CN111482147A - Continuous preparation method and continuous preparation device of self-assembled aerogel particles of low-dimensional material - Google Patents
Continuous preparation method and continuous preparation device of self-assembled aerogel particles of low-dimensional material Download PDFInfo
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Abstract
The invention relates to a continuous preparation method and a continuous preparation device of self-assembled aerogel particles of a low-dimensional material. The preparation method comprises the following steps: continuously extruding the raw materials by taking the low-dimensional material slurry as the raw materials, immersing the raw materials into a coagulating bath, and cutting, granulating, coagulating, washing and drying the low-dimensional material slurry in the coagulating bath; wherein: the outlet of the raw material is immersed below the liquid level of the coagulating bath or just contacts with the liquid level of the coagulating bath, the density of the low-dimensional material slurry is more than that of the coagulating bath, and the viscosity of the low-dimensional material slurry enables the low-dimensional material slurry to keep the shape in the coagulating bath. The continuous preparation device is designed according to the preparation method, and the continuous preparation method and the continuous preparation device can realize continuous and large-scale preparation of the self-assembled aerogel particles of the low-dimensional material, improve the preparation efficiency of the aerogel particles, and have practical significance for expanding the application field and realizing the practicability of the aerogel.
Description
Technical Field
The invention relates to a continuous preparation method and a continuous preparation device of self-assembled aerogel particles of a low-dimensional material.
Background
The low-dimensional material self-assembled aerogel has the characteristics of low density, high porosity, high specific surface area, low thermal conductivity, low dielectric constant and the like, and has wide application in the fields of adsorption, separation, catalysis, chemical industry, water treatment, sensors, aerospace, building heat preservation, energy storage and conversion and the like.
At present, the preparation method of the low-dimensional material self-assembly aerogel mainly comprises a sol-gel method, a hydrothermal method, a solvothermal method, a chemical vapor deposition method, a precursor conversion method and the like. The size and shape of the self-assembled aerogel prepared by the methods are generally limited by a raw material container or a template for synthesis, and the method has the problem of difficult continuous and large-scale preparation. These problems have hindered the use of self-assembled aerogels.
With the research and application of the self-assembled aerogel made of low-dimensional materials becoming more extensive, the realization of the efficient, continuous and large-scale preparation of the self-assembled aerogel has practical and important significance, but a feasible technology or a product is still lacked at present.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
The invention aims to provide a continuous preparation method and a continuous preparation device for self-assembled aerogel particles of a low-dimensional material, so that the self-assembled aerogel particles of the low-dimensional material can be continuously prepared on a large scale, the preparation efficiency of the aerogel particles is improved, and the continuous preparation method and the continuous preparation device have practical significance for expanding the application field and realizing the practicability of aerogel.
Solution scheme
In order to realize the purpose of the invention, the invention provides the following technical scheme:
a method for the continuous preparation of self-assembled aerogel particles of low dimensional material comprising the steps of: continuously extruding the raw materials by taking the low-dimensional material slurry as the raw materials, immersing the raw materials into a coagulating bath, and cutting, granulating, coagulating, washing and drying the low-dimensional material slurry in the coagulating bath; wherein: the outlet of the raw material is immersed below the liquid level of the coagulating bath or just contacts with the liquid level of the coagulating bath, the density of the low-dimensional material slurry is more than that of the coagulating bath, and the viscosity of the low-dimensional material slurry enables the low-dimensional material slurry to keep the shape in the coagulating bath.
Further, in a possible implementation manner, the above-mentioned continuous preparation method includes that the low-dimensional material slurry includes a low-dimensional material solvent and a low-dimensional material dispersed in the low-dimensional material solvent; the low-dimensional material solvent is as follows: water or a mixed solvent composed of water and a water-soluble organic solvent;
the low dimensional material comprises: at least one of a two-dimensional material, a one-dimensional material, or a zero-dimensional material;
the two-dimensional material comprises graphene oxide, graphene, graphite nanosheets and at least one of layered phosphates, hydroxides, double hydroxides, silicates, clays, chalcogenides, oxides, nitrides, carbides, black phosphorus, elemental metals and metal-organic frameworks;
the one-dimensional material comprises at least one of a carbon nano tube, a carbon nano fiber, a silicon carbide whisker, a copper nano wire and a titanium dioxide nano wire;
the zero-dimensional material comprises at least one of fullerene, quantum dot and nanocluster.
Further, in a possible implementation manner of the continuous preparation method, the mass fraction of the low-dimensional material in the low-dimensional material slurry is 0.1% -20%; further optionally, the mass fraction of the low-dimensional material in the low-dimensional material slurry is 1% -10%.
Further, in a possible implementation manner, the coagulation bath includes a coagulant and a coagulant solvent contained in a container.
Further, in a possible implementation manner of the above-described continuous production method, the coagulant solvent may be water or a mixed solvent composed of water and a water-soluble organic solvent.
Further, in a possible implementation manner of the above continuous preparation method, the coagulant includes a metal salt, a cationic surfactant, a cationic polymer, and the like; further optionally at least one of potassium chloride, sodium chloride, calcium chloride, potassium nitrate, sodium nitrate, calcium nitrate, sodium sulfate, potassium sulfate, polyethyleneimine, cetyltrimethylammonium bromide, or polydiallyldimethylammonium chloride.
Further, in a possible implementation manner, the mass ratio of the coagulant to the solvent is 1: (10-800); optionally 1: (20-200); further optionally 1: (60-100).
Further, in a possible implementation manner, the continuous preparation method has the solidification time of 30min-3 d; alternatively 1-24 h; further optionally 2-8 h.
Further, in a possible implementation manner, the continuous preparation method comprises the following steps: taking low-dimensional material slurry as a raw material, continuously extruding the raw material from an extrusion molding die through a conveying device, immersing the raw material into a coagulating bath in a coagulating bath container, carrying out section granulation on the raw material in the coagulating bath by using a section granulating device, sinking the raw material subjected to section granulation into the bottom of the container and further solidifying to form particles, washing and drying to obtain aerogel particles; wherein:
the density of the low-dimensional material slurry is greater than that of the coagulating bath, and the viscosity of the low-dimensional material slurry enables the low-dimensional material slurry to be coagulated and formed in the coagulating bath;
the conveying device comprises the following components: the driving force providing device is connected with the conveying pipeline and is used for providing driving force for sucking, conveying and extruding low-dimensional material slurry in the conveying pipeline;
the extrusion molding die is connected to the outlet of the conveying pipeline, and the outlet of the extrusion molding die is immersed below the liquid level of the coagulating bath or just contacts with the surface of the coagulating bath, so that the target shape is set for the extrusion of the low-dimensional material slurry;
the container for containing the coagulating bath is arranged below the extrusion molding neck ring;
and the cutting part of the cutting and granulating device is arranged in the container for containing the coagulating bath and is used for cutting the slurry extruded into the container for containing the coagulating bath into sections.
Further, in a possible implementation manner of the continuous preparation method, after the low-dimensional material slurry is extruded from the extrusion molding die and contacts with the coagulating bath, the surface of the slurry is coagulated to form a semi-solid shell layer, and the semi-solid shell layer is cut by the cutting and granulating device; the fresh section formed by cutting is solidified to form a semi-solid shell layer after contacting with a coagulating bath, thereby forming the effect of granulation.
Further, in a possible implementation manner, the continuous preparation method can control the length of the aerogel particles by adjusting the extrusion rate of the slurry in the extrusion molding die and the cutting rate of the segmenting and granulating device; wherein, the speed of extruding the slurry can be adjusted by the flow rate or the rotating speed of a peristaltic pump, a rotary vane pump or an injection pump; the cutting rate can be adjusted by the rotational speed of the blade, the reciprocating cutting frequency of the wire cutting device, the impact cutting frequency of the water cutting, and the like. The aerogel particles in the invention are only a name of the obtained product, are not particularly limited to round objects, and the cross section of the aerogel particles can be adjusted according to the shape of the die, and the length of the aerogel particles can also be adjusted.
Further, in a possible implementation manner, the above-mentioned continuous preparation method comprises at least one of freeze drying, forced air drying, natural airing, vacuum drying or supercritical drying.
The invention also provides a continuous preparation device of the self-assembled aerogel particles of the low-dimensional material, which comprises the following components:
a conveying device; the conveying device comprises the following components:
a delivery line;
and, a driving force providing means; the driving force providing device is connected with the conveying pipeline and is used for providing driving force for sucking, conveying and extruding low-dimensional material slurry in the conveying pipeline;
extruding and molding a neck ring mold; the extrusion molding die is connected to the outlet of the conveying pipeline, and when the extrusion molding die is used, the outlet of the extrusion molding die is immersed below the liquid level of the coagulating bath or just contacts with the surface of the coagulating bath, so that the target shape is set for the extrusion of low-dimensional material slurry;
a container for holding a coagulation bath; the container for containing the coagulating bath is arranged below the extrusion molding neck ring;
and, a cutting and pelletizing device; and the cutting part of the cutting and granulating device is arranged in the container for containing the coagulating bath and is used for cutting the slurry extruded into the container for containing the coagulating bath into sections.
Further, in a possible implementation manner, the above-mentioned continuous preparation device may be a peristaltic pump, a rotary vane pump or a syringe pump. Peristaltic pumps, rotary vane pumps or syringe pumps are all existing conveying devices, and of course, the conveying devices and the devices for providing driving force for sucking, conveying and extruding the conveying materials in the conveying pipelines can be directly used as the conveying devices in the continuous preparation device. In addition, the arrangement of the conveying pipeline can be one or more, and the conveying pipeline can be adjusted according to the requirement; the driving force providing device can be arranged such that one driving force providing device provides driving force for a plurality of conveying pipelines, or a plurality of driving force providing devices respectively provide driving force for a plurality of conveying pipelines, and the driving force providing devices can be selected according to production requirements.
Further, in a possible implementation manner of the continuous preparation apparatus, the material of the conveying pipeline may be at least one of a polymer material, a metal material, or a biological material. The thickness and length of the pipe can be adjusted according to the technical requirements of the pulp extrusion device.
Further, in a possible implementation manner of the above continuous preparation device, the extrusion molding die may be a single-hole die, a multi-hole die, or a plurality of single-hole dies. Increasing the number of dies can increase the production efficiency of the aerogel particles.
Further, in a possible implementation manner, the continuous preparation device can obtain aerogel particles with different shapes and sizes by selecting the neck molds with different cross-sectional shapes and sizes; further, the cross-sectional shape may be: the shape of the aerogel particles prepared correspondingly is cylindrical, triangular prism, cube, cuboid, hexagonal prism, irregular cylinder and the like.
Further, in a possible implementation manner, the above continuous preparation device is a rotary blade cutting, linear cutting or water stream cutting device; optionally a rotary blade.
Further, in a possible implementation manner, the above-mentioned continuous preparation device comprises a sharp blade capable of rotating to cut and a motor driving the blade to rotate to cut.
Advantageous effects
(1) The embodiment of the invention provides a continuous preparation method of self-assembled aerogel particles of a low-dimensional material. The preparation method has high production efficiency and can be used for continuous large-scale preparation; the preparation method has few limiting conditions, and does not need to consider the influence of the distance between the liquid drop and the liquid level of the coagulation bath on the product and the surface tension problem of the coagulation bath; the preparation method is flexible in application, and the product of the technology is not limited to round balls formed by liquid drops, but also can generate aerogel particles in various shapes.
(2) The embodiment of the invention also provides a continuous preparation device of the self-assembled aerogel particles of the low-dimensional material, and the preparation device has the advantages of simple equipment, simplicity and convenience in operation, wide application range, capability of performing various-scale preparation and the like; the production apparatus has few restrictions, and does not need to consider the influence of the distance between the liquid droplet and the surface of the coagulation bath on the product and the problem of the surface tension of the coagulation bath.
(3) The continuous preparation device provided by the embodiment of the invention is flexible in application, can realize continuous preparation by selecting the peristaltic pump, can be used for small-scale and large-scale preparation, and has good applicability; the injection pump is limited by the injector and is suitable for small-scale continuous preparation; the rotary vane pump has large size and power, is suitable for industrial scale, and has poor applicability as a peristaltic pump.
(4) The continuous preparation device provided by the embodiment of the invention is flexible in application, the product of the device is not limited to round balls formed by liquid drops, and aerogel particles with different shapes and sizes can be obtained by selecting different cross-section shapes and sizes.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is a photograph of graphene oxide/α -zirconium phosphate composite aerogel particles prepared according to example 2 of the present invention.
Fig. 2 is a scanning electron microscope picture of a cross section of the graphene oxide/α -zirconium phosphate composite aerogel particles prepared in example 2 of the present invention.
Fig. 3 is a high-power scanning electron microscope picture of a cross section of the graphene oxide/α -zirconium phosphate composite aerogel particles prepared in example 2 of the present invention.
Fig. 4 is a photograph of the graphene oxide aerogel particles prepared in example 3 of the present invention.
Fig. 5A and 5B are schematic structural views of an apparatus for continuously preparing self-assembled aerogel particles of a low-dimensional material according to example 6 of the present invention, in which: 11-conveying pipeline, 12-driving force providing device, 2-extrusion molding die, 3-container for holding coagulating bath, 4-section cutting and granulating device and 41-cutting position.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
The raw materials used in the following examples are all commercial products except α -zirconium phosphate α -zirconium phosphate was prepared by hydrothermal method at 180 ℃ using zirconium oxychloride and concentrated phosphoric acid (85% concentration).
Example 1
Using 100g of graphene oxide aqueous dispersion (mass fraction is 2%) as a raw material, continuously extruding the raw material into a coagulating bath (mass fraction of calcium chloride serving as a coagulant, mass fraction of ethanol serving as a coagulant is 10%, and mass fraction of water serving as a coagulant is 85%) through a peristaltic pump and four circular-section extrusion molding dies with the diameter of 5mm, immersing an outlet of the raw material below the liquid level of the coagulating bath, and granulating by a rotary blade section granulating device, wherein the density of the graphene oxide aqueous dispersion is higher than that of the coagulating bath, so that the bottom of a container containing the coagulating bath is sunk in the granulating process, whether the density of the graphene oxide aqueous dispersion is higher than that of the coagulating bath is not required to be confirmed through complicated density measurement, and the floating, suspending or sinking state of the graphene oxide aqueous dispersion in the coagulating bath can be known through visual observation, this also applies in the following examples; and the viscosity of the graphene oxide aqueous dispersion is large enough to keep the shape in a coagulating bath;
adjusting the flow rate of a peristaltic pump to be 20ml/min, the rotating speed of a motor of a section-cutting granulation device to be 100r/min, preparing a cylindrical hydrogel product through continuous slurry extrusion and intermittent blade cutting, and solidifying for 3 hours in a solidification bath;
and washing the solidified product with water for 5 times, and freeze-drying to obtain cylindrical and fine graphene oxide aerogel particles.
Because the three measures of continuous material conveying of the peristaltic pump, simultaneous extrusion of a plurality of mouth molds and continuous cutting of the rotary blade are adopted, the preparation device provided by the embodiment has the advantages of high preparation efficiency, convenience in continuous and large-scale preparation and the like.
Example 2
Mixing 150g of graphene oxide aqueous dispersion (mass fraction is 2%) and 80g of α -zirconium phosphate aqueous dispersion (mass fraction is 5%) into viscous slurry by ultrasonic treatment and mechanical stirring for 2h, adding 4g of ethanolamine into α -zirconium phosphate aqueous dispersion before mixing, carrying out ultrasonic stirring for 1h, stripping, continuously extruding the slurry into a coagulating bath (mass fraction of coagulant cetyl trimethyl ammonium bromide is 1%, mass fraction of coagulant solvent-water is 99%) through a peristaltic pump and a circular cross-section extrusion forming die with the diameter of 5mm, immersing an outlet of the raw material below the liquid level of the coagulating bath, and carrying out granulation through a rotary blade cutting device, wherein the density of the slurry is higher than that of the coagulating bath, so that the obtained granules sink to the bottom of a container containing the coagulating bath, and the viscosity of the slurry is large enough to keep the shape in the coagulating bath;
adjusting the speed of extruding slurry by a peristaltic pump to be 5ml/min, adjusting the rotating speed of a motor of a section-cutting granulation device to be 100r/min, preparing a cylindrical product by continuous slurry extrusion and intermittent blade cutting, and solidifying for 5 hours in a solidification bath;
washing the solidified product with ethanol and water for 3 times respectively, and freeze-drying to obtain cylindrical graphene oxide/α -zirconium phosphate composite aerogel particles (figure 1).
The cross section of the graphene oxide/α -zirconium phosphate composite aerogel particles prepared in this example was observed by a scanning electron microscope, and as shown in fig. 2, the inside thereof was a porous structure formed by a thin-walled support.
Further observation under a high power scanning electron microscope, as in fig. 3, the thin-walled structure was composed of graphene oxide sheets and hexagonal α -zirconium phosphate sheets encapsulated therein.
Example 3
Continuously extruding 80g of graphene oxide aqueous dispersion (the mass fraction is 2%) serving as a raw material into a coagulating bath (the mass fraction of a coagulant, namely polyethyleneimine is 2%, and the mass fraction of a coagulant, namely solvent and water is 98%) through a peristaltic pump and a circular-section extrusion molding die with the diameter of 1.2cm, wherein an outlet of the raw material just contacts with the liquid surface of the coagulating bath, and granulating through a rotary blade section cutting device, wherein the density of the graphene oxide aqueous dispersion is higher than that of the coagulating bath, so that the obtained granules sink to the bottom of a container containing the coagulating bath, and the viscosity of the graphene oxide aqueous dispersion is large enough to keep the shape in the coagulating bath;
adjusting the speed of extruding slurry by a peristaltic pump to be 30ml/min, adjusting the rotating speed of a motor of a section-cutting granulation device to be 100r/min, preparing a cylindrical product by continuous slurry extrusion and intermittent blade cutting, and solidifying for 2h in a solidification bath;
the solidified product was washed with water 4 times, and freeze-dried to obtain cylindrical, relatively coarse graphene oxide aerogel particles, as shown in fig. 4.
Example 4
Fully mixing 50m L graphene oxide aqueous dispersion (mass fraction is 2%) and 50m L carbon nanotube aqueous dispersion (mass fraction is 1%) through mechanical stirring and ultrasonic action for 12 hours to form graphene oxide/carbon nanotube composite slurry;
filling a 60m L syringe with the raw materials, immersing the outlet of the raw materials below or just contacting the liquid level of the coagulating bath, continuously extruding the raw materials into the coagulating bath (mass fraction of the coagulating agent polyethyleneimine is 2%, mass fraction of the coagulating agent solvent-water is 98%) through a syringe pump and a circular cross-section extrusion molding die with the diameter of 5mm, and granulating the raw materials by a rotary blade cutting device, wherein the density of the slurry is higher than that of the coagulating bath, so that the granulation is sunk to the bottom of a container containing the coagulating bath, and the viscosity of the slurry is large enough to keep the shape in the coagulating bath;
adjusting the extrusion speed of an injection pump to be 4ml/min, the rotating speed of a motor of a section-cutting granulation device to be 120r/min, preparing a cylindrical product through continuous slurry extrusion and intermittent blade cutting, and solidifying for 4 hours in a solidification bath;
and washing the solidified product with water for 5 times, and freeze-drying to obtain cylindrical graphene oxide/carbon nanotube composite aerogel particles.
Example 5
Mixing 100g of graphene oxide aqueous dispersion (with the mass fraction of 2%) and 100g of montmorillonite aqueous dispersion (with the mass fraction of 10%) for 1 hour through mechanical stirring and ultrasonic treatment to form graphene oxide/montmorillonite composite slurry; continuously extruding the slurry into a coagulating bath (the mass fraction of a coagulating agent cetyl trimethyl ammonium bromide is 2%, the mass fraction of a coagulating agent solvent-ethanol is 10%, and the mass fraction of a coagulating agent solvent-water is 88%) through a peristaltic pump and a square section extrusion molding die with the side length of 8mm, immersing an outlet of the raw material below the liquid level of the coagulating bath or just contacting the liquid level of the coagulating bath, and granulating by wire cutting, wherein the density of the slurry is higher than that of the coagulating bath, so that the obtained granules sink to the bottom of a container for containing the coagulating bath, and the viscosity of the slurry is enough to keep the shape in the coagulating bath;
the wire used for wire cutting is a nylon wire with the diameter of about 0.1mm, and a hand-held reciprocating cutting mode is adopted; continuous intermittent cutting can also be realized by adopting a mechanical reciprocating device;
adjusting the extrusion speed of a peristaltic pump to 40ml/min, cutting the wire for 1 time per second, preparing a cuboid product through continuous slurry extrusion and intermittent wire cutting, and solidifying for 5 hours in a coagulating bath;
washing the solidified product with an ethanol aqueous solution (the mass fraction of ethanol is 40 percent, and the mass fraction of water is 60 percent) for 5 times, and naturally airing to prepare the cuboid graphene oxide/montmorillonite composite aerogel particles.
Example 6
As shown in fig. 5A and 5B, a continuous preparation apparatus of self-assembled aerogel particles of a low dimensional material includes the following components:
a conveying device; the conveying device comprises the following components:
a delivery line 11;
and, a driving force providing device 12; the driving force providing device 12 is connected with the conveying pipeline 11 and is used for providing driving force for sucking, conveying and extruding low-dimensional material slurry in the conveying pipeline 11;
extruding and molding a neck ring mold 2; the extrusion molding die 2 is connected to the outlet of the conveying pipeline 11, and when the extrusion molding die 2 is used, the outlet of the extrusion molding die 2 is immersed below the liquid level of the coagulating bath or just contacts with the surface of the coagulating bath, and is used for setting a target shape for the extrusion of low-dimensional material slurry;
a container 3 for holding a coagulation bath; the container 3 for containing the coagulating bath is arranged below the extrusion molding neck ring 2;
and, a section-cutting granulation device 4; the cutting portion 41 of the cutting and granulating device 4 is provided in the coagulation bath container 3, and cuts the slurry extruded into the coagulation bath container 3.
Alternatively, in the above continuous preparation apparatus, the delivery device may be a peristaltic pump, a rotary vane pump or a syringe pump. Peristaltic pumps, rotary vane pumps or syringe pumps are all existing conveying devices, and of course, the conveying devices and the devices for providing driving force for sucking, conveying and extruding the conveying materials in the conveying pipelines can be directly used as the conveying devices in the continuous preparation device. In addition, the arrangement of the conveying pipeline can be one or more, and the conveying pipeline can be adjusted according to the requirement; the driving force providing device can be arranged such that one driving force providing device provides driving force for a plurality of conveying pipelines, or a plurality of driving force providing devices respectively provide driving force for a plurality of conveying pipelines, and the driving force providing devices can be selected according to production requirements.
Optionally, in the continuous preparation apparatus, the material of the conveying pipeline 11 may be at least one of a polymer material, a metal material, or a biological material. The thickness and length of the pipe can be adjusted according to the technical requirements of the pulp extrusion device.
Alternatively, in the continuous production apparatus, the extrusion molding die 2 may be a single-hole die, a multi-hole die, or a plurality of single-hole dies. Increasing the number of dies can increase the production efficiency of the aerogel particles.
Optionally, in the continuous preparation apparatus, the aerogel particles of different shapes and sizes can be obtained by selecting the neck molds of different cross-sectional shapes and sizes; further, the cross-sectional shape may be: the shape of the aerogel particles prepared correspondingly is cylindrical, triangular prism, cube, cuboid, hexagonal prism, irregular cylinder and the like.
Optionally, in the continuous preparation apparatus, the cutting and granulating apparatus 4 performs cutting with a rotary blade, linear cutting, or water stream cutting; optionally a rotary blade.
Alternatively, in the above continuous production apparatus, the rotary blade cutting unit includes a sharp blade capable of rotary cutting, and a motor for driving the blade to rotate for cutting.
The technical solution of the invention is not limited thereto; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for the continuous preparation of self-assembled aerogel particles of low dimensional material comprising the steps of: continuously extruding the raw materials by taking the low-dimensional material slurry as the raw materials, immersing the raw materials into a coagulating bath, and cutting, granulating, coagulating, washing and drying the low-dimensional material slurry in the coagulating bath; wherein: the outlet of the raw material is immersed below the liquid level of the coagulating bath or just contacts with the liquid level of the coagulating bath, the density of the low-dimensional material slurry is more than that of the coagulating bath, and the viscosity of the low-dimensional material slurry enables the low-dimensional material slurry to keep the shape in the coagulating bath.
2. The continuous production method according to claim 1, characterized in that: the low-dimensional material slurry comprises a low-dimensional material solvent and a low-dimensional material dispersed in the low-dimensional material solvent;
the low-dimensional material solvent is as follows: water or a mixed solvent composed of water and a water-soluble organic solvent;
the low-dimensional material comprises at least one of a two-dimensional material, a one-dimensional material or a zero-dimensional material;
the two-dimensional material comprises graphene oxide, graphene, graphite nanosheets and at least one of layered phosphates, hydroxides, double hydroxides, silicates, clays, chalcogenides, oxides, nitrides, carbides, black phosphorus, elemental metals and metal-organic frameworks;
the one-dimensional material comprises at least one of a carbon nano tube, a carbon nano fiber, a silicon carbide whisker, a copper nano wire and a titanium dioxide nano wire;
the zero-dimensional material comprises at least one of fullerene, quantum dot and nanocluster.
3. The continuous production method according to claim 2, characterized in that: the mass fraction of the low-dimensional material in the low-dimensional material slurry is 0.1-20%; further optionally, the mass fraction of the low-dimensional material in the low-dimensional material slurry is 1% -10%;
and/or the mixing mode of dispersing the low-dimensional material in the low-dimensional material solvent comprises the following steps: at least one of sonication, mechanical agitation, or direct mixing in a rotary vane pump.
4. The continuous production method according to claim 1, characterized in that: the coagulating bath comprises a coagulating agent and a coagulating agent solvent, wherein the coagulating agent solvent is water or a mixed solvent composed of water and a water-soluble organic solvent, and the coagulating agent comprises at least one of metal salt, cationic surfactant and cationic polymer;
optionally, the coagulant is at least one of potassium chloride, sodium chloride, calcium chloride, potassium nitrate, sodium nitrate, calcium nitrate, sodium sulfate, potassium sulfate, polyethyleneimine, cetyltrimethylammonium bromide, or polydiallyldimethylammonium chloride;
optionally, the mass ratio of coagulant to solvent is 1: (10-800); further optionally 1: (20-200); still further alternatively 1: (60-100).
5. The continuous production method according to claim 1, characterized in that: the solidification time is 30min-3 d; alternatively 1-24 h; further optionally 2-8 h.
6. The continuous production method according to claim 1, characterized in that: the method comprises the following steps: taking low-dimensional material slurry as a raw material, continuously extruding the raw material from an extrusion molding die through a conveying device, immersing the raw material into a coagulating bath in a coagulating bath container, carrying out section granulation on the raw material in the coagulating bath by using a section granulating device, sinking the raw material subjected to section granulation into the bottom of the container and further solidifying to form particles, washing and drying to obtain aerogel particles; wherein:
the outlet of the raw material is immersed below the liquid level of the coagulation bath or just contacts with the liquid level of the coagulation bath;
the density of the low-dimensional material slurry is greater than that of the coagulating bath;
the viscosity of the low-dimensional material slurry enables the low-dimensional material slurry to keep the shape in a coagulating bath;
the conveying device comprises the following components: the driving force providing device is connected with the conveying pipeline and is used for providing driving force for sucking, conveying and extruding low-dimensional material slurry in the conveying pipeline;
the extrusion molding die is connected to the outlet of the conveying pipeline, and the outlet of the extrusion molding die is immersed below the liquid level of the coagulating bath or just contacts with the surface of the coagulating bath, so that the target shape is set for the extrusion of the low-dimensional material slurry;
the coagulating bath container is arranged below the extrusion molding neck mold;
and the cutting part of the cutting and granulating device is arranged in the coagulating bath container and is used for cutting the slurry extruded into the coagulating bath container into sections.
7. The continuous production method according to claim 1, characterized in that: after the low-dimensional material slurry is extruded and contacts with the coagulating bath, the surface of the slurry is coagulated to form a semi-solid shell layer, and the semi-solid shell layer is cut off; the fresh section formed by cutting is solidified to form a semi-solid shell layer after contacting with a coagulating bath, thereby forming the effect of granulation.
8. The continuous production method according to claim 6, characterized in that: controlling the length of aerogel particles by adjusting the extrusion rate of slurry in an extrusion molding die and the cutting rate of a section-cutting granulating device;
and/or, adjusting the cross section of the aerogel particles by controlling the shape of the extrusion molding die.
9. An apparatus for the continuous preparation of self-assembled aerogel particles of low dimensional material comprising the following components:
a conveying device; the conveying device comprises the following components:
a delivery line;
and, a driving force providing means; the driving force providing device is connected with the conveying pipeline and is used for providing driving force for sucking, conveying and extruding low-dimensional material slurry in the conveying pipeline;
extruding and molding a neck ring mold; the extrusion molding die is connected to the outlet of the conveying pipeline, and when the extrusion molding die is used, the outlet of the extrusion molding die is immersed below the liquid level of the coagulating bath or just contacts with the surface of the coagulating bath, so that the target shape is set for the extrusion of low-dimensional material slurry;
a coagulation bath container; the coagulating bath container is arranged below the extrusion molding neck mold;
and, a cutting and pelletizing device; and the cutting part of the cutting and granulating device is arranged in the coagulating bath container and is used for cutting the slurry extruded into the coagulating bath container into sections.
10. The continuous production apparatus according to claim 9, characterized in that: the delivery device is a peristaltic pump, a rotary vane pump or a syringe pump, preferably a peristaltic pump.
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