CN114751422A - Difficult-to-desorb tourmaline surface whitening treatment method and tourmaline @ molecular sieve composite material with core-shell structure - Google Patents

Difficult-to-desorb tourmaline surface whitening treatment method and tourmaline @ molecular sieve composite material with core-shell structure Download PDF

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CN114751422A
CN114751422A CN202210155108.2A CN202210155108A CN114751422A CN 114751422 A CN114751422 A CN 114751422A CN 202210155108 A CN202210155108 A CN 202210155108A CN 114751422 A CN114751422 A CN 114751422A
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tourmaline
molecular sieve
reaction kettle
powder
tourmaline powder
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余巍
彭虎
黎锦晖
黄文燕
利志彬
王平
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Foshan Jiuwuqi Technology Co ltd
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    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract

The invention relates to the technical field of tourmaline functional materials, in particular to a difficult-to-desorb tourmaline surface whitening treatment method and a tourmaline @ molecular sieve composite material with a core-shell structure, which is prepared by adopting the method. The method comprises the steps of crushing, feeding, alkali reaction, filtering and washing, acid neutralization, iron removal, washing, drying and the like. The invention creatively can grow a layer of sodalite on the surface of the tourmaline, is very firm and not easy to fall off, obviously improves the whiteness to 55-65, solves the technical problems of lower whiteness and easy desorption of the existing tourmaline powder, obtains the tourmaline @ molecular sieve composite functional material with the core-shell structure, realizes the synergistic effect of the functions of the tourmaline and the zeolite molecular sieve, leads the tourmaline to be industrialized, and has very good application prospect in the fields of coating, building, environmental protection and the like.

Description

Difficult-to-desorb tourmaline surface whitening treatment method and tourmaline @ molecular sieve composite material with core-shell structure
Technical Field
The invention relates to the technical field of tourmaline functional materials, in particular to a difficult-to-desorb tourmaline surface whitening treatment method and a tourmaline @ molecular sieve composite material with a core-shell structure, which is prepared by adopting the method.
Background
Tourmaline is a silicate mineral with iron, aluminum, sodium and lithium ring structure and characterized by containing boron, and has unique properties of piezoelectricity, pyroelectric property, conductivity, far infrared radiation, anion release and the like. For example, under the condition of changing temperature and pressure, the potential difference of tourmaline crystals can be caused, the surrounding air is ionized, the hit electrons are attached to adjacent water and oxygen molecules and are converted into negative air ions, namely negative oxygen ions, the generated negative oxygen ions move in the air and transport negative charges to bacteria, dust, smoke particles, water drops and the like, and the charges are combined with the particles, so that the air purification effect is achieved, and the health of human beings is facilitated. Tourmaline integrates the properties of various mineral functional materials due to the special structure thereof, can be compounded with other materials by a physical or chemical method to prepare various functional composite materials, and is applied to the fields of environmental protection, electronics, medicines, chemical industry, building materials and the like. For example, the inventor's master thesis "tourmaline thermal alteration product and performance research under alkaline conditions" that uses natural mineral tourmaline as raw material and discusses that tourmaline synthesizes sodalite, cancrinite, analcime and other composite materials under alkaline hydrothermal environment.
The tourmaline resource quantity in China, especially the black tourmaline, is very rich, and the utilization potential is very large. But the basic research and comprehensive development and utilization of the mineral characteristics of the tourmaline are only in the initial stage. As the vast majority of tourmaline in nature is black (as shown in figure 1, the black tourmaline powder in nature is less than 200 meshes, smooth in surface and 17 in whiteness value), the problems of darker color and low whiteness greatly limit the application range. For this reason, it is necessary to whiten tourmaline during use. At present, the tourmaline powder whitening treatment method mainly adopts a surface coating modification method, for example: coating with inorganic substance (such as nanometer titanium oxide and zinc oxide) or organic substance (such as paraffin and stearic acid), or mechanically coating. However, the inorganic matter or organic matter and the surface of tourmaline do not react chemically, and only rely on physical method or van der waals combination, the coating is fixed on the particle surface after treatment, so the adhesion force coated by the above method is not enough, the tourmaline surface has desorption phenomenon, the whiteness can only reach 30-40, therefore, how to make the tourmaline surface not desorb, improve its whiteness, become the present technical difficulty; in addition, because the tourmaline powder particles have large specific surface area and high specific surface energy, agglomeration is easy to generate in the modification processing process, so that the dispersion is not uniform, and the performance of the tourmaline is influenced. Therefore, the existing whitening treatment method is difficult to industrialize, thereby restricting the application of black tourmaline.
Disclosure of Invention
The invention aims to provide a tourmaline surface whitening treatment method difficult to desorb and a tourmaline @ molecular sieve composite material with a core-shell structure prepared by adopting the method aiming at the defects of the prior art, so as to solve the problems that the existing tourmaline powder has lower whiteness and is difficult to disperse and the existing surface coating modification whitening method is easy to desorb.
The purpose of the invention is realized by the following technical scheme:
provides a tourmaline surface whitening treatment method which is not easy to desorb, comprising the following steps:
(1) crushing: pulverizing tourmaline to below 325 mesh to obtain tourmaline powder;
(2) feeding: tourmaline powder and NaOH are mixed according to the weight ratio of (75-90): (5-20) respectively putting the materials into an alkali type reaction kettle, wherein the volume of the added tourmaline powder occupies 75-85% of the space of the alkali type reaction kettle, preparing a solution by using NaOH, pumping the solution into the reaction kettle, stirring uniformly, and adding a water glass solution into the alkali type reaction kettle to reach 95% of the space of the reaction kettle; the modulus of the water glass solution is 1.4-1.8, and the Baume degree is 40-45;
in the step, the weight ratio and the water content of the tourmaline powder and NaOH during reaction and the space proportion of the tourmaline powder in the alkali reaction kettle are controlled, which is a very key technical point. Firstly, the concentration of tourmaline and NaOH solution needs to be controlled to ensure that the water content is low, because if the concentration is thinner and the water content is high, sodalite formed in the reaction process is easily washed away by the solution and cannot be attached to the surface of tourmaline; on the contrary, the concentration of the tourmaline cannot be too high, otherwise the tourmaline is agglomerated together to form a plate, and sodalite cannot grow on the surface of the plate; secondly, the inventor discovers in a large number of experimental processes that the reaction kettle space occupied by the tourmaline powder in the reaction process is a key, when the volume of the added tourmaline powder is controlled to occupy 75-85% of the space of the basic reaction kettle and water glass with a certain concentration is subsequently added until the volume reaches 95% of the space of the reaction kettle, the rolling space of the reaction of the raw materials in the reaction kettle can be greatly reduced, so that a large amount of sodalite generated by the reaction is attached to the surface of the tourmaline, namely the tourmaline grows on the surface of the tourmaline, which is a key technical point discovered by the inventor through a large number of experimental researches, for example, according to a conventional thought, a conventional hydrothermal synthesis reaction is adopted, for example, according to a technical scheme recorded in tourmaline thermal corrosion products and performance researches under an alkaline condition, the sodalite is synthesized by the tourmaline under an alkaline hydrothermal environment, but cannot be attached to the surface of the tourmaline, but only in solution systems, which completely fails to achieve the object of the present invention.
(3) Alkali reaction: heating the basic reaction kettle to 150-300 ℃, keeping the temperature for 5-48 hours, enabling the basic reaction kettle to slowly roll and rotate, and cooling after the reaction is finished to obtain tourmaline powder and molecular sieve mixed slurry;
the step also has two key points, on one hand, the reaction temperature is controlled to be 150-300 ℃, and then the solution in the reaction kettle is vaporized to ensure that the pressure is more than 1.5MPa and a certain critical state is achieved, so that the tourmaline is positioned between tourmaline powder and sodium silicate medium under the action of solution transpirationThe dispersion is uniform and wanders in the space of the reaction kettle to react with NaOH, and because the external sodium silicate is in a high-concentration state, the sodium silicate formed by the primary reaction with the tourmaline cannot diffuse away at a higher concentration, and only can be attached to the surface of the tourmaline to continue and dissociate Al2O3Reaction to produce sodalite, or unequal Al2O3Reacting with sodium silicate to produce sodalite after dissociation, so that the sodalite can firmly grow on the surface of the tourmaline; on the other hand, the reaction kettle can not be stirred in the reaction process, but can rotate at a low speed, and the stirring in the reaction kettle can damage the sodalite growth process on the surface of the tourmaline, so that the sodalite does not grow on the surface of the tourmaline, but the reaction kettle still needs to roll at a low speed, so that the synthesis of the tourmaline powder @ molecular sieve can not be disturbed, and the tourmaline can not be sunk and hardened, thereby solving the two technical difficulties.
(4) Filtering and washing: sequentially filtering and washing the tourmaline powder and molecular sieve mixed slurry obtained in the step (3), and removing water glass to obtain tourmaline powder and molecular sieve slurry;
(5) acid neutralization: putting the tourmaline powder @ molecular sieve slurry obtained in the step (4) with the water glass removed into an acid type reaction kettle, adding a hydrochloric acid solution under a slow stirring state, regulating the pH value of the acid type reaction kettle to be 6.5, and neutralizing residual alkali to enable residual water glass to generate white carbon black; and adding appropriate amount of SnCl2Make Fe3O4Accelerated formation of FeCl3；
In the step, residual water glass and NaOH still exist in the obtained tourmaline powder @ molecular sieve slurry, so the obtained tourmaline powder @ molecular sieve slurry enters an acid type reaction kettle for neutralization reaction, and the residual water glass Na is used2SiO3Generating white carbon SiO2And a salt; in the process, a certain amount of water is added to be beneficial to stirring and mixing uniformly, and the slow stirring is to prevent the tourmaline powder @ molecular sieve structure from being damaged; adding SnCl in proper amount2Can accelerate Fe3O4To FeCl3Thereby eliminating Fe3O4Impact on whiteness.
(6) Iron removing: removing magnetite from the tourmaline powder @ molecular sieve slurry obtained in the step (5) by adopting a wet magnetic separation process, and further improving whiteness;
(7) washing and drying: and (3) washing and desalting the tourmaline @ molecular sieve slurry obtained in the step (6), floating part of white carbon black, and drying to obtain tourmaline powder with a sodalite layer growing on the surface, namely tourmaline @ molecular sieve powder.
In the technical scheme, in the step (1), the mass concentration of the NaOH solution is 20-30%.
In the technical scheme, in the step (3), the rolling rotation speed of the alkali type reaction kettle is controlled to be 1-5 r/min, and the rotation speed can ensure that the synthesis of tourmaline powder and molecular sieve cannot be disturbed in the reaction and the bottom of tourmaline cannot be hardened.
In the technical scheme, in the step (4), the tourmaline powder and molecular sieve mixed slurry is heated to 60-80 ℃ for filtering. Because the water glass has certain viscosity at normal temperature, when the water glass is filtered at 60-80 ℃, the viscosity of the water glass can be reduced, so that the water glass can be filtered and removed more easily.
In the technical scheme, in the step (5), the temperature of the acid neutralization reaction is controlled to be 45-55 ℃, the reaction time is 2-8 h, and the stirring speed is 5-10 r/min. Wherein, the heating is carried out to 45-55 ℃, which is beneficial to accelerating the acid reaction; the stirring speed is controlled to be 5-10 r/min, and the tourmaline powder @ molecular sieve structure can be prevented from being damaged.
In the technical scheme, in the step (5), the mass concentration of the hydrochloric acid solution is 18-20%, and the mass concentration of SnCl is2The addition amount of (A) is 0.1% of the total mass of the tourmaline powder.
In the technical scheme, in the step (6), the magnetic field intensity of the magnetic separation is greater than 6000 Gs.
In the above technical solution, in the step (7), the number of washing times is three.
The invention also provides a tourmaline @ molecular sieve composite material with a core-shell structure, which is prepared by adopting the tourmaline surface whitening treatment method difficult to desorb.
In the technical scheme, the whiteness of the tourmaline powder and molecular sieve composite materialThe specific surface area reaches 55 to 65, and is 5 to 10m2(iv) g. Further, the specific surface area can be selectively controlled according to the thickness of the molecular sieve required.
Through the analysis, the invention has the following advantages:
(1) by adopting the method of the invention, the tourmaline powder is dispersed uniformly and freely sways in the reaction kettle space to react without agglomeration and hardening by controlling the weight ratio and the water content of the tourmaline powder and NaOH, the space proportion of the tourmaline powder in the alkali type reaction kettle in the reaction process and controlling key comprehensive processes of slow rolling rotation, reaction temperature and the like of the reaction kettle, and simultaneously, under the condition of mutual noninterference, the surface of each tourmaline particle reacts with the NaOH to react with SiO on the surface of the tourmaline2And Al2O3Reacting and firmly growing a layer of sodalite nano-micro particles. Therefore, the invention can creatively grow other minerals on the surface of the tourmaline, compared with the prior art which relies on a physical method or a van der waals combined surface coating modification whitening method, the sodalite grown on the surface of the tourmaline is of a chemical bond structure, so the tourmaline is very firm and not easy to fall off, the whiteness of the tourmaline is obviously improved, and the whiteness can reach 55-65, thereby solving the technical problems of darker color, lower whiteness, easy desorption and difficult dispersion of the existing tourmaline powder, leading the tourmaline to be industrialized and having good application prospect in the fields of paint, building, environmental protection and the like;
(2) The sodalite belongs to one of zeolite molecular sieves, and BET analysis shows that the porous sodalite with adsorption capacity grows on the surface of tourmaline, the pore diameter of the porous sodalite is about 0.71nm, and the porous sodalite has an excellent adsorption function on formaldehyde, TVOCs and other harmful gases, so that the tourmaline @ molecular sieve composite functional material with a core-shell structure is obtained, the synergistic effect of the tourmaline @ molecular sieve composite functional material and the zeolite molecular sieves is realized, the functions of the tourmaline and the zeolite molecular sieves are realized, and the application field of the tourmaline is greatly expanded.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is an SEM electron micrograph of a natural black tourmaline powder.
Fig. 2 is an SEM electron microscope image of the tourmaline @ molecular sieve composite material with the core-shell structure.
Fig. 3 is an XRD analysis diagram of the tourmaline @ molecular sieve composite material with the core-shell structure.
Fig. 4 is an XRD two-dimensional phase diagram of the tourmaline @ molecular sieve composite material with the core-shell structure.
Fig. 5 is a BET analysis diagram of the tourmaline @ molecular sieve composite material with a core-shell structure of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to these examples.
Example 1:
the tourmaline surface whitening treatment method difficult to desorb comprises the following steps:
(1) crushing: pulverizing tourmaline to below 325 mesh to obtain tourmaline powder;
(2) feeding: mixing tourmaline powder and NaOH according to a weight ratio of 75: 20, respectively adding the tourmaline powder into an alkali type reaction kettle, wherein the volume of the added tourmaline powder accounts for 75% of the space of the alkali type reaction kettle, preparing a solution with the mass concentration of 30% by using NaOH, pumping the solution into the reaction kettle, uniformly stirring, and adding a water glass solution into the alkali type reaction kettle to reach 95% of the space of the reaction kettle; the modulus of the water glass solution is 1.4-1.8, and the Baume degree is 40-45;
(3) alkali reaction: heating the basic reaction kettle to 150 ℃, keeping the temperature for 48 hours, enabling the basic reaction kettle to slowly roll and rotate, enabling the rotation speed to be 2r/min, and cooling after the reaction is finished to obtain tourmaline powder and molecular sieve mixed slurry;
(4) heating, filtering and washing: heating the mixed slurry of the tourmaline powder and the molecular sieve obtained in the step (3) to 60-80 ℃, then sequentially filtering and washing, and removing water glass to obtain a tourmaline powder and molecular sieve slurry;
(5) Acid neutralization: putting the tourmaline powder @ molecular sieve slurry obtained in the step (4) with the water glass removed into an acid type reaction kettle, adding a hydrochloric acid solution with the mass concentration of 20% under the slow stirring state of 6r/min, regulating the pH value of the acid type reaction kettle to be 6.5, controlling the temperature of acid neutralization reaction to be 45 ℃ and the reaction time to be 8 hours, and neutralizing residual alkali to enable residual water glass to generate white carbon black; adding SnCl accounting for 0.1 percent of the total mass of the tourmaline powder2Make Fe3O4Accelerated formation of FeCl3；
(6) Iron removing: removing magnetite from the tourmaline powder @ molecular sieve slurry obtained in the step (5) by adopting a wet magnetic separation process, wherein the magnetic field intensity of magnetic separation is more than 6000 Gs;
(7) washing and drying: and (3) washing the tourmaline @ molecular sieve slurry obtained in the step (6) for three times for desalting, floating part of white carbon black, and drying to obtain tourmaline powder with a layer of sodalite growing on the surface, namely the tourmaline @ molecular sieve powder.
Example 2:
the tourmaline surface whitening treatment method not easy to desorb comprises the following steps:
(1) crushing: pulverizing tourmaline to below 325 mesh to obtain tourmaline powder;
(2) feeding: mixing tourmaline powder and NaOH according to a weight ratio of 90: 10, respectively adding the tourmaline powder into an alkali reaction kettle, wherein the volume of the added tourmaline powder accounts for 85% of the space of the alkali reaction kettle, preparing a solution with the mass concentration of 20% by using NaOH, pumping the solution into the reaction kettle, uniformly stirring, and adding a water glass solution into the alkali reaction kettle to reach 95% of the space of the reaction kettle; the modulus of the water glass solution is 1.4-1.8, and the Baume degree is 40-45;
(3) Alkali reaction: heating the basic reaction kettle to 200 ℃, keeping the temperature for 20 hours, enabling the basic reaction kettle to slowly roll and rotate, enabling the rotation speed to be 3r/min, and cooling after the reaction is finished to obtain tourmaline powder and molecular sieve mixed slurry;
(4) heating, filtering and washing: heating the mixed slurry of the tourmaline powder and the molecular sieve obtained in the step (3) to 60-80 ℃, then sequentially filtering and washing, and removing water glass to obtain a tourmaline powder and molecular sieve slurry;
(5) acid neutralization: putting the tourmaline powder @ molecular sieve slurry obtained in the step (4) with the water glass removed into an acid type reaction kettle, adding a hydrochloric acid solution with the mass concentration of 19% under a slow stirring state of 10r/min, regulating the pH value of the acid type reaction kettle to be 6.5, controlling the temperature of acid neutralization reaction to be 50 ℃ and the reaction time to be 5 hours, and neutralizing residual alkali to enable residual water glass to generate white carbon black; adding SnCl accounting for 0.1 percent of the total mass of the tourmaline powder2Of Fe3O4Accelerated formation of FeCl3；
(6) Iron removing: removing magnetite from the tourmaline powder @ molecular sieve slurry obtained in the step (5) by adopting a wet magnetic separation process, wherein the magnetic field intensity of magnetic separation is more than 6000 Gs;
(7) washing and drying: and (3) washing the tourmaline @ molecular sieve slurry obtained in the step (6) for three times for desalting, floating part of white carbon black, and drying to obtain tourmaline powder with a layer of sodalite growing on the surface, namely the tourmaline @ molecular sieve powder.
Example 3:
the tourmaline surface whitening treatment method not easy to desorb comprises the following steps:
(1) crushing: pulverizing tourmaline to below 325 mesh to obtain tourmaline powder;
(2) feeding: mixing tourmaline powder and NaOH according to a weight ratio of 85: 15, respectively adding the tourmaline powder into the basic reaction kettle, wherein the volume of the added tourmaline powder accounts for 80% of the space of the basic reaction kettle, preparing 25% solution by using NaOH, pumping the solution into the reaction kettle, uniformly stirring, and adding the water glass solution into the basic reaction kettle to reach 95% of the space of the reaction kettle; the modulus of the water glass solution is 1.4-1.8, and the Baume degree is 40-45;
(3) alkali reaction: heating the basic reaction kettle to 250 ℃, keeping the temperature for 30 hours, enabling the basic reaction kettle to slowly roll and rotate, enabling the rotation speed to be 1r/min, and cooling after the reaction is finished to obtain tourmaline powder and molecular sieve mixed slurry;
(4) heating, filtering and washing: heating the mixed slurry of the tourmaline powder and the molecular sieve obtained in the step (3) to 60-80 ℃, then sequentially filtering and washing, and removing water glass to obtain a tourmaline powder and molecular sieve slurry;
(5) acid neutralization: putting the tourmaline powder @ molecular sieve slurry obtained in the step (4) with the water glass removed into an acid type reaction kettle, adding a hydrochloric acid solution with the mass concentration of 20% under a slow stirring state of 8r/min, regulating the pH value of the acid type reaction kettle to be 6.5, controlling the temperature of acid neutralization reaction to be 55 ℃ and the reaction time to be 2 hours, and neutralizing residual alkali to enable residual water glass to generate white carbon black; adding SnCl accounting for 0.1 percent of the total mass of the tourmaline powder 2Of Fe3O4Accelerated formation of FeCl3；
(6) Iron removing: removing magnetite from the tourmaline powder @ molecular sieve slurry obtained in the step (5) by adopting a wet magnetic separation process, wherein the magnetic field intensity of magnetic separation is more than 6000 Gs;
(7) washing and drying: and (3) washing the tourmaline @ molecular sieve slurry obtained in the step (6) for three times for desalting, floating part of white carbon black, and drying to obtain tourmaline powder with a layer of sodalite growing on the surface, namely the tourmaline @ molecular sieve powder.
Example 4:
the tourmaline surface whitening treatment method not easy to desorb comprises the following steps:
(1) crushing: pulverizing tourmaline to below 325 mesh to obtain tourmaline powder;
(2) feeding: mixing tourmaline powder and NaOH according to a weight ratio of 80: 5, respectively putting the tourmaline powder into the basic reaction kettle, wherein the volume of the added tourmaline powder accounts for 80% of the space of the basic reaction kettle, preparing a solution with the mass concentration of 30% by using NaOH, pumping the solution into the reaction kettle, and adding the water glass solution into the basic reaction kettle to reach 95% of the space of the reaction kettle after uniformly stirring; the modulus of the water glass solution is 1.4-1.8, and the Baume degree is 40-45;
(3) alkali reaction: heating the basic reaction kettle to 300 ℃, keeping the temperature for 5 hours, enabling the basic reaction kettle to slowly roll and rotate, enabling the rotation speed to be 5r/min, and cooling after the reaction is finished to obtain tourmaline powder and molecular sieve mixed slurry;
(4) Heating, filtering and washing: heating the mixed slurry of the tourmaline powder and the molecular sieve obtained in the step (3) to 60-80 ℃, then sequentially filtering and washing, and removing water glass to obtain a tourmaline powder and molecular sieve slurry;
(5) acid neutralization: putting the tourmaline powder @ molecular sieve slurry obtained in the step (4) with the water glass removed into an acid type reaction kettle, adding a hydrochloric acid solution with the mass concentration of 18% under the condition of stirring at a slow speed of 5r/min, regulating the pH value of the acid type reaction kettle to be 6.5, controlling the temperature of acid neutralization reaction to be 50 ℃ and the reaction time to be 3 hours, and neutralizing residual alkali to enable residual water glass to generate white carbon black; adding SnCl accounting for 0.1 percent of the total mass of the tourmaline powder2Make Fe3O4Accelerated formation of FeCl3；
(6) Iron removing: removing magnetite from the tourmaline powder @ molecular sieve slurry obtained in the step (5) by adopting a wet magnetic separation process, wherein the magnetic field intensity of magnetic separation is more than 6000 Gs;
(7) washing and drying: and (3) washing the tourmaline @ molecular sieve slurry obtained in the step (6) for three times for desalting, floating part of white carbon black, and drying to obtain tourmaline powder with a layer of sodalite growing on the surface, namely the tourmaline @ molecular sieve powder.
Experimental methods and analyses:
1. surface morphology by SEM observation
The result of SEM observation of the tourmaline @ molecular sieve powder after reaction in example 3 was shown in FIG. 2.
Fig. 2a and 2b show that under 30 μm and 2 μm high power microscope, respectively, a layer of sodalite particles grows on the outer surface of the tourmaline, and the surface is not smooth, very firm and not easy to fall off.
2. XRD analyte phase composition
Examples 1 to 4 and experimental example 6 were selected, and the main technical scheme of experimental example 6 was the same as that of example 1, except that the temperature of the alkali reaction in step (3) was 350 ℃. XRD analysis was performed separately, and the results are shown in fig. 3 and 4.
In FIG. 3: 2 theta is 24.11 degrees and represents a sodalite peak, and can be seen that in the basic reaction kettle, the amount of sodalite growing on the surface of the tourmaline is more and more along with the increase of the reaction temperature, and when the reaction temperature is higher than 300 ℃, for example, the reaction temperature is 350 ℃, the amount of the tourmaline is very small, which indicates that the tourmaline basically reacts completely, and mainly contains sodalite. Therefore, the temperature of the alkali reaction should be controlled to be 150-300 ℃.
In the two-dimensional phase diagram of fig. 4, T represents tourmaline, S represents sodalite, and M represents magnetite. Three zones are divided in fig. 4: zone T represents tourmaline only; the T @ S area indicates that sodalite grows on the surface of the tourmaline; the T @ S-M region represents tourmaline @ sodalite and magnetite. Obviously, the T @ S region of the tourmaline with sodalite growing on the surface is mainly concentrated in the range of 150-300 ℃.
3. BET analysis
The BET analysis was performed on the tourmaline @ molecular sieve powder obtained in example 2, and the result is shown in fig. 5.
In the specific surface analysis curve of fig. 5, the adsorption curve and the desorption curve do not coincide, which indicates that the tourmaline @ molecular sieve powder obtained by the present invention has porous adsorption function, i.e. porous sodalite with adsorption capacity grows on the surface of tourmaline, and the pore size can be seen in the small graph of fig. 5, which is about 0.71 nm.
4. Whiteness measurement
The tourmaline @ molecular sieve powder obtained in examples 1 to 4 was tested by a colorimeter, and the results are shown in table 1.
TABLE 1 whiteness values of tourmaline @ molecular sieve powders obtained by the methods of examples 1 to 4
Example 1 Example 2 Example 3 Example 4
Whiteness degree 55 60 63 65
The above-mentioned embodiments are only for convenience of description, and are not intended to limit the present invention in any way, and those skilled in the art will understand that the technical features of the present invention can be modified or changed by other equivalent embodiments without departing from the scope of the present invention.

Claims (10)

1. A tourmaline surface whitening treatment method which is not easy to desorb is characterized in that: the method comprises the following steps:
(1) crushing: pulverizing tourmaline to below 325 mesh to obtain tourmaline powder;
(2) feeding: tourmaline powder and NaOH are mixed according to the weight ratio of (75-90): (5-20) respectively putting the materials into an alkali type reaction kettle, wherein the volume of the added tourmaline powder occupies 75-85% of the space of the alkali type reaction kettle, preparing a solution by using NaOH, pumping the solution into the reaction kettle, stirring uniformly, and adding a water glass solution into the alkali type reaction kettle to reach 95% of the space of the reaction kettle; the modulus of the water glass solution is 1.4-1.8, and the Baume degree is 40-45;
(3) alkali reaction: heating the basic reaction kettle to 150-300 ℃, keeping the temperature for 5-48 hours, enabling the basic reaction kettle to slowly roll and rotate, and cooling after the reaction is finished to obtain tourmaline powder and molecular sieve mixed slurry;
(4) filtering and washing: sequentially filtering and washing the tourmaline powder @ molecular sieve mixed slurry obtained in the step (3), and removing water glass to obtain tourmaline powder @ molecular sieve slurry;
(5) acid neutralization: putting the tourmaline powder @ molecular sieve slurry obtained in the step (4) with the water glass removed into an acid type reaction kettle, adding a hydrochloric acid solution under a slow stirring state, regulating the pH value of the acid type reaction kettle to be 6.5, and neutralizing residual alkali to enable residual water glass to generate white carbon black; and adding appropriate amount of SnCl 2Make Fe3O4Accelerated formation of FeCl3；
(6) Iron removing: removing magnetite from the tourmaline powder @ molecular sieve slurry obtained in the step (5) by adopting a wet magnetic separation process;
(7) washing and drying: and (4) washing and desalting the tourmaline @ molecular sieve slurry obtained in the step (6), floating partial white carbon black, and drying to obtain tourmaline powder with a layer of sodalite growing on the surface in a coating manner, namely tourmaline @ molecular sieve powder.
2. The tourmaline surface whitening treatment method not easy to desorb according to claim 1, characterized in that: in the step (1), the mass concentration of the NaOH solution is 20-30%.
3. The tourmaline surface whitening treatment method not easy to desorb as claimed in claim 1, which is characterized in that: in the step (3), the rolling rotation rate of the basic reaction kettle is controlled to be 1-5 r/min.
4. The tourmaline surface whitening treatment method not easy to desorb according to claim 1, characterized in that: in the step (4), the tourmaline powder and molecular sieve mixed slurry is heated to 60-80 ℃ for filtering.
5. The tourmaline surface whitening treatment method not easy to desorb as claimed in claim 1, which is characterized in that: in the step (5), the temperature of the acid neutralization reaction is controlled to be 45-55 ℃, the reaction time is 2-8 hours, and the stirring speed is 5-10 r/min.
6. The tourmaline surface whitening treatment method according to claim 1, which is characterized in thatCharacterized in that: in the step (5), the mass concentration of the hydrochloric acid solution is 18-20%, and the SnCl is2The addition amount of (B) is 0.1% of the total mass of the tourmaline powder.
7. The tourmaline surface whitening treatment method not easy to desorb as claimed in claim 1, which is characterized in that: in the step (6), the magnetic field intensity of the magnetic separation is more than 6000 Gs.
8. The tourmaline surface whitening treatment method not easy to desorb as claimed in claim 1, which is characterized in that: in the step (7), the number of washing times is three.
9. A tourmaline @ molecular sieve composite material with a core-shell structure is characterized in that: the tourmaline @ molecular sieve composite material with the core-shell structure is prepared by adopting the method of any one of claims 1 to 8.
10. The tourmaline @ molecular sieve composite material with a core-shell structure as claimed in claim 9, wherein: the whiteness of the tourmaline powder @ molecular sieve composite material is 55-65, and the specific surface area is 5-10 m2/g。
CN202210155108.2A 2022-02-21 2022-02-21 Difficult-to-desorb tourmaline surface whitening treatment method and tourmaline @ molecular sieve composite material with core-shell structure Pending CN114751422A (en)

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