CN112194150A - Preparation method of fly ash-based microporous and hierarchical porous zeolite molecular sieve - Google Patents
Preparation method of fly ash-based microporous and hierarchical porous zeolite molecular sieve Download PDFInfo
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Abstract
The invention discloses a green preparation method of a fly ash-based microporous and hierarchical porous zeolite molecular sieve, which comprises the following steps: mixing a sodium hydroxide solution and the fly ash, and efficiently extracting silicon-aluminum components and residual carbon particles in the fly ash by utilizing a microwave-ultrasonic-ultraviolet light synergistic activation technology to replace a traditional high-energy-consumption alkali fusion technology to obtain high-purity aluminosilicate precursor liquid; supplementing an aluminum source or a structure directing agent or deionized water in the precursor liquid, marking an aluminosilicate precursor liquid as an A1 liquid, adding a tetrapropyl ammonium hydroxide solution into the A1 liquid as an A2 liquid, dissolving sodium metaaluminate in the deionized water as a B liquid, and dropwise adding the B liquid into the A1 liquid and stirring to obtain a C liquid. And placing one of the A1 liquid, the A2 liquid and the C liquid in the liner of a high-pressure reaction kettle for reaction, after the reaction, carrying out suction filtration on materials in the kettle, washing until the pH value is neutral, drying and roasting to obtain a solid product. The invention has the advantages that: the method avoids impurity removal process, simplifies multi-stage hole process, and has the advantages of simple operation, short reaction time, energy conservation and high purity of the obtained product.
Description
Technical Field
The invention relates to the technical field of fly ash recycling, in particular to a green preparation method of a fly ash-based microporous and hierarchical porous zeolite molecular sieve.
Background
The zeolite molecular sieve is a hydrated aluminosilicate crystal, has a skeleton structure with a plurality of pore passages with uniform pore diameters and regularly arranged cavities, and is widely used as an industrial catalyst in the fields of petrochemical industry, fine chemical industry and the likeIon exchanger, adsorption separating agent and washing assistant. The cost for synthesizing the zeolite molecular sieve by using the purified industrial raw materials is higher, and the main component in the fly ash is the main raw material SiO for synthesizing the zeolite molecular sieve2And Al2O3The fly ash is used for replacing the purification chemical raw materials, so that the production cost can be saved, waste can be changed into valuable, and the recycling of solid waste is realized.
Except for a main raw material vitreous body for synthesizing the zeolite molecular sieve, the fly ash has higher proportion of crystal phase substances, mainly comprises mullite, quartz, tricalcium aluminate, melilite, periclase and the like, wherein the mullite and the quartz have the highest content, and the crystal phases are inactive substances; the fly ash activation is to activate crystal phase substances under proper conditions, and measures such as mechanical grinding, screening, high-temperature roasting, acid treatment, alkali fusion and the like are usually adopted in industry to improve the utilization rate of raw materials.
In the traditional hydrothermal synthesis method, crystal phase substances in the fly ash are difficult to directly dissolve in the process of preparing the zeolite molecular sieve, and in the alkali fusion method, a certain amount of NaOH is mixed with the fly ash raw material before hydrothermal synthesis reaction, and the mixture is heated in a crucible to 773K-973K for activating the crystal phase substances. The alkali fusion method is also the most effective method for activating crystalline phase substances in the traditional process, but the method is too high in energy consumption and long in time consumption.
In addition, although the microporous zeolite molecular sieve has realized application value in various fields such as gas storage, selective adsorption, high-efficiency ion exchange, catalyst carriers and the like, in part of organic industrial catalysis, the narrow micropore diameter (< 2nm) and the lengthened pore passage of the zeolite molecular sieve seriously restrict the diffusion of large-size reactants and product molecules in crystals, so that the contact of the reactant molecules and active sites of the crystals is hindered, a large amount of carbon is deposited in the crystals within a short time, the molecular sieve is passivated, and the catalytic performance and the service life of the catalyst are seriously reduced. Therefore, a multi-level mesoporous (2-50nm) system is introduced into the traditional zeolite molecular sieve, so that the problem of macromolecular diffusion limitation can be solved, the added value of the product can be greatly improved, and the multi-level mesoporous zeolite molecular sieve is widely applied to the fields of adsorption separation, drug slow release and the like by virtue of the great advantages in the aspect of mass transfer due to the pore size distribution of different dimensions in the material.
Therefore, the development of a process technology for preparing the microporous and hierarchical porous zeolite molecular sieve by using the fly ash as a raw material is an important content of high-end utilization of the fly ash, and the process technology development aims to solve the following two key problems by combining the research bases of domestic and foreign industries: 1. compared with pure chemical raw materials, the fly ash has a complex chemical composition, so that the problems of impurity removal and activation of the raw materials are solved when the fly ash is used as the raw material for preparing zeolite molecular sieve products; the method utilizes the microwave-ultrasonic-ultraviolet light synergistic activation technology to efficiently extract the silicon-aluminum component and the residual carbon granules in the fly ash, replaces the traditional high-energy-consumption alkali fusion method to obtain aluminosilicate precursor liquid with higher purity, and lays a foundation for synthesizing the high-crystallinity zeolite molecular sieve in the next step; 2. the mature preparation process of the hierarchical pore zeolite molecular sieve still needs to additionally add a mesoporous pore-forming agent, such as a carbon nano material of a hard template, high-molecular organosilane of a soft template and the like, so that the problems of complex synthesis process, poor product crystallinity and the like are caused; according to the invention, the 'natural carbon particles' in the fly ash are innovatively nanocrystallized in the activation process and directly used as a hard template agent required by the multi-stage porosification of the zeolite molecular sieve, so that the process step of additionally adding the template agent is omitted; the nano carbon particles do not react with zeolite molecular sieve gel, but block the growth of the zeolite molecular sieve in a physical space occupying mode, and mesoporous channels are left in or among the crystals of the microporous zeolite molecular sieve after the nano carbon particles are removed by later-stage roasting, so that the preparation of the fly ash-based hierarchical pore zeolite molecular sieve is realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a fly ash-based microporous and hierarchical pore zeolite molecular sieve, which solves the problems of the prior art, such as difficult activation of crystalline phase silicon-aluminum species or high activation energy consumption, complex hierarchical pore process, poor product crystallinity and the like.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a fly ash-based microporous and hierarchical porous zeolite molecular sieve comprises the following steps:
1) ball milling the fly ash, and sieving with a 900-mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of 3-5mol/L sodium hydroxide solution into a special-shaped three-necked bottle, and adding 13.33-40g of pulverized fuel ash subjected to ball milling and sieving for mixing, wherein the volume of the sodium hydroxide solution is 5-15;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 20-40min, wherein the ultrasonic power is 20-25 KHz;
4) setting the temperature of the reactor at 90-110 ℃, carrying out microwave treatment for 1-3 hours, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 1-3 hours by ultrasound; the wavelength of the ultraviolet module is 365nm, the power is 250W, and the action time is 1-2 hours; according to different chemical compositions of the fly ash in different producing areas, parameters of the microwave module, the ultrasonic module and the ultraviolet module can be freely regulated and controlled in the activation process, and the three modules can simultaneously act in a synergistic manner;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain aluminosilicate precursor liquid;
6) analyzing the content of silicon-aluminum elements in the precursor liquid in the step 5), and calculating the amount of an aluminum source (sodium metaaluminate) or a structure directing agent (tetrapropylammonium hydroxide) or deionized water to be supplemented according to the material ratio required by synthesis of different zeolite molecular sieves;
7) taking a microwave high-pressure reaction kettle with 100 plus 150mL as a calculation reference, adding 25-50mL of the aluminosilicate precursor liquid obtained in the step 5) into a beaker with 100 plus 200mL, and marking as A1 liquid;
8) according to the material requirement of a product to be synthesized, 6.3-11.7g of tetrapropylammonium hydroxide solution with the mass fraction of 40% can be added into 25-50mL of A1 liquid under magnetic stirring at 600r/min, and the mixture is sealed and stirred for 5min and is marked as A2 liquid;
9) according to the material requirement of a product to be synthesized, 1.48-4.10g of sodium metaaluminate is dissolved in 25-71mL of deionized water under the high-speed stirring of 1200r/min, and the solution is stirred for about 5min until the solution is clear and transparent, and is marked as solution B;
10) putting a certain amount of the liquid B into an automatic dropping device, slowly dropping the liquid B into the liquid A1 at the speed of 0.5 drop/second, and keeping the liquid A1 to be stirred at the high speed of 1200r/min during the feeding period; after the dropwise addition is finished, sealing, continuously stirring and aging for 30min to obtain a solution C;
11) placing the A1 liquid or the A2 liquid or the C liquid into a 100-plus-150 mL microwave high-pressure reaction kettle lining, wherein the lining is made of polytetrafluoroethylene, the shell is made of special PEEK, and the upper limit of the reaction kettle which can resist high pressure is 6 MPa; setting the microwave high-pressure reaction temperature at 90-140 deg.c, the pressure of the pressure inside the reactor of 0.6-1.6MPa and the reaction time of 20-40 min;
12) and after the high-pressure reaction is finished, performing suction filtration on the materials in the kettle, washing until the pH value is neutral, drying and roasting to obtain a solid product.
Preferably, the zeolite molecular sieve in the step 6) has a crystal form: one of SOD, LTA and MFI.
Preferably, the aluminum source in the step 6) is sodium metaaluminate.
Preferably, the structure directing agent in the step 6) is tetrapropylammonium hydroxide.
Compared with the prior art, the invention has the advantages that:
the microwave-ultrasonic-ultraviolet light three-module synergistic effect replaces the traditional high-temperature alkali fusion technology, the defects of high energy consumption, complex impurity removal process and the like in the existing fly ash activation technology are overcome, and meanwhile, the natural residual carbon particles in the fly ash are converted into a natural hard template agent for synthesizing the hierarchical pore zeolite molecular sieve under the ultrasonic action; the method has the advantages of simple and convenient operation, short microwave reaction time, energy conservation, simplified process, high product purity and the like, is a simple and feasible practical method, and provides a new idea and a new method for preparing the microporous and hierarchical zeolite molecular sieve by using the fly ash.
Drawings
FIG. 1 is an XRD pattern of the products of examples 1 and 2 of the present invention;
FIG. 2 is a graph showing the nitrogen adsorption curves and pore size distribution of the products of examples 1 and 2 of the present invention;
FIG. 3 is SEM images of products of example 1(a) and example 2(b) of the present invention;
FIG. 4 is an XRD pattern of the products of examples 3 and 4 of the present invention;
FIG. 5 is a graph showing the nitrogen adsorption curves and pore size distribution of the products of examples 3 and 4 of the present invention;
FIG. 6 is SEM images of products of example 3(a) and example 4(b) of the present invention;
FIG. 7 is an XRD pattern of the products of examples 5 and 6 of the present invention;
FIG. 8 is a graph showing the nitrogen adsorption curves and pore size distribution of the products of examples 5 and 6;
FIG. 9 is SEM images of products of example 5(a) and example 6(b) of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings by way of examples.
The chemical composition and content of the fly ash used in the experiment are quantitatively analyzed by adopting X-ray fluorescence spectroscopy (XRF), and the fly ash comprises the following main components: SiO 22And Al2O3And CaO, MgO, Na2O，TiO2，Fe2O3Etc.; quantitatively analyzing the content of the silicon-aluminum element in the precursor liquid by adopting an Inductively Coupled Plasma (ICP) spectrum generation technology; analyzing the crystal form of the zeolite molecular sieve by adopting an X-ray diffraction technology (XRD); the appearance and the granularity of the product are represented by adopting a Scanning Electron Microscope (SEM); and (3) characterizing the specific surface area and the pore size distribution of the multilevel pores of the material by adopting a nitrogen physical adsorption technology.
Example 1:
the fly ash is selected from Zhenyuan county of Guizhou, and the chemical composition of the fly ash is shown in Table 1; the ICP test results for the precursor fluids are shown in table 2.
1) Ball milling the fly ash, and sieving with 900 mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of sodium hydroxide solution with the concentration of 4mol/L into a special-shaped three-necked bottle, and adding 20g of pulverized fuel ash subjected to ball milling and sieving for mixing, wherein the volume of the sodium hydroxide solution is 10;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 40min, wherein the ultrasonic power is 20 KHz;
4) setting the temperature of the reactor at 100 ℃, carrying out microwave treatment for 2 hours, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 2 hours by ultrasound; the action time of the ultraviolet light module is accumulated for 1 hour;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain 168mL of fly ash aluminosilicate precursor liquid; transferring 25mL of the solution into a 100mL beaker, and recording the solution as solution A;
6) weighing 1.48g of sodium metaaluminate, dissolving in 25mL of deionized water under high-speed stirring at 1200r/min, and stirring for about 5min until the solution is clear and transparent, and marking as solution B;
7) putting the liquid B in the step 6) into an automatic dropping device, slowly dropping the liquid B into the liquid A at the speed of 0.5 drop/second, and keeping the liquid A stirring at the high speed of 1200r/min during the feeding period; after the dropwise adding is finished, sealing, continuously stirring and aging for 30min to obtain white viscous mixed material C liquid;
8) putting all the solution C obtained in the step 7) into a 100mL microwave high-pressure reaction kettle; setting the final temperature of the microwave high-pressure reaction to be 100 ℃, and heating the reaction to be performed by the following steps: raising the temperature to 100 ℃ for 3min, and keeping the temperature for 30min at the pressure of about 0.9 MPa;
9) after the high-pressure reaction is finished, the materials in the kettle are filtered and washed until the pH value is neutral to obtain a solid product, and the solid product is dried and roasted, and then analyzed and characterized by XRD, BET, SEM, TEM and other testing means to obtain the crystallinity and the pore structure characteristics of the product.
TABLE 1 Main chemical component content of fly ash from Zhenyuan county, Guizhou
TABLE 2 content of Si-Al element in the precursor liquid of example 1
As can be seen from fig. 1: the product synthesized in the example 1 has an LTA crystal form, good crystallinity and no impurity peak; from the nitrogen adsorption curve in fig. 2, it can be seen that: the product synthesized in the embodiment 1 has no obvious lag ring, the pore size distribution is mainly micropore, and no mesopore distribution; as can be seen from fig. 3: the product synthesized in example 1 has a cubic morphology typical of microporous LTA zeolite, and the particle size distribution is relatively uniform; as can be seen from table 10: the total specific surface area of the product after calcium ion exchange is 529.268m2(iv)/g, total pore volume 0.2310 cc/g; in conclusion: example 1 the product prepared was a microporous LTA zeolite molecular sieve.
Example 2:
the fly ash is selected from Zhenyuan county of Guizhou, and the chemical composition of the fly ash is shown in Table 1; the ICP test results for the precursor fluids are shown in table 3.
1) Ball milling the fly ash, and sieving with 900 mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of sodium hydroxide solution with the concentration of 4mol/L into a special-shaped three-necked bottle, and adding 40g of pulverized fuel ash subjected to ball milling and sieving for mixing;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 40min, wherein the ultrasonic power is 20 KHz;
4) setting the temperature of the reactor at 100 ℃, carrying out microwave treatment for 2 hours, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 2 hours by ultrasound; the action time of the ultraviolet light module is accumulated for 1 hour;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain 171mL of fly ash aluminosilicate precursor liquid; transferring 25mL of the solution into a 200mL beaker, and recording the solution as solution A;
6) weighing 4.1g of sodium metaaluminate, dissolving in 71mL of deionized water under high-speed stirring at 1200r/min, and stirring for about 5min until the solution is clear and transparent, and marking as solution B;
7) putting the liquid B in the step 6) into an automatic dropping device, slowly dropping the liquid B into the liquid A at the speed of 0.5 drop/second, and keeping the liquid A stirring at the high speed of 1200r/min during the feeding period; after the dropwise adding is finished, sealing, continuously stirring and aging for 30min to obtain a white viscous mixed material which is marked as liquid C;
8) putting all the solution C obtained in the step 7) into a 150mL microwave high-pressure reaction kettle; setting the final temperature of the microwave high-pressure reaction to be 90 ℃, and heating the reaction to be carried out according to the following steps: raising the temperature to 90 ℃ within 5min, and keeping the temperature for 40min, wherein the pressure is about 0.6 MPa;
9) after the high-pressure reaction is finished, the materials in the kettle are filtered and washed until the pH value is neutral to obtain a solid product, and the solid product is dried and roasted, and then analyzed and characterized by XRD, BET, SEM, TEM and other testing means to obtain the crystallinity and the pore structure characteristics of the product.
TABLE 3 content of Si-Al element in precursor liquid of example 2
As can be seen from fig. 1: the product synthesized in the example 2 has an LTA crystal form, good crystallinity and no impurity peak; from the nitrogen adsorption curve in fig. 2, it can be seen that: the product synthesized in the example 2 has obvious hysteresis loop, and the pore size distribution shows that the product not only has micropore distribution, but also has a large amount of mesoporous distribution with 20nm as the main part; as can be seen from fig. 3: the product synthesized in the embodiment 2 has a spherical shape, and the particle size distribution is uniform; as can be seen from table 10: the total specific surface area of the product after calcium ion exchange is 458.394m2(ii)/g, total pore volume 1.246 cc/g; in conclusion: example 2 the product produced was a hierarchical pore LTA zeolite molecular sieve.
Example 3:
the fly ash is selected from Jinsha county, Guizhou, and the chemical composition of the fly ash is shown in Table 4; the ICP test results for the precursor fluids are shown in table 5.
1) Ball milling the fly ash, and sieving with 900 mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of 5mol/L sodium hydroxide solution into a special-shaped three-necked bottle, and adding 13.33g of pulverized fuel ash subjected to ball milling and sieving for mixing, wherein the concentration of the sodium hydroxide solution is 15 mol/L;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 20min, wherein the ultrasonic power is 25 KHz;
4) setting the temperature of the reactor at 110 ℃, carrying out microwave treatment for 1 hour, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 1 hour by ultrasound; the action time of the ultraviolet light module is accumulated for 1 hour;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain 161mL of fly ash aluminosilicate precursor liquid;
6) directly transferring 50mL of the precursor liquid obtained in the step 5) into a 100mL microwave high-pressure reaction kettle; setting the final temperature of the microwave high-pressure reaction to be 130 ℃, and heating the reaction to be carried out according to the following steps: heating to 100 deg.C for 3min, maintaining at 100 deg.C for 1min, continuously heating to 130 deg.C for 2min, maintaining for 20min, and maintaining at 1.3 MPa;
9) after the high-pressure reaction is finished, the materials in the kettle are filtered and washed until the pH value is neutral to obtain a solid product, and the solid product is dried and roasted, and then analyzed and characterized by XRD, BET, SEM, TEM and other testing means to obtain the crystallinity and the pore structure characteristics of the product.
TABLE 4 Main chemical component content of fly ash from Guizhou Jinsha county
TABLE 5 content of Si-Al element in precursor liquid of example 3
As can be seen from fig. 4: the product synthesized in the embodiment 3 has an SOD crystal form and good crystallinity; from the nitrogen adsorption curve in FIG. 5Therefore, the following steps are carried out: the product synthesized in the embodiment 3 has no obvious lag ring and no mesoporous distribution; as can be seen from fig. 6: the product synthesized in the embodiment 3 has a spherical shape, the particle size distribution is uniform, and the particle size is about 2.5 microns; as can be seen from table 10: the total specific surface area of the product was 19.513m2(iv)/g, total pore volume 0.069 cc/g; in conclusion: example 1 the product prepared was a microporous SOD zeolite molecular sieve.
Example 4:
the fly ash is selected from Jinsha county, Guizhou, and the chemical composition of the fly ash is shown in Table 4; the ICP test results for the precursor fluids are shown in table 6.
1) Ball milling the fly ash, and sieving with 900 mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of 5mol/L sodium hydroxide solution into a special-shaped three-necked bottle, and adding 28.57g of pulverized fuel ash subjected to ball milling and sieving for mixing;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 20min, wherein the ultrasonic power is 25 KHz;
4) setting the temperature of the reactor at 110 ℃, carrying out microwave treatment for 1 hour, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 1 hour by ultrasound; the action time of the ultraviolet light module is accumulated for 1 hour;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain 164mL of fly ash aluminosilicate precursor liquid;
6) directly transferring 50mL of the precursor liquid obtained in the step 5) into a 100mL microwave high-pressure reaction kettle; setting the final temperature of the microwave high-pressure reaction to be 110 ℃, and heating the reaction to be performed by the following steps: raising the temperature to 110 ℃ within 6min, keeping the temperature for 30min, and keeping the pressure at about 1.1 MPa;
7) after the high-pressure reaction is finished, the materials in the kettle are filtered and washed until the pH value is neutral to obtain a solid product, and the solid product is dried and roasted, and then analyzed and characterized by XRD, BET, SEM, TEM and other testing means to obtain the crystallinity and the pore structure characteristics of the product.
TABLE 6 content of Si-Al element in precursor liquid of example 4
As can be seen from fig. 4: the product synthesized in the example 4 has SOD crystal form and good crystallinity; from the nitrogen adsorption curve in fig. 5, it can be seen that: the product synthesized in the embodiment 4 has obvious hysteresis loop and has mesoporous distribution of 20-40 nm; as can be seen from fig. 6: the product synthesized in the embodiment 4 has a spherical shape, a rough surface, uniform particle size distribution and a particle size of about 1-2 microns; as can be seen from table 10: the total specific surface area of the product was 32.100m2(iv)/g, total pore volume 0.1320 cc/g; in conclusion: example 4 the product prepared was a hierarchical pore SOD zeolite molecular sieve.
Example 5:
the fly ash is selected from Zunyi in Guizhou, and the chemical composition of the fly ash is shown in Table 7; the ICP test results for the precursor fluids are shown in table 8.
1) Ball milling the fly ash, and sieving with 900 mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of 3mol/L sodium hydroxide solution into a special-shaped three-necked bottle, and adding 33.33g of pulverized fuel ash subjected to ball milling and sieving for mixing;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 30min, wherein the ultrasonic power is 23 KHz;
4) setting the temperature of the reactor at 90 ℃, carrying out microwave treatment for 3 hours, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 3 hours by ultrasound; the action time of the ultraviolet light module is accumulated for 2 hours;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain 182mL of fly ash aluminosilicate precursor liquid;
6) measuring 50mL of the obtained front body fluid of 5) in a 150mL beaker, and marking as solution A; under the stirring of a medium speed of 600r/min, 11.7g of tetrapropylammonium hydroxide solution with the mass fraction of 40 percent is added, and the stirring and aging are continued for 15min to obtain solution B;
7) putting the solution B obtained in the step 6) into a 100mL microwave high-pressure reaction kettle; setting the final temperature of the microwave high-pressure reaction to be 140 ℃, and heating the reaction to be performed by the following steps: heating to 100 deg.C for 3min, maintaining for 1min, continuously heating to 140 deg.C for 5min, maintaining for 30min, and maintaining at pressure of 1.6 MPa;
8) after the high-pressure reaction is finished, the materials in the kettle are filtered and washed until the pH value is neutral to obtain a solid product, and the solid product is dried and roasted, and then analyzed and characterized by XRD, BET, SEM, TEM and other testing means to obtain the crystallinity and the pore structure characteristics of the product.
TABLE 7 Zunyi content of main chemical components of fly ash in Guizhou
TABLE 8 content of Si-Al element in precursor liquid of example 5
As can be seen from fig. 7: the product synthesized in example 5 has an MFI crystal form and has good crystallinity; from the nitrogen adsorption curve in fig. 8, it can be seen that: the product synthesized in the embodiment 5 has no obvious lag ring, the pore size distribution is mainly micropore, and no mesopore distribution; as can be seen from fig. 9: the product synthesized in the embodiment 5 has a typical flat cuboid shape, and the particle size distribution is uniform; as can be seen from table 10: the total specific surface area of the product was 404.043m2(iv)/g, total pore volume 0.1812 cc/g; in conclusion: example 5 the product produced was a microporous MFI zeolite molecular sieve.
Example 6:
the fly ash is selected from Zunyi in Guizhou, and the chemical composition of the fly ash is shown in Table 7; the ICP test results for the precursor fluids are shown in table 9.
1) Ball milling the fly ash, and sieving with 900 mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of 3mol/L sodium hydroxide solution into a special-shaped three-necked bottle, and adding 16.67g of pulverized fuel ash subjected to ball milling and sieving for mixing, wherein the volume of the solution is 12;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 30min, wherein the ultrasonic power is 23 KHz;
4) setting the temperature of the reactor at 90 ℃, carrying out microwave treatment for 3 hours, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 3 hours by ultrasound; the action time of the ultraviolet light module is accumulated for 2 hours;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrate and centrifuged supernatant, and mixing the liquid to obtain 176mL of fly ash aluminosilicate precursor liquid;
6) measuring 50mL of the obtained front body fluid of 5) in a 150mL beaker, and marking as solution A; adding 6.3g of tetrapropylammonium hydroxide solution with the mass fraction of 40% into the solution at the medium speed of 600r/min under stirring, continuing stirring and aging for 15min, and marking as solution B;
7) putting the solution B obtained in the step 6) into a 100mL microwave high-pressure reaction kettle; setting the final temperature of the microwave high-pressure reaction to be 130 ℃, and heating the reaction to be carried out according to the following steps: heating to 100 deg.C for 5min, maintaining for 1min, continuously heating to 130 deg.C for 6min, maintaining for 30min, and maintaining at pressure of 1.4 MPa;
8) after the high-pressure reaction is finished, the materials in the kettle are filtered and washed until the pH value is neutral to obtain a solid product, and the solid product is dried and roasted, and then analyzed and characterized by XRD, BET, SEM, TEM and other testing means to obtain the crystallinity and the pore structure characteristics of the product.
TABLE 9 content of Si-Al element in the precursor liquid of example 6
As can be seen from fig. 7: the product synthesized in example 6 has an MFI crystal form and is good in crystallinity; from the nitrogen adsorption curve in fig. 8, it can be seen that: the product synthesized in example 6 has obvious hysteresis loop, and not only has micropore distribution, but also has a large amount of mesoporous distribution of 20-40nm(ii) a As can be seen from fig. 9: the product synthesized in the embodiment 6 has a stacked cluster morphology, and the particle size distribution is relatively uniform; as can be seen from table 10: the total specific surface area of the product was 407.636m2(iv)/g, total pore volume 0.8811 cc/g; in conclusion: example 5 the product produced was a hierarchical pore MFI zeolite molecular sieve.
TABLE 10 Nitrogen adsorption data for the products of the examples
| Nitrogen adsorption test | Total specific surface area (m)2/g) | Total pore volume (cc/g) |
| Example 1 (product already calcium ion exchanged) | 529.268 | 0.2310 |
| Example 2 (product already calcium ion exchanged) | 458.394 | 1.246 |
| Example 3 | 19.513 | 0.069 |
| Example 4 | 32.100 | 0.1320 |
| Example 5 | 404.043 | 0.1812 |
| Example 6 | 407.636 | 0.8811 |
The above embodiments are combined to show that: under the condition of the invention, the synthesis of the zeolite molecular sieves with different crystal forms and micropores and multilevel pores can be realized by fine adjustment of main synthesis parameters, such as silicon-aluminum ratio, alkali liquor concentration, microwave high-pressure reaction temperature and time, heating rate and the like, because of different crystallization environments, the zeolite nucleation rate and the crystal nucleus growth rate are different; the temperature, the slow heating rate and the lower final temperature are favorable for the symbiotic growth of the natural carbon particle hard template and the zeolite seed crystal, so that the hierarchical pore zeolite molecular sieve is formed; and the higher temperature rise rate and the higher final temperature are favorable for the rapid growth of the seed crystals to form the microporous zeolite molecular sieve with large grain size.
The practice of the present invention, it is to be understood that the scope of the invention is not limited to such specific statements and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (4)
1. A preparation method of a fly ash-based microporous and hierarchical porous zeolite molecular sieve is characterized by comprising the following steps:
1) ball milling the fly ash, and sieving with a 900-mesh sieve;
2) according to the liquid-solid ratio (mL: g) adding 200mL of 3-5mol/L sodium hydroxide solution into a special-shaped three-necked bottle, and adding 13.33-40g of pulverized fuel ash subjected to ball milling and sieving for mixing, wherein the volume of the sodium hydroxide solution is 5-15;
3) placing the three-mouth bottle in a microwave-ultrasonic-ultraviolet light combined catalytic synthesizer, placing an immersion ultrasonic alloy probe at the top mouth, and carrying out ultrasonic treatment on the mixed solution for 20-40min, wherein the ultrasonic power is 20-25 KHz;
4) setting the temperature of the reactor at 90-110 ℃, carrying out microwave treatment for 1-3 hours, automatically outputting by a microwave module according to the power of 0-1000W, and continuously acting for 1-3 hours by ultrasound; the wavelength of the ultraviolet module is 365nm, the power is 250W, and the action time is 1-2 hours; according to different chemical compositions of the fly ash in different producing areas, parameters of the microwave module, the ultrasonic module and the ultraviolet module can be freely regulated and controlled in the activation process, and the three modules can simultaneously act in a synergistic manner;
5) after the reaction is finished, performing suction filtration on all materials in the three-mouth bottle in the step 4), then continuously centrifuging the filter paper residues at a high speed of 8000r/min, collecting all suction filtration filtrates and centrifuged supernatant, and mixing the liquids to obtain aluminosilicate precursor liquid;
6) analyzing the content of silicon-aluminum elements in the precursor liquid in the step 5), and calculating the amount of an aluminum source (sodium metaaluminate) or a structure directing agent (tetrapropylammonium hydroxide) or deionized water to be supplemented according to the material ratio required by synthesis of different zeolite molecular sieves;
7) taking a microwave high-pressure reaction kettle with 100 plus 150mL as a calculation reference, adding 25-50mL of the aluminosilicate precursor liquid obtained in the step 5) into a beaker with 100 plus 200mL, and marking as A1 liquid;
8) according to the material requirement of a product to be synthesized, 6.3-11.7g of tetrapropylammonium hydroxide solution with the mass fraction of 40% is added into 25-50mL of A1 liquid under the magnetic stirring of 600r/min, and the mixture is sealed and stirred for 5min and is marked as A2 liquid;
9) according to the requirement of materials of a product to be synthesized, 1.48-4.10g of sodium metaaluminate is dissolved in 25-71mL of deionized water under the high-speed stirring of 1200r/min, and the solution is stirred for about 5min until the solution is clear and transparent and is marked as solution B;
10) putting a certain amount of the liquid B into an automatic dropping device, slowly dropping the liquid B into the liquid A1 at the speed of 0.5 drop/second, and keeping the liquid A1 to be stirred at the high speed of 1200r/min during the feeding period; after the dropwise addition is finished, sealing, continuously stirring and aging for 30min to obtain a solution C;
11) placing the A1 liquid or the A2 liquid or the C liquid into a 100-plus-150 mL microwave high-pressure reaction kettle lining, wherein the lining is made of polytetrafluoroethylene, the shell is made of special PEEK, and the upper limit of the reaction kettle which can resist high pressure is 6 MPa; setting the microwave high-pressure reaction temperature at 90-140 deg.c, the pressure of the pressure inside the reactor of 0.6-1.6MPa and the reaction time of 20-40 min;
12) and after the high-pressure reaction is finished, performing suction filtration on the materials in the kettle, washing until the pH value is neutral, drying and roasting to obtain a solid product.
2. The method for preparing a fly ash-based microporous and hierarchical pore zeolite molecular sieve according to claim 1, wherein the method comprises the following steps: the crystal form of the zeolite molecular sieve in the step 6) is as follows: one of SOD, LTA and MFI.
3. The method for preparing a fly ash-based microporous and hierarchical pore zeolite molecular sieve according to claim 1, wherein the method comprises the following steps: and in the step 6), the aluminum source is sodium metaaluminate.
4. The method for preparing a fly ash-based microporous and hierarchical pore zeolite molecular sieve according to claim 1, wherein the method comprises the following steps: the structure directing agent in the step 6) is tetrapropylammonium hydroxide.
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