CN108910912A - A kind of preparation method of SAPO-35 molecular sieve - Google Patents
A kind of preparation method of SAPO-35 molecular sieve Download PDFInfo
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- CN108910912A CN108910912A CN201810532851.9A CN201810532851A CN108910912A CN 108910912 A CN108910912 A CN 108910912A CN 201810532851 A CN201810532851 A CN 201810532851A CN 108910912 A CN108910912 A CN 108910912A
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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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- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract
The invention discloses a kind of preparation methods of SAPO-35 molecular sieve, include the following steps：1. by Al2(SO4)3·18H2O is dissolved in deionized water, then slowly middle that orthophosphoric acid solution is added, and stirs 2h；2. gas phase SiO is added2And deionized water, stir 30min；3. hexamethylene imine is added dropwise（HMI）, it is eventually adding required GLU amount holding and is vigorously stirred until forming uniform gel.4. by the gel of acquisition（pH=6.2-7.5）It is transferred in autoclave and crystallization 24 hours at 200 DEG C, centrifugation is washed 3 times, 70 DEG C are dried overnight, and 5. 550 DEG C of roasting 8h are up to SAPO-35.For the present invention using hexamethylene imine as organic formwork, gucosamine synthesizes small pore silicoaluminophosphate SAPO-35 as additive.Pure SAPO-35 material obtains in short reaction time.
Description
Technical field
The invention belongs to molecular sieve catalyst technical fields, and in particular to a kind of SAPO-35 molecular sieve preparation method.
Background technique
Zeolite and zeolite-type molecular sieves are as the catalyst in the reaction of many chemical industries, due to its interesting characteristic quilt
Research extensively.Their orderly microporous crystal structures and chemical component make this material have thermal stability, molecular sieve property, height
A variety of special natures such as specific surface area, shape selective and controllable acidity.1961, F D ' yvoire delivered hydrogenation for the first time
The synthesis of aluminium phosphate (AlPO), after several years, in the early 1980s, Union Carbide Corporation report it is several novel
The synthesis for the aluminum oxide molecular sieve (SAPO) that AlPO material and silicon replace.Silicon is different aluminophosphate frameworks (with the electronics such as SiO2)
Structure substitution may generate net negative charge to this frame, if proton is compensated, these substances provide for bronsted
Acid gives these materials.The development of SAPO molecular sieve has caused a great interest, due to they controllable slight acidity and
Microcellular structure, this assigns their potential sizable potentiality of industrial catalyst.
Many small pore silicoaluminophosphate molecular sieves, such as SAPO-34, SAPO-18, STA-7 or SAPO-35 (IZA skeleton packet
Include CHA, AEI, SAV, LEV）A kind of particularly interesting material because they shown in MTO reaction higher activity and
Selectivity.These materials are that their rapid deactivation is by macromolecule as the major defect of catalyst in this course
Amount hydrocarbon deposited in micropore hole and caused by, blocking stomata entrance and hinder reactant and intermediate enters activity
Site.However, synthesis condition is adjustable, to control the property of some materials, such as crystalline size or transgranular mesoporous presence, this
It is the key parameter for influencing catalyst life during MTO.In this sense, by reducing crystalline size or in crystal
Middle generation mesoporous can postpone to observe inactivation in many SAPO catalyst, so that reactant and product diffusion are promoted,
To make catalyst keep higher conversion ratio in a long time.Have several strategies can be used to improve above situation zeolite and
The physicochemical properties of zeolite catalyst pass through control synthetic parameters.Different additive or template are used in microporous crystal
Agent (such as carbon black, supramolecular structure) sugar or polymer, which are added in synthesized gel rubber, to be possible to create mesoporous, has been found to increase
Non- micropore (mesoporous and external) surface.Also there are other methods, such as microwave-assisted hydrothermal synthesis or modification synthesis condition (if any
Machine template or aluminium, silicon source and its content can get nanoscale SAPO material, the service life in MTO to reduce crystalline size
It is obviously longer than traditional catalyst.
Summary of the invention
Use hexamethylene imine as organic formwork the object of the present invention is to provide a kind of, gucosamine is closed as additive
At the preparation method of small pore silicoaluminophosphate SAPO-35 molecular sieve.
To achieve the above object, the technical solution adopted by the present invention is that, a kind of preparation method of SAPO-35 molecular sieve is wrapped
Include following steps：
1）By Al2(SO4)3·18H2O is dissolved in deionized water, is then slowly added into 34wt% orthophosphoric acid solution, stirs 2h；
2）Gas phase SiO is added2And deionized water, stir 30min；
3）Hexamethylene imine is added dropwise（HMI）, it is eventually adding required GLU（Gucosamine）Amount keep be vigorously stirred until
Form uniform gel；
4）By the gel of acquisition（pH = 6.2-7.5）It is transferred to crystallization in autoclave, is centrifuged, is washed 3 times, it is dry；,
5）550 DEG C of roasting 8h removal organic formworks are up to SAPO-35 molecular sieve.
Preferably, step 3）Middle gained gel mol composition 1Al2O3﹒ 1P2O5﹒ 0.6SiO2﹒ 1.5HMI ﹒ 55H2O ﹒ xGLU（x
=0-4.5）.
Preferably, step 4）Middle crystallization condition be 200 DEG C of static crystallizations for 24 hours.
Preferably, step 4）Middle drying condition is to be dried overnight at 70 DEG C.
The beneficial effect comprise that：The present invention is using hexamethylene imine as organic formwork, gucosamine conduct
Additive synthesizes small pore silicoaluminophosphate SAPO-35, and pure SAPO-35 material obtains in short reaction time, average crystalline size
Change in 2-50 μ m, and is strongly depend on the amount for being added to the aminoglucose of synthesized gel rubber.Therefore, gucosamine is shown
The effect of crystal growth modifier, accurately controls crystalline size, can obtain the SAPO-35 crystal of required size.
Detailed description of the invention
Fig. 1 is that gel constitutive molar ratio is 1Al2O3：1P2O5：0.6SiO2：1.5HMI：55H2O：xGLU（x=0-4.5）System
The XRD diagram of standby SAPO-35 molecular sieve, abscissa is angle in Fig. 1, and ordinate is crystallinity.Wherein the value of x is respectively
0, 0.15, 0.5 , 1.5, 3, 4.5 .A is the XRD diagram for not roasting sample in figure, and B is the XRD diagram of sample after roasting.
Synthesized sample is illustrated as LEV topological structure as can be seen from this figure, and as the ratio of the GLU of addition is increased to from 0
4.5, crystallinity reduces；Compared with the sample before roasting, crystallinity reduces sample after roasting.
Fig. 2 is that gel constitutive molar ratio is 1Al2O3：1P2O5：0.6SiO2：1.5HMI：55H2O：xGLU（x=0-4.5）System
The SEM of standby SAPO-35 molecular sieve schemes, and as can be seen from the figure with the addition of gucosamine, crystalline size reduces, on a small quantity
Gucosamine be also beneficial to form uniform rhomboidan, this demonstrate gucosamine to crystal growth have Modification effect,
It can inhibit its growth in conjunction with SAPO-35 plane of crystal.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, and but the scope of the present invention is not limited thereto.
Embodiment 1
By Al2(SO4)3·18H2O is dissolved in deionized water, then slowly middle that orthophosphoric acid solution is added（34wt%）, stirring
2h；4g gas phase SiO is added2With remaining the desired amount of deionized water, 30min is stirred；19.6g hexamethylene imine is added dropwise
（HMI）, it is eventually adding required GLU amount holding and is vigorously stirred until forming uniform gel, gel constitutive molar ratio is 1Al2O3：
1P2O5：0.6SiO2：1.5HMI：55H2O：xGLU（The value of x is respectively 0,0.15,0.5,1.5,3,4.5）；It will obtain
Gel（pH = 6.2-7.5）Being transferred to 200 DEG C of static crystallizations in autoclave, for 24 hours, centrifugation is dried at washing 3 times, 70 DEG C
At night, 550 DEG C of roasting 8h are up to SAPO-35 molecular sieve.
When the value of x is respectively 0,0.15,0.5,1.5,3,4.5, the SAPO-35 molecular sieve of the preparation of embodiment 1
XRD diagram is as shown, the SEM figure of SAPO-35 molecular sieve is as shown in Figure 2.
Abscissa is angle in Fig. 1, and ordinate is crystallinity.A is the XRD diagram for not roasting sample in figure, and B is roasting
The XRD diagram of sample afterwards.Synthesized sample is illustrated as LEV topological structure as can be seen from this figure, and with the GLU's of addition
Ratio increases to 4.5 from 0, and crystallinity reduces；Compared with the sample before roasting, crystallinity reduces sample after roasting.
It can be seen that the addition with gucosamine from the Fig. 2, crystalline size reduces, and a small amount of gucosamine is also advantageous
In forming uniform rhomboidan, this demonstrate gucosamines to have Modification effect to crystal growth, can be with SAPO-35 crystal
Surface combines, and inhibits its growth.
Claims (5)
1. a kind of preparation method of SAPO-35 molecular sieve, it is characterised in that include the following steps：
1）By Al2(SO4)3·18H2O is dissolved in deionized water, is then slowly added into orthophosphoric acid solution, stirs 2h；
2）Gas phase SiO is added2And deionized water, stir 30min；
3）Hexamethylene imine is added dropwise, is eventually adding gucosamine holding and is vigorously stirred until forming uniform gel；
4）The gel of acquisition is transferred to crystallization in autoclave, is centrifuged, is washed, it is dry；
5）550 DEG C of roasting 8h are up to SAPO-35 molecular sieve.
2. the preparation method of SAPO-35 molecular sieve as described in claim 1, it is characterised in that：Step 3）Middle gained gel mole
Ingredient 1Al2O3﹒ 1P2O5﹒ 0.6SiO2﹒ 1.5HMI ﹒ 55H2O ﹒ xGLU, x=0-4.5.
3. the preparation method of SAPO-35 molecular sieve as described in claim 1, it is characterised in that：Step 4）Middle crystallization condition is 200
DEG C static crystallization is for 24 hours.
4. the preparation method of SAPO-35 molecular sieve as described in claim 1, it is characterised in that：Step 4）Middle drying condition is 70
It is dried overnight at DEG C.
5. using the SAPO-35 composite molecular screen of claim 1-4 either method preparation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052288A (en) * | 2019-05-27 | 2019-07-26 | 河南师范大学 | A kind of metal-modified molecular sieve SPAO-34 of chlorination and its preparation method and application |
| CN113209974A (en) * | 2021-05-06 | 2021-08-06 | 淮阴工学院 | Mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst and preparation method and application thereof |
-
2018
- 2018-05-29 CN CN201810532851.9A patent/CN108910912A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| IRENE PINILLA-HERRERO等: ""Unexpected crystal growth modifier effect of glucosamine as additive in the synthesis of SAPO-35"", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052288A (en) * | 2019-05-27 | 2019-07-26 | 河南师范大学 | A kind of metal-modified molecular sieve SPAO-34 of chlorination and its preparation method and application |
| CN113209974A (en) * | 2021-05-06 | 2021-08-06 | 淮阴工学院 | Mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst and preparation method and application thereof |
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