CN112624141B - Preparation method of MFI molecular sieve membrane - Google Patents
Preparation method of MFI molecular sieve membrane Download PDFInfo
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- CN112624141B CN112624141B CN201910950778.1A CN201910950778A CN112624141B CN 112624141 B CN112624141 B CN 112624141B CN 201910950778 A CN201910950778 A CN 201910950778A CN 112624141 B CN112624141 B CN 112624141B
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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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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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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- 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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention discloses a preparation method of an MFI molecular sieve membrane. The method comprises the following steps: 1) mixing the seed crystal with an amination reagent, and carrying out amination reaction to prepare an amination seed crystal; 2) mixing a silicon source, a template agent A, water and an optionally added aluminum source to prepare a mixed sol; 3) mixing the aminated seed crystal obtained in the step 1) with the mixed sol obtained in the step 2), and uniformly stirring to obtain a mixed material; 4) and (4) placing the carrier in the mixed material obtained in the step 3) for in-situ crystallization to obtain the MFI molecular sieve membrane. The MFI molecular sieve prepared by the method has good thickness and compactness, and the permeability of the molecular sieve membrane is obviously improved.
Description
Technical Field
The invention relates to a preparation method of a molecular sieve membrane, in particular to a preparation method of an MFI molecular sieve membrane.
Background
The membrane separation technology is a new separation, purification and purification technology, and is widely applied to the fields of food, beverage, metallurgy, paper making, textile, pharmacy, automobile, biology, chemical industry and the like. The inorganic membrane can be classified into an inorganic membrane and an organic membrane according to the membrane material, and the inorganic membrane has excellent chemical stability, thermal stability and mechanical strength compared to the organic membrane. The molecular sieve membrane is a representative one of inorganic membranes, and has a pore canal with a certain shape, a controllable structure, adjustable and uniform pore diameter distribution and a pore diameter size close to a molecular size. The molecular sieve membrane has specific pore structure, so that the molecular sieve membrane has selective permeability and shape-selective catalysis, and can be modified by ion exchange. The molecular sieve membrane has attractive application prospects in the fields of membrane separation, membrane catalysis, membrane reactors and the like due to the separation and catalysis at the molecular level, and has become a research hotspot of inorganic membrane materials in recent years.
The molecular sieve membranes can be divided into three major types, namely filling membranes (embedded membranes), self-supporting membranes and supporting membranes, and the supporting molecular sieve membranes have all the characteristics of molecular sieves, so that the supporting molecular sieve membranes become the molecular sieve membranes with the most development potential. The preparation method of the supporting molecular sieve membrane mainly comprises four types, namely a hydrothermal in-situ generation method, a secondary crystallization method, a microwave synthesis method and a gas phase crystallization method. However, the MFI molecular sieve membrane prepared by the above method has many defects, and the thickness, permeability and the like of the MFI molecular sieve membrane are to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an MFI molecular sieve membrane. The MFI molecular sieve membrane prepared by the method has good thickness and compactness, and the permeability of the molecular sieve membrane is obviously improved.
The invention provides a preparation method of an MFI molecular sieve membrane, which comprises the following steps:
1) mixing the seed crystal with an amination reagent, and carrying out amination reaction to prepare an amination seed crystal;
2) mixing a silicon source, a template agent A, water and an optionally added aluminum source to prepare a mixed sol;
3) uniformly mixing the aminated seed crystal obtained in the step 1) with the mixed sol obtained in the step 2) to obtain a mixed material;
4) and (4) placing the carrier in the mixed material obtained in the step 3) for in-situ crystallization to obtain the MFI molecular sieve membrane.
In the step 1), the seed crystal is an MFI molecular sieve seed crystal prepared by a conventional method in the field.
In the step 1), the amination reagent is one or more of a polyethyleneimine solution, a diethanolamine solution, an ethanolamine solution and a pentaethylenehexamine solution. In the step 1), the mass concentration of the amination reagent is 0.1-10%. The seed crystal accounts for 0.1-50% of the mass of the amination reagent.
In the step 1), the amination reaction time is 0.1-48 h, and the temperature is 10-150 ℃; the amination reaction is carried out under stirring conditions.
In the step 1), after the amination reaction, the aminated seed crystal can be obtained through the steps of filtering, washing and the like.
In the step 2), the silicon source is at least one selected from silicon dioxide, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate and silica sol. The aluminum source is at least one selected from aluminum isopropoxide, pseudo-boehmite, alumina, aluminum nitrate, aluminum chloride and aluminum sulfate. The template agent A is at least one selected from tetrapropylammonium hydroxide, tetrapropylammonium bromide, tripropylamine and propylenediamine.
In step 2), the silicon source is theoretically generated into SiO2Metering, theoretical production of Al from Al source2O3The silicon source, the aluminum source, the template agent A and the water are added according to the weight ratio: h2O/SiO2＝1～1000；A/SiO2＝0.03～10；Al2O3/SiO2＝0～2。
In the step 3), the addition amount of the aminated seed crystal accounts for the silicon source SiO in the mixed sol by mass20.1 to 5 percent.
In the step 4), the carrier is one or more of porous materials such as alumina, silicon oxide, stainless steel and the like. The carrier can be pretreated firstly, and the pretreatment comprises acid treatment and alkali treatment, and the preferable process is as follows: and respectively soaking the carrier in an acidic solution and an alkaline solution in sequence, and then washing, drying and roasting to obtain the pretreated carrier. Wherein the acid solution is at least one of hydrochloric acid, acetic acid and the like, and the mass concentration of the acid solution is 0.1-2%. The alkaline solution is at least one of sodium hydroxide, potassium hydroxide and the like, and the mass concentration of the alkaline solution is 0.2-1.5%. The soaking time of the acid treatment is 1-24 hours, and the soaking time of the alkaline treatment is 1-24 hours.
In the step 4), the in-situ crystallization conditions are as follows: the crystallization temperature is 70-200 ℃, preferably 80-180 ℃, and the crystallization time is 0.1-5 days, preferably 0.2-4 days.
And 4) selecting conventional post-treatment steps for the crystallized material according to actual needs, such as washing, drying, roasting and the like to obtain the MFI molecular sieve membrane. The washing can be carried out by adopting deionized water to be neutral, and the drying conditions are as follows: drying for 12-48 hours at 80-150 ℃, wherein the roasting conditions are as follows: roasting at 300-550 ℃ for 5-24 hours.
Compared with the prior art, the invention has the following advantages:
according to the method for preparing the MFI molecular sieve membrane, amination treatment is carried out on the seed crystal, the modified seed crystal is placed in sol obtained by mixing a silicon source, an aluminum source, a template agent A and water to obtain a mixed material, and then a carrier is placed in the mixed material to carry out in-situ crystallization. In addition, the preparation process is simple and easy to control, and the molecular sieve membrane has high quality.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the MFI molecular sieve membrane obtained [ example 1 ];
fig. 2 is an XRD pattern of the MFI molecular sieve membrane obtained [ example 1 ].
Detailed Description
The present invention is described in detail by the following specific examples, but it should be understood that the scope of the present invention is not limited by the specific embodiments.
In the present invention, the SEM test was performed on a germany ZEISS Merlin field emission scanning electron microscope; XRD testing was performed on a SHIMADZU XRD-6000 diffractometer. A copper target ka light source (λ ═ 0.15432nm), tube voltage 40kV, tube current 80mA, and scanning speed 2 °/min were used.
The carriers adopted in the embodiments and the comparative examples of the invention are tubular alumina carriers, and the carriers are pretreated as follows: the preparation method comprises the following steps of respectively and sequentially soaking an alumina carrier in 1% hydrochloric acid and 1% sodium hydroxide solution for 12 hours, washing the alumina carrier to be neutral by deionized water, drying the alumina carrier at 100 ℃ for 12 hours, roasting the alumina carrier at 400 ℃ for 8 hours, and sealing two ends of the alumina carrier.
[ example 1 ]
Mixing MFI molecular sieve seed crystals in 100g of diethanolamine aqueous solution with the mass concentration of 1%, wherein the mass of the added MFI molecular sieve seed crystals is 1% of that of the diethanolamine aqueous solution, stirring for 1 hour at room temperature, filtering and washing to obtain aminated seed crystals; adding silica sol, tetrapropylammonium hydroxide and water into a stainless steel reaction kettle with a polytetrafluoroethylene lining body, and uniformly mixing to obtain mixed sol, wherein the silicon source generates SiO theoretically2The silica sol, tetrapropylammonium hydroxide (A) and water are added according to the weight ratio: h2O/SiO2＝120；A/SiO20.15; takes SiO as silicon source in the mixed sol2Adding 1 wt% of aminated seed crystal into the mixed sol, and stirring at room temperature for 3h until the mixture is uniform to obtain a mixed material; and then putting the pretreated alumina carrier with two sealed ends into the mixed material, and crystallizing for 48 hours at 180 ℃ under the self pressure after sealing. And after crystallization, taking out the carrier, repeatedly washing the carrier for a plurality of times by using deionized water until the value of the solution is neutral, and then drying the carrier at 110 ℃ for 24 hours and roasting the carrier at 400 ℃ for 10 hours to obtain the compact and uniform MFI molecular sieve membrane a. SEM is shown in figure 1, and XRD is shown in figure 2. From the XRD pattern of fig. 2, the molecular sieve membrane is MFI molecular sieve membrane.
[ example 2 ]
Mixing MFI molecular sieve seed crystals in 100g of aqueous solution of diethanolamine with the mass concentration of 1%, wherein the mass of the MFI molecular sieve seed crystals is 0.5% of the mass of the aqueous solution of the diethanolamine, stirring for 1 hour at 50 ℃, filtering and washing to obtain aminated seed crystals; adding alumina, silica sol, tetrapropylammonium hydroxide and water into a stainless steel reaction kettle with a polytetrafluoroethylene lining body, and uniformly mixing to obtain mixed sol, wherein a silicon source generates SiO theoretically2Metering, theoretical production of Al from Al source2O3The silica sol, tetrapropylammonium hydroxide (A) and water are added according to the weight ratio: h2O/SiO2＝500；A/SiO2＝0.10；Al2O3/SiO20.01; SiO is used as silicon source in the mixed sol2Adding 5 wt% of aminated seed crystal into the mixed sol, and stirring at room temperature for 3h until the mixture is uniform to obtain a mixed material; and then putting the pretreated alumina carrier with two sealed ends into the mixed material, and crystallizing for 48 hours at the self pressure of 180 ℃. And (3) taking out the carrier after crystallization is finished, repeatedly washing the carrier for a plurality of times by using deionized water until the value of the solution is neutral, and then drying the carrier at 110 ℃ for 24 hours and roasting the carrier at 400 ℃ for 10 hours to obtain the compact and uniform MFI molecular sieve membrane b. The SEM and XRD patterns were similar to those of example 1.
[ example 3 ]
The procedure is otherwise as in example 2, except that the aminating agent is 100g of a 0.5% strength by mass aqueous diethanolamine solution. Mixed sol and silicon source are theoretically generated into SiO2Metering, theoretical production of Al from Al source2O3The silica sol, tetrapropylammonium hydroxide (A) and water are added according to the weight ratio: h2O/SiO2＝500；A/SiO2＝0.10；Al2O3/SiO20.03. Finally obtaining the compact and uniform MFI molecular sieve membrane c. The SEM and XRD patterns were similar to those of example 1.
Comparative example 1
The difference from example 1 is that: the MFI molecular sieve seed crystal is not aminated, but directly added into the mixed sol to obtain the MFI molecular sieve membrane d. The XRD pattern was similar to that of example 1.
[ example 4 ]
Xylene isomers were separated by a conventional method using the molecular sieve membranes (a, b, c) prepared in examples 1 to 3 and the molecular sieve membrane (d) prepared in comparative example 1, and the results are shown in table 1, wherein the concentration ratio of p-xylene/m-xylene in the raw material was 1/3 and the temperature was 160 ℃.
TABLE 1
Claims (8)
1. A preparation method of an MFI molecular sieve membrane comprises the following steps:
1) mixing the seed crystal with an amination reagent, and carrying out amination reaction to prepare an amination seed crystal;
2) mixing a silicon source, a template agent A, water and an optionally added aluminum source to prepare a mixed sol;
3) mixing the aminated seed crystal obtained in the step 1) with the mixed sol obtained in the step 2), and uniformly stirring to obtain a mixed material;
4) placing the carrier in the mixed material obtained in the step 3) for in-situ crystallization to prepare an MFI molecular sieve membrane;
in the step 1), the amination reagent is one or more of a polyethyleneimine solution, a diethanolamine solution, an ethanolamine solution and a pentaethylenehexamine solution; the added seed crystal accounts for 0.1-50% of the mass of the amination reagent;
theoretical production of SiO from silicon source2Metering, theoretical production of Al from Al source2O3The silicon source, the aluminum source, the template agent A and the water are added according to the weight ratio: h2O/ SiO2=1~1000；A/SiO2=0.03~10；Al2O3/SiO2=0~2；
In the step 3), the addition amount of the aminated seed crystal accounts for the silicon source SiO in the mixed sol by mass20.1% -5% of the total weight.
2. The method of claim 1, wherein: the mass concentration of the amination reagent is 0.1-10%.
3. The method of claim 1, wherein: in the step 1), the amination reaction time is 0.1-48 h, and the temperature is 10-150 ℃; the amination reaction is carried out with stirring.
4. The method of claim 1, wherein: in the step 2), the silicon source is selected from at least one of silicon dioxide, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate and silica sol; the aluminum source is at least one selected from aluminum isopropoxide, pseudo-boehmite, alumina, aluminum nitrate, aluminum chloride and aluminum sulfate; the template agent A is at least one selected from tetrapropylammonium hydroxide, tetrapropylammonium bromide, tripropylamine and propylenediamine.
5. The method of claim 1, wherein: in the step 4), the carrier is one or more of alumina, silica and stainless steel.
6. The method of claim 1, wherein: in the step 4), the in-situ crystallization conditions are as follows: the crystallization temperature is 70-200 ℃, and the crystallization time is 0.1-5 days.
7. The method of claim 1, wherein: in the step 4), the in-situ crystallization conditions are as follows: the crystallization temperature is 80-180 ℃, and the crystallization time is 0.2-4 days.
8. The method of claim 1, wherein: in the step 4), washing, drying and roasting the material subjected to in-situ crystallization to prepare the MFI molecular sieve membrane, wherein the drying conditions are as follows: drying for 12-48 hours at 80-150 ℃, wherein the roasting condition is as follows: roasting at 300-550 ℃ for 5-24 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386260A (en) * | 2013-06-27 | 2013-11-13 | 青岛科技大学 | Method for synthesizing ZSM-5 molecular sieve membrane on alpha-Al2O3 carrier surface |
| CN103896300A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Preparation method of high-performance SAPO (silicoaluminophosphate)-34 molecular sieve membrane |
| CN107902668A (en) * | 2017-11-20 | 2018-04-13 | 中国科学院山西煤炭化学研究所 | A kind of self-supporting film shape MFI molecular sieves and preparation method |
| CN108744997A (en) * | 2018-05-31 | 2018-11-06 | 南京工业大学 | A kind of electrostatic self-assembled crystal seed painting method being used to prepare molecular screen membrane |
| CN109806729A (en) * | 2019-04-04 | 2019-05-28 | 江西师范大学 | The preparation method and application of AlPO-18 molecular screen membrane |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896300A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Preparation method of high-performance SAPO (silicoaluminophosphate)-34 molecular sieve membrane |
| CN103386260A (en) * | 2013-06-27 | 2013-11-13 | 青岛科技大学 | Method for synthesizing ZSM-5 molecular sieve membrane on alpha-Al2O3 carrier surface |
| CN107902668A (en) * | 2017-11-20 | 2018-04-13 | 中国科学院山西煤炭化学研究所 | A kind of self-supporting film shape MFI molecular sieves and preparation method |
| CN108744997A (en) * | 2018-05-31 | 2018-11-06 | 南京工业大学 | A kind of electrostatic self-assembled crystal seed painting method being used to prepare molecular screen membrane |
| CN109806729A (en) * | 2019-04-04 | 2019-05-28 | 江西师范大学 | The preparation method and application of AlPO-18 molecular screen membrane |
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