CN106673001A - Synthesis method of ZSM-11 molecular sieve and ZSM-11 molecular sieve synthesized through same - Google Patents
Synthesis method of ZSM-11 molecular sieve and ZSM-11 molecular sieve synthesized through same Download PDFInfo
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Abstract
The invention relates to a synthesis method of a ZSM-11 molecular sieve and the ZSM-11 molecular sieve synthesized through same, and mainly solves the problems in the prior art that the product purity of the synthesized ZSM-11 molecular sieve is not high, and the content of an impurity ZSM-5 molecular sieve is high. According to the synthesis method disclosed by the invention, the problems are preferably solved by adopting the technical scheme which comprises the following steps of 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, and the synthesis method can be used in industrial production of the ZSM-11 composite molecular sieve.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-11 molecular sieves and its ZSM-11 molecules of synthesis
Sieve.
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 the shape-selective choosing of small molecule
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.
However, Mark E.Davis et al. researchs find, using TBAB or tetrabutyl hydrogen-oxygen
It is not pure phase to change the ZSM-11 molecular sieves that ammonium is template synthesis, but containing ZSM-5 molecules
Sieve crystalline phase not net product (Microporous and Mesoporous Materials, 49 (2001)
163-169).Wherein the content of ZSM-5 molecular sieve can be up to 20 weight %.
The content of the invention
One of the technical problem to be solved is the ZSM-11 molecules that prior art has synthesis
Sieve product purity is not high, a kind of high problem of impurity ZSM-5 molecular sieve content, there is provided new ZSM-11
The synthetic method of molecular sieve.The two of the technical problem to be solved are to provide a kind of new
ZSM-11 molecular sieves.
To solve one of above-mentioned technical problem, the technical scheme that the present invention takes is as follows：A kind of ZSM-11
The synthetic method of molecular sieve, being included under crystallization condition makes silicon source, silicon source, alkali source, organic formwork
Agent and water are contacted, the step of to obtain molecular sieve；Optionally, the molecule for obtaining described in roasting
The step of sieve；Wherein, the organic formwork agent R is selected from 1,3- hexamethylenes dimethylamine or Isosorbide-5-Nitrae-hexamethylene two
At least one in methylamine.
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)：(0～0.2)：(0.05～2.0)：(5～100)；It is excellent
Elect 1 as：(0.005～0.04)：(0.01～0.1)：(0.1～1.0)：(10～50)；More preferably 1：(0.01～0.03)：
(0.01～0.09)：(0.1～0.8)：(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 2～7 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.
To solve the two of above-mentioned technical problem, the technical scheme that the present invention takes is as follows：A kind of ZSM-11
Molecular sieve, the impurity content in zeolite product 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 in zeolite product is selected from unformed SiO2, be different from
In at least one molecular sieve, metal oxide, quartz, tridymite, the cristobalite of ZSM-11 extremely
Few one kind；It is preferably selected from unformed SiO2、ZSM-5、ZSM-23、ZSM-22、Beta、MCM-22、
At least one in MOR, Y type, X-type, A type molecular sieve；More preferably unformed SiO2、ZSM-5
In at least one.
In above-mentioned technical proposal, the existence form of the impurity in zeolite product include physical mixed,
At least one in cocrystallization.
In above-mentioned technical proposal, it is preferable that the impurity in zeolite product is deposited in cocrystallization form
Content be not higher than the ZSM-5 molecular sieve of 10 weight %.
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 zeolite product is directly synthesized, ZSM-11 in product
Molecular sieve purity can be up to 98 weight %.The inventive method is simple, and raw material is cheap, is adapted to big rule
Mould industrial production, achieves preferable technique effect.
Description of the drawings
Fig. 1 is【Embodiment 1】The XRD spectrum of the ZSM-11 molecular sieves of synthesis.
Fig. 2 is【Comparative example 1】The XRD spectrum of the ZSM-11 molecular sieves of synthesis.
【Embodiment 1】With【Comparative example 1】In two samples XRD spectra in Nearby diffraction maximum is occurred in that, these diffraction maximums and ZSM-11
The characteristic diffraction peak of molecular sieve coincide.However,【Comparative example 1】In sample XRD spectra in
(2 θ=24.45 °) nearby more occurs in that a diffraction corresponding to ZSM-5 molecular sieve
Peak (arrow is indicated in Fig. 2).When the ZSM-5 molecular sieve impurity content in ZSM-11 molecular sieves
During more than 10 mass %, the peak is high-visible.Fig. 2 shows【Comparative example 1】In sample contain
ZSM-5 molecular sieve crystalline phase.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
In the context of the present specification, the existence form of so-called impurity, including physical mixed, altogether
Crystallization.Wherein, physical mixed refers between ZSM-11 molecular sieve crystals and impurity without chemical phase interaction
With；Cocrystallization refers in the crystal of ZSM-11 zeolite products simultaneously comprising ZSM-11 molecular sieves
The structure cell of structure cell and impurity.
In the context of the present specification, it is included in below example and comparative example, molecule
The measuring method of ZSM-11 molecular sieve crystal contents is in sieve product：Using DIFFaX software moulds
Draw up has the powder of the ZSM-11 molecular sieves of different ZSM-11 crystalline phases and ZSM-5 crystal contents
XRD spectra, by embodiment and comparative example gained ZSM-11 zeolite products and by DIFFaX
The spectrogram contrast of software simulation obtains the content of ZSM-11 molecular sieves in zeolite 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 point in 5 hours in 550 DEG C of air
Son sieve.ZSM-11 molecular sieve contents are 94 weight % in product.
【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=0.08, H2O/SiO2=30,
150 DEG C of crystallization 60 hours.ZSM-11 molecular sieve contents are 97 weight % in product.
【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=0.09, H2O/SiO2=25,
150 DEG C of crystallization 70 hours.ZSM-11 molecular sieve contents are 96 weight % in product.
【Embodiment 4】
Together【Embodiment 1】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=60,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.08, H2O/SiO2=25,
150 DEG C of crystallization 70 hours.ZSM-11 molecular sieve contents are 95 weight % in product.
【Embodiment 5】
Together【Embodiment 1】, simply the material proportion (mol ratio) of reactant be：SiO2/Al2O3
=50,1,3- hexamethylene dimethylamine/SiO2=0.5, NaOH/SiO2=0.07, H2O/SiO2=25,
150 DEG C of crystallization 3 days.ZSM-11 molecular sieve contents are 98 weight % in product.
【Embodiment 6】
Together【Embodiment 1】, aluminum sulfate is simply adopted for silicon source, the material proportion of reactant (mole
Than) be：SiO2/Al2O3=70,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.07,
H2O/SiO2=20, in 150 DEG C of crystallization 70 hours.ZSM-11 molecular sieve contents are 97 in product
Weight %.
【Embodiment 7】
Together【Embodiment 6】, the material proportion (mol ratio) of reactant is：SiO2/Al2O3=50,
1,3- hexamethylenes dimethylamine/SiO2=0.3, NaOH/SiO2=0.08, H2O/SiO2=23, at 150 DEG C
Crystallization 70 hours.ZSM-11 molecular sieve contents are 97 weight % in product.
【Embodiment 8】
Together【Embodiment 1】, aluminum nitrate is simply adopted for silicon source, the material proportion of reactant (mole
Than) be：SiO2/Al2O3=40,1,3- hexamethylene dimethylamine/SiO2=0.3, NaOH/SiO2=0.09,
H2O/SiO2=20, in 150 DEG C of crystallization 70 hours.ZSM-11 molecular sieve contents are 96 in product
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
=0.09, H2O/SiO2=20, in 150 DEG C of crystallization 72 hours.ZSM-11 molecular sieves contain in product
Measure as 98 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=0.09, H2O/SiO2
=20, in 150 DEG C of crystallization 72 hours.ZSM-11 molecular sieve contents are 98 weight % in product.
【Comparative example 1】
According to document CN201110214475, TBAH is adopted for template, by 204
Gram TBAH aqueous solution (TBAOH, 10 weight %) and 2.87 grams of aluminium hydroxide (Al2O3,
35 weight %) mixing, mol ratio TBAOH/Al2O3=8, in 150 DEG C react 20 hours, afterwards
Add 47 grams of silica gel (SiO2, 98.4 weight %) and 2.4 grams of ZSM-11 crystal seeds mixing, must mix
Thing mol ratio is：SiO2/Al2O3=80, TBAOH/SiO2=0.1, H2O/SiO2=13, at 110 DEG C
Constant temperature 5 hours, then it is warming up to 150 DEG C of crystallization 48 hours.Jing is filtered, washed, being dried, roasting
ZSM-11 zeolite products are obtained afterwards, and ZSM-11 molecular sieve contents are 88 weight % in product.
Claims (10)
1. a kind of synthetic method of ZSM-11 molecular sieves, 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.
2. the synthetic method of ZSM-11 molecular sieves according to claim 1, it is characterised in that
The mol ratio of the silicon source, source of aluminium, the alkali source, the organic formwork agent R and water is 1：
(0.0005～0.05)：(0～0.2)：(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 molecular sieves according to claim 2, it is characterised in that
The mol ratio of the silicon source, source of aluminium, the alkali source, the organic formwork agent R and water is 1：
(0.005～0.04)：(0.01～0.1)：(0.1～1.0)：(10～50)；
The crystallization condition includes：145～175 DEG C of crystallization temperature, crystallization time 2～7 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 molecular sieves according to claim 3, it is characterised in that
The mol ratio of the silicon source, source of aluminium, the alkali source, the organic formwork agent R and water is 1：
(0.01～0.03)：(0.01～0.09)：(0.1～0.8)：(12～50).
5. the synthetic method of ZSM-11 molecular sieves according to claim 1, it is characterised in that
Mode of heating adopts direct-fired mode, or by the way of heating using microwave, or using direct
Heating and the complex method of heating using microwave.
6. the ZSM-11 molecular sieves that the arbitrary methods described of Claims 1 to 5 synthesizes, it is characterised in that
Impurity content in zeolite product is not higher than 10 weight %, preferably no greater than 5 weight %, more preferably
Not higher than 3 weight %.
7. ZSM-11 molecular sieves according to claim 6, it is characterised in that molecular sieve is produced
Impurity in product is selected from unformed SiO2, different from least one molecular sieve, the metal oxygen of ZSM-11
At least one in compound, quartz, tridymite, cristobalite.
8. ZSM-11 molecular sieves according to claim 7, it is characterised in that molecular sieve is produced
Impurity in product is selected from unformed SiO2、ZSM-5、ZSM-23、ZSM-22、Beta、MCM-22、
At least one in MOR, Y type, X-type, A type molecular sieve；It is preferred that unformed SiO2、ZSM-5
In at least one.
9. ZSM-11 molecular sieves according to claim 6, it is characterised in that molecular sieve is produced
The existence form of the impurity in product includes at least one in physical mixed, cocrystallization.
10. ZSM-11 molecular sieves according to claim 6, it is characterised in that molecular sieve is produced
Impurity in product is the ZSM-5 molecular sieve that the content existed in cocrystallization form is not higher than 10 weight %.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111103313A (en) * | 2018-10-25 | 2020-05-05 | 中国石油天然气股份有限公司 | X-ray diffraction method for determining content of cristobalite phase in ZSM-22 molecular sieve |
| CN111153413A (en) * | 2020-01-15 | 2020-05-15 | 延长中科（大连）能源科技股份有限公司 | Preparation method of ZSM-11 molecular sieve |
| CN111205160A (en) * | 2020-01-15 | 2020-05-29 | 延长中科（大连）能源科技股份有限公司 | Method for synthesizing ethylbenzene from benzene and ethanol |
| CN115010144A (en) * | 2021-03-03 | 2022-09-06 | 中国科学院大连化学物理研究所 | Method for synthesizing sheet ZSM-11 molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| CN1240193A (en) * | 1999-04-21 | 2000-01-05 | 中国石油化工集团公司 | Ultrafine granule five-element circular type zeolite |
| CN1367758A (en) * | 1999-07-13 | 2002-09-04 | 美孚石油公司 | Synthesis of ZSM-5 and ZSM-11 |
-
2015
- 2015-11-09 CN CN201510753805.8A patent/CN106673001B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108881A (en) * | 1977-08-01 | 1978-08-22 | Mobil Oil Corporation | Synthesis of zeolite ZSM-11 |
| CN1240193A (en) * | 1999-04-21 | 2000-01-05 | 中国石油化工集团公司 | Ultrafine granule five-element circular type zeolite |
| CN1367758A (en) * | 1999-07-13 | 2002-09-04 | 美孚石油公司 | Synthesis of ZSM-5 and ZSM-11 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111103313A (en) * | 2018-10-25 | 2020-05-05 | 中国石油天然气股份有限公司 | X-ray diffraction method for determining content of cristobalite phase in ZSM-22 molecular sieve |
| CN111153413A (en) * | 2020-01-15 | 2020-05-15 | 延长中科（大连）能源科技股份有限公司 | Preparation method of ZSM-11 molecular sieve |
| CN111205160A (en) * | 2020-01-15 | 2020-05-29 | 延长中科（大连）能源科技股份有限公司 | Method for synthesizing ethylbenzene from benzene and ethanol |
| CN111205160B (en) * | 2020-01-15 | 2023-04-07 | 延长中科（大连）能源科技股份有限公司 | Method for synthesizing ethylbenzene from benzene and ethanol |
| CN115010144A (en) * | 2021-03-03 | 2022-09-06 | 中国科学院大连化学物理研究所 | Method for synthesizing sheet ZSM-11 molecular sieve |
| CN115010144B (en) * | 2021-03-03 | 2024-02-23 | 中国科学院大连化学物理研究所 | Synthesis method of flaky ZSM-11 molecular sieve |
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