CN114289133B - Nano treatment method of layered clay mineral - Google Patents
Nano treatment method of layered clay mineral Download PDFInfo
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- CN114289133B CN114289133B CN202111655886.XA CN202111655886A CN114289133B CN 114289133 B CN114289133 B CN 114289133B CN 202111655886 A CN202111655886 A CN 202111655886A CN 114289133 B CN114289133 B CN 114289133B
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Abstract
The invention discloses a nano-processing method of layered clay minerals. The processing method comprises the following steps: s1: microwave pretreatment, namely weighing a proper amount of layered clay mineral and putting the layered clay mineral into a microwave heating furnace for heating; s2: step (2) ultrafine grinding, namely weighing a proper amount of sample obtained in the step (S1), putting the sample into a zirconia ball-milling tank by adopting a wet ball-milling method and using absolute ethyl alcohol as a medium, fully and uniformly stirring the mixture, and carrying out ball milling; s3: ultrasonic cavitation stripping, namely taking the sample obtained in the step S2 and a dispersing agent in a centrifugal tube, and ultrasonically stripping for 2-5 hours to obtain a suspension; s4: and (4) centrifuging the suspension obtained in the step (S3) to obtain supernatant, and drying the supernatant in vacuum to obtain the nano layered clay mineral material. According to the invention, the layered clay mineral is stripped and nanocrystallized in a targeted manner through a microwave-mechanical force-ultrasonic multiple physical force field, so that the nanoscale effect is remarkably improved, the process is continuous and controllable, and the method has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of mineral resource deep processing, in particular to a nano treatment method of layered clay minerals.
Background
The natural clay mineral is a non-metal mineral with a regular unit structure and a layered structure mostly formed by aluminosilicate frameworks, and as a natural nano material, a nano-scale microstructure exists in the aluminosilicate frameworks, such as interlaminar domains of kaolinite, montmorillonite and rectorite, and pore channel structures of sepiolite and zeolite, and the natural clay mineral has an excellent nano-scale effect. At present, the nano clay minerals have wide application in the fields of biology, environment, energy and the like, such as: kaolinite uses abundant active groups on its surface to regulate metal oxygenThe oxygen vacancy of the oxide is used for improving the catalytic performance; the carbon hybridized montmorillonite nanosheet can remarkably improve the adsorption effect due to the synergistic adsorption effect; DOX-Mn loading with halloysite nanotube as carrier 3 O 4 Has excellent antitumor curative effect and extremely low side effect; the selective battery diaphragm added by the montmorillonite nanosheets can obviously inhibit polysulfide diffusion and plays a role in protecting the anode. Therefore, the nano-scale effect of the clay mineral can be utilized to provide innovative solutions for various fields.
However, the problems of low nano-scale utilization rate, unobvious effect, incapability of large-scale application and the like exist in the prior clay mineral application, such as low intercalation rate, poor pore channel accumulation and poor surface activity. Around the above problems, a key starting point is that the nanoscale particle size can significantly enhance the nanoscale effect, and the main technical measures at present mainly comprise structure dissociation and micro-nano-scale. On one hand, the nano effect is improved by depolymerizing the original mineral structure through chemical intercalation combined with ultrasonic stripping, and on the other hand, the application effect is improved by preparing the nano material through clay mineral acid-base treatment. The research process is complex, the flow is complex, the selectivity to the quality of the raw ores in different producing areas is high, especially the final excellent effect is obtained, the process control is severe, and the popularization and the production are not facilitated.
Disclosure of Invention
The present invention is directed to a method for processing layered clay minerals into nano-particles, which overcomes the above-mentioned disadvantages of the prior art.
The invention relates to a layered clay mineral nanocrystallization method, which comprises the following steps:
s1: microwave pretreatment, namely weighing a proper amount of layered clay mineral and putting the layered clay mineral into a microwave heating furnace for heating;
s2: carrying out stage ultrafine grinding, namely weighing a proper amount of sample obtained in the step S1, and carrying out ball milling by adopting a wet ball milling method;
s3: ultrasonic cavitation stripping, namely taking the sample obtained in the step S2 and a dispersing agent in a centrifugal tube, and ultrasonically stripping for 2-5 hours to obtain a suspension;
s4: and (4) centrifuging the suspension obtained in the step (S3) to obtain supernatant, and drying the supernatant in vacuum to obtain the nano layered clay mineral material.
Further, in the step S1, a mode of firstly carrying out continuous heating and then carrying out intermittent heating is adopted, the continuous heating power is 200-3000W, the continuous heating time is 30-300S, the subsequent heating power is 250-2000W, the heating time is 10-50S, the single pause time of the intermittent heating process is 10-50S, and the total intermittent heating time is 100-600S.
Further, with absolute ethyl alcohol as a medium, putting a sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to a certain mass ratio, and fully and uniformly stirring, wherein the mass ratio of the sample to the zirconia balls to the absolute ethyl alcohol is (2-5).
Further, in step S2, the ball milling is a three-stage ball milling:
the rotating speed of the first section is 300-500r/min, the ball milling time is 2-24h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling process again, the rotating speed is intermittently increased to 700-800r/min in the stage, and the time duration of each time is 20-40min;
the rotation speed of the second stage is 400-600r/min, the ball milling time is 2-24h, the rotation speed is intermittently increased to 700-800r/min in the stage, and the ball milling time is 20-40min each time;
the rotating speed of the third stage is 200-400r/min, the ball milling time is 2-24h, the rotating speed is increased to 700-800r/min intermittently in the stage, and the ball milling time is 20-40min each time;
and after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 20-50 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball milling sample.
Furthermore, the diameter of the zirconia ball is 2-8mm.
Further, in the step S3, the dispersing agent is absolute ethyl alcohol, and ultrasonic stripping is carried out for 2-5h under the condition of room-temperature circulating water cooling, wherein the ultrasonic stripping parameter is 400-600W and 3000-8000kHz.
Further, in step S4, the centrifugation speed is 1000-5000r/min, and the centrifugation time is 5-30min.
Further, in step S4, the supernatant is dried at 20-50 ℃ for 1-4h.
According to the invention, the microwave pretreatment of the layered clay mineral is adopted to assist in improving the stripping effect; the stage superfine grinding can perform uniform mechanical stripping aiming at mineral particles with different particle sizes; the ultrasonic cavitation stripping can further promote the stripping effect and the integral dispersion effect of the fine mineral particles.
According to the invention, the layered clay mineral is stripped and nanocrystallized in a targeted manner through a microwave-mechanical force-ultrasonic multiple physical force field, so that the nanoscale effect is remarkably improved, the process is continuous and controllable, and the method has a wide application prospect.
According to the method of the invention D50 is obtained<200nm, and the particle size distribution is uniform; the nano-sheets are uniformly dispersed on the micro-morphology, the main diffraction peak (001) disappears, and the nano-sheets are completely peeled; the specific surface area reaches 79.3m 2 G, pore volume of 0.18m 3 (iv)/g, nano-scale layered clay mineral material exhibiting pore-like properties.
Drawings
FIG. 1 SEM image of rectorite raw ore of example 1;
FIG. 2 SEM image of nano-sized rectorite of example 1;
FIG. 3 TEM image of the rectorite raw ore of example 1;
FIG. 4 TEM image of nano-sized rectorite of example 1;
FIG. 5 XRD patterns of the rectorite raw ore and nano-sized rectorite of example 1;
FIG. 6 BET plot of raw and nano-sized rectorite of example 1;
FIG. 7 is a particle size distribution diagram of nano-sized montmorillonite of example 3;
FIG. 8 TEM image of a nanometerized montmorillonite of example 3;
FIG. 9 is a graph showing a particle size distribution of the ball-milled rectorite alone in comparative example 1;
FIG. 10 is a particle size distribution plot of the sonicated rectorite alone of comparative example 2;
FIG. 11 particle size distribution plots for the rectorite raw ore, the one-stage treated rectorite and the three-stage treated rectorite of example 1 and comparative example 3.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.
Example 1
The purpose of this example is to explore the effect of a stage of grinding, and the operation steps are as follows
(1) Microwave pretreatment
In each operation, a proper amount of layered clay mineral is weighed and put into a microwave heating furnace for heating. A thermocouple was used to monitor the sample temperature in real time during the heating process. And respectively processing the samples by adopting intermittent heating, and naturally cooling the samples after heating.
The power of the continuous microwave heating process is 2000W;
the continuous microwave heating time is 150s;
the power of the intermittent heating process is 1500W;
the single heating time of the intermittent heating process is 20s;
the single pause time of the intermittent heating process is 20s;
the total time of the intermittent heating process is 300s.
(2) Staged superfine grinding
Weighing a proper amount of the sample obtained in the step (1), and adopting a wet ball milling method and absolute ethyl alcohol as a medium. And (3) putting the sample, the zirconia balls and the absolute ethyl alcohol into a zirconia ball-milling tank according to the mass ratio of 2.
The rotation speed of the first stage is 500r/min, the ball milling time is 12h, after ball milling for 6h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling solution again, the rotation speed is intermittently increased to 700r/min in the stage, and the time duration of each time is 30min.
The rotation speed of the second stage is 600r/min, the ball milling time is 6h, the rotation speed is intermittently increased to 700r/min in the second stage, and the ball milling time is 30min each time.
The rotating speed of the third section is 400r/min, the ball milling time is 6h, the rotating speed is intermittently increased to 700r/min in the third section, and the ball milling time is 30min each time.
And after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 40 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball-milled sample.
Preferably, the zirconia balls at this stage have a diameter of 2mm.
(3) Ultrasonic cavitation exfoliation
Putting the sample prepared in the step (2) into a 10ml centrifuge tube per 1g, and taking absolute ethyl alcohol as a solvent, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (400W, 4000kHz) stripping for 4h under the condition of circulating cooling water at room temperature, transferring the obtained suspension into a centrifugal machine under a sealed condition, centrifuging, and sucking 2/3 of the supernatant liquid by using a suction pipe to obtain a small amount of dispersion liquid. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying box, and drying the vacuum drying box for 2 hours at 50 ℃ to obtain the processed nano-grade rectorite, wherein the contrast of an SEM image of an attached figure 1 and an SEM image of a figure 2 shows that the appearance of the processed rectorite is changed from an agglomeration state to a small particle accumulation; as can be seen from the comparison of the TEM images of FIGS. 3 and 4, the treated rectorite presents uniformly dispersed nano-sheets and maintains the structure of the raw ore; the XRD pattern of figure 5 shows that the rectorite after treatment has the same peak shape, the main diffraction peak (001) disappears, and the abrasion is complete; as can be seen from the BET diagram of FIG. 6, the specific surface area of the treated rectorite reached 79.3m 2 G, pore volume of 0.18m 3 In/g, pore-like properties occur. As can be seen from the particle size of FIG. 11, the particle size of the treated rectorite is reduced, and the D50 is<200nm。
Example 2
The purpose of this example is to examine the effect of this process on the nanocrystallization of kaolinite, and the procedure is as follows.
(1) Microwave pretreatment
In each operation, a proper amount of kaolinite is weighed and put into a microwave heating furnace for heating. A thermocouple was used to monitor the sample temperature in real time during the heating process. And respectively adopting two modes of continuous heating and intermittent heating to treat the sample, and naturally cooling the sample after heating.
The power of the continuous microwave heating process is 2000W;
the continuous microwave heating time is 150s;
the power of the intermittent heating process is 1500W;
the single heating time of the intermittent heating process is 20s;
the single pause time of the intermittent heating process is 20s;
the total time of the batch heating process was 300s.
(2) Staged superfine grinding
Weighing a proper amount of the sample obtained in the step (1), and adopting a wet ball milling method and absolute ethyl alcohol as a medium. Putting the sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to the mass ratio of 2.
The rotation speed of the first stage is 500r/min, the ball milling time is 12h, after ball milling for 6h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling solution again, the rotation speed is intermittently increased to 700r/min in the stage, and the time duration of each time is 30min.
The rotation speed of the second stage is 600r/min, the ball milling time is 6h, the rotation speed is intermittently increased to 700r/min in the second stage, and the ball milling time is 30min each time.
The rotating speed of the third stage is 400r/min, the ball milling time is 6h, the rotating speed is intermittently increased to 700r/min in the third stage, and the ball milling time is 30min each time.
And after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 40 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball-milled sample.
Preferably, the zirconia balls at this stage have a diameter of 2mm.
(3) Ultrasonic cavitation exfoliation
Putting the sample prepared in the step (2) into a 10ml centrifuge tube per 1g, and taking absolute ethyl alcohol as a solvent, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (400W, 4000 kHz) stripping is carried out for 4h under the condition of circulating cooling water at room temperature, the obtained suspension is transferred to a centrifuge under a sealed condition for centrifugation, and the supernatant liquid 2/3 of the upper part is absorbed by a suction pipe to obtain a small amount of dispersion liquid. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying oven, and drying for 2 hours at 50 ℃ to obtain the nano kaolinite after the first-stage grinding treatment.
Example 3
The purpose of this example was to examine the effect of this process on the nanocrystallization of montmorillonite, and the procedure was as follows.
(1) Microwave pretreatment
In each operation, a proper amount of montmorillonite is weighed and placed in a microwave heating furnace for heating. A thermocouple was used to monitor the sample temperature in real time during the heating process. And respectively adopting two modes of continuous heating and intermittent heating to treat the sample, and naturally cooling the sample after heating.
The power of the continuous microwave heating process is 2000W;
the continuous microwave heating time is 150s;
the power of the intermittent heating process is 1500W;
the single heating time of the intermittent heating process is 20s;
the single pause time of the intermittent heating process is 20s;
the total time of the intermittent heating process is 300s.
(2) Stage superfine grinding
Weighing a proper amount of the sample obtained in the step (1), and adopting a wet ball milling method and absolute ethyl alcohol as a medium. Putting the sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to the mass ratio of 2.
The rotation speed of the first stage is 500r/min, the ball milling time is 12h, after ball milling for 6h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling solution again, the rotation speed is intermittently increased to 700r/min in the stage, and the time duration of each time is 30min.
The rotation speed of the second stage is 600r/min, the ball milling time is 6h, the rotation speed is intermittently increased to 700r/min in the second stage, and the ball milling time is 30min each time.
The rotating speed of the third stage is 400r/min, the ball milling time is 6h, the rotating speed is intermittently increased to 700r/min in the third stage, and the ball milling time is 30min each time.
And after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 40 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball-milled sample.
Preferably, the diameter of the zirconia balls at this stage is 2mm.
(3) Ultrasonic cavitation exfoliation
Putting the sample prepared in the step (2) into a 10ml centrifuge tube per 1g, and taking absolute ethyl alcohol as a solvent, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (400W, 4000kHz) stripping for 4h under the condition of circulating cooling water at room temperature, transferring the obtained suspension into a centrifugal machine under a sealed condition, centrifuging, and sucking 2/3 of the supernatant liquid by using a suction pipe to obtain a small amount of dispersion liquid. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying oven, and drying for 2h at 50 ℃ to obtain the nano-montmorillonite after one-stage grinding treatment, wherein the D50=0.376 μm of the treated montmorillonite can be seen from the attached figure 7; as can be seen from FIG. 8, the treated montmorillonite shows well-dispersed nanosheets in the microscopic morphology.
Example 4
The purpose of this example is to explore the rationality of setting the minimum value of the parameter range of the method, and the operation steps are as follows
(1) Microwave pretreatment
In each operation, a proper amount of layered clay mineral is weighed and put into a microwave heating furnace for heating. A thermocouple was used to monitor the sample temperature in real time during the heating process. And respectively processing the samples by adopting intermittent heating, and naturally cooling the samples after heating.
The power of the continuous microwave heating process is 200W;
the continuous microwave heating time is 30s;
the power of the intermittent heating process is 250W;
the single heating time in the intermittent heating process is 10s;
the single pause time of the intermittent heating process is 10s;
the total time of the intermittent heating process was 100s.
(2) Staged superfine grinding
Weighing a proper amount of the sample obtained in the step (1), and adopting a wet ball milling method and absolute ethyl alcohol as a medium. Putting the sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to the mass ratio of 2.
The first stage has a rotation speed of 300r/min and a ball milling time of 2h, and the rotation speed is intermittently increased to 700r/min in the first stage, wherein the time duration of each time is 30min.
The second stage has rotation speed of 400r/min and ball milling time of 2 hr, and the rotation speed is raised intermittently to 700r/min for 30min each time.
The rotating speed of the third section is 200r/min, the ball milling time is 2h, the rotating speed is intermittently increased to 700r/min in the third section, and the ball milling time is 30min each time.
And after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 40 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball-milled sample.
Preferably, the zirconia balls at this stage have a diameter of 2mm.
(3) Ultrasonic cavitation exfoliation
Putting the sample prepared in the step (2) into a 10ml centrifuge tube per 1g, and taking absolute ethyl alcohol as a solvent, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (400W, 3000 kHz) stripping for 4h under the condition of circulating cooling water at room temperature, transferring the obtained suspension to a centrifuge under a sealed condition for centrifugation, and sucking 2/3 of the supernatant liquid from the top by a suction pipe to obtain a small amount of dispersion liquid. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying oven, and drying for 2 hours at 50 ℃ to obtain the nanoscale layered clay mineral.
Example 5
The purpose of this embodiment is to investigate the rationality of setting the maximum value of the parameter range of the method, and the operation steps are as follows
(1) Microwave pretreatment
In each operation, a proper amount of layered clay mineral is weighed and put into a microwave heating furnace for heating. A thermocouple was used to monitor the sample temperature in real time during the heating process. And respectively processing the samples by adopting intermittent heating, and naturally cooling the samples after heating.
The power of the continuous microwave heating process is 3000W;
the continuous microwave heating time is 300s;
the power of the intermittent heating process is 2000W;
the single heating time of the intermittent heating process is 50s;
the single pause time of the intermittent heating process is 50s;
the total time of the intermittent heating process was 600s.
(2) Staged superfine grinding
Weighing a proper amount of the sample obtained in the step (1), and adopting a wet ball milling method and absolute ethyl alcohol as a medium. Putting the sample, zirconia balls and absolute ethyl alcohol into a zirconia ball milling tank according to the mass ratio of 5.
The rotating speed of the first stage is 500r/min, the ball milling time is 24h, after ball milling for 6h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling solution again, and the rotating speed is intermittently increased to 700r/min in the stage, wherein the time duration of each time is 30min.
The rotation speed of the second stage is 600r/min, the ball milling time is 24h, the rotation speed is intermittently increased to 700r/min in the second stage, and the ball milling time is 30min each time.
The rotating speed of the third section is 400r/min, the ball milling time is 24h, the rotating speed is intermittently increased to 700r/min in the third section, and the ball milling time is 30min each time.
And after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 40 ℃, and after drying, putting the powder into a mortar for full grinding to obtain a ball milling sample.
Preferably, the zirconia balls at this stage have a diameter of 2mm.
(3) Ultrasonic cavitation exfoliation
Putting the sample prepared in the step (2) into a 10ml centrifuge tube per 1g, and taking absolute ethyl alcohol as a solvent, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (600W, 8000 kHz) stripping was carried out for 4 hours under circulating cooling water at room temperature, the resulting suspension was transferred to a centrifuge under a sealed condition and centrifuged, and the supernatant 2/3 of the above was taken up with a pipette to obtain a small amount of dispersion. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying oven, and drying for 2 hours at 50 ℃ to obtain the nanoscale layered clay mineral.
Comparative example 1
The purpose of this comparative example is to compare the effect of the lamellar clay mineral only treated by ball milling and the effect of the clay mineral treated by the method.
Weighing proper amount of rectorite, and adopting a wet ball milling method and absolute ethyl alcohol as a medium. Putting the sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to the mass ratio of 2.
The rotation speed of the first stage is 500r/min, the ball milling time is 12h, after ball milling for 6h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling solution again, the rotation speed is intermittently increased to 700r/min in the stage, and the time duration of each time is 30min.
The rotation speed of the second stage is 600r/min, the ball milling time is 6h, the rotation speed is intermittently increased to 700r/min in the second stage, and the ball milling time is 30min each time.
The rotating speed of the third section is 400r/min, the ball milling time is 6h, the rotating speed is intermittently increased to 700r/min in the third section, and the ball milling time is 30min each time.
And after the three-stage ball milling is finished, taking out the ball milling tank, separating the grinding balls from the mixed slurry by using a screen, drying the mixed slurry at 40 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball-milled sample.
The results of the examination show in fig. 9, and the rectorite sample D50=2.473 μm after ball milling treatment only has the antifriction effect not reaching the nanometer level and does not have the effect of nanocrystallization of layered clay minerals.
Comparative example 2
The purpose of this comparative example is to compare the effect after the ultrasonic treatment and this method only are carried out to laminar clay mineral.
Weighing 1g of rectorite in a centrifuge tube, weighing 10ml of absolute ethyl alcohol, and adding the absolute ethyl alcohol into the centrifuge tube, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (400W, 4000kHz) stripping for 3h under the condition of room-temperature circulating water cooling, transferring the obtained suspension to a centrifugal machine under a sealed condition, centrifuging, and sucking 2/3 of the supernatant liquid by using a suction pipe to obtain a small amount of dispersion liquid. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying oven, and drying for 2 hours at 40 ℃ to obtain the nano layered clay mineral material.
The results of the detection show in figure 10, the rectorite sample D50=4.613 μm after only ultrasonic treatment, the sample granularity does not reach the nanometer level, the ultrasonic treatment only plays a role in dispersing layered clay minerals, does not reduce the granularity, and does not generate a nanocrystallization effect on the layered clay minerals; similarly, the microwave treatment only has a pretreatment effect on layered clay minerals, so that internal strain is activated, and mechanical stripping is assisted; only the physical force fields of microwave, ball milling mechanical force and ultrasound are supplemented with each other, so that the layered clay mineral can be subjected to nano treatment in a targeted manner.
Comparative example 3
The purpose of this comparative example is to explore the effect of three-stage grinding, and the operation steps are as follows.
The procedure (1) was as in example 1, and step (2) was as follows
(2) Staged superfine grinding
Weighing a proper amount of the sample obtained in the step (1), and adopting a wet ball milling method and absolute ethyl alcohol as a medium. Putting the sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to the mass ratio of 2.
The rotation speed of the first stage is 500r/min, the ball milling time is 12h, after ball milling for 6h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling solution again, the rotation speed is intermittently increased to 700r/min in the stage, and the time duration of each time is 30min.
The rotation speed of the second stage is 600r/min, the ball milling time is 6h, the rotation speed is intermittently increased to 700r/min in the second stage, and the ball milling time is 30min each time.
The rotating speed of the third section is 400r/min, the ball milling time is 6h, the rotating speed is intermittently increased to 700r/min in the third section, and the ball milling time is 30min each time.
The three-stage ball milling is repeated for three times (in the first embodiment, one time), after the end, the ball milling tank is taken out, the grinding balls and the mixed slurry are separated by using a screen, the mixed slurry is dried at 40 ℃, and after the drying, the powder is put into a mortar for fully grinding to obtain a ball milling sample.
Preferably, the zirconia balls at this stage have a diameter of 2mm.
The operation step (3) is the same as the embodiment 1, and after the operation is finished, the rectorite after three-stage ore grinding treatment is obtained. The effect can be seen in figure 11, the grain size of the rectorite after three-stage ore grinding is increased, the D50=2.464 μm, and hard agglomeration occurs, so that the nano treatment effect on the layered clay mineral can be obtained within the parameter range set by the method.
Comparative example 4
The purpose of this comparative example is to compare the effect of the ultrasonic frequency, the procedure is as follows
The operation steps (1) and (2) are the same as those in the embodiment (1), and the operation step (3) is as follows:
(3) Ultrasonic cavitation exfoliation
Putting the sample prepared in the step (2) into a 10ml centrifuge tube per 1g, and taking absolute ethyl alcohol as a solvent, wherein the volume of the absolute ethyl alcohol is not more than 2/3 of that of the centrifuge tube. Ultrasonic (300W, 1000kHz) stripping for 4h under the condition of circulating cooling water at room temperature, transferring the obtained suspension to a centrifuge under a sealed condition for centrifugation, and sucking 2/3 of the supernatant liquid by a suction pipe to obtain a small amount of dispersion liquid. Transferring the dispersion liquid into a watch glass, putting the watch glass into a vacuum drying oven, and drying for 2 hours at 50 ℃ to obtain the layered clay mineral which is agglomerated and unevenly dispersed.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (6)
1. A nano-processing method of layered clay mineral is characterized in that: the method comprises the following steps:
s1: microwave pretreatment, namely weighing a proper amount of layered clay mineral and putting the layered clay mineral into a microwave heating furnace for heating;
s2: carrying out stage ultrafine grinding, namely weighing a proper amount of sample obtained in the step S1, and carrying out ball milling by adopting a wet ball milling method;
s3: ultrasonic cavitation stripping, namely taking the sample obtained in the step S2 and a dispersing agent in a centrifugal tube, and ultrasonically stripping for 2-5 hours to obtain a suspension;
s4: centrifuging the suspension obtained in the step S3 to obtain supernatant, and drying the supernatant in vacuum to obtain a nano layered clay mineral material;
in the step S2, the ball milling is three-stage ball milling:
the rotation speed of the first stage is 300-500r/min, the ball milling time is 2-24h, a proper amount of absolute ethyl alcohol needs to be added into the ball milling process again, the rotation speed is intermittently increased to 700-800r/min in the stage, and the time duration of each time is 20-40min;
the rotation speed of the second stage is 400-600r/min, the ball milling time is 2-24h, the rotation speed is intermittently increased to 700-800r/min in the stage, and the ball milling time is 20-40min each time;
the rotating speed of the third section is 200-400r/min, the ball milling time is 2-24h, the rotating speed is increased to 700-800r/min intermittently in the third section, and the ball milling time is 20-40min each time;
after the three-section ball milling is finished, taking out the ball milling tank, separating the milling balls from the mixed slurry by using a screen, drying the mixed slurry at the temperature of 20-50 ℃, and after drying, putting the powder into a mortar for fully grinding to obtain a ball milling sample;
in the step S3, the dispersing agent is absolute ethyl alcohol, ultrasonic stripping is carried out for 2-5h under the condition of room-temperature circulating water cooling, and the ultrasonic stripping parameters are 400-600W and 3000-8000kHz.
2. The method of claim 1, wherein the nano-treatment of layered clay mineral comprises: in the step S1, a mode of firstly carrying out continuous heating and then carrying out intermittent heating is adopted, the continuous heating power is 200-3000W, the continuous heating time is 30-300S, the subsequent heating power is 250-2000W, the heating time is 10-50S, the single pause time of the intermittent heating process is 10-50S, and the total intermittent heating time is 100-600S.
3. The method of claim 1, wherein the nano-treatment of layered clay mineral comprises: the method comprises the following steps of taking absolute ethyl alcohol as a medium, putting a sample, zirconia balls and absolute ethyl alcohol into a zirconia ball-milling tank according to a certain mass ratio, and fully and uniformly stirring, wherein the mass ratio of the sample to the zirconia balls to the absolute ethyl alcohol is 2-5.
4. The method of claim 3, wherein the nano-treatment of layered clay mineral comprises: the diameter of the zirconia ball is 2-8mm.
5. The method of claim 1, wherein the nano-treatment of layered clay mineral comprises: in step S4, the centrifugation speed is 1000-5000r/min, and the centrifugation time is 5-30min.
6. The method of claim 1, wherein the nano-treatment of layered clay mineral comprises: in step S4, the supernatant is dried at 20-50 ℃ for 1-4h.
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