CN111115654A - Method for synthesizing molecular sieve - Google Patents
Method for synthesizing molecular sieve Download PDFInfo
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- CN111115654A CN111115654A CN201811275604.1A CN201811275604A CN111115654A CN 111115654 A CN111115654 A CN 111115654A CN 201811275604 A CN201811275604 A CN 201811275604A CN 111115654 A CN111115654 A CN 111115654A
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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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- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The present invention belongs to the field of zeolite molecular sieve synthesizing technology, and is especially method of synthesizing molecular sieve in super-gravitational and super-short time. And filtering, washing and drying after crystallization to obtain the uniformly distributed nano zeolite product. The invention has the advantages of low synthesis cost, ultra-short aging crystallization time, high purity of the obtained zeolite, simple operation process, high yield of a single kettle and capability of reducing the discharge of mother liquor. Sample XRD showed the resulting product to be well crystalline. SEM showed that the nano zeolites appeared to be uniformly distributed. Can be used for industrially synthesizing molecular sieves.
Description
Technical Field
The invention relates to a method for synthesizing molecular sieves, belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to a method for synthesizing zeolite molecular sieves with different sizes in a supergravity ultrashort time.
Background
Because of the action of centrifugal force, the liquid is highly dispersed in the filler layer, the turbulence degree is increased, the mixing is intensified, and the mass transfer efficiency is greatly improved. Compared with the traditional equipment, the volume mass transfer coefficient of the super-gravity rotating bed can be improved by 1-2 orders of magnitude, so that the purposes of reducing the size of the equipment, reducing the investment cost and shortening the crystallization time can be achieved. The synthesis aging time of the conventional molecular sieve is 4-48h, and the cost is high.
CN108217674A discloses a hypergravity method of a silicon-aluminum molecular sieve, which adopts an internal circulation hypergravity reactor as a reaction device, a silicon source and an aluminum source are simultaneously pumped into the hypergravity reactor through a liquid inlet pipe, the retention time in the hypergravity reactor is 1-30h, and the internal is heated at the same time, so as to obtain the molecular sieve. CN201210287914.1 discloses a preparation method of a mesoporous ZSM-5 zeolite molecular sieve, which takes tetraethoxysilane as a silicon source, sodium metaaluminate as an aluminum source and a bifunctional triammonium quaternary ammonium salt cationic surfactant as a template agent, and prepares the mesoporous zeolite molecular sieve with ZSM-5 micropore crystallization pore walls by a hydrothermal synthesis method under an alkaline condition. The quaternary ammonium salt surfactant adopted by the invention is used as a ZSM-5 zeolite structure guiding agent to generate micropores, and the aggregation of long hydrophobic alkyls at two ends of the micropores forms mesopores. The invention effectively changes the amorphous pore wall structure of the traditional mesoporous material, enables the traditional mesoporous material to have crystallized pore walls, greatly improves the acidity and hydrothermal stability of the mesoporous material, and the prepared mesoporous ZSM-5 zeolite molecular sieve has a special mesopore/micropore multiple pore structure, can avoid the defect of a single pore structure, improves the mass transfer efficiency, and has wide application prospect in the aspects of macromolecule catalysis, adsorption, separation and the like. CN201310020530.8 introduces a ZSM-5 zeolite synthesis method, which uses a polar molecule, namely hexadecyl trimethyl ammonium bromide to intercalate layered silicate Na-kenyaite to obtain a Na-kenyaite-CTAB intercalation compound, then uses tetraalkyl ammonium hydroxide as a template agent to synthesize a ZSM-5 type molecular sieve, and strips the product to obtain a flaky ZSM-5 molecular sieve crystal. The intercalation process enlarges the interlayer spacing and keeps a certain distance to avoid mutual fusion, the growth speed is controlled in the crystallization process to ensure that the molecular sieve can nucleate and grow along the laminate of the layered substance, after the reaction is finished, the template agent and the polar molecules are removed, and finally, the two-dimensional structure of the layered substance is also kept while the molecular sieve is obtained, thereby greatly improving the contactability of the macromolecular reactant and the active acid center and improving the reaction performance. CN200910072747.7 describes a preparation method of ZSM-5 molecular sieve, adding pre-crystallization seed crystal into a gel system for synthesizing nano ZSM-5 molecular sieve without template agent, then crystallizing at 160-180 ℃ for 24 hours, cooling to room temperature, centrifugally filtering, washing, drying and roasting the product to obtain the ZSM-5 molecular sieve without impurity phase.
In the method described in the above patent, the aging process is complicated, the crystallization process is basically static crystallization, the zeolite growth process is not stirred, the required aging time is 4 to 48 hours, the reaction time is long, and the synthesis process for preparing the molecular sieve is complicated.
Among them, CN108217674A, although a supergravity reactor is also used, is mainly to realize controllable particle size, controllable structure, and needs to be realized at higher rotation speed.
The invention uses the hypergravity reactor to strengthen the microscopic process, uses the cheap silicon source, controls the proportion thereof, stirs in the crystallization process, greatly shortens the aging time to less than 1 hour, greatly shortens the crystallization time, and promotes the synthesis efficiency.
Disclosure of Invention
The key technical problems to be solved by the invention are that the zeolite molecular sieve prepared by the prior art has complex synthesis steps, long aging time, low synthesis efficiency and long crystallization time. The invention provides a novel method for synthesizing molecular sieves, which has the characteristics that when the method is used for synthesizing the molecular sieves, the synthesis step is simple and convenient to realize under the low rotating speed of a supergravity reactor, the industrialization is easy, the aging time is greatly shortened to be within one hour, the crystallization efficiency is improved, and the molecular sieves with different sizes are obtained.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for synthesizing molecular sieve uses a supergravity reactor, and features that the retention time of reaction material in the supergravity reactor is less than 60 min.
In the technical scheme, the preferable retention time is less than 45 minutes; preferably less than 30 minutes.
In the technical scheme, the preferable retention time is 1min-10 min; preferably 3min-8 min.
In the above technical solutions, the residence time in the hypergravity reactor is referred to as aging time.
In the technical scheme, the temperature of the hypergravity reactor is preferably not more than 80 ℃; more preferably not more than 60 ℃; preferably room temperature.
In the above technical scheme, the rotation speed of the reactor is preferably 1000-.
In the technical scheme, the flow rate of the reactor is preferably 20ml/min-1000 ml/min.
The method comprises the following specific steps:
the mixture ratio of the materials is as follows:
H2O/SiO2＝5-1000；T/SiO20.1-200; Si/Al is 50- ∞; weighing quantitative template agent T, silicon source and aluminum source; after the flow of the super-gravity metering pump is corrected, washing is carried out for standby; introducing the solution into a hypergravity reactor, adjusting the flow and the hypergravity rotation speed, circularly entering the hypergravity reactor, and recovering the solution after the solution is kept for a certain time to obtain a liquid to be crystallized; then placing the mixture in a closed crystallization kettle, and crystallizing at high temperature for 4-24 hours at 60-300 ℃ under the stirring of 10-1000 rpm; cooling to room temperature, washing and centrifuging the product, and drying to obtain ZSM-5 zeolites with different sizes; the template agent T is one or at least one of n-propylamine, organic piperidine alkali, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide and quaternary ammonium salt.
The method comprises the following specific steps:
the mixture ratio of the materials is as follows:
the feeding molar ratio of the synthetic mother liquor is
H2O/SiO2＝5-1000；17Na2O/SiO21-100; the synthesis comprises the following specific steps: dissolving sodium hydroxide in deionized water, stirring vigorously, adding an aluminum source into the mixed solution, and adding a silicon source after the mixed solution is uniformly stirred; after the flow of the super-gravity metering pump is corrected, washing is carried out for standby; introducing the solution into a hypergravity reactor, adjusting the flow and the hypergravity rotation speed, circularly entering the hypergravity reactor, and recovering the solution after the solution is kept for a certain time to obtain a liquid to be crystallized; then placing the mixture in a closed crystallization kettle at the temperature of between 50 and 300 ℃ and at the temperature of 1High-temperature crystallization is carried out for 2 to 24 hours under the stirring of 0 to 1000 rpm; and cooling to room temperature, washing and centrifuging the product, and drying to obtain FAU zeolite with different sizes.
The silicon source is one or at least one of cheap silica sol and sodium silicate; the aluminum source is one or at least one of aluminum sulfate octadecahydrate, aluminum isopropoxide or metaaluminate, aluminate, sodium metaaluminate and aluminum sheet.
The product of the invention is zeolite molecular sieve, and the supergravity reactor is mainly used in the aging crystallization growth process of zeolite for supergravity mixing, the retention time is ultrashort, and meanwhile, stirring is added in the crystallization process, so that the aging crystallization time is greatly shortened, the zeolite synthesis is controlled, and uniform zeolite is obtained. Meanwhile, the synthesis method not only can effectively improve the synthesis efficiency, but also has the characteristics of good parallelism, repeatability, operability and the like, and has better practicability and effectiveness. The method for synthesizing the molecular sieve has the unexpected technical effect, avoids the long aging time in the traditional preparation method, has high crystallinity of the obtained molecular sieve, ultrashort aging crystallization time and high single kettle efficiency, uses the silicon source as a cheap raw material, is more suitable for industrialization, and is simple, convenient and feasible. The ZSM-5 zeolite prepared by the method is applied to olefin cracking reaction, and the nano ZSM-5 catalyst has good catalytic effect after the reaction time is 6 hours at the reaction temperature of 550 ℃, the conversion rate of butylene reaches 89%, and the selectivity of propylene reaches 25%.
The following examples further illustrate the method for synthesizing nano molecular sieves uniformly distributed in different sizes in a short time by supergravity.
Drawings
Some of the figures in the examples are set forth in the accompanying drawings.
Figure 1 is the XRD spectrum of the product of example 1.
FIG. 2 is an SEM photograph of the product of example 1.
FIG. 3 is an SEM photograph of the product of comparative example 2.
FIG. 4 is an XRD photograph of the product of comparative example 3.
Detailed Description
The invention is further described below by way of examples.
Example 1
The synthesis method comprises the following steps: and (4) after the flow of the supergravity metering pump is corrected, washing for later use. 9g of tetrapropylammonium hydroxide and 0.09g of aluminum sulfate octadecahydrate were added to 15g of water, and 6.7g of silica sol was added. And (3) introducing the solution into a supergravity reactor, adjusting the flow rate to be 50ml/min, adjusting the supergravity rotating speed to be 1500rpm, circularly introducing the solution into the supergravity reactor, and recovering the solution after the solution stays for 8min to obtain the liquid to be crystallized. Then placing the mixture into a crystallization kettle, heating to 180 ℃, stirring at 150rpm, crystallizing for 8 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product.
FIG. 1 is an XRD spectrum of the product obtained in example 1, and it can be seen that the product has a characteristic diffraction peak of ZSM-5 and has a higher crystallinity. FIG. 2 is an SEM photograph of the product obtained in example 1, and it can be seen that the sample exhibits a uniform morphology.
Example 2
The same conditions as in example 1 were used, the residence time was changed to 15min and the flow rate in the hypergravity reactor was adjusted to 60ml/min to obtain the final product. The XRD characterization result of the sample shows that the product has a ZSM-5 characteristic diffraction peak, and the SEM picture shows that the sample is a uniform nano ZSM-5 molecular sieve, and the particle size is slightly increased.
Example 3
The same conditions as in example 1 were used, the residence time was varied to 20min and the rotational speed of the hypergravity reactor was adjusted to 1600rpm to obtain the final product. The XRD characterization result of the sample shows that the product has a ZSM-5 characteristic diffraction peak, and the SEM picture shows that the sample is a uniform nano ZSM-5 molecular sieve with uniform particle size.
Example 4
The same conditions as in example 1 were used, the residence time was varied to 30min and the flow rate of the hypergravity reactor was adjusted to 60/min to obtain the final product. The XRD characterization result of the sample shows that the product has a ZSM-5 characteristic diffraction peak, and the SEM picture shows that the sample is a uniform nano ZSM-5 molecular sieve with uniform particle size.
Example 5
The same conditions as in example 1 were used, the residence time was varied to 40min and the rotational speed of the hypergravity reactor was adjusted to 1600rpm to obtain the final product. The XRD characterization result of the sample shows that the product has a ZSM-5 characteristic diffraction peak, and the SEM picture shows that the sample is a uniform nano ZSM-5 molecular sieve with uniform particle size.
Example 6
The final product was obtained by adjusting the hypergravity rotation speed to 1400rpm using the same conditions as in example 1. The XRD characterization result of the sample shows that the product has a ZSM-5 characteristic diffraction peak, and the SEM picture shows that the sample is a uniform nano ZSM-5 molecular sieve.
Example 7
The same conditions as in example 1 were used, and the crystallization stirring speed was changed to 250rpm, to obtain the final product. The XRD characterization result of the sample shows that the product has a ZSM-5 characteristic diffraction peak, and the SEM picture shows that the sample is a uniform nano ZSM-5 molecular sieve.
Example 8
The synthesis method comprises the following steps: adding 3g of tetrapropylammonium bromide and 0.05g of aluminum sulfate octadecahydrate into 13.2g of water, adding 8.7g of silica sol, introducing the solution into a supergravity reactor, adjusting the flow rate to be 60ml/min, adjusting the supergravity rotating speed to be 1600rpm, circularly entering the supergravity reactor, and after 8min, recovering the solution to obtain the liquid to be crystallized. Then placing the mixture into a crystallization kettle, heating to 180 ℃, stirring at 150rpm, crystallizing for 8 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product.
Example 9
The synthesis method comprises the following steps: adding 1.8g of tetrapropylammonium bromide and 0.014g of aluminum isopropoxide into 10g of water, adding 6.7g of silica sol, introducing the solution into a supergravity reactor, adjusting the flow rate to be 60ml/min, adjusting the supergravity rotating speed to be 1600rpm, circularly entering the supergravity reactor, and recovering the solution after 7min to obtain the liquid to be crystallized. Then placing the mixture into a crystallization kettle, heating to 180 ℃, stirring at 150rpm, crystallizing for 8 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product.
Example 10
The synthesis method comprises the following steps: according to the proportion of SiO2:Al2O3:Na2O:H2Dissolving sodium hydroxide in deionized water at a ratio of 12.8:1.00:17.00:675, stirring vigorously, adding an aluminum source into the mixed solution, and adding a silicon source into the mixed solution after the mixed solution is stirred uniformly; after the flow of the super-gravity metering pump is corrected, washing is carried out for standby; introducing the solution into a hypergravity reactor, adjusting the flow and the hypergravity rotation speed, circularly entering the hypergravity reactor, and recovering the solution after the solution is kept for a certain time to obtain a liquid to be crystallized; then placing the mixture into a closed crystallization kettle, and crystallizing the mixture at a high temperature for 2 to 24 hours at a temperature of between 50 and 300 ℃ under stirring at a speed of between 10 and 1000 rpm; and cooling to room temperature, washing and centrifuging the product, and drying to obtain the uniform FAU zeolite.
Comparative example 1
Using the same conditions as in example 1, the amount of tetrapropylammonium hydroxide was changed to 0g to obtain a final product.
Comparative example 2
The final product was obtained by changing the speed of the supergravity to 5rpm under the same conditions as in example 1. The sample XRD characterization results show that the product crystallinity is decreased.
FIG. 3 is a SEM characterization of the sample, showing that the product is not uniform.
Comparative example 3
For comparison, no hypergravity reactor was introduced. The synthesis method comprises the following steps: 9g of tetrapropylammonium hydroxide and 0.09g of aluminum sulfate octadecahydrate were added to 15g of water, and 6.7g of silica sol was added. Stirring for 8 min. Then placing the mixture into a crystallization kettle, heating to 180 ℃, stirring at 150rpm, crystallizing for 8 hours, cooling to room temperature after the reaction is finished, washing and centrifuging for 3 times by deionized water, drying for 12 hours at 80 ℃, and roasting to obtain the final product. The XRD pattern of the resulting product is FIG. 4, and the product is seen to be amorphous.
Claims (10)
1. A method for synthesizing molecular sieve uses a supergravity reactor, and features that the retention time of reaction material in the supergravity reactor is less than 60 min.
2. A method of synthesizing a molecular sieve according to claim 1, characterized in that the residence time is less than 45 minutes; preferably less than 30 minutes.
3. A method of synthesizing a molecular sieve according to claim 1, characterized in that the residence time is 1min to 10 min; preferably 3min-8 min.
4. The method of synthesizing a molecular sieve of claim 1, characterized in that the temperature of the hypergravity reactor does not exceed 100 ℃; preferably not more than 80 ℃; more preferably not more than 60 ℃; preferably room temperature.
5. The method of synthesizing a molecular sieve of claim 1, wherein the rotational speed of the high gravity reactor is 10 to 3000 rpm; preferably 1000-.
6. The method of synthesizing a molecular sieve of claim 1, wherein the high gravity reactor flow rate is from 10ml/min to 5000 ml/min; preferably 20ml/min to 1000 ml/min.
7. The method for synthesizing the molecular sieve according to claim 1, which is characterized by comprising the following specific steps:
the mixture ratio of the materials is as follows:
H2O/SiO2＝5-1000；T/SiO20.1-200; Si/Al is 50- ∞; weighing quantitative template agent T, silicon source and aluminum source; after the flow of the super-gravity metering pump is corrected, washing is carried out for standby; introducing the solution into a hypergravity reactor, adjusting the flow and the hypergravity rotation speed, circularly entering the hypergravity reactor, and recovering the solution after the solution is kept for a certain time to obtain a liquid to be crystallized; then placing the mixture in a closed crystallization kettle, and crystallizing at high temperature for 4-24 hours at 60-300 ℃ under the stirring of 10-1000 rpm; cooling to room temperature, washing and centrifuging the product, and drying to obtain ZSM-5 zeolites with different sizes; the template agent T is one or more of n-propylamine, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetramethylammonium bromide, tetraethylammonium bromide and quaternary ammonium saltOne of them is less.
8. The method for synthesizing the molecular sieve according to claim 1, which is characterized by comprising the following specific steps:
the mixture ratio of the materials is as follows:
the feeding molar ratio of the synthetic mother liquor is
H2O/SiO2＝5-1000；17Na2O/SiO21-100; Si/Al is 1-20; the synthesis comprises the following specific steps: dissolving sodium hydroxide in deionized water, stirring vigorously, adding an aluminum source into the mixed solution, and adding a silicon source after the mixed solution is uniformly stirred; after the flow of the super-gravity metering pump is corrected, washing is carried out for standby; introducing the solution into a hypergravity reactor, adjusting the flow and the hypergravity rotation speed, circularly entering the hypergravity reactor, and recovering the solution after the solution is kept for a certain time to obtain a liquid to be crystallized; then placing the mixture into a closed crystallization kettle, and crystallizing the mixture at a high temperature for 2 to 24 hours at a temperature of between 50 and 300 ℃ under stirring at a speed of between 10 and 1000 rpm; and cooling to room temperature, washing and centrifuging the product, and drying to obtain FAU zeolites with different sizes.
9. The method for synthesizing the molecular sieve according to claim 1, wherein the silicon source is one or at least one of cheap silica sol, sodium silicate; the aluminum source is one or at least one of aluminum sulfate octadecahydrate, aluminum isopropoxide or metaaluminate, aluminate, sodium metaaluminate and aluminum sheet.
10. The method of claim 1, wherein the supergravity reactor is washed with ethanol, water, acid, base, and water sequentially.
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| CN112678844A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for regulating morphology of molecular sieve |
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