CN104445250A - Method for synthesizing MFI type zeolite from Magadiite - Google Patents
Method for synthesizing MFI type zeolite from Magadiite Download PDFInfo
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Abstract
The invention relates to a method for synthesizing MFI type zeolite from Magadiite, for mainly solving the problems that in the existing MFI type zeolite preparation technique a great amount of template agent is used, alkali needs to be added, and a corresponding hydrogen type molecular sieve can only be prepared after ammonium ion exchange. According to the technical scheme, the method comprises the following steps: mixing Magadiite, quaternary ammonium salt Q and water in the following ratios: the ratio of quaternary ammonium salt Q to SiO2 is 0.01 to 0.20, and the ratio of H2O to SiO2 is 1 to 50, thereby obtaining a mixture; crystallizing the mixture for 2-90 hours at 120-190 DEG C, and washing and drying a crystallization product, thereby obtaining MFI type zeolite, wherein the quaternary ammonium salt is a compound as shown in the formula R4N+X-, in the formula, R is selected from at least one of the alkyl with the carbon atom number of 1-20; X- is at least one of C1-, Br- and I-, the technical problems are relatively well solved, and the method can be used in industrial production for preparing MFI type zeolite.
Description
Technical field
The present invention relates to a kind of Magadiite that utilizes and synthesize the method for MFI type zeolite, particularly utilize Magadiite as silicon source and aluminium source to synthesize the method for MFI type zeolite.
Background technology
Zeolite molecular sieve, owing to having unique duct shape selectivity, unique solid acid character and excellent ion-exchange character, is thus applied widely, and in absorption, the aspects such as separation and catalysis have shown their huge commercial application value all.Such as at refining of petroleum and chemical field, the application of Y zeolite brings the revolution of a hop to petroleum catalytic cracking technology, and other molecular sieve catalyst, as ZSM-5 zeolite, mordenite, β zeolite, MCM-22 zeolite, the application of SAPO-34 molecular sieve etc. brings substantial breakthrough also to the important refining of petroleum of cracking, reformation, isomerization, aromatic disproportion and alkylation, methanol conversion etc. and Chemical Engineering Technology.Therefore in view of the vital role of molecular sieve in many industrial circles, in document and patent for the research of recruit's sieve and the research of novel synthesis always all very abundant.
The source of molecular sieve mainly contains two aspects, and one is obtain from nature mineral, and two is obtained by the way of synthetic, and some molecular sieve can be obtained by these two kinds of approach, but some molecular sieve can only be obtained by the method for synthetic.At refining of petroleum and chemical field, most molecular sieve catalysts is all obtained by the way of synthetic.Conventional molecular sieve artificial synthesis is hydrothermal synthesis method, as ZSM-5 (US 3702886), ZSM-11 (US 3709979), ZSM-23 (US 4076842), ZSM-35 (US 4016245), Zeolite beta (US 3308069), SAPO-34 (US 4440871), MCM-22 (US 4954325).Use water heat transfer zeolite molecular sieve to be generally first by silicon source compound, aluminum source compound, alkali, template, and water etc. is obtained by reacting starting sol, then the hydro-thermal reaction of this colloidal sol under enclosed system obtains the molecular sieve product of crystallization.Silicon sol generally can be used, silica gel, water glass, White Carbon black and organosilicon etc. in silicon source, and aluminium source generally uses Tai-Ace S 150, aluminum nitrate, sodium metaaluminate, alumina sol, organoaluminum and pseudo-boehmite etc., and alkali can be organic bases, ammoniacal liquor, NaOH, KOH etc.Wherein alkali is the important factor affecting Zeolite synthesis, but excessive alkali can make molecular sieve dissolve, product yield is reduced, simultaneously, the introducing of mineral alkali will make to prepare acidic molecular sieve increases a step, namely to the exchange process of metallic cation, this process makes process costs increase, and wastewater treatment capacity increases.
Have document and patent report, some lamellar compounds also can use as silicon source and synthesize zeolite molecular sieve, and the advantage being carried out synthesis of molecular sieve by this path is that template consumption is few, and crystallization condition is relatively gentle, and gained crystal is more regular.US 4676958 adopts Magadiite as silicon source to synthesize multiple zeolite molecular sieve, comprises ZSM-5, ZSM-12, ZSM-39, ZSM-48, SSZ-15 etc., the Magadiite itself adopted due to this invention does not contain aluminium, therefore needs to add aluminium source and alkali source again in reaction system.
Document (Microporous Materials 11 (1997) 45-51), document (Microporous and Mesoporous Materials 69 (2004) 85-96) and document (Microporous and Mesoporous Materials 135 (2010) 143-148) all use Magadiite to synthesize ZSM-5 zeolite molecular sieve as silicon source or silicon and aluminum source, also all add oxyhydroxide as alkali source in reaction system.
Summary of the invention
To be solved by this invention is large, the problem that needs could prepare after adding alkali and needing ammonium ion exchange corresponding hydrogen type molecular sieve of template consumption in existing MFI type zeolite technology of preparing, there is provided a kind of Magadiite that utilizes newly to synthesize the method for MFI type zeolite, the method have that quaternary ammonium salt. template dosage amounts is few, in reaction system without the need to adding the advantage that oxyhydroxide, the MFI zeolite product purity that obtains are high, prepare hydrogen type molecular sieve without the need to ammonium ion exchange.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method utilizing Magadiite to synthesize MFI type zeolite, comprises Magadiite, quaternary ammonium salt Q, Yi Jishui, form mixture: quaternary ammonium salt Q/SiO according to following mol ratio
2=0.01 ~ 0.20, H
2o/ SiO
2=1 ~ 50; And then by said mixture crystallization 2 ~ 90 hours at 120 ~ 190 DEG C, crystallization product, through washing, dry, obtains MFI type zeolite; Wherein, quaternary ammonium salt is the compound with following chemical formula: R
4n
+x
-, wherein: it is at least one in the alkyl of 1 ~ 20 that R is selected from carbonatoms, X
-for Cl
-, Br
-and I
-in at least one.
The method of the synthesis MFI type zeolite described in technique scheme, is characterized in that in mixture, each component has following molar ratio: Q/SiO
2=0.01 ~ 0.1, H
2o/ SiO
2=5 ~ 50.Wherein SiO in Magadiite
2content calculate with 77.6%.
The method of the synthesis MFI type zeolite described in technique scheme, is characterized in that mixture crystallization 6 ~ 80 hours at 125 ~ 180 DEG C.
The method of the synthesis MFI type zeolite described in technique scheme, is characterized in that quaternary ammonium salt is the compound with following chemical formula: R
4n
+x
-
Wherein: it is at least one in the alkyl of 2 ~ 20 that R is selected from carbonatoms, X
-for Cl
-and Br
-in at least one, be preferably 4-propyl bromide, 4-propyl ammonium chloride, tetraethylammonium bromide, etamon chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, at least one in dimethyl diethyl brometo de amonio and dimethyl diethylammonium chloride.
The method of the synthesis MFI type zeolite described in technique scheme, is characterized in that Magadiite used synthesizes through the following steps and obtains:
A) according to 10SiO
2: (0.0 ~ 3.5) Y
2o
3: (0.5-2.8) alkaline matter A:(0.05-5) organism R:(0.05-5) an alkali metal salt S:(85-400) H
2the mol ratio of O, by silicon source, heteroatoms source Y
2o
3, alkaline matter A, organism R, an alkali metal salt S and water Homogeneous phase mixing obtain mixture; Wherein silicon source is selected from silicon sol, solid silicone, gas-phase silica, at least one in soft silica or organic silicone grease; Alkaline matter A for being selected from Lithium Oxide 98min, sodium oxide, potassium oxide, Cs2O, lithium hydroxide, sodium hydroxide, potassium hydroxide, at least one in rubidium hydroxide and cesium hydroxide; An alkali metal salt S is selected from oxalate, vitriol, acetate, nitrate, the carbonate of alkali metal, at least one in phosphoric acid salt and halogenide; Element Y is selected from Al, at least one in B and Ga;
B) by said mixture at 125 ~ 185 DEG C, hydrothermal crystallizing 10 ~ 160 hours.
The method of the synthesis MFI type zeolite described in technique scheme, it is characterized in that synthesizing in the method for Magadiite, the mol ratio of mixture is 10SiO
2: (0.0 ~ 2.5) Y
2o
3: (0.6 ~ 2.4) alkaline matter A:(1.0 ~ 5.0) organism R:(1.0 ~ 5.0) an alkali metal salt S:(85 ~ 300) H
2o.
The method of the synthesis MFI type zeolite described in technique scheme, is characterized in that synthesizing in the method for Magadiite, mixture hydrothermal crystallizing 12 ~ 150 hours at 135 ~ 175 DEG C.
The method of the synthesis MFI type zeolite described in technique scheme, it is characterized in that synthesizing in the method for Magadiite, organism R is crown ether, at least one in polyoxyethylene glycol and tetraethylene glycol dimethyl ether.
The method of the synthesis MFI type zeolite described in technique scheme, it is characterized in that synthesizing in the method for Magadiite, the molecular weight of organism R is between 200 to 1000.
In technique scheme, in the method for synthesis Magadiite, element Y is selected from Al, at least one in B and Ga;
In the method for synthesis Magadiite, organism R is crown ether, at least one in polyoxyethylene glycol and tetraethylene glycol dimethyl ether; Quaternary ammonium salt is 4-propyl bromide, 4-propyl ammonium chloride, tetraethylammonium bromide, etamon chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, at least one in dimethyl diethyl brometo de amonio and dimethyl diethylammonium chloride.
MFI type zeolite synthetic method provided by the present invention has the following advantages: 1) quaternary ammonium salt. template dosage amounts is few; 2) in reaction system without the need to adding oxyhydroxide; 3) the MFI zeolite product purity obtained is high; 4) just corresponding hydrogen type molecular sieve can directly be prepared without the need to ammonium ion exchange; 5) pattern of gained MFI zeolite is based on thin bulk.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the Magaditte material that embodiment 1 uses
Fig. 2 is the XRD figure of the MFI zeolite that embodiment 1 obtains
Fig. 3 is the scanning electron microscope (SEM) photograph of the Magadiite material that embodiment 1 uses
Fig. 4 is the scanning electron microscope (SEM) photograph of the MFI zeolite that embodiment 1 obtains
Below by embodiment, the invention will be further elaborated, but therefore do not limit the scope of the invention.
Embodiment
[embodiment 1]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2：1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 86 hours, after reaction terminates after washing, drying, is accredited as Magaditte material through XRD.
Mixed with 0.8 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.09，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 150
ocrystallization 40 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 2]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2：1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 86 hours, after reaction terminates after washing, drying, is accredited as Magaditte material through XRD.
Mixed with 0.8 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.09，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 3]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2：1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 86 hours, after reaction terminates after washing, drying, is accredited as Magaditte material through XRD.
Mixed with 0.8 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.09，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 180
ocrystallization 24 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 4]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2：1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 86 hours, after reaction terminates after washing, drying, is accredited as Magaditte material through XRD.
Mixed with 0.18 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.02，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 5]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, the sodium metaaluminate of 0.0572 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.05Al
2O
3: 1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.4 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.045，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 6]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, the sodium metaaluminate of 0.0572 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.05Al
2O
3: 1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.8 gram of TEABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TEABr/SiO
2=0.10，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 180
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 7]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, the sodium metaaluminate of 0.0572 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.05Al
2O
3: 1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.8 gram of TBABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TBABr/SiO
2=0.085，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 180
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 8]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, the sodium metaaluminate of 0.0572 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.05Al
2O
3: 1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.2 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.023，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 9]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, the sodium metaaluminate of 0.0572 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.05Al
2O
3: 1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.4 gram of TPABr and 10 ml deionized water by the above-mentioned Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.045，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 180
ocrystallization 24 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 10]
By the NaF of 0.2932 gram, 2.6074 the aqueous sodium hydroxide solution of gram 30wt%, the boric acid of 0.3452 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 9.8 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.4B
2O
3: 1.0NaF: 1.5Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.4 gram of TPABr and 10 ml deionized water by the above-mentioned boracic Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.045，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 11]
By the NaF of 0.2932 gram, 2.6074 the aqueous sodium hydroxide solution of gram 30wt%, the boric acid of 0.863 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 9.8 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 1.0B
2O
3: 1.0NaF: 1.5Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.4 gram of TPABr and 10 ml deionized water by the above-mentioned boracic Magadiite of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.045，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 12]
By the NaF of 0.2932 gram, 1.6762 the aqueous sodium hydroxide solution of gram 30wt%, the 16 water gallium sulfates of 0.155 gram, PEG 300 (molecular-weight average is about the polyoxyethylene glycol of the 300) solution of 10 grams of 50wt%, the silicon sol solution of the 40wt% of the water of 10.3 grams and 8.1 milliliters mixes, and the mol ratio of gained mixture is:
10SiO
2: 0.05Ga
2O
3: 1.0NaF: 0.9Na
2O: 2.5PEG 300: 175H
2O
Said mixture is moved in reactor in 160
oc crystallization 102 hours, through washing, drying after reaction terminates, XRD is accredited as Magaditte material.
Mixed with 0.4 gram of TPABr and 10 ml deionized water by the above-mentioned gallium Magadiite that contains of 2.0 grams, the mol ratio of mixed serum is:
TPABr/SiO
2=0.045，H
2O/SiO
2=16.67
Then above-mentioned slurries are placed in closed reactor, in 130
ocrystallization 60 hours under C, solid product is accredited as MFI zeolite through XRD after washing drying.
[embodiment 13]
Hydrogen is containing the synthesis of aluminium MFI zeolite
By 2.0 grams by embodiment 5 obtain containing aluminium MFI zeolite in air atmosphere in 550 DEG C of roastings 5 hours Hydrogen containing aluminium MFI zeolite, wherein Na
2the content of O is lower than 1.5%.
Claims (10)
1. synthesize a method for MFI type zeolite, comprise Magadiite, quaternary ammonium salt Q, Yi Jishui, form mixture according to following mol ratio: quaternary ammonium salt Q/SiO
2=0.01 ~ 0.20, H
2o/ SiO
2=1 ~ 50; And then by said mixture crystallization 2 ~ 90 hours at 120 ~ 190 DEG C, crystallization product, through washing, dry, obtains MFI type zeolite; Wherein, quaternary ammonium salt is the compound with following chemical formula: R
4n
+x
-, wherein: it is at least one in the alkyl of 1 ~ 20 that R is selected from carbonatoms, X
-for Cl
-, Br
-and I
-in at least one.
2. the method for synthesis MFI type zeolite according to claim 1, is characterized in that in mixture, each component has following molar ratio quaternary ammonium salt Q/SiO
2=0.01 ~ 0.1, H
2o/ SiO
2=5 ~ 50.
3. the method for synthesis MFI type zeolite according to claim 1, is characterized in that mixture crystallization 6 ~ 80 hours at 125 ~ 180 DEG C.
4. the method for synthesis MFI type zeolite according to claim 1, is characterized in that Magadiite used synthesizes through the following steps and obtains:
A) according to 10SiO
2: (0.0 ~ 3.5) Y
2o
3: (0.5-2.8) alkaline matter A:(0.05-5) organism R:(0.05-5) an alkali metal salt S:(85-400) H
2the mol ratio of O, by silicon source, heteroatoms source Y
2o
3, alkaline matter A, organism R, an alkali metal salt S and water Homogeneous phase mixing obtain mixture; Wherein silicon source is selected from silicon sol, solid silicone, gas-phase silica, at least one in soft silica or organic silicone grease; Alkaline matter A for being selected from Lithium Oxide 98min, sodium oxide, potassium oxide, Cs2O, lithium hydroxide, sodium hydroxide, potassium hydroxide, at least one in rubidium hydroxide and cesium hydroxide; An alkali metal salt S is selected from oxalate, vitriol, acetate, nitrate, the carbonate of alkali metal, at least one in phosphoric acid salt and halogenide;
B) by said mixture at 125 ~ 185 DEG C, hydrothermal crystallizing 10 ~ 160 hours, obtains Magadiite.
5. the method for synthesis MFI type zeolite according to claim 4, it is characterized in that synthesizing in the method for Magadiite, the mol ratio of mixture is 10SiO
2: (0.0 ~ 2.5) Y
2o
3: (0.6 ~ 2.4) alkaline matter A:(1.0 ~ 5.0) organism R:(1.0 ~ 5.0) an alkali metal salt S:(85 ~ 300) H
2o.
6. the method for synthesis MFI type zeolite according to claim 4, is characterized in that synthesizing in the method for Magadiite, mixture hydrothermal crystallizing 12 ~ 150 hours at 135 ~ 175 DEG C.
7. the method for synthesis MFI type zeolite according to claim 4, it is characterized in that synthesizing in the method for Magadiite, the molecular weight of organism R is between 200 to 1000.
8. the method for synthesis MFI type zeolite according to claim 4, it is characterized in that synthesizing in the method for Magadiite, element Y is selected from Al, at least one in B and Ga.
9. the method for synthesis MFI type zeolite according to claim 4, it is characterized in that synthesizing in the method for Magadiite, organism R is crown ether, at least one in polyoxyethylene glycol and tetraethylene glycol dimethyl ether.
10. the method for synthesis MFI type zeolite according to claim 1, it is characterized in that quaternary ammonium salt is 4-propyl bromide, 4-propyl ammonium chloride, tetraethylammonium bromide, etamon chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, at least one in dimethyl diethyl brometo de amonio and dimethyl diethylammonium chloride.
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| US8153099B2 (en) * | 2008-05-21 | 2012-04-10 | Industry-University Cooperation Foundation Sogang University | Uniformly b-oriented MFI zeolite membrane with variable thickness supported on substrate and preparation method thereof |
| CN103073004A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Preparation method of two-dimensional layered-structure material magadiite |
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| US8153099B2 (en) * | 2008-05-21 | 2012-04-10 | Industry-University Cooperation Foundation Sogang University | Uniformly b-oriented MFI zeolite membrane with variable thickness supported on substrate and preparation method thereof |
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| CN111974443A (en) * | 2019-05-22 | 2020-11-24 | 中国科学院大连化学物理研究所 | Catalyst for preparing acrylic acid and methyl acrylate, preparation method and application thereof |
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