CN106673002A - Synthesis method of ZSM-11/ZSM-5 composite molecular sieve and composite molecular sieve synthesized through same - Google Patents
Synthesis method of ZSM-11/ZSM-5 composite molecular sieve and composite molecular sieve synthesized through same Download PDFInfo
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Abstract
The invention relates to a synthesis method of a ZSM-11/ZSM-5 composite molecular sieve and a composite molecular sieve synthesized through same. The synthesis method comprises the steps: enabling a silicon source, an aluminum source, an alkali source and an organic template agent to be in contact with water under a crystallization condition, thus obtaining a molecular sieve; optionally, roasting the obtained molecular sieve, wherein the organic template agent R is selected from at least one of 1,3-cyclohexanol dimethylamine or 1,4-cyclohexanol dimethylamine. The synthesis method disclosed by the invention can be used in industrial production of the ZSM-11/ZSM-5 composite molecular sieve.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-11/ZSM-5 composite molecular screens and its synthesis
Composite molecular screen.
Background technology
ZSM-11 molecular sieves are first in 20 century 70s by mobil oil oil company (Mobil)
Secondary synthesis.Follow-up study finds that ZSM-11 molecular sieves belong to tetragonal crystal system, ZSM-11 and ZSM-5
Molecular sieve belongs to Pentasil families.The structure similarity of two kinds of molecular sieves is secondary structure unit
Laminated structure with same form；Difference is that neighboring secondary construction unit is between layers
Symmetry it is different.It is related that ZSM-5 meets symmetrical centre；And ZSM-11 meets minute surface correlation, tool
The ten-ring two dimension straight hole road in a directions and b directions is parallel to, pore size is 0.54nm × 0.53
nm.Contrast ZSM-11 molecular sieves find that the XRD spectra of the two exists with ZSM-5 molecular sieve
Have differences at 2 θ=22.4～24.8 ° and 44.5～46 °, see the table below.
ZSM-11 is contrasted with ZSM-5 molecular sieve XRD diffraction maximums
Because the pore size of ZSM-11 molecular sieves is less than ZSM-5 molecular sieve, in small molecule type choosing is selected
Catalytic performance more more preferable than ZSM-5 molecular sieve may be shown in selecting property catalytic reaction.
The synthesis of ZSM-11 molecular sieves adopts TBAB or TBAH for organic mould
Plate agent.United States Patent (USP) US3709979 discloses a kind of using tetraalkyl cation (R4X+, X is
N or P, R are alkyl, can be methyl, ethyl, propyl group, butyl, benzyl or triphenyl) do
Template synthesizes the method for ZSM-11 molecular sieves.Chinese patent CN201210003750 discloses one
Plant and adopt TBAB for organic formwork agent, while adding crystal seed synthesis ZSM-11 molecular sieves
Method.Chinese patent CN201310697846 discloses one kind using TBAH and 1,8-
Octamethylenediamine is the method that compound organic formwork agent synthesizes ZSM-11 molecular sieves.Chinese patent
CN201410322401 discloses one kind and adopts TBAH or TBAB for organic
The method of template ZSM-11 molecular sieve of the synthesis containing B element.Chinese patent CN102464335
Disclose one kind and adopt TBAB or TBAH for organic formwork agent, while addition
EU-1 molecular sieve seeds synthesize the method for ZSM-11 molecular sieves.Chinese patent CN201110214475
Disclose and a kind of adopt TBAH and synthesize ZSM-11 molecular sieves for template fractional crystallization
Method.
The content of the invention
One of the object of the invention aims to provide a kind of conjunction of new ZSM-11/ZSM-5 composite molecular screens
Into method.The ZSM-11/ZSM-5 composite molecular screens of the method synthesis have ZSM-11 crystal contents
Height, and the characteristics of the controllable wide ranges of the content of ZSM-11 crystalline phases.The two of the object of the invention are intended to
A kind of ZSM-11/ZSM-5 composite molecular screens of methods described synthesis are provided.
One of for achieving the above object, the technical scheme that the present invention takes is as follows：It is a kind of
The synthetic method of ZSM-11/ZSM-5 composite molecular screens, being included under crystallization condition makes silicon source, aluminium
Source, alkali source, organic formwork agent and water contact, the step of to obtain molecular sieve；Optionally,
The step of molecular sieve obtained described in roasting；Wherein, the organic formwork agent R is selected from 1,3- hexamethylenes
At least one in dimethylamine or 1,4- hexamethylene dimethylamine.
In above-mentioned technical proposal, the silicon source, source of aluminium, the alkali source, the organic formwork
The mol ratio of agent R and water is 1：(0.0005～0.05)：(0.001～0.8)：(0.05～2.0)：(5～100)；
Preferably 1：(0.005～0.04)：(0.05～0.6)：(0.05～1.0)：(10～50)；More preferably 1：
(0.003～0.025)：(0.09～0.5)：(0.08～0.8)：(12～50).
In above-mentioned technical proposal, the crystallization condition includes：130～190 DEG C of crystallization temperature, crystallization
1～10 day time；Preferably 145～175 DEG C of crystallization temperature, crystallization time 2～10 days.
In above-mentioned technical proposal, the roasting condition includes：300～800 DEG C of sintering temperature, roasting
1～10 hour time；Preferably 400～650 DEG C of sintering temperature, roasting time 3～6 hours；Roasting
Burning atmosphere is air or oxygen.
In above-mentioned technical proposal, the silicon source is selected from silicic acid, silica gel, Ludox, silicic acid tetraalkyl
At least one in ester, sodium metasilicate, waterglass or white carbon；It is preferably selected from silicic acid, silica gel, silicon
At least one in colloidal sol or silicic acid tetraalkyl ester.
In above-mentioned technical proposal, source of aluminium selected from aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate,
At least one in aluminum sulfate, kaolin or montmorillonite；Be preferably selected from aluminium hydroxide, sodium aluminate or
At least one in aluminum nitrate.
In above-mentioned technical proposal, the alkali source is selected from the alkali with alkali metal or alkaline-earth metal as cation；
Preferably NaOH.
In above-mentioned technical proposal, mode of heating adopts direct-fired mode, or is added using microwave
The mode of heat, or using the complex method directly heated with heating using microwave；It is preferred that adopt directly heating
Mode.
Two for achieving the above object, the technical scheme that the present invention takes is as follows：It is a kind of
ZSM-11/ZSM-5 composite molecular screens, in the composite molecular screen, the content of ZSM-11 crystalline phases is not
Less than 90 weight %, preferably 75 weight %, more preferably 60 weight %, more preferably 45 weight %,
More preferably 30 weight %.
In above-mentioned technical proposal, impurity is contained in the composite molecular screen, impurity content is not higher than 10
Weight %, preferably no greater than 5 weight %, more preferably no higher than 3 weight %.
In above-mentioned technical proposal, the impurity is selected from unformed SiO2, different from ZSM-11 and
In at least one molecular sieve, metal oxide, quartz, tridymite, the cristobalite of ZSM-5 at least
It is a kind of.It is preferred that unformed SiO2、ZSM-23、ZSM-22、Beta、MCM-22、MOR、Y
At least one in type, X-type, A type molecular sieve；More preferably unformed SiO2, in MOR extremely
Few one kind.
In above-mentioned technical proposal, in the composite molecular screen ZSM-11/ZSM-5 composite molecular screens and
The existence form of impurity includes at least one in physical mixed, cocrystallization.
In above-mentioned technical proposal, it is preferable that the impurity be content be not higher than 10 weight % nothing determine
Type SiO2。
The inventive method is using at least one in 1,3- hexamethylenes dimethylamine or 1,4- hexamethylene dimethylamine
As organic formwork agent, high-purity ZSM-11/ZSM-5 composite molecular screen product is directly synthesized, has been produced
The purity of ZSM-11/ZSM-5 composite molecular screens can be up to 98 weight %, ZSM-11 crystalline phases in product
Content it is adjustable in the range of 30～98 weight %.The inventive method is simple, and raw material is cheap, is adapted to
Large-scale industrial production, achieves preferable technique effect.
Description of the drawings
Fig. 1 is【Embodiment 1】The XRD spectrum of the ZSM-11/ZSM-5 composite molecular screens of synthesis.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
In the context of the present specification, so-called ZSM-11/ZSM-5 composite molecular screens and impurity
Existence form, including physical mixed, cocrystallization.Wherein, physical mixed refers to ZSM-11/ZSM-5
Without chemical interaction between composite molecular screen crystal and impurity；Cocrystallization refers to ZSM-11/ZSM-5
In the crystal of composite molecular screen product simultaneously the structure cell comprising ZSM-11/ZSM-5 composite molecular screens with
The structure cell of impurity.
In the context of the present specification, it is included in below example and comparative example, is combined
The assay method of ZSM-11 molecular sieves crystal content is in zeolite product：It is soft using DIFFaX
Part ZSM-11/ZSM-5 of the simulation with difference ZSM-11 crystalline phases and ZSM-5 crystal contents is answered
The powder X-ray RD spectrogram of molecular sieve is closed, by embodiment gained ZSM-11/ZSM-5 composite molecular screens
Product obtains ZSM-11 in composite molecular screen product with the spectrogram contrast simulated by DIFFaX softwares
The content of molecular sieve.
In the context of the present specification, it is included in below example and comparative example, is combined
The assay method of the content of impurity is in zeolite product：The X of the content based on thing phase and the thing phase
X ray diffraction peak intensity is directly proportional, and the peak intensity of all diffraction maximums in XRD spectra is added, and obtains
Total I, by the peak intensity of the characteristic diffraction peak of correspondence ZSM-11 and ZSM-5 molecular sieve in spectrogram
It is added, obtains total I ', (1-I '/I) × 100% is the impurity content in product.
In the case where not clearly indicating, all percentages, the part being previously mentioned in this specification
Number, ratio etc. are all on the basis of weight, unless do not met this area when on the basis of weight
The conventional understanding of technical staff.
【Embodiment 1】
By sodium aluminate (Al2O343.0 weight %, Na2Weight % of O 35.0) 18.6 grams, NaOH
11.9 grams of (96.0 weight %), 1980.0 grams of deionized water, 1,3- hexamethylene dimethylamine (99.0 weight
%) 234.7 grams and Ludox (SiO240.0 weight %) 825.0 grams be well mixed, the thing of reactant
Expect that proportioning (mol ratio) is：
SiO2/Al2O3=70
1,3- hexamethylenes dimethylamine/SiO2=0.3
NaOH/SiO2=0.09
H2O/SiO2=25
After being well mixed, in being fitted into stainless steel cauldron, under agitation in 150 DEG C of crystallization 3 days.It is brilliant
Change is filtered after terminating, washs, is dried, then roasting obtains ZSM-11/ZSM-5 in 5 hours in 550 DEG C of air
Composite molecular screen.In composite molecular screen product ZSM-11 molecular sieve contents be 94 weight %, impurity
Content is 1 weight %.
【Embodiment 2】
Together【Embodiment 1】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=70,1,3- hexamethylene dimethylamine/SiO2=0.2, NaOH/SiO2=0.15, H2O/SiO2=30,
150 DEG C of crystallization 72 hours.ZSM-11 molecular sieve contents are 80 weight % in composite molecular screen product,
Impurity content is 1 weight %.
【Embodiment 3】
Together【Embodiment 1】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=70,1,3- hexamethylene dimethylamine/SiO2=0.4, NaOH/SiO2=0.18, H2O/SiO2=25,
150 DEG C of crystallization 70 hours.ZSM-11 molecular sieve contents are 50 weight % in composite molecular screen product,
Impurity content is 0.5 weight %.
【Embodiment 4】
Together【Embodiment 1】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=70,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.28, H2O/SiO2=25,
150 DEG C of crystallization 70 hours.ZSM-11 molecular sieve contents are 40 weight % in composite molecular screen product,
Impurity content is 2 weight %.
【Embodiment 5】
Together【Embodiment 1】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=50,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.18, H2O/SiO2=25,
150 DEG C of crystallization 3 days.ZSM-11 molecular sieve contents are 79 weight % in composite molecular screen product, miscellaneous
Matter content is 1 weight %.
【Embodiment 6】
Together【Embodiment 1】, aluminum sulfate is simply adopted for silicon source, the material proportion of reactant (mole
Than) be：SiO2/Al2O3=200,1,3- hexamethylene dimethylamine/SiO2=0.2, NaOH/SiO2=0.35,
H2O/SiO2=20, in 150 DEG C of crystallization 70 hours.ZSM-11 molecules in composite molecular screen product
Sieve content is 65 weight %, and impurity content is 2 weight %.
【Embodiment 7】
Together【Embodiment 6】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=80,1,3- hexamethylene dimethylamine/SiO2=0.5, NaOH/SiO2=0.6, H2O/SiO2=23,
150 DEG C of crystallization 60 hours.ZSM-11 molecular sieve contents are 57 weight % in composite molecular screen product,
Impurity content is 3 weight %.
【Embodiment 8】
Together【Embodiment 1】, aluminum nitrate is simply adopted for silicon source, the material proportion of reactant (mole
Than) be：SiO2/Al2O3=90,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.19,
H2O/SiO2=20, in 150 DEG C of crystallization 70 hours.ZSM-11 molecules in composite molecular screen product
Sieve content is 85 weight %, and impurity content is 2 weight %.
【Embodiment 9】
Together【Embodiment 1】, Isosorbide-5-Nitrae-hexamethylene dimethylamine is simply adopted for template, the material of reactant
Proportioning (mol ratio) is：SiO2/Al2O3=70, Isosorbide-5-Nitrae-hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2
=0.14, H2O/SiO2=20, in 150 DEG C of crystallization 72 hours.ZSM-11 in composite molecular screen product
Molecular sieve content is 74 weight %, and impurity content is 1 weight %.
【Embodiment 10】
Together【Embodiment 1】, simply using the mixing of 1,3- hexamethylenes dimethylamine and Isosorbide-5-Nitrae-hexamethylene dimethylamine
Thing is template, and the material proportion (mol ratio) of reactant is：SiO2/Al2O3=70,1,3- hexamethylene
Dimethylamine/SiO2=0.2, Isosorbide-5-Nitrae-hexamethylene dimethylamine/SiO2=0.2, NaOH/SiO2=0.20, H2O/SiO2
=20, in 150 DEG C of crystallization 36 hours.ZSM-11 molecular sieve contents are in composite molecular screen product
78 weight %, impurity content is 4 weight %.
Claims (10)
1. a kind of synthetic method of ZSM-11/ZSM-5 composite molecular screens, under being included in crystallization condition
The contact of silicon source, silicon source, alkali source, organic formwork agent and water is made, the step of to obtain molecular sieve；
Optionally, the step of molecular sieve for obtaining described in roasting；Wherein, the organic formwork agent R
At least one in 1,3- hexamethylenes dimethylamine or 1,4- hexamethylene dimethylamine.
2. the synthetic method of ZSM-11/ZSM-5 composite molecular screens according to claim 1,
Characterized in that, the silicon source, source of aluminium, the alkali source, the organic formwork agent R and water
Mol ratio is 1：(0.0005～0.05)：(0.001～0.8)：(0.05～2.0)：(5～100)；
The crystallization condition includes：130～190 DEG C of crystallization temperature, crystallization time 1～10 day；
And the roasting condition includes：300～800 DEG C of sintering temperature, roasting time 1～10 is little
When, calcination atmosphere is air or oxygen；
The silicon source is selected from silicic acid, silica gel, Ludox, silicic acid tetraalkyl ester, sodium metasilicate, waterglass
Or at least one in white carbon；Source of aluminium selected from aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate,
At least one in aluminum sulfate, kaolin or montmorillonite；The alkali source is selected from alkali metal or alkaline earth gold
Belong to the alkali for cation.
3. the synthetic method of ZSM-11/ZSM-5 composite molecular screens according to claim 2,
Characterized in that, the silicon source, source of aluminium, the alkali source, the organic formwork agent R and water
Mol ratio is 1：(0.005～0.04)：(0.05～0.6)：(0.05～1.0)：(10～50)；
The crystallization condition includes：145～175 DEG C of crystallization temperature, crystallization time 2～10 days；
And the roasting condition includes：400～650 DEG C of sintering temperature, roasting time 3～6 hours；
At least one of the silicon source in silicic acid, silica gel, Ludox or silicic acid tetraalkyl ester；Institute
State at least one of the silicon source in aluminium hydroxide, sodium aluminate or aluminum nitrate；The alkali source is selected from hydrogen-oxygen
Change sodium.
4. the synthetic method of ZSM-11/ZSM-5 composite molecular screens according to claim 3,
Characterized in that, the silicon source, source of aluminium, the alkali source, the organic formwork agent R and water
Mol ratio is 1：(0.003～0.025)：(0.09～0.5)：(0.08～0.8)：(12～50).
5. the synthetic method of ZSM-11/ZSM-5 composite molecular screens according to claim 1,
Characterized in that, mode of heating adopts direct-fired mode, or by the way of heating using microwave,
Or using the complex method directly heated with heating using microwave.
6. the ZSM-11/ZSM-5 composite molecular screens that the arbitrary methods described of Claims 1 to 5 synthesizes,
Characterized in that, in the composite molecular screen, the content of ZSM-11 crystalline phases is not less than 90 weight %,
It is preferred that 75 weight %, more preferably 60 weight %, more preferably 45 weight %, more preferably 30 weight %.
7. ZSM-11/ZSM-5 composite molecular screens according to claim 6, it is characterised in that
Contain impurity in the composite molecular screen, impurity content is not higher than 10 weight %, preferably no greater than 5
Weight %, more preferably no higher than 3 weight %；
The impurity is selected from unformed SiO2, different from least one point of ZSM-11 and ZSM-5
At least one in sub- sieve, metal oxide, quartz, tridymite, cristobalite.
8. ZSM-11/ZSM-5 composite molecular screens according to claim 7, it is characterised in that
The impurity is selected from unformed SiO2、ZSM-23、ZSM-22、Beta、MCM-22、MOR、
At least one in Y types, X-type, A type molecular sieve；It is preferred that unformed SiO2, in MOR extremely
Few one kind.
9., according to the arbitrary described ZSM-11/ZSM-5 composite molecular screens of claim 6～8, it is special
Levy and be, in the composite molecular screen, the presence shape of ZSM-11/ZSM-5 composite molecular screens and impurity
Formula includes at least one in physical mixed, cocrystallization.
10., according to the arbitrary described ZSM-11/ZSM-5 composite molecular screens of claim 6～9, it is special
Levy and be, the impurity is the unformed SiO that content is not higher than 10 weight %2。
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Cited By (1)
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| CN114797961A (en) * | 2021-01-19 | 2022-07-29 | 中国科学院大连化学物理研究所 | Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction |
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| CN114797961A (en) * | 2021-01-19 | 2022-07-29 | 中国科学院大连化学物理研究所 | Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction |
| CN114797961B (en) * | 2021-01-19 | 2023-09-26 | 中国科学院大连化学物理研究所 | Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene |
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