Equipment and method for organic saponification in hydrometallurgy

Abstract

The invention belongs to the technical field of hydrometallurgy, and particularly relates to equipment and a method for organic saponification in hydrometallurgy, a pulse fluid technology and an ultrasonic technology are simultaneously applied to organic saponification in hydrometallurgy, and a pulse fluid utilizes an enhanced reaction process of an external mechanical force field. Circulating heat preservation water conducts ultrasonic waves to act on the reaction process to enhance mass transfer mixing, and the reactor has a good mixing effect and mass transfer and heat transfer characteristics, is simple and accurate to control, is particularly suitable for multi-phase reaction, and has a very remarkable effect in the aspect of enhanced transfer. Through efficient phase mixing and precise control of the pulse fluid technology, the use amount of saponification liquid in the wet smelting process can be remarkably reduced, the saponification efficiency of an extraction agent is improved, ammonia loss and environmental hazards caused by ammonia volatilization in the process are avoided, and meanwhile precise control over process parameters and full-automatic control over multi-stage continuous extraction are achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy, and in particular relates to an apparatus and a method for organic saponification in hydrometallurgy. Background Art

[0002] Acidic organic phosphine extractants represented by di(2-ethylhexyl) phosphate (P204), 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (P507), di(2, 4, 4-trimethylpentyl)phosphinic acid (Cyanex 272) are widely used extractants in the hydrometallurgical extraction process. They are widely used in the separation of nickel, cobalt, rare earth elements, and scattered elements (Ga 3 + 、In 3+ etc.) and impurity elements (Fe 3+ 、Al 3+ , Ca 2+ , Mn 2+ 、Zn 2+ Sc 3+ deep purification of the

[0003] The reaction process of acidic organic phosphine extractants and metal ions can be described as the bonding process of acid anions and metal ions to form neutral extractants. As the solvent extraction reaction proceeds, H + The content of will gradually increase, resulting in a downward trend in the extraction efficiency of the target metal ions. In order to weaken the negative impact of the pH change of the aqueous phase on the extraction performance of acidic organic phosphine extractants, the industry usually adds a pre-saponification step before the extraction process. The specific operation is to use alkaline substances (NaOH, NH 4 OH, Ca(OH) 2 etc.) and acidic organic phosphine extractants to neutralize them in advance to reduce the H generated during the extraction process. + At present, in order to meet the requirements of environmental protection, relevant enterprises all use ammonia soap process to reduce the generation of high-salt wastewater.

[0004] Industrial pre-saponification treatment is usually carried out in an extraction tank, and the multi-stage countercurrent saponification process is also relatively mature in the actual production process. However, due to the open tank body, the water seal cannot completely prevent the emission of ammonia odor, and is not conducive to the precise control of the temperature in each tank body. When the two phases are mixed, the mechanical stirring efficiency in the stirring chamber is low, the oil-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] In order to solve the problems existing in the prior art, the main purpose of the present invention is to provide an apparatus and method for organic saponification in hydrometallurgy.

[0006] According to one aspect of the present invention, the present invention provides the following technical solution: A device for organic saponification in hydrometallurgy is a tower-type packed bed pulse fluid reactor, comprising: Pulse fluid generating device, light phase inlet section, heavy phase inlet section, filling section, light phase outlet section, heavy phase outlet section, circulating water ultrasonic heating device; The pulse fluid generator is located at the bottom of the equipment, generating a periodic external mechanical force field, and transmitting it to the fluid in the equipment to form tiny micro beads, thereby enhancing mass transfer and improving contact efficiency; the filling section is located in the middle of the equipment, and is filled with fillers in a random pile manner; 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 outside of the filling section is connected to a heat exchange jacket, and the heat exchange jacket is connected to the circulating water ultrasonic heating device through a pipeline; The heavy phase enters the equipment from the heavy phase inlet, passes through the filling section from top to bottom, and is produced from the heavy phase outlet section 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 from bottom to top, and under the action of the pulse fluid generating device, it undergoes continuous two-phase exchange and phase separation, and is finally produced from the light phase outlet section at the top of the equipment as overflow.

[0007] As a preferred embodiment of the equipment for organic saponification in wet smelting described in the present invention, the light phase inlet is connected to a light phase storage container, and a connecting pipe is provided with a light phase feed flow pump; the heavy phase inlet is connected to a heavy phase storage container, and a connecting pipe is provided with a heavy phase feed flow pump; and the heavy phase outlet is provided with a heavy phase outlet flow valve.

[0008] As a preferred embodiment of the device for organic saponification in hydrometallurgy described in the present invention, the light phase outlet section and the heavy phase outlet section are also provided with observation holes for observing the interface between the two phases.

[0009] As a preferred embodiment of the device for organic saponification in wet smelting described in the present invention, the pulse fluid generating device is a diaphragm oscillation pump.

[0010] To solve the above technical problem, according to another aspect of the present invention, the present invention provides the following technical solution: A method for organic saponification in hydrometallurgy, comprising the following steps: S1. Pure water (heavy phase) is introduced into the equipment from the heavy phase inlet to form a continuous phase. 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 rate; S2. After the heavy phase feed flow rate is stable, the extracted organic phase (light 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 rate; S3. When the light phase feed flow rate is stable, adjust the heavy phase outlet flow valve and observe the two-phase interface through the observation hole. When the position of the phase interface remains stable, a stable heavy phase discharge flow rate is obtained; S4, replace the heavy phase from pure water to saponified liquid, introduce it into the equipment from 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 position of the interface is stable; S5. Turn on the pulse fluid generating device and adjust the oscillation frequency and amplitude; at the same time, turn on the circulating water ultrasonic heating device to monitor the liquid temperature in the equipment in real time to maintain the temperature in the equipment stable, and at the same time adjust the ultrasonic frequency to enhance the full mixing and mass transfer between the light phase and the heavy phase; S6, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer in the equipment has reached equilibrium, and the heavy phase at this time is the completely saponified organic phase.

[0011] As a preferred embodiment of the method for organic saponification in hydrometallurgy described in the present invention, wherein: in the step S1, the pure water (heavy phase) comes from an ultrapure water machine.

[0012] As a preferred embodiment of the method for organic saponification in hydrometallurgy described in the present invention, wherein: in the step S2, the extracted organic phase is an acidic phosphine extractant-solvent oil mixture, wherein the acidic phosphine extractant accounts for 5-50 vol%, and the solvent oil accounts for 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)phosphinic acid (Cyanex 272); and the solvent oil is industrial kerosene.

[0013] As a preferred embodiment of the method for organic saponification in hydrometallurgy described in the present invention, wherein: in the 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).

[0014] As a preferred embodiment of the method for organic saponification in wet smelting described in the present invention, wherein: in the step S4, the saponification solution is an alkaline aqueous solution, preferably ammonia water or sodium hydroxide solution, the ammonia concentration is 1.0~8.0 mol / L, and the sodium hydroxide solution concentration is 0.5~3.0 mol / L.

[0015] As a preferred embodiment of the method for organic saponification in wet smelting described in the present invention, in step S5, the pulse fluid generating device can enable the two phases in the device to obtain different oscillation frequencies and amplitudes, with a frequency of 0.25~1.0Hz and an amplitude of 1~5cm.

[0016] As a preferred embodiment of the method for organic saponification in wet smelting described in the present invention, wherein: in step S5, the circulating water temperature is 40-50°C; the ultrasonic frequency of the circulating water ultrasonic heating device is 20-40kHz.

[0017] As a preferred embodiment of the method for organic saponification in hydrometallurgy described in the present invention, wherein: in the step S6, the saponification rate of the qualified light phase effluent is 60-80%; the OH content of the qualified heavy phase effluent is 1.34%. - The concentration of OH in the saponified qualified heavy phase effluent is not higher than 0.2 mol / L. - The concentration of OH in the saponification qualified heavy phase effluent is not higher than 0.1 mol / L. - The concentration is not higher than 0.05mol / L.

[0018] The beneficial effects of the present invention are as follows: The present invention provides an apparatus and method for organic saponification in hydrometallurgy, which simultaneously applies pulse fluid technology and ultrasonic technology to organic saponification in hydrometallurgy, wherein the pulse fluid utilizes the intensified reaction process of an external mechanical force field, and conducts ultrasonic waves through circulating heat-insulating water to act on the reaction process to intensify mass transfer and mixing, and has good mixing effect and mass transfer and heat transfer characteristics, and is simple and precise to control, and is particularly suitable for multiphase reactions, and has a significant effect in terms of enhanced transfer. Through the efficient phase mixing and precise control of pulse fluid technology, the amount of saponification liquid used in the hydrometallurgy process can be significantly saved, the saponification efficiency of the extractant can be improved, and the ammonia loss and environmental hazards caused by the volatilization of ammonia in the process can be avoided, while the precise control of process parameters and the fully automated control of multi-stage continuous extraction can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0020] Figure 1 It is a schematic diagram of the structure of the equipment used for organic saponification in hydrometallurgy according to the present invention.

[0021] Among them, 1-pulse fluid generating device, 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 liquid container, 12-heavy phase effluent liquid container.

[0022] The realization of the effects, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0023] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0024] The present invention provides an apparatus and method for organic saponification in hydrometallurgy, which has the following advantages: (1) The use of pulse fluid technology and ultrasonic technology can significantly save the amount of saponification liquid used in the wet smelting process and improve the saponification efficiency of the extractant. The organic phase is extracted by countercurrent saponification with an alkaline aqueous solution. The alkaline aqueous solution is the continuous phase and fills the equipment filled with fillers. The extracted organic phase enters the equipment from the bottom of the tower and passes through the small holes of the distribution plate to form dispersed oil droplets (dispersed phase) and flows upward through the water layer. The oil droplets come into countercurrent contact with the water flow, and the H + The oil is transferred to the water phase through the surface of the oil droplets, and the cations in the water phase enter the oil phase. When the oil droplets pass through the packing layer, due to the external strong mechanical force, the oil droplets are continuously cut into small oil droplets, ensuring a larger oil-water contact area and accelerating the extraction rate. Compared with the existing mixed clarification extraction tank extraction technology, the pulse fluid technology can significantly improve the two-phase mass transfer efficiency, so that under the condition of achieving the same saponification effect, the use of alkaline aqueous solution is greatly reduced. In other words, the pulse fluid technology can maximize the organic saponification efficiency while ensuring the two-phase mass transfer efficiency.

[0025] (2) It can avoid ammonia loss and environmental damage caused by ammonia volatilization during the process. Existing mixed clarification extraction tanks usually use water seals, which cannot completely prevent ammonia volatilization. The concentration of ammonia solution used for saponification is usually high. Long-term volatilization into the environment under high temperature environment will cause great harm to the human body and the environment. The equipment has the characteristics of airtightness and continuity. It can effectively prevent ammonia from volatilizing into the external air under high temperature conditions, thereby avoiding a series of hazards.

[0026] (3) The use of pulse fluid technology and ultrasonic technology can achieve 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, and the systematic error and accidental error are large, which requires tedious manual control. Thanks to the tower continuous structure of the equipment, the parameters of each stage of the equipment are stable and controllable, and the tower body phase interface, circulating water temperature, and inlet and outlet valve position flow can be fully automatically controlled, reducing human errors, and the operation difficulty is low, which improves its safety.

[0027] like Figure 1 As shown, the present invention provides an apparatus for organic saponification in hydrometallurgy, which is a tower-type packed bed pulse fluid reactor, comprising: Pulse fluid generating device 1, light phase inlet section 2, heavy phase inlet section 3, filling section 4, light phase outlet section 5, heavy phase outlet section 6, circulating water ultrasonic heating device 10; The pulse fluid generating device 1 is located at the bottom of the device, generating a periodic external mechanical force field, and transmitting it to the fluid in the device to form tiny micro beads, thereby enhancing mass transfer and improving contact efficiency; the filling section 4 is located in the middle of the device, and is filled with fillers in a random pile manner; the light phase inlet section 2 is located below the filling section 4 and is provided with a light phase inlet; the heavy phase inlet section 3 is located above the filling section 4 and is provided with a heavy phase inlet; the heavy phase outlet section 6 is located at the bottom of the device and is provided with a heavy phase outlet; the light phase outlet section 5 is located at the top of the device and is provided with a light phase outlet; the outside of the filling section 4 is connected to a heat exchange jacket, and the heat exchange jacket is connected to the circulating water ultrasonic heating device 10 through a pipeline; The heavy phase enters the equipment from the heavy phase inlet, passes through the filling section 4 from top to bottom, and is produced 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 generating device 1, it undergoes continuous two-phase exchange and phase separation with the continuous phase, and is finally produced from the light phase outlet section 5 at the top of the equipment.

[0028] Preferably, the light phase inlet is connected to the light phase storage container 7, and the connecting pipe is provided with a light phase feed flow pump; the heavy phase inlet is connected to the heavy phase storage container 8 (also including an ultrapure water machine 9, the pure water comes from the ultrapure water machine 9), 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.

[0029] Preferably, the light phase outlet section 5 and the heavy phase outlet section 6 are also provided with observation holes for observing the interface between the two phases.

[0030] Preferably, the pulse fluid generating device 1 is a diaphragm oscillation pump.

[0031] Preferably, the connecting pipe of the device of the present invention is provided with a valve and / or a pressure gauge as required.

[0032] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0033] Example 1 A method for organic saponification in hydrometallurgy, comprising the following steps: S1. Use the flow pump to pass pure water (heavy phase) into the pulse fluid reactor from the top to form a continuous phase. When the heavy phase flows out from the top heavy phase outlet, adjust the heavy phase feed flow pump flow rate to 10.1dm 3 / h and stable; S2. The extracted organic phase (light phase) flows from the bottom of the tower into the pulse fluid reactor through a flow pump to form a dispersed phase. The extracted organic phase (light phase) is a mixture of 36 vol% P507 + 64 vol% industrial kerosene. When the light phase flows out from the top heavy phase outlet, adjust the light phase feed flow pump flow rate to 84.3 dm 3 / h and is stable, at this time the ratio of heavy phase flow to light phase flow is 1 / 8.4; 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; S4, close the pure water control valve, open the saponification liquid control valve, and allow the saponification liquid to pass into the pulse fluid reactor from the top, wherein the saponification liquid is 8 mol / L ammonia solution; S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency in the equipment to 0.67 Hz and the amplitude to 3 cm; turn on the circulating water ultrasonic heating device, adjust the ultrasonic frequency to 40 kHz, and control the circulating water flow rate to 120 dm 3 / h, the circulating water temperature is controlled at 42°C, and after full balance, the liquid temperature in the equipment is stabilized at 41°C; S6, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer 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 - The concentrations are shown in Table 1. The results show that the saponification rate of the light phase effluent is 72.3%; the OH in the heavy phase effluent is - The concentration is 0.05 mol / L. The organic phase and the aqueous phase are well separated.

[0034] Table 1 Example 2 A method for organic saponification in hydrometallurgy, comprising the following steps: S1. Use the flow pump to pass pure water (heavy phase) into the pulse fluid reactor from the top to form a continuous phase. When the heavy phase flows out from the top heavy phase outlet, adjust the heavy phase feed flow pump flow rate to 10.1dm 3 / h and stable; A2. The extracted organic phase (light phase) is flowed from the bottom of the tower into the pulse fluid reactor through a flow pump to form a dispersed phase. The extracted organic phase (light phase) is a mixture of 30 vol% P204 + 70 vol% industrial kerosene. When the light phase flows out from the top heavy phase outlet, adjust the light phase feed flow pump flow rate to 42.5 dm 3 / h and is stable, at this time the ratio of heavy phase flow to light phase flow is 1 / 4.2; 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; S4, close the pure water control valve, open the saponification liquid control valve, and allow the saponification liquid to pass into the pulse fluid reactor from the top, wherein the saponification liquid is a 3 mol / L ammonia solution; S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency in the equipment to 1.0 Hz and the amplitude to 3 cm; turn on the circulating water ultrasonic heating device, adjust the ultrasonic frequency to 30 kHz, and control the circulating water flow rate to 120 dm 3 / h, the circulating water temperature is controlled at 52℃, and after full balance, the liquid temperature in the equipment is stabilized at 50℃; S6, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer 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 - The concentrations are shown in Table 2. The results show that the saponification rate of the light phase effluent is 65.3%; the OH content of the heavy phase effluent is - The concentration was 0.04 mol / L. The organic phase and the aqueous phase were well separated.

[0035] Table 2 Example 3 A method for organic saponification in hydrometallurgy, comprising the following steps: S1. Use the flow pump to pass pure water (heavy phase) into the pulse fluid reactor from the top to form a continuous phase. When the heavy phase flows out from the top heavy phase outlet, adjust the heavy phase feed flow pump flow rate to 20.6dm 3 / h and stable; S2. The extracted organic phase (light phase) flows into the pulse fluid reactor from the bottom through a flow pump to form a dispersed phase. The extracted organic phase (light phase) is a new 30 vol% Cyanex 272 + 70 vol% industrial kerosene mixture. When the light phase flows out from the top heavy phase outlet, adjust the light phase feed flow pump flow rate to 92.2 dm 3 / h and is stable, at this time the ratio of heavy phase flow to light phase flow is 1 / 4.5; 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; S4, close the pure water control valve, open the saponification liquid control valve, and allow the saponification liquid to pass into the pulse fluid reactor from the top, wherein the saponification liquid is a 3 mol / L sodium hydroxide solution; S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency in 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 120dm 3 / h, the circulating water temperature is controlled at 46.5℃, and after full balance, the liquid temperature in the equipment is stabilized at 45℃; S6, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer 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 - The concentrations are shown in Table 3. The results show that the saponification rate of the light phase effluent is 61.2%; - The concentration is 0.05 mol / L. The organic phase and the aqueous phase are well separated.

[0036] Table 3 Comparative Example 1 The difference from Example 1 is that the organic saponification is carried out in a mixing and clarifying tank, which includes the following steps: S1. Add pure water (heavy phase) from the top to the mixing and settling tank. The mixing chamber volume of the mixing and settling tank is 150L, ​​the settling chamber volume is 600L, the number of stages is 15, and the stirring blade speed is 900r / min. The pure water temperature is 40°C. Stop when the heavy phase volume accounts for 1 / 9 of the tank volume. S2. Add the extracted organic phase (light phase) from one side to the mixing and settling tank. The loaded organic phase (light phase) is a new 36 vol% P507 + 64 vol% industrial kerosene mixture at a temperature of 40°C. When the light phase flows out of the overflow port of the extraction tank, adjust the light phase feed flow pump flow rate to 85.5 dm 3 / h and adjust the heavy phase feed flow pump flow rate to 10.5dm 3 / h and is stable, at this time the ratio of heavy phase flow to light phase flow is 1 / 8.1; S3, open the flow valve of the heavy phase outlet of the extraction tank to keep the phase interface position of the clarification chamber stable; S4, close the pure water control valve, open the saponification liquid control valve, so that the heavy phase is switched from pure water to saponification liquid, the saponification liquid is 8 mol / L ammonia solution, S5, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer 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 - The concentrations are shown in Table 4. The results show that the saponification rate of the light phase effluent is 52.8%; - The concentration is 0.8mol / L.

[0037] Table 4 Comparative Example 2 The difference from Example 1 is that a circulating water heating device is used to replace the circulating water ultrasonic heating device, and the circulating water is not subjected to ultrasonic treatment.

[0038] A method for organic saponification in hydrometallurgy, comprising the following steps: S1. Use the flow pump to pass pure water (heavy phase) into the pulse fluid reactor from the top to form a continuous phase. When the heavy phase flows out from the top heavy phase outlet, adjust the heavy phase feed flow pump flow rate to 10.1dm 3 / h and stable; S2. The extracted organic phase (light phase) flows from the bottom of the tower into the pulse fluid reactor through a flow pump to form a dispersed phase. The extracted organic phase (light phase) is a mixture of 36 vol% P507 + 64 vol% industrial kerosene. When the light phase flows out from the top heavy phase outlet, adjust the light phase feed flow pump flow rate to 84.3 dm 3 / h and is stable, at this time the ratio of heavy phase flow to light phase flow is 1 / 8.4; 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; S4, close the pure water control valve, open the saponification liquid control valve, and allow the saponification liquid to pass into the pulse fluid reactor from the top, wherein the saponification liquid is 8 mol / L ammonia solution; S5. Turn on the pulse fluid generator and control the two-phase oscillation frequency in 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 120dm 3 / h, the circulating water temperature is controlled at 42°C, and after full balance, the liquid temperature in the equipment is stabilized at 41°C; S6, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer 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 - The concentrations are shown in Table 5. The results show that the saponification rate of the light phase effluent is 58.3%; the OH content of the heavy phase effluent is - The concentration is 0.55mol / L.

[0039] Table 5 It can be seen from the above embodiments and comparative examples that the saponification rate of comparative example 1 using an extraction tank under the same conditions is significantly reduced, and the utilization rate of the saponified liquid is correspondingly low; under the condition that comparative example 2 uses a pulse fluid generator but does not perform circulating water ultrasound, the utilization rate of the saponified liquid for organic saponification is greatly reduced. Example 1 uses pulse fluid technology and ultrasonic technology to act on the organic saponification reaction at the same time, which has obvious advantages in saving the amount of saponified liquid and improving the saponification efficiency.

[0040] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification under the inventive concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. An apparatus for organic saponification in hydrometallurgy, characterized in that: include: Pulse fluid generating device, light phase inlet section, heavy phase inlet section, filling section, light phase outlet section, heavy phase outlet section, 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 outside of the filling section is connected to a heat exchange jacket, and the heat exchange jacket is connected to the circulating water ultrasonic heating device through a pipeline; The heavy phase enters the equipment from 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 from the light phase inlet, passes through the filling section from bottom to top, and under the action of the pulse fluid generating device, undergoes continuous two-phase exchange and phase separation with the continuous phase, and finally overflows and is produced from the light phase outlet section at the top of the equipment.

2. The device for organic saponification in hydrometallurgy according to claim 1, characterized in that: The light phase inlet is connected to the light phase storage container, and the connecting pipe is provided with a light phase feed flow pump; the heavy phase inlet is connected to the 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 device 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 interface between the two phases.

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

5. A method for organic saponification in hydrometallurgy, characterized in that: The device for organic saponification in hydrometallurgy according to any one of claims 1 to 4 comprises the following steps: S1. Pure water is introduced into the equipment from the heavy phase inlet to form a continuous phase. 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 rate; S2. After the heavy phase feed flow rate is stable, the extracted 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 rate; S3. When the light phase feed flow rate is stable, adjust the heavy phase outlet flow valve and observe the two-phase interface through the observation hole. When the position of the phase interface remains stable, a stable heavy phase discharge flow rate is obtained; S4. Replace the pure water with saponified liquid, and introduce it into the equipment from 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 position of the interface is stable; S5. Turn on the pulse fluid generating device and adjust the oscillation frequency and amplitude; at the same time, turn on the circulating water ultrasonic heating device to monitor the liquid temperature in the equipment in real time to maintain the temperature in the equipment stable, and at the same time adjust the ultrasonic frequency to enhance the full mixing and mass transfer between the light phase and the heavy phase; S6, real-time detection of the saponification rate of the light phase effluent and the OH in the heavy phase effluent - concentration, saponification rate of the light phase effluent and OH in the heavy phase effluent - When the concentration is stable, it can be considered that the two-phase mass transfer in the equipment has reached equilibrium, and the heavy phase at this time is the completely saponified organic phase.

6. The method for organic saponification in hydrometallurgy according to claim 5, characterized in that: In step S2, the extracted organic phase is an acidic phosphine extractant-solvent oil mixture, wherein the acidic phosphine extractant accounts for 5-50 vol%, and the solvent oil accounts for 50-95 vol%; the acidic phosphine extractant is one of di(2-ethylhexyl) phosphate, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester or di(2, 4, 4-trimethylpentyl)phosphinic acid; the solvent oil is industrial kerosene; 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).

7. The method for organic saponification in hydrometallurgy according to claim 5, characterized in that: In the step S4, the saponification solution is an alkaline aqueous solution.

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

9. The method for organic saponification in hydrometallurgy according to claim 5, characterized in that: In step S5, the temperature of the circulating water is 40-50° C.; the ultrasonic frequency of the circulating water ultrasonic heating device is 20-40 kHz.

10. The method for organic saponification in hydrometallurgy according to claim 5, characterized in that: In step S6, the saponification rate of the qualified light phase effluent is 60-80%; the OH content of the qualified heavy phase effluent is 1. - The concentration is not higher than 0.2 mol / L.

Images