CN105753011A - Superfine zeolite molecular sieve and synthesis method thereof - Google Patents
Superfine zeolite molecular sieve and synthesis method thereof Download PDFInfo
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- CN105753011A CN105753011A CN201610070477.6A CN201610070477A CN105753011A CN 105753011 A CN105753011 A CN 105753011A CN 201610070477 A CN201610070477 A CN 201610070477A CN 105753011 A CN105753011 A CN 105753011A
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- molecular sieve
- zeolite molecular
- ethanol
- sodium hydroxide
- tpaoh
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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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract
The invention belongs to the technical field of catalysts and application thereof, in particular to a superfine zeolite molecular sieve and a synthesis method thereof. The synthesis method comprises the following steps: weighing tetrapropylammonium hydroxide, alcohol, sodium hydroxide and tetraethoxysilane; firstly mixing the tetrapropylammonium hydroxide with the alcohol, then adding the sodium hydroxide, further slowly dropwise adding the tetraethoxysilane while stirring intensely, and then performing thermal reaction for 12-24 hours after dropwise adding the tetraethoxysilane; then transferring reactants into a hydrothermal reactor, reacting at a temperature of 100-120 DEG C for 24-48 hours, washing the reactants by the alcohol after hydrothermal reaction is finished, filtering and centrifugalizing, eliminating supernatant liquid, performing ultrasonic treatment on a reserve part for 1-2 hours, taking out the reserve part, and calcinating the reserve part at a temperature of 480-540 DEG C for 4-8 hours; finally, grinding and sieving, thereby obtaining the superfine zeolite molecular sieve. Compared with the prior art, the superfine zeolite molecular sieve provided by the invention is efficient and environmentally friendly, and takes the alcohol as a dispersing agent; the preparation method is capable of solving the technical problems of difficulty in generation of nano products, low yield, high pollution, high cost and the like during preparation of zeolite molecular sieves in the prior art.
Description
[technical field]
The invention belongs to chemical field, specifically a kind of ultrafine zeolite molecular sieve and synthetic method thereof.
[background technology]
Mobile oil company of the U.S. is synthesized a kind of containing organic amine cation in eighties of last century sixties end
Zeolite molecular sieve.Owing to it has many unique in terms of chemical composition, crystal structure and physico-chemical property,
Therefore in a lot of organic catalytic reactions, show the catalysis efficiency of excellence, industrially obtained increasingly
It is widely applied, becomes the most promising new catalyst of one of petrochemical industry.
Current laboratory synthesis of zeolite molecular sieves mainly has template agent method and non-template agent method, either
Which kind of, all there are the following problems: product mostly is stock size, and the condition generating nano-scale product is difficult to slap
Hold；Partial synthesis method comprises intermediate product virose to human body or raw material.
It is known that zeolite molecular sieve is a kind of new catalyst being widely used in catalytic field, itself
Simultaneously because its porosity characteristic as the numerous organic reaction of catalyst, can have concurrently again and serve as catalyst
The ability of substrate.Chinese patent CN201510112650.X, CN201510112646.3 using zeolite as catalysis
It is loaded modified that agent substrate carries out metal ion, achieves good catalytic effect.Chinese patent
CN201510224342.6, CN201410098297.X describe the synthesis of several catalyst being associated with zeolite
Method.
[summary of the invention]
Present invention aim to solve above-mentioned deficiency and a kind of ultrafine zeolite molecular sieve and synthesis thereof are provided
A kind of method, it is provided that nanoscale mountainite molecular sieve with ethanol as dispersant efficient, eco-friendly,
Solve prepared by prior art zeolite molecular sieve be difficult to generate nano-scale product, yield is low, pollution is high,
High in cost of production technical problem.
A kind of ultrafine zeolite molecular sieve of design for achieving the above object, described molecular sieve is with TPAOH
For template, with tetraethyl orthosilicate for silicon source, with ethanol as dispersant.
In described molecular sieve, each material molar ratio is, TPAOH: ethanol: sodium hydroxide: just
Silester=18-19:900:0.7-1.4:40-80.
Described molecular sieve does not contains aluminum, and described Molecular Sieve Morphology is square or cuboid, described molecular sieve chi
Very little less than 100nm.
The synthetic method of this ultrafine zeolite molecular sieve, comprises the following steps:
1) TPAOH, ethanol, sodium hydroxide and tetraethyl orthosilicate are weighed；
2) first mix TPAOH and ethanol, add sodium hydroxide, then acutely stirring
Under conditions of mixing, it is slowly added dropwise tetraethyl orthosilicate, drips off rear insulation reaction 12-24h；
3) again reactant is moved in hydrothermal reactor, is placed in 100-120 DEG C of reaction 24-48h,
After hydro-thermal reaction terminates, with ethanol wash reactant filter centrifugation, remove the supernatant,
After the ultrasonic 1-2h of member-retaining portion, take out and be placed in 480-540 DEG C of calcining 4-8h, finally grind
Sieve, obtain ultrafine zeolite molecular sieve.
Step 1) in, TPAOH, ethanol, sodium hydroxide, the molar ratio of tetraethyl orthosilicate are
18-19:900:0.7-1.4:40-80.
The present invention compared with the existing technology, has the advantage that
(1) the invention belongs to the one of template agent method, with the hydro-thermal that conventional template agent method needs about 180 DEG C
Reaction temperature is compared, and reaction temperature of the present invention is lower；
(2) compared with traditional organic dispersing agent, toxic by-products of the present invention greatly reduces, and reduces preparation
Cost, decreases environmental pollution, directly eliminates aluminium compound, eliminate the process of dealuminzation time simultaneously synthesizing
Cost, has preferable development prospect；
(3) invention replaces the template synthetic method of conventional molecular sieve, it is provided that a kind of efficient, environment friend
The method of the good nanoscale mountainite molecular sieve with ethanol as dispersant；
(4) prepare zeolite molecular sieve during the present invention solves prior art to be difficult to generate nano-scale product, receipts
Rate is low, pollution is high, high in cost of production technical problem.
[detailed description of the invention]
The invention provides a kind of ultrafine zeolite molecular sieve, this molecular sieve with TPAOH as template,
With tetraethyl orthosilicate for silicon source, with ethanol as dispersant, prepare ultrafine zeolite molecular sieve by one-step method.Its
Each material molar ratio is, TPAOH: ethanol: sodium hydroxide: tetraethyl orthosilicate=18-19:900:
0.7-1.4:40-80.This molecular sieve does not contains aluminum, and molecular sieve microscopic appearance is square or cuboid, and
Its microscopic dimensions is less than 100nm.
Present invention also offers the synthetic method of a kind of ultrafine zeolite molecular sieve, comprise the following steps:
1) TPAOH, ethanol, sodium hydroxide and tetraethyl orthosilicate, tetrapropyl hydrogen are weighed
Amine-oxides, ethanol, sodium hydroxide, the molar ratio of tetraethyl orthosilicate are 18-19:900:
0.7-1.4:40-80；
2) first mix TPAOH and ethanol, add sodium hydroxide, then acutely stirring
Under conditions of mixing, it is slowly added dropwise tetraethyl orthosilicate, drips off rear insulation reaction 12-24h；
3) again reactant is moved in hydrothermal reactor, is placed in 100-120 DEG C of reaction 24-48h,
After hydro-thermal reaction terminates, with ethanol wash reactant filter centrifugation, remove the supernatant,
After the ultrasonic 1-2h of member-retaining portion, take out and be placed in 480-540 DEG C of calcining 4-8h, finally grind
Sieve, obtain ultrafine zeolite molecular sieve.
The present invention by regulation TPAOH, ethanol, sodium hydroxide, the ratio of tetraethyl orthosilicate,
The kind of dispersant, stirs the response time, hydrothermal temperature and response time and calcination time, permissible
Obtaining the ultrafine zeolite molecular sieve that purity is higher, it is possible to ensure its size uniform, crystalline size is less than 100nm,
The zeolite molecular sieve that particle diameter is 40-80nm can be obtained.The zeolite molecular sieve purity that the present invention prepares is high, nothing
Malicious, degradable, easily separated, anti-poisoning capability is strong, reusable, reduces preparation cost, decreases
Environmental pollution, improves catalytic efficiency, is better than the stock size molecule obtained under reaction condition in traditional method
Sieve.This catalyst, using ultrafine zeolite molecular sieve crystal as activity unit, has multi-pore channel structure, more typically
The molecular sieve of size has bigger specific surface area and the contact area with reactant, can be used as tradition point
The more excellent succedaneum of sub-sieve catalyst, it is possible to it is anti-that other catalysis activity units of modified load carry out other catalysis
Should.
The present invention is made further explained below below in conjunction with specific embodiment:
Embodiment 1
First mixing 0.18mol TPAOH and 9mol ethanol, add 0.007mol sodium hydroxide,
Finally under conditions of being stirred vigorously, it is slowly added dropwise 0.4mol tetraethyl orthosilicate, drips off rear insulation reaction 12h,
Again reactant is moved in hydrothermal reactor, be placed in 120 DEG C reaction 24h, hydro-thermal reaction terminate after with ethanol
Washing reaction thing filter centrifugation, remove the supernatant, takes out and be placed in 500 DEG C after the ultrasonic 1-2h of member-retaining portion
Calcining 4h finally grinds to sieve and obtains ultrafine zeolite molecular sieve 3.64g, and product average-size is about 53nm.
Embodiment 2
First mixing 0.19mol TPAOH and 9mol ethanol, add 0.008mol sodium hydroxide,
Finally under conditions of being stirred vigorously, it is slowly added dropwise 0.4mol tetraethyl orthosilicate, drips off rear insulation reaction 12h,
Again reactant is moved in hydrothermal reactor, be placed in 120 DEG C reaction 48h, hydro-thermal reaction terminate after with ethanol
Washing reaction thing filter centrifugation, remove the supernatant, takes out and be placed in 520 DEG C and forge after the ultrasonic 2h of member-retaining portion
Burning 8h finally grinds to sieve and obtains ultrafine zeolite molecular sieve 3.43g, and product average-size is about 61nm.
Embodiment 3
First mixing 0.18mol TPAOH and 9mol ethanol, add 0.010mol sodium hydroxide,
Finally under conditions of being stirred vigorously, it is slowly added dropwise 0.8mol tetraethyl orthosilicate, drips off rear insulation reaction 12h,
Again reactant is moved in hydrothermal reactor, be placed in 120 DEG C reaction 48h, hydro-thermal reaction terminate after with ethanol
Washing reaction thing filter centrifugation, remove the supernatant, takes out and be placed in 540 DEG C and forge after the ultrasonic 2h of member-retaining portion
Burning 8h finally grinds to sieve and obtains ultrafine zeolite molecular sieve 3.58g, and product average-size is about 49nm.
The present invention is not limited by above-mentioned embodiment, other any spirit without departing from the present invention
With the change made under principle, modify, substitute, combine, simplify, all should be the substitute mode of equivalence, all
Within being included in protection scope of the present invention.
Claims (5)
1. a ultrafine zeolite molecular sieve, it is characterised in that: described molecular sieve with TPAOH as template,
With tetraethyl orthosilicate for silicon source, with ethanol as dispersant.
2. ultrafine zeolite molecular sieve as claimed in claim 1, it is characterised in that in described molecular sieve, each raw material
Mol ratio is, TPAOH: ethanol: sodium hydroxide: tetraethyl orthosilicate=18-19:900:
0.7-1.4:40-80。
3. ultrafine zeolite molecular sieve as claimed in claim 1 or 2, it is characterised in that: described molecular sieve does not contains
Aluminum, described Molecular Sieve Morphology is square or cuboid, and described molecular sieve is smaller in size than 100nm.
4. the synthetic method of a ultrafine zeolite molecular sieve, it is characterised in that comprise the following steps:
1) TPAOH, ethanol, sodium hydroxide and tetraethyl orthosilicate are weighed；
2) first mix TPAOH and ethanol, add sodium hydroxide, then acutely stirring
Under conditions of mixing, it is slowly added dropwise tetraethyl orthosilicate, drips off rear insulation reaction 12-24h；
3) again reactant is moved in hydrothermal reactor, is placed in 100-120 DEG C of reaction 24-48h,
After hydro-thermal reaction terminates, with ethanol wash reactant filter centrifugation, remove the supernatant,
After the ultrasonic 1-2h of member-retaining portion, take out and be placed in 480-540 DEG C of calcining 4-8h, finally grind
Sieve, obtain ultrafine zeolite molecular sieve.
5. the synthetic method of ultrafine zeolite molecular sieve as claimed in claim 4, it is characterised in that: step 1) in,
TPAOH, ethanol, sodium hydroxide, the molar ratio of tetraethyl orthosilicate are 18-19:900:
0.7-1.4:40-80。
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| CN201610070477.6A CN105753011A (en) | 2016-02-01 | 2016-02-01 | Superfine zeolite molecular sieve and synthesis method thereof |
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| CN201610070477.6A CN105753011A (en) | 2016-02-01 | 2016-02-01 | Superfine zeolite molecular sieve and synthesis method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120589A (en) * | 2010-12-30 | 2011-07-13 | 中国天辰工程有限公司 | S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation |
| CN102500243A (en) * | 2011-11-17 | 2012-06-20 | 常州大学 | Preparation method for molecular sieve/organic composite permeable vaporization membrane |
-
2016
- 2016-02-01 CN CN201610070477.6A patent/CN105753011A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120589A (en) * | 2010-12-30 | 2011-07-13 | 中国天辰工程有限公司 | S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation |
| CN102500243A (en) * | 2011-11-17 | 2012-06-20 | 常州大学 | Preparation method for molecular sieve/organic composite permeable vaporization membrane |
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