CN112573533B - Method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof - Google Patents
Method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of solid waste resource utilization, and discloses a method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof, wherein the method comprises the following steps: (1) the method comprises the following steps of (1) judging whether an Al source needs to be added or not according to the type of target zeolite by using biomass ash as a raw material to obtain a target solid raw material; (2) putting a target solid raw material and an alkali solution into a ball milling tank together according to a solid-liquid ratio of 10-25 g:100ml by using the alkali solution, mixing, and simultaneously adding at least two grinding balls with the same material and diameter specification, wherein the diameters of the grinding balls are within a range of 5-10 mm; (3) placing the ball milling tank in a planetary ball mill to perform grinding treatment, wherein Si coexists in a reaction system in the grinding process 4+ 、Al 3+ And metal cations in the alkaline solution, to form zeolites. The invention can obtain the required directional zeolite product under the conditions of normal temperature and normal pressure and convenient operation and control by the blending of the reaction participants, the key ingredient ratio and the design of other reaction conditions.
Description
Technical Field
The invention belongs to the field of solid waste resource utilization, and particularly relates to a method for preparing zeolite by directionally regulating and controlling biomass ash and application thereof.
Background
At present, many researches on resource utilization of ash residues of agriculture and forestry biomass power plants are carried out at home and abroad, mainly focusing on soil improvement and restoration, pollutant adsorption, infrastructure construction, composite material preparation and the like, but some problems still exist for realizing complete resource utilization of biomass ash in large-scale industrial production. Agriculture and forestry biomass has various sources and varieties, and has variable seasons, and the combustion process and conditions of the biomass direct-fired power plant also have differences, so that biomass ash residues formed after combustion have different components and different particle sizes, and the current single resource utilization mode is difficult to be suitable for all ash residues types.
On the other hand, Holler synthesized zeolite by using Al and Si in fly ash as early as 1985, but the research on the conversion of biomass ash into zeolite by predecessors is less, the fly ash contains Si and Al, and the mass ratio of the two is higher, and the synthesis of zeolite by using fly ash is naturally conceivable; however, the biomass ash contains Si, K, Na, etc. as main components, and has a large difference from zeolite. Previous studies have shown that when SiO 2 /Al 2 O 3 When 2, Na-a type zeolite is formed; when 2.2<＝SiO 2 /Al 2 O 3 <When 3, Na — X zeolite is formed; when SiO 2 /Al 2 O 3 >3, Na-Y zeolite, usually SiO, is formed 2 /Al 2 O 3 The Y-type zeolite with the molar ratio of more than 6 needs to be synthesized by adding a directing agent additionally. In the method for preparing zeolite, Al is in the traditional hydrothermal process 3+ And Si 4+ The reactivity of (2) is low. The alkali fusion-hydrothermal two-step process increases the cost of zeolite synthesis (alkali)The melting temperature is 500 ℃ and 600 ℃). Unlike conventional methods, the molten salt method can synthesize zeolite without adding water. The multi-step method and the molten salt method have high cost and complicated steps, thereby limiting the application of the method. The microwave heating method is also beneficial to the rapid and uniform heating of substances and the dissolution of Si and Al in ash, and the method for synthesizing the zeolite by ultrasonic pretreatment has similar effect to the method for synthesizing the zeolite by microwave heating pretreatment, but the two methods are only suitable for laboratory scale synthesis, which greatly limits the industrial application of the method. And the mechanical grinding can be realized by grinding equipment such as a planetary ball mill and the like, so that the industrial application is realized.
As described above, the biomass ash contains a large amount of Si element, and if it can be applied to zeolite synthesis, resource utilization of the biomass ash can be further achieved. Also, the synthetic methods used in previous studies have serious drawbacks with respect to zeolite synthesis, limiting their development and use.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention aims to provide a method for preparing zeolite by directionally regulating and controlling biomass ash and an application thereof, wherein biomass ash is used as a raw material, and a desired directional zeolite product can be obtained under normal temperature and pressure and under convenient control conditions by designing the blending of reaction participants, the key ingredient ratio thereof and other reaction conditions. By using the method of the invention and taking NaOH as an example of alkali liquor, the method can obviously accelerate Si in ash by utilizing the fact that partial high temperature can be generated on the surface of a reactant in a ball milling process 4+ And Al 3+ With Na in solution + The ions combine to further promote the formation of zeolite products.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing zeolite by directional control of biomass ash, comprising the steps of:
(1) the method comprises the following steps of (1) judging whether an Al source needs to be added to construct a target solid raw material or not according to the type of target zeolite and the relative content of Si and Al in the biomass ash raw material by adopting biomass ash as a raw material;
if an Al source needs to be added, matching the biomass ash raw material with the Al source to obtain a target solid raw material; wherein the Al source is sodium aluminate or potassium aluminate;
if the Al source does not need to be added, directly taking the biomass ash raw material as a target solid raw material;
(2) using NaOH solution with the concentration of 1-4 mol/L or KOH solution with the concentration of 1-4 mol/L as alkali solution, putting the target solid raw material and the alkali solution into a ball milling tank together according to the solid-to-liquid ratio of 10-25 g:100ml, mixing, and simultaneously adding at least two grinding balls with the same material and diameter specification, wherein the diameters of the grinding balls are within the range of 5-10 mm;
(3) placing the ball milling tank in a planetary ball mill to perform grinding treatment, setting the rotation speed of the grinding treatment to be 200-500 rpm, and setting the grinding time to be 4-20 h; in the polishing process, Si coexists in the reaction system 4+ 、Al 3+ And metal cations in the alkali solution are combined to form zeolite; and after the grinding treatment is finished, taking out the ball milling tank, pouring out the solution together with the solid, centrifugally separating, filtering, drying the filter residue, and removing the grinding balls to obtain the zeolite product.
As a further preferred aspect of the present invention, in the step (1):
when the type of the target zeolite is A-type zeolite, SiO in the target solid raw material 2 /Al 2 O 3 The molar ratio is 2: 1; correspondingly, the zeolite product in the step (3) is a type A zeolite;
when the type of the target zeolite is X-type zeolite, SiO in the target solid raw material 2 /Al 2 O 3 A molar ratio of 2.2 or more and 3 or less; correspondingly, the zeolite product in the step (3) is X-type zeolite;
when the type of the target zeolite is Y-type zeolite, SiO in the target solid raw material 2 /Al 2 O 3 The molar ratio is more than 3; correspondingly, the zeolite product in the step (3) is Y-type zeolite.
As a further preferred aspect of the present invention, in the step (2), the grinding balls are zirconia grinding balls or agate grinding balls;
preferably, the ratio of the mass of the target solid raw material to the total mass of the grinding balls is 1: 12;
when the grinding ball is a zirconia grinding ball, the grinding balls with the same material and the at least two diameter specifications are as follows: 50-100 zirconia grinding balls with the diameter of 5mm and 30-37 zirconia grinding balls with the diameter of 10mm are arranged in each 8g of the target solid raw material;
when the grinding balls are agate grinding balls, the grinding balls with the same material and the at least two diameter specifications are as follows: every 8g of the target solid raw material comprises 80-150 agate grinding balls with the diameter of 5mm and 75-84 agate grinding balls with the diameter of 10 mm.
As a further preferred aspect of the present invention, in the step (1), the biomass ash is preferably SiO 2 Is higher than 80% of biomass ash.
As a further preference of the present invention, the biomass ash is preferably selected from rice hull ash and bagasse ash.
As a further preferred aspect of the present invention, in the step (3), the drying is performed at 85 ℃ for 24 hours.
According to another aspect of the present invention there is provided the use of a zeolite product obtained by the above process for the adsorption of heavy metal elements.
Through the technical scheme, compared with the prior art, the grinding method has the advantages that grinding balls with various diameter specifications are used for grinding, local high temperature is formed on the surface of a reactant in the grinding process, the Si element in the biomass ash and the Al element in the Al source (including the original Al element in the biomass ash raw material) are dissolved into the solution under the coordination of strong alkaline solution (such as NaOH solution), and the Si coexisting in the solution 4+ 、Na + And Al 3+ Combined to form the desired zeolite product (mechanism for K) + Substitution of Na + As well as applicable).
According to the invention, SiO in the reaction system is controlled according to different types of the added Al source and biomass 2 /Al 2 O 3 In a molar ratio to produce the desired A-, X-or Y-form of the zeoliteStone, enabling the directional preparation of zeolites. According to the invention, whether an Al source needs to be added into the biomass ash raw material to obtain a target solid raw material can be judged according to the relative contents of Si and Al in the biomass ash raw material; the target solid feedstock (which must comprise a biomass ash feedstock, optionally including an Al source) presents several situations:
i. when SiO is contained in the target solid raw material 2 /Al 2 O 3 The molar ratio is 2: 1, the final synthesized by the method is A-type zeolite;
when SiO is in the target solid raw material 2 /Al 2 O 3 The molar ratio is (2-2.2): 1, the final synthesized by the method is a mixed product of A-type zeolite and X-type zeolite;
when SiO is in the target solid raw material 2 /Al 2 O 3 The molar ratio is (2.2-3): 1, the final synthesized by the method is X-type zeolite;
when SiO in the target solid feedstock 2 /Al 2 O 3 The molar ratio is more than 3: the final synthesis of the Y-type zeolite (if SiO) by the method of the invention 2 /Al 2 O 3 If the molar ratio is more than 6, a directing agent is required to be added after the ball milling and before the drying so as to synthesize the Y-type zeolite).
The results of the series of studies of the subject group of the present inventors have shown that the mechanical grinding not only makes the particle size of the reactant fine and exposes the surface of the reactant to facilitate the reaction by utilizing the local high temperature during the reaction. The previous research of the subject group takes the fly ash as a raw material, and the result shows that the fly ash can be synthesized into the zeolite by a mechanical grinding method, the adsorption removal rate of the synthesized zeolite on cationic heavy metals Pb (II) is up to 92.5 percent, and the adsorption removal rate on Cr (VI) is up to 35.7 percent. However, it should be noted that the fly ash mainly contains Si element and Al element, and the Si element and Al element mainly exist as amorphous aluminosilicate, which has the characteristics similar to the chemical composition of zeolite, and thus can be synthesized easily. Different from the earlier research, the invention mainly utilizes the main chemical composition Si (Si element is mainly amorphous II) in the biomass ashIn the form of silicon oxide), Al can be additionally added to adjust different SiO 2 /Al 2 O 3 The purpose of synthesizing A type, X type or Y type zeolite is achieved by the mol ratio. According to the invention, the biomass ash is synthesized into the zeolite by a mechanical grinding method, the method is reported for the first time that the biomass ash is utilized to synthesize the zeolite, and the fly ash also contains a small amount of heavy metal elements.
Specifically, the present invention has the following advantages:
1. the method utilizes the high content of Si in the biomass ash (the biomass ash raw material is usually rich in Si element and less in Al element, for example, the content of Si element in the rice hull ash can reach more than 90 percent), so the method has high selectivity on the biomass ash; and SiO is adjusted by adding an aluminium source, such as sodium aluminate 2 /Al 2 O 3 The mol ratio, the oriented synthesis of the needed zeolite;
2. by adopting the biomass ash, the aluminum source and the alkali solution as reaction participants and selecting the ball milling process with proper process conditions for processing, the whole reaction process can be operated at normal temperature and normal pressure without participation of complex reaction conditions such as high temperature and high pressure, and the like, and the method has the advantages of no waste gas emission, energy saving and environmental protection; in addition, the method of the invention utilizes the planetary ball mill, can carry out treatment under the conditions of normal temperature and normal pressure, and can be used for large-scale production; in addition, the biomass ash raw material applicable to the method has no requirement on the particle size, so that the method has wider application range;
3. the zeolite synthesized by the method can be used for treating heavy metal Pb in polluted wastewater 2+ Has good adsorption and removal effects.
In conclusion, the invention can utilize the specific Si source in the biomass ash, can be matched with an aluminum source to be added, adjusts the Si/Al molar ratio, and directionally obtains the zeolite product required in actual production and life.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2a is an SEM image of a rice hull ash feedstock of the present invention, and FIG. 2b is an SEM image of a zeolite product of example 1.
FIG. 3 is an XRD pattern of the rice hull ash raw material of the present invention and the zeolite product of example 1 (in which SOD peaks correspond to sodalite, which is also a kind of zeolite).
FIG. 4 shows the raw material of rice hull ash of the present invention, zeolite products of examples 1 and 2 and heavy metal Pb 2+ The adsorption removal rate and the equilibrium adsorption amount of the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the method of the invention is to mix biomass ash, aluminum source and alkali liquor, grind the mixture at normal temperature and normal pressure by adopting a plurality of grinding balls with different diameters, dissolve high content Si in the biomass ash by utilizing local high temperature and alkalinity of the solution, and add Al source and Na + And combining, centrifugally separating, filtering and drying to obtain a zeolite crystal sample.
The following are specific examples, in which the grinding balls used are all made of zirconia:
example 1
A process for the preparation of Na-A type zeolite, comprising the steps of:
(1) dissolving 40g of NaOH reagent in 1L of deionized water to prepare a NaOH solution with the concentration of 1 mol/L;
(2) rice hull ash (SiO in ash) with the mass of 4.624g 2 91 percent of mass fraction), 5.376g of sodium aluminate and 40ml of the alkali solution prepared in the step 1 are placed in a ball milling tank with the volume of 250ml for mixing, and 96 zirconia grinding balls with the diameter of 5mm and 41 zirconia grinding balls with the diameter of 10mm are added;
(3) putting the ball milling tank into a planetary ball mill, and working for 20 hours under the conditions of normal temperature and normal pressure and the rotating speed of 350 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Example 2
A process for the preparation of a Na-X zeolite comprising the steps of:
(1) 160g of NaOH reagent is taken and dissolved in 1L of deionized water to prepare NaOH solution with the concentration of 4 mol/L;
(2) biomass ash (SiO in ash) with a mass of 6.112g 2 87 percent of mass fraction), 5.224g of sodium aluminate and 40ml of the alkali solution prepared in the step 1 are placed in a ball milling tank with the volume of 250ml, and 80 zirconia grinding balls with the diameter of 5mm and 50 zirconia grinding balls with the diameter of 10mm are added;
(3) putting the ball milling tank into a planetary ball mill, and working for 8 hours at normal temperature and normal pressure and at the rotating speed of 350 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Example 3
A process for the preparation of a Na-X zeolite comprising the steps of:
(1) 160g of NaOH reagent is taken and dissolved in 1L of deionized water to prepare NaOH solution with the concentration of 4 mol/L;
(2) biomass ash (SiO in ash) with mass of 7.000g 2 85 percent of mass fraction), 5.580g of sodium aluminate and 40ml of the alkali solution prepared in the step 1 are placed in a ball milling tank with the volume of 250ml for mixing, and 90 zirconia grinding balls with the diameter of 5mm and 55 zirconia grinding balls with the diameter of 10mm are added;
(3) putting the ball milling tank into a planetary ball mill, and working for 24 hours under the conditions of normal temperature and normal pressure and the rotating speed of 500 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Example 4
A process for the preparation of a Na-X zeolite comprising the steps of:
(1) dissolving 80g of NaOH reagent in 1L of deionized water to prepare a NaOH solution with the concentration of 2 mol/L;
(2) biomass ash (SiO in ash) with a mass of 6.112g 2 87 percent of mass fraction), 5.224g of sodium aluminate and 40ml of the alkali solution prepared in the step 1 are placed in a ball milling tank with the volume of 250ml for mixing, and 80 zirconia grinding balls with the diameter of 5mm and 50 zirconia grinding balls with the diameter of 10mm are added;
(3) putting the ball milling tank into a planetary ball mill, and working for 20 hours under the conditions of normal temperature and normal pressure and the rotating speed of 200 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Example 5
A process for the preparation of Na-Y zeolite comprising the steps of:
(1) dissolving 40g of NaOH reagent in 1L of deionized water to prepare a NaOH solution with the concentration of 1 mol/L;
(2) biomass ash (SiO in ash) with a mass of 8.000g 2 91 percent of mass fraction), 4.331g of sodium aluminate and 40ml of the alkali solution prepared in the step 1 are placed in a ball milling tank with the volume of 250ml for mixing, and 90 zirconia grinding balls with the diameter of 5mm and 54 zirconia grinding balls with the diameter of 10mm are added;
(3) putting the ball milling tank into a planetary ball mill, and working for 20 hours under the conditions of normal temperature and normal pressure and the rotating speed of 350 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Example 6
A method for preparing Na-Y zeolite comprising the steps of:
(1) 160g of NaOH reagent is taken and dissolved in 1L of deionized water to prepare NaOH solution with the concentration of 4 mol/L;
(2) biomass ash (SiO in ash) with a mass of 8.000g 2 87 percent of mass fraction), 3.984g of sodium aluminate and the alkali prepared in the step 1Putting 40ml of the solution into a ball milling tank with the volume of 250ml, and adding 140 agate milling balls with the diameter of 5mm and 122 agate milling balls with the diameter of 10 mm;
(3) putting the ball milling tank into a planetary ball mill, and working for 8 hours at normal temperature and normal pressure and at the rotating speed of 350 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Example 7
A process for the preparation of Na-Y zeolite comprising the steps of:
(1) 160g of NaOH reagent is taken and dissolved in 1L of deionized water to prepare NaOH solution with the concentration of 4 mol/L;
(2) biomass ash (SiO in ash) with a mass of 7.000g 2 85% by mass), 2.465g of sodium aluminate and 40ml of the alkali solution prepared in the step 1 are placed in a ball milling tank with the volume of 250ml for mixing, and 130 agate grinding balls with the diameter of 5mm and 94 agate grinding balls with the diameter of 10mm are added;
(3) putting the ball milling tank into a planetary ball mill, and working for 24 hours under the conditions of normal temperature and normal pressure and the rotating speed of 500 rpm;
(4) taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, filtering, and drying at 85 ℃ for 24 hours to obtain the required zeolite product.
Performance testing
FIGS. 2a and 2b are SEM images of the rice hull ash as used in the present invention and the zeolite product of example 1, respectively, in a scanning electron microscope. It can be seen that the particles in the biomass ash raw sample are relatively regular, and the zeolite product obtained by the preparation process of the invention has rough surface and agglomeration phenomenon, and obvious regular crystal formation can be seen.
The size of the specific surface area of the rice hull ash used in the present invention as it is and the zeolite samples in examples 1 and 2 were analyzed using a fully automatic specific surface area and pore analyzer (Micromeritics, model: ASAP 2020). The results are shown in Table 1.
TABLE 1 specific surface area size of Rice Hull Ash and synthesized Zeolite
As can be seen from table 1, the zeolite products synthesized in examples 1 and 2 have 5-fold and 14-fold increases in specific surface area, respectively, as compared to the rice hull ash raw material. Therefore, the zeolite synthesized in the examples has an enhanced adsorption effect as compared with the rice hull ash raw material.
FIG. 3 is an XRD pattern of rice hull ash starting material and zeolite product from example 1 of the present invention measured by X' Pert Pro X-ray diffractometer, wherein A is Na-A type zeolite (molecular formula is Na) 12 Al 12 Si 12 O 48 (H 2 O) 27 ) SOD is sodalite (molecular formula is Na) 8 Al 6 Si 6 O 24 (OH) 2 (H 2 O) 2 ). The test parameters are as follows: the 2 theta angle ranges from 10 deg. to 65 deg., and the measurement step size is 0.013 deg.. It can be seen that the rice hull ash had a substantially amorphous composition, and after the treatment in the examples, a new crystalline peak appeared, which was analyzed to be a Na-A zeolite peak, and a part of the Na-A zeolite was converted into SOD (sodalite) due to the relationship between the time and the alkali concentration in the present examples.
0.4g of each of the rice hull ash raw material used in the experiment, the zeolite product synthesized in example 1, and the zeolite synthesized in example 2 was added to Pb 2+ The results of adsorption experiments performed for 180min in a solution having a concentration of 50mg/L and a volume of 40ml are shown in FIG. 4. It can be seen that the rice hull ash used in this test had a low unburned C content due to Si as the main component, and therefore heavy metals Pb were present 2+ The adsorption removal effect of (2) was not good, whereas the zeolites synthesized in examples 1 and 2 had heavy metal Pb 2+ The adsorption and removal rate of the catalyst is over 95 percent.
In the above examples, the synthesis of Na-type zeolite was exemplified, and when KOH solution was used instead of NaOH solution, K-type zeolite (specifically, K-A-type zeolite, K-X-type zeolite or K-Y-type zeolite, SiO in the target solid raw material was synthesized 2 /Al 2 O 3 The molar ratio of the required compound to Na typeThe zeolite is the same). In addition, because the biomass ash contains the Si element and the Al element, if the relative content of the Si element and the Al element meets the preparation requirement of the type of the target zeolite, no additional Al source is needed. The above examples are merely illustrative of the present invention, and the number of both small-sized grinding balls and large-sized grinding balls may be changed in proportion when the quality of the target solid raw material is changed.
In addition, other types of biomass ash can be used in the present invention in addition to rice hull ash (rice hull ash is a herbaceous ash and generally has a high Si content, while like woody biomass ash, such as wood biomass ash, has a low Si content, but is equally applicable to the present invention). In the invention, the biomass ash and SiO in the target solid raw material 2 、Al 2 O 3 The mass percentage of (b) is determined by conventional XRF (the content of Si element and Al element is measured by XRF, and the measurement results are expressed in the form of oxides).
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A method for preparing zeolite by directionally regulating biomass ash is characterized by comprising the following steps:
(1) the method comprises the following steps of (1) judging whether an Al source needs to be added to construct a target solid raw material or not according to the type of target zeolite and the relative content of Si and Al in the biomass ash raw material by adopting biomass ash as a raw material;
if an Al source needs to be added, matching the biomass ash raw material with the Al source to obtain a target solid raw material; wherein the Al source is sodium aluminate or potassium aluminate;
if the Al source does not need to be added, directly taking the biomass ash raw material as a target solid raw material;
(2) using NaOH solution with the concentration of 1-4 mol/L or KOH solution with the concentration of 1-4 mol/L as alkali solution, putting the target solid raw material and the alkali solution into a ball milling tank together according to the solid-to-liquid ratio of 10-25 g:100ml, mixing, and simultaneously adding at least two grinding balls with the same material and diameter specification, wherein the diameters of the grinding balls are within the range of 5-10 mm;
(3) placing the ball milling tank in a planetary ball mill to perform grinding treatment, setting the rotation speed of the grinding treatment to be 200-500 rpm, and setting the grinding time to be 4-20 h; in the polishing process, Si coexists in the reaction system 4+ 、Al 3+ And metal cations in the alkali solution are combined to form zeolite; after the grinding treatment is finished, taking out the ball milling tank, pouring out the solution in the ball milling tank together with the solid, centrifugally separating, filtering, drying the filter residue and removing the grinding balls to obtain a zeolite product;
wherein, in the step (1):
when the type of the target zeolite is A-type zeolite, SiO in the target solid raw material 2 /Al 2 O 3 The molar ratio is 2: 1; correspondingly, the zeolite product in the step (3) is a type A zeolite;
when the type of the target zeolite is X-type zeolite, SiO in the target solid raw material 2 /Al 2 O 3 A molar ratio of 2.2 or more and 3 or less; correspondingly, the zeolite product in the step (3) is X-type zeolite;
when the type of the target zeolite is Y-type zeolite, SiO in the target solid raw material 2 /Al 2 O 3 The molar ratio is more than 3; correspondingly, the zeolite product in the step (3) is Y-type zeolite;
in the step (2), the grinding balls are zirconia grinding balls or agate grinding balls;
the ratio of the mass of the target solid raw material to the total mass of the grinding balls is 1: 12;
when the grinding ball is a zirconia grinding ball, the grinding balls with the same material and the at least two diameter specifications are as follows: every 8g of the target solid raw material, 50-100 zirconia grinding balls with the diameter of 5mm and 30-37 zirconia grinding balls with the diameter of 10mm are used;
when the grinding balls are agate grinding balls, the grinding balls with the same material and the at least two diameter specifications are as follows: every 8g of the target solid raw material comprises 80-150 agate grinding balls with the diameter of 5mm and 75-84 agate grinding balls with the diameter of 10 mm.
2. The method of claim 1, wherein in step (1), the biomass ash is SiO 2 Is higher than 80% of biomass ash.
3. The method of claim 2, wherein the biomass ash is selected from the group consisting of rice hull ash and bagasse ash.
4. The method according to claim 1, wherein in the step (3), the drying is carried out at 85 ℃ for 24 h.
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