CN110127718A - A kind of ZSM-35/ZSM-5 composite molecular screen and preparation method thereof - Google Patents
A kind of ZSM-35/ZSM-5 composite molecular screen and preparation method thereof Download PDFInfo
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- CN110127718A CN110127718A CN201910449975.5A CN201910449975A CN110127718A CN 110127718 A CN110127718 A CN 110127718A CN 201910449975 A CN201910449975 A CN 201910449975A CN 110127718 A CN110127718 A CN 110127718A
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- molecular sieve
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- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
- C01B39/445—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 using at least one organic template directing agent
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
-
- 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
Abstract
The invention discloses a kind of ZSM-35/ZSM-5 composite molecular screens and preparation method thereof, the composite molecular screen has the structure feature of FER topological structure and MFI topological structure molecular sieve simultaneously, the isopropylamine for generating ZSM-35 molecular sieve but also guiding generation ZSM-5 molecular sieve can be oriented to as template by using, and ZSM-35/ZSM-5 composite molecular screen is prepared in hydrothermal synthesis.Obtained composite molecular screen stable structure, composition is controllable, has excellent performance.Preparation method step is simple and convenient to operate, and is easy to industrial applications.
Description
Technical field
The invention belongs to field of chemical technology, it is related to a kind of composite molecular screen and preparation method thereof, specifically, being related to
It is a kind of while there is ZSM-35 molecular sieve structure and the composite molecular screen of ZSM-5 molecular sieve structure and preparation method thereof.
Background technique
Composite molecular screen is the composite crystal formed by two or more different topology structure molecular sieve combination, generally
It is able to maintain the self property of every kind of molecular sieve structure, while unique cellular structure and Acidity can also be generated, it is anti-in catalysis
The feature different from single molecular sieve is shown in answering.CN94113403.2 discloses ZSM-5/ZSM-11 composite molecular screen,
It is applied in catalytic cracked dry gas ethylbenzene reaction process as catalyst, shows and be substantially better than ZSM-5 molecular sieve catalyst
Reactivity worth.In order to organically combine the characteristic of different topology structure molecular sieve to improve the catalytic perfomance of catalyst, grind
The persons of studying carefully have developed a series of composite molecular screens in succession.CN1583562A discloses a kind of FAU/BEA double-micropore composite molecular sieve,
CN106946268A discloses a kind of MOR/ZSM-35 composite molecular screen, and CN101003379A discloses a kind of ZSM-35/MCM-
22 composite molecular screens.Due to the particularity of compound molecule sieve structure, so composite molecular screen, which is provided with, is substantially better than single molecule
The Acidity feature and cellular structure feature of sieve, can overcome the limitation of single molecular sieve self structure, can preferably meet combustion
The demand of material and chemicals production chemical process industrial applications, has broad application prospects.
ZSM-35 molecular sieve has FER topological structure, the octatomic ring for possessing ten-ring duct (4.2 × 5.4) and intersecting
Duct (3.5 × 4.8), at the same the hexatomic ring duct parallel with ten-ring duct and octatomic ring duct be crossed to form one it is ellipse
Spherical small cage, referred to as " ferrierite cage ".ZSM-5 molecular sieve have MFI topological structure, possess ten-ring straight hole road (5.3 ×
5.6) with the Z-shaped duct of ten-ring (5.1 × 5.5), duct intersects to form three dimensional intersection cellular structure.ZSM-35 molecular sieve and
ZSM-5 molecular sieve belongs to ten-ring cellular structure molecular sieve, respectively in methanol-to-olefins, catalytic cracking, olefin cracking, isomery
Unique catalytic performance is shown in the reaction such as change, and since there are many Spatial Dimensions of multiplicity and connection for ten-ring molecular sieve
Type, each molecular sieve show different catalytic characteristics again in same reaction.Therefore, compound point of ZSM-35/ZSM-5 is developed
Son sieve will combine the advantage of ZSM-35 molecular sieve and ZSM-5 molecular sieve, in the reaction process such as olefin cracking and methanol-to-olefins
Show unique catalytic.Currently, not there is the open report of ZSM-35/ZSM-5 composite molecular screen.
Summary of the invention
The purpose of the present invention is to propose to a kind of ZSM-35/ZSM-5 composite molecular screen, which has FER simultaneously
The structure feature of topological structure and MFI topological structure molecular sieve generates ZSM-35 molecular sieve but also guiding life using that can be oriented to
It is template at the isopropylamine of ZSM-5 molecular sieve, ZSM-35/ZSM-5 composite molecular screen is prepared in hydrothermal synthesis.What is obtained answers
Conjunction molecular sieve structure is stable, composition is controllable, has excellent performance.Preparation method step is simple and convenient to operate, and is easy to industrial applications.
Realize the specific technical solution of the object of the invention:
A kind of ZSM-35/ZSM-5 composite molecular screen, feature are that the molecular sieve has ZSM-35 molecular sieve and ZSM-5 molecular sieve
Structure feature, wherein ZSM-35 molecular sieve accounts for the 5 ~ 95% of composite molecular screen composition；The preparation method of the composite molecular screen, including
Step in detail below:
The preparation of first step reaction mixture
By the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water 1:(0.015 ~ 0.1 in molar ratio):
(0.15 ~ 0.23): (0.1 ~ 1.0): (10 ~ 50) be uniformly mixed, prepare reaction mixture, wherein the silicon source be silica solution,
At least one of silica gel and waterglass, the silicon source are at least one of sodium metaaluminate, aluminum sulfate and aluminum nitrate, described
Alkali source be NaOH, the template is isopropylamine；
Second step hydro-thermal process
It will be transferred in closed reactor through reaction mixture made from upper step, it is small in 150~190 DEG C of hydro-thermal process 24~72
When, the ZSM-35/ZSM-5 composite molecular screen is obtained after being then filtered, washed, dried, being roasted.
Compared with existing technology, the present invention has following remarkable advantage:
1, there is not ZSM-35/ZSM-5 composite molecular screen at present, which has expanded compound point containing ZSM-35 molecular sieve
The type of son sieve.
2, ZSM-35/ZSM-5 composite molecular screen stable structure, composition are controllable.
3, synthesis process is simple, easy to operate, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the XRD spectra of ZSM-35/ZSM-5 composite molecular screen, ZSM-35 molecular sieve and ZSM-5 molecular sieve；
Fig. 2 is the electromicroscopic photograph figure for the ZSM-35/ZSM-5 composite molecular screen that embodiment 1 is prepared.
Specific embodiment
The operating procedure of all embodiments according to the above technical scheme is operated.
Embodiment 1
The preparation of first step reaction mixture
By the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water 1:0.05:0.18 in molar ratio:
0.6:20 is uniformly mixed, and prepares reaction mixture, wherein it is sodium metaaluminate that the silicon source, which is silica solution, the silicon source, institute
The alkali source stated is NaOH, and the template is isopropylamine；
Second step hydro-thermal process
To be transferred in closed reactor through reaction mixture made from upper step, in 170 DEG C hydro-thermal process 72 hours, then pass through
The ZSM-35/ZSM-5 composite molecular screen is obtained after filter, washing, dry, roasting.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is as shown in figure 1 shown in A, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 72% of molecular sieve.
The XRD spectra from Fig. 1 is it is found that ZSM-35/ZSM-5 composite molecular screen has ZSM-35 molecular sieve and ZSM-5 simultaneously
The structure feature of molecular sieve；The stereoscan photograph from Fig. 2 it is found that ZSM-35/ZSM-5 composite molecular screen by biggish sheet
ZSM-35 molecular sieve and lesser fine particle ZSM-5 molecular sieve intertexture symbiosis are formed.
Embodiment 2
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.24:0.6:20 is uniformly mixed, and prepares reaction mixture.
It obtains in the XRD spectra and Fig. 1 of product ZSM-35 molecular sieve shown in B, is pure phase FER topological structure molecular sieve.
Embodiment 3
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.14:0.6:20 is uniformly mixed, and prepares reaction mixture.
It obtains in the XRD spectra and Fig. 1 of product ZSM-5 molecular sieve shown in C, is pure phase MFI topological structure molecular sieve.
Embodiment 4
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.16:0.8:50 is uniformly mixed, and prepares reaction mixture.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 33% of molecular sieve.
Embodiment 5
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.20:1.0:50 is uniformly mixed, and prepares reaction mixture.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 89% of molecular sieve.
Embodiment 6
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.23:0.5:15 is uniformly mixed, and prepares reaction mixture.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 93% of molecular sieve.
Embodiment 7
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.22:0.6:20 is uniformly mixed, and prepares reaction mixture, and the silicon source is the sodium metaaluminate for being 7:3 according to weight ratio
With the mixture of aluminum sulfate.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 90% of molecular sieve.
Embodiment 8
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.16:0.3:25 is uniformly mixed, and prepares reaction mixture.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 15% of molecular sieve.
Embodiment 9
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.15:0.6:20 is uniformly mixed, and prepares reaction mixture.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 8% of molecular sieve.
Embodiment 10
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.025:0.18:0.6:20 is uniformly mixed, and prepares reaction mixture；
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for compound point
The 68% of son sieve.
Embodiment 11
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.025:0.18:0.5:30 is uniformly mixed, and prepares reaction mixture；Second step in 190 DEG C hydro-thermal process 24 hours
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for compound point
The 68% of son sieve.
Embodiment 12
Except for the following differences, remaining is with embodiment 1 for implementation process:
In the first step by the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water in molar ratio 1:
0.05:0.20:0.6:20 is uniformly mixed, and prepares reaction mixture, and the silicon source is the silica solution and silicon for being 8:2 according to weight ratio
Glue mixture；Second step in 150 DEG C hydro-thermal process 36 hours.
The XRD spectra of product ZSM-35/ZSM-5 composite molecular screen is similar with A in Fig. 1, and wherein ZSM-35 molecular sieve accounts for multiple
Close the 85% of molecular sieve.
Claims (3)
1. a kind of preparation method of ZSM-35/ZSM-5 composite molecular screen, it is characterised in that this method comprising the following specific steps
The preparation of first step reaction mixture
By the SiO in silicon source2, Al in silicon source2O3, OH in alkali source-, template and water 1:(0.015 ~ 0.1 in molar ratio):
(0.15 ~ 0.23): (0.1 ~ 1.0): (10 ~ 50) be uniformly mixed, prepare reaction mixture, wherein the silicon source be silica solution,
At least one of silica gel and waterglass, the silicon source are at least one of sodium metaaluminate, aluminum sulfate and aluminum nitrate, described
Alkali source be NaOH, the template is isopropylamine；
Second step hydro-thermal process
It will be transferred in closed reactor through reaction mixture made from the first step, it is small in 150~190 DEG C of hydro-thermal process 24~72
When, the ZSM-35/ZSM-5 composite molecular screen is obtained after being then filtered, washed, dried, being roasted.
2. ZSM-35/ZSM-5 composite molecular screen made from a kind of claim 1 the method.
3. ZSM-35/ZSM-5 composite molecular screen according to claim 2, which is characterized in that the molecular sieve has ZSM-35
The structure feature of molecular sieve and ZSM-5 molecular sieve, wherein ZSM-35 molecular sieve accounts for the 5 ~ 95% of composite molecular screen composition.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112619698A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-35 composite molecular sieve and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112619698A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | ZSM-5/ZSM-35 composite molecular sieve and preparation method thereof |
| CN112619698B (en) * | 2019-09-24 | 2023-03-10 | 中国石油化工股份有限公司 | ZSM-5/ZSM-35 composite molecular sieve and preparation method thereof |
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Application publication date: 20190816 |