CN106185977A - A kind of method of green syt ZSM 5 molecular sieve - Google Patents
A kind of method of green syt ZSM 5 molecular sieve Download PDFInfo
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- CN106185977A CN106185977A CN201610500555.1A CN201610500555A CN106185977A CN 106185977 A CN106185977 A CN 106185977A CN 201610500555 A CN201610500555 A CN 201610500555A CN 106185977 A CN106185977 A CN 106185977A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention belongs to Zeolite synthesis field, a kind of method relating to green syt ZSM 5 molecular sieve.The method is using the natural minerals of low silica-alumina ratio and high silica alumina ratio as the whole silicon sources needed for synthesis of molecular sieve and aluminum source, uses sub-molten salt medium to activate low silica-alumina ratio mineral, then uses high-temperature roasting to activate high silica alumina ratio mineral；Two kinds of mineral, alkali, crystal seed and water after activation is mixed according to a certain percentage, it is not necessary to add any template, under hydrothermal condition, carry out crystallization obtain product ZSM 5 molecular sieve.By the ratio of two kinds of mineral in regulation synthesis material, the silica alumina ratio of product molecule sieve can be regulated.It is characteristic of the invention that and need not add chemistry silicon and aluminum source, and do not use template, not only extend raw material range prepared by molecular screen material, and the production cost of molecular sieve is greatly reduced, considerably improve the green of molecular screen material production process, there is preferable prospects for commercial application.
Description
Technical field
The invention belongs to Zeolite synthesis field, a kind of method being specifically related to green syt ZSM-5 molecular sieve.
Background technology
Mobil company of the U.S. the most successfully developed ZSM-5 molecular sieve (US 3702886) in 1972, owing to it has
Unique three-dimensional open-framework, shape selective catalysis performance, excellent heat and feature such as hydrothermal stability and high catalytic activity, by extensively
General it is applied to multiple fields such as petrochemical industry, fine chemistry industry and environmental conservation.At present, the research of relevant ZSM-5 molecular sieve synthesis
Being growing on and on, researcher proposes multiple synthetic method in succession, and the most most popular is the low one-tenth meeting green chemical industry theory
Originally, green synthesis method.
At present, ZSM-5 molecular sieve is typically to be existed by inorganic chemical products such as Ludox, waterglass, sodium silicate and aluminum sulfate
The hydrothermal crystallization method synthesis of classics is used under the conditions of alkalescence.Although it is easily-controllable that this method has mature technology, process conditions
System, high quality, but the inorganic chemical being used as ZSM-5 molecular sieve synthesis material in this process route is all
Preparing through numerous and diverse reaction and separation process from the natural minerals rich in sial, production process route length, material consumption energy consumption are high, greatly
There is serious disposal of pollutants in most processes, and because the price of synthesis material is of a relatively high, the production cost causing molecular sieve is inclined
High.If it is possible to directly with the natural minerals rich in silicon and aluminum for Material synthesis molecular sieve, not only abundant raw material source,
And can greatly shorten the synthetic route from raw mineral materials to molecular sieve product, the energy of process of producing molecular sieve is greatly reduced
Consumption, material consumption and disposal of pollutants, and significantly reduce production cost, thus the green syt for molecular sieve opens up new approach, has
Vast potential for future development.
Kovo etc. (Journal of Materials Chemistry, 2009,19 (34): 6207-6212) are with Buddhist nun's day
Leah Kaolin is aluminum source and part silicon source, and additional sodium metasilicate, for supplementing silicon source, successfully synthesizes under the conditions of conventional hydrothermal
ZSM-5 molecular sieve, the characterization result such as X-ray diffraction (XRD) and Flied emission environmental scanning electronic microscope (FESEM) shows, synthesized
Degree of crystallinity and the purity of ZSM-5 molecular sieve sample are the most relatively low, and there is a large amount of unreacted amorphous substance.US 4091007
Disclose a kind of method that Kaolin prepares ZSM-5 molecular sieve, the reaction mixture of the method include alkali metal ion, 4 third
Base amine ion, silicon source, aluminum source and water, aluminum source therein is provided by Kaolin, and described reactant mixture is brilliant at 75 ~ 205 DEG C
Change 1 hour to 60 days, available ZSM-5 molecular sieve.CN 101722024 discloses a kind of ZSM-5 molecular sieve/rectorite and is combined
Material and preparation method thereof, this composite is aluminum source and the part silicon utilizing natural rectorite mineral to provide synthesis of molecular sieve
Source, and as the substrate of molecular sieve growth, the crystalline product formed through in-situ crystallization.In this composite, ZSM-5 molecule
The weight/mass percentage composition of sieve is for being not less than 10%, and the silica alumina ratio of ZSM-5 molecular sieve is 20 to 60.Prepared by employing the method answers
Condensation material has the hydrothermal stability of excellence.
Use said method can obtain ZSM-5 molecular sieve or ZSM-5 molecular sieve/mineral composite, but in synthesis
Time be required to carry out the silica alumina ratio that feeds intake of modulation synthetic system by additional chemistry silicon source, it is impossible to be completely free of inorganic chemical
Rely on；Additionally, building-up process still uses organic formwork agent, cause the synthesis high expensive of molecular sieve and there is disposal of pollutants.
In order to solve these problems, CN 103848439 discloses the synthetic method of a kind of type ZSM 5 molecular sieve.The method
It is using natural minerals as the whole silicon sources needed for synthesis of molecular sieve and aluminum source, with 4-propyl bromide for micropore template, in
Carry out crystallization under hydrothermal condition and obtain product ZSM-5 molecular sieve.The ZSM-5 molecular sieve using the method to obtain is step hole
Material, it is 70% to 120% relative to the degree of crystallinity of the conventional ZSM-5 molecular sieve synthesized by with pure chemistry reagent as raw material, and
By the ratio of two kinds of mineral in regulation synthesis material, the silica alumina ratio of product molecule sieve can be regulated.Although this process does not uses
Chemistry silicon and aluminum source and mesoporous template, significantly reduce synthesis cost and the disposal of pollutants of molecular sieve, but the most do not put
The de-dependence to micropore template.
US 4257885 discloses the method for a kind of Template-free method synthesis ZSM-5 molecular sieve, uses the method to obtain
ZSM-5 molecular sieve has higher hydrophobic/lipophile so that it is can optionally adsorb in water and other liquid phases or gas phase
Organic substance.CN 85100463 discloses one and does not use any organic formwork agent, directly with waterglass, mineral acid, aluminium salt or aluminum
Hydrochlorate is the method for Material synthesis ZSM-5 molecular sieve, and the method greatly reduces production cost, improves single-autoclave yield rate, and
Shortening crystallization time, also solving that the Zeolite synthesis cost that the use of organic amine caused is high, environmental pollution is serious etc. asks
Topic.Hereafter, lot of domestic and international researcher also reports the method (CN 85100463 of Template-free method synthesis ZSM-5 molecular sieve;
Zeolites, 1989, 9(89): 363-370; Microporous and Mesoporous Materials, 2006,
92 (1): 181-188), but it is all with inorganic chemicals such as waterglass, Ludox, sodium aluminate, aluminum sulfate as raw material, unreal
Green syt the most truly.
In sum, recent domestic scholar has carried out substantial amounts of in terms of low cost, green syt ZSM-5 molecular sieve
Study and achieve bigger progress, carry out molecule as substituted relatively costly inorganic chemistry silicon and aluminum source with cheap natural minerals
The synthesis of sieve, or in building-up process, do not use costliness and produce the organic amine template polluted.But up to now, there is no
Entirely it is whole silicon and aluminum source with natural minerals, does not use the research of template synthesis ZSM-5 molecular sieve to report.Owing to ZSM-5 type divides
Son sieve be one of widely used molecular screen material in petrochemical industry, therefore, completely with natural minerals as raw material, without template
The technology of agent green syt ZSM-5 molecular sieve will have broad application prospects.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that the side of a kind of green syt ZSM-5 molecular sieve
Method.The method is provided the whole silicon sources required for synthesis and aluminum source by natural minerals, it is not necessary to add the chemical silicon of other forms
Source and aluminum source, under conditions of Template-free method, obtain ZSM-5 molecular sieve through hydrothermal crystallizing.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of method of green syt ZSM-5 molecular sieve, provides the whole silicon sources needed for Zeolite synthesis with natural clay mineral
With aluminum source, and do not use any template, prepare ZSM-5 molecular sieve through hydrothermal crystallization method.
A kind of method of green syt ZSM-5 molecular sieve, comprises the following steps:
(1) activation of mineral: activating low silica-alumina ratio mineral, high silica alumina ratio mineral respectively, wherein low silica-alumina ratio mineral are adopted
Activating with sub-molten salt medium, high silica alumina ratio mineral use high-temperature roasting mode to carry out activation processing；
(2) crystallization: low silica-alumina ratio mineral, high silica alumina ratio mineral after step (1) being activated mix with sodium hydroxide, water and crystal seed
Close, aging after carry out hydrothermal crystallizing, and the inventory controlling various raw material makes the mol ratio of each material in synthetic system to be
0.01~0.25 Na2O: 1 SiO2: 0.01~0.5 Al2O3: 10~80 H2O；Product crystallization obtained cools down, is filtered to remove
Mother solution, gained filter cake washes with water to neutrality and obtains ZSM-5 molecular sieve after drying.
The silica alumina ratio of the low silica-alumina ratio mineral described in step (1) below 10, the sial mole of high silica alumina ratio mineral
Ratio is more than 30.
Further, described low silica-alumina ratio mineral are in rectorite, montmorillonite, bentonite, attapulgite and Kaolin
One or more, described high silica alumina ratio mineral are kieselguhr and/or white carbon.
Sub-molten salt medium described in step (1) is NaOH-H2O system；During low silica-alumina ratio mineral activation, low silica-alumina ratio ore deposit
Thing and NaOH-H2The mass ratio of O sub-molten salt medium is 1:1 ~ 10, and activation temperature is 100 ~ 400 DEG C.
In step (1), the sintering temperature of the activation processing of high silica alumina ratio mineral is 500 ~ 1000 DEG C, and roasting time is 1 ~ 10
h。
Crystal seed described in step (2) is: use the SiO produced with Catalyst Factory, Nankai Univ first during synthesis2With
Al2O3The ZSM-5 molecular sieve product that mol ratio is 38 be crystal seed prepare ZSM-5 molecular sieve product；In follow-up all experiments
In be all that the ZSM-5 molecular sieve product prepared first with the present invention is as crystal seed；The addition of crystal seed is SiO in synthetic system2Always
The 1 ~ 15% of quality.
Preferably, in the synthetic system described in step (2), the mol ratio of each material is 0.05 ~ 0.20 Na2O: 1
SiO2: 0.02~0.05 Al2O3: 10~60 H2O。
Aging described in step (2) is to carry out at 50 ~ 80 DEG C, and ageing time is 2 ~ 24 h.
Crystallization described in step (2) is to carry out at 130 ~ 210 DEG C, and crystallization time is 18 ~ 72 h.
Preferably, the crystallization described in step (2) is to carry out at 150 ~ 200 DEG C.
The beneficial effects of the present invention is:
1) present invention is provided the whole silicon sources required for synthesis and aluminum source by natural minerals, it is not necessary to add the chemistry of other forms
Silicon source and aluminum source, under conditions of Template-free method, obtain ZSM-5 molecular sieve through hydrothermal crystallizing；The method not only can significantly drop
The production cost of low molecule sieve synthesis, and the green of building-up process can be greatly enhanced；
2) the inventive method is used can to obtain having different crystallinity, the ZSM-5 molecular sieve of different silica alumina ratio, its relative crystallinity
Being 60 ~ 100%, mole silica alumina ratio is 2.0 to 48.0.
Accompanying drawing explanation
Fig. 1-Fig. 8 is the XRD spectra of the embodiment of the present invention 1 to embodiment 8 gained type ZSM 5 molecular sieve.
Detailed description of the invention
Specifically, the method for the green syt ZSM-5 molecular sieve that the present invention provides comprises the following steps:
(1) activation of low silica-alumina ratio mineral: by low silica-alumina ratio mineral and NaOH-H2O sub-molten salt medium is according to the matter of 1:1 ~ 1:10
Amount ratio mixes, as the raw material of synthesis ZSM-5 molecular sieve, wherein said NaOH-after then drying at 100 ~ 400 DEG C
H2O sub-molten salt medium is to be 10:1 ~ 1:5 preparation by sodium hydrate solid and deionized water according to mass ratio；
(2) activation of high silica alumina ratio mineral: by high silica alumina ratio mineral at 500 ~ 1000 DEG C after roasting 1 ~ 10 h, as synthesis
The raw material of ZSM-5 molecular sieve；
(3) synthesis material that addition deionized water, crystal seed, step (1) obtain in the synthesis material that step (2) obtains, regulation
In synthetic system, the mol ratio of each material is 0.01 ~ 0.25 Na2O: 1 SiO2: 0.01~0.5 Al2O3: 10~80 H2O；
SiO during wherein the addition of crystal seed is synthetic system2The 1 ~ 15% of gross mass, by the mixture that obtains at 50 ~ 80 DEG C aging 2
After ~ 24 h, in 130 ~ 210 DEG C of crystallization 18 ~ 72 h, obtain crystallization product；
(4) crystallization product step (3) obtained cools down, is filtered to remove mother solution, and filter cake is washed with deionized to neutral, dry
Obtain type ZSM 5 molecular sieve.
The present invention is provided the whole silicon sources required for synthesis of molecular sieve and aluminum source by natural mineral raw, it is not necessary to add it
The chemical silicon source of his form or aluminum source, widened the application of natural minerals and the raw material sources of synthesis of molecular sieve；And not
Use any organic formwork agent, reduce the synthesis cost of molecular sieve, decrease disposal of pollutants.
Heretofore described low silica-alumina ratio mineral refer to silica alumina ratio natural minerals below 10；Described high sial
Silica alumina ratio natural minerals more than 30 is referred to than mineral.Therefore, in method of the present invention, the sky of low silica-alumina ratio
So mineral are in addition to rectorite, it is also possible to select the natural minerals such as montmorillonite, bentonite, attapulgite, Kaolin；High silicon mineral removes
Outside kieselguhr, also can be selected for the white carbon prepared with natural minerals.
Crystal seed employed in the present invention: the ZSM-5 molecular sieve produced with Catalyst Factory, Nankai Univ during synthesis first produces
Product (SiO2With Al2O3Mol ratio be 38) be that crystal seed prepares ZSM-5 molecular sieve product；And in follow-up all experiments be all
The ZSM-5 molecular sieve product prepared first with the present invention is as crystal seed.
Implementation process and the beneficial effect of generation of the present invention is described in detail, it is intended to help to read below by way of specific embodiment
Reader is more fully understood that essence and the feature of the present invention, not as can the restriction of practical range to this case.
Relative crystallinity described in embodiment is according to ASTM D 5758-01 standard, with products therefrom and molecular sieve mark
In the XRD spectra of sample, 2 θ angles are 22.5 ~ 25.0oBetween the ratio of characteristic peak area sum, be expressed as a percentage, standard specimen be with
Conventional chemical reagent is the ZSM-5 molecular sieve (Catalyst Factory, Nankai Univ produces, and its silica alumina ratio is 38) of Material synthesis, will
Its degree of crystallinity is defined as 100%.
Product silica alumina ratio is characterized by x-ray fluorescence (XRF) method, uses Rigaku ZSX-100e4580 type X
Ray fluorescence spectrometer, the silica alumina ratio of the molecular sieve described in the present invention refers to SiO2With Al2O3Mol ratio.
Each embodiment Minerals and the selection of crystal seed: kieselguhr, rectorite, Kaolin and montmorillonite used are commercially available
Product.Diatomaceous it is mainly composed of: SiO2Content be 93.2 wt.%, Al2O3Content be 3.31 wt.%；Rectorite
It is mainly composed of: SiO2Content be 43.2 wt.%, Al2O3Content be 37.2 wt.%；Kaolinic it is mainly composed of:
SiO2Content be 50.5 wt.%, Al2O3Content be 44.6 wt.%；Being mainly composed of of montmorillonite: SiO2Content be
60.0 wt.%, Al2O3Content be 16.5 wt.%；Crystal seed used by embodiment 1 is the ZSM-that Catalyst Factory, Nankai Univ produces
5 zeolite product (SiO2With Al2O3Mol ratio be 38), the crystal seed used by embodiment 2-8 is obtained by embodiment 1
ZSM-5 molecular sieve product.
Embodiment 1
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 700 DEG C of roasting 6 h, standby；Weigh 6.00 g rectorite powder
After end, 9.00 g sodium hydrate solids and 45.00 g deionized water mix homogeneously, dry at 250 DEG C, standby；
2) system with molecular sieve for preparing is standby: weighs diatomite powder 10.40 g after above-mentioned roasting, adds 1.35 g sodium hydroxide, 0.75 g
Above-mentioned rectorite powder, 0.20 g crystal seed and the 60.20 g deionized waters processed, the mol ratio of regulation synthetic system is
0.137 Na2O: 1 SiO2: 0.0273 Al2O3: 20.4 H2O；Mix and blend 8 h at 60 DEG C；This mixture is moved into
In band teflon-lined rustless steel crystallizing kettle, it is warming up to 180 DEG C of static crystallization 48 h；After crystallization terminates, cooling, mistake
Filtering mother solution, solid product washing is to neutrality, drying to obtain crystallization product at 120 DEG C.Through XRD determining, its thing belongs to mutually
In ZSM-5 molecular sieve, product, the relative crystallinity of type ZSM 5 molecular sieve is 97%, and product silica alumina ratio is 35, and its XRD spectra is shown in
Fig. 1.
Embodiment 2
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 10.00 g diatomite powders at 500 DEG C of roasting 10 h, standby；Weigh 6.00 g rectorites
After powder, 12.00 g sodium hydrate solids and 12.00 g deionized water mix homogeneously, dry at 350 DEG C, standby；
2) system with molecular sieve for preparing is standby: weigh diatomite powder 7.92 g after above-mentioned roasting, add 0.68 g sodium hydrate solid, 2.10
Above-mentioned rectorite powder, 1.15 g crystal seeds and the 46.50 g deionized waters processed of g, the mol ratio of regulation synthetic system is
0.2 Na2O: 1 SiO2: 0.04 Al2O3: 20 H2O；Mix and blend 4 h at 70 DEG C.This mixture is moved into band poly-four
In the rustless steel crystallizing kettle of fluorothene liner, it is warming up to 200 DEG C of static crystallization 18 h.After crystallization terminates, cool down, be filtered to remove
The washing of mother solution, solid product, to neutral, be dried at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to ZSM-5 mutually
Molecular sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 65%, and product silica alumina ratio is 23, and its XRD spectra is shown in Fig. 2.
Embodiment 3
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 800 DEG C of roasting 4 h, standby；Weigh 5.00 g rectorite powder
After end, 5.00 g sodium hydrate solids and 2.00 g deionized water mix homogeneously, dry at 150 DEG C, standby；
2) system with molecular sieve for preparing is standby: weigh diatomite powder 4.00 g after above-mentioned roasting, add 0.44 g sodium hydrate solid, 1.0
Above-mentioned rectorite powder, 0.20 g crystal seed and the 59.16 g deionized waters processed of g, the mol ratio of regulation synthetic system is
0.18 Na2O: 1 SiO2: 0.047 Al2O3: 50 H2O；Mix and blend 6 h at 80 DEG C.This mixture is moved into band poly-
In the rustless steel crystallizing kettle of tetrafluoroethene liner, it is warming up to 170 DEG C of static crystallization 60 h.After crystallization terminates, cool down, excessively filter
Go the washing of mother solution, solid product to neutral, be dried at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to mutually
ZSM-5 molecular sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 92%, and product silica alumina ratio is 20, and its XRD spectra is shown in figure
3。
Embodiment 4
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 600 DEG C of roasting 5 h, standby；Weigh 5.00 g rectorite powder
After end, 10.00 g sodium hydrate solids and 20.00 g deionized water mix homogeneously, dry at 300 DEG C, standby；
2) system with molecular sieve for preparing is standby: weigh diatomite powder 6.65 g after above-mentioned roasting, add 0.56 g sodium hydrate solid, 1.05
Above-mentioned rectorite powder, 0.10 g crystal seed and the 57.40 g deionized waters processed of g, the mol ratio of regulation synthetic system is
0.15 Na2O: 1 SiO2: 0.032 Al2O3: 30 H2O；Mix and blend 20 h at 50 DEG C.This mixture is moved into band poly-
In the rustless steel crystallizing kettle of tetrafluoroethene liner, it is warming up to 160 DEG C of static crystallization 72 h.After crystallization terminates, cool down, excessively filter
Go the washing of mother solution, solid product to neutral, be dried at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to mutually
ZSM-5 molecular sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 73%, and product silica alumina ratio is 30, and its XRD spectra is shown in figure
4。
Embodiment 5
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 1000 DEG C of roasting 2 h, standby；Weigh 8.00 g rectorites
After powder, 10.00 g sodium hydrate solids and 30.00 g deionized water mix homogeneously, dry at 280 DEG C, standby；
2) system with molecular sieve for preparing is standby: weigh diatomite powder 5.40 g after above-mentioned roasting, add 0.28 g sodium hydrate solid, 0.23
Above-mentioned rectorite powder, 0.40 g crystal seed and the 61.00 g deionized waters processed of g, the mol ratio of regulation synthetic system is
0.06 Na2O: 1 SiO2: 0.025 Al2O3: 40 H2O；Mix and blend 12 h at 70 DEG C.This mixture is moved into band poly-
In the rustless steel crystallizing kettle of tetrafluoroethene liner, it is warming up to 175 DEG C of static crystallization 36 h.After crystallization terminates, cool down, excessively filter
Go the washing of mother solution, solid product to neutral, be dried at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to mutually
ZSM-5 molecular sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 77%, and product silica alumina ratio is 38, and its XRD spectra is shown in figure
5。
Embodiment 6
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 750 DEG C of roasting 8 h, standby.Weigh 20.00 g rectorites
After powder, 20.00 g sodium hydrate solids and 10.00 g deionized water mix homogeneously, dry at 380 DEG C, standby；
2) system with molecular sieve for preparing is standby: weigh diatomite powder 12.50 g after above-mentioned roasting, add 1.10 g sodium hydrate solids,
Above-mentioned rectorite powder, 0.30 g crystal seed and the 53.50 g deionized waters processed of 1.00 g, mole joining of regulation synthetic system
Ratio is 0.10 Na2O: 1 SiO2: 0.3 Al2O3: 15 H2O；Mix and blend 16 h at 65 DEG C.This mixture is moved into band
In teflon-lined rustless steel crystallizing kettle, it is warming up to 165 DEG C of static crystallization 24 h.After crystallization terminates, cool down, filter
Remove mother solution, solid product washing extremely neutrality, be dried at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to mutually
ZSM-5 molecular sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 85%, and product silica alumina ratio is 32, and its XRD spectra is shown in figure
6。
Embodiment 7
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 800 DEG C of roasting 4 h, standby；Weigh 9.00 g kaolin powders
After end, 9.00 g sodium hydrate solids and 45.00 g deionized water mix homogeneously, dry at 250 DEG C, standby；
2) system with molecular sieve for preparing is standby: weighs diatomite powder 10.18 g after above-mentioned roasting, adds 1.14 g sodium hydroxide, 0.84 g
Above-mentioned kaolin powder, 0.10 g crystal seed and the 60.20 g deionized waters processed, the mol ratio of regulation synthetic system is
0.12 Na2O: 1 SiO2: 0.032 Al2O3: 20 H2O；Mix and blend 8 h at 70 DEG C；This mixture is moved into band poly-
In the rustless steel crystallizing kettle of tetrafluoroethene liner, it is warming up to 170 DEG C of static crystallization 24 h；After crystallization terminates, cool down, excessively filter
Go the washing of mother solution, solid product to neutrality, drying to obtain crystallization product at 120 DEG C.Through XRD determining, its thing belongs to mutually
ZSM-5 molecular sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 88%, and product silica alumina ratio is 30, and its XRD spectra is shown in figure
7。
Embodiment 8
A kind of method of green syt ZSM-5 molecular sieve, concretely comprises the following steps:
1) activation of mineral: weigh 20.00 g diatomite powders at 600 DEG C of roasting 6 h, standby；Weigh 9.00 g montmorillonite powder
After end, 9.00 g sodium hydrate solids and 45.00 g deionized water mix homogeneously, dry at 200 DEG C, standby；
2) system with molecular sieve for preparing is standby: weighs diatomite powder 4.00 g after above-mentioned roasting, adds on 0.50 g sodium hydroxide, 0.90 g
Stating montmorillonite powder, 0.15 g crystal seed and the 66.00 g deionized waters processed, the mol ratio of regulation synthetic system is 0.18
Na2O: 1 SiO2: 0.03 Al2O3: 55 H2O；Mix and blend 6 h at 65 DEG C；This mixture is moved into band polytetrafluoroethyl-ne
In the rustless steel crystallizing kettle of alkene liner, it is warming up to 180 DEG C of static crystallization 36 h；After crystallization terminates, cool down, be filtered to remove mother solution,
Solid product washing is to neutrality, drying to obtain crystallization product at 120 DEG C.Through XRD determining, its thing belongs to ZSM-5 molecule mutually
Sieve, in product, the relative crystallinity of type ZSM 5 molecular sieve is 90%, and product silica alumina ratio is 30, and its XRD spectra is shown in Fig. 8.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (10)
1. the method for a green syt ZSM-5 molecular sieve, it is characterised in that: provide Zeolite synthesis institute with natural clay mineral
The whole silicon sources needed and aluminum source, and do not use any template, ZSM-5 molecular sieve is prepared through hydrothermal crystallization method.
The method of green syt ZSM-5 molecular sieve the most according to claim 1, it is characterised in that: comprise the following steps:
(1) activation of mineral: activating low silica-alumina ratio mineral, high silica alumina ratio mineral respectively, wherein low silica-alumina ratio mineral are adopted
Activating with sub-molten salt medium, high silica alumina ratio mineral use high-temperature roasting mode to carry out activation processing；
(2) crystallization: low silica-alumina ratio mineral, high silica alumina ratio mineral after step (1) being activated mix with sodium hydroxide, water and crystal seed
Close, aging after carry out hydrothermal crystallizing, and the inventory controlling various raw material makes the mol ratio of each material in synthetic system to be:
0.01~0.25 Na2O: 1 SiO2: 0.01~0.5 Al2O3: 10~80 H2O；Product cooling crystallization obtained, is filtered to remove
Mother solution, gained filter cake washes with water to neutrality and obtains ZSM-5 molecular sieve after drying.
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: low described in step (1)
The silica alumina ratio of silica alumina ratio mineral is below 10, and the silica alumina ratio of high silica alumina ratio mineral is more than 30.
4. according to the method for the green syt ZSM-5 molecular sieve described in Claims 2 or 3, it is characterised in that: described low sial
It is one or more in rectorite, montmorillonite, bentonite, attapulgite and Kaolin than mineral, described high silica alumina ratio mineral
For kieselguhr and/or white carbon.
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: described in step (1)
Sub-molten salt medium is NaOH-H2O system；During low silica-alumina ratio mineral activation, low silica-alumina ratio mineral and NaOH-H2O sub-molten salt medium
Mass ratio is 1:1 ~ 10, and activation temperature is 100 ~ 400 DEG C.
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: high sial in step (1)
Being 500 ~ 1000 DEG C than the sintering temperature of the activation processing of mineral, roasting time is 1 ~ 10 h.
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: crystal seed in step (2)
Addition is SiO in synthetic system2The 1 ~ 15% of gross mass.
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: described in step (2)
In synthetic system, the mol ratio of each material is: 0.05 ~ 0.20 Na2O: 1 SiO2: 0.02~0.05 Al2O3: 10~60
H2O。
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: described in step (2)
Aging is to carry out at 50 ~ 80 DEG C, and ageing time is 2 ~ 24 h.
The method of green syt ZSM-5 molecular sieve the most according to claim 2, it is characterised in that: described in step (2)
Crystallization be to carry out at 130 ~ 210 DEG C, crystallization time is 18 ~ 72 h.
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