CN115784251B - Method for preparing molecular sieve by utilizing waste wind power blades - Google Patents
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Abstract
The invention relates to the field of solid waste treatment, and discloses a method for preparing a molecular sieve by using waste wind power blades. The method comprises the following steps: (1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes; (2) Reacting the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase; (3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate; (4) Mixing the filtrate with a liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials. The method can solve the problem of resource utilization of the existing waste wind power blades, the silicon element in the waste wind power blades can be fully utilized to prepare the molecular sieve, the prepared molecular sieve does not contain impurities, and the performance is more excellent in subsequent application.
Description
Technical Field
The invention relates to the field of solid waste treatment, in particular to a method for preparing a molecular sieve by utilizing waste wind power blades.
Background
Wind power generation is an important low-carbon development mode at present, and the scale of wind power generation is continuously increased at present. With the continuous development of wind power generation, wind power plants which are put into use at an early stage are also retired in succession, the service life of the wind power plants is usually about 20 years, and the existing retired wind power plants face the problem of disposing various wastes. The wind power blade is an important part of wind power generation equipment, the process of recovering and disposing the wind power blade is particularly complex due to the particularity of the material of the wind power blade, and useful components in the waste wind power blade are not fully reused.
The molecular sieve is an artificially synthesized hydrated aluminosilicate with the function of screening molecules, has high adsorption capacity, strong selectivity and high temperature resistance, and is widely applied to the fields of organic chemical industry, petrochemical industry and new materials at present. At present, the trend of preparing the molecular sieve by utilizing industrial solid wastes is already a trend, the solid wastes commonly used for preparing the molecular sieve at present comprise fly ash, coal gangue, tailings and the like, but the molecular sieve prepared by utilizing the solid wastes has higher impurity content, and the application of the molecular sieve is influenced subsequently.
Disclosure of Invention
The invention aims to solve the problems of resource recovery of waste wind power blades and high impurity content in a molecular sieve prepared from solid wastes in the prior art, and provides a method for preparing the molecular sieve by using the waste wind power blades.
In order to achieve the above object, the present invention provides a method for preparing a molecular sieve by using waste wind power blades, which is characterized in that the method comprises the following steps:
(1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes;
(2) Reacting the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase;
(3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate;
(4) Mixing the filtrate with the liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials;
the roasting agent comprises a main roasting agent and an auxiliary roasting agent, wherein the main roasting agent is metal carbonate and/or alkali metal hydroxide, and the auxiliary roasting agent is bicarbonate.
Preferably, the metal carbonate is sodium carbonate and/or potassium carbonate;
the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
the bicarbonate is selected from one or more of sodium bicarbonate, ammonium bicarbonate and potassium bicarbonate;
and/or the weight ratio of the main roasting agent to the auxiliary roasting agent is 2-6.
Preferably, in step (2), the reaction conditions include: the temperature is 350-500 ℃, and the time is 2-4h;
and/or, the catalyst is sodium hydroxide or potassium hydroxide;
and/or the weight ratio of the catalyst to the used amount of the waste wind power blade is 2-10.
Preferably, in step (3), the calcination conditions include: the temperature is 600-1000 ℃, and the time is 2-10h.
Preferably, in the step (3), the weight ratio of the solid phase to the roasting agent is 1.
Preferably, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution;
and/or the concentration of hydroxide ions in the alkaline solution is 0.5-12mol/L.
Preferably, the liquid-solid ratio of the alkaline solution to the solid phase in leaching in step (2) is 5-20mL:1g of a compound;
and/or the leaching time is 1-5h.
Preferably, the aluminum source is selected from one or more than two of sodium metaaluminate, aluminum sulfate, aluminum nitrate and sodium aluminate;
and/or, in the mixed material in the step (4), the mass ratio of the silicon element to the aluminum element is 1-2.
Preferably, in step (4), the mixing conditions include: the temperature is 40-95 ℃ and the time is 1-6h;
and/or the aging time is 4-72h;
and/or the conditions of the hydrothermal reaction comprise: the temperature is 80-150 ℃ and the time is 6-36h.
The invention provides a molecular sieve prepared by the method for preparing the molecular sieve by utilizing the waste wind power blades.
The method can successfully perform resource treatment on the waste wind power blades, is simple and convenient in treatment mode, can convert resin in the waste wind power blades into micromolecular polymers through supercritical reaction on crushed waste wind power blades, and can play a role in pore forming and the like in the subsequent molecular sieve preparation process.
Drawings
FIG. 1 is an XRD spectrum of the molecular sieves prepared in examples 1-3.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing a molecular sieve by utilizing waste wind power blades, which is characterized by comprising the following steps of:
(1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes;
(2) Reacting the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase;
(3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate;
(4) Mixing the filtrate with the liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials;
in a specific embodiment, the step of pretreating the waste wind power blade includes: and cutting and crushing the waste wind power blade to obtain the crushed material of the waste wind power blade.
In a preferred embodiment, the particle size of the waste wind power blade crushed aggregates is 120-200 meshes.
In the method provided by the invention, in order to facilitate subsequent leaching of silicon element in the waste wind power blade as much as possible, the particle size of the crushed waste wind power blade needs to be limited within the range provided by the invention.
In the method, the main components of the waste wind power blade are glass fiber and resin, and the glass fiber contains silicon dioxide and aluminum oxide. Based on the total weight of the waste wind power blades, the content of the silicon dioxide is 45-80wt%, the content of the aluminum oxide is 0.5-10wt%, and the content of the resin is 10-45wt%.
In the method, the reaction in the step (2) is a supercritical reaction of resin in the waste wind power blade and water, the reaction needs to be carried out in a closed environment, the resin in the waste wind power blade is converted into a small molecular polymer after the supercritical reaction, the small molecular polymer exists in a liquid phase of a reaction system, in the subsequent preparation process of the molecular sieve, pore-forming can be carried out on the small molecular polymer in the reaction process, so that the prepared molecular sieve has a larger specific surface area, and in the subsequent preparation reaction process of the molecular sieve, the small molecular polymer can play a role in structure guiding in the hydrothermal crystallization process of the molecular sieve, so that the morphology and the structure of the prepared molecular sieve are more regular, the mixing of raw materials in the reaction can be promoted to be more uniform, the framework charge of the molecular sieve is balanced, the morphology and the internal structure of the molecular sieve are further more regular, and the molecular sieve has more excellent properties.
In a particular embodiment, in step (2), the catalyst is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
In the method, the catalyst is used for promoting the generation of the supercritical reaction of the waste wind power blade and water and maintaining the reaction.
In a specific embodiment, the specific process of step (2) comprises: dissolving a catalyst in water under a closed condition, then immersing the waste wind power blade crushed aggregates in the water in which the catalyst is dissolved, carrying out supercritical reaction at a certain temperature, carrying out solid-liquid separation on a reaction system after the reaction is finished to obtain a solid phase and a liquid phase, and then cleaning and drying the solid phase.
In a specific embodiment, in the step (2), the weight ratio of the catalyst to the used amount of the waste wind power blade is 2-10, preferably 3-6. Specifically, the weight ratio of the catalyst to the used amount of the waste wind power blade can be from 2.
In a specific embodiment, in step (2), the conditions of the reaction include: the temperature is 350-500 deg.C, preferably 360-400 deg.C, and the time is 2-4h, preferably 2.5-3.5h. Specifically, the temperature of the reaction may be 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃; the reaction time can be 2h, 3h or 4h.
In a specific embodiment, in step (2), the solid phase obtained by solid-liquid separation after completion of the supercritical reaction is mainly composed of glass fibers, and the liquid phase is mainly composed of a small-molecule polymer.
In the method, the solid-phase product obtained in the step (2) is mixed with a roasting agent and calcined, the roasting agent and the solid-phase product react at a high temperature to change silicon element in the solid-phase product into silicate, change aluminum element into meta-aluminate and then leach in alkaline or aqueous solution.
In the method of the present invention, the firing agent includes a main firing agent and an auxiliary firing agent. The main roasting agent is metal carbonate and/or alkali metal hydroxide; the auxiliary roasting agent is bicarbonate.
In particular embodiments, the metal carbonate is sodium carbonate and/or potassium carbonate; the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide; the bicarbonate is selected from one or more of sodium bicarbonate, ammonium bicarbonate and potassium bicarbonate.
In a particular embodiment, the weight ratio of the main firing agent to the auxiliary firing agent is from 2 to 6, preferably from 3 to 5, to 1.
In the method, the main roasting agent is used for reacting with the glass fiber in the roasting process to convert silicon dioxide and aluminum oxide in the glass fiber into silicate compounds and meta-aluminate compounds, and the auxiliary roasting agent is used for accelerating the reaction of the main roasting agent and the glass fiber and carrying out pore-forming on the roasted product in the reaction process, so that the subsequent process of leaching the roasted product in water or alkaline solution is facilitated.
In a particular embodiment, the weight ratio of the solid phase to the amount of the roasting agent is 1. Specifically, the weight ratio of the solid phase to the roasting agent can be 1.
In the method, when the using amount of the roasting agent is too large, the excessive part of the roasting agent enters the product, the adverse effect on the purity of silicon and aluminum of the subsequently prepared molecular sieve is generated, when the using amount of the roasting agent is too small, the leaching amount of silicon in the waste wind power blade is too low, and the utilization rate of the silicon in the subsequently waste wind power blade is too low. In the method, the dosage of the main roasting agent and the auxiliary roasting agent is limited, in the roasting agent, when the dosage of the main roasting agent is too large relative to the dosage of the auxiliary roasting agent, a roasted product obtained by subsequent roasting is easy to agglomerate, so that elements in the roasted product are not easy to leach, and when the dosage of the auxiliary roasting agent in the roasting agent is too high relative to the dosage of the main roasting agent, the reaction of the waste wind power blade and the main roasting agent is incomplete.
In a specific embodiment, in step (3), the conditions of the calcination reaction include: the reaction temperature is 600-1000 ℃, and the reaction time is 2-10h.
In a preferred embodiment, the conditions of the calcination include: the temperature is 650-950 ℃, and the time is 3-6h. Specifically, the temperature of the calcination may be 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃; the calcination time may be 3h, 4h, 5h or 6h.
According to the method, the calcination reaction conditions and the dosage relation of the roasting agent and the waste wind power blade crushed aggregates are directly related to the leaching rates of silicon elements and aluminum elements in subsequent calcination products, the silicon elements and the aluminum elements in the waste wind power blades are completely leached by limiting the calcination process conditions and the dosage of the roasting agent, and useful elements in the waste wind power blades are applied to the preparation of the molecular sieve.
In a specific embodiment, the calcined product contains a silicate compound and a meta-aluminate compound, the calcined product is subsequently leached in water or an alkaline solution, the silicate compound and the meta-aluminate compound in the calcined product are dissolved, and the main components of the filtrate obtained by filtering after the leaching are silicate and meta-aluminate.
In the method, by controlling the supercritical reaction conditions and the calcination process, the silicon element and the aluminum element in the waste wind power blade can be leached as far as possible, so that the method is applied to the preparation of the molecular sieve.
In a specific embodiment, in the step (3), the leaching time is 1-5h, and the leaching temperature is 50-100 ℃.
In a specific embodiment, in order to facilitate the leaching of the effective components in the calcined product as much as possible, the liquid-solid ratio of the alkaline solution to the calcined product is controlled to be 5-20mL:1g, preferably 8-15mL:1g. Specifically, the liquid-to-solid ratio of the alkaline solution to the calcined product may be 8mL:1g, 9mL:1g, 10mL:1g, 11mL:1g, 12mL:1g, 13mL:1g, 14mL:1g or 15mL:1g of the total weight of the composition.
In a specific embodiment, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution, and the concentration of hydroxide ions in the alkaline solution is 0.5-12mol/L, preferably 2-5mol/L.
In particular embodiments, the aluminum source is selected from one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate, and sodium aluminate.
In a preferred embodiment, the aluminum source is selected from one of sodium metaaluminate, aluminum sulfate, aluminum nitrate and sodium aluminate.
In a more preferred embodiment, the aluminum source is selected from sodium aluminate.
In a specific embodiment, in the step (4), the filtrate obtained in the step (3) and the liquid phase obtained in the step (2) are uniformly mixed, then an aluminum source is dissolved in the uniformly mixed solution to obtain a uniform solution, and the components of the obtained molecular sieve are controlled by controlling the ratio of the amounts of the aluminum element and the silicon element in the finally obtained solution.
In a specific embodiment, in the mixed material in the step (4), the mass ratio of the silicon element to the aluminum element is 1-2. Specifically, the ratio of the amount of the substance of the silicon element to the aluminum element may be 1.
In the method of the present invention, in the step (4), the mixing conditions include: the mixing temperature is 40-95 deg.C, preferably 60-90 deg.C, and mixing time is 1-6 hr, preferably 2-4 hr.
In a specific embodiment, in step (4), the mixing manner may be microwave-assisted mixing, ultrasonic mixing or physical stirring mixing.
In a particular embodiment, the aging time is between 4 and 72 hours, preferably between 10 and 30 hours. In the present invention, the temperature for aging may be normal temperature. Specifically, the aging time may be 10h, 15h, 20h, 25h, or 30h.
In a specific embodiment, the conditions of the hydrothermal reaction include: the temperature of the hydrothermal reaction is 80-150 ℃, and the time of the hydrothermal reaction is 6-36h.
In a preferred embodiment, the conditions of the hydrothermal reaction include: the temperature of the hydrothermal reaction is 90-120 ℃, and the time of the hydrothermal reaction is 8-24h. Specifically, the temperature of the hydrothermal reaction may be 90 ℃, 100 ℃, 110 ℃ or 120 ℃; the hydrothermal reaction time can be 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h.
In a specific embodiment, in the step (4), after the hydrothermal reaction is finished, the product of the hydrothermal reaction is washed and dried, and the drying temperature is 50 to 105 ℃, preferably 60 to 90 ℃.
According to a first embodiment of the method for preparing the molecular sieve by using the waste wind power blades, the method comprises the following steps:
(1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes;
(2) Reacting the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase;
(3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate;
(4) Mixing the filtrate with the liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials;
the roasting agent comprises a main roasting agent and an auxiliary roasting agent; the main roasting agent is selected from metal carbonate and/or alkali metal hydroxide; the auxiliary roasting agent is bicarbonate;
the metal carbonate is sodium carbonate and/or potassium carbonate;
the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
the bicarbonate is selected from one or more of sodium bicarbonate, ammonium bicarbonate and potassium bicarbonate;
the weight ratio of the main roasting agent to the auxiliary roasting agent is 2-6.
According to another embodiment of the method for preparing the molecular sieve by using the waste wind power blades, the method comprises the following steps:
(1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes;
(2) Reacting the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase;
(3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate;
(4) Mixing the filtrate with the liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials;
the roasting agent comprises a main roasting agent and an auxiliary roasting agent; the main roasting agent is selected from metal carbonate and/or alkali metal hydroxide; the auxiliary roasting agent is bicarbonate;
the metal carbonate is sodium carbonate and/or potassium carbonate;
the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
the bicarbonate is selected from one or more of sodium bicarbonate, ammonium bicarbonate and potassium bicarbonate;
the weight ratio of the main roasting agent to the auxiliary roasting agent is 2-6.
In step (2), the reaction conditions include: the temperature is 350-500 ℃, and the time is 2-4h;
the catalyst is sodium hydroxide or potassium hydroxide;
the weight ratio of the catalyst to the used amount of the waste wind power blade is 2-10.
According to another embodiment of the method for preparing the molecular sieve by using the waste wind power blades, the method comprises the following steps:
(1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes;
(2) Reacting the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase;
(3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate;
(4) Mixing the filtrate with the liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials;
the roasting agent comprises a main roasting agent and an auxiliary roasting agent; the main roasting agent is selected from metal carbonate and/or alkali metal hydroxide; the auxiliary roasting agent is bicarbonate;
the metal carbonate is sodium carbonate and/or potassium carbonate;
the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
the bicarbonate is selected from one or more of sodium bicarbonate, ammonium bicarbonate and potassium bicarbonate;
the weight ratio of the main roasting agent to the auxiliary roasting agent is 2-6.
In step (2), the reaction conditions include: the temperature is 350-500 ℃, and the time is 2-4h;
the catalyst is sodium hydroxide or potassium hydroxide;
the weight ratio of the catalyst to the used amount of the waste wind power blade is 2-10;
in step (3), the calcination conditions include: the temperature is 600-1000 ℃, and the time is 2-10h.
The invention provides a molecular sieve prepared by the method for preparing the molecular sieve by utilizing the waste wind power blades.
In the method, the molecular sieve prepared by the method is of a silicon-aluminum structure, and the specific surface area of the molecular sieve can reach 200m 2 More than g.
In a preferred embodiment, the crystal form of the molecular sieve prepared by the method of the present invention includes both the type a molecular sieve and the type X molecular sieve, which is a mixture of the two molecular sieves.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.
The waste wind power blades used in the following examples and comparative examples are from a certain wind farm in Liaoning.
In the following examples 1 to 3, the contents of silica, alumina and resin in the used waste wind power blades are shown in table 1.
TABLE 1
Example 1
(1) Cutting and crushing the waste wind power blades to obtain crushed waste wind power blades (the particle size is less than 100 meshes);
(2) Under a closed condition, 50g of the waste wind power blade crushed aggregates obtained in the step (1) are subjected to supercritical reaction in an aqueous solution, the using amount of a catalyst sodium hydroxide is 3g, the reaction temperature is 360 ℃, the reaction time is 3h, and then solid-liquid separation is carried out to obtain 40.3g of a solid phase and a liquid phase;
(3) Mixing the solid phase obtained in the step (2) with 50g of main roasting agent (sodium carbonate) and 10g of auxiliary roasting agent (sodium bicarbonate), and then calcining at 750 ℃ for 3h; after calcination, placing the obtained calcined product into 600mL of sodium hydroxide solution (the concentration of hydroxide ions is 5 mol/L) to leach (the liquid-solid ratio of the NaOH solution to the calcined product is 5.9mL; filtering to obtain filtrate after leaching;
(4) Mixing sodium aluminate with the liquid phase obtained in the step (2) and the filtrate obtained in the step (3) at 80 ℃ for 3 hours by using a microwave-assisted method, wherein the mass ratio of silicon elements to aluminum elements in the mixed material is 1.6; and after the hydrothermal reaction is finished, washing the obtained product, and drying at 80 ℃ to obtain the product molecular sieve.
Example 2
(1) Cutting and crushing the waste wind power blades to obtain crushed waste wind power blades (the particle size is smaller than 100 meshes);
(2) Under a closed condition, 50g of the waste wind power blade crushed aggregates obtained in the step (1) are subjected to supercritical reaction in an aqueous solution, the amount of a catalyst sodium hydroxide is 4g, the reaction temperature is 370 ℃, the reaction time is 3.5h, and then solid-liquid separation is carried out to obtain 40.2g of a solid phase and a liquid phase;
(3) Mixing the solid phase obtained in the step (2) with 69g of main roasting agent (potassium carbonate) and 11g of auxiliary roasting agent (potassium bicarbonate), and then calcining at 800 ℃ for 4 hours; after calcination, placing the obtained calcined product into 650mL of sodium hydroxide solution (the concentration of hydroxide ions is 5 mol/L) for leaching (the liquid-solid ratio of the NaOH solution to the calcined product is 5.3mL; filtering to obtain filtrate after leaching;
(4) Mixing sodium aluminate with the liquid phase obtained in the step (2) and the filtrate obtained in the step (3) at 70 ℃ for 2 hours by using a microwave-assisted method, wherein the mass ratio of silicon elements to aluminum elements in the mixed material is 1.2; and after the hydrothermal reaction is finished, drying the obtained product at 100 ℃ to obtain the molecular sieve product.
Example 3
(1) Cutting and crushing the waste wind power blades to obtain crushed waste wind power blades (the particle size is less than 100 meshes);
(2) Taking 50g of the waste wind power blade crushed aggregates obtained in the step (1) to perform supercritical reaction in an aqueous solution under a closed condition, wherein the dosage of a catalyst potassium hydroxide is 5g, the reaction temperature is 400 ℃, the reaction time is 4h, and then performing solid-liquid separation to obtain 39.09g of a solid phase and a liquid phase;
(3) Mixing the solid phase obtained in the step (2) with 90g of main roasting agent (sodium carbonate) and 30g of auxiliary roasting agent (sodium bicarbonate), and then calcining at 850 ℃ for 5 hours; after calcining and sintering, putting the obtained calcined product into 800mL of sodium hydroxide solution (the concentration of hydroxide ions is 5 mol/L) to leach (the liquid-solid ratio of the NaOH solution to the calcined product is 15 mL; filtering to obtain filtrate after leaching;
(4) Mixing sodium aluminate with the liquid phase obtained in the step (2) and the filtrate obtained in the step (3) at 70 ℃ for 3.5 hours by using a microwave-assisted method, wherein the mass ratio of silicon elements to aluminum elements in the mixed material is 1.6; and after the hydrothermal reaction is finished, drying the obtained product at 80 ℃ to obtain the molecular sieve product.
Example 4
The procedure was as in example 1, except that the amount of sodium carbonate as the main calcination agent in step (3) was 70g.
Example 5
The procedure was as in example 1, except that in step (3), the amount of sodium carbonate as the main calcination agent was 15g and the amount of the auxiliary calcination agent was 45g.
Example 6
The procedure of example 1 was followed, except that the amount of the main firing agent was changed to 32.5g and the amount of the auxiliary firing agent was changed to 6.5g in step (3).
Example 7
The procedure of example 1 was followed, except that the amount of the main firing agent was changed to 222.5g and the amount of the auxiliary firing agent was changed to 44.5g in step (3).
Comparative example 1
The method is implemented according to the method in the example 1, and is different from the method in that no roasting agent is added in the step (3), and the waste wind power blade crushed aggregates are directly roasted to obtain a roasted product.
Comparative example 2
The process was carried out as in example 1, except that in step (2), only the main firing agent was added and no auxiliary firing agent was added.
Comparative example 3
The process was carried out as in example 1, except that in step (2), only the auxiliary firing agent was added and the main firing agent was not added.
Comparative example 4
The method is implemented according to the embodiment 1, and is different from the method that in the step (1), the waste wind power blades are cut and crushed to obtain waste wind power blade crushed aggregates with the particle size of 50-80 meshes.
Test example
Test example 1
The molecular sieves prepared in examples 1 to 3 were tested by XRD, and their XRD spectra are shown in fig. 1, and it can be known that the molecular sieves prepared in examples 1 to 3 are a mixture of a type a molecular sieve and a type X molecular sieve by comparing with a standard PDF card.
Test example 2
The utilization rate of silicon elements in the waste wind power blades is as follows: testing the content of silicon element in the molecular sieve obtained in the example 1-7 and the product obtained by the comparison 1-4 by using an X-ray fluorescence spectrometry, and calculating the utilization rate of the silicon element in the waste wind power blade, wherein the calculation formula is as follows, and the test result is shown in Table 2;
the utilization ratio of silicon element% = the content of silicon element in molecular sieve/the content of silicon element in waste wind power blade.
Testing of specific surface area of molecular sieve: the specific surface area of the molecular sieve was measured using a full-automatic specific surface and pore size analyzer (BET test method), and the results are shown in table 2.
Testing of molecular sieve purity: the products obtained in examples 1 to 7 and comparative examples 1 to 4 were tested for SiO by X-ray fluorescence spectroscopy 2 With Al 2 O 3 And calculating the purity of the molecular sieve silicon aluminum, the result is shown in table 2, and the calculation formula is as follows:
molecular sieve silicon aluminum purity% = SiO in molecular sieve 2 Content of (1) + Al in molecular sieves 2 O 3 Content of (c).
Potassium hydrogen phthalate (DBP) absorption: the tests were carried out according to the method of Standard HG/T3072-2008 and the test results are shown in Table 2.
TABLE 2
The results in table 2 show that the method for preparing the molecular sieve by using the waste wind power blades can successfully realize resource recycling of the waste wind power blades, and can successfully use silicon elements in the waste wind power blades as much as possible for preparing the molecular sieve, so that the prepared molecular sieve has high silicon-aluminum purity and large specific surface area.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A method for preparing a molecular sieve by utilizing waste wind power blades is characterized by comprising the following steps:
(1) Pretreating the waste wind power blades to obtain crushed waste wind power blades with the particle size of less than or equal to 100 meshes;
(2) Carrying out supercritical reaction on the waste wind power blade crushed aggregates in an aqueous solution in the presence of a catalyst, and then carrying out solid-liquid separation to obtain a solid phase and a liquid phase;
(3) Mixing the solid phase with a roasting agent, then calcining, leaching the calcined product in water or an alkaline solution, and filtering to obtain a filtrate;
(4) Mixing the filtrate with the liquid phase and an aluminum source, and then sequentially carrying out aging and hydrothermal reaction on the mixed materials;
the roasting agent comprises a main roasting agent and an auxiliary roasting agent, wherein the main roasting agent is metal carbonate and/or alkali metal hydroxide, and the auxiliary roasting agent is bicarbonate;
the catalyst is sodium hydroxide or potassium hydroxide.
2. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the metal carbonate is sodium carbonate and/or potassium carbonate;
the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
the bicarbonate is selected from one or more of sodium bicarbonate, ammonium bicarbonate and potassium bicarbonate.
3. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the weight ratio of the main roasting agent to the auxiliary roasting agent is 2-6.
4. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein in the step (2), the supercritical reaction conditions comprise: the temperature is 350-500 ℃, and the time is 2-4h.
5. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the weight ratio of the catalyst to the used amount of the waste wind power blades is 2-10.
6. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein in the step (3), the calcining conditions comprise: the temperature is 600-1000 ℃, and the time is 2-10h.
7. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein in the step (3), the weight ratio of the solid phase to the roasting agent is 1.
8. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution.
9. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the concentration of hydroxide ions in the alkaline solution is 0.5-12mol/L.
10. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the liquid-solid ratio of the alkaline solution to the calcined product in leaching in the step (3) is 5-20mL:1g of the total weight of the composition.
11. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the leaching time is 1-5h.
12. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the aluminum source is one or more selected from sodium metaaluminate, aluminum sulfate, aluminum nitrate and sodium aluminate.
13. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein in the mixed material in the step (4), the mass ratio of the silicon element to the aluminum element is 1-2.
14. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein in the step (4), the mixing conditions comprise: the temperature is 40-95 ℃ and the time is 1-6h.
15. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the aging time is 4-72h.
16. The method for preparing the molecular sieve by using the waste wind power blades as claimed in claim 1, wherein the hydrothermal reaction conditions comprise: the temperature is 80-150 ℃ and the time is 6-36h.
17. The molecular sieve prepared by the method for preparing the molecular sieve by using the waste wind power blades as claimed in any one of claims 1 to 16.
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