CN115430372A - Three-dimensional porous attapulgite microsphere and preparation method and application thereof - Google Patents
Three-dimensional porous attapulgite microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional porous attapulgite microsphere and a preparation method and application thereof. The preparation method comprises the following steps: s1, activating attapulgite by acid; s2, mixing the acid-activated attapulgite with the nanocellulose fibers and water, and performing ball milling to obtain an attapulgite suspension; s3, sucking the attapulgite suspension into an injector, and dropping the attapulgite suspension into liquid nitrogen at a constant speed for directional freezing to obtain molded attapulgite microspheres; s4, placing the formed attapulgite microspheres into a freeze dryer to obtain three-dimensional porous attapulgite microspheres, and regulating the size, the density and the graded porous characteristics of the three-dimensional porous attapulgite microspheres by regulating the concentration of an attapulgite suspension and the size of a needle head of the injector, so that the problem that the existing balling method is uncontrollable is solved, the loading capacity of the attapulgite microspheres on the phase change material reaches 85%, and the heat storage effect is excellent.
Description
Technical Field
The invention relates to the technical field of phase change heat storage materials, in particular to a three-dimensional porous attapulgite microsphere and a preparation method and application thereof.
Background
The phase-change heat storage technology is an energy storage technology which utilizes the fact that when the state of a substance changes, heat is absorbed or released, and the temperature of the substance is kept relatively constant, and is one of important forms of heat energy storage. The phase-change heat storage technology can convert light energy into heat energy or store redundant heat in industrial production, so that the problems of non-uniformity and intermittency in the heat supply and demand process and mismatching of energy sources in space and strength are solved. The phase-change heat storage technology is expected to realize the high-efficiency utilization of clean energy, solve the problems of fossil fuel resource shortage, environmental pollution and the like, and has wide application prospects in the fields of solar energy utilization, industrial waste heat recovery, building energy conservation and the like.
The core of the phase-change heat storage material consists of two parts, including a phase-change material and a supporting base material. In recent years, the preparation of support matrix materials with high loading and good thermal stability has been the focus of research. The clay mineral material has a natural porous structure, has the advantages of wide sources, low price, good thermal stability and the like, and can effectively load the phase-change material and prevent the phase-change material from leaking in a molten state.
The Chinese patent with the application number of 202110788767.5 prepares modified minerals into mixed liquid, and then the mixed liquid is subjected to spray drying to prepare mineral microspheres, and the mineral microspheres are mixed with a phase-change material and then subjected to vacuum impregnation to obtain a heat storage material, however, the size, density and pore size structure of the mineral microspheres prepared by spray drying are uncontrollable, and uniform mineral microspheres cannot be produced. In addition, in the existing preparation technology of the three-dimensional microspheres, no report exists that the volume ratio of pores with different sizes in the microspheres can be adjusted. The pores with different sizes in the microsphere have important influence on the loading capacity and leakage prevention capacity of the phase change material, so that the development of a technology with controllable size, density and pore volume ratio of different levels has great significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of three-dimensional porous attapulgite microspheres which have controllable sizes, adjustable pore diameter ratios of different levels and high loading capacity of phase change materials, aiming at the defects of the prior art.
The invention relates to a preparation method of three-dimensional porous attapulgite microspheres, which comprises the following steps:
s1, mixing attapulgite with an acid solution, and heating and stirring to obtain acid-activated attapulgite;
s2, mixing the acid-activated attapulgite with the nanocellulose fibers and water, and performing ball milling to obtain an attapulgite suspension;
s3, sucking the attapulgite suspension into an injector, and dropping the attapulgite suspension into liquid nitrogen at a constant speed for directional freezing to obtain molded attapulgite microspheres;
s4, placing the formed attapulgite microspheres into a freeze dryer, and drying to obtain three-dimensional porous attapulgite microspheres;
wherein, the size, density and graded porosity of the three-dimensional porous attapulgite microspheres are regulated and controlled by regulating and controlling the concentration of the attapulgite suspension and the size specification of the needle of the injector.
Further, in the step S1, the grade of the attapulgite is more than 75%, and the granularity is between 100 meshes and 400 meshes; the acid solution is hydrochloric acid solution or sulfuric acid solution with the concentration of 1-4 mol/L; the acid activation process comprises: mixing solid and liquid, heating and stirring, separating solid from liquid, washing and drying; wherein the mixing ratio of the attapulgite to the acid solution is 1-2 parts of attapulgite and 5-10 parts of the acid solution; the heating temperature is 50-80 ℃, the stirring speed is 500-1000r/min, and the activation time is 2-6 h.
Further, in the step S2, the attapulgite, the fiber bundle nanofibers and the water are calculated according to the following parts by weight:
attapulgite: 1 to 10 portions of
Cellulose nanofibers: 0.5 to 5 portions of
Water: 10 to 20 portions.
Further, in step S2, the ball milling time is 1-3 hours, and the rotating speed is 200-400 r/min.
Further, in step S3, the needle gauge of the syringe is 14-32G, and the corresponding inner diameter is 0.11-1.54 mm.
Further, in the step S3, the attapulgite suspension is dripped into liquid nitrogen at the speed of 5-30 mL/h; the concentration of the attapulgite suspension is 1 to 12 weight percent; the density of the three-dimensional porous attapulgite microspheres obtained in the step S4 is in a linear relationship with the concentration of the attapulgite suspension, Y =12.18+14.28X, X is the weight mass percent of the attapulgite in the attapulgite suspension, Y is the density of the three-dimensional porous attapulgite microspheres, and the unit is mg/cm 3 。
Further, in step S4, in the freeze drying process, the sample temperature is-30 to-10 ℃, the vacuum degree is 3 to 10Pa, and the duration is 24 to 48 hours.
The three-dimensional porous attapulgite microsphere prepared by the preparation method.
The application of the three-dimensional porous attapulgite microspheres is that the three-dimensional porous attapulgite microspheres and the phase change material are mixed and then are subjected to vacuum impregnation to obtain the attapulgite phase change heat storage microspheres.
Further, in the step S5, the dosage relationship between the three-dimensional porous attapulgite microspheres and the phase change material is as follows: 15-50 wt.%, phase change material: 50-85 wt.%.
Further, in step S5, the phase change material includes one of stearic acid, paraffin, polyethylene glycol, and lauric acid; in the vacuum impregnation process: the mixed material is vacuumized to-0.1 MPa at normal temperature, heated to 40-80 ℃ and kept for 30-60 min.
The invention mixes attapulgite and cellulose nano-fiber, uses a freezing casting method to orient and ball the well dispersed attapulgite suspension to prepare the three-dimensional porous attapulgite microsphere, regulates the size, the density and the graded porosity characteristics of the three-dimensional porous attapulgite microsphere by regulating the concentration of the attapulgite suspension and the size specification of a needle of an injector, can prepare the three-dimensional porous attapulgite microsphere with controllable diameter, density and different grade pore diameter ratios by the method, solves the problem that the existing ball forming method is uncontrollable, and ensures that the loading capacity of the three-dimensional porous attapulgite microsphere reaches 85 percent by controlling the pore structure characteristics of the three-dimensional porous attapulgite microsphere, thereby having excellent heat storage effect.
The three-dimensional porous attapulgite microsphere provided by the invention has a continuous through pore structure, the pore wall has directional arrangement characteristics, and the diameter can be adjusted to 2-4 mm; the density of the microspheres is linear with the solution concentration and is represented by: y =12.18+14.28X.
The three-dimensional porous attapulgite microsphere provided by the invention has a hierarchical pore structure, wherein the volume ratio of pore diameters of four sizes of <100nm, 100-1000 nm, 1000-10000 nm and 10000-300000 nm can be adjusted, and the preparation method is simple and environment-friendly. The loading capacity of the phase-change material can reach 85%, and the prepared phase-change heat storage microspheres have good heat storage performance.
Drawings
FIG. 1 is an electron micrograph of the acid-activated attapulgite prepared in example 1;
FIG. 2 is a photograph of three-dimensional porous attapulgite microspheres prepared in example 1;
FIG. 3 is an electron micrograph of the three-dimensional porous attapulgite microsphere prepared in example 1;
FIG. 4 is a photograph of three-dimensional porous attapulgite microspheres prepared in example 2;
FIG. 5 is a photograph of three-dimensional porous attapulgite microspheres prepared in example 3;
FIG. 6 is a graph showing the results of the diameter of three-dimensional porous attapulgite microspheres prepared by changing the size of the needle and the concentration of the attapulgite suspension according to the technical scheme of this example 3;
FIG. 7 is a graph showing the results of the density of three-dimensional porous attapulgite microspheres prepared by changing the size of the needles and the concentration of the attapulgite suspension according to the technical scheme of this example 3;
FIG. 8 is a graph showing the volume ratio of different levels of the three-dimensional porous attapulgite microspheres prepared by changing the size of the needle and the concentration of the attapulgite suspension according to the technical scheme of this example 3;
FIG. 9 is a DSC curve of the mineral-based heat storage microspheres prepared in example 4;
FIG. 10 is a DSC curve of the mineral-based heat storage microspheres prepared in this example 5;
fig. 11 is a DSC curve of the mineral-based heat storage microspheres prepared in example 6.
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:
in this example, three-dimensional porous attapulgite microspheres with different diameters, densities and pore diameters were prepared by using a 27-gauge syringe needle.
The attapulgite crude ore is subjected to grading treatment to obtain attapulgite powder with the grade of 200 meshes for later use. Adding a certain amount of attapulgite powder into 1mol/L hydrochloric acid solution, wherein the solid-liquid mass ratio is 1. And after the reaction is finished, cooling to room temperature, carrying out suction filtration, then washing to neutrality by using deionized water, taking out a filter cake, and finally carrying out forced air drying at 80 ℃ for 24 hours to obtain the acid-activated attapulgite.
Mixing 30g of nano cellulose fiber with the solid content of 2% and 30mL of deionized water, and respectively adding 0.61g, 1.86g, 3.16g, 4.52g and 5.94g of acid-activated attapulgite into the mixed solution to obtain the following solutions: 1wt.%, 3wt.%, 5wt.%, 7wt.%, 9wt.% of the mixed solution. And placing the mixed solution in a planetary ball mill for ball milling for 3h at the rotating speed of 300r/min to obtain uniform and stable attapulgite suspension.
The attapulgite suspension is filled into a syringe, and the needle adopts 27 gauge and has a diameter of 0.21mm. The syringe is fixed on a syringe pump, and the suspension is injected into liquid nitrogen for directional molding at the speed of 10ml/h-20ml/h according to the concentration difference. And then collecting the attapulgite microspheres formed in the liquid nitrogen, and freeze-drying at-50 ℃ under the condition of 10Pa to finally obtain the three-dimensional porous attapulgite microspheres. The naming format of the porous attapulgite microsphere is XY, X represents the content of attapulgite, Y represents the size of a needle, such as 127 represents that the content of the attapulgite is 1wt.%, and the three-dimensional porous attapulgite microsphere is injected by a 27-gauge needle.
Referring to the attached FIG. 1, in order to prepare the acid-activated attapulgite electron micrograph according to the technical scheme of the embodiment, the result shows that the attapulgite aggregates are separated, and the rod crystal bundles are deagglomerated into small bundles or single rod crystal forms.
Referring to the attached figure 2, the photo of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment shows that the microsphere has a complete, regular and stable structure.
Referring to the attached figure 3, shown is an electron micrograph of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment, and the result shows that the attapulgite is oriented and arranged, and the three-dimensional porous structure with highly interconnected and graded components is formed.
Refer to attached table 1 for the size and hierarchical pore structure characteristics of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment.
TABLE 1
Example 2:
in this example, a 22-gauge injection needle is used to prepare three-dimensional porous attapulgite microspheres with different diameters, densities and pore diameters.
The raw attapulgite ore is subjected to grading treatment to obtain 300-mesh attapulgite powder for later use. Adding a certain amount of attapulgite powder into 2mol/L hydrochloric acid solution with a solid-liquid mass ratio of 1:8, stirring at 50 ℃ for 5h with a stirring speed of 400r/min. And after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing to be neutral by using deionized water, taking out a filter cake, and finally carrying out forced air drying at 80 ℃ for 24h to obtain the acid-activated attapulgite.
Mixing 30g of nano-cellulose fiber with the solid content of 2% and 30mL of deionized water, and respectively adding 0.61g, 1.86g, 3.16g, 4.52g and 5.94g of acid-activated attapulgite into the mixed solution to obtain a mixture with the concentrations of: 1wt.%, 3wt.%, 5wt.%, 7wt.%, 9wt.% of the mixed solution. And ball-milling the mixed solution in a planetary ball mill for 2 hours at the rotating speed of 400r/min to obtain uniform and stable attapulgite suspension.
Placing attapulgite suspension into a syringe, and selecting 22 gauge needle with diameter of 0.41mm. The syringe is fixed on a syringe pump, and the suspension is injected into liquid nitrogen for directional forming at the speed of 8-20 mL/h according to the concentration difference. And then collecting the attapulgite microspheres formed in the liquid nitrogen, and freeze-drying at-50 ℃ under the condition of 10Pa to finally obtain the three-dimensional porous attapulgite microspheres.
The acid-activated attapulgite prepared according to the technical scheme of the embodiment is similar to that of the embodiment 1.
Referring to the attached figure 4, the photo of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment shows that the microsphere has a complete, regular and stable structure.
Example 3:
in this example, a 18-gauge injection needle was used to prepare three-dimensional porous attapulgite microspheres with different diameters, densities and pore diameters.
The attapulgite crude ore is subjected to grading treatment to obtain attapulgite powder with the grade of 300 meshes for later use. Adding a certain amount of attapulgite powder into 2mol/L hydrochloric acid solution with a solid-liquid mass ratio of 1:6, stirring at 50 ℃ for 5h with a stirring speed of 500r/min. And after the reaction is finished, cooling to room temperature, carrying out suction filtration, washing to be neutral by using deionized water, taking out a filter cake, and finally carrying out forced air drying at 80 ℃ for 24h to obtain the acid-activated attapulgite.
Mixing 30g of nano cellulose fiber with the solid content of 2% and 30mL of deionized water, and respectively adding 0.61g, 1.86g, 3.16g, 4.52g and 5.94g of acid-activated attapulgite into the mixed solution to obtain the following solutions: 1wt.%, 3wt.%, 5wt.%, 7wt.%, 9wt.% of the mixed solution. And ball-milling the mixed solution in a planetary ball mill for 2 hours at the rotating speed of 400r/min to obtain uniform and stable attapulgite suspension.
The attapulgite suspension is filled into a syringe, and the needle is 18 gauge and has a diameter of 0.84mm. The syringe is fixed on a syringe pump, and the suspension is injected into liquid nitrogen for directional forming at the speed of 8-20 mL/h according to the concentration difference. And then collecting the attapulgite microspheres formed in the liquid nitrogen, and freeze-drying at-50 ℃ under the condition of 10Pa to finally obtain the three-dimensional porous attapulgite microspheres.
The acid-activated attapulgite prepared according to the technical scheme of the embodiment is similar to that of the embodiment 1.
Referring to the attached figure 5, the photo of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment shows that the microsphere has a complete, regular and stable structure.
Referring to the attached figure 6, the diameter of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment can be adjusted by 2-4 mm according to different needle sizes and concentrations.
Referring to the attached figure 7, for the density of the three-dimensional porous attapulgite microspheres prepared according to the technical scheme of the embodiment, the density of the microspheres can be adjusted according to different needle sizes and concentrations.
Referring to the attached figure 8, for the volume ratio of different grade pore sizes of the three-dimensional porous attapulgite microsphere prepared according to the technical scheme of the embodiment, the graded porous characteristic of the microsphere can be adjusted according to different needle sizes and concentration sizes.
The three-dimensional porous attapulgite microsphere provided by the invention has a directional arrangement structure and hierarchical porous characteristics, and has pore structures with four sizes of <100nm, 100-1000 nm, 1000-10000 nm and 10000-300000 nm, so that the three-dimensional porous attapulgite microsphere can be applied to loading phase change materials and preparing high-performance composite heat storage materials.
Example 4:
in the embodiment, the mineral-based heat storage microspheres are prepared by taking three-dimensional porous attapulgite as a supporting matrix and stearic acid as a phase change material.
Mixing 1g of three-dimensional porous attapulgite microspheres and 6g of stearic acid, putting the mixture into a vacuum oven, vacuumizing to 0.1MPa, heating to 80 ℃, keeping for one hour, opening the oven, keeping for 10min under normal pressure, and repeating for 3 times to ensure that the microspheres are fully impregnated with the stearic acid. And after the impregnation is finished, cooling the microspheres to room temperature, taking out the microspheres, and removing redundant stearic acid to obtain the mineral-based heat storage microspheres named SAXY.
Referring to fig. 9, the mineral-based heat storage microspheres prepared according to the technical scheme of this embodiment have good heat storage performance.
Example 5:
in the embodiment, the mineral-based heat storage microspheres are prepared by taking three-dimensional porous attapulgite as a supporting matrix and paraffin as a phase change material.
Taking 1g of three-dimensional porous attapulgite microspheres and 5g of paraffin, mixing, putting into a vacuum oven, vacuumizing to 0.1MPa, heating to 40 ℃, keeping for one hour, opening the oven, keeping for 10min under normal pressure, and repeating for 3 times to ensure that the microspheres are fully impregnated with stearic acid. And after the impregnation is finished, taking out the microspheres after the microspheres are cooled to room temperature, and removing redundant stearic acid to obtain the mineral-based heat storage microspheres named as PWXY.
Referring to fig. 10, the results of the mineral-based heat storage microspheres prepared according to the technical scheme of this embodiment show that the microspheres have good heat storage properties.
Example 6:
in the embodiment, the mineral-based heat storage microspheres are prepared by taking three-dimensional porous attapulgite as a supporting matrix and octadecanol as a phase change material.
Mixing 1g of three-dimensional porous attapulgite microspheres and 6g of paraffin, putting the mixture into a vacuum oven, vacuumizing to 0.1MPa, heating to 60 ℃, keeping for one hour, opening the oven, keeping for 10min under normal pressure, and repeating for 3 times to ensure that the microspheres are fully impregnated with stearic acid. And after the impregnation is finished, taking out the microspheres after the microspheres are cooled to room temperature, and removing redundant stearic acid to obtain the mineral-based heat storage microspheres.
Referring to fig. 11, the results of the mineral-based heat storage microspheres prepared according to the technical solution of this embodiment show that they have good heat storage properties.
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 (10)
1. A preparation method of three-dimensional porous attapulgite microspheres is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing attapulgite with an acid solution, and heating and stirring to obtain acid-activated attapulgite;
s2, mixing the acid-activated attapulgite with the nano cellulose fibers and water, and performing ball milling to obtain an attapulgite suspension;
s3, sucking the attapulgite suspension into an injector, and dropping the attapulgite suspension into liquid nitrogen at a constant speed for directional freezing to obtain molded attapulgite microspheres;
s4, placing the formed attapulgite microspheres into a freeze dryer, and drying to obtain three-dimensional porous attapulgite microspheres;
wherein, the size, density and graded porosity of the three-dimensional porous attapulgite microspheres are regulated and controlled by regulating and controlling the concentration of the attapulgite suspension and the size specification of the needle head of the injector.
2. The preparation method of the three-dimensional porous attapulgite microsphere of claim 1, wherein the preparation method comprises the following steps: in the step S1, the grade of the attapulgite is more than 75%, and the granularity is between 100 meshes and 400 meshes; the acid solution is hydrochloric acid solution or sulfuric acid solution with the concentration of 1-4 mol/L; the acid activation process comprises: mixing solid and liquid, heating and stirring, separating solid from liquid, washing and drying; wherein the mixing ratio of the attapulgite to the acid solution is 1-2 parts of attapulgite and 5-10 parts of the acid solution; the heating temperature is 50-80 ℃, the stirring speed is 500-1000r/min, and the activation time is 2-6 h.
3. The preparation method of the three-dimensional porous attapulgite microsphere of claim 1, wherein the preparation method comprises the following steps: in the step S2, the attapulgite, the fiber bundle nanofibers and the water are calculated according to the following parts by weight:
attapulgite: 1 to 10 portions of
Cellulose nanofibers: 0.5 to 5 portions of
Water: 10-20 parts;
in the step S2, the ball milling time is 1-3 hours, and the rotating speed is 200-400 r/min.
4. The preparation method of the three-dimensional porous attapulgite microsphere of claim 1, wherein the preparation method comprises the following steps: in step S3, the specification of the needle head of the injector is 14-32G, and the corresponding inner diameter is 0.11-1.54 mm.
5. The method for preparing the three-dimensional porous attapulgite microspheres according to claim 1, wherein the method comprises the following steps: in the step S3, the attapulgite suspension is dripped into liquid nitrogen at the speed of 5-30 mL/h; the concentration of the attapulgite suspension is 1 to 12 weight percent; the density of the three-dimensional porous attapulgite microspheres obtained in the step S4 is in a linear relationship with the concentration of the attapulgite suspension, Y =12.18+14.28X, X is the weight mass percentage of the attapulgite in the attapulgite suspension, and Y is the density of the three-dimensional porous attapulgite microspheres, and the unit is mg/cm 3 。
6. The method for preparing the three-dimensional porous attapulgite microspheres according to claim 1, wherein the method comprises the following steps: in the step S4, in the freeze drying process, the sample temperature is-30 to-10 ℃, the vacuum degree is 3 to 10Pa, and the duration is 24 to 48 hours.
7. The three-dimensional porous attapulgite microspheres prepared by the preparation method of any one of claims 1 to 6.
8. The use of the three-dimensional porous attapulgite microspheres according to claim 7, wherein: and mixing the three-dimensional porous attapulgite microspheres with the phase change material, and then carrying out vacuum impregnation to obtain the attapulgite phase change heat storage microspheres.
9. The use of the three-dimensional porous attapulgite microspheres according to claim 7, wherein: the dosage relation of the three-dimensional porous attapulgite microspheres and the phase change material is that the three-dimensional porous attapulgite microspheres: 15-50 wt.%, phase change material: 50-85 wt.%.
10. The use of the three-dimensional porous attapulgite microspheres according to claim 7, wherein: the phase-change material comprises one of stearic acid, paraffin, polyethylene glycol and lauric acid; in the vacuum impregnation process: the mixed material is vacuumized to-0.1 MPa at normal temperature, heated to 40-80 ℃ and kept for 30-60 min.
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