CN102452665A - Method for preparing layered zeolite with MWW structure - Google Patents
Method for preparing layered zeolite with MWW structure Download PDFInfo
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- CN102452665A CN102452665A CN2010105139629A CN201010513962A CN102452665A CN 102452665 A CN102452665 A CN 102452665A CN 2010105139629 A CN2010105139629 A CN 2010105139629A CN 201010513962 A CN201010513962 A CN 201010513962A CN 102452665 A CN102452665 A CN 102452665A
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Abstract
The invention relates to a method for preparing a layered zeolite with MWW structure and aims to solve problems of severe toxicity and environmental pollution of a prior art using hexamethylene imines as a template. According to the invention, silicon source, aluminium source, template (T), alkali metal cation M, seed crystal and water are mixed into a mixture, wherein molar ratios of the mixture are as below: SiO2 / Al2O3 equals to 1-200; H2O / SiO2 equals to 5-500; OH<-> / SiO2 equals to 0.01-4; M<+> / SiO2 equals to 0.01-4; and T / SiO2 equals to 0.01-4; the mixture is crystallized for 1-400 h at 30-200 DEG C to obtain a crystallization product, which is the layered zeolite with MWW structure; and the template T is non-equivalence tetra-allkylammonium cation. The above technical scheme well solves the problems and can be applied to industrial production of layered zeolite with MWW structure.
Description
Technical field
The present invention relates to the method that a kind of preparation has the layered zeolite of MWW structure, this zeolite MCM-56 zeolite that is otherwise known as.
Background technology
Zeolite molecular sieve is one type and passes through shared SiO
2And AlO
2Tetrahedron (or other can form tetrahedral respective element) summit and the crystal aluminosilicate with molecule duct or cage (or containing the crystallisate that other can form the tetrahedron element) that forms.The field such as synthetic that is widely used in refining of petroleum, petroleum chemistry, meticulous and specialty chemicals, it has IX, shape selective catalysis, the molecular sieve function of grading.
The zeolites catalytic material of three-dimensional structure has stronger acid active sites and selects the shape effect, and its channel diameter is generally less than 1 nanometer, can't hold bigger reactant molecule.Compare with three-dimensional structure zeolites catalytic material, mesopore molecular sieve such as MCM-41 etc. has larger aperture, but hole wall is amorphous, acid weak, poor stability.Clay class stratiform catalytic material has abundant diffusion admittance, but also has the problem of active and poor stability.
Layered zeolite has bigger specific surface area and strongly-acid outside surface active site (suitable with corresponding three-dimensional structure zeolite acidity) as the unique solid acid catalyst material of structure, and macromole is shown very excellent absorption and catalytic performance.Optimize synthesis technique through (1), can prepare the layer molecule sieve that the macromole height can reach the outside surface active sites that has of high-specific surface area; (2) through suitable modification, as regulate silica alumina ratio, introduce heteroatoms, active ingredient that load is fit to etc., the layered zeolite material can be used as the efficient catalyst material and is applied in the corresponding macromolecular reaction.This layer molecule sieve can be used for petrochemical industry, synthetic etc. like light materialization of heavy oil, condensed-nuclei aromatics lighting, ethylbenzene, isopropyl benzene.
U.S. Pat 5362697 has been introduced the preparation method of a kind of MCM-56, and its Si/Al of the layered zeolite with MWW structure of this method preparation is than less than 17.5, during as template, exists toxicity big, the problem that contaminate environment is serious with hexamethylene imine.It is template that the present invention adopts the non-equivalence tetraalkylammonium cation, and additives such as the mixture of interpolation alkali metal chloride and oxyhydroxide, crystal seed have successfully solved this problem.
Summary of the invention
Technical problem to be solved by this invention is that the preparation that exists in the prior art has in the layered zeolite process of MWW structure a large amount of hexamethylene imines that use severe toxicity of needs as template; Bring huge potential safety hazard to enterprise production process; And the storage of template, transportation, use and the relevant high problem of handling cost, provide a kind of new preparation to have the method for the layered zeolite of MWW structure.This method has that cost is low, toxicity is little, environment amenable advantage when preparation MWW structure layered zeolite.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: at first silicon source, aluminium source, template (T), alkali metal chloride and alkali metal hydroxide and water are mixed, the mixture mole consists of: SiO
2/ Al
2O
3=1～200; H
2O/SiO
2=5～500; OH
-/ SiO
2=0.01～4; M
+/ SiO
2=0.01～4; T/SiO
2=0.01～4; Mixture is under 30～200 ℃ of conditions, and crystallization got crystallized product in 1～400 hour, and this product has the layered zeolite of MWW structure; Said template T is the non-equivalence tetraalkylammonium cation, has following general formula:
Wherein R1 is-(CH
2)
mCH
3
R2 is-(CH
2)
nCH
3
R3 is-(CH
2)
lCH
3
R4 is-(CH
2)
kCH
3
Wherein m >=n, and m＞l, m＞k m is 1,2,3,4
N is 0,1,2,3,4
L is 0,1,2,3
K is 0,1,2,3
M
+Be alkali metal cation, take from least a among Li, Na, K, Ru, the Cs.
In the technique scheme, the silicon source is selected from least a in tetraethyl silicate, soft silica, silicon sol, silica gel, zeyssatite or the water glass; The aluminium source is selected from least a in white lake, aluminum isopropylate, ASBD, sodium aluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, the aluminum oxide; Alkali metal cation M
+/ SiO
2Mol ratio be 0.01～3; Alkali metal cation is taken from the mixture of its muriate and oxyhydroxide, and alkali metal chloride and alkali metal hydroxide mol ratio are 0.02～50.
Temperature of reaction is 60～200 ℃, and the reaction times is 5～200 hours, and the reactant constitutive molar ratio is SiO
2/ Al
2O
3=2～100, H
2O/SiO
2=7～350, OH
-/ SiO
2=0.01～2, T/SiO
2=0.01～2, M
+/ SiO
2=0.01～2.
The crystal seed that adds final MWW structure layered zeolite weight 0.02～40% before the crystallization in the raw mix.
Need the hexamethylene imine template of the severe toxicity of use in a large number in the layered zeolite process of synthesizing the MWW structure owing to having used the non-equivalence tetraalkylammonium cation to replace among the present invention; Alkali metal cation and crystal seed have been added simultaneously again; Strengthened the structure-directing effect of synthetic system to product; Improve the generating rate of the layered zeolite of synthetic system MWW structure, shortened crystallization time.Reduced template agent simultaneously, when having eliminated in the prior art with hexamethylene imine as template, existed toxicity big, the problem that contaminate environment is serious has obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Description of drawings
Fig. 1 is the X-ray diffraction spectrum of synthetic MWW layered zeolite.
Fig. 2 is the low temperature conditioning adsorption/desorption graphic representation of synthetic MWW layered zeolite.
The XRD spectrum has one more to change the peak at 7 °～11 ° among Fig. 1, shows that preparation MWW zeolite is the layered zeolite of unordered accumulation.
Fig. 2 has shown that the layer molecule sieve of the inventive method preparation has tangible pore characteristics; Occurred tangible hysteresis loop in the absorption dividing potential drop greater than 0.6 o'clock simultaneously, shown very tangible mesoporous character, this is because synthetic product is a laminate structure; Has high outer surface area; Its unordered accumulation forms mesoporously in a large number, causes adsorption curve a very big hysteresis loop to occur.
Embodiment
[embodiment 1]
Building-up process of the present invention is following: take by weighing silicon sol (40 weight %) 150 grams (1 mole), ASBD 30 grams (0.05), dimethyl-diethylammonium volatile caustic (20wt%) aqueous solution 75 grams (0.1 mole), sodium-chlor 11.6 grams (0.2 mole); Sodium hydroxide 4 gram (0.1 mole), crystal seed 8 grams, and zero(ppm) water 50 grams mix and stirred 18 hours; The paste-like mixture is poured in the crystallizing kettle; 140 ℃ of crystallization were taken out product after 4 days in the immigration baking oven, filtered, washed; The XRD powdery diffractometry spectrum of dried product exhibited detects judges that this zeolite crystallite is the zeolite with stratiform WMM structure; Concrete X-ray diffraction spectrum is seen accompanying drawing 1, and its XRD spectrum has one more to change the peak at 7 °～11 °, shows that the product that the present invention prepares is the layered zeolite of unordered accumulation.Diffraction data is seen table 1.Its low temperature conditioning adsorption/desorption curve is seen accompanying drawing 2; Shown tangible pore characteristics among the figure; Occurred tangible hysteresis loop in the absorption dividing potential drop greater than 0.6 o'clock simultaneously, embodied showing very tangible mesoporous character, this is because synthetic product is a laminate structure; Have high outer surface area, cause adsorption curve a very big hysteresis loop to occur.
Table 1
Extremely strong (the I/I of vs=
0=75～100), the strong (I/I of s=
0=50～74), the medium (I/I of m=
0=25～49)
Weak (the I/I of w=
0=0～24)
[embodiment 2～9]
The synthesis step of [embodiment 2～9] is identical with [embodiment 1] with method, just changes raw material variety and proportioning, crystallization temperature, crystallization time, template, crystal seed and proportioning.Synthetic zeolite product detects through XRD powdery diffractometry spectrum judges that this zeolite crystallite is the layered zeolite with similar MWW topological framework, and concrete X-ray diffraction spectrum is consistent with accompanying drawing 1.Concrete data are identical with table 1.Template: with the representative of different English letter, specifically as shown in table 2 according to m, n, k, the different template molecule formulas that get of l value in the template general formula.The synthetic system proportioning raw materials is as shown in table 3.
This method replaces the hexamethylene imine template that needs a large amount of severe toxicity that use in the prior art with the non-equivalence tetraalkylammonium cation, through adding alkali metal cation and crystal seed in preparation stratiform zeolite molecular sieve process; Improve the generating rate of the layered zeolite of synthetic system MWW structure, shortened crystallization time, reduced cost; When having eliminated in the prior art with hexamethylene imine as template; Exist toxicity big, the problem that contaminate environment is serious has obtained better technical effect.
Table 2
| Template | m | n | k | l |
| B | 1 | 0 | 0 | 0 |
| C | 2 | 2 | 1 | 1 |
| D | 2 | 2 | 0 | 0 |
| E | 3 | 3 | 2 | 2 |
| F | 3 | 2 | 0 | 1 |
| G | 3 | 2 | 1 | 1 |
| H | 4 | 3 | 3 | 1 |
| I | 4 | 4 | 2 | 2 |
| J | 4 | 3 | 0 | 3 |
Table 3
*Contain tetra-alkyl ammonium hydroxide 20 weight %;
*Silicon sol: contain SiO
240 weight %; The mole number in silicon source calculates with Siliciumatom in the silicon source.The mole number in aluminium source calculates with aluminium atom in the aluminium source.
Claims (6)
1. method for preparing layered zeolite with MWW structure, at first with silicon source, aluminium source, template (T), alkali metal chloride and alkali metal hydroxide and water blended mixture, the mixture mol ratio consists of:
SiO
2/Al
2O
3＝1～200；H
2O/SiO
2＝5～500；OH
-/SiO
2＝0.01～4；M
+/SiO
2＝0.01～4；
T/SiO
2＝0.01～4；
Under 30～200 ℃ of conditions, crystallization got crystallized product in 1～400 hour with mixture, and this product has the layered zeolite of MWW structure; Said template T is the non-equivalence tetraalkylammonium cation, has following general formula:
Wherein R1 is-(CH
2)
mCH
3
R2 is-(CH
2)
nCH
3
R3 is-(CH
2)
lCH
3
R4 is-(CH
2)
kCH
3
Wherein m >=n, and m＞l, m＞k m is 1,2,3,4
N is 0,1,2,3,4
L is 0,1,2,3
K is 0,1,2,3
M
+Be alkali metal cation, take from least a among Li, Na, K, Ru, the Cs.
2. said preparation has the method for the layered zeolite of MWW structure according to claim 1, it is characterized in that the silicon source is selected from least a in tetraethyl silicate, soft silica, silicon sol, silica gel, zeyssatite or the water glass; The aluminium source is selected from least a in white lake, aluminum isopropylate, ASBD, sodium aluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, the aluminum oxide.
3. said preparation has the method for the layered zeolite of MWW structure according to claim 1, it is characterized in that M
+/ SiO
2Mol ratio be 0.01～3.
4. said preparation has the method for the layered zeolite of MWW structure according to claim 1, it is characterized in that temperature of reaction is 60～200 ℃, and the reaction times is 5～200 hours, and the reactant constitutive molar ratio is SiO
2/ Al
2O
3=2～100, H
2O/SiO
2=7～350, OH
-/ SiO
2=0.01～2, T/SiO
2=0.01～2, M
+/ SiO
2=0.01～2.
5. said preparation has the method for the layered zeolite of MWW structure according to claim 1, it is characterized in that alkali metal cation is taken from the mixture of its muriate and oxyhydroxide, and alkali metal chloride and alkali metal hydroxide mol ratio are 0.02～50.
6. said preparation has the method for the layered zeolite of MWW structure according to claim 1, it is characterized in that before crystallization, adding in the raw mix crystal seed of final MWW structure layered zeolite weight 0.02～40%.
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Cited By (7)
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| WO2015043114A1 (en) * | 2013-09-24 | 2015-04-02 | 中国石油化工股份有限公司 | Molecular sieve, manufacturing method therefor, and uses thereof |
| CN105080599A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Layered zeolite type alkylaromatic isomerisation catalyst |
| CN105217646A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | The method of synthesizing Si-Al zeolite molecular sieve |
| CN105271300A (en) * | 2014-07-02 | 2016-01-27 | 中国石油化工股份有限公司 | Molecular sieve catalyst, and preparation method and application thereof |
| CN106517234A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Dynamic hydrothermal synthesis method of exfoliated type MWW lamellar molecular sieve |
| CN108439425A (en) * | 2018-04-27 | 2018-08-24 | 南开大学 | A kind of ETL types molecular sieve and its manufacturing method |
| CN114229866A (en) * | 2021-12-31 | 2022-03-25 | 华南理工大学 | Method for synthesizing mesoporous MCM-56 zeolite molecular sieve |
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Cited By (11)
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| WO2015043114A1 (en) * | 2013-09-24 | 2015-04-02 | 中国石油化工股份有限公司 | Molecular sieve, manufacturing method therefor, and uses thereof |
| US10099935B2 (en) | 2013-09-24 | 2018-10-16 | China Petroleum & Chemical Corporation | Molecular sieve, manufacturing method therefor, and uses thereof |
| CN105080599A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Layered zeolite type alkylaromatic isomerisation catalyst |
| CN105080599B (en) * | 2014-05-14 | 2018-02-09 | 中国石油化工股份有限公司 | It is layered zeolite type alkyl aromatic hydrocarbon isomerization catalyst |
| CN105271300A (en) * | 2014-07-02 | 2016-01-27 | 中国石油化工股份有限公司 | Molecular sieve catalyst, and preparation method and application thereof |
| CN105271300B (en) * | 2014-07-02 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of molecular sieve catalyst, preparation method and application |
| CN105217646A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | The method of synthesizing Si-Al zeolite molecular sieve |
| CN105217646B (en) * | 2014-07-03 | 2017-06-20 | 中国石油化工股份有限公司 | The method of synthesizing Si-Al zeolite molecular sieve |
| CN106517234A (en) * | 2016-11-07 | 2017-03-22 | 西北大学 | Dynamic hydrothermal synthesis method of exfoliated type MWW lamellar molecular sieve |
| CN108439425A (en) * | 2018-04-27 | 2018-08-24 | 南开大学 | A kind of ETL types molecular sieve and its manufacturing method |
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Application publication date: 20120516 |