CN113816396A - Method for processing crystallized slurry of nano molecular sieve and method for preparing nano molecular sieve - Google Patents

Method for processing crystallized slurry of nano molecular sieve and method for preparing nano molecular sieve Download PDF

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CN113816396A
CN113816396A CN202111122036.3A CN202111122036A CN113816396A CN 113816396 A CN113816396 A CN 113816396A CN 202111122036 A CN202111122036 A CN 202111122036A CN 113816396 A CN113816396 A CN 113816396A
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molecular sieve
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powder
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CN113816396B (en
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齐静
张堃
李云
李伟
雍晓静
刘琰
王杰
武燕娟
关翀
金政伟
张伟
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Suzhou Zhiting New Material Technology Co ltd
National Energy Group Ningxia Coal Industry Co Ltd
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National Energy Group Ningxia Coal Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/00—Particle morphology
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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Abstract

The invention relates to the field of molecular sieves, and discloses a method for processing crystallized slurry of a nano molecular sieve and a method for preparing the nano molecular sieve. The processing method of the nanometer molecular sieve crystallization slurry comprises the following steps: (1) vacuum drying the crystallized slurry of the nano molecular sieve to obtain a solid product; (2) crushing the solid product to obtain powder; (3) mixing the powder with a solvent, and then carrying out ultrasonic oscillation treatment to obtain a solid-liquid mixed system; (4) filtering the solid-liquid mixing system to obtain a filter cake and a filtrate; wherein the filter cake contains molecular sieve grains, and the filtrate is evaporated to obtain the template agent and recycled. The method provided by the invention can simultaneously realize the filtration of the nano molecular sieve and the recovery of the template agent, the recovered template agent can be used as a raw material for preparing the nano molecular sieve for recycling, the process is simple, and the product yield is high.

Description

Method for processing crystallized slurry of nano molecular sieve and method for preparing nano molecular sieve
Technical Field
The invention relates to the field of molecular sieves, in particular to a method for processing crystallized slurry of a nano molecular sieve and a method for preparing the nano molecular sieve.
Background
The hydrothermal synthesis method is the main method for artificially synthesizing the molecular sieve at present, wherein the steps after the crystallization reaction comprise: and (3) filtering and washing the synthetic slurry (removing part of the template agent and metal ions), drying and dehydrating, and roasting to remove the template agent (decomposing the template agent). The removal of the template agent is usually realized through two steps, and the filtration and washing are used as the first step, so whether the ideal filtration and separation effect can be obtained or not can produce great influence on the quality, yield, cost and the like of the subsequently prepared molecular sieve product. For the filtration and washing of the non-nano molecular sieve (the particle size of the molecular sieve is more than 100 nanometers), conventional methods such as suction filtration, filter pressing and the like can be adopted, and the purpose of filtration and washing can be achieved because the pore size of the filter material is less than or equal to the size of the molecular sieve particles, and meanwhile, the recovery of part of the template agent can be realized. The particle size of the nano molecular sieve is less than 100 nanometers, the amount of the template agent used in the synthesis process is more, the nano molecular sieve presents a stable suspension state in the synthetic slurry, and the solid-liquid separation is difficult to realize by the conventional filtering method. The existing reported methods such as membrane separation, high-speed freezing centrifugation, flocculation and the like can realize solid-liquid separation of the nano molecular sieve, but have low treatment efficiency, high energy consumption and limited industrial application.
CN101053712A discloses a method for filtering and separating ultrafine molecular sieve and recovering mother liquor, which comprises the following steps: a) firstly, stirring the superfine molecular sieve slurry in a storage tank, and fully and uniformly pulping; then the superfine molecular sieve slurry is conveyed into a specially designed filtering device by a pump; filtering the superfine molecular sieve slurry by a filtering device, and then feeding the filtrate into a collecting tank; finally, the concentrated slurry returns to the storage tank; b) the filter device receives the superfine molecular slurry to make rapid turbulent motion in a flow channel provided with filter cloth, and forms a layer of thin filter cake on the filter cloth, and liquid in the superfine molecular slurry vertically penetrates through the thin filter cake and the filter cloth to permeate out, so that a form that the flow direction of the superfine molecular sieve slurry is vertically staggered with the flow direction of filtrate is formed; the filtrate can be collected into mother liquor after entering a collecting tank. The method has complex process and small treatment capacity, and is not suitable for actual industrial production.
CN103752083B discloses a filtering separation method of nano molecular sieve slurry, which comprises the steps of adjusting the pH of the nano molecular sieve slurry to 8-8.5 by using inorganic acid, and then carrying out at least one time of pressure filtration; dissolving the filter cake obtained by filter pressing in water to obtain a mixture, adjusting the pH value to be less than or equal to 5 by using organic acid, and carrying out at least one time of filter pressing. The method can realize the recovery of the nano molecular sieve particles, but repeated filtration is needed for many times, and the recovery of the template agent is not involved.
CN1261215C discloses a method for filtering a nano molecular sieve, which comprises the step of adding an alkaline medium, a non-electrolyte and water into a molecular sieve slurry, wherein the alkaline medium is added in an amount that the pH of a mixture is more than or equal to 12, and the volume ratio of the molecular sieve slurry to the non-electrolyte to the water is 1: (1-5): (0-2). The method can flocculate molecular sieve while inhibiting uncrystallized SiO2And (4) flocculation. The method cannot filter the nanometer molecular sieve due to the addition of alkaline substancesMeanwhile, the template agent is recovered.
In conclusion, how to provide a simple and reliable method for simultaneously realizing filtration of nano molecular sieve slurry and recovery of a template agent is a problem to be solved in the field of nano molecular sieve production at present.
Disclosure of Invention
The invention aims to provide a method for treating crystallized slurry of a nano molecular sieve and a method for preparing the nano molecular sieve, aiming at the problems that the nano molecular sieve in the prior art is difficult to filter, low in efficiency and difficult to simultaneously recover a template agent.
In order to achieve the above object, a first aspect of the present invention provides a method for processing a crystallized slurry of nano molecular sieve, the method comprising:
(1) vacuum drying the crystallized slurry of the nano molecular sieve to obtain a solid product;
(2) crushing the solid product to obtain powder;
(3) mixing the powder with a solvent, and then carrying out ultrasonic oscillation treatment to obtain a solid-liquid mixed system;
(4) filtering the solid-liquid mixing system to obtain a filter cake and a filtrate; wherein the filter cake contains molecular sieve grains, and the filtrate is evaporated to obtain the template agent and recycled.
The second aspect of the present invention provides a method for preparing a nano molecular sieve, wherein the method comprises the step of drying and roasting a filter cake obtained by the method for treating the crystallized slurry of the nano molecular sieve provided by the first aspect of the present invention to obtain the nano molecular sieve.
Through the technical scheme, the method provided by the invention has the following beneficial effects:
(1) the filtration of the nano molecular sieve can be realized, and the template agent is recovered;
(2) the recovered template agent can be used as a raw material for preparing the nano molecular sieve for recycling, so that the production cost is reduced, and the benefit is improved;
(3) the process is simple, the complex and expensive equipment can be avoided, and the product yield is high;
(4) the prepared nano-sized particles have good dispersibility and low agglomeration degree.
Drawings
FIG. 1 is an XRD pattern of molecular sieves A1 and A2 prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of molecular sieves B1 and B2 prepared in example 2 of the present invention;
FIG. 3 is a scanning electron micrograph of molecular sieve A1 prepared according to example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of molecular sieve B1 prepared according to example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of molecular sieve A2 prepared according to example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of molecular sieve B2 prepared according to example 2 of the present invention.
Detailed Description
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 following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for processing crystallized slurry of a nano molecular sieve, which comprises the following steps:
(1) vacuum drying the crystallized slurry of the nano molecular sieve to obtain a solid product;
(2) crushing the solid product to obtain powder;
(3) mixing the powder with a solvent, and then carrying out ultrasonic oscillation treatment to obtain a solid-liquid mixed system;
(4) filtering the solid-liquid mixing system to obtain a filter cake and a filtrate; wherein the filter cake contains molecular sieve grains, and the filtrate is evaporated to obtain the template agent and recycled.
In the invention, the nano molecular sieve crystallization slurry is formed after the nano molecular sieve raw material, the template agent and the solvent are mixed and hydrothermally synthesized and crystallized, and comprises molecular sieve grains, the template agent, a silicon source, an aluminum source, a phosphorus source, water, alkali and an auxiliary agent. Preferably, the average particle size of the molecular sieve crystal grains is 1-100 nm;
preferably, the templating agent is an organic amine;
preferably, the content of the template in the crystallized slurry of the nano molecular sieve is 0-50 wt%.
In some embodiments of the present invention, in step (1), the vacuum drying may be performed by using equipment conventionally used in the art for vacuum drying, and the present invention is not particularly limited thereto, and may be, for example, a vacuum drying oven, a rotary vacuum dryer, or a vacuum tray dryer. In the vacuum drying process, a filter is preferably added at the vacuumizing port of the equipment to avoid extracting the molecular sieve grains in the crystallized slurry in the vacuumizing process.
In the invention, the vacuum drying can evaporate and separate water in the crystallized slurry and low boiling point organic matters generated by the decomposition of part of the template agent in the crystallization reaction to obtain a solid product. For better evaporation separation effect, preferably, the vacuum drying conditions include: the temperature is 30-60 ℃ and the time is 10-12 h.
In some embodiments of the present invention, in step (1), the solid product contains molecular sieve grains and a template, and preferably, the solid product contains water in an amount of not more than 2 wt% to facilitate the subsequent step of pulverization.
In some embodiments of the present invention, in step (2), the pulverization may be performed by a method conventional in the art as long as the solid product can be pulverized and a powder is obtained, and for example, the pulverization may be performed by a high-speed pulverizer, a jet mill, or a ball mill.
In the present invention, the particle size of the powder is a factor having an important influence on the filtering of the molecular sieve and the recovery effect of the template. The large particle size can cause that the template agent in the powder particles can not be fully contacted with the solvent in the subsequent step, thereby reducing the recovery rate of the template agent; the particle size is smaller, which is more beneficial to the dissolution and recovery of the template agent in the solvent, but the difficulty of the subsequent solid-liquid separation is increased, and the filtration efficiency of the molecular sieve is influenced. For better molecular sieve filtration and template agent recovery, the powder preferably has a particle size of 80-200 meshes.
In the present invention, it is preferable that the water content in the powder is not higher than 2 wt% to facilitate the subsequent recovery of the template.
In some embodiments of the present invention, in step (3), the solvent is preferably one or more of water, methanol, ethanol, and acetone, and is used for extracting the template in the powder. In order to obtain better template agent extraction effect, the mass ratio of the powder to the solvent is preferably 1: (1-5).
In the present invention, the mixing is not particularly limited as long as the powder material can be sufficiently dispersed in the solvent. Preferably, the powder material can be added into the solvent at room temperature, and the mechanical stirring is started until the powder material is uniformly dispersed in the solvent.
In some embodiments of the present invention, in step (3), the ultrasonic oscillation treatment can further enhance the extraction effect of the solvent on the template agent, and at the same time, helps to separate out impurities in the powder material, and preferably, the conditions of the ultrasonic oscillation include: the temperature is 40-60 deg.C, frequency is 20-40Hz, and time is 2-4 h. In the obtained solid-liquid mixed system, the particle size of the solid particles is in the range of 10 to 100. mu.m, and therefore, it can be filtered by a conventional solid-liquid separation method.
In some embodiments of the present invention, in step (4), the filtration may adopt a method conventionally used in the art for solid-liquid separation in molecular sieve preparation, such as centrifugation, suction filtration, and pressure filtration. The main component in the filter cake obtained after filtration is molecular sieve crystal grains which can be used in the subsequent preparation steps of the nano molecular sieve.
In the present invention, the evaporation treatment of the filtrate is preferably performed by vacuum concentration to separate the template from the solvent, and for example, the evaporation treatment may be performed using a rotary vacuum evaporator. For better separation and recovery of the template agent, preferably, the evaporation treatment conditions include: the temperature is 50-80 ℃ and the time is 1-3 h.
According to the invention, the nano molecular sieve crystallization slurry is subjected to vacuum drying, the molecular sieve crystal grains dispersed in the nano molecular sieve crystallization slurry, unreacted residual template agent and a small amount of residual molecular sieve preparation raw materials are combined into a solid product, and then the solid product is converted into powder with a specific particle size range through crushing, so that the powder meets the extraction effect of a solvent on the template agent, and meanwhile, the solid-liquid separation can be realized by using a conventional method, and further, the template agent is recovered. The method for treating the crystallized slurry of the nano molecular sieve has the advantages of simple process and strong practicability, can effectively solve the problems of high difficulty, low efficiency and high cost of filtering the nano molecular sieve, and simultaneously realizes the recovery of the template agent.
The second aspect of the present invention provides a method for preparing a nano molecular sieve, wherein the method comprises the step of drying and roasting a filter cake obtained by the method for treating the crystallized slurry of the nano molecular sieve provided by the first aspect of the present invention to obtain the nano molecular sieve.
In the above production method, preferably, the conditions under which the filter cake is dried include: the temperature is 80-120 ℃, and the time is 8-24 h; the conditions for roasting after drying include: the temperature is 500-600 ℃, and the time is 4-10 h.
In the invention, the nano molecular sieve product prepared by the method has excellent dispersibility and low agglomeration degree.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates the processing of a crystallized slurry of a ZSM-5 nanosized molecular sieve and the preparation of the molecular sieve according to the method of the present invention.
(1) Preparing crystallized slurry: ZSM-5 nanomolecular sieve crystallization slurry was prepared according to the method disclosed in the section "Van Grieken R, Sotelo J L, Menendez J M.et al, organic crystallization mechanism in the synthesis of nanocrystalline ZSM-5[ J ]. microporous Mesopro Mater,2000,39(1-2):135 & 147" 2.1Samples preparation ";
(2) taking 500g of the ZSM-5 nano molecular sieve crystallized slurry prepared in the step (1), and carrying out vacuum drying for 12h at the temperature of 60 ℃ to obtain a solid product;
(3) crushing the solid product to obtain 20g of 150-mesh powder with the water content of 2 wt%;
(4) adding the powder into 100g of water (namely the mass ratio of the powder to the solvent is 1: 5), stirring and uniformly mixing, and carrying out ultrasonic oscillation treatment for 3h at the temperature of 50 ℃ and the frequency of 40Hz to obtain a solid-liquid mixed system;
(5) carrying out suction filtration on the solid-liquid mixed system to obtain a filter cake and filtrate; evaporating the filtrate at 80 ℃ for 3h to obtain a template agent (marked as M1), and recovering;
(6) and (3) drying the filter cake obtained in the step (5) at 120 ℃ for 24h, and then roasting at 550 ℃ for 6h to obtain the molecular sieve (recorded as A1).
Preparing the molecular sieve by using the recovered template agent:
the molecular sieve was prepared according to the method disclosed in the section "Van Grieken R, Sotelo J L, Menendez J M.et al, organic crystallization mechanism in the synthesis of nanocrystalline ZSM-5[ J ]. microporous Mesopoprer Mater,2000,39(1-2): 135-147" section "2.1 Samples preparation", wherein the molecular sieve (designated A2) was prepared using M1 recovered in the above step (5) as a templating agent.
Example 2
This example illustrates the processing of crystallized slurry of nano Beta molecular sieve and the preparation of the molecular sieve according to the method of the present invention.
(1) Preparing crystallized slurry: preparing nano Beta molecular sieve crystallized slurry according to the method disclosed in example 1 in CN 102464330B;
(2) taking 2000g of the nano Beta molecular sieve crystallized slurry prepared in the step (1), and carrying out vacuum drying for 10h at the temperature of 45 ℃ to obtain a solid product;
(3) crushing the solid product to obtain 800g of 100-mesh powder with the water content of 0.5 wt%;
(4) adding the powder into 800g of 50 wt% ethanol aqueous solution (namely the mass ratio of the powder to the solvent is 1: 1), stirring and uniformly mixing, and carrying out ultrasonic oscillation treatment for 2h under the conditions of 40 ℃ and the frequency of 35Hz to obtain a solid-liquid mixed system;
(5) carrying out suction filtration on the solid-liquid mixed system to obtain a filter cake and filtrate; evaporating the filtrate at 65 ℃ for 2h to obtain a template (marked as M2), and recovering;
(6) and (3) drying the filter cake obtained in the step (5) at 100 ℃ for 12h, and then roasting at 550 ℃ for 6h to obtain the molecular sieve (recorded as B1).
Preparing the molecular sieve by using the recovered template agent:
a molecular sieve was prepared as disclosed in example 1 in CN102464330B, wherein the molecular sieve (denoted as B2) was prepared using M2 recovered in the above step (5) as a template.
Example 3
This example illustrates the processing of a crystalline slurry of Silicalite-1 nanosized molecular sieves and the preparation of the molecular sieves according to the method of the present invention.
(1) Preparing crystallized slurry: the Silicalite-1 nanometer molecular sieve crystallization slurry is prepared according to the method disclosed in the section of 1.1 preparation of Silicalite-1 in the literature' Yi Shuangfeng, Xuebuqing, Silicalite-1 nanometer crystal size control synthesis [ J ]. advanced chemical school, 2003,24(7): 1169-;
(2) taking 200g of the Silicalite-1 molecular sieve crystallized slurry prepared in the step (1), and carrying out vacuum drying for 11h at the temperature of 30 ℃ to obtain a solid product;
(3) crushing the solid product to obtain 100g of 120-mesh powder with the water content of 1 wt%;
(4) adding the powder into 300g of mixed solution of ethanol and acetone (the mass ratio of the ethanol to the acetone is 2: 1) (namely the mass ratio of the powder to the solvent is 1: 3), stirring and uniformly mixing, and then carrying out ultrasonic oscillation treatment for 2.5h under the conditions of 45 ℃ and 30Hz frequency to obtain a solid-liquid mixed system;
(5) carrying out suction filtration on the solid-liquid mixed system to obtain a filter cake and filtrate; evaporating the filtrate at 50 ℃ for 1h to obtain a template agent (marked as M3), and recovering;
(6) and (3) drying the filter cake obtained in the step (5) at 80 ℃ for 10h, and then roasting at 500 ℃ for 8h to obtain the molecular sieve (recorded as C1).
Preparing the molecular sieve by using the recovered template agent:
the molecular sieve was prepared according to the method disclosed in "preparation of 1.1 Silicalite-1" in Yi Shuangfeng, Xuebi Qing. Silicalite-1 nanocrystals, proceedings of chemistry of advanced schools, 2003,24(7): 1169-.
Example 4
This example illustrates the processing of a crystallized slurry of a ZSM-5 nanosized molecular sieve and the preparation of the molecular sieve according to the method of the present invention.
(1) Preparing crystallized slurry: the same as example 1;
(2) taking 200g of ZSM-5 molecular sieve crystallized slurry prepared in the step (1), and carrying out vacuum drying for 10h at 40 ℃ to obtain a solid product;
(3) crushing the solid product to obtain 100g of 80-mesh powder with the water content of 1.5 wt%;
(4) adding the powder into 100g of methanol (namely the mass ratio of the powder to the solvent is 1: 1, stirring and uniformly mixing, and carrying out ultrasonic oscillation treatment for 4h at the temperature of 55 ℃ and the frequency of 20Hz to obtain a solid-liquid mixed system;
(5) carrying out suction filtration on the solid-liquid mixed system to obtain a filter cake and filtrate; evaporating the filtrate at 70 ℃ for 3h to obtain a template agent (marked as M4), and recovering;
(6) and (3) drying the filter cake obtained in the step (5) at 120 ℃ for 8h, and then roasting at 600 ℃ for 4h to obtain the molecular sieve (recorded as D1).
Preparing the molecular sieve by using the recovered template agent:
the molecular sieve was prepared according to the method disclosed in the section "Van Grieken R, Sotelo J L, Menendez J M.et al, organic crystallization mechanism in the synthesis of nanocrystalline ZSM-5[ J ]. microporous Mesopoprer Mater,2000,39(1-2): 135-147" section "2.1 Samples preparation", wherein the molecular sieve (D2) was prepared using M4 recovered in the above step (5) as a templating agent.
Example 5
This example illustrates the processing of crystallized slurry of nano Beta molecular sieve and the preparation of the molecular sieve according to the method of the present invention.
(1) Preparing crystallized slurry: preparing nano Beta molecular sieve crystallized slurry according to the method disclosed in example 1 in CN 102464330B;
(2) taking 100g of the nano Beta molecular sieve crystallized slurry prepared in the step (1), and carrying out vacuum drying for 12h at 50 ℃ to obtain a solid product;
(3) crushing the solid product to obtain 50g of 200-mesh powder with the water content of 2%;
(4) adding the powder into 200g of ethanol (namely, the mass ratio of the powder to the solvent is 1: 4, stirring and uniformly mixing, and carrying out ultrasonic oscillation treatment for 3.5h at the temperature of 60 ℃ and the frequency of 25Hz to obtain a solid-liquid mixed system;
(5) carrying out suction filtration on the solid-liquid mixed system to obtain a filter cake and filtrate; evaporating the filtrate at 60 ℃ for 2h to obtain a template agent (marked as M5), and recovering;
(6) and (3) drying the filter cake obtained in the step (5) at 90 ℃ for 16h, and then roasting at 550 ℃ for 7h to obtain the molecular sieve (recorded as E1).
Preparing the molecular sieve by using the recovered template agent:
a molecular sieve was prepared as disclosed in example 1 in CN102464330B, wherein the molecular sieve (designated as E2) was prepared using M5 recovered in the above step (5) as a template.
Comparative example 1
The method of example 1 was used except that in the step (3), the powder had a particle size of 50 mesh and the conditions were otherwise the same as in example 1. The recovered template agent is marked as D1-M1, and the prepared molecular sieve is marked as D1-A1; the molecular sieve prepared by using the recovered template agent is marked as D1-A2.
Comparative example 2
The method of example 1 was used except that in the step (3), the moisture content of the powder was 5% by weight, and the other conditions were the same as in example 1. The recovered template agent is marked as D2-M1, and the prepared molecular sieve is marked as D2-A1; the molecular sieve prepared by using the recovered template agent is marked as D2-A2.
Test example
1. X-ray diffraction testing of molecular sieves
The molecular sieves a1 and a2 prepared in example 1 and the molecular sieves B1 and B2 prepared in example 2 were examined by X-ray diffraction analysis, and the results are shown in fig. 1 and 2.
As can be seen from fig. 1, in the X-ray diffraction patterns of a1 and a2, distinct MFI structure diffraction peaks appear at 8 °, 8.8 °, 23.5 °, 29.8 ° and 45.1 ° of 2 θ, indicating that a1 and a2 are both ZSM-5 nano molecular sieves; as can be seen from fig. 2, in the X-ray diffraction patterns of B1 and B2, distinct MFI structure diffraction peaks appear at both 7.8 ° and 22.4 ° 2 θ, indicating that both B1 and B2 are nano Beta molecular sieves. Therefore, the template agent recovered by the method for treating the nano molecular sieve crystallization slurry provided by the invention can be directly used as a raw material for preparing the molecular sieve for recycling.
2. Recovery of template agent
The recovery rates of the templating agents in examples 1-5 and comparative examples 1-2 were respectively calculated according to the following formulas, and the results are shown in Table 1.
Figure BDA0003277599650000121
Wherein, P is the recovery rate of the template agent;
W1the template agent mass recovered after the filtration and separation of the nano molecular sieve crystallized slurry;
W2the mass of the raw material template agent which is used for preparing the nano molecular sieve.
TABLE 1
Figure BDA0003277599650000122
As can be seen from table 1, the processing method of the crystallized slurry of nano molecular sieve (i.e. preparing molecular sieves a1, B1, C1, D1 and E1) provided by the present invention has higher recovery rate of the template agent than the technical scheme of the conventional separation method (i.e. preparing molecular sieves a2, B2, C2, D2 and E2). Whereas comparative examples 1 and 2 did not employ the process of the present invention, the templating agent recovery was significantly lower.
3. Dispersivity of molecular sieve products
The results of the scanning electron microscope tests on the molecular sieves a1 and a2 prepared in example 1 and the molecular sieves B1 and B2 prepared in example 2 are shown in fig. 3 to 6, respectively.
In fig. 3 and 4, the particles of molecular sieves a1 and B1 prepared from the filter cake obtained by the method for treating crystallized slurry of nano molecular sieve of the present invention are well and uniformly distributed, and the agglomeration phenomenon is not obvious; in contrast, the molecular sieves a2 and B2 prepared by the conventional method in fig. 5 and 6 have non-uniform particle distribution and serious agglomeration. The comparison shows that the nano-sized particles prepared by the method have good dispersibility and low agglomeration degree.
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 combinations of various technical features 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 (10)

1. A method for processing crystallized slurry of a nano molecular sieve is characterized by comprising the following steps:
(1) vacuum drying the crystallized slurry of the nano molecular sieve to obtain a solid product;
(2) crushing the solid product to obtain powder;
(3) mixing the powder with a solvent, and then carrying out ultrasonic oscillation treatment to obtain a solid-liquid mixed system;
(4) filtering the solid-liquid mixing system to obtain a filter cake and a filtrate; wherein the filter cake contains molecular sieve grains, and the filtrate is evaporated to obtain the template agent and recycled.
2. The method of claim 1, wherein the crystallized slurry of nanomolecular sieve comprises molecular sieve crystallites, a templating agent, a source of silicon, a source of aluminum, a source of phosphorus, water, a base, and a promoter;
preferably, the templating agent is an organic amine;
preferably, in the nano molecular sieve crystallization slurry, the content of the template agent is 0-50 wt%;
preferably, the average particle size of the molecular sieve grains is 1-100 nm.
3. The method of claim 1 or 2, wherein in step (1), the vacuum dried strip comprises: the temperature is 30-60 ℃ and the time is 10-12 h.
4. The method according to claim 1 or 2, wherein in the step (2), the powder has a particle size of 80 to 200 mesh and a water content of not more than 2% by weight.
5. The method according to claim 1 or 2, wherein in step (3), the solvent is one or more of water, methanol, ethanol and acetone.
6. The method according to claim 5, wherein in the step (3), the mass ratio of the powder to the solvent is 1: (1-5).
7. The method according to claim 5 or 6, wherein in step (3), the conditions of the ultrasonic oscillation process include: the temperature is 40-60 deg.C, frequency is 20-40Hz, and time is 2-4 h.
8. The method according to claim 1 or 2, wherein in step (4), the conditions of the evaporation process include: the temperature is 50-80 ℃ and the time is 1-3 h.
9. A preparation method of the nano molecular sieve is characterized in that the filter cake in the claim 1 is dried and roasted to obtain the nano molecular sieve.
10. The method of claim 9, wherein the drying conditions comprise: the temperature is 80-120 ℃, and the time is 8-24 h; the roasting conditions comprise: the temperature is 500-600 ℃, and the time is 4-10 h.
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Citations (5)

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US20050063901A1 (en) * 2003-09-24 2005-03-24 Miller Stephen J. Preparation of molecular sieves involving spray drying
CN102319583A (en) * 2011-06-03 2012-01-18 神华集团有限责任公司 Method for removing residual silicasol in SAPO-34 molecular sieve product
CN106044793A (en) * 2016-08-05 2016-10-26 江苏天诺新材料科技股份有限公司 Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate
CN112250084A (en) * 2020-09-25 2021-01-22 浙江浙能技术研究院有限公司 Method for rapidly heat treating CHA molecular sieve slurry
CN112624146A (en) * 2021-01-12 2021-04-09 国家能源集团宁夏煤业有限责任公司 Molecular sieve and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050063901A1 (en) * 2003-09-24 2005-03-24 Miller Stephen J. Preparation of molecular sieves involving spray drying
CN102319583A (en) * 2011-06-03 2012-01-18 神华集团有限责任公司 Method for removing residual silicasol in SAPO-34 molecular sieve product
CN106044793A (en) * 2016-08-05 2016-10-26 江苏天诺新材料科技股份有限公司 Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate
CN112250084A (en) * 2020-09-25 2021-01-22 浙江浙能技术研究院有限公司 Method for rapidly heat treating CHA molecular sieve slurry
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