Nanometer yttrium oxide continuous preparation system and process method based on multi-modal fluid regulation and control

Abstract

The invention discloses a nano yttrium oxide continuous preparation system and process method based on multi-modal fluid regulation and control, the nano yttrium oxide continuous preparation system comprises an yttrium salt storage tank, a precipitant storage tank and a surface modifier storage tank, the bottom of the yttrium salt storage tank and the bottom of the precipitant storage tank are connected with a high-pressure plunger pump I through pipelines; the liquid outlet end of the first high-pressure plunger pump is connected with a first Coriolis mass flow meter through a pipeline, and the liquid outlet end of the first Coriolis mass flow meter is connected with a micro-reaction pressure balancer through a pipeline. Through cooperative use of the structure and the process method, the preparation method has the advantages of small particle size distribution span reduction, high specific surface area stability and low dispersion index, a'pressure-flow-viscosity 'triple closed-loop control system is developed, meanwhile, a yttrium ion concentration-solution viscosity relation model is established, and the stability of the solution is improved. A Y-shaped staggered runner mixer is utilized to obtain an innovative anti-crystallization runner design, and a micro-groove array is processed on the inner wall of a runner through laser, so that mixing is facilitated.

Description

Technical Field

[0001] The present invention relates to the technical field of rare earth nanomaterial preparation, and in particular to a nano-yttrium oxide continuous preparation system and process method based on multimodal fluid regulation. Background Art

[0002] Rare earth nanomaterials are functional materials based on rare earth elements (lanthanides, scandium and yttrium) and prepared in combination with nanotechnology. Their properties are derived from the unique electronic layer structure of rare earth elements and the surface / size effects of nanomaterials.

[0003] Traditional processes for producing nano-yttrium oxide primarily utilize reactors. These nano-yttrium oxides suffer from the following drawbacks: a wide particle size distribution, low specific surface area stability, and a high dispersion index. To address these technical challenges, we have designed a continuous nano-yttrium oxide production system and process based on multimodal fluid control. Summary of the Invention

[0004] The purpose of the present invention is to provide a continuous preparation system and process method for nano yttrium oxide based on multimodal fluid regulation, which has the advantages of a small particle size distribution span, high specific surface area stability and a low dispersion index, and solves the problems of nano yttrium oxide produced using a reactor, which has a large particle size distribution span, low specific surface area stability and a high dispersion index.

[0005] To achieve the above-mentioned object, the present invention provides the following technical solution: a continuous preparation system of nano-yttrium oxide based on multimodal fluid regulation, comprising an yttrium salt storage tank, a precipitant storage tank and a surface modifier storage tank, wherein the bottoms of the yttrium salt storage tank and the precipitant storage tank are connected to a high-pressure plunger pump through a pipeline, the liquid outlet of the high-pressure plunger pump is connected to a Coriolis mass flowmeter through a pipeline, the liquid outlet of the Coriolis mass flowmeter is connected to a micro-reaction pressure balancer through a pipeline, the liquid outlets of the two micro-reaction pressure balancers are connected to a three-way buffer tube through a pipeline, and the liquid outlet of the three-way buffer tube is connected to a micro-reaction pressure balancer through a pipeline. The pipeline is connected to a Y-type staggered flow channel mixer, the liquid outlet end of the Y-type staggered flow channel mixer is connected to a spiral expansion flow channel crystallizer through a pipeline, the liquid outlet end of the spiral expansion flow channel crystallizer is connected to a honeycomb multi-chamber aging device through a pipeline, the liquid outlet end of the honeycomb multi-chamber aging device is connected to an in-situ pH / ORP monitor through a pipeline, the liquid outlet end of the in-situ pH / ORP monitor is connected to a microwave-assisted dryer through a pipeline, the material outlet end of the microwave-assisted dryer is connected to a supercritical CO2 processor through a pipeline, and the material outlet end of the supercritical CO2 processor is connected to an air flow classifier.

[0006] Preferably, the liquid outlet of the surface modifier storage tank is connected to a high-pressure plunger pump 2 through a pipeline, the liquid outlet of the high-pressure plunger pump 2 is connected to a Coriolis mass flowmeter 2 through a pipeline, and the liquid outlet of the Coriolis mass flowmeter 2 is used in conjunction with the discharge end of the airflow classifier.

[0007] Preferably, a heater is installed inside the yttrium salt storage tank, and an ultrasonic disperser is installed inside the precipitant storage tank. The temperature control accuracy of the heater is ±0.3° C., and the frequency of the ultrasonic disperser is 40 kHz.

[0008] Preferably, two filling channels are installed on the top of the yttrium salt storage tank, the precipitant storage tank and the surface modifier storage tank.

[0009] Preferably, the flow range of the high-pressure plunger pump is 0.1-50 mL / min, the pulsation coefficient is <0.5%, and the accuracy of the Coriolis mass flowmeter is ±0.1% FS.

[0010] Preferably, the flow channel diameter inside the Y-type staggered flow channel mixer is 1.5mm, the diameter of the spiral expansion flow channel crystallizer gradually changes to 1.5-5mm, and the inner wall of the flow channel of the Y-type staggered flow channel mixer is laser-processed into a micro-groove array with a groove depth of 50μm and a spacing of 200μm.

[0011] Preferably, the operating temperature of the in-situ pH / ORP monitor is 0-150° C., the frequency of the microwave-assisted dryer is 2.45 GHz, and the power is adaptively adjusted, and the critical pressure of the supercritical CO2 processor is 7.38 MPa.

[0012] A process for continuous preparation of nano-yttrium oxide based on multimodal fluid regulation includes the above-mentioned continuous preparation system, and the method of use further includes the following steps:

[0013] Step 1: Prepare a 0.8 mol / L yttrium nitrate solution in the yttrium salt storage tank, and control the conductivity between 1800±50μS / cm. The heater is in operation during the preparation process. Prepare a 3:1 molar ratio urea-ammonia aqueous solution in the precipitant storage tank. Turn on the ultrasonic disperser during the preparation process for 30 minutes.

[0014] Step 2: Turn on the high-pressure plunger pump 1 at the bottom of the yttrium salt storage tank and the precipitant storage tank respectively, and simultaneously deliver the yttrium nitrate solution and the urea-ammonia mixed solution in a volume ratio of 1:1.2; when the high-pressure plunger pump 1 is turned on, the Coriolis mass flowmeter 1 and the micro-reaction pressure balancer are turned on simultaneously.

[0015] Step 3: The yttrium nitrate solution and the urea-ammonia mixed solution enter the Y-type staggered flow channel mixer through the three-way buffer tube, and use the Y-type staggered flow channel mixer to carry out the primary reaction and complete the instantaneous nucleation (heating rate 10℃ / s); after instantaneous nucleation, they enter the spiral expansion flow channel crystallizer to carry out the secondary reaction and gradient cooling (85℃→60℃ / 5min) and crystallization; finally, they enter the honeycomb multi-chamber aging device to carry out the tertiary aging reaction. During the reaction, the CO2 / N2 mixed gas is used, and the volume ratio of the two is 1:4.

[0016] Step 4: After using an in-situ pH / ORP monitor to detect the pH and ORP value of the material discharged from the honeycomb multi-chamber ageing device, it enters the microwave-assisted dryer for drying. The drying process is primary drying at 60°C → deep dehydration at 80°C (water content <0.3%); after drying, it enters the supercritical CO2 processor and is maintained at 32MPa and 50°C for 2 hours.

[0017] Step 5: The supercritical treated material enters the air classifier for classification and is discharged after classification. At this time, the high-pressure plunger pump 2 and the Coriolis mass flowmeter 2 are turned on to spray the surface modifier in the surface modifier tank and mix it with the discharged material.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The present invention, through the combined use of the above-mentioned structure and process method, has the advantages of a small particle size distribution span, high specific surface area stability, and a low dispersion index. This application has developed a "pressure-flow-viscosity" triple closed-loop control system, and simultaneously established a yttrium ion concentration-solution viscosity relationship model. The Y-type staggered flow channel mixer is used to obtain an innovative anti-crystallization flow channel design, and the laser processing micro-groove array on the inner wall of the flow channel is conducive to mixing. Furthermore, the Y-type staggered flow channel mixer and the spiral expansion flow channel crystallizer are used to distribute the nucleation and growth stages, reducing the occurrence of uneven particle size distribution caused by differences in nucleation rates. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a structural schematic diagram of the present invention.

[0021] In the figure: 1. Yttrium salt storage tank; 2. Heater; 3. High-pressure plunger pump 1; 4. Coriolis mass flowmeter 1; 5. Micro-reaction pressure balancer; 6. Three-way buffer tube; 7. Y-type staggered flow channel mixer; 8. Spiral expansion flow channel crystallizer; 9. Honeycomb multi-chamber aging device; 10. In-situ pH / ORP monitor; 11. Microwave-assisted dryer; 12. Supercritical CO2 processor; 13. Air flow classifier; 14. Surface modifier storage tank; 15. Precipitant storage tank; 16. Ultrasonic disperser; 17. High-pressure plunger pump 2; 18. Coriolis mass flowmeter 2. DETAILED DESCRIPTION

[0022] See also Figure 1 The continuous preparation system of nano-yttrium oxide based on multimodal fluid regulation includes an yttrium salt storage tank 1, a precipitant storage tank 15 and a surface modifier storage tank 14. The bottoms of the yttrium salt storage tank 1 and the precipitant storage tank 15 are connected to a high-pressure plunger pump 3 through a pipeline. The liquid outlet of the high-pressure plunger pump 3 is connected to a Coriolis mass flowmeter 4 through a pipeline. The liquid outlet of the Coriolis mass flowmeter 4 is connected to a micro-reaction pressure balancer 5 through a pipeline. The liquid outlets of the two micro-reaction pressure balancers 5 are connected to a three-way buffer tube 6 through a pipeline. The liquid outlet of the three-way buffer tube 6 is connected to a Y-type staggered flow channel mixer through a pipeline. The liquid outlet of the Y-type staggered flow channel mixer 7 is connected to the spiral expansion flow channel crystallizer 8 through a pipeline, the liquid outlet of the spiral expansion flow channel crystallizer 8 is connected to the honeycomb multi-chamber aging device 9 through a pipeline, the liquid outlet of the honeycomb multi-chamber aging device 9 is connected to the in-situ pH / ORP monitor 10 through a pipeline, the liquid outlet of the in-situ pH / ORP monitor 10 is connected to the microwave-assisted dryer 11 through a pipeline, the material outlet of the microwave-assisted dryer 11 is connected to the supercritical CO2 processor 12 through a pipeline, and the material outlet of the supercritical CO2 processor 12 is connected to the airflow classifier 13.

[0023] The liquid outlet end of the surface modifier storage tank 14 is connected to a high-pressure plunger pump 17 through a pipeline, and the liquid outlet end of the high-pressure plunger pump 17 is connected to a Coriolis mass flowmeter 18 through a pipeline. The liquid outlet end of the Coriolis mass flowmeter 18 is used in conjunction with the discharge end of the air flow classifier 13; the model of the high-pressure plunger pump 17 is the same as that of the high-pressure plunger pump 3, and the model of the Coriolis mass flowmeter 18 is the same as that of the Coriolis mass flowmeter 4.

[0024] A heater 2 is installed inside the yttrium salt storage tank 1, and an ultrasonic disperser 16 is installed inside the precipitant storage tank 15. The temperature control accuracy of the heater 2 is ±0.3°C, and the frequency of the ultrasonic disperser 16 is 40kHz.

[0025] Two filling channels are installed on the top of the yttrium salt storage tank 1, the precipitant storage tank 15 and the surface modifier storage tank 14;

[0026] The flow range of the high-pressure plunger pump 3 is 0.1-50 mL / min, the pulsation coefficient is <0.5%, the accuracy of the Coriolis mass flowmeter 4 is ±0.1% FS, and the Coriolis mass flowmeter 4 has an internal integrated temperature compensation module;

[0027] The diameter of the flow channel inside the Y-shaped staggered flow channel mixer 7 is 1.5 mm, and the diameter of the spiral expansion flow channel crystallizer 8 gradually changes to 1.5-5 mm. The inner wall of the flow channel of the Y-shaped staggered flow channel mixer 7 is laser-processed with a micro-groove array with a groove depth of 50 μm and a spacing of 200 μm.

[0028] The operating temperature of the in-situ pH / ORP monitor 10 is 0-150° C., the frequency of the microwave-assisted dryer 11 is 2.45 GHz, and the power is adaptively adjusted. The critical pressure of the supercritical CO2 processor 12 is 7.38 MPa.

[0029] A process for continuous preparation of nano-yttrium oxide based on multimodal fluid regulation includes the above-mentioned continuous preparation system, and the method of use further includes the following steps:

[0030] Step 1: Prepare a 0.8 mol / L yttrium nitrate solution in the yttrium salt storage tank 1, and control the conductivity between 1800±50μS / cm. During the preparation process, the heater 2 is in operation. Prepare a 3:1 molar ratio urea-ammonia aqueous solution in the precipitant storage tank 15. Turn on the ultrasonic disperser 16 during the preparation process for 30 minutes.

[0031] Step 2: Turn on the high-pressure plunger pump 3 at the bottom of the yttrium salt storage tank 1 and the precipitant storage tank 15 respectively, and simultaneously deliver the yttrium nitrate solution and the urea-ammonia mixed solution at a volume ratio of 1:1.2; when the high-pressure plunger pump 3 is turned on, the Coriolis mass flowmeter 4 and the micro-reactor pressure balancer 5 are turned on simultaneously.

[0032] Step 3: The yttrium nitrate solution and the urea-ammonia mixed solution enter the Y-type staggered flow channel mixer 7 through the three-way buffer tube 6, and use the Y-type staggered flow channel mixer 7 to carry out a primary reaction to complete instantaneous nucleation (heating rate 10℃ / s); after instantaneous nucleation, they enter the spiral expansion flow channel crystallizer 8 to carry out a secondary reaction and gradient cooling (85℃→60℃ / 5min) and crystallization; finally, they enter the honeycomb multi-chamber aging device 9 to carry out a tertiary aging reaction. During the reaction, CO2 / N2 mixed gas is used, and the volume ratio of the two is 1:4.

[0033] Step 4: After using the in-situ pH / ORP monitor 10 to detect the pH and ORP value of the material discharged from the honeycomb multi-chamber ageing device 9, it enters the microwave-assisted dryer 11 for drying. The drying process is 60°C primary drying → 80°C deep dehydration (water content <0.3%); after drying, it enters the supercritical CO2 processor 12 and is maintained at 32MPa and 50°C for 2 hours.

[0034] Step 5: The supercritically treated material enters the air classifier 13 for classification. After classification, the material is discharged. At this time, the high-pressure plunger pump 17 and the Coriolis mass flowmeter 18 are turned on to spray the surface modifier in the surface modifier tank 14 to mix with the discharged material; after air classification, narrowly distributed particles with D50 = 25 ± 3 nm are obtained.

[0035] Example 1:

[0036] A process for continuous preparation of nano-yttrium oxide based on multimodal fluid regulation includes the above-mentioned continuous preparation system, and the method of use further includes the following steps:

[0037] Step 1: Prepare a 0.8 mol / L yttrium chloride solution in the yttrium salt storage tank 1, and control the conductivity between 1800±50μS / cm. During the preparation process, the heater 2 is in operation. Prepare a 3:1 molar ratio urea-ammonia mixed solution in the precipitant storage tank 15. Turn on the ultrasonic disperser 16 during the preparation process for 30 minutes. The pH of the yttrium chloride solution is adjusted to a control range of 8.0-8.8.

[0038] Step 2: Turn on the high-pressure plunger pump 3 at the bottom of the yttrium salt storage tank 1 and the precipitant storage tank 15 respectively, and simultaneously deliver the yttrium chloride solution and the urea-ammonia mixed solution in a volume ratio of 1:1.2; when the high-pressure plunger pump 3 is turned on, the Coriolis mass flowmeter 4 and the micro-reaction pressure balancer 5 are turned on simultaneously.

[0039] Step 3: The yttrium chloride solution and the urea-ammonia mixed solution enter the Y-type staggered flow channel mixer 7 through the three-way buffer tube 6, and use the Y-type staggered flow channel mixer 7 to carry out a primary reaction to complete instantaneous nucleation (heating rate 10℃ / s); after instantaneous nucleation, they enter the spiral expansion flow channel crystallizer 8 to carry out a secondary reaction and gradient cooling (85℃→60℃ / 5min) and crystallization; finally, they enter the honeycomb multi-chamber aging device 9 to carry out a tertiary aging reaction. During the reaction, CO2 / N2 mixed gas is used, and the volume ratio of the two is 1:4.

[0040] Step 4: After using the in-situ pH / ORP monitor 10 to detect the pH and ORP value of the material discharged from the honeycomb multi-chamber ageing device 9, it enters the microwave-assisted dryer 11 for drying. The drying process is 60°C primary drying → 80°C deep dehydration (water content <0.3%); after drying, it enters the supercritical CO2 processor 12 and is maintained at 32MPa and 50°C for 2 hours.

[0041] Step 5: The supercritically treated material enters the air classifier 13 for classification. After classification, the material is discharged. At this time, the high-pressure plunger pump 17 and the Coriolis mass flowmeter 18 are turned on to spray the surface modifier in the surface modifier tank 14 to mix with the discharged material; after air classification, narrowly distributed particles with D50 = 25 ± 3 nm are obtained.

[0042] Comparison table of process data for the production of nano-yttrium oxide using traditional reactors, yttrium nitrate systems, and yttrium chloride systems

[0043]

[0044] The above data were verified through 50 batches of experiments; further, this solution achieved controllable preparation of nano-yttrium oxide by integrating precision fluid control and process parameter optimization, with significant advantages in particle size uniformity and process stability.

[0045] In summary: This nano-yttrium oxide continuous preparation system and process method based on multimodal fluid regulation, through the coordinated use of structure and process methods, solves the problems of nano-yttrium oxide produced using a reactor, such as a large particle size distribution span, low specific surface area stability, and a high dispersion index.

Claims

1. A continuous preparation system for nano-yttrium oxide based on multimodal fluid regulation, comprising an yttrium salt storage tank (1), a precipitant storage tank (15) and a surface modifier storage tank (14), characterized in that: The bottoms of the yttrium salt storage tank (1) and the precipitant storage tank (15) are both connected to a high-pressure plunger pump (3) through a pipeline, the liquid outlet of the high-pressure plunger pump (3) is connected to a Coriolis mass flowmeter (4) through a pipeline, the liquid outlet of the Coriolis mass flowmeter (4) is connected to a micro-reaction pressure balancer (5) through a pipeline, the liquid outlets of the two micro-reaction pressure balancers (5) are commonly connected to a three-way buffer tube (6) through a pipeline, the liquid outlet of the three-way buffer tube (6) is connected to a Y-type staggered flow channel mixer (7) through a pipeline, and the liquid outlet of the Y-type staggered flow channel mixer (7) is connected to A spiral expansion channel crystallizer (8) is connected, the liquid outlet of the spiral expansion channel crystallizer (8) is connected to a honeycomb multi-chamber aging device (9) through a pipeline, the liquid outlet of the honeycomb multi-chamber aging device (9) is connected to an in-situ pH / ORP monitor (10) through a pipeline, the liquid outlet of the in-situ pH / ORP monitor (10) is connected to a microwave-assisted dryer (11) through a pipeline, the material outlet of the microwave-assisted dryer (11) is connected to a supercritical CO2 processor (12) through a pipeline, and the material outlet of the supercritical CO2 processor (12) is connected to an airflow classifier (13).

2. The continuous preparation system of nano-yttrium oxide based on multimodal fluid control according to claim 1, characterized in that: The liquid outlet of the surface modifier storage tank (14) is connected to a high-pressure plunger pump (17) through a pipeline, and the liquid outlet of the high-pressure plunger pump (17) is connected to a Coriolis mass flowmeter (18) through a pipeline. The liquid outlet of the Coriolis mass flowmeter (18) is used in conjunction with the discharge end of the airflow classifier (13).

3. The continuous preparation system of nano-yttrium oxide based on multimodal fluid control according to claim 1, characterized in that: A heater (2) is installed inside the yttrium salt storage tank (1), and an ultrasonic disperser (16) is installed inside the precipitant storage tank (15). The temperature control accuracy of the heater (2) is ±0.3°C, and the frequency of the ultrasonic disperser (16) is 40kHz.

4. The continuous preparation system of nano-yttrium oxide based on multimodal fluid control according to claim 1, characterized in that: Two filling channels are installed on the top of the yttrium salt storage tank (1), the precipitant storage tank (15) and the surface modifier storage tank (14).

5. The continuous preparation system of nano-yttrium oxide based on multimodal fluid control according to claim 1, characterized in that: The flow range of the high-pressure plunger pump (3) is 0.1-50 mL / min, the pulsation coefficient is <0.5%, and the accuracy of the Coriolis mass flowmeter (4) is ±0.1% FS.

6. The continuous preparation system of nano-yttrium oxide based on multimodal fluid control according to claim 1, characterized in that: The flow channel diameter inside the Y-shaped staggered flow channel mixer (7) is 1.5 mm, the diameter of the spiral expansion flow channel crystallizer (8) gradually changes to 1.5-5 mm, and the inner wall of the flow channel of the Y-shaped staggered flow channel mixer (7) is laser-processed with a micro-groove array, with a groove depth of 50 μm and a spacing of 200 μm.

7. The continuous preparation system of nano-yttrium oxide based on multimodal fluid control according to claim 1, characterized in that: The operating temperature of the in-situ pH / ORP monitor (10) is 0-150° C., the frequency of the microwave-assisted dryer (11) is 2.45 GHz, and the power is adaptively adjusted. The critical pressure of the supercritical CO2 processor (12) is 7.38 MPa.

8. A process for continuous preparation of nano-yttrium oxide based on multimodal fluid control, characterized by: The process comprises the continuous preparation system of claims 1 to 7 above, and the method of use further comprises the following steps: Step 1: Prepare a 0.8 mol / L yttrium nitrate solution in an yttrium salt storage tank (1), and control the conductivity between 1800±50 μS / cm. During the preparation process, the heater (2) is in an operating state; prepare a urea-ammonia aqueous solution with a molar ratio of 3:1 in a precipitant storage tank (15), and turn on the ultrasonic disperser (16) during the preparation process for 30 minutes. Step 2: respectively start the high-pressure plunger pump 1 (3) at the bottom of the yttrium salt storage tank (1) and the precipitant storage tank (15), and simultaneously deliver the yttrium nitrate solution and the urea-ammonia mixed solution in a volume ratio of 1:1.2; when the high-pressure plunger pump 1 (3) is turned on, the Coriolis mass flowmeter 1 (4) and the micro-reaction pressure balancer (5) are simultaneously turned on. Step 3: The yttrium nitrate solution and the urea-ammonia mixed solution enter the Y-type staggered flow channel mixer (7) through the three-way buffer tube (6), and use the Y-type staggered flow channel mixer (7) to perform a primary reaction to complete instantaneous nucleation (heating rate 10°C / s); after instantaneous nucleation, they enter the spiral expansion flow channel crystallizer (8) to perform a secondary reaction and gradient cooling (85°C→60°C / 5min) and crystallization; finally, they enter the honeycomb multi-chamber aging device (9) to perform a tertiary aging reaction. During the reaction, CO2 / N2 mixed gas is used, and the volume ratio of the two is 1:

4. Step 4: After the pH and ORP value of the material discharged from the honeycomb multi-chamber aging device (9) are tested using an in-situ pH / ORP monitor (10), the material enters a microwave-assisted dryer (11) for drying. The drying process is primary drying at 60°C → deep dehydration at 80°C (water content <0.3%); after drying, the material enters a supercritical CO2 processor (12) and is maintained at 32MPa and 50°C for 2 hours. Step 5: The supercritical treated material enters the air classifier (13) for classification, and the material is discharged after classification. At this time, the high-pressure plunger pump 2 (17) and the Coriolis mass flowmeter 2 (18) are turned on to spray the surface modifier in the surface modifier storage tank (14) to mix with the discharged material.

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