CN105502429B - A kind of preparation method of mesopore molecular sieve - Google Patents
A kind of preparation method of mesopore molecular sieve Download PDFInfo
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- CN105502429B CN105502429B CN201511011517.1A CN201511011517A CN105502429B CN 105502429 B CN105502429 B CN 105502429B CN 201511011517 A CN201511011517 A CN 201511011517A CN 105502429 B CN105502429 B CN 105502429B
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- molecular sieve
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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
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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
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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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of preparation method of mesopore molecular sieve, belong to porous material preparing technical field.The preparation method is comprised the following steps：（1）Deionized water and acid or alkali are added in the flotation cell of flotation device, are stirred；（2）Template is added in flotation cell and is stirred, open flotation device intake valve, scrape foam when there is foam rise to open scraper plate；（3）Silicon source is slowly brought into flotation cell with gas negative pressure by air inlet pipe to be stirred to colloidal sol is formed, intake valve is closed after 30 60min, be transferred in ptfe autoclave；（4）Reactor is placed in baking oven, is taken out after 24 ~ 72h of crystallization at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then 4 6h be calcined at 500 600 DEG C obtain meso-porous molecular sieve material.Mesopore molecular sieve product one-tenth porosity that the present invention is prepared is high, aperture is homogeneous, and the method is wide using scope, with extraordinary application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of mesopore molecular sieve, and in particular to one kind is carried out using mining unit flotation device
The method of synthesising mesoporous molecular screen material.Belong to porous material preparing technical field.
Background technology
Mesoporous material is that in 1992, proposition was synthesized using surfactant as template first by Mobil companies of the U.S.
Go out serial M41S mesoporous materials, aperture is in 2-10nm.The material has surface area big（1000m2）, the features such as high adsorption capacity.
Subsequent many researchers on this basis, using template method out various mesoporous materials, such as SBA-15, MCM-
48, MCM-22 etc., the field is obtained broad based growth, aperture is adjustable in the range of 2-50nm.
The synthesis of mesoporous material is usually to be synthesized using template agent method, i.e., using such as cetyl front three（Second）Bromide
The surfactants such as ammonium, P123 are template, and tetraethyl orthosilicate is silicon source, is stirred in alkaline solution or acid solution,
Then crystallization is for a period of time.It is obtained finally by washing, filtering, dry and roasting.But convention stir is all in beaker or flask
Middle use magnetic agitation, mixing torque is relatively small, and the uniformity for forming colloidal sol to template is uncontrollable, often results in local caking
So as to the one-tenth porosity for being the mesoporous material for synthesizing is low.So while mesoporous material is more early developed, and energy actual industrial should
It is little.
The content of the invention
The present invention is intended to provide a kind of preparation method of mesopore molecular sieve, there is provided one kind utilizes the synthesising mesoporous material of flotation device
Material, the method for making the activating agent for being uniformly dissolved and not formed micella be removed using scraper plate by high-speed stirred, so as to realize preparing
The method of the meso-porous molecular sieve material that one-tenth porosity is high, aperture is homogeneous.
A kind of preparation method of mesopore molecular sieve that the present invention is provided, comprises the following steps：
（1）Deionized water and acid or alkali are added in the flotation cell of flotation device, flotation device agitator is opened；
The concentration of acid or alkali is 0.1mol/L-1mol/L；
（2）Template is added to 5-30min is stirred in flotation cell, mixing speed is 1650r/min-2100r/min, is opened
Open flotation device intake valve and adjust air inflow for 0.05m3/ h~0.1m3/ h, scrapes foam when there is foam rise to open scraper plate；
Template is 0.05-1.2: 1 with the mol ratio of acid, and template is 0.5-2: 1 with the mol ratio of alkali；
（3）The air inflow for controlling flotation device air inlet pipe is 0.01m3/ h~0.02m3/ h, by silicon source by air inlet pipe with gas
Negative pressure is slowly brought flotation cell into and is stirred to colloidal sol is formed, and intake valve is closed after 30-60min, and setting mixing speed is 120-
During 480 r/min, colloidal sol is transferred in ptfe autoclave from drain hole；
Silicon source with acid mol ratio be：0.5-6.5: 1, silicon source is 1-5: 1 with the mol ratio of alkali；
（4）Reactor is placed in baking oven, at 100 DEG C after 24 ~ 72h of crystallization take out, by product it is scrubbed, filtering, dry
After obtain solid product, then 4-6h be calcined at 500-600 DEG C obtain meso-porous molecular sieve material.
In such scheme, the acid is hydrochloric acid or sulfuric acid.
In such scheme, the alkali is any one in NaOH, KOH or ammoniacal liquor.
In such scheme, the template is cetyl trimethylammonium bromide, cetyltriethylammonium bromide, P123
Or any one in F127.
In such scheme, the silicon source is tetraethyl orthosilicate or waterglass.
In such scheme, the raw material proportioning is respectively：
Synthesize MCM-41 mol ratio be：SiO2: CTAB: alkali=1: 0.25-0.60: 0.5-1；
Synthesize MCM-48 mol ratio be：SiO2: CTAB: alkali=1: 0.35-0.45: 0.20-0.35；
Synthesize MCM-50 mol ratio be：SiO2: CTAB: alkali=1: 0.85-1.67: 0.85-0.95；
Synthesize SBA-15 mol ratio be：SiO2: P123: acid=1: 0.0165-0.185: 0.15-0.5；
Synthesize SBA-16 mol ratio be：SiO2: F127: acid=1: 0.10-0.50: 1.5-2.
Flotation device is the flotation machinery for separating mineral, and the single-trough flotating machine of use for laboratory is simple and reliable for structure, work
It is continuous durable.It is using the effect of flotation device in the present invention：1）Strong stirring action, rotating speed can reach 2100 r/min；
2）Sufficient air can be sucked, and bubble is small（Diameter is in the range of 0.1~1.0mm）It is uniformly dispersed；3）In course of reaction
Rotating speed and aeration quantity are adjustable：Template formation foam not into colloid can be scraped in time.
Beneficial effects of the present invention：
（1）Synthesis high speed stirring makes template be uniformly dispersed, it is easy to form micella, and the unnecessary template not formed
Agent forms regular beneficial to mesoporous uniformity by bubble band sol-gel of sening as an envoy to, it is to avoid form compact-type non-porous substance.
（2）Simple to operate in synthesis, product treatment is convenient, the synthetic technology method is easily promoted.
（3）Synthetic method applicability is wide, and various mesoporous materials can all be prepared using the method, preceding with extraordinary application
Scape.
Brief description of the drawings
Fig. 1 is the graph of pore diameter distribution of the mesoporous material of embodiment 1.
Fig. 2 is the graph of pore diameter distribution of the mesoporous material of embodiment 3.
Fig. 3 is the graph of pore diameter distribution of the mesoporous material of embodiment 5.
Fig. 4 is the graph of pore diameter distribution of the mesoporous material of embodiment 7.
Fig. 5 is the graph of pore diameter distribution of the mesoporous material of embodiment 9.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：
From XFD-0.75 type flotation machines, the 1mol/L NaOH of 0.70L deionized waters and 25mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 9.2g CTAB（Cetyl trimethylammonium bromide）Be added in flotation cell with
1750r/min stirs 20min, opens flotation device intake valve and adjusts air inflow for 0.1m3/ h, scraper plate is opened when there is foam rise
Foam is scraped.By 21g TEOS（Tetraethyl orthosilicate）By air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought into floating
Select groove to be stirred, intake valve is closed after 60min, colloidal sol is released from drain hole under 120r/min stirring at low speed and moves into poly- four
In PVF reactor.Reactor is placed in baking oven, at 100 DEG C after crystallization 72h take out, by product it is scrubbed, filtering, dry
After obtain solid product, then 6h be calcined at 500 DEG C obtain MCM-41 meso-porous molecular sieve materials.
As shown in Fig. 1 graph of pore diameter distribution, its pore size distribution is in 3.9nm or so, and peak narrower explanation aperture in aperture is mainly single, and
Explanation pore-forming is not distributed at other numerical value only in this scope.
Embodiment 2：
From XFD-0.75 type flotation machines, the 1mol/L NaOH of 0.70L deionized waters and 25mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 22g CTAB（Cetyl trimethylammonium bromide）Be added in flotation cell with
1750r/min stirs 20min, opens flotation device intake valve and adjusts air inflow for 0.1m3/ h, scraper plate is opened when there is foam rise
Foam is scraped.By 21g TEOS（Tetraethyl orthosilicate）By air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought into floating
Select groove to be stirred, intake valve is closed after 60min, colloidal sol is released from drain hole under 300r/min stirring at low speed and moves into poly- four
In PVF reactor.Reactor is placed in baking oven, at 100 DEG C after crystallization 72h take out, by product it is scrubbed, filtering, dry
After obtain solid product, then 6h be calcined at 500 DEG C obtain MCM-41 meso-porous molecular sieve materials.Its pore size distribution is in 3.7nm.
Implementation method 3：
From XFD-0.75 type flotation machines, the 1mol/L NaOH of 0.65L deionized waters and 100mL are added to flotation device
Flotation cell in, open flotation device agitator.89g CTAB are added in flotation cell 20min is stirred with 1650r/min, opened
Flotation device intake valve simultaneously adjusts air inflow for 0.1m3/ h, scrapes foam when there is foam rise to open scraper plate.By 145g TEOS
By air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought flotation cell into and is stirred, and intake valve is closed after 60min,
Colloidal sol is released in immigration ptfe autoclave from drain hole under 300r/min stirring at low speed.Reactor is placed in baking oven
In, crystallization is taken out after 3 days at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then be calcined at 600 DEG C
6h obtains MCM-48 meso-porous molecular sieve materials.Its pore size distribution in 3.3nm or so, as shown in Figure 2.
Implementation method 4：
From XFD-0.75 type flotation machines, the 1mol/L NaOH of 0.65L deionized waters and 100mL are added to flotation device
Flotation cell in, open flotation device agitator.114g CTAB are added in flotation cell 20min is stirred with 1650r/min, opened
Open flotation device intake valve and adjust air inflow for 0.1m3/ h, scrapes foam when there is foam rise to open scraper plate.By 145g
TEOS is by air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought flotation cell into and is stirred, and air inlet is closed after 60min
Valve, releases colloidal sol from drain hole under 220r/min stirring at low speed in moving into ptfe autoclave.Reactor is placed in
In baking oven, crystallization is taken out after 3 days at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then at 600 DEG C
Roasting 6h obtains MCM-48 meso-porous molecular sieve materials.Its pore size distribution is in 3.5nm.
Implementation method 5：
From XFD-0.75 type flotation machines, the 1mol/L NaOH of 0.72L deionized waters and 45mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 32.7g CTAB（Cetyl trimethylammonium bromide）Be added in flotation cell with
1900r/min stirs 30min, opens flotation device intake valve and adjusts air inflow for 0.05m3/ h, scrapes when there is foam rise to open
Plate scrapes foam.By 22g TEOS（Tetraethyl orthosilicate）By air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought into
Flotation cell is stirred, and intake valve is closed after 60min, is released colloidal sol from drain hole under 250r/min stirrings and is moved into polytetrafluoro
In ethylene reaction kettle.Reactor is placed in baking oven, at 100 DEG C after crystallization 60h take out, by product it is scrubbed, filtering, dry after
Solid product is obtained, then roasting 5h obtains MCM-50 meso-porous molecular sieve materials at 550 DEG C.Its pore-size distribution is in 5.2nm or so.Such as
Fig. 3, aperture peak wider range but aperture is single.
Implementation method 6：
From XFD-0.75 type flotation machines, the 1mol/L NaOH of 0.72L deionized waters and 45mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 64g CTAB（Cetyl trimethylammonium bromide）Be added in flotation cell with
2100r/min stirs 30min, opens flotation device intake valve and adjusts air inflow for 0.05m3/ h, scrapes when there is foam rise to open
Plate scrapes foam.By 22g TEOS（Tetraethyl orthosilicate）By air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought into
Flotation cell is stirred, and intake valve is closed after 60min, is released colloidal sol from drain hole under 280r/min stirrings and is moved into polytetrafluoro
In ethylene reaction kettle.Reactor is placed in baking oven, at 100 DEG C after crystallization 60h take out, by product it is scrubbed, filtering, dry after
Solid product is obtained, then roasting 5h obtains MCM-50 meso-porous molecular sieve materials at 550 DEG C.Its pore size distribution is in 5.1nm.
Implementation method 7：
From XFD-0.75 type flotation machines, the 1mol/L HCl of 0.72L deionized waters and 31mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 18.4g P123（Molecular weight is 5800）It is added in flotation cell with 1950r/min
Stirring 10min, opens flotation device intake valve and adjusts air inflow for 0.1m3/ h, scrapes foam when there is foam rise to open scraper plate
Go out.By 40g TEOS by air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought flotation cell into and is stirred, after 60min
Intake valve is closed, is released colloidal sol from drain hole under 200r/min stirrings in moving into ptfe autoclave.By reactor
Be placed in baking oven, crystallization is taken out after 3 days at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then 600
5h is calcined at DEG C and obtains SBA-15 meso-porous molecular sieve materials.In 7.4nm or so such as Fig. 4, peak scope in aperture is narrower and hole for its pore size distribution
Footpath is single, illustrates that pore-size distribution is regular.
Implementation method 8：
From XFD-0.75 type flotation machines, the 1mol/L HCl of 0.71L deionized waters and 30mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 200g P123（Molecular weight is 5800）It is added in flotation cell with 1950r/min
Stirring 10min, opens flotation device intake valve and adjusts air inflow for 0.1m3/ h, scrapes foam when there is foam rise to open scraper plate
Go out.By 39g TEOS by air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought flotation cell into and is stirred, after 60min
Intake valve is closed, is released colloidal sol from drain hole under 200r/min stirrings in moving into ptfe autoclave.By reactor
Be placed in baking oven, crystallization is taken out after 3 days at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then 600
5h is calcined at DEG C and obtains SBA-15 meso-porous molecular sieve materials.Its pore size distribution is in 7.6nm.
Implementation method 9：
From XFD-0.75 type flotation machines, the 1mol/L HCl of 0.53L deionized waters and 230mL are added to flotation device
In flotation cell, flotation device agitator is opened.By 193g F127（Molecular weight is 12600）It is added in flotation cell with 2100r/min
Stirring 25min, opens flotation device intake valve and adjusts air inflow for 0.1m3/ h, scrapes foam when there is foam rise to open scraper plate
Go out.By 32g TEOS by air inlet pipe with gas（0.01m3/ h flows）Negative pressure is slowly brought flotation cell into and is stirred, after 60min
Intake valve is closed, is released colloidal sol from drain hole under 300r/min stirring at low speed in moving into ptfe autoclave.Will be anti-
Answer kettle to be placed in baking oven, crystallization is taken out after 1 day at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then
4h is calcined at 600 DEG C and obtains SBA-16 meso-porous molecular sieve materials.Its pore size distribution is as shown in Figure 5 in 8.4nm or so.
Implementation method 10：
From XFD-0.75 type flotation machines, the 1mol/L HCl of 0.52L deionized waters and 226mL are added to flotation device
In flotation cell, flotation device agitator is opened.949g F127 are added in flotation cell 25min is stirred with 2100r/min, opened
Flotation device intake valve simultaneously adjusts air inflow for 0.1m3/ h, scrapes foam when there is foam rise to open scraper plate.31g TEOS are led to
Air inlet pipe is crossed with gas（0.01m3/ h flows）Negative pressure is slowly brought flotation cell into and is stirred, and intake valve is closed after 60min,
Colloidal sol is released in immigration ptfe autoclave from drain hole under 400r/min stirring at low speed.Reactor is placed in baking oven
In, crystallization is taken out after 3 days at 100 DEG C, by product is scrubbed, filtering, dry after obtain solid product, then be calcined at 600 DEG C
4h obtains SBA-16 meso-porous molecular sieve materials.Its pore size distribution is in 8.5nm.
Claims (6)
1. a kind of preparation method of mesopore molecular sieve, it is characterised in that comprise the following steps：
（1）Deionized water and acid or alkali are added in the flotation cell of flotation device, flotation device agitator is opened；
The concentration of acid or alkali is 0.1mol/L-1mol/L；
（2）Template is added to 5-30min is stirred in flotation cell, mixing speed is 1650r/min~2100r/min, is opened
Flotation device intake valve simultaneously adjusts air inflow for 0.05m3/ h~0.1m3/ h, scrapes foam when there is foam rise to open scraper plate；
Template is 0.05-1.2: 1 with the mol ratio of acid, and template is 0.5-2: 1 with the mol ratio of alkali；
（3）The air inflow for controlling flotation device air inlet pipe is 0.01m3/ h~0.02m3/ h, by silicon source by air inlet pipe with gas negative pressure
Slow flotation cell of bringing into is stirred to colloidal sol is formed, and intake valve is closed after 30-60min, and setting mixing speed is 120-480
During r/min, colloidal sol is transferred in ptfe autoclave from drain hole；
Silicon source with acid mol ratio be：0.5-6.5: 1, silicon source is 1-5: 1 with the mol ratio of alkali；
（4）Reactor is placed in baking oven, at 100 DEG C after 24 ~ 72h of crystallization take out, by product it is scrubbed, filtering, dry after
To solid product, then roasting 4-6h obtains meso-porous molecular sieve material at 500-600 DEG C.
2. the preparation method of mesopore molecular sieve according to claim 1, it is characterised in that the acid is hydrochloric acid or sulfuric acid.
3. the preparation method of mesopore molecular sieve according to claim 1, it is characterised in that the alkali is NaOH, KOH or ammonia
Any one in water.
4. the preparation method of mesopore molecular sieve according to claim 1, it is characterised in that the template is cetyl
Any one in trimethylammonium bromide, cetyltriethylammonium bromide, P123 or F127.
5. the preparation method of mesopore molecular sieve according to claim 1, it is characterised in that the silicon source is tetraethyl orthosilicate
Or waterglass.
6. the preparation method of mesopore molecular sieve according to claim 1, it is characterised in that：Silicon source, template, acid or alkali
Proportioning is respectively：
Synthesize MCM-41 mol ratio be：SiO2: CTAB: alkali=1: 0.25-0.60: 0.5-1；
Synthesize MCM-48 mol ratio be：SiO2: CTAB: alkali=1: 0.35-0.45: 0.20-0.35；
Synthesize MCM-50 mol ratio be：SiO2: CTAB: alkali=1: 0.85-1.67: 0.85-0.95；
Synthesize SBA-15 mol ratio be：SiO2: P123: acid=1: 0.0165-0.185: 0.16-0.5；
Synthesize SBA-16 mol ratio be：SiO2: F127: acid=1: 0.10-0.50: 1.5-2.
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| CN109019626B (en) * | 2017-06-12 | 2020-07-28 | 中国石油化工股份有限公司 | All-silicon mesoporous material, preparation method thereof and application thereof in rearrangement reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608987A (en) * | 2004-11-12 | 2005-04-27 | 太原理工大学 | Spherical mesoporous molecular sieve with narrow particle size distribution and its prepn |
| CN1915818A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing sieve of containing titanium MCM-41 |
| CN101205073A (en) * | 2006-12-21 | 2008-06-25 | 中国石油大学(北京) | Method for preparing aluminium-containing MCM-41 molecular sieve |
| CN102092741A (en) * | 2010-12-27 | 2011-06-15 | 大连理工大学 | Nano mesoporous molecular sieve and synthesis method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608987A (en) * | 2004-11-12 | 2005-04-27 | 太原理工大学 | Spherical mesoporous molecular sieve with narrow particle size distribution and its prepn |
| CN1915818A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing sieve of containing titanium MCM-41 |
| CN101205073A (en) * | 2006-12-21 | 2008-06-25 | 中国石油大学(北京) | Method for preparing aluminium-containing MCM-41 molecular sieve |
| CN102092741A (en) * | 2010-12-27 | 2011-06-15 | 大连理工大学 | Nano mesoporous molecular sieve and synthesis method thereof |
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