CN112875721B - Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body - Google Patents
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- CN112875721B CN112875721B CN202110028862.5A CN202110028862A CN112875721B CN 112875721 B CN112875721 B CN 112875721B CN 202110028862 A CN202110028862 A CN 202110028862A CN 112875721 B CN112875721 B CN 112875721B
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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 mesoporous ZSM-5 molecular sieve macroscopic body, which is characterized in that dilute solution containing ZSM-5 seed crystal, starch or cyclodextrin, aluminum source, silicon source and template agent are fully stirred and mixed to prepare slurry, and then strip extrusion is carried out to prepare the slurry into sheets or strips. And (3) placing the sheet-shaped or strip-shaped objects in a wheel drawer type container, then treating the objects in a high-temperature high-pressure steam atmosphere, and generating ZSM-5 macroscopic bodies from both the silicon source and the aluminum source. Roasting in oxygen-containing gas atmosphere to produce 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 rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body.
Background
ZSM-5 molecular sieve is a microporous molecular sieve and is formed by ordered self-assembly of Si-Al-O bonds. The pore diameter of the catalyst is similar to that of aromatic hydrocarbon, so that the catalyst has shape selective effect, and Si-Al-O bond has acidity, so that the catalyst is widely applied to the preparation of aromatic hydrocarbon from methanol and various dehydration reactions and esterification reactions in petroleum refining. It has recently been discovered that if the nano molecular sieve has stacked mesopores, diffusion can be enhanced, and the lifetime of the catalyst at high temperatures can be increased. However, the conventional method for preparing ZSM-5 molecular sieve is liquid phase hydrothermal synthesis, and has the characteristics of high temperature, high pressure and balance between crystallization and dissolution in liquid phase, so that the rate is low. Filtration of the resulting nano-and micron-sized molecular sieves is a technical challenge, time consuming and labor consuming. On the other hand, if ZSM-5 seed crystals are provided, a solid-solid conversion method can be used to produce a nano molecular sieve. However, the formation of such stacked mesopores is random, and has the disadvantage of not easily controlling the ratio and pore structure. At present, ZSM-5 with a multilevel structure has been 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 oversized pores, no mechanical strength and easy pulverization during use.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body, which combines the advantages of a steam-assisted conversion method, and simultaneously combines a high-pressure extrusion method with a pore-forming agent so that the pore-forming agent has microcosmic orientation arrangement, thereby generating the mesoporous ZSM-5 molecular sieve macroscopic body with high strength.
In order to achieve the above purpose, the invention provides a method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body, comprising the following steps:
step (1): fully stirring the dilute solution containing ZSM-5 seed crystal, starch or cyclodextrin, an aluminum source, a silicon source and a template agent to prepare slurry.
Step (2): extruding the slurry into strips to prepare sheets or strips; the extrusion process is that the solution is extruded, collected and recycled.
Step (3): placing the sheet-like or strip-like object in a wheel drawer type container, placing water under the container, and controlling the amount of water without contacting the sheet-like or strip-like object in a liquid form; and then annealing, controlling the back pressure of the container to be not more than 3MPa, and discharging the redundant water vapor through a back pressure valve. And generating ZSM-5 macroscopic bodies by using both a silicon source and an aluminum source.
Step (4): 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 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 mesoporous ZSM-5 molecular sieve macroscopic body, wherein a silicon source is one or more of sodium silicate and tetraethoxysilane.
The invention relates to a method for rapidly preparing 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 mesoporous ZSM-5 molecular sieve macroscopic body comprises the step of adding 3-5% of the mass of an aluminum source (calculated by alumina) by mass of starch or cyclodextrin. The template agent is 3-5% of the mass of the aluminum source (calculated as aluminum oxide). The mass ratio of the silicon source (calculated as silicon oxide) to the aluminum source (calculated as aluminum oxide) is 10:1-80:1, and the mass ratio of the dilute solution containing ZSM-5 seed crystal to the aluminum source (calculated as aluminum oxide) is 100:1-400: 1.
the invention relates to a method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body, wherein the pushing pressure of extrusion in the step (2) is 2-5MPa.
According to the method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body, the oxygen-containing atmosphere roasted in the step (4) contains 5-100% of oxygen, the selection of other gases is not particularly limited, the effect of the method is not affected by other gases, and the rest is preferably nitrogen and argon.
The invention relates to a method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body, wherein the concentration of a dilute solution containing ZSM-5 seed crystal 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 macroscopic body has the characteristic (thickness or diameter) size of 0.2mm-10mm; the shape is a sheet or a strip; the mesopores are 5-12nm pores, and account for 30-60% of all pores (the sum of micropores and mesopores).
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 150-300 ℃ and the stewing time is 1-6 hours.
In the step (4) of the invention, the roasting 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 the raw materials, extrudes the raw materials into strips, omits crystallization and filtration links in the solution, and shortens the preparation time by 30-50%.
The preparation method of the invention firstly utilizes the high-pressure extrusion process to lead microscopic pore formers and the like to be arranged directionally, thereby being beneficial to forming regular mesopores, and the extrusion of the formed raw materials into regular shapes, the filling amount in the wheel drawer type container is low, the pressure drop is low, the crystallization process in high-temperature steam is beneficial, and the equipment cost is reduced by 30-50%.
The preparation method adopts steam to convert and crystallize the molecular sieve, breaks the equilibrium limiting relation 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 preparation method, in the drying and roasting processes, the material volume is contracted in the processes of desorbing water and removing pore-forming agent and template agent, and macroscopic regular mesopores are naturally formed. Compared with the original nano molecular sieve, the stacking mesopores are more ordered, the material has strength, the abrasion rate is reduced by 20 to 40 percent,
the strip extrusion process of the preparation method can conveniently form sheet-shaped or strip-shaped materials with different diameters and thicknesses according to the needs, and the preparation method is convenient to use. Reduces the complex procedures of the prior nano molecular sieve and secondary granulation, and reduces the preparation cost 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 the following specific embodiments. It should not be construed that the scope of the above subject matter of the present invention is limited to the following examples.
Example 1
A ZSM-5 seed crystal-containing dilute solution (concentration: 1mg ZSM-5/liter), starch and an aluminum source (sodium metaacid), a silicon source (sodium silicate), and a template agent (tetrapropylammonium hydroxide) were mixed together, wherein the starch was added in an amount of 3% of the aluminum source (calculated as alumina), the template agent was added in an amount of 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 10:1, and the mass ratio of the ZSM-5 seed crystal-containing dilute solution was 100:1. Stirring was carried out at 60℃for 0.1 hour to obtain a slurry. The extrusion process is that the solution is extruded, collected and recycled.
The slurry was extruded into a sheet having a thickness of 0.2mm (propelling pressure: 2 MPa). The tablets are placed in a wheel-drawer container, water is placed under the container, and the amount of water is controlled not to contact the tablets or strips in liquid form. Then stewing for 6 hours at 150 ℃, controlling the back pressure of the container not to exceed 3MPa, and discharging the redundant water vapor through a back pressure valve. And converting the silicon source and the aluminum source to generate a ZSM-5 macroscopic body. ZSM-5 macrosubstance was subjected to an oxygen-containing atmosphere (5% O) 2 The balance of nitrogen) is baked at 400-700 ℃, and the starch/cyclodextrin and the template agent are removed to generate the mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores are 5-12nm pores, which account for 30% of all pores (sum of micropores and mesopores).
Example 2
A ZSM-5 seed-containing dilute solution (concentration: 100mg ZSM-5/liter), cyclodextrin and an aluminum source (sepiolite, dissolved with sulfuric acid), a silicon source (ethyl orthosilicate), a templating agent (tetrapropylammonium bromide) were mixed together, wherein the amount of cyclodextrin added was 3% of the aluminum source (calculated as alumina), the amount of templating agent added 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 ZSM-5 seed-containing dilute solution was 400:1. Stirring was carried out at 25℃for 3 hours to give a slurry. The extrusion process is that the solution is extruded, collected and recycled.
The slurry was extruded into strips (propelling pressure 3 MPa) to prepare 10mm diameter strips. The strips are placed in a wheel-drawer container, water is placed under the container, and the amount of water is controlled so as not to contact the sheet or strip in liquid form. Then stewing for 1 hour at 300 ℃, controlling the back pressure of the container not to exceed 3MPa, and discharging the redundant water vapor through a back pressure valve. And converting the silicon source and the aluminum source to generate a ZSM-5 macroscopic body. ZSM-5 macrosubstance was subjected to an oxygen-containing atmosphere (100% O) 2 ) Roasting at 700 ℃ to remove cyclodextrin and template agent, and generating mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores are 5-12nm and account for 60% of all the pores (the sum of micropores and mesopores).
Example 3
A ZSM-5 seed crystal-containing dilute solution (concentration: 70mg ZSM-5/liter), starch and an aluminum source (sodium aluminum sulfate), a silicon source (ethyl orthosilicate), and a template agent (tetrabutylammonium hydroxide) were mixed together, wherein the addition amount of cyclodextrin was 3% of the aluminum source (calculated as aluminum oxide), the addition amount of the template agent was 3% of the aluminum source (calculated as aluminum oxide), the mass ratio of the silicon source (calculated as silicon oxide) to the aluminum source (calculated as aluminum oxide) was 40:1, and the mass ratio of the ZSM-5 seed crystal-containing dilute solution was 240:1. Stirring was carried out at 50℃for 3 hours to give a slurry. The slurry was extruded (propelling pressure: 2.5 MPa) to prepare a sheet having a thickness of 3 mm. The extrusion process is that the solution is extruded, collected and recycled.
The tablets are placed in a wheel-drawer 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 for 3 hours at 200 ℃, controlling the back pressure of the container not to exceed 3MPa, and discharging the redundant water vapor through a back pressure valve. And converting the silicon source and the aluminum source to generate a ZSM-5 macroscopic body. Roasting ZSM-5 macroscopic body at 500 ℃ under oxygen-containing atmosphere (air), removing starch and template agent, and generating mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores are 5-12nm and account for 40% of all the pores (the sum of micropores and mesopores).
Example 4
A ZSM-5 seed crystal-containing dilute solution (concentration: 30mg ZSM-5/liter), cyclodextrin and an aluminum source (pseudo-boehmite, dissolved with sulfuric acid), a silicon source (ethyl orthosilicate), a templating agent (tetrabutylammonium bromide) were mixed together, wherein the amount of cyclodextrin added was 3% of the aluminum source (calculated as alumina), the amount of templating agent added was 3% 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 50:1, and the mass ratio of the ZSM-5 seed crystal-containing dilute solution was 300:1. Stirring was carried out at 50℃for 3 hours to give a slurry. The slurry was extruded (propelling pressure: 2.5 MPa) to prepare a bar having a diameter of 0.2 mm. The extrusion process is that the solution is extruded, collected and recycled.
The strips are placed in a wheel-drawer container, water is placed under the container, and the amount of water is controlled so as not to contact the sheet or strip in liquid form. Then stewing for 6 hours at 250 ℃, controlling the back pressure of the container not to exceed 3MPa, and discharging the redundant water vapor through a back pressure valve. And converting the silicon source and the aluminum source to generate a ZSM-5 macroscopic body. Roasting ZSM-5 macroscopic body at 500 ℃ under an oxygen-containing atmosphere (50% oxygen, 50% argon), removing cyclodextrin and template agent, and generating mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores are 5-12nm and account for 42% of all the pores (the sum of micropores and mesopores).
Example 5
A dilute solution containing ZSM-5 seed crystals (concentration: 60mg ZSM-5/liter), starch and an aluminum source (sodium metaaluminate), a silicon source (ethyl orthosilicate), a templating agent (50% tetrabutylammonium bromide, 50% tetrapropylammonium hydroxide) was mixed together, wherein the amount of cyclodextrin added was 4% of the aluminum source (calculated as aluminum oxide), the amount of templating agent added was 4% of the aluminum source (calculated as aluminum oxide), the mass ratio of the silicon source (calculated as silicon oxide) to the aluminum source (calculated as aluminum oxide) was 36:1, and the mass ratio of the dilute solution containing ZSM-5 seed crystals was 220:1. Stirring was carried out at 50℃for 3 hours to give a slurry. The slurry was extruded into strips (propulsion pressure 2.5 MPa) to prepare strips with a diameter of 5 mm. The extrusion process is that the solution is extruded, collected and recycled.
The strips are placed in a wheel-drawer container, water is placed under the container, and the amount of water is controlled so as not to contact the sheet or strip in liquid form. Then stewing for 6 hours at 250 ℃, controlling the back pressure of the container not to exceed 3MPa, and discharging the redundant water vapor through a back pressure valve. And converting the silicon source and the aluminum source to generate a ZSM-5 macroscopic body. Roasting ZSM-5 macroscopic body at 550 ℃ under an oxygen-containing atmosphere (50% oxygen, 50% argon), removing starch and template agent, and generating mesoporous ZSM-5 molecular sieve macroscopic body. The mesopores are 5-12nm pores, which account for 35% of all pores (sum of micropores and mesopores).
Claims (10)
1. The method for rapidly preparing the mesoporous ZSM-5 molecular sieve macroscopic body is characterized by comprising the following steps of:
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 slurry;
step (2): extruding the slurry under the pressure of 2-5MPa to prepare a sheet or strip; when the solution is extruded in the extrusion process, collecting the solution and recycling the solution;
step (3): placing the sheet-like or strip-like object in a wheel drawer type container, placing water under the container, and controlling the amount of water without contacting the sheet-like or strip-like object in a liquid form; then stewing, controlling the back pressure of the container to be not more than 3MPa, and discharging 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;
step (4): roasting the ZSM-5 macroscopic body in an oxygen-containing atmosphere, and removing starch or cyclodextrin and a template agent to obtain a mesoporous ZSM-5 molecular sieve macroscopic body;
wherein in the step (3), the stewing temperature is 150-300 ℃ and the stewing time is 1-6 hours.
2. The method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body according to claim 1, wherein the aluminum source is at least one of sodium metaaluminate, sodium aluminum sulfate, pseudo-boehmite, and sepiolite; the pseudoboehmite and/or sepiolite are dissolved using sulfuric acid.
3. The method for rapidly preparing mesoporous ZSM-5 molecular sieve macrostructures as recited in claim 1, wherein the silicon source is at least one of sodium silicate and ethyl orthosilicate.
4. The method for rapidly preparing mesoporous ZSM-5 molecular sieve macrostructures according to 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 mesoporous ZSM-5 molecular sieve macrostructures according to claim 1, wherein the aluminum source is calculated as alumina and the starch or cyclodextrin is added in an amount of 3-5wt% of the aluminum source; the addition amount of the template agent is 3-5wt% 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 ZSM-5 seed crystal to the aluminum source is 100:1-400: 1.
6. the method for rapidly preparing mesoporous ZSM-5 molecular sieve macrostructures as recited in claim 1, wherein in step (4), the oxygen content of the calcined oxygen-containing atmosphere is 5-100%.
7. The method for rapidly preparing mesoporous ZSM-5 molecular sieve macrostructures according to claim 1, characterized in that the concentration of the dilute solution containing ZSM-5 seeds is 1-100mg ZSM-5/liter.
8. The method for rapidly preparing a mesoporous ZSM-5 molecular sieve macroscopic body according to claim 1, wherein the size of the mesoporous ZSM-5 molecular sieve macroscopic body is 0.2mm-10mm; the mesoporous ZSM-5 molecular sieve macroscopic body is in a sheet shape or a strip shape; the mesoporous ZSM-5 molecular sieve macroscopic body has 5-12nm holes accounting for 30-60% of all holes.
9. The method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic according to claim 1, wherein in the step (1), the stirring temperature is 25 to 60 ℃ and the stirring time is 0.1 to 3 hours.
10. The method for rapidly preparing mesoporous ZSM-5 molecular sieve macrostructures as recited in claim 1, wherein in step (4), the calcination temperature is 400-700 ℃.
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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 |
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