CN-122010161-A - Trinity coupling reinforced rare earth oxide preparation method and device

CN122010161ACN 122010161 ACN122010161 ACN 122010161ACN-122010161-A

Abstract

The application relates to the technical field of rare earth functional material preparation, and particularly discloses a method and a device for preparing rare earth oxide through trinity coupling reinforcement. The preparation device comprises an ultrasonic-microwave composite resonant cavity, a micro-channel reaction unit, an ultrasonic unit, a microwave heating unit, a pulse synchronous triggering module and a multi-parameter linkage closed-loop control module, and can realize in-situ synchronous coupling of the micro-channel, ultrasonic and microwave with the cavity. The preparation method is implemented based on the device and sequentially comprises the five steps of raw material preparation, parameter presetting, coupling reaction, closed-loop regulation and control and product collection, and can realize the space-time synchronous propulsion of precursor nucleation, agglomeration inhibition and in-situ crystallization. The device and the preparation method can effectively improve the mass transfer efficiency of the rare earth oxide preparation process, inhibit the agglomeration of product particles, improve the stability and the production efficiency of continuous production, and adapt to the large-scale preparation requirement of high-end rare earth oxide.

Inventors

YIN SHAOHUA
CHEN WANGYING
LI SHIWEI
ZHANG LIBO
LIU YUEYU

Assignees

昆明理工大学

Dates

Publication Date: 20260512
Application Date: 20260415

Claims (10)

1. The preparation method of the three-in-one coupling reinforced rare earth oxide is characterized by being implemented based on an ultrasonic-microwave-microchannel in-situ coupling reactor with a cavity, wherein the reactor is integrated equipment with a microchannel reaction unit, an ultrasonic unit and a microwave heating unit integrated in the same sealed cavity, and the preparation method comprises the following steps of: s1, preparing raw materials, namely respectively preparing rare earth salt feed liquid and a precipitant; S2, presetting parameters, namely presetting operation parameters of an ultrasonic unit, a microwave heating unit and a feeding unit of the reactor, setting the pulse period of ultrasonic waves to be the same as that of microwaves, matching microwave output power and ultrasonic power according to a preset linear relation, and setting feeding flow rate to regulate and control material flow states in a microchannel reaction module; s3, coupling reaction, namely synchronously feeding the prepared rare earth salt feed liquid and the precipitant into a microchannel reaction module of a reactor directly through a double-plunger metering pump according to a preset molar ratio, and synchronously starting an ultrasonic unit and a microwave heating unit to synchronously perform the ultrasonic action, the microwave action and the mixing reaction process in the microchannel reaction module in situ in the same cavity; s4, closed-loop regulation and control, namely detecting the pH value, the temperature, the conductivity and the crystal nucleus particle diameter data of a reaction system in real time through an online sensor, and synchronously adjusting the feeding parameters of the two paths of feeding units, the operating parameters of the ultrasonic unit and the operating parameters of the microwave heating unit in a linkage manner according to the detection data; S5, collecting products, namely carrying out solid-liquid separation, washing, drying and calcining treatment on the reaction slurry output by the reactor to obtain rare earth oxide powder products.
2. The method for preparing the three-in-one coupling reinforced rare earth oxide according to claim 1, wherein in the step S1, the concentration of the rare earth salt solution is controlled to be 0.5-1mol/L, the concentration of the precipitant is controlled to be 0.75-1.5mol/L, the molar ratio of the precipitant to rare earth ions is set according to the type of the precipitant, the molar ratio of oxalic acid to sodium carbonate precipitation system is 1.5-1.8:1, the molar ratio of ammonium bicarbonate precipitation system is 3.0-3.6:1, and the molar ratio of urea precipitation system is 3.0-10:1.
3. The method of claim 1, wherein in step S1, the rare earth salt solution is prepared from one of single rare earth nitrate, single rare earth chloride, mixed rare earth nitrate or mixed rare earth chloride, and the precipitant is prepared from one or more of oxalic acid, ammonium bicarbonate, sodium carbonate and urea.
4. The method of claim 1, wherein in step S2, the feeding flow rate is set to make the Reynolds number of the materials in the micro-channel reaction module 2000-8000, the pulse frequency of the ultrasonic unit is set to 10-50kHz, and the pulse duty ratio is set to 30-70%.
5. The method for preparing the three-in-one coupling reinforced rare earth oxide according to claim 1, wherein in the step S2, the pulse frequency and the pulse duty ratio of the microwave heating unit are the same as those of the ultrasonic unit, the peak time of the ultrasonic pulse and the peak time of the microwave electric field are overlapped in time sequence through the pulse synchronous triggering module, and the linear matching relation between the microwave output power and the ultrasonic power is that the microwave output power is linearly increased along with the increase of the ultrasonic power.
6. The method for preparing the three-in-one coupling enhanced rare earth oxide according to claim 1, wherein in the step S2, the residence time of the material in the micro-channel reaction module is controlled by adjusting the feeding flow rate, so that the residence time and the pulse period of the ultrasonic unit and the pulse period of the microwave unit are in an integral multiple relationship.
7. The preparation method of the trinity coupling reinforced rare earth oxide is characterized in that in the step S3, the reaction temperature is controlled to be 60-180 ℃ through microwave selective heating, the system heating rate is controlled to be matched with the ultrasonic power lifting rate in the reaction process, and the system heating rate and the ultrasonic power lifting rate are in a linear positive correlation.
8. The method for preparing the rare earth oxide reinforced by the trinity coupling is characterized in that in the step S4, the linkage adjustment mode is that when the particle size of a precursor crystal nucleus is detected to be larger than a particle size threshold value on line, ultrasonic power and micro-channel feeding flow rate are synchronously increased, microwave output power and pulse frequency are correspondingly adjusted, when a pH value deviation interval of a system is detected on line, flow ratio and microwave heating temperature of two paths of feeding are synchronously adjusted, and ultrasonic pulse duty ratio is correspondingly adjusted, the particle size threshold value is 50-200nm, and the pH value interval is set to be 1.5-2.0 of an oxalic acid precipitation system, 6-7 of an ammonium bicarbonate precipitation system, 6-7 of a sodium carbonate precipitation system and 5.5-6 of a urea mineralization system according to system types.
9. The utility model provides a preparation facilities of rare earth oxide that trinity coupling was reinforceed, its characterized in that is used for the preparation method of rare earth oxide that trinity coupling was reinforceed of any one of claims 1-8, including pressure-bearing shell (1), the upper surface of pressure-bearing shell (1) is provided with control module (2), the inner wall fixedly connected with first microwave heating unit (3), first ultrasonic unit (4) and supporting shoe (5) of pressure-bearing shell (1), the lower surface fixedly connected with backup pad (6) of supporting shoe (5), the lower surface of backup pad (6) is provided with microchannel reaction module (9), the inside fixedly connected with second microwave heating unit (7) and second ultrasonic unit (8) of backup pad (6), feed inlet (10) have been seted up to one end of microchannel reaction module (9), and discharge gate (12) have been seted up to the other end, the outer wall fixedly connected with double-column stopper (11) of microchannel reaction module (9), the outer wall fixedly connected with backup pad (6) and pressure-bearing shell (1).
10. The preparation device of the three-in-one coupling reinforced rare earth oxide is characterized in that the first microwave heating unit (3) and the second microwave heating unit (7) are used for forming a uniform microwave resonance field covering a full flow channel of a micro-channel reaction module (9) and forming a coupling reinforced action area which is overlapped with an ultrasonic field, the first ultrasonic unit (4) and the second ultrasonic unit (8) are used for forming a uniform ultrasonic focusing field covering the full flow channel of the micro-channel reaction module (9) and synchronously restraining precursor crystal nucleus aggregation, and the control module (2) is used for synchronously regulating and controlling operation parameters of the first microwave heating unit (3), the second microwave heating unit (7), the first ultrasonic unit (4) and the second ultrasonic unit (8) and feeding parameters of a double-plunger metering pump (11) and realizing multi-parameter linkage closed-loop regulation and control of double-field pulse timing synchronization and the whole reaction process.

Description

Trinity coupling reinforced rare earth oxide preparation method and device Technical Field The application relates to the technical field of rare earth functional material preparation, in particular to a method and a device for preparing rare earth oxide by three-in-one coupling reinforcement. Background Rare earth oxide is an indispensable core functional material in the fields of high-end manufacturing such as electronic information, catalytic chemical industry, new energy, precision ceramics and the like, and the particle size uniformity, the dispersity and the crystal phase stability of powder directly influence the comprehensive performance of downstream application devices. The liquid phase precipitation method is a main flow process for industrialized preparation of rare earth oxide at present by virtue of the characteristics of strong process suitability, controllable production cost and easy large-scale amplification, and micro-channel, ultrasonic and microwave technologies are often introduced into the preparation flow to realize optimized improvement of product performance in order to improve the mixed mass transfer effect, inhibit particle agglomeration and accelerate crystallization process in the preparation process of the precipitation method in industry. The prior rare earth oxide preparation field is mainly applied to the technology in a combined mode of synergy of two types of fields, the step-by-step propulsion of each process is generally realized by a sectional type serial process route, the in-situ deep coupling of the same cavity of ultrasonic wave, microwave and micro-channel is difficult to realize, the space-time cleavage among the processes enables the precursor nucleation, agglomeration inhibition and in-situ crystallization processes to be unable to synchronously advance, the problems of poor system mass transfer efficiency and easy agglomeration of product particles are easily caused, and the stability and production efficiency of continuous production are also difficult to ensure, so that the method is a core technical problem to be solved in the current industry. Disclosure of Invention The application provides a three-in-one coupling reinforced rare earth oxide preparation method and device, which aims at solving the problems that in the prior art, in-situ deep coupling of three cavities of ultrasound, microwaves and micro-channels is difficult to realize, so that mass transfer efficiency is poor, products are easy to agglomerate, and continuous production stability and efficiency are insufficient in the rare earth oxide preparation process. In a first aspect, the application provides a preparation method of a rare earth oxide reinforced by trinity coupling, which adopts the following technical scheme: The preparation method of the three-in-one coupling reinforced rare earth oxide is implemented based on an ultrasonic-microwave-microchannel in-situ coupling reactor with a cavity, wherein the reactor is integrated equipment with a microchannel reaction unit, an ultrasonic unit and a microwave heating unit integrated in the same sealed cavity, and the preparation method comprises the following steps: s1, preparing raw materials, namely respectively preparing rare earth salt feed liquid and a precipitant; S2, presetting parameters, namely presetting operation parameters of an ultrasonic unit, a microwave heating unit and a feeding unit of the reactor, setting the pulse period of ultrasonic waves to be the same as that of microwaves, matching microwave output power and ultrasonic power according to a preset linear relation, and setting feeding flow rate to regulate and control material flow states in a microchannel reaction module; s3, coupling reaction, namely synchronously feeding the prepared rare earth salt feed liquid and the precipitant into a microchannel reaction module of a reactor directly through a double-plunger metering pump according to a preset molar ratio, and synchronously starting an ultrasonic unit and a microwave heating unit to synchronously perform the ultrasonic action, the microwave action and the mixing reaction process in the microchannel reaction module in situ in the same cavity; s4, closed-loop regulation and control, namely detecting the pH value, the temperature, the conductivity and the crystal nucleus particle diameter data of a reaction system in real time through an online sensor, and synchronously adjusting the feeding parameters of the two paths of feeding units, the operating parameters of the ultrasonic unit and the operating parameters of the microwave heating unit in a linkage manner according to the detection data; S5, collecting products, namely carrying out solid-liquid separation, washing, drying and calcining treatment on the reaction slurry output by the reactor to obtain rare earth oxide powder products. By adopting the technical scheme, as three core processes of micro-channel mixing, ultrasonic action and microwave action are int