CN112919489B - Hierarchical pore molecular sieve particles and preparation method thereof - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- 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
In order to provide a molecular sieve material which can be used as a loudspeaker rear cavity filler and has richer pore structure and easier operation in the preparation process and a preparation method thereof, the invention adopts a hierarchical pore FAU type molecular sieve as a forming raw material and simultaneously uses a water-in-oil microemulsion method for forming, and the method specifically comprises the following steps: step 1, synthesizing to obtain an FAU type molecular sieve; step 2, modifying the FAU molecular sieve obtained in the step one by oxalic acid to obtain a modified FAU molecular sieve; and 3, carrying out adhesion forming on the modified FAU molecular sieve by adopting a water-in-oil microemulsion method and drying to obtain porous molecular sieve particles, wherein the adhesive used in the water-in-oil microemulsion method comprises polyacrylic acid and styrene-acrylic emulsion. The invention also provides a loudspeaker adopting the porous molecular sieve particles as rear cavity filler.
Description
Technical Field
The invention relates to a molecular sieve material and a preparation method thereof, in particular to a hierarchical pore molecular sieve particle and a preparation method thereof.
Background
In the prior art, a certain amount of gas absorption material is usually required to be placed in the rear cavity resonance space of the loudspeaker. Through putting into resonance space with the porous material of appropriate size as gas absorption material, based on the adsorption and desorption process of pore to the air, can realize the virtual increase of speaker back cavity resonance space volume to make speaker low frequency band resonant frequency reduce.
Materials used as a filler for the back cavity of a micro-speaker to improve the low frequency response performance of the speaker system are currently focused on zeolite molecular sieves. It is reported in the patent (CN 103098490B) that a material with pores with larger internal surface (i.e. first pores with diameter in the range of micropores) can be used to construct the absorber, while a material with larger pores (i.e. second pores with diameter in the range of mesopores) formed between the zeolite particles after molding increases the virtual acoustic volume more and the resonance shift value more. In the patent, MFI, FER and other types of molecular sieves are used as forming raw materials, and the influence of different forming methods and assembled multi-stage hole rear cavity fillers with different sizes on the low-frequency response performance of a loudspeaker is researched. Further, the patent also indicates that the material containing both micropores and mesopores has a better effect in improving the low frequency responsiveness of the speaker than the material containing only micropores.
However, the molecular sieves used in the above patents are all microporous molecular sieves, which do not have mesopores, and the mesopores in the product particles are formed mainly among the particles due to the process of adhesive molding, so that the proportion of the mesopores in the product is small, and the gas adsorption and desorption amount is still not ideal. In addition, the forming method used in the above patent requires high technical equipment (fluidized bed, spraying method) or requires a cutting process to obtain particles with a suitable size (hot plate method), and is inconvenient to operate.
Disclosure of Invention
In order to solve the problems, the invention provides a molecular sieve material which can be used as a loudspeaker rear cavity filler and has richer pore structure and easier operation in the preparation process and a preparation method thereof. Specifically, the invention adopts the following technical scheme:
the invention provides a preparation method of hierarchical pore molecular sieve particles used as a loudspeaker rear cavity filler, which is characterized by comprising the following steps: step 1, synthesizing to obtain an FAU type molecular sieve; step 2, modifying the FAU molecular sieve obtained in the step one by oxalic acid to obtain a modified FAU molecular sieve; and 3, carrying out adhesion forming on the modified FAU molecular sieve by adopting a water-in-oil microemulsion method and drying to obtain porous molecular sieve particles, wherein the adhesive used in the water-in-oil microemulsion method comprises polyacrylic acid and styrene-acrylic emulsion.
The preparation method of the hierarchical pore molecular sieve particles provided by the invention can also have the technical characteristics that the step 2 comprises the following steps: step 2-1: dissolving oxalic acid crystals in deionized water to obtain an oxalic acid solution with the concentration of 0.1 mol/L; step 2-2: adding the FAU type molecular sieve obtained in the step 1 into the oxalic acid solution obtained in the step 2-1, ensuring that the mass volume of the FAU type molecular sieve and the oxalic acid solution is not more than 1, and stirring at high speed for at least 45 minutes at 90 ℃; step 2-3: and (3) filtering out a solid product obtained by stirring in the step (2-2) in a suction filtration manner, washing the solid product with deionized water for multiple times until a washing liquid is neutral, and drying the washing liquid at the temperature of 60-80 ℃ to obtain the modified FAU type molecular sieve.
The preparation method of the hierarchical pore molecular sieve particles provided by the invention can also have the technical characteristics that the step 3 comprises the following steps: step 3-1: adding Cetyl Trimethyl Ammonium Bromide (CTAB) into deionized water, heating, stirring and dissolving; step 3-2: adding 50% polyacrylic acid solution and styrene-acrylic emulsion into the solution obtained in the step 3-1, and stirring for at least 30 minutes to obtain suspension; step 3-3: adding the modified FAU type molecular sieve into the suspension obtained in the step 3-2, and stirring for at least 30 minutes until uniform and stable slurry is formed; step 3-4: and (3) adding the slurry obtained in the step (3-3) into 45mL of ethyl acetate under high-speed stirring, quickly pouring the microemulsion system onto a hot plate at the temperature of 140-160 ℃ after the formation of microspheres is observed, and shoveling down after the microemulsion system is dried to obtain the hierarchical pore molecular sieve particles.
Further, in the preparation method of the hierarchical pore molecular sieve particles provided by the invention, the mass ratio of the modified FAU type molecular sieve to CTAB to polyacrylic acid to acrylic emulsion = 3.8.
The preparation method of the hierarchical pore molecular sieve particles provided by the invention can also have the technical characteristics that the step 1 comprises the following steps: step 1-1, preparing an alkaline solution; step 1-2, dividing the prepared alkaline solution into two parts, adding aluminate with a preset amount into one part, adding silicate with a preset amount into the other part, and respectively stirring and dissolving; step 1-3, mixing the two solutions obtained in the step 1-2, and stirring for a preset time under a preset temperature condition to obtain a suspension; step 1-4, placing the suspension obtained in the step 1-3 into a sealed reaction kettle, and performing crystallization reaction under the condition of a preset temperature; and 1-5, taking out a product obtained by the crystallization reaction in the step 1-4, washing and drying to obtain the FAU type molecular sieve.
Further, in the preparation method of the hierarchical pore molecular sieve particles provided by the invention, the molar ratio of each substance in the suspension in the steps 1-3 is SiO 2 :Na 2 O:Al 2 O 3 :H 2 O＝1:4.5:0.2:180。
The invention also provides hierarchical pore molecular sieve particles, which are characterized by being prepared by the preparation method. In addition, the invention also provides a loudspeaker adopting the multilevel pore molecular sieve particles as rear cavity filler.
Action and effects of the invention
According to the hierarchical pore molecular sieve particles and the preparation method thereof provided by the invention, on one hand, the FAU type molecular sieve obtained by synthesis and modification is used as a forming raw material, and the FAU type molecular sieve has larger pore volume, so that the formed particles have richer pore channel structures, and the gas absorption and desorption capacity is increased, thereby further enhancing the low-frequency correspondence of a loudspeaker system when the particles are used as a loudspeaker rear cavity filler; on the other hand, the water-in-oil microemulsion method is used during molding, so that the requirements on molding equipment can be reduced, meanwhile, the size of molded particles can be regulated and controlled by adjusting the addition amount of the adhesive and the proportion of the oil phase and the water phase during preparation, products with different particle sizes can be obtained by simply screening after preparation is finished, additional chopping treatment is not needed, and the preparation process is easy to realize and control.
Drawings
FIG. 1 is an SEM photograph of hierarchical pore molecular sieve particles prepared according to an embodiment of the present invention;
FIG. 2 is a nitrogen adsorption and desorption curve of an example of the present invention. Wherein, fig. 2 (a) is the FAU type molecular sieve synthesized in step 1, fig. 2 (B) is the modified FAU molecular sieve obtained in step 2, and fig. 2 (C) is the hierarchical pore molecular sieve particles obtained in step 3;
FIG. 3 is a graph of the impedance of the hierarchical pore molecular sieve particles prepared in accordance with an embodiment of the present invention at various loadings;
FIG. 4 is a graph of impedance curves for different sized hierarchical pore molecular sieve particles according to embodiments of the present invention;
FIG. 5 is a graph of the impedance of the hierarchical pore molecular sieve particles at different binder ratios according to an embodiment of the present invention;
FIG. 6 is an X-ray diffraction pattern of a hierarchical pore molecular sieve particle under different concentration oxalic acid treatment conditions according to an embodiment of the present invention;
fig. 7 is a graph of the impedance of the hierarchical pore molecular sieve particles for various concentrations of oxalic acid treatment in accordance with an embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings. The reagents used in the following examples are commercially available and the conditions of the experimental work not indicated are referred to in the art.
< example >
The hierarchical pore molecular sieve particles of this example were prepared as follows.
Step 1, synthesizing an FAU type molecular sieve, which specifically comprises the following steps:
step 1-1: dissolving 100g of NaOH in 1100mL of deionized water, and stirring until the solution is clear;
step 1-2: the prepared NaOH solution was divided into two portions, and 11.71g NaAlO was added to one portion 2 And 101.5g of Na is added into the other part 2 SiO 3 ·9H 2 O, stirring respectively until the mixture is clear;
step 1-3: mixing the two solutions obtained in the step 1-2 and stirring the mixed solution for 5 hours at the temperature of-2 ℃, wherein the molar ratio of each substance in the mixed system is SiO 2 :Na 2 O:Al 2 O 3 :H 2 O＝1:4.5:0.2:180；
Step 1-4: placing the suspension obtained in the step 1-3 into a sealed stainless steel reaction kettle, and crystallizing for 18 hours at the temperature of 60 ℃;
step 1-5: and (4) taking out the crystallized product obtained in the step (1-4), centrifuging, washing for a plurality of times by using deionized water, and drying at the temperature of 60-80 ℃ to obtain the FAU type molecular sieve for later use.
Step 2, modifying the FAU type molecular sieve obtained in the step 1, and specifically comprising the following steps:
step 2-1: dissolving 5.67g of oxalic acid crystal in 450g of deionized water to obtain an oxalic acid solution with the concentration of 0.1 mol/L;
step 2-2: adding 45g of the FAU type molecular sieve obtained in the step 1 into the oxalic acid solution obtained in the step 2-1, ensuring that the ratio of the mass (g) of the FAU type molecular sieve to the volume (mL) of the oxalic acid solution is 1, and stirring at a high speed for 45 minutes at the temperature of 90 ℃;
step 2-3: and (3) filtering out a solid product obtained by stirring in the step (2-2) in a suction filtration manner, washing the solid product with deionized water for multiple times until a washing liquid is neutral, and drying the washing liquid at the temperature of 60-80 ℃ to obtain the modified FAU type molecular sieve.
And 3, molding the modified FAU type molecular sieve obtained in the step 2, and specifically comprising the following steps:
step 3-1: 0.19g of cetyltrimethylammonium bromide (CTAB) was added to 5.25g of deionized water, and dissolved by stirring with heating as appropriate;
step 3-2: adding 0.1g of 50% polyacrylic acid solution and 0.1g of styrene-acrylic emulsion into the solution obtained in the step 3-1, and stirring for 30 minutes to obtain a suspension;
step 3-3: adding 3.5g of the modified FAU type molecular sieve into the suspension obtained in the step 3-2, and stirring for at least 30 minutes until a uniform and stable slurry is formed, wherein the mass ratio of the modified FAU type molecular sieve to CTAB to polyacrylic acid to propyl emulsion = 70;
step 3-4: the slurry obtained in step 3-3 was added to 45mL of ethyl acetate under high speed stirring with a syringe, and after the formation of microspheres was observed, the microemulsion system was quickly poured onto a hot plate at 150 ℃ and, after drying, gently scooped down with a spatula.
The following are performance tests of different porous grade molecular sieve particles made in the examples of the present invention and made by varying the conditions of the examples. The test speaker (back volume 1 mL) used in the following test was from austin technologies (zhenjiang) ltd; the acoustic performance testing system is from Beijing ruisen New Spectroscopy, inc.
Fig. 1 is an SEM photograph of the hierarchical pore molecular sieve particles prepared in the example of the present invention.
The scales in FIG. 1 are 100 μm, 1 μm, and 10 μm, respectively.
As shown in fig. 1, the porous molecular sieve prepared in this example has uniform particles, and the single particles are oblate spherical, which may be caused by the collapse of the originally spherical particles due to gravity during the drying process.
FIG. 2 is a nitrogen adsorption and desorption curve of an example of the present invention. Wherein, fig. 2 (a) is the FAU type molecular sieve synthesized in step 1, fig. 2 (B) is the modified FAU molecular sieve obtained in step 2, fig. 2 (C) is the hierarchical pore molecular sieve particles obtained in step 3, and the abscissa in each figure is the adsorption/desorption rate (P/P) 0 ) The ordinate represents the adsorption amount (cm) 3 ，g -1 ，STP)。
As shown in fig. 2, nitrogen adsorption and desorption experiments are performed on the products obtained in the steps of this embodiment, and it can be concluded from the nitrogen adsorption and desorption results that the oxalic acid modification causes an obvious mesoporous structure to appear in the FAU molecular sieve, and the part of the mesoporous structure is retained in the bonding process.
Fig. 3 is an impedance curve for different loadings of the hierarchical pore molecular sieve particles prepared in accordance with embodiments of the present invention. In the impedance curve, the abscissa is frequency (Hz) and the ordinate is impedance (ohm).
The porous molecular sieve prepared by the embodiment of the invention is screened, and the impedance curve of the porous molecular sieve is tested after particles with the diameter in the range of 125-280 mu m are filled in the rear cavity of a loudspeaker, and the result is shown in figure 3. In fig. 3, the different curves correspond to different loadings, respectively, namely: empty (not filled), filled 1/4, filled 1/2, filled 3/4, full.
As can be seen from fig. 3, the larger the filling amount is, the stronger the effect of reducing the resonance frequency of the speaker is, in the case where the particles are the same. The resonant frequency of the test speaker was 805.03Hz when not filled and 656.15Hz when filled, the resonant frequency being reduced by 148.88Hz. Filling the hierarchical pore molecular sieve particles can reduce the resonance frequency by 18.49% with the resonance frequency of 100% when not filled.
FIG. 4 is a graph of the impedance of example embodiments of the present invention for different sized hierarchical pore molecular sieve particles.
The porous molecular sieve prepared in the embodiment of the invention is screened to obtain particles with different diameter ranges, and the particles are respectively filled in the rear cavity of the loudspeaker and then an impedance curve is tested, and the result is shown in fig. 4. In fig. 4, the different curves correspond to different particle diameters, respectively, namely: empty (not filled), particle size > 355 μm, particle size 280-355 μm, particle size 125-280 μm.
As can be seen from fig. 4, the low frequency response of the speaker is significantly improved as the particle diameter is reduced. Because the testing equipment limits, particles smaller than 125 μm can leak out of the loudspeaker to cause inaccurate testing results, and the particle diameter range is more than 125 μm. However, as can be inferred from fig. 4, as the particle diameter is further reduced, the low frequency responsiveness of the speaker can be further improved.
FIG. 5 is a graph of the impedance of the hierarchical pore molecular sieve particles for different binder ratios according to an example of the present invention.
Referring to the above steps of this example, porous molecular sieve particles were prepared, but the addition amounts of polyacrylic acid and styrene-acrylic emulsion were adjusted so that the ratios of the substances in step 3-3 were changed, and then the porous molecular sieve particles prepared under the conditions of different ratios were respectively filled in the rear cavity of a speaker to test an impedance curve, and the results are shown in fig. 5. In fig. 5, the binder ratio is calculated as the modified FAU molecular sieve to polyacrylic acid to styrene-acrylic emulsion mass ratio, curve Q1 is 70.
As can be seen from fig. 5, the increase in the amount of the binder may deteriorate the low frequency response improving effect of the material on the speaker, and the reason for this may be that too much binder blocks the pores in the molecular sieve particles, so that the gas adsorption/desorption capacity thereof is reduced, and the low frequency response improving effect thereof is deteriorated.
Fig. 6 is an X-ray diffraction pattern of the hierarchical pore molecular sieve particles under different concentration oxalic acid treatment conditions of an example of the invention, and fig. 7 is an impedance curve of the hierarchical pore molecular sieve particles under different concentration oxalic acid treatment conditions of an example of the invention.
Referring to the above steps of this example, porous molecular sieve particles were prepared, but the molar concentration of oxalic acid prepared in step 2-1 was adjusted so that the molar concentration of oxalic acid used in step 2-2 was changed, and then the porous molecular sieve particles prepared under the different molar concentrations of oxalic acid were subjected to X-ray diffraction detection, respectively, and the results are shown in fig. 6. In FIG. 6, the spectral lines As made, 010M, 025M, 050M correspond to 0M oxalic acid (i.e., no oxalic acid treatment), 0.1M oxalic acid (same As in the examples), 0.25M oxalic acid, and 0.5M oxalic acid, respectively.
In addition, the porous molecular sieve particles prepared under the different oxalic acid molar concentrations are respectively filled in a rear cavity of a loudspeaker and then an impedance curve is tested, and the result is shown in fig. 7. In FIG. 7, the curves Empty, as made, 010M, 025M, 050M correspond to no loading, no oxalic acid treatment, 0.1M oxalic acid, 0.25M oxalic acid, and 0.5M oxalic acid, respectively.
As can be seen from fig. 6, the higher the concentration of oxalic acid, the less distinct the peaks in the X-ray diffraction pattern of the porous grade molecular sieve particles produced therefrom, indicating that the degree of structural damage of oxalic acid to the starting molecular sieve increases with increasing concentration. As can be seen from fig. 7, the porous grade molecular sieve particles prepared by the higher concentration oxalic acid treatment still improve the low frequency response of the speaker, but the improvement effect is not as good as that of the lower concentration (e.g. 0.1M). The results of fig. 6 and 7 illustrate that the treatment with appropriate oxalic acid concentration can generate mesopores after the FAU-type molecular sieve is modified, so that the gas absorption and desorption capacity of the finally molded particles can be increased, and the low-frequency response of the speaker can be better improved.
Effects and effects of the embodiments
According to the hierarchical pore molecular sieve particles and the preparation method thereof provided by the embodiment, on one hand, the FAU type molecular sieve is synthesized and modified by oxalic acid, and the modified FAU type molecular sieve is further adopted as a forming raw material, and has larger pore volume, so that the formed particles have richer pore channel structures, the gas absorption and desorption capacity is increased, and the low-frequency correspondence of a loudspeaker system is further enhanced when the particles are used as a loudspeaker rear cavity filler. On the other hand, polyacrylic acid solution and styrene-acrylic emulsion are used in the adhesion forming process, a water-in-oil microemulsion system is formed, and the requirement on forming equipment can be reduced by the water-in-oil microemulsion method. Meanwhile, when the water-in-oil microemulsion is used for preparation, the size of the formed particles can be regulated and controlled by regulating the addition amount of the adhesive and the proportion of the oil phase and the water phase, products with different particle sizes can be obtained by simple screening after the preparation is finished, additional chopping treatment is not needed, and the preparation process is easy to realize and control.
In the embodiment, the concentration of oxalic acid used in the modification process is 0.1M, so that modification can be completed to generate mesopores in the FAU type molecular sieve, but the structure of the FAU type molecular sieve is not seriously damaged, and finally, the porous molecular sieve particles with better effect of improving the low-frequency response of the loudspeaker can be prepared.
In the examples, the mass ratio of the modified FAU type molecular sieve to the polyacrylic acid to the styrene-acrylic emulsion in the forming process is 70.8.
In addition, after the porous molecular sieve particles prepared in the embodiment are screened according to the particle size, the speaker is filled with the particles with smaller particle size, so that the low-frequency response of the speaker can be obviously improved. The test speaker used in the embodiment is special for testing, and the sealing performance is slightly poor in order to ensure that the filler can be repeatedly opened and installed, so that particles in the range of 125-280 mu m are more suitable; however, in practice, since commercial speakers do not require repeated opening and generally have better sealing properties, smaller particles, i.e., particles of 125 μm or less, can be used.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (6)
1. A method for preparing hierarchical pore molecular sieve particles used as a loudspeaker rear cavity filler is characterized by comprising the following steps:
step 1, synthesizing to obtain an FAU type molecular sieve;
step 2, modifying the FAU molecular sieve obtained in the step one by adopting 0.1mol/L oxalic acid to obtain a modified FAU molecular sieve;
step 3, carrying out adhesive molding on the modified FAU molecular sieve by adopting a water-in-oil microemulsion method and drying to obtain the porous molecular sieve particles, wherein the adhesive used in the water-in-oil microemulsion method comprises polyacrylic acid and styrene-acrylic emulsion,
wherein, step 3 comprises the following steps:
step 3-1: adding Cetyl Trimethyl Ammonium Bromide (CTAB) into deionized water, heating, stirring and dissolving;
step 3-2: adding styrene-acrylic emulsion and 50% polyacrylic acid solution into the solution obtained in the step 3-1, and stirring for at least 30 minutes to obtain suspension;
step 3-3: adding a modified FAU type molecular sieve into the suspension obtained in the step 3-2, and stirring for at least 30 minutes until a uniform and stable slurry is formed, wherein the mass ratio of the modified FAU type molecular sieve to the molecular sieve is CTAB;
step 3-4: and (3) adding the slurry obtained in the step (3-3) into 45mL of ethyl acetate under high-speed stirring, quickly pouring a microemulsion system onto a hot plate at the temperature of 140-160 ℃ after the formation of microspheres is observed, and shoveling down after the microemulsion system is dried to obtain the hierarchical pore molecular sieve particles.
2. The method of making hierarchical pore molecular sieve particles of claim 1, characterized in that:
wherein, step 2 includes the following steps:
step 2-1: dissolving oxalic acid crystals in deionized water to obtain an oxalic acid solution with the concentration of 0.1 mol/L;
step 2-2: adding the FAU type molecular sieve obtained in the step 1 into the oxalic acid solution obtained in the step 2-1, ensuring that the mass volume ratio of the FAU type molecular sieve to the oxalic acid solution is not more than 1 and 10, and stirring at high speed for at least 45 minutes at 90 ℃;
step 2-3: and (3) filtering out a solid product obtained by stirring in the step (2-2) through suction filtration, washing the solid product with deionized water for multiple times until a washing liquid is neutral, and drying the washing liquid at the temperature of 60-80 ℃ to obtain the modified FAU type molecular sieve.
3. The method of making hierarchical pore molecular sieve particles of claim 1, characterized in that:
wherein, step 1 includes the following steps:
step 1-1, preparing an alkaline solution;
step 1-2, dividing the prepared alkaline solution into two parts, adding aluminate with a preset amount into one part, adding silicate with a preset amount into the other part, and respectively stirring and dissolving;
step 1-3, mixing the two solutions obtained in the step 1-2, and stirring for a preset time under a preset temperature condition to obtain a suspension;
step 1-4, placing the suspension obtained in the step 1-3 into a sealed reaction kettle, and performing crystallization reaction at a preset temperature;
and 1-5, taking out a product obtained by the crystallization reaction in the step 1-4, washing and drying to obtain the FAU type molecular sieve.
4. The method of making hierarchical pore molecular sieve particles of claim 3, wherein:
wherein the mol ratio of each substance in the suspension liquid in the step 1-3 is SiO 2 :Na 2 O:Al 2 O 3 :H 2 O＝1:4.5:0.2:180。
5. A hierarchical pore molecular sieve particle, characterized in that it is prepared by the preparation process according to any one of claims 1 to 4.
6. A loudspeaker characterized in that the rear chamber of the loudspeaker is filled with the hierarchical pore molecular sieve particles of claim 5.
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