CN113880103B - Beta molecular sieve and synthesis method and application thereof - Google Patents
Beta molecular sieve and synthesis method and application thereof Download PDFInfo
- Publication number
- CN113880103B CN113880103B CN202010626580.0A CN202010626580A CN113880103B CN 113880103 B CN113880103 B CN 113880103B CN 202010626580 A CN202010626580 A CN 202010626580A CN 113880103 B CN113880103 B CN 113880103B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- beta molecular
- mixture
- alcohol
- silicon source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a Beta molecular sieve and a synthesis method thereof. The Beta molecular sieve has the crystal grain shape of waxberry, the surface of the crystal grain is provided with mesopores, the average size of the pore opening of the mesopores is 20-30nm, and the average edge distance of the adjacent mesopores is 20-40nm. The synthesis process of the molecular sieve comprises the following steps: 1) Contacting water, urea, surfactant, cycloalkane, alcohol and a silicon source to obtain a mixture A; 2) Treating the mixture A to obtain silica pellets; 3) Contacting silica pellets, tetraethylammonium hydroxide solution and an aluminum source to obtain a mixture B; 4) Mixture B was treated to give Yang Meizhuang Beta molecular sieve. The Beta molecular sieve synthesized by the invention contains abundant mesopores, which is beneficial to improving the diffusion efficiency of reaction molecules among crystals.
Description
Technical Field
The invention belongs to the technical field of catalytic chemistry and chemical engineering, and particularly relates to a Beta molecular sieve, a synthesis method and application thereof.
Background
The Beta molecular sieve is a high-silicon molecular sieve which is synthesized for the first time in 1967 by the Mobil company, and the generation of the Beta molecular sieve marks the beginning of the second generation of molecular sieve-high-silicon molecular sieve research age. Beta molecular sieve is a high silicon zeolite with three-dimensional twelve-membered ring cross pore canal system structure. The crystal skeleton is formed by connecting tetragonal system A and monoclinic system B, C along the [001] direction. Wherein, the channels are mutually perpendicular along the [100] and [010] directions, and the aperture is about 0.66 multiplied by 0.77nm. The aperture of the curved pore canal is about 0.56 multiplied by 0.65nm along the [001] direction and the [010] direction. The Beta molecular sieve has unique three-dimensional pore canal structure, proper acidity and good hydrothermal stability, and has very wide application in the fields of petrochemical industry and fine chemical industry.
The synthesis of Beta molecular sieves is reported to be relatively more, such as patent CN110860307A, CN105271287A and the like, but Beta molecular sieves directly synthesized by a conventional method are generally of microporous structures, which are not beneficial to the diffusion and transmission of reaction molecules inside molecular sieve crystals and among the crystals. If the molecular sieve of the synthesized molecular sieve has mesopores, the diffusion rate of the reaction molecules in the molecular sieve crystal or among the molecular sieve crystals is inevitably accelerated, which is beneficial to improving the conversion rate in the reaction process. Patent CN108217675a discloses a preparation method of a hollow single crystal Beta molecular sieve. The method is characterized in that a hollow monocrystalline Beta molecular sieve is directly prepared from gel formed by fully mixing a silicon source, an aluminum source, inorganic alkali, a microporous template agent and an organic additive lactam R through one-step hydrothermal crystallization, and synthesized products are formed by orderly stacking and connecting primary nano particles.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the Beta molecular sieve synthesized in the prior art is of a microporous structure or the surface of the molecular sieve has no mesopores.
The second technical problem to be solved by the invention is to provide a synthesis method of Beta molecular sieve which is one of the technical problems to be solved.
In order to solve one of the technical problems, the invention provides a Beta molecular sieve, wherein the shape of crystal grains is waxberry-shaped, the surfaces of the crystal grains are provided with mesopores, and the average size of the mesopore opening is 20-30nm.
The mesoporous orifice on the surface of the Beta molecular sieve crystal grain is round or similar to round, and the average edge distance of adjacent mesoporous pores is 20-40nm.
The specific surface area of the Beta molecular sieve is 600-850m 2 ·g -1 Mesoporous volume of 0.86-0.95cm 3 ·g -1 。
The Beta molecular sieve SiO 2 /Al 2 O 3 =8.8-50 (in mass ratio), the grain size averages 400-900nm.
In order to solve the second technical problem, another aspect of the present invention provides a Beta molecular sieve synthesis method, which includes the following steps:
1) Contacting water, urea, surfactant, cycloalkane, alcohol and a silicon source to obtain a mixture A;
2) Processing the mixture A to obtain silica pellets;
3) Contacting silica pellets, tetraethylammonium hydroxide solution and an aluminum source to obtain a mixture B;
4) Mixture B was treated to give Yang Meizhuang Beta molecular sieve.
Further, the above step 2) preferably further comprises a step of post-firing the silica pellets to remove organic matters.
In the above technical solution, preferably, the surfactant in step 1) is one or more of cetyltrimethylammonium bromide, octadecyl trimethyl ammonium bromide or eicosyl trimethyl ammonium bromide.
In the above technical solution, preferably, the cycloalkane in step 1) is one or more of cyclopentane, cyclohexane and cycloheptane.
In the above technical solution, preferably, the alcohol in step 1) is one or more of n-butanol, n-pentanol and n-hexanol.
In the above technical solution, preferably, the silicon source in step 1) is one or more of tetramethyl silicate, tetraethyl silicate, and tetrapropyl silicate.
In the above technical solution, preferably, the mass ratio of water, urea, surfactant, cycloalkane, alcohol and silicon source in step 1) is: silicon source = 35-65; urea: silicon source = 0.6-1.8; and (2) a surfactant: silicon source = 0.6-1.8; cycloalkane: silicon source = 35-65; alcohol: silicon source = 2.5-5.5.
In the above technical solution, preferably, the process of preparing the silica pellets from the mixture a in the step 2) is: and (3) stirring the mixture A in a closed container for 4-12 h at 100-140 ℃. The average diameter of the prepared silicon dioxide pellets is 300-400nm, the surface is rugged, and the specific surface area is 600-800m 2 /g。
In the above technical solution, preferably, in step 3), the aluminum source is one or more of pseudo-boehmite, sodium metaaluminate, and aluminum isopropoxide.
In the above technical solution, preferably, in step 3), the mass ratio of the silica pellets, the tetraethylammonium hydroxide solution and the aluminum source is that the silica pellets: tetraethylammonium hydroxide = 4-8; silica pellets (per SiO) 2 Calculation): aluminium source (according to Al) 2 O 3 Calculated) =8.8-47 (mass ratio).
In the above technical solution, preferably, the processing in step 4) is: and (3) carrying out gas-solid phase crystal transformation treatment on the mixture B. The gas-solid phase crystal transformation treatment is to conduct alcohol steam treatment on the mixture B in the presence of water and ethanol, wherein the treatment time is 24-72h, and the temperature is 100-120 ℃.
In the above technical scheme, preferably, the mass ratio of water to ethanol is 0.5-2, and the mass ratio of the mixture B to the mixture of water and ethanol is 0.5-2.
The alcohol vapor treatment process is that a porous partition board is placed in the middle of a closed container, a dried mixture B is placed on the partition board, a water and ethanol mixture is placed under the partition board, and the mixture B is not contacted with the water and ethanol mixture.
In a further aspect, the present invention provides a process for the liquid phase alkylation of benzene and ethylene using the Beta molecular sieve described above or a molecular sieve synthesized by the synthesis process described above. The liquid phase alkylation method of benzene and ethylene is that the reaction temperature is 170-175 ℃, the pressure is 3.0-4.0MPa, and the ethylene mass space velocity is 5-6h -1 Benzene and ethylene are subjected to alkylation reaction under the condition that the molar ratio of benzene to ethylene is 1.5-3.
The Beta molecular sieve synthesized by the invention contains rich mediumPores, which facilitate the enhancement of the diffusion rate of reactive molecules within and between the crystals of the molecular sieve during the reaction. The molecular sieve of the invention is applied to the liquid phase alkylation reaction of benzene and ethylene, and the ethylene conversion rate is obviously improved. At the reaction temperature of 170-175 ℃, the pressure of 3.0-4.0MPa and the ethylene mass space velocity of 5-6h -1 The ethylene conversion rate is 70% -75% after the reaction is continuously carried out for 6 hours under the condition that the mole ratio of benzene to ethylene is 1.5-3.
Drawings
FIG. 1 is an SEM photograph of silica pellets prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of a bayberry-like Beta molecular sieve prepared in example 1 of the present invention;
FIG. 3 is an XRD spectrum of the waxberry-shaped Beta molecular sieve prepared in example 1 of the invention;
FIG. 4 is an SEM photograph of a Beta molecular sieve prepared according to comparative example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by the embodiments.
The diameter of the silica pellets, the grain size of the Yang Meizhuang Beta molecular sieve, the mesoporous size and the average mesoporous distance are all obtained by calculating the average value after counting at least 100 data in corresponding SEM pictures; siO of Beta molecular sieve 2 /Al 2 O 3 The ratio (calculated by mass) is obtained by ICP test; the mesoporous volume of the Beta molecular sieve is obtained through a nitrogen adsorption and desorption test.
SEM pictures were obtained using a Hitachi S-4800 cold field emission high resolution scanning electron microscope from Hitachi.
ICP testing was performed using a Kontron Model S-35 type ICP-AES analyzer, with 50mg of the sample completely dissolved in 50g of hydrofluoric acid solution prior to testing.
The specific surface area and mesoporous pore volume of the material were tested at liquid nitrogen temperature using BEL-MAX specific surface area and pore size analyzer from BELSORP Corp.
[ example 1]
The implementation isThe method is used for synthesizing the waxberry-shaped Beta molecular sieve, and the specific synthesis process is as follows: 1200 g of water, 30 g of urea, 30 g of eicosyl trimethyl ammonium bromide, 1000 g of cycloheptane, 80 g of n-amyl alcohol and 20 g of tetraethyl silicate are mixed in a closed container at 110 ℃ for 10 hours to obtain a mixture A1, after the mixture A1 is stirred, the mixture A1 is separated, washed, dried and roasted to obtain silica pellets with organic matters removed, SEM pictures of the silica pellets are shown in figure 1, the average diameter of the silica pellets is 360nm, and the specific surface area of the silica pellets is 750m through nitrogen absorption and desorption test 2 /g。
6 g of silica pellets, 0.728 g of pseudo-boehmite (alumina content 70 wt.%) and 4 g of tetraethylammonium hydroxide solution (25 wt.% aqueous solution) were mixed uniformly to obtain a mixture B1.
Then placing a porous partition board in the middle of a closed container, placing 5 g of dried mixture B1 on the partition board, placing a mixed solution of 2.5 g of water and 2.5 g of ethanol under the partition board, enabling the mixture B1 not to contact with the mixed solution of water and ethanol, treating the closed container at 110 ℃ for 48 hours, and washing, drying and roasting after the completion of the treatment to obtain the waxberry-shaped Beta molecular sieve M1.
ICP testing of SiO 2 /Al 2 O 3 The SEM photograph of the beta molecular sieve was 11.7, and the average grain size was 550nm as shown in FIG. 2. The grain has waxberry shape, mesoporous grains are round, the average size of mesoporous orifice is 25nm, the average edge distance of adjacent mesoporous pores is 30nm, XRD spectrum is shown in figure 3, characteristic diffraction peak belonging to Beta molecular sieve appears, and the specific surface area of Beta molecular sieve is 820m 2 ·g -1 Mesoporous volume of 0.91cm 3 ·g -1 。
[ example 2 ]
The embodiment is used for synthesizing the waxberry-shaped Beta molecular sieve, and the specific synthesis process is as follows: 720 g of water, 14 g of urea, 14 g of cetyltrimethylammonium bromide, 750 g of cyclopentane, 55 g of n-butanol and 20 g of tetramethyl silicate are mixed in a closed container at 120 ℃ for 6 hours to obtain a mixture A2, and after the completion, the mixture A2 is separated, washed, dried and roasted to obtain silica pellets with the organic matters removed, wherein the average diameter of the silica pellets is as follows310nm, and a specific surface area of 780m as measured by nitrogen adsorption and desorption 2 /g。
6 g of silica pellets, 0.182 g of pseudo-boehmite (alumina content 70 wt.%) and 3.428 g of tetraethylammonium hydroxide solution (25 wt.% aqueous solution) were mixed uniformly to obtain a mixture B2.
Then placing a porous partition board in the middle of a closed container, placing 5 g of dried mixture B2 on the partition board, placing a mixed solution of 1.5 g of water and 1.2 g of ethanol under the partition board, enabling the mixture B2 not to contact with the mixed solution of water and ethanol, treating the closed container at 118 ℃ for 26 hours, and washing, drying and roasting after the completion of the treatment to obtain the waxberry-shaped Beta molecular sieve M2.
ICP testing of SiO 2 /Al 2 O 3 The average grain size of the beta molecular sieve was 46.8 and was 450nm. The grain shape is waxberry-shaped, the surface of the grain has mesopores, the average size of the mesopore opening is 28nm, the average edge distance of the adjacent mesopores is 38nm, and the specific surface area of the beta molecular sieve is 750m 2 ·g -1 Mesoporous volume of 0.88cm 3 ·g -1 。
[ example 3 ]
The embodiment is used for synthesizing the waxberry-shaped Beta molecular sieve, and the specific synthesis process is as follows: 1000 g of water, 34 g of urea, 34 g of octadecyl trimethyl ammonium bromide, 1200 g of cyclohexane, 100 g of n-hexanol and 20 g of tetrapropyl silicate are mixed in a closed container for 4.5h at 135 ℃ to obtain a mixture A3, after the mixture A3 is stirred for 4.5h, the mixture A3 is separated, washed, dried and roasted to obtain silica pellets with the organic matters removed, the average diameter of the silica pellets is 380nm, and the specific surface area of the silica pellets is 620m through a nitrogen absorption desorption test 2 /g。
6 g of silica pellets, 0.952 g of pseudo-boehmite (alumina content 70 wt.%) and 3.1 g of tetraethylammonium hydroxide solution (25 wt.% aqueous solution) were mixed uniformly to obtain a mixture B3. Then placing a porous partition board in the middle of a closed container, placing 5 g of dried mixture B3 on the partition board, placing a mixed solution of 4.5 g of water and 3.5 g of ethanol under the partition board, enabling the mixture B3 not to contact with the mixed solution of water and ethanol, treating the closed container at 105 ℃ for 70 hours, and washing, drying and roasting after the completion of the treatment to obtain the waxberry-shaped Beta molecular sieve M3.
ICP testing of SiO 2 /Al 2 O 3 9.1, average grain size of beta molecular sieve is 880nm, grain shape is waxberry-like, mesoporous is arranged on the surface of the grain, average size of mesoporous aperture is 22nm, average edge distance of adjacent mesoporous aperture is 25nm, and specific surface area of beta molecular sieve is 680m 2 ·g -1 Mesoporous volume of 0.90cm 3 ·g -1 。
Comparative example 1
As compared with example 1, the prepared silica pellets were replaced with commercially available silica powder (manufacturer: qingdao silica gel technology Co., ltd.; model: B400; particle size 300-400 nm), and the rest was the same.
The synthesis process of the Beta molecular sieve is as follows: 6 g of silica fume, 0.728 g of pseudo-boehmite (alumina content 70 wt.%) and 4 g of tetraethylammonium hydroxide solution (25 wt.% aqueous solution) were mixed uniformly to obtain a mixture B.
Then placing a porous partition board in the middle of a closed container, placing 5 g of dried mixture B on the partition board, placing a mixed solution of 2.5 g of water and 2.5 g of ethanol under the partition board, enabling the mixture B not to contact with the mixed solution of water and ethanol, treating the closed container at 110 ℃ for 48 hours, and washing, drying and roasting after the completion of the treatment to obtain the Beta molecular sieve D1.
ICP testing of SiO 2 /Al 2 O 3 As shown in FIG. 4, SEM photograph of beta molecular sieve is 11.7, the average grain size is 200nm, and the surface of the grains has no mesoporous. Beta molecular sieve with specific surface area of 520m 2 ·g -1 The total pore volume is 0.21cm 3 ·g -1 。
[ example 4 ]
The waxberry-shaped Beta molecular sieves M1-M3 and D1 prepared in the examples 1-3 and the comparative example 1 are respectively applied to the liquid phase alkylation reaction of benzene and ethylene, and the ethylene mass airspeed is 6h at the reaction temperature of 175 ℃ and the pressure of 4.0MPa -1 After the reaction was continuously carried out for 6 hours under the condition that the molar ratio of benzene to ethylene was 2, the conversion of ethylene was measured, and the measurement results are shown in Table 1 below.
TABLE 1 liquid phase alkylation reaction results of benzene and ethylene
| Sequence number | Molecular sieve | Ethylene conversion% |
| 1 | M1 | 73 |
| 2 | M2 | 71 |
| 3 | M3 | 74 |
| 4 | D1 | 51 |
Claims (10)
1. The synthesis method of the Beta molecular sieve comprises the steps that the morphology of grains of the Beta molecular sieve is Yang Meizhuang, mesopores are arranged on the surfaces of the grains, and the average size of the mesopore orifice is 20-30nm; the specific surface area of the Beta molecular sieve is 600-850m 2 ·g -1 Mesoporous volume of 0.86-0.95cm 3 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The synthesis method comprises the following steps:
1) Contacting water, urea, surfactant, cycloalkane, alcohol and a silicon source to obtain a mixture A;
2) Stirring the mixture A in a closed container to prepare silica pellets, and roasting the silica pellets to remove organic matters;
3) Contacting the silica pellets with organic matters removed, tetraethylammonium hydroxide solution and an aluminum source to obtain a mixture B;
4) Performing alcohol steam treatment on the mixture B in the presence of water and ethanol to obtain a Yang Meizhuang Beta molecular sieve;
the mass ratios of the water, urea, surfactant, naphthene, alcohol and silicon source in the step 1) are respectively as follows: silicon source = 35-65; urea: silicon source = 0.6-1.8; and (2) a surfactant: silicon source = 0.6-1.8; cycloalkane: silicon source = 35-65; alcohol: silicon source = 2.5-5.5;
the stirring temperature in the step 2) is 100-140 ℃;
the mass ratio of the silicon dioxide pellets, the tetraethylammonium hydroxide solution and the aluminum source in the step 3) is that: tetraethylammonium hydroxide = 4-8; according to SiO 2 Calculated silica spheres and Al 2 O 3 The calculated mass ratio of the aluminum source is 8.8-47;
the mass ratio of water to ethanol in the step 4) is 0.5-2, and the mass ratio of the mixture B to the mixture of water and ethanol is 0.5-2;
the alcohol vapor treatment time in the step 4) is 24-72h, and the temperature is 100-120 ℃.
2. The method for synthesizing Beta molecular sieve according to claim 1, wherein the surfactant in step 1) is one or more of cetyltrimethylammonium bromide, octadecyltrimethylammonium bromide or eicosyltrimethylammonium bromide; the cycloalkane is one or more of cyclopentane, cyclohexane and cycloheptane; the alcohol is one or more of n-butanol, n-amyl alcohol and n-hexanol; the silicon source is one or more of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate.
3. The method for synthesizing Beta molecular sieves according to claim 1, wherein the stirring time in the step 2) is 4h to 12h.
4. The method for synthesizing Beta molecular sieve according to claim 1, wherein the average diameter of the silica pellets from which the organic matter is removed is 300-400nm, and the specific surface area is 600-800m 2 /g。
5. The method for synthesizing Beta molecular sieves according to claim 1, wherein the alcohol vapor treatment in step 4) is: and (3) carrying out gas-solid phase crystal transformation treatment on the mixture B.
6. A Beta molecular sieve synthesized according to the synthesis method of any one of claims 1-5.
7. The Beta molecular sieve according to claim 6, wherein the mesoporous pores on the surface of the Beta molecular sieve grains are round or similar round, and the average edge distance between adjacent mesoporous pores is 20-40nm.
8. The Beta molecular sieve according to claim 6, wherein in the Beta molecular sieve, siO 2 /Al 2 O 3 =8.8-50, the grain size averages 400-900nm.
9. A process for the liquid phase alkylation of benzene and ethylene using the Beta molecular sieve of any one of claims 6 to 8 or synthesized using the synthesis method of any one of claims 1 to 5.
10. The process for the liquid phase alkylation of benzene and ethylene according to claim 9, wherein the reaction temperature is 170-175 ℃, the pressure is 3.0-4.0MPa, and the ethylene mass space velocity is 5-6h -1 Benzene and ethylene are subjected to alkylation reaction under the condition that the molar ratio of benzene to ethylene is 1.5-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010626580.0A CN113880103B (en) | 2020-07-01 | 2020-07-01 | Beta molecular sieve and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010626580.0A CN113880103B (en) | 2020-07-01 | 2020-07-01 | Beta molecular sieve and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113880103A CN113880103A (en) | 2022-01-04 |
| CN113880103B true CN113880103B (en) | 2023-06-06 |
Family
ID=79012343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010626580.0A Active CN113880103B (en) | 2020-07-01 | 2020-07-01 | Beta molecular sieve and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113880103B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101299366A (en) * | 2008-03-13 | 2008-11-05 | 复旦大学 | Magnetic inorganic nano corpuscle/zeolite nucleocapsid type composite microsphere and preparation method thereof |
| WO2015001095A1 (en) * | 2013-07-05 | 2015-01-08 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Process for the preparation of organo-template free supported zeolite layers |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102262349B1 (en) * | 2013-07-04 | 2021-06-08 | 토탈 리서치 앤드 테크놀로지 펠루이 | Catalyst compositions comprising small size molecular sieves crystals deposited on a porous material |
| CN106179471B (en) * | 2016-07-12 | 2018-12-18 | 太原理工大学 | Spherical hollow catalyst of hydrogen production by ethanol steam reforming and preparation method thereof |
| CN107082436B (en) * | 2017-04-14 | 2019-11-26 | 武汉理工大学 | A kind of preparation method of mesoporous micro porous molecular sieve |
| CN109748291A (en) * | 2017-11-06 | 2019-05-14 | 中国科学院上海硅酸盐研究所 | A kind of preparation method with super large mesoporous hierarchical porous structure zeolite molecular sieve |
| CN111115854A (en) * | 2018-10-30 | 2020-05-08 | 芜湖美的厨卫电器制造有限公司 | Scale inhibitor coated mesoporous microsphere, preparation method thereof, water heater and liner |
| CN109529922A (en) * | 2018-11-30 | 2019-03-29 | 中国科学院大连化学物理研究所 | A kind of Beta@Silicalite-1 type core-shell molecular sieve and its preparation method and application |
| CN109368654A (en) * | 2018-11-30 | 2019-02-22 | 中国科学院大连化学物理研究所 | A kind of preparation method of nano Si licalite-1 molecular sieve |
| CN109721078A (en) * | 2019-02-26 | 2019-05-07 | 吉林大学 | A method of mesopore molecular sieve is prepared without mesoporous template Direct Hydrothermal method in the system that mesoporous silicon oxide is silicon source presoma |
-
2020
- 2020-07-01 CN CN202010626580.0A patent/CN113880103B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101299366A (en) * | 2008-03-13 | 2008-11-05 | 复旦大学 | Magnetic inorganic nano corpuscle/zeolite nucleocapsid type composite microsphere and preparation method thereof |
| WO2015001095A1 (en) * | 2013-07-05 | 2015-01-08 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Process for the preparation of organo-template free supported zeolite layers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113880103A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3165280B1 (en) | Scm-11 molecular sieve, a process for producing same and use thereof | |
| US8840864B2 (en) | Method of preparing ZSM-5 zeolite using nanocrystalline ZSM-5 seeds | |
| CN107512728B (en) | Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores | |
| CN108002396B (en) | Method for synthesizing Silicalite-1 molecular sieve by taking TPABr as template agent | |
| CN105983437A (en) | Catalyst containing MWW-structured molecular sieve as well as preparation method and application of catalyst | |
| JP6879680B2 (en) | Method for producing high silica chabazite type zeolite and high silica chabazite type zeolite | |
| CN110028080A (en) | A kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity | |
| CN113880103B (en) | Beta molecular sieve and synthesis method and application thereof | |
| CN103145145B (en) | Method for synthesizing SAPO-34 molecular sieve by taking A type zeolite as silicon source | |
| CN108285151A (en) | A kind of Ce same order elements LTL molecular sieves and preparation method thereof | |
| CN115490243B (en) | Short b-axis HZSM-5 zeolite molecular sieve and preparation method and application thereof | |
| CN104760971A (en) | Beta molecular sieve alkali-free metal ion synthesis method | |
| CN107986296B (en) | A-type molecular sieve with high silica-alumina ratio and preparation method thereof | |
| CN115010146B (en) | Multistage hole ZSM-5 nano aggregate molecular sieve and preparation method thereof | |
| CN112850742B (en) | Hierarchical pore Y-type molecular sieve and synthesis method thereof | |
| CN113880107A (en) | ZSM-5 molecular sieve and synthesis method and application thereof | |
| CN112456511B (en) | SAPO-34 molecular sieve, and preparation method and application thereof | |
| CN110642262B (en) | Method for synthesizing SAPO-35 molecular sieve by using double templates | |
| CN115196650A (en) | Metal modified mesoporous ZSM-5 molecular sieve and preparation method thereof | |
| CN114031092A (en) | Preparation method of SAPO-20 molecular sieve | |
| CN116060106A (en) | Al-SBA-15/beta core-shell composite molecular sieve and preparation method and application thereof | |
| CN109835913B (en) | Synthesis method of rare earth EU-1 hierarchical pore molecular sieve | |
| CN107973305B (en) | Mesoporous-rich IMF structure molecular sieve and preparation method thereof | |
| CN115140746B (en) | ZSM-5 molecular sieve with cascade hole distribution and preparation method thereof | |
| JP2022545768A (en) | Aluminosilicate structure having novel structure and skein-like morphology, method for producing same, and HPLC column filled with same as stationary phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |