CN110342532A - The preparation method of difunctional MFI zeolite nano ply - Google Patents
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Abstract
The invention discloses a kind of preparation methods of difunctional MFI zeolite nano ply, include the following steps: (1), MFI layered zeolite is placed in 15wt% aqueous ammonium nitrate solution, it carries out ion exchange 2 ~ 4 times, after 110 DEG C of dryings, then the lower 550 DEG C of roastings 4h of air atmosphere, obtains Hydrogen MFI layered zeolite；(2), the functionalized silane graft of alkalinity is modified MFI zeolite in Hydrogen MFI zeolite or first with silane, then it is acted on again by grafted silane with basic group, obtains the MFI zeolite novel organic-inorganic composite material with acid and alkaline bifunctional.The MFI zeolite of the method for the present invention preparation is in acid strength, acid amount and acid active bit distribution is adjustable controllable and layer structure with biggish specific surface area and surface silicone hydroxyl abundant (grafting position).
Description
Technical field
The invention belongs to materials chemistry and field of catalyst preparation, specially a kind of difunctional MFI zeolite nano ply
The preparation method of catalyst carries out the surface hydroxyl on functionalized silane and zeolite nano ply with alkaline functional anti-
It answers, prepares stable structure, has with acid and alkaline bifunctional MFI zeolite is novel while soda acid activated centre is suitable for
Machine-inorganic composite materials.
Background technique
Aromatic compounds play an important role in fields such as medicine, pesticide and petrochemical industries.Deacetalization-
Knoevenagel reaction is to synthesize a kind of effective way of aromatic compounds.The carrying out of the reaction needs soda acid double activity center
Concerted catalysis effect, selection have the function of different activities position moderately disperse and the double-function catalyzing material that matches be realization its
The key effectively carried out.
Researcher has carried out extensive work in the preparation of difunction catalyst.To such as provide acid function sulfonic acid,
Phosphoric acid and carboxylic acid etc. and provide alkaline functional organic base and a variety of organic amines graft on silica-base catalyst (J. Catal.,
2007, 247, 379; J. Catal., 2012, 291, 63; Chem. Mater., 2012, 24, 2433;
Catal. Sci. Technol., 2015,5,690).Although urging with soda acid function can be prepared using these methods
, the acid strength of prepared catalyst and alkali agent, but be also faced with following deficiency in the preparation of catalyst and catalysis reaction: 1)
Intensity not easy-regulating.Acid-Base strengths appropriate catalysts are for the deacetalization-Knoevenagel activity reacted and choosing
Selecting property is most important.But it is limited, is difficult for differential responses pair by selected grafted acid or alkali itself acid strength or base strength
The demand of Acid-Base strengths prepares corresponding catalysis material；2), acid active sites and basic activated column pitch are difficult to.It is right
In deacetalization-Knoevenagel catalyst, catalytic performance is not only the same as acid active sites and basic activated position
It measures related to intensity and closely related with spacing between the two.But in the preparation of existing bifunctional catalyst, acidity is living
Property position and basic activated position and the intrinsic inorganic active position of carrier combination be it is random, thus, acid, basic active site spacing
It is difficult to, it is especially prominent when preparing soda acid multifunction catalyst with silicon substrate carrier.
Compared with numerous carrier materials, MFI zeolite molecular sieve has acid function, and its acid strength and acids type can pass through
Change its Nomenclature Composition and Structure of Complexes and carry out effective modulation, meets deacetalization-Knoevenagel reaction to acid function
Demand effectively solves in conventional difunction catalyst preparation process, and acid strength is not easy the deficiency of modulation, and due to zeolite
Itself intrinsic Acidity, need to only graft basic silane on its surface can be realized difunctionalization, simplify the preparation of catalyst
Program.Therefore, it theoretically analyzes, MFI zeolite has the potential advantages as difunction catalyst carrier.
Although MFI zeolite has the potential advantages as difunction catalyst carrier, by its port size and outside
The small limitation in surface is difficult effectively to graft the organosilan containing basic functionality thereon.In addition, using
When deacetalization-Knoevenagel reaction prepares aromatic compounds, often it is related to large-sized reaction substrate, zeolite
Lesser port size also can generate limitation to the diffusion of large scale reaction substrate.In recent years, R. Ryoo team proposes with double
Quaternary ammonium cation surfactant is the new method of template synthetic zeolite nano ply.For example, successfully being synthesized using this method
Out in b axis direction thickness be only 2nm MFI zeolite nano ply (Nature, 2009,461,246).With conventional boiling
Stone is compared, and zeolite nano ply can also mention in addition to the accessibility, solid tumor performance with acid active sites are high
For biggish specific surface area and surface silicone hydroxyl abundant (grafting position).Although the material removes the process of template in roasting
In, polycondensation can occur for silicone hydroxyl abundant between MFI nano ply, but through K. Na etc. further study showed that passing through modulation crystallization
Condition and synthetic system composition, also can be changed assembling and the arrangement mode of MFI zeolite nano ply, disorderly arranged zeolite nanometer
The product that synusia is fired after removing template is still able to maintain meso pore characteristics (Chem. Mater., 2011,23,1273).
Therefore, using MFI zeolite nano ply acid strength, acid amount and acid active bit distribution it is adjustable controllable and have compared with
It is the features such as big specific surface area and surface silicone hydroxyl abundant (grafting position), strong by the quantity for regulating and controlling to graft basic activated position
Degree and position prepare difunction catalyst, have important answer in deacetalization-Knoevenagel reaction
With value.
Summary of the invention
It is an object of that present invention to provide a kind of preparation methods of difunctional MFI zeolite nano ply, are based on the conduct of MFI zeolite
The acid strength of catalyst and base strength are not easy in the presence of material of main part catalysis deacetalization-Knoevenagel reaction
Regulation, acid active sites and basic activated column pitch are difficult to etc. main insufficient, a kind of are functionalized using alkalinity to disclose
The silane method directly reacted with the surface hydroxyl on MFI nano ply prepare the difunctional MFI zeolite nanometer of soda acid
The technical solution of synusia multifunctional material method.
The present invention is achieved by the following technical scheme:
A kind of preparation method of difunctional MFI zeolite nano ply, includes the following steps:
(1), MFI layered zeolite is placed in 15wt% aqueous ammonium nitrate solution, progress ion exchange 2 ~ 4 times, after 110 DEG C of dryings, so
The lower 550 DEG C of roastings 4h of air atmosphere afterwards, obtains Hydrogen MFI layered zeolite；
(2), the functionalized silane graft of alkalinity is modified MFI zeolite in Hydrogen MFI zeolite or first with silane, then
It is acted on again by grafted silane with basic group, obtains the MFI zeolite novel organic-inorganic with acid and alkaline bifunctional
Composite material.
Wherein, the silane be linear alkyl amine, alkyl diamine, alkyl triamine, replace or to substituted aromatic amine.
Wherein, step (2) specifically:
I, Hydrogen MFI layered zeolite is dried in vacuo 3h at 120 DEG C, be placed in the toluene solution of water removal, alkaline function is added
The silane of change, for 24 hours, cold filtration, obtained solid carries out Soxhlet pumping in the mixed solution of methylene chloride and ether for 90 DEG C of reflux
It mentions for 24 hours, then dry 12h at 80 DEG C, obtained solid is the MFI zeolite novel organic-inorganic with acid and alkaline bifunctional
Composite material.
In step I, the functionalized silane of alkalinity is aminopropyl trimethoxysilane.
II, Hydrogen MFI layered zeolite is dried in vacuo 3h at 120 DEG C, be placed in the toluene solution of water removal, is added organic
Silane, for 24 hours, cold filtration, obtained solid carries out soxhlet type in the mixed solution of methylene chloride and ether for 90 DEG C of reflux
For 24 hours, then dry 12h at 80 DEG C, obtains the MFI of silanization；
The MFI of silanization, zinc chloride, acetic acid, hexamethylene and formalin are placed in three-necked flask, in hydrogen chloride gas atmosphere
Under be stirred at room temperature for 24 hours, then product is filtered, is washed with ethyl alcohol and deionized water, 4h, products obtained therefrom are dried in vacuo at 120 DEG C
For the MFI of chloromethylation；
The MFI of chloromethylation is mixed in the toluene solution of dehydration with piperazine, 12h is stirred, then obtained solid exists
Soxhlet type is carried out for 24 hours in the mixed solution of methylene chloride and ether, and products obtained therefrom is the MFI with acid and alkaline bifunctional
Zeolite novel organic-inorganic composite material.
In step II, organosilan is phenyl trimethoxy.
MFI layered zeolite the preparation method is as follows: sodium hydroxide, organic formwork agent and ethyl alcohol are dissolved into aqueous solution first
In, then at 65 DEG C, continues that the solution that silicon source and sulfuric acid form is slowly added dropwise in above-mentioned solution under stirring, maintain
2h；Silicon source is added in the above-mentioned mixed solution under stirring after cooling；Then 2h is stirred at 65 DEG C；Mixed liquor is packed into
In stainless steel cauldron with polytetrafluoroethyllining lining, 140 DEG C are put into, 3 ~ 9d of crystallization, is then washed in the rotary oven of 50rmp
It washs, obtains MFI layered zeolite after 110 DEG C of dryings.
Wherein, silicon source, silicon source, sodium hydroxide, organic formwork agent, sulfuric acid, the molar ratio of second alcohol and water are (0 ~ 4): 100:
30:10:18:(200~800):4000。
The silicon source is ethyl orthosilicate, waterglass, silica solution or white carbon black.
Source of aluminium is sodium metaaluminate, aluminium isopropoxide or aluminum sulfate.
The organic formwork agent is the dimer (C of tetrabutyl quaternary ammonium base and tetrapropyl quaternary ammonium base3H7)3N+(CH2)nN+
(C3H7)3。
MFI nano ply prepared by the present invention acid strength, acid amount and acid active bit distribution it is adjustable controllable and have compared with
The layer structure of big specific surface area and surface silicone hydroxyl abundant (grafting position).
The advantages of preparation method of difunctional MFI zeolite nano ply of the present invention, is: not only using this method
Can will various basic groups of different nature it is immobilized on MFI zeolitic material, and prepared composite material while there is acid
Property and alkaline two kinds of active sites, possess acid and alkaline two kinds of catalysis, and soda acid active sites are in quantity, intensity and position
Aspect matched can be catalyzed complicated tandem reaction.
Detailed description of the invention
Fig. 1 shows the FT-IR spectrograms of Hydrogen MFI zeolite nano ply sample.
Fig. 2 indicates the FT-IR spectrogram of the MFI zeolite nano ply sample of aminopropyl trimethoxysilane.
Specific embodiment
Specific embodiments of the present invention are described in detail below.
One, organic formwork agent is prepared
1, the dimer (C of organic formwork agent tetrapropyl quaternary ammonium base3H7)3N+(CH2)nN+(C3H7)3Synthesis according to following schemes
Synthesis.
Scheme 1
0.1mol iodopropane and 0.8 ~ 1.2mol Diaminoalkane are mixed in 100mL butanone solution, 0.1mol carbonic acid is added
Potassium stirs 12h at 65 DEG C, is cooled to room temperature, filters, and ether washing, 60 DEG C of vacuum drying, obtained solid is quaternary ammonium base.
2, the synthesis of organic formwork agent tetrabutyl quaternary ammonium alkali-dimer is illustrated according to Scheme 1 and is synthesized.
0.1mol iodobutane and 0.8 ~ 1.2mol Diaminoalkane are mixed in 100mL butanone solution, 0.1mol is added
Potassium carbonate stirs 12h at 65 DEG C, is cooled to room temperature, filters, and ether washing, 60 DEG C of vacuum drying, obtained solid is quaternary ammonium
Alkali.
Two, MFI layered zeolite is prepared
Sodium hydroxide, organic formwork agent and ethyl alcohol are dissolved into aqueous solution first, then at 65 DEG C, continuing will under stirring
The solution of silicon source and sulfuric acid composition is slowly added dropwise in above-mentioned solution, maintains 2h.Silicon source is added to stirring after cooling
Under above-mentioned mixed solution in.Then 2h is stirred at 65 DEG C.It is anti-that mixed liquor is packed into the stainless steel with polytetrafluoroethyllining lining
It answers in kettle, is put into 140 DEG C, 3 ~ 9d of crystallization, is washed out in the rotary oven of 50rmp, and the boiling of MFI stratiform is obtained after 110 DEG C of dryings
Stone.
Wherein, silicon source (sodium metaaluminate, aluminium isopropoxide or aluminum sulfate), silicon source (ethyl orthosilicate, waterglass, silica solution or
White carbon black), the molar ratio of sodium hydroxide, organic formwork agent, sulfuric acid, second alcohol and water is (0,0.25,0.5,1,2,4):
100:30:10:18:(200,400, 800):4000。
Three, Hydrogen MFI layered zeolite is prepared
MFI layered zeolite is placed in 15wt% aqueous ammonium nitrate solution, is carried out ion exchange 2 ~ 4 times, it is then empty after 110 DEG C of dryings
Atmosphere encloses lower 550 DEG C of roastings 4h, obtains Hydrogen MFI layered zeolite.
As shown in Figure 1,970cm-1Neighbouring characteristic peak belongs to the absorption peak of Si-OH, 3460cm-1Neighbouring characteristic peak ownership
In-OH stretching vibration absworption peak, illustrates that MFI zeolite nano ply possesses zeolite feature, have grafting modification power.
Four, difunctional MFI zeolite nano ply is prepared
1, basic activated position is introduced under the conditions of different solvents, temperature and time according to grafting method shown in Scheme 2
Onto MFI nano ply, organosilan used include linear alkyl amine, alkyl diamine, alkyl triamine, replace and to substitution
Aromatic amine.
Scheme 2
Specific step is as follows: 2.0g Hydrogen MFI layered zeolite being dried in vacuo 3h at 120 DEG C, is placed in the toluene of 50mL water removal
In solution, 3.0g aminopropyl trimethoxysilane is added, for 24 hours, cold filtration, obtained solid is in methylene chloride and second for 90 DEG C of reflux
Soxhlet type is carried out for 24 hours in the mixed solution of ether, then dry 12h at 80 DEG C, obtained solid is with the double function of acid and alkalinity
The MFI zeolite novel organic-inorganic composite material of energy.
As shown in Fig. 2, 3300cm-1And 1640cm-1Neighbouring characteristic peak belongs to-NH2The characteristic peak of stretching vibration, illustrates ammonia
Propyl trimethoxy silicane is successfully grafted on MFI zeolite nano ply.
2, according to grafting method shown in Scheme3 by basic activated position under the conditions of different solvents, temperature and time
Be introduced on MFI nano ply, organosilan used include linear alkyl amine, alkyl diamine, alkyl triamine, replace and it is right
Substituted aromatic amine.
Scheme 3
Specific step is as follows: (1) 2.0g Hydrogen MFI layered zeolite being dried in vacuo 3h at 120 DEG C, be placed in 50mL water removal
In toluene solution, be added 3.0g phenyltrimethoxysila,e, 90 DEG C of reflux for 24 hours, cold filtration, obtained solid in methylene chloride and
Soxhlet type is carried out for 24 hours in the mixed solution of ether, and then dry 12h at 80 DEG C, obtains the MFI of silanization.
(2), by MFI, 4g zinc chloride of 2.0g silanization, 3mL acetic acid, 20mL hexamethylene and 10mL formalin (37%)
It is placed in three-necked flask, is stirred at room temperature under hydrogen chloride gas atmosphere for 24 hours, then filters product, with ethyl alcohol and deionized water
It washs, 4h is dried in vacuo at 120 DEG C, products obtained therefrom is the MFI of chloromethylation.
(3), the MFI of chloromethylation is mixed in the toluene solution of dehydration with piperazine, 12h is stirred, then by institute
It obtains solid and carries out soxhlet type for 24 hours in the mixed solution of methylene chloride and ether, products obtained therefrom is double with acid and alkalinity
The MFI zeolite novel organic-inorganic composite material of function.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although ginseng
It is described in detail according to the embodiment of the present invention, those skilled in the art should understand that, to technical solution of the present invention
It is modified or replaced equivalently, without departure from the spirit and scope of technical solution of the present invention, the present invention should all be covered by
In the protection scope of claims.
Claims (9)
1. a kind of preparation method of difunctional MFI zeolite nano ply, characterized by the following steps:
(1), MFI layered zeolite is placed in 15wt% aqueous ammonium nitrate solution, progress ion exchange 2 ~ 4 times, after 110 DEG C of dryings, so
The lower 550 DEG C of roastings 4h of air atmosphere afterwards, obtains Hydrogen MFI layered zeolite；
(2), the functionalized silane graft of alkalinity is modified MFI zeolite in Hydrogen MFI zeolite or first with silane, then
It is acted on again by grafted silane with basic group, obtains the MFI zeolite novel organic-inorganic with acid and alkaline bifunctional
Composite material.
2. the preparation method of difunctional MFI zeolite nano ply according to claim 1, it is characterised in that: the silane is line
Property alkylamine, alkyl diamine, alkyl triamine, replace or to substituted aromatic amine.
3. the preparation method of difunctional MFI zeolite nano ply according to claim 2, it is characterised in that: step (2) is specific
Are as follows:
I, Hydrogen MFI layered zeolite is dried in vacuo 3h at 120 DEG C, be placed in the toluene solution of water removal, alkaline function is added
The silane of change, for 24 hours, cold filtration, obtained solid carries out Soxhlet pumping in the mixed solution of methylene chloride and ether for 90 DEG C of reflux
It mentions for 24 hours, then dry 12h at 80 DEG C, obtained solid is the MFI zeolite novel organic-inorganic with acid and alkaline bifunctional
Composite material；
II, Hydrogen MFI layered zeolite is dried in vacuo 3h at 120 DEG C, be placed in the toluene solution of water removal, organosilicon is added
Alkane, for 24 hours, cold filtration, obtained solid carries out soxhlet type for 24 hours in the mixed solution of methylene chloride and ether for 90 DEG C of reflux,
Then dry 12h at 80 DEG C, obtains the MFI of silanization；
The MFI of silanization, zinc chloride, acetic acid, hexamethylene and formalin are placed in three-necked flask, in hydrogen chloride gas atmosphere
Under be stirred at room temperature for 24 hours, then product is filtered, is washed with ethyl alcohol and deionized water, 4h, products obtained therefrom are dried in vacuo at 120 DEG C
For the MFI of chloromethylation；
The MFI of chloromethylation is mixed in the toluene solution of dehydration with piperazine, 12h is stirred, then obtained solid exists
Soxhlet type is carried out for 24 hours in the mixed solution of methylene chloride and ether, and products obtained therefrom is the MFI with acid and alkaline bifunctional
Zeolite novel organic-inorganic composite material.
4. the preparation method of difunctional MFI zeolite nano ply according to claim 2, it is characterised in that: in step I, alkalinity
Functionalized silane is aminopropyl trimethoxysilane；In step II, organosilan is phenyl trimethoxy.
5. the preparation method of difunctional MFI zeolite nano ply according to claim 1, it is characterised in that: MFI layered zeolite
The preparation method is as follows: being first dissolved into aqueous solution sodium hydroxide, organic formwork agent and ethyl alcohol, then at 65 DEG C, persistently stir
It mixes and the solution that silicon source and sulfuric acid form is slowly added dropwise in above-mentioned solution under state, maintain 2h；Silicon source is added after cooling
In above-mentioned mixed solution under to stirring；Then 2h is stirred at 65 DEG C；Mixed liquor is packed into and has polytetrafluoroethyllining lining
Stainless steel cauldron in, be put into 140 DEG C, 3 ~ 9d of crystallization, is washed out in the rotary oven of 50rmp, obtains after 110 DEG C of dryings
MFI layered zeolite.
6. the preparation method of difunctional MFI zeolite nano ply according to claim 5, it is characterised in that: silicon source, silicon source, hydrogen
Sodium oxide molybdena, organic formwork agent, sulfuric acid, the molar ratio of second alcohol and water are (0 ~ 4): 100:30:10:18:(200 ~ 800): 4000.
7. the preparation method of difunctional MFI zeolite nano ply according to claim 6, it is characterised in that: the silicon source is positive
Silester, waterglass, silica solution or white carbon black.
8. the preparation method of difunctional MFI zeolite nano ply according to claim 6, it is characterised in that: source of aluminium is inclined
Sodium aluminate, aluminium isopropoxide or aluminum sulfate.
9. the preparation method of difunctional MFI zeolite nano ply according to claim 6, it is characterised in that: the organic formwork
Agent is the dimer (C of tetrabutyl quaternary ammonium base and tetrapropyl quaternary ammonium base3H7)3N+(CH2)nN+(C3H7)3。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163142A (en) * | 2012-02-09 | 2013-08-22 | Tottori Univ | Catalyst for producing para-substituted aromatic hydrocarbon, method for producing the catalyst, and method for producing the para-substituted aromatic hydrocarbon by using the catalyst |
| CN105199540A (en) * | 2015-10-21 | 2015-12-30 | 哈尔滨工程大学 | Method for preparing fluorosilane-modified HZSM-5 molecular sieve epoxy resin for magnesium-lithium alloy surface coating |
| CN106000458A (en) * | 2016-05-23 | 2016-10-12 | 北京化工大学 | Efficient multi-phase acid-base double-functional catalyst and preparation method thereof |
| CN108408738A (en) * | 2018-05-29 | 2018-08-17 | 广东工业大学 | Playing cards room type MFI molecular sieves with high stability and its preparation method and application |
| CN109395768A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | A kind of functionalization ZSM-5 molecular sieve |
-
2019
- 2019-07-08 CN CN201910610367.8A patent/CN110342532B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163142A (en) * | 2012-02-09 | 2013-08-22 | Tottori Univ | Catalyst for producing para-substituted aromatic hydrocarbon, method for producing the catalyst, and method for producing the para-substituted aromatic hydrocarbon by using the catalyst |
| CN105199540A (en) * | 2015-10-21 | 2015-12-30 | 哈尔滨工程大学 | Method for preparing fluorosilane-modified HZSM-5 molecular sieve epoxy resin for magnesium-lithium alloy surface coating |
| CN106000458A (en) * | 2016-05-23 | 2016-10-12 | 北京化工大学 | Efficient multi-phase acid-base double-functional catalyst and preparation method thereof |
| CN109395768A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | A kind of functionalization ZSM-5 molecular sieve |
| CN108408738A (en) * | 2018-05-29 | 2018-08-17 | 广东工业大学 | Playing cards room type MFI molecular sieves with high stability and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| FANPENG SHANG ET AL.: "Synthesis, characterization and catalytic application of bifunctional", 《CATALYSIS COMMUNICATIONS》 * |
| KYUNGSU NA ET AL.: "Pillared MFI Zeolite Nanosheets of a Single-Unit-Cell Thickness", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 晋春等: "MCM-41介孔分子筛共价键联钴酞菁的制备，表征及性质", 《无机化学学报》 * |
| 朱洪法: "《催化剂载体》", 30 April 1980, 化学工业出版社 * |
| 赵骏等: "《有机化学》", 31 August 2018, 中国医药科技出版社 * |
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