an apparatus and method for organic saponification in hydrometallurgical processes, which has the following advantages:

[0037] (1) The use of pulsed fluid technology and ultrasonic technology can significantly reduce the amount of saponification liquid used in the hydrometallurgical process and improve the saponification efficiency of the extractant. The organic phase is extracted using countercurrent saponification with an alkaline aqueous solution. The alkaline aqueous solution is a continuous phase that fills the packed equipment. The extracted organic phase, entering the equipment from the bottom of the tower, forms dispersed oil droplets (dispersed phase) after passing through the small holes in the distribution plate. These droplets flow upwards through the water layer, and the oil droplets come into countercurrent contact with the water flow. The H+ in the oil droplets... + Extraction occurs through the surface of oil droplets into the aqueous phase, while cations in the aqueous phase enter the oil phase. As oil droplets pass through the packing layer, external mechanical forces continuously break them into smaller droplets, ensuring a larger oil-water contact area and accelerating the extraction rate. Compared with existing mixed-clarification extraction tank technology, pulsed fluid technology significantly improves the two-phase mass transfer efficiency, greatly reducing the amount of alkaline aqueous solution used while achieving the same saponification effect. In other words, pulsed fluid technology can maximize organic saponification efficiency while ensuring efficient two-phase mass transfer.

[0038] (2) It can avoid ammonia loss and environmental hazards caused by ammonia volatilization during the process. Existing mixing and clarifying extraction tanks usually use water seals, which cannot completely prevent ammonia volatilization. The concentration of ammonia solution used for saponification is usually high, and long-term volatilization into the environment at high temperatures can cause great harm to human health and the environment. The equipment has the characteristics of being airtight and continuous, which can effectively prevent ammonia from volatilizing into the outside air under high-temperature conditions, thereby avoiding a series of hazards.

[0039] (3) The use of pulsed fluid technology and ultrasonic technology enables precise control of process parameters and fully automated control of multi-stage continuous extraction. The parameters of each stage of the extraction tank are affected by the precision of the tank body, resulting in large systematic and random errors, which requires cumbersome manual adjustment. Thanks to the tower-type continuous structure of the equipment, the parameters of each stage of the equipment are stable and controllable. The phase interface of the tower body, the temperature of the circulating water, and the flow rate of the inlet and outlet valve positions can be fully automated, reducing human error, and the operation is simple and safe.

[0040] like Figure 1 As shown, the present invention provides an apparatus for organic saponification in hydrometallurgical processes, which is a tower-type packed bed pulsed fluid reactor, comprising:

[0041] 1. Pulse fluid generator; 2. Light phase inlet section; 3. Heavy phase inlet section; 4. Filling section; 5. Light phase outlet section; 6. Heavy phase outlet section; 7. Circulating water ultrasonic heating device; 8.

[0042] The pulsed fluid generator 1 is located at the bottom of the equipment, generating a periodic external mechanical force field and transmitting it to the fluid inside the equipment, causing it to form tiny microspheres, thereby enhancing mass transfer and improving contact efficiency; the filling section 4 is located in the middle of the equipment, and its interior is filled with packing material in a random packing manner; the light phase inlet section 2 is located below the filling section 4 and has a light phase inlet; the heavy phase inlet section 3 is located above the filling section 4 and has a heavy phase inlet; the heavy phase outlet section 6 is located at the bottom of the equipment and has a heavy phase outlet; the light phase outlet section 5 is located at the top of the equipment and has a light phase outlet; a heat exchange jacket is connected to the outside of the filling section 4, and the heat exchange jacket is connected to the circulating water ultrasonic heating device 10 through a pipeline;

[0043] The heavy phase enters the equipment from the heavy phase inlet, passes through the filling section 4 from top to bottom, and is extracted from the heavy phase outlet section 6 at the bottom of the equipment as a continuous phase medium; the light phase enters the equipment from the light phase inlet, passes through the filling section 4 from bottom to top, and under the action of the pulse fluid generator 1, it continuously exchanges and separates phases with the continuous phase, and finally overflows from the light phase outlet section 5 at the top of the equipment.

[0044] Preferably, the light phase inlet is connected to the light phase storage container 7, and the connecting pipe is equipped with a light phase feed flow pump; the heavy phase inlet is connected to the heavy phase storage container 8 (which also includes an ultrapure water machine 9, the pure water of which comes from the ultrapure water machine 9), and the connecting pipe is equipped with a heavy phase feed flow pump; the heavy phase outlet is equipped with a heavy phase outlet flow valve.

[0045] Preferably, the light phase outlet section 5 and the heavy phase outlet section 6 are also provided with observation holes for observing the two-phase interface.

[0046] Preferably, the pulse fluid generating device 1 is a diaphragm oscillating pump.

[0047] Preferably, the connecting pipe of the device of the present invention is equipped with a valve and / or a pressure gauge as needed.

[0048] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0049] Example 1

[0050] A method for organic saponification in hydrometallurgical processes includes the following steps:

[0051] S1. Pure water (heavy phase) is introduced into the pulsed fluid reactor from the top using a flow pump to form a continuous phase. Once the heavy phase flows out from the top heavy phase outlet, the flow rate of the heavy phase feed pump is adjusted to 10.1 dm³. 3 / h and stable;

[0052] S2. The extractable organic phase (light phase) is pumped from the bottom of the column into the pulsed fluid reactor to form a dispersed phase. The extractable organic phase (light phase) is a mixture of 36 vol% P507 and 64 vol% industrial kerosene. When the light phase flows out from the top heavy phase outlet, the flow rate of the light phase feed pump is adjusted to 84.3 dm³. 3 / h and stabilized, at which point the ratio of heavy phase flow rate to light phase flow rate was 1 / 8.4;

[0053] S3. When the light phase feed flow rate is stable, open the heavy phase outlet flow valve at the bottom of the tower, adjust the heavy phase outlet flow valve and observe the two-phase interface through the observation hole at the top of the tower to keep the phase interface position stable.

[0054] S4. Close the pure water control valve and open the saponification liquid control valve to allow the saponification liquid to enter the pulse fluid reactor from the top. The saponification liquid is an 8mol / L ammonia solution.

[0055] S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency inside the equipment to 0.67Hz and the amplitude to 3cm; turn on the circulating water ultrasonic heating device, adjust the ultrasonic frequency to 40kHz, and control the circulating water flow rate to 120dm³. 3 / h, the circulating water temperature is controlled at 42℃, and after full balancing, the liquid temperature in the equipment is stabilized at 41℃;

[0056] S6. Real-time monitoring of the saponification rate of the light phase effluent and the OH content in the heavy phase effluent. - Concentration, saponification rate of light phase effluent and OH in heavy phase effluent - When the concentration is stable, it can be considered that the mass transfer between the two phases in the equipment has reached equilibrium. The saponification rate of the light phase effluent and the OH content in the heavy phase effluent at different reaction times are also considered. - Concentrations are shown in Table 1. The results indicate that the saponification rate of the light phase effluent was 72.3%; the OH- concentration in the heavy phase effluent... - The concentration is 0.05 mol / L. The organic and aqueous phases separate well.

[0057] Table 1

[0058]

[0059] Example 2

[0060] A method for organic saponification in hydrometallurgical processes includes the following steps:

[0061] S1. Pure water (heavy phase) is introduced into the pulsed fluid reactor from the top using a flow pump to form a continuous phase. Once the heavy phase flows out from the top heavy phase outlet, the flow rate of the heavy phase feed pump is adjusted to 10.1 dm³. 3 / h and stable;

[0062] A2. The extractable organic phase (light phase) is fed from the bottom of the column into the pulsed fluid reactor using a flow pump to form a dispersed phase. The extractable organic phase (light phase) is a mixture of 30 vol% P2O4 and 70 vol% industrial kerosene. Once the light phase flows out from the top heavy phase outlet, the flow rate of the light phase feed pump is adjusted to 42.5 dm³. 3 / h and stabilized, at which point the ratio of heavy phase flow rate to light phase flow rate was 1 / 4.2;

[0063] S3. When the light phase feed flow rate is stable, open the bottom heavy phase outlet flow valve, adjust the heavy phase outlet flow valve and observe the two-phase interface through the top observation hole to keep the phase interface position stable.

[0064] S4. Close the pure water control valve and open the saponification liquid control valve to allow the saponification liquid to enter the pulse fluid reactor from the top. The saponification liquid is a 3mol / L ammonia solution.

[0065] S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency inside the equipment to 1.0Hz and the amplitude to 3cm; turn on the circulating water ultrasonic heating device, adjust the ultrasonic frequency to 30kHz, and control the circulating water flow rate to 120dm³. 3 / h, the circulating water temperature is controlled at 52℃, and after full balancing, the liquid temperature in the equipment is stabilized at 50℃;

[0066] S6. Real-time monitoring of the saponification rate of the light phase effluent and the OH content in the heavy phase effluent. - Concentration, saponification rate of light phase effluent and OH in heavy phase effluent - When the concentration is stable, it can be considered that the mass transfer between the two phases in the equipment has reached equilibrium. The saponification rate of the light phase effluent and the OH content in the heavy phase effluent at different reaction times are also considered. - Concentrations are shown in Table 2. The results indicate that the saponification rate of the light phase effluent is 65.3%; the OH- concentration in the heavy phase effluent... - The concentration is 0.04 mol / L. The organic and aqueous phases separate well.

[0067] Table 2

[0068]

[0069] Example 3

[0070] A method for organic saponification in hydrometallurgical processes includes the following steps:

[0071] S1. Pure water (heavy phase) is introduced into the pulsed fluid reactor from the top using a flow pump to form a continuous phase. Once the heavy phase flows out from the top heavy phase outlet, the flow rate of the heavy phase feed pump is adjusted to 20.6 dm³. 3 / h and stable;

[0072] S2. The extractable organic phase (light phase) is fed into the pulsed fluid reactor from the bottom using a flow pump to form a dispersed phase. The extractable organic phase (light phase) is a fresh mixture of 30 vol% Cyanex 272 and 70 vol% industrial kerosene. Once the light phase flows out from the top heavy phase outlet, the flow rate of the light phase feed pump is adjusted to 92.2 dm³. 3 / h and stabilized, at which point the ratio of heavy phase flow rate to light phase flow rate was 1 / 4.5;

[0073] S3. When the light phase feed flow rate is stable, open the bottom heavy phase outlet flow valve, adjust the heavy phase outlet flow valve and observe the two-phase interface through the top observation hole to keep the phase interface position stable.

[0074] S4. Close the pure water control valve and open the saponification liquid control valve to allow the saponification liquid to enter the pulse fluid reactor from the top. The saponification liquid is a 3 mol / L sodium hydroxide solution.

[0075] S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency inside the equipment to 0.67Hz and the amplitude to 3cm; turn on the circulating water ultrasonic heating device, adjust the ultrasonic frequency to 20kHz, and control the circulating water flow rate to 120dm³. 3 / h, the circulating water temperature is controlled at 46.5℃, and after full balancing, the liquid temperature inside the equipment is stabilized at 45℃;

[0076] S6. Real-time monitoring of the saponification rate of the light phase effluent and the OH content in the heavy phase effluent. - Concentration, saponification rate of light phase effluent and OH in heavy phase effluent - When the concentration is stable, it can be considered that the mass transfer between the two phases in the equipment has reached equilibrium. The saponification rate of the light phase effluent and the OH content in the heavy phase effluent at different reaction times are also considered. - Concentrations are shown in Table 3. The results indicate that the saponification rate of the light phase effluent was 61.2%; the OH content in the heavy phase effluent... - The concentration is 0.05 mol / L. The organic and aqueous phases separate well.

[0077] Table 3

[0078]

[0079] Comparative Example 1

[0080] The difference from Example 1 is that an organic saponification is performed using a mixing clarification tank, which includes the following steps:

[0081] S1. Add pure water (heavy phase) from the top into the mixing and clarification tank. The mixing chamber of the mixing and clarification tank has a volume of 150L, ​​a clarification chamber volume of 600L, 15 stages, and a stirring paddle speed of 900r / min. The temperature of the pure water is 40℃. Stop when the volume of the heavy phase occupies 1 / 9 of the tank volume.

[0082] S2. The extracted organic phase (light phase) is added to the mixing and clarifying tank from one side. The loaded organic phase (light phase) is a fresh mixture of 36 vol% P507 and 64 vol% industrial kerosene at a temperature of 40°C. When the light phase flows out of the overflow port of the extraction tank, the flow rate of the light phase feed pump is adjusted to 85.5 dm³. 3 Simultaneously adjust the heavy phase feed pump flow rate to 10.5 dm³ / h. 3 / h and stabilized, at which point the ratio of heavy phase flow rate to light phase flow rate was 1 / 8.1;

[0083] S3. Open the heavy phase outlet flow valve of the extraction tank to keep the phase interface position in the clarification chamber stable;

[0084] S4. Close the pure water control valve and open the saponification liquid control valve to switch the heavy phase from pure water to the saponification liquid, which is an 8 mol / L ammonia solution.

[0085] S5. Real-time monitoring of the saponification rate of the light phase effluent and the OH- content in the heavy phase effluent. - Concentration, saponification rate of light phase effluent and OH in heavy phase effluent - When the concentration is stable, it can be considered that the mass transfer between the two phases in the equipment has reached equilibrium. The saponification rate of the light phase effluent and the OH content in the heavy phase effluent at different reaction times are also considered. -The concentrations are shown in Table 4. The results indicate that the saponification rate of the light phase effluent was 52.8%; the OH content in the heavy phase effluent... - The concentration is 0.8 mol / L.

[0086] Table 4

[0087]

[0088] Comparative Example 2

[0089] The difference from Example 1 is that a circulating water heating device is used instead of a circulating water ultrasonic heating device, and the circulating water is not ultrasonically treated.

[0090] A method for organic saponification in hydrometallurgical processes includes the following steps:

[0091] S1. Pure water (heavy phase) is introduced into the pulsed fluid reactor from the top using a flow pump to form a continuous phase. Once the heavy phase flows out from the top heavy phase outlet, the flow rate of the heavy phase feed pump is adjusted to 10.1 dm³. 3 / h and stable;

[0092] S2. The extractable organic phase (light phase) is pumped from the bottom of the column into the pulsed fluid reactor to form a dispersed phase. The extractable organic phase (light phase) is a mixture of 36 vol% P507 and 64 vol% industrial kerosene. When the light phase flows out from the top heavy phase outlet, the flow rate of the light phase feed pump is adjusted to 84.3 dm³. 3 / h and stabilized, at which point the ratio of heavy phase flow rate to light phase flow rate was 1 / 8.4;

[0093] S3. When the light phase feed flow rate is stable, open the heavy phase outlet flow valve at the bottom of the tower, adjust the heavy phase outlet flow valve and observe the two-phase interface through the observation hole at the top of the tower to keep the phase interface position stable.

[0094] S4. Close the pure water control valve and open the saponification liquid control valve to allow the saponification liquid to enter the pulse fluid reactor from the top. The saponification liquid is an 8mol / L ammonia solution.

[0095] S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency within the equipment to 0.67Hz and the amplitude to 3cm; turn on the circulating water heating device and control the circulating water flow rate to 120dm³. 3 / h, the circulating water temperature is controlled at 42℃, and after full balancing, the liquid temperature in the equipment is stabilized at 41℃;

[0096] S6. Real-time monitoring of the saponification rate of the light phase effluent and the OH content in the heavy phase effluent. - Concentration, saponification rate of light phase effluent and OH in heavy phase effluent -When the concentration is stable, it can be considered that the mass transfer between the two phases in the equipment has reached equilibrium. The saponification rate of the light phase effluent and the OH content in the heavy phase effluent at different reaction times are also considered. - Concentrations are shown in Table 5. The results indicate that the saponification rate of the light phase effluent was 58.3%; the OH- concentration in the heavy phase effluent... - The concentration is 0.55 mol / L.

[0097] Table 5

[0098]

[0099] As can be seen from the above examples and comparative examples, the saponification rate of Comparative Example 1, using an extraction tank under the same conditions, is significantly lower, and the utilization rate of the saponification liquid is correspondingly lower. In Comparative Example 2, using a pulsed fluid generator but without circulating water ultrasound, the utilization rate of the saponification liquid in organic saponification is greatly reduced. Example 1, employing both pulsed fluid technology and ultrasonic technology in the organic saponification reaction, has significant advantages in saving saponification liquid and improving saponification efficiency.

[0100] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for organic saponification in hydrometallurgy, characterized by, The equipment for organic saponification in hydrometallurgy adopted includes: a pulse fluid generating device, a light phase inlet section, a heavy phase inlet section, a filling section, a light phase outlet section, a heavy phase outlet section and a circulating water ultrasonic heating device; the pulse fluid generating device is located at the bottom of the equipment, the filling section is located in the middle of the equipment and is filled with fillers, the light phase inlet section is located below the filling section and is provided with a light phase inlet; the heavy phase inlet section is located above the filling section and is provided with a heavy phase inlet; the heavy phase outlet section is located at the bottom of the equipment and is provided with a heavy phase outlet; the light phase outlet section is located at the top of the equipment and is provided with a light phase outlet; the filling section is externally connected with a heat exchange jacket, and the circulating water ultrasonic heating device is located on one side of the filling section and is connected with the heat exchange jacket through a pipeline; and the method comprises the following steps: S1, pure water is introduced into the equipment from the heavy phase inlet to form a continuous phase, and after the pure water flows out from the heavy phase outlet, the heavy phase feed flow pump is adjusted to obtain a stable heavy phase feed flow; S2, after the heavy phase feed flow is stabilized, the extraction organic phase is introduced into the equipment from the light phase inlet through a flow pump to form a dispersed phase; when the light phase flows out from the light phase outlet, the light phase feed flow pump is adjusted to obtain a stable light phase feed flow; the extraction organic phase is an acid phosphine-solvent oil mixture, wherein the proportion of the acid phosphine is 5-50vol%, and the proportion of the solvent oil is 50-95vol%; when the light phase feed flow is stable, the ratio of the heavy phase feed flow to the light phase feed flow is 1:(3-9); S3, when the light phase feed flow is stable, the heavy phase outlet flow valve is adjusted and the two-phase interface is observed through the observation hole, and when the phase interface position remains stable, a stable heavy phase discharge flow is obtained; S4, the pure water is replaced with a saponification solution, which is introduced into the equipment from the heavy phase inlet, the previous heavy phase flow is maintained, and the two-phase interface is observed through the observation hole until the phase interface position is stable; S5, the pulse fluid generating device is turned on, the oscillation frequency and amplitude are adjusted; at the same time, the circulating water ultrasonic heating device is turned on, the liquid temperature in the equipment is monitored in real time, the temperature in the equipment is maintained stable, the ultrasonic frequency is adjusted, the mixing and mass transfer between the light phase and the heavy phase are strengthened; the circulating water temperature is 40-50℃; the ultrasonic frequency of the circulating water ultrasonic heating device is 20-40kHz; the ultrasonic wave is transmitted through the circulating heat preservation water to strengthen the mass transfer and mixing in the reaction process, which has good mixing effect and mass transfer and heat transfer characteristics, is simple and accurate to control, and is especially suitable for multiphase reactions and has very significant effect in strengthening the transfer; S6, real-time detection of the saponification rate of the light phase effluent and the OH - concentration, the saponification rate of the light phase effluent and the OH - concentration of the heavy phase effluent are stable, it is considered that the two-phase mass transfer in the equipment reaches equilibrium, at this time the heavy phase is the completely saponified organic phase; the saponification rate of the saponification qualified light phase effluent is 60-80%; the OH - concentration of the saponification qualified heavy phase effluent is not higher than 0.2 mol / L.

2. The process for organic saponification in hydrometallurgy according to claim 1, characterized in that, The light phase inlet is connected with a light phase storage container, and the connecting pipe is provided with a light phase feed flow pump; the heavy phase inlet is connected with a heavy phase storage container, and the connecting pipe is provided with a heavy phase feed flow pump; the heavy phase outlet is provided with a heavy phase outlet flow valve.

3. The process for organic saponification in hydrometallurgy according to claim 1, characterized in that, The light phase outlet section and the heavy phase outlet section are also provided with observation holes for observing the two-phase interface.

4. The process for organic saponification in hydrometallurgy according to claim 1, characterized in that, The pulse fluid generating device is a diaphragm oscillation pump.

5. The process for organic saponification in hydrometallurgy according to claim 1, characterized in that, In step S2, the acid phosphine is one of di(2-ethylhexyl)phosphate, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester or di(2,4,4-trimethylpentyl) phosphinic acid; and the solvent oil is industrial kerosene.

6. The process for organic saponification in hydrometallurgy according to claim 1, characterized in that, In step S4, the saponification solution is an alkaline aqueous solution.

7. The method for organic saponification in hydrometallurgy according to claim 1, characterized in that, In the step S5, the pulse fluid generating device can make the two phases in the device obtain different oscillation frequencies and amplitudes, the frequency is 0.25-1.0 Hz, and the amplitude is 1-5 cm.

Images