CN110451519A - A kind of eutectic material and preparation method thereof containing MTW structure - Google Patents
A kind of eutectic material and preparation method thereof containing MTW structure Download PDFInfo
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- CN110451519A CN110451519A CN201910767015.3A CN201910767015A CN110451519A CN 110451519 A CN110451519 A CN 110451519A CN 201910767015 A CN201910767015 A CN 201910767015A CN 110451519 A CN110451519 A CN 110451519A
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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
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2006/12—Surface area
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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
- C01P2006/14—Pore volume
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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 present invention provides a kind of eutectic material and preparation method thereof containing MTW structure, and by percentage to the quality, which includes 1.2% to 98% MTW structural material, remaining is BEA or MOR structural material；Si/Al atomic ratio is 1~6000:1 in eutectic material.It is mixed under conditions of pH value is greater than 7 by the way that the raw materials such as element silicon, aluminium element, water, organic molecule will be contained, later by mixed substance crystallization 20 to 200 hours under the conditions of 120-200 DEG C, product separation is obtained into the eutectic material of the structure containing MTW later, this method can overcome the prior art that can not provide MTW/MOR eutectic molecular sieve and the single technical problem of MTW/BEA eutectic molecular sieve product category.
Description
Technical field
The present invention relates to molecular screen material technical field, be specifically related to a kind of eutectic material containing MTW structure and its
Preparation method.
Background technique
Zeolite molecular sieve is a kind of crystalline microporous material with skeleton structure, due to its with specific pore size,
Structure feature, biggish specific surface area, suitable mechanical strength, the applicability to chemical reaction and the selectivity to catalysis reaction
Controllable advantage is often applied in many catalysis reactions, especially in petroleum refining and processing, coal chemical industry, gas chemical industry, life
Substance industry and polymer precursor preparation etc. have a wide range of applications.
The non-crossing duct of one-dimensional linear that there is MTW structure molecular screen material twelve-ring to constitute, between mesoporous and greatly
Pore size between porous molecular sieve can effectively realize the shape selective catalysis conversion to most of organic molecules, MTW structure point
Son sieve because have good thermostable, unique cellular structure and can modulation acidity, in petroleum refining and chemical field, alkane
Catalytic activity, product well are shown in many acid catalyzed reactions such as hydrocarbon cracking, isomerization, reformation and the alkylation of aromatic hydrocarbons
Selectivity and catalytic stability.
Two kinds of (or a variety of) molecular sieve crystals can shape due to fault or the incorrect order arrangement of same or similar infinite component unit
Eutectic (intergrowth) molecular sieve crystal of Cheng Xin.Eutectic molecular sieve is capable of the cellular structure and Acidity of modulation molecular sieve,
I.e. there are two types of the respective response characteristics of molecular sieve in catalysis reaction, and show the exclusive collaboration different from mechanical mixture sample
Effect and reactivity worth have caused the extensive concern of industry, are the research and development focus of current industrial catalysis molecular sieve.
Have document report (J.Nat.Gas Chem.2007,16,37-41) by MTW/MFI eutectic molecular sieve catalysis toluene with
The reaction result of methanol methylation dimethylbenzene processed shows the catalytic performance of eutectic molecular sieve than simple MFI, MTW and the two
The catalyst of mechanical mixture is good.
CN201310532438.X discloses a kind of Beta/ZSM-12 composite molecular screen and its synthetic method, this method are
By alkali source, silicon source, addition is super with glucose solution after silicon source, water and template mix pre- crystallization with ingredient sequence by a certain percentage
The ZSM-12 molecular sieve of sonication, hydrothermal crystallizing obtain the composite molecular screen containing Beta and ZSM-12.
CN201510666029.8 discloses a kind of preparation of bulk Beta/ZSM-12 coexisting molecular sieve, and this method uses
Solvent evaporated method, by inorganic base, quaternary ammonium salt, silicon source, silicon source and deionized water are mixed with ingredient sequence by a certain percentage, and stirring is old
Solvent is evaporated after change, then Crystallizing treatment, Beta/ZSM-12 Intergrown molecular screen method is made and is characterized in that particle is in bulk,
Particle size is 2~4 μm.
CN104549466A discloses fabricated in situ ZSM-5/Beta Intergrown molecular sieve catalyst and preparation method thereof, the party
Silicon source, Beta molecular sieve, silicon source and water are mixed in a certain ratio spray shaping at band atomized microball, by microballoon, alkali source, aluminium by method
Source, template and water are mixed in a certain ratio carry out hydro-thermal process, obtain the coexisting molecular sieve containing ZSM-5 and Beta.
The synthetic method of coexisting molecular sieve still has some shortcomings at present, the composite construction of the coexisting molecular sieve such as synthesized
And crystal percentage is not easy to control, and synthesis cost is high, and preparation process is complicated, and eutectic molecular sieve type is single etc., affect eutectic point
The application of son sieve.
Summary of the invention
The first technical problem to be solved by the present invention is to provide a kind of eutectic material of structure containing MTW, solves existing skill
Art can not provide MTW/MOR eutectic molecular sieve, MTW/BEA eutectic molecular sieve product category single technical problem.
The second technical problem to be solved by the present invention is to provide a kind of preparation method of above-mentioned eutectic material, and this method can
To be used to produce the eutectic material of the structure containing MTW, overcome the process of the eutectic material of prior art production structure containing MTW it is cumbersome,
The problem of expensive starting materials.
In order to realize above-mentioned one of technical problem, the present invention provides a kind of eutectic material containing MTW structure, with quality
Percentages, including 1.2% to 98% MTW structural material, remaining is BEA or MOR structural material；Si/Al in eutectic material
Atomic ratio is 1~6000:1.
Further embodiment is that the specific surface area of eutectic material is 90m2/ g to 810m2/ g, pore volume 0.02cm3/ g is extremely
0.55cm3/ g, average grain diameter are 0.1 μm to 30 μm.
Preferably, the content of MTW structural material is 5% to 90%.
Preferably, the mass percentage of silica is 50% to 99.99% in eutectic material.
In order to realize the two of above-mentioned technical problem, preparation method provided by the invention, comprising the following steps: 1) by water,
Substance containing aluminium element, the substance containing element silicon, alkaline matter mixing；2) that step 1) is obtained mixture stirring is 0.1 small
Up to 50 hours；3) mixture obtained by step 2) is heated to 120 DEG C to 190 DEG C, keep mixture pressure 0.1MPa extremely
15MPa, and keep the temperature range 20 hours to 200 hours；4) mixture obtained by step 3) is adjusted to different from step 3)
130 DEG C to 200 DEG C of another temperature spot, keep mixture pressure in 0.1MPa to 15MPa, and at such a temperature keep 15 hours
To 190 hours；5) step 4) products therefrom is taken out, obtains the eutectic material of the structure containing MTW by separation.
Preferably, the substance containing aluminium element be meta-aluminate, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium hydroxide, intend it is thin
At least one of diaspore, kaolin, montmorillonite；Substance containing element silicon be waterglass, silica solution, white carbon black, flyash,
At least one of kaolin, montmorillonite, attapulgite, ethyl orthosilicate；Alkaline matter is sodium hydroxide, rubidium hydroxide, hydrogen
At least one of cesium oxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, tetra-alkyl ammonium hydroxide.
Further embodiment is that the mixture in step 1) is alkalinity, and pH value is 7.5 to 14.
Further embodiment is that the mixing time in step 2) is 0.3 hour to 10 hours.
Further embodiment is, temperature range is 120 DEG C to 190 DEG C in step 3), pressure limit 0.4MPa extremely
10MPa, time range was at 20 hours to 150 hours.
Further embodiment is that temperature range is within the scope of 135 DEG C to 189 DEG C in step 4), and pressure limit exists
0.5MPa to 9MPa, time range was at 20 hours to 140 hours.
The beneficial effects of the present invention are: the eutectic material of structure containing MTW prepared using the above method, material granule, which removes, to be contained
Have outside MTW structure, there are also BEA or MOR structures, and the specific surface area of eutectic material is in 90m2/ g to 810m2/ g, pore volume exist
0.02cm3/ g to 0.55cm3/ g, the average grain diameter of eutectic material are 0.1 μm to 30 μm.MTW structure is included at least in eutectic material
Material, and the content of MTW structural material be 5%~90% (mass percent), wherein the content of silica be 50%~
99.99% (mass percent).The preparation method of the eutectic material of the structure containing MTW provided, this method can be used to produce to contain
MTW structure eutectic material overcomes the prior art that can not provide MTW/MOR eutectic molecular sieve and MTW/BEA eutectic molecular sieve product
The single technical problem of type.
Detailed description of the invention
Fig. 1 is the scanning electron microscope sem figure for the MTW/BEA zeolite molecular sieve that the embodiment of the present invention 1 is prepared.
Fig. 2 is the XRD diagram for the MTW/BEA zeolite molecular sieve that the embodiment of the present invention 1 is prepared.
Fig. 3 is the scanning electron microscope sem figure for the MTW/MOR zeolite molecular sieve that the embodiment of the present invention 3 is prepared.
Fig. 4 is the XRD diagram for the MTW/BEA zeolite molecular sieve that the embodiment of the present invention 4 is prepared.
The invention will be further described with reference to the accompanying drawings and embodiments.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.Institute in following embodiments
Reagent, material etc., is commercially available unless otherwise specified.
Embodiment 1
(1) raw material configures: taking 19.256g water to be added in 25% tetraethyl ammonium hydroxide solution of 65.96g, into solution
Sodium aluminate 0.89g, potassium hydroxide 0.8g is added, 40% silica solution of 48.607g is slowly added dropwise into solution while stirring, continues
Stir about 1 hour.
(2) above-mentioned solution is transferred to reaction kettle, is placed in crystallization 48 hours in 140 DEG C of baking oven.
(3) reaction kettle taking-up is placed in 160 DEG C of baking oven crystallization 72 hours.
(4) last handling process: crystallization product is filtered or is centrifugated, to distill water washing to product leacheate pH for 7-
8, in an oven with dry 8-12 hours under the conditions of 80 DEG C of temperature, finally in Muffle furnace with 1-4 DEG C/rate be warming up to
Continue roasting 4-6 hours at 500-600 DEG C, obtains final zeolite molecules sieve mesh border product.
According to mass percent meter, products therefrom structural material containing 58%MTW, remaining is BEA structural material；Eutectic material
Middle Si/Al atomic ratio is 40:1, and the specific surface area of eutectic material is 510m2/ g, pore volume 0.09cm3/ g, average grain diameter are 3 μ
m。
Embodiment 2
(1) raw material configures: taking 19.256g water to be added in 20g tetraethylammonium bromide, sodium aluminate is added into solution
68.607g silica solution is slowly added dropwise in 0.69g, sodium hydroxide 1.2g into solution while stirring, continues stir about 1 hour.
(2) above-mentioned solution is transferred to reaction kettle, is placed in crystallization 48 hours in 140 DEG C of baking oven.
(3) reaction kettle taking-up is placed in 160 DEG C of baking oven crystallization 96 hours.
(4) crystallization product is filtered or is centrifugated, to distill water washing to product leacheate pH for 7-8, in an oven
With dry 8-12 hours under the conditions of 80 DEG C of temperature, finally in Muffle furnace with 1-4 DEG C/rate be warming up at 500-600 DEG C
Continue roasting 4-6 hours, obtains final zeolite molecules sieve mesh border product.
According to mass percent meter, products therefrom structural material containing 37%MTW, remaining is MOR structural material；Eutectic material
Middle Si/Al atomic ratio is 29:1, and the specific surface area of eutectic material is 530m2/ g, pore volume 0.15cm3/ g, average grain diameter are 2 μ
m。
Embodiment 3
(1) raw material configures: taking 29.256g water to be added to 35.96g methyl triethyl ammonium chloride, aluminic acid is added into solution
50.607g silica solution is slowly added dropwise in sodium 0.29g, sodium hydroxide 0.9g into solution while stirring, continues stir about 1 hour.
(2) above-mentioned solution is transferred to reaction kettle, is placed in crystallization 72 hours in 140 DEG C of baking oven.
(3) reaction kettle taking-up is placed in 160 DEG C of baking oven crystallization 72 hours.
(4) crystallization product is filtered or is centrifugated, to distill water washing to product leacheate pH for 7-8, in an oven
With dry 8-12 hours under the conditions of 80 DEG C of temperature, finally in Muffle furnace with 1-4 DEG C/rate be warming up at 500-600 DEG C
Continue roasting 4-6 hours, obtains final zeolite molecules sieve mesh border product.
According to mass percent meter, products therefrom structural material containing 78%MTW, remaining is MOR structural material；Eutectic material
Middle Si/Al atomic ratio is 89:1, and the specific surface area of eutectic material is 390m2/ g, pore volume 0.09cm3/ g, average grain diameter are 1 μ
m。
Embodiment 4
(1) raw material configures: taking 49.256g water to be added in 25.96g tetraethyl ammonium iodide, sodium aluminate is added into solution
68.607g silica solution is slowly added dropwise in 0.02g, sodium hydroxide 3g into solution while stirring, continues stir about 1 hour.
(2) above-mentioned solution is transferred to reaction kettle, is placed in crystallization 72 hours in 140 DEG C of baking oven.
(3) reaction kettle taking-up is placed in 160 DEG C of baking oven crystallization 96 hours.
(4) crystallization product is filtered or is centrifugated, to distill water washing to product leacheate pH for 7-8, in an oven
With dry 8-12 hours under the conditions of 80 DEG C of temperature, finally in Muffle furnace with 1-4 DEG C/rate be warming up at 500-600 DEG C
Continue roasting 4-6 hours, obtains final zeolite molecules sieve mesh border product.
According to mass percent meter, products therefrom structural material containing 90%MTW, remaining is BEA structural material；Eutectic material
Middle Si/Al atomic ratio is 500:1, and the specific surface area of eutectic material is 397m2/ g, pore volume are in 0.18cm3/ g, average grain diameter 8
μm。
Embodiment 5-20
By raw materials such as siliceous, aluminium, alkaline matters, according to the preparation condition of table 1, according to the same steps implemented in 1 to 4 into
Row operation, can be obtained the eutectic material of structure containing MTW.
Table 1
Finally it is emphasized that the above description is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is right
For those skilled in the art, the present invention can have various change and change, all within the spirits and principles of the present invention,
Any modification, equivalent substitution, improvement and etc. done, should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of eutectic material containing MTW structure, it is characterised in that:
By percentage to the quality, including 1.2% to 98% MTW structural material, remaining be BEA or MOR structural material；
Si/Al atomic ratio is 1~6000:1 in the eutectic material.
2. eutectic material according to claim 1, it is characterised in that:
The specific surface area of the eutectic material is 90m2/ g to 810m2/ g, pore volume 0.02cm3/ g to 0.55cm3/ g, average grain
Diameter is 0.1 μm to 30 μm.
3. eutectic material according to claim 1, it is characterised in that:
The content of the MTW structural material is 5% to 90%.
4. eutectic material according to claim 1, it is characterised in that:
The mass percentage of silica is 50% to 99.99% in the eutectic material.
5. such as the preparation method of the described in any item eutectic materials of Claims 1-4, which comprises the following steps:
1) water, the substance containing aluminium element, the substance containing element silicon, alkaline matter are mixed；
2) mixture for obtaining step 1) stirs 0.1 hour to 50 hours；
3) mixture obtained by step 2) is heated to 120 DEG C to 190 DEG C, keeps mixture pressure in 0.1MPa to 15MPa, and protect
Hold the temperature range 20 hours to 200 hours；
4) mixture obtained by step 3) is adjusted to 130 DEG C to 200 DEG C of another temperature spot different from step 3), keeps mixture
Pressure is kept for 15 hours to 190 hours in 0.1MPa to 15MPa, and at such a temperature；
5) step 4) products therefrom is taken out, obtains the eutectic material of the structure containing MTW by separation.
6. preparation method according to claim 5, it is characterised in that:
Substance containing aluminium element is meta-aluminate, aluminum sulfate, aluminum nitrate, aluminium chloride, aluminium hydroxide, boehmite, kaolinite
At least one of soil, montmorillonite；Substance containing element silicon be waterglass, silica solution, white carbon black, flyash, kaolin, cover it is de-
At least one of soil, attapulgite, ethyl orthosilicate；Alkaline matter is sodium hydroxide, rubidium hydroxide, cesium hydroxide, hydrogen-oxygen
Change at least one of potassium, lithium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, tetra-alkyl ammonium hydroxide.
7. preparation method according to claim 5, it is characterised in that:
The mixture that step 1) obtains is alkalinity, and pH value is 7.5 to 14.
8. preparation method according to claim 5, it is characterised in that:
Mixing time in step 2) is 0.3 hour to 10 hours.
9. preparation method according to claim 5, it is characterised in that:
In step 3) temperature range be 120 DEG C to 190 DEG C, pressure limit in 0.4MPa to 10MPa, time range at 20 hours extremely
150 hours.
10. according to the described in any item preparation methods of claim 5 to 9, it is characterised in that:
Temperature range is within the scope of 135 DEG C to 189 DEG C in step 4), and pressure limit is in 0.5MPa to 9MPa, and time range is 20
Hour was to 140 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880110A (en) * | 2021-10-25 | 2022-01-04 | 南昌大学 | Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101384366A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | A high throughput process for manufacturing molecular sieves |
| CN101679055A (en) * | 2007-05-25 | 2010-03-24 | Ifp公司 | Novel process for preparing zeolite eu-1 |
| CN103058220A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of BETA-MOR symbiotic molecular sieve |
| CN107955639A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of six alkane cracking of carbon |
| CN108275698A (en) * | 2018-03-19 | 2018-07-13 | 中国石油大学(北京) | A kind of Beta/ZSM-12 symbiosis zeolite molecular sieve and preparation method thereof |
-
2019
- 2019-08-20 CN CN201910767015.3A patent/CN110451519B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101384366A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | A high throughput process for manufacturing molecular sieves |
| CN101679055A (en) * | 2007-05-25 | 2010-03-24 | Ifp公司 | Novel process for preparing zeolite eu-1 |
| US20100178241A1 (en) * | 2007-05-25 | 2010-07-15 | Simone Goergen | Novel process for preparing eu-1 zeolite |
| CN103058220A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of BETA-MOR symbiotic molecular sieve |
| CN107955639A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of six alkane cracking of carbon |
| CN108275698A (en) * | 2018-03-19 | 2018-07-13 | 中国石油大学(北京) | A kind of Beta/ZSM-12 symbiosis zeolite molecular sieve and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880110A (en) * | 2021-10-25 | 2022-01-04 | 南昌大学 | Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof |
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