CN104445269B - A kind of low silicon content molecular sieve SAPO 34 and preparation method thereof - Google Patents
A kind of low silicon content molecular sieve SAPO 34 and preparation method thereof Download PDFInfo
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- CN104445269B CN104445269B CN201410709520.XA CN201410709520A CN104445269B CN 104445269 B CN104445269 B CN 104445269B CN 201410709520 A CN201410709520 A CN 201410709520A CN 104445269 B CN104445269 B CN 104445269B
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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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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- 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
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
Abstract
The present invention provides a kind of low silicon content molecular sieve SAPO 34 and preparation method thereof, belongs to synthesis and the preparing technical field of molecular sieve.Comprise the following steps：Plastic, hydrothermal crystallizing, post processing.Wherein, molar ratio of material is SiO in the raw material2：Al2O3：P：R：H2O=0.01~0.15：0.3~1.5：3：0.5~8.0：30~150.Described phosphorus source is the mixture of phosphorous acid and phosphoric acid, and mol ratio is H3PO4：H3PO3=0.5~9.Described organic amine template is triethylamine.The preparation method for the low silicon content molecular sieve SAPO 34 that the present invention is provided, step is simple, simple operation, remains to obtain the few product of impurity, the expanding production suitable for industry in low silicon rate of charge.
Description
Technical field
The present invention relates to the synthesis of molecular sieve and preparing technical field, more particularly to a kind of low silicon content molecular sieve SAPO-
34 and preparation method thereof.
Background technology
Aluminium silicophosphate molecular sieve SAPO-34 skeletons are made up of Si, P, Al, O element, belong to chabazite structure, international zeolite
Association is named as CHA.Cage type channel system with octatomic ring opening, free 0.43 nanometer of diameter, belongs to trigonal system,
Unit cell dimension is a=b=1.37nm, c=1.48nm.Due to there is Si-O-Al connections in SAPO-34 skeleton structure,
So that the molecular sieve produces acidity.Their heat endurance and hydrothermal stability is all higher, is deposited in high temperature and a large amount of water vapours
There is absorption stability and skeleton stability under the conditions.Just because of its unique small structure and suitable moderate strength
Acidity, it is shown very high activity and alkene selection in catalysis methanol/dimethyl ether reaction for preparing light olefins (MTO)
Property.
European patent EP 0103117 discloses a kind of SAPO-34 Zeolite synthesis method, and one of its technical characterstic is to use
The mixture of tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and di-n-propylamine is template.United States Patent (USP) US4440871
Disclosed SAPO-34 synthetic methods also use same template.The main deficiency of above method is the price phase of template
To costliness, it is unfavorable for industrial production.Patent ZL92112230.6 reports one kind using phosphoric acid as phosphorus source, less expensive
Triethylamine as template synthesize SAPO-34 method.
The content of silicon is higher in the molecular sieve that above-mentioned synthetic method reported in the literature is obtained, the progress of some chemical reactions
It is directly bad with the molecular sieve effect of these high silicon contents, the short life of molecular sieve, this is accomplished by the silicon phosphorus for producing low silicon content
Sour aluminum molecular screen.But, carried out according to the above method, in reduction raw material after the rate of charge of silicon source, in SAPO-34 building-up process
The impurity such as SAPO-5 are easily produced, obtained product is the mixture of all kinds molecular sieve, and is difficult to the SAPO- of acquisition pure phase
34, it is unfavorable for industrializing expanding production.
The content of the invention
When the problem to be solved in the present invention is existing aluminium silicophosphate molecular sieve SAPO-34 synthesis, the throwing of silicon source in raw material
Material after reduction than being also easy to produce impurity, it is difficult to obtains pure phase SAPO-34 molecular sieves, is unfavorable for the amplification production of industry.
It is an object of the invention to provide a kind of low silicon content molecular sieve SAPO-34 preparation methods.The low silicon content point
Son sieve SAPO-34 preparation method comprises the following steps：
(1) plastic：Silicon source, silicon source, phosphorus source, organic amine template (R) and water are well mixed synthesis colloid, plastic is made
When temperature be 20~50 DEG C；
(2) hydrothermal crystallizing：After the synthesis colloid ultrasonication that step (1) is obtained, in 160~225 DEG C and spontaneous pressure
10~300h of hydrothermal crystallizing under power,
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, drying, aluminium silicophosphate molecule is produced
Sieve SAPO-34；
Wherein, in the raw material, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, phosphorus source is in terms of P, and molar ratio of material is：
SiO2：Al2O3：P：R：H2O=0.01~0.15：0.3~1.5：3：0.5~8.0：30~150；
Described phosphorus source is the mixture of phosphoric acid and phosphorous acid, the mol ratio H of its material3PO4：H3PO3=0.5~9；
Described organic amine template is triethylamine.
Further, molar ratio of material is in the raw material：SiO2：Al2O3：P：R：H2O=0.05~0.09：0.5~
1.2：3：1.0~5.0：30~150.
Preferably, the mol ratio of material is in described phosphorus source：H3PO4：H3PO3=1~5.
Further, the addition sequence of described phosphorus source, silicon source, silicon source and organic amine template is：Sequentially add silicon source,
Phosphorus source, silicon source, organic amine template, or be followed successively by silicon source, organic amine template, phosphorus source, silicon source, or be followed successively by phosphorus source, silicon source,
Organic amine template, silicon source, or it is followed successively by phosphorus source, silicon source, silicon source, organic amine template.
Further, source of aluminium is boehmite, aluminium isopropoxide, isobutanol aluminum, aluminium hydroxide, aluminum oxide and aluminium
One or more in salt, silicon source is silica gel, Ludox, the aeroge of silicon, white carbon, one kind in tetraethyl orthosilicate or several
Kind.
Preferably, the temperature of hydrothermal crystallizing is 190~200 DEG C in step (2), and the time is 20~50h, and drying temperature is
60-80℃。
Preferably, in the step (2), ultrasonic wave is 20~35kHz, 1~4h of processing time.
Second object of the present invention is to provide a kind of low silicon content molecular sieve SAPO-34, and it is by above-mentioned preparation method
It is prepared from.
The present invention has the advantages and positive effects of：The preparation for the low silicon content molecular sieve SAPO-34 that the present invention is provided
Method, step is simple, simple operation, using the mixture of phosphoric acid and phosphorous acid as phosphorus source, triethylamine as template, compared with
Under low silicon source rate of charge, the aluminium silicophosphate molecular sieve SAPO-34 crystallinity being prepared from is high, mutually uniform, substantially free of impurities
SAPO-5, the expanding production suitable for industry.The template used in the present invention is cheap, is used beneficial to industrial.This
Optimized in invention and use phosphoric acid and phosphorous acid as phosphorus source, and optimize its mol ratio, reduce the impurity produced in synthesis
SAPO-5.In the present invention further synthesis colloid after it is carried out it is ultrasonically treated, and screen except suitable frequency and time,
Beneficial to the progress of colloid crystallization.Present invention also offers more preferred material order of addition, there is provided the preferred of hydrothermal crystallizing
Temperature and time, prepares the higher aluminium silicophosphate molecular sieve SAPO-34 of catalytic performance, and impurity is reduced during it is synthesized, and is obtained
Product crystallinity is high, mutually uniform.
Brief description of the drawings
Fig. 1 is the low silicon content molecular sieve SAPO-34 prepared in the present embodiment 1 X-ray diffractogram (XRD).
Fig. 2 is the low silicon content molecular sieve SAPO-34 prepared in the present embodiment 1 optical microscope.
Embodiment
In order to be better understood from the present invention, the present invention is further retouched with reference to specific embodiments and the drawings
State.
Raw material in following examples is ordinary commercial products, wherein：The molar concentration of phosphoric acid is 15mol/l, and silicon is molten
SiO in glue2Content be 5.9mol/l, SiO in white carbon2Content be 90wt%, the middle Al of boehmite2O3Content
For 67.25wt%.
Embodiment 1
A kind of low silicon content molecular sieve SAPO-34 preparation method, comprises the following steps：
(1) plastic：With 500ml water dissolve 264g phosphorous acid, in stirring be added dropwise 200ml phosphoric acid, by this mixed acid solution with
16.9ml Ludox is mixed, and is afterwards mixed it with the solution of 500ml water with 212.3g boehmites and is stirred rapidly, while stirring
Mix side and add 202.4g triethylamines, stir 1h, rear to add 500ml water, well mixed to synthesize colloid, gelling temperature is 25 DEG C.
(2) hydrothermal crystallizing：Moved into after the synthesis colloid 20kHz ultrasounds 1h that step (1) is obtained in stainless steel cauldron,
Hydrothermal crystallizing 30h under 190 DEG C and self-generated pressure.
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, 60 DEG C of drying, aluminium silicophosphate is produced
Molecular sieve SAPO-34.
Its characteristic diffraction peak is presented in the aluminium silicophosphate molecular sieve SAPO-34 prepared as seen from Figure 1, and 2 θ angles are attached at 26 °
There is obvious bimodal appearance near and 31 ° of vicinity, and with larger intensity, show that gained sample has very high crystallinity.
In Fig. 1,7.5 ° of SAPO-5 characteristic peak does not almost have nearby, it was demonstrated that its impurity SAPO-5 contents are extremely low.
Fig. 2 is the optical microscope of 40 times made of aluminium silicophosphate molecular sieve SAPO-34 object lens, it is known that institute's score
Son sieve is in cubic, is typical SAPO-34 molecular sieves shape.
Embodiment 2
A kind of low silicon content molecular sieve SAPO-34 preparation method, comprises the following steps：
(1) plastic：82g phosphorous acid is dissolved with 500ml water, 133.3ml phosphoric acid is added dropwise in stirring, mixed acid solution is obtained.
Mixture A is obtained after 4g white carbons are well mixed with the mixed solution of 100ml water with mixed acid solution.By 200g boehmites
Powder is well mixed to obtain mixture B with 200ml water.Mixture A is added in mixture B afterwards and stirred rapidly, after 40min
202.4g triethylamines and 500ml water are added while stirring, and stirring 1h must synthesize colloid, and gelling temperature is 30 DEG C.
(2) hydrothermal crystallizing：Moved into after the synthesis colloid 30kHz ultrasounds 2h that step (1) is obtained in stainless steel cauldron,
Hydrothermal crystallizing 24h under 192 DEG C and self-generated pressure.
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, 70 DEG C of drying, aluminium silicophosphate is produced
Molecular sieve SAPO-34.
Embodiment 3
A kind of low silicon content molecular sieve SAPO-34 preparation method, comprises the following steps：
(1) plastic：61.5g phosphorous acid is dissolved with 600ml water, 150ml phosphoric acid is added dropwise afterwards, this mixed acid aqueous solution is added
Enter into 364.3g aluminium isopropoxide solid powders rapid stirring 120min, 303.6g triethylamines are added while stirring, water is added
1000ml, is eventually adding 4.7g white carbons, continues to stir 2h after being stirred until homogeneous, 35 DEG C must synthesize colloid.
(2) hydrothermal crystallizing：Moved into after the synthesis colloid 25kHz ultrasounds 3h that step (1) is obtained in stainless steel cauldron,
Hydrothermal crystallizing 36h under 196 DEG C and self-generated pressure.
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, 75 DEG C of drying, aluminium silicophosphate is produced
Molecular sieve SAPO-34.
Embodiment 4
A kind of low silicon content molecular sieve SAPO-34 preparation method, comprises the following steps：
(1) plastic：Be slowly added to after 500ml water and 151.7g boehmites are stirred 404.8g triethylamines and
The stirring of 500ml water is with obtaining mixture A.49.2g phosphorous acid is dissolved with 1L water, 160ml phosphoric acid is added dropwise afterwards, this is mixed into sour water
Solution is added in mixture A, and 90min is stirred rapidly, and 16.7g tetraethyl orthosilicates are added while stirring, water is added afterwards
160ml, is stirred until homogeneous, 42 DEG C of plastics, obtains synthesis colloid.
(2) hydrothermal crystallizing：Moved into after the synthesis colloid 35kHz ultrasounds 2.5h that step (1) is obtained in stainless steel cauldron,
Hydrothermal crystallizing 45h under 198 DEG C and self-generated pressure.
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, 65 DEG C of drying, aluminium silicophosphate is produced
Molecular sieve SAPO-34.
Embodiment 5
A kind of low silicon content molecular sieve SAPO-34 preparation method, comprises the following steps：
(1) plastic：With 1L water dissolve 41g phosphorous acid, afterwards be added dropwise 166.7ml phosphoric acid, by this mixed acid solution with
15.3ml Ludox and 430ml water mixing, then 182g boehmite solid powders are poured into, 120min is stirred rapidly, while stirring
Mix side and add 506g triethylamines and water 1L, stirring 240min is to that must synthesize colloid after uniform, and gelling temperature is 48 DEG C.
(2) hydrothermal crystallizing：Moved into after the synthesis colloid 20kHz ultrasounds 4h that step (1) is obtained in stainless steel cauldron,
Hydrothermal crystallizing 48h under 200 DEG C and self-generated pressure..
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, 80 DEG C of drying, aluminium silicophosphate is produced
Molecular sieve SAPO-34.
Embodiments of the invention are described in detail above, but the content is only presently preferred embodiments of the present invention,
It is not to be regarded as the practical range for limiting the present invention.All equivalent changes made according to the scope of the invention and improvement etc., all should
Still belong within this patent covering scope.
Claims (6)
1. a kind of low silicon content molecular sieve SAPO-34 preparation method, it is characterised in that：Comprise the following steps：
(1) plastic：Silicon source, silicon source, phosphorus source, organic amine template (R) and water are well mixed synthesis colloid is made, during plastic
Temperature is 20~50 DEG C；
(2) hydrothermal crystallizing：The synthesis colloid ultrasonication that step (1) is obtained, ultrasonic wave is 20~35kHz, processing time 1
~4h, 10~300h of hydrothermal crystallizing under 160~225 DEG C and self-generated pressure,
(3) post-process：By the collection of products after hydrothermal crystallizing in step (2), washing, drying, low silicon content molecular sieve is produced
SAPO-34；
Wherein, in the raw material, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, phosphorus source is in terms of P, and molar ratio of material is：SiO2：
Al2O3：P：R：H2O=0.01~0.15：0.3~1.5：3：0.5~8.0：30~150；
Described phosphorus source is the mixture of phosphoric acid and phosphorous acid, the mol ratio H of its material3PO4：H3PO3=0.5~9；
Described organic amine template is triethylamine.
2. low silicon content molecular sieve SAPO-34 according to claim 1 preparation method, it is characterised in that：The raw material
Middle molar ratio of material is：SiO2：Al2O3：P：R：H2O=0.05~0.09：0.5~1.2：3：1.0~5.0：30~150.
3. low silicon content molecular sieve SAPO-34 according to claim 2 preparation method, it is characterised in that：Described phosphorus
The mol ratio of material is in source：H3PO4：H3PO3=1~5.
4. low silicon content molecular sieve SAPO-34 according to claim 2 preparation method, it is characterised in that：Described phosphorus
Source, silicon source, the addition sequence of silicon source and organic amine template are：It is followed successively by silicon source, phosphorus source, silicon source, organic amine template, or according to
Secondary is silicon source, organic amine template, phosphorus source, silicon source, or is followed successively by phosphorus source, silicon source, organic amine template, silicon source, or is followed successively by
Phosphorus source, silicon source, silicon source, organic amine template.
5. according to any described low silicon content molecular sieve SAPO-34 of claim 1-4 preparation method, it is characterised in that：Institute
It is the one or more in boehmite, aluminium isopropoxide, isobutanol aluminum, aluminium hydroxide, aluminum oxide and aluminium salt, silicon to state silicon source
Source is the one or more in silica gel, Ludox, the aeroge of silicon, white carbon, tetraethyl orthosilicate.
6. according to any described low silicon content molecular sieve SAPO-34 of claim 1-4 preparation method, it is characterised in that：Step
Suddenly the temperature of hydrothermal crystallizing is 190~200 DEG C in (2), and the time is 20~50h, and drying temperature is 60~80 DEG C.
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| CN106542547B (en) * | 2016-08-03 | 2018-12-14 | 刘希尧 | A kind of preparation method of the SAPO-34 molecular sieve of high activity low silicon content |
| CN107128949A (en) * | 2017-05-27 | 2017-09-05 | 江苏有容催化技术研究所有限公司 | A kind of method of the synthesis molecular sieves of SAPO 34 |
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| WO2003106341A1 (en) * | 2002-06-12 | 2003-12-24 | Exxonmobil Chemical Patents Inc. | Synthesis of aluminophosphates and silicoaluminophosphates |
| CN102336413B (en) * | 2010-11-29 | 2013-04-17 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN103130241B (en) * | 2013-03-21 | 2015-05-27 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN103641131B (en) * | 2013-12-10 | 2015-02-18 | 吉林大学 | Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof |
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