CN112875721A - Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body - Google Patents
Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body Download PDFInfo
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- CN112875721A CN112875721A CN202110028862.5A CN202110028862A CN112875721A CN 112875721 A CN112875721 A CN 112875721A CN 202110028862 A CN202110028862 A CN 202110028862A CN 112875721 A CN112875721 A CN 112875721A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, which comprises the steps of fully stirring and mixing a dilute solution containing ZSM-5 seed crystals, starch or cyclodextrin, an aluminum source, a silicon source and a template agent to prepare a slurry, extruding strips, preparing together and preparing into a sheet or strip. And (3) placing the flaky or strip-shaped object in a drawer-type container, and then treating the flaky or strip-shaped object in a high-temperature and high-pressure steam atmosphere to enable the silicon source and the aluminum source to generate a ZSM-5 macroscopic body. Then roasting in the atmosphere of oxygen-containing gas to generate the mesoporous ZSM-5 macroscopic body. The method has the advantages of high preparation speed, adjustable silicon-aluminum ratio, low cost and the like.
Description
Technical Field
The invention belongs to the field of chemical processes, and particularly relates to a method for quickly preparing a mesoporous ZSM-5 molecular sieve macroscopic body.
Background
The ZSM-5 molecular sieve is a microporous molecular sieve and is formed by orderly self-assembling Si-Al-O bonds. The pore canal has similar diameter to that of aromatic hydrocarbon, so that it has shape selective effect and acid Si-Al-O bond, so that it may be used widely in petroleum refining, methanol to prepare aromatic hydrocarbon, various dewatering reactions and esterification reactions. Recently, it has been found that if the nano molecular sieve has stacked mesopores, the diffusion can be enhanced, and the service life of the catalyst at high temperature can be improved. However, the conventional method for preparing the ZSM-5 molecular sieve is liquid phase hydrothermal synthesis, has the characteristics of high temperature, high pressure and balanced crystallization and dissolution in a liquid phase, and is slow in speed. The filtration of the obtained nano and micron molecular sieves is a technical challenge and is time-consuming and labor-consuming. On the other hand, if ZSM-5 seed crystals are provided, the nano molecular sieve can be produced by a solid-solid conversion method. However, such stacked mesopores are random in formation and have a disadvantage that it is difficult to control the ratio and the pore structure. At present, ZSM-5 with a multi-stage structure is reported, but the preparation method is complex, the reagent is expensive, and the preparation time is long. The prepared mesoporous ZSM-5 macroscopic body has the defects of overlarge pores, no mechanical strength and easy pulverization in use.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for quickly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, which combines the advantages of a steam-assisted conversion method, and simultaneously adopts a method of combining a high-pressure strip extrusion method and a pore-forming agent, so that the pore-forming agent has microcosmic and directional arrangement, and the mesoporous ZSM-5 molecular sieve macroscopic body with high strength is generated.
In order to achieve the aim, the invention provides a method for quickly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, which comprises the following steps:
step (1): fully stirring the dilute solution containing the ZSM-5 seed crystal, starch or cyclodextrin, an aluminum source, a silicon source and a template agent to prepare slurry.
Step (2): extruding the pulp into strips to prepare sheets or strips; and extruding the solution in the strip extruding process, and collecting and recycling the solution.
And (3): putting the sheet or strip-shaped object into a drawer-type container, putting water below the container, and controlling the amount of the water without contacting the sheet or strip-shaped object in a liquid form; then stewing the furnace, controlling the back pressure of the container not to exceed 3MPa, and discharging the excessive water vapor through a back pressure valve. And (3) generating a ZSM-5 macroscopic body by using the silicon source and the aluminum source.
And (4): and roasting the ZSM-5 macroscopic body in an oxygen-containing atmosphere, and removing starch or cyclodextrin and a template agent to obtain the mesoporous ZSM-5 molecular sieve macroscopic body.
The invention relates to a method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, wherein an aluminum source is one or more of sodium metaaluminate, sodium aluminum sulfate, pseudo-boehmite (dissolved by sulfuric acid), sepiolite (dissolved by sulfuric acid) and the like.
The invention relates to a method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, wherein a silicon source is one or more of sodium silicate and tetraethoxysilane.
The invention discloses a method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, wherein a template agent is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium hydroxide and tetrabutylammonium bromide.
The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body comprises the step of adding starch or cyclodextrin, wherein the mass of the added starch or cyclodextrin is 3-5% of the mass of an aluminum source (calculated by alumina). The template agent is 3-5% of the mass of the aluminum source (calculated as alumina). The mass ratio of the silicon source (calculated by silicon oxide) to the aluminum source (calculated by aluminum oxide) is 10: 1-80: 1, and the mass ratio of the mass of the ZSM-5 seed crystal-containing dilute solution to the mass of the aluminum source (calculated by aluminum oxide) is 100: 1-400: 1.
the method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body has the advantage that the pushing pressure of the extrusion strip in the step (2) is 2-5 MPa.
According to the method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body, the oxygen-containing atmosphere calcined in the step (4) is gas with the oxygen content of 5-100%, the selection of the rest gas is not particularly limited, the effect of the method is not influenced by the types of other gases, and the rest gas is preferably nitrogen or argon.
The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body has the advantages that the concentration of a dilute solution containing ZSM-5 seed crystals is 1-100 mgZSM-5/liter.
The invention relates to a method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, wherein the characteristic (thickness or diameter) size of the macroscopic body is 0.2mm-10 mm; the shape is sheet or strip; the mesopores of the composite material account for 30-60% of all pores (the sum of micropores and mesopores) with the diameter of 5-12 nm.
In the step (1), the stirring temperature is 25-60 ℃, and the stirring time is 0.1-3 hours.
In the step (3), the stewing temperature is 150-.
In the step (4) of the present invention, the calcination temperature is 400-700 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention directly stirs and mixes all raw materials and extrudes the raw materials into strips, thereby omitting crystallization and filtration links in the solution and shortening the preparation time by 30-50%.
The preparation method of the invention firstly utilizes the high-pressure strip extrusion process to ensure that the microcosmic pore-forming agents and the like are directionally arranged, thus being beneficial to forming regular mesopores, leading the formed raw materials to be extruded into strips with regular shapes, reducing the loading amount and pressure in a wheel drawer type container, being beneficial to the crystallization process in high-temperature steam and reducing the equipment cost by 30-50 percent.
The preparation method of the invention adopts steam to carry out the conversion and crystallization of the molecular sieve, breaks through the balance limit relationship between the temperature and the pressure of the liquid-phase hydrothermal method, can use high-temperature steam, not only improves the crystallinity of the molecular sieve, but also saves the preparation time by about 30 to 50 percent,
in the drying and roasting process of the preparation method, the material volume shrinks in the processes of desorbing moisture and removing pore-forming agent and template agent, and macroscopic regular mesopores are naturally formed. Compared with the prior nano molecular sieve, the accumulated mesopores are more ordered, and simultaneously, the material has the advantages of strength, reduced wear rate by 20-40%,
the strip extruding process of the preparation method can conveniently form sheet-shaped or strip-shaped materials with different diameters and thicknesses according to needs, and the preparation method is convenient to use. The complex procedures of the original nano molecular sieve and secondary granulation are reduced, and the preparation cost is reduced by 20 percent.
The preparation method has the advantages of high preparation speed, adjustable silicon-aluminum ratio, low cost and the like.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Example 1
A dilute solution containing ZSM-5 seed crystals (concentration: 1mg of ZSM-5/liter), starch, an aluminum source (sodium meta-acid), a silicon source (sodium silicate) and a template agent (tetrapropylammonium hydroxide) are mixed together, wherein the addition amount of the starch is 3% of that of the aluminum source (calculated as alumina), the addition amount of the template agent is 5% of that of the aluminum source (calculated as alumina), the mass ratio of the silicon source (calculated as silica) to the aluminum source (calculated as alumina) is 10:1, and the mass ratio of the aluminum source (calculated as alumina) to the mass of the dilute solution containing ZSM-5 seed crystals is 100: 1. The mixture was stirred at 60 ℃ for 0.1 hour to prepare a slurry. And extruding the solution in the strip extruding process, and collecting and recycling the solution.
Extruding the pulp into strips (the pushing pressure is 2MPa), and preparing into sheets with the thickness of 0.2mmAnd (4) forming a substance. The tablets are placed in a drawer-type container, water is placed under the container, and the amount of water is controlled not to contact the tablets or strips in a liquid form. Then stewing is carried out for 6 hours at 150 ℃, the back pressure of the container is controlled not to exceed 3MPa, and the excess water vapor is discharged through a back pressure valve. And (3) converting a silicon source and an aluminum source to generate the ZSM-5 macroscopic body. ZSM-5 macrostructures are placed in an oxygen-containing atmosphere (5% O)2And the balance of nitrogen) at the temperature of 400-. The mesopores of the composite material account for 30 percent of all pores (the sum of micropores and mesopores) with the pores of 5-12 nm.
Example 2
A dilute solution containing ZSM-5 seed crystals (concentration: 100mg ZSM-5/liter), cyclodextrin and an aluminum source (sepiolite, dissolved with sulfuric acid), a silicon source (ethyl orthosilicate), and a template (tetrapropylammonium bromide) were mixed together, wherein the addition amount of cyclodextrin was 3% of the aluminum source (calculated as alumina), the addition amount of the template was 5% of the aluminum source (calculated as alumina), the mass ratio of the silicon source (calculated as silica) to the aluminum source (calculated as alumina) was 80:1, and the mass ratio of the dilute solution containing ZSM-5 seed crystals was 400: 1. The mixture was stirred at 25 ℃ for 3 hours to prepare a slurry. And extruding the solution in the strip extruding process, and collecting and recycling the solution.
The slurry was extruded into a rod (pushing pressure 3MPa) to prepare a rod having a diameter of 10 mm. The noodles are placed in a drawer-type container, water is placed under the container, and the amount of water is controlled so as not to contact the tablets or noodles in liquid form. Then stewing is carried out for 1 hour at 300 ℃, the back pressure of the container is controlled not to exceed 3MPa, and the excess water vapor is discharged through a back pressure valve. And (3) converting a silicon source and an aluminum source to generate the ZSM-5 macroscopic body. ZSM-5 macrostructures are placed in an oxygen-containing atmosphere (100% O)2) Roasting at 700 ℃, removing cyclodextrin and a template agent, and generating the mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores of the composite material are 5-12nm pores, and account for 60% of all pores (the sum of micropores and mesopores).
Example 3
A dilute solution containing ZSM-5 seed crystals (concentration: 70mg ZSM-5/liter), starch, an aluminum source (sodium aluminum sulfate), a silicon source (ethyl orthosilicate) and a template (tetrabutylammonium hydroxide) are mixed together, wherein the addition amount of cyclodextrin is 3% of that of the aluminum source (calculated as alumina), the addition amount of the template is 3% of that of the aluminum source (calculated as alumina), the mass ratio of the silicon source (calculated as silica) to that of the aluminum source (calculated as alumina) is 40:1, and the mass ratio of the ZSM-5 seed crystals-containing dilute solution is 240: 1. The mixture was stirred at 50 ℃ for 3 hours to prepare a slurry. The slurry was extruded into a bar (pushing pressure 2.5MPa) to prepare a sheet having a thickness of 3 mm. And extruding the solution in the strip extruding process, and collecting and recycling the solution.
The tablets are placed in a drawer-type container, water is placed under the container, and the amount of water is controlled so as not to contact the tablets or strips in liquid form. Then stewing is carried out for 3 hours at the temperature of 200 ℃, the back pressure of the container is controlled not to exceed 3MPa, and the excess water vapor is discharged through a back pressure valve. And (3) converting a silicon source and an aluminum source to generate the ZSM-5 macroscopic body. Roasting the ZSM-5 macroscopic body at 500 ℃ in an oxygen-containing atmosphere (air), removing starch and a template agent, and generating the mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores of the composite material are 5-12nm pores, and account for 40% of all pores (the sum of micropores and mesopores).
Example 4
A dilute solution containing ZSM-5 seed crystals (concentration: 30mg ZSM-5/liter), cyclodextrin and an aluminum source (pseudo-boehmite, dissolved with sulfuric acid), a silicon source (tetraethoxysilane) and a template agent (tetrabutylammonium bromide) are mixed together, wherein the addition amount of the cyclodextrin is 3% of that of the aluminum source (calculated as alumina), the addition amount of the template agent is 3% of that of the aluminum source (calculated as alumina), the mass ratio of the silicon source (calculated as silica) to the aluminum source (calculated as alumina) is 50:1, and the mass ratio of the dilute solution containing ZSM-5 seed crystals is 300: 1. The mixture was stirred at 50 ℃ for 3 hours to prepare a slurry. The slurry was extruded into a rod (pushing pressure 2.5MPa) to prepare a rod having a diameter of 0.2 mm. And extruding the solution in the strip extruding process, and collecting and recycling the solution.
The noodles are placed in a drawer-type container, water is placed under the container, and the amount of water is controlled so as not to contact the tablets or noodles in liquid form. Then stewing is carried out for 6 hours at 250 ℃, the back pressure of the container is controlled not to exceed 3MPa, and the excess water vapor is discharged through a back pressure valve. And (3) converting a silicon source and an aluminum source to generate the ZSM-5 macroscopic body. Roasting the ZSM-5 macroscopic body at 500 ℃ in an oxygen-containing atmosphere (50% of oxygen and 50% of argon), and removing cyclodextrin and a template agent to generate the mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores of the composite material are 5-12nm pores, and account for 42% of all pores (the sum of micropores and mesopores).
Example 5
A dilute solution containing ZSM-5 seeds (concentration: 60mg ZSM-5/liter), starch and an aluminum source (sodium metaaluminate), a silicon source (ethyl orthosilicate), a template agent (50% tetrabutylammonium bromide, 50% tetrapropylammonium hydroxide) were mixed together, wherein the addition amount of cyclodextrin was 4% of the aluminum source (in terms of alumina), the addition amount of the template agent was 4% of the aluminum source (in terms of alumina), the mass ratio of the silicon source (in terms of silica) to the aluminum source (in terms of alumina) was 36:1, and the mass ratio of the dilute solution containing ZSM-5 seeds was 220: 1. The mixture was stirred at 50 ℃ for 3 hours to prepare a slurry. The slurry was extruded into a rod (pushing pressure 2.5MPa) to prepare a rod having a diameter of 5 mm. And extruding the solution in the strip extruding process, and collecting and recycling the solution.
The noodles are placed in a drawer-type container, water is placed under the container, and the amount of water is controlled so as not to contact the tablets or noodles in liquid form. Then stewing is carried out for 6 hours at 250 ℃, the back pressure of the container is controlled not to exceed 3MPa, and the excess water vapor is discharged through a back pressure valve. And (3) converting a silicon source and an aluminum source to generate the ZSM-5 macroscopic body. Roasting the ZSM-5 macroscopic body at 550 ℃ in an oxygen-containing atmosphere (50% of oxygen and 50% of argon), removing starch and a template agent, and generating the mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores of the composite material are pores with the diameter of 5-12nm, and account for 35 percent of all pores (the sum of micropores and mesopores).
Claims (12)
1. A method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body is characterized by comprising the following steps:
step (1): fully stirring a dilute solution containing ZSM-5 seed crystals, starch or cyclodextrin, an aluminum source, a silicon source and a template agent to prepare a slurry;
step (2): extruding the pulp into strips to prepare sheets or strips; when a solution is extruded in the strip extruding process, collecting the solution and recycling;
and (3): putting the sheet or strip-shaped object into a drawer-type container, putting water below the container, and controlling the amount of the water without contacting the sheet or strip-shaped object in a liquid form; then stewing the furnace, controlling the back pressure of the container not to exceed 3MPa, and discharging the redundant water vapor through a back pressure valve; converting a silicon source and an aluminum source to generate a ZSM-5 molecular sieve macroscopic body;
and (4): and roasting the ZSM-5 macroscopic body in an oxygen-containing atmosphere, and removing starch or cyclodextrin and a template agent to obtain the mesoporous ZSM-5 molecular sieve macroscopic body.
2. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein the aluminum source is at least one of sodium metaaluminate, sodium aluminum sulfate, pseudoboehmite, and sepiolite; the pseudoboehmite and/or sepiolite are dissolved using sulfuric acid.
3. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein the silicon source is at least one of sodium silicate and ethyl orthosilicate.
4. The method for the rapid preparation of mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein the template is at least one of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetrabutylammonium hydroxide and tetrabutylammonium bromide.
5. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein the amount of the aluminum source is 3-5 wt% of the amount of the starch or the cyclodextrin, calculated by the aluminum oxide; the addition amount of the template agent is 3-5 wt% of the aluminum source; the silicon source is calculated by silicon oxide, the aluminum source is calculated by aluminum oxide, and the mass ratio of the silicon source to the aluminum source is 10: 1-80: 1; the mass ratio of the dilute solution containing the ZSM-5 seed crystal to the aluminum source is (100: 1) - (400): 1.
6. the method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein in the step (2), the pushing pressure of the extrusion bar is 2-5 MPa.
7. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein in the step (4), the oxygen content of the calcined oxygen-containing atmosphere is 5-100% of the gas.
8. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein the concentration of the dilute solution containing the ZSM-5 seed crystals is 1-100mg ZSM-5/liter.
9. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as claimed in claim 1, wherein the size of the mesoporous ZSM-5 molecular sieve macroscopic body is 0.2mm-10 mm; the shape of the mesoporous ZSM-5 molecular sieve macroscopic body is a sheet or a strip; the mesopores of the mesoporous ZSM-5 molecular sieve macroscopic body are in pores of 5-12nm, and account for 30-60% of all pores.
10. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein in the step (1), the stirring temperature is 25-60 ℃ and the stirring time is 0.1-3 hours.
11. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein in the step (3), the annealing temperature is 150-.
12. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body as recited in claim 1, wherein in the step (4), the calcination temperature is 400-700 ℃.
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| CN110028080A (en) * | 2019-05-30 | 2019-07-19 | 天津金玺科技发展有限公司 | A kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity |
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2021
- 2021-01-11 CN CN202110028862.5A patent/CN112875721B/en active Active
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| US6022519A (en) * | 1995-05-24 | 2000-02-08 | Kuboto Corporation | Method of manufacturing crystalline microporous material |
| CN1915820A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain without bonding agent |
| CN103030156A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Preparation method of binderless ZSM-5 molecular sieve |
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