CN106185977B - 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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- CN106185977B CN106185977B CN201610500555.1A CN201610500555A CN106185977B CN 106185977 B CN106185977 B CN 106185977B CN 201610500555 A CN201610500555 A CN 201610500555A CN 106185977 B CN106185977 B CN 106185977B
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- 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
Abstract
The invention belongs to Zeolite synthesis fields, are related to a kind of method of green syt ZSM-5 molecular sieve.This method is whole silicon sources and silicon source needed for using the natural minerals of low silica-alumina ratio and high silica alumina ratio as synthesis of molecular sieve, is activated to low silica-alumina ratio mineral using sub-molten salt medium, 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, without adding any template, crystallization is carried out under hydrothermal condition and obtains product ZSM-5 molecular sieve.By adjusting the ratio of two kinds of mineral in synthesis material, the silica alumina ratio of adjustable product molecule sieve.It is characteristic of the invention that not needing to add chemical silicon and aluminum source, and template is not used, the raw material range of molecular screen material preparation is not only extended, but also the production cost of molecular sieve is greatly reduced, the green of molecular screen material production process is considerably improved, there is preferable prospects for commercial application.
Description
Technical field
The invention belongs to Zeolite synthesis fields, and in particular to a kind of method of green syt ZSM-5 molecular sieve.
Background technique
Mobil company of the U.S. successfully developed ZSM-5 molecular sieve (US 3702886) in 1972 for the first time, since it has
It is the features such as unique three-dimensional open-framework, shape selective catalysis performance, excellent heat and hydrothermal stability and high catalytic activity, wide
It is general to be applied to the multiple fields such as petrochemical industry, fine chemistry industry and environmental protection.Currently, the research of related ZSM-5 molecular sieve synthesis
Be growing on and on, researcher proposes a variety of synthetic methods in succession, wherein it is most popular be meet green chemical industry theory it is low at
Originally, green synthesis method.
Currently, ZSM-5 molecular sieve is usually to be existed by inorganic chemical products such as silica solution, waterglass, sodium metasilicate and aluminum sulfate
Using classical hydrothermal crystallization method synthesis under alkaline condition.Although this method has mature technology, process conditions easily-controllable
System, high quality, but the inorganic chemical for being used as in this process route ZSM-5 molecular sieve synthesis material is all
It is made from the natural minerals rich in sial by many and diverse reaction and separation process, production process route is long, material consumption energy consumption is high, greatly
There are serious disposals of pollutants for most processes, and because the price of synthesis material is relatively high, cause the production cost of molecular sieve inclined
It is high.If it is possible to not only raw material sources are abundant directly using the natural minerals rich in silicon and aluminium as Material synthesis molecular sieve,
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 production cost is significantly reduced, so that the green syt for molecular sieve opens up new approach, have
Vast potential for future development.
(Journal of Materials Chemistry, 2009,19 (34) such as Kovo:6207-6212) with Buddhist nun day
Leah kaolin is silicon source and part silicon source, and additional sodium metasilicate is supplement silicon source, is successfully synthesized under the conditions of conventional hydrothermal
ZSM-5 molecular sieve, the characterization results such as X-ray diffraction (XRD) and Flied emission environmental scanning electronic microscope (FESEM) show synthesized
The crystallinity and purity of ZSM-5 molecular sieve sample are lower, and there are a large amount of unreacted amorphous substances.US 4091007
A kind of method for preparing ZSM-5 molecular sieve with kaolin is disclosed, the reaction mixture of this method includes alkali metal ion, 4 third
Base amine ion, silicon source, silicon source and water, silicon source therein are provided by kaolin, and the reaction mixture is brilliant at 75 ~ 205 DEG C
Change 1 hour to 60 days, ZSM-5 molecular sieve can be obtained.It is compound that CN 101722024 discloses a kind of ZSM-5 molecular sieve/rectorite
Material and preparation method thereof, the composite material are to provide the silicon source and part silicon of synthesis of molecular sieve using natural rectorite mineral
Source, and the matrix as molecular sieve growth, the crystalline product formed through in-situ crystallization.In the composite material, ZSM-5 molecule
The mass percentage of sieve be not less than 10%, and the silica alumina ratio of ZSM-5 molecular sieve be 20 to 60.Using answering for this method preparation
Condensation material has excellent hydrothermal stability.
ZSM-5 molecular sieve or ZSM-5 molecular sieve/mineral composite can be obtained using the above method, however synthesized
When be required to be completely free of come the silica alumina ratio that feeds intake of modulation synthetic system to inorganic chemical by additional chemical silicon source
It relies on；In addition, synthesis process still uses organic formwork agent, lead to that the synthesis cost of molecular sieve is higher and there are disposals of pollutants.
In order to solve these problems, CN 103848439 discloses a kind of synthetic method of type ZSM 5 molecular sieve.This method
It is whole silicon sources and silicon source needed for using natural minerals as synthesis of molecular sieve, using 4-propyl bromide as micropore template agent, in
Crystallization is carried out under hydrothermal condition obtains product ZSM-5 molecular sieve.The ZSM-5 molecular sieve for using this method to obtain is step hole
Material, the crystallinity relative to conventional ZSM-5 molecular sieve synthesized by by raw material of pure chemistry reagent for 70% to 120%, and
By adjusting the ratio of two kinds of mineral in synthesis material, the silica alumina ratio of adjustable product molecule sieve.Although the process does not use
Chemical silicon and aluminum source and mesoporous template significantly reduce the synthesis cost and disposal of pollutants of molecular sieve, but do not put still
The de- dependence to micropore template agent.
US 4257885 discloses a kind of method of Template-free method synthesis ZSM-5 molecular sieve, is obtained using this method
ZSM-5 molecular sieve is with higher hydrophobic/lipophilic, allows to selectively adsorb in water and other liquid phases or gas phase
Organic matter.CN 85100463 discloses one kind without using any organic formwork agent, directly with waterglass, inorganic acid, aluminium salt or aluminium
Hydrochlorate is the method for Material synthesis ZSM-5 molecular sieve, and this method greatly reduces production cost, improves single-autoclave yield rate, and
Crystallization time is shortened, also solving that Zeolite synthesis caused by the use of organic amine is at high cost, 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):It 181-188), but is using inorganic chemicals such as waterglass, silica solution, sodium aluminate, aluminum sulfate as raw material, not in fact
Now green syt truly.
In conclusion recent domestic scholar has carried out largely in terms of low cost, green syt ZSM-5 molecular sieve
It studies and makes great progress, such as substitute relatively expensive inorganic chemistry silicon and aluminum source with cheap natural minerals and carry out molecule
The synthesis of sieve, or in the synthesis process without using expensive and generation pollution organic amine template.But it so far, there is no
It is entirely whole silicon and aluminum sources, without using the research report of template synthesis ZSM-5 molecular sieve with natural minerals.Due to ZSM-5 type point
Son sieve is one of widely used molecular screen material in petrochemical industry, therefore, completely using 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
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of side of green syt ZSM-5 molecular sieve
Method.This method whole silicon sources and silicon source required for being synthesized by natural minerals offer, do not need the chemical silicon of addition other forms
Source and silicon source obtain ZSM-5 molecular sieve through hydrothermal crystallizing under conditions of Template-free method.
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, whole needed for providing Zeolite synthesis with natural clay mineral
Silicon source and silicon source, and any template is not used, ZSM-5 molecular sieve is made through hydrothermal crystallization method.
A kind of method of green syt ZSM-5 molecular sieve, includes the following steps：
（1）The activation of mineral：Low silica-alumina ratio mineral, high silica alumina ratio mineral are activated respectively, wherein low silica-alumina ratio mine
Object is activated using sub-molten salt medium, and high silica alumina ratio mineral are activated using high-temperature roasting mode；
（2）Crystallization：By step（1）Low silica-alumina ratio mineral, high silica alumina ratio mineral and sodium hydroxide, water and crystal seed after activation
Mixing, the inventory for carrying out hydrothermal crystallizing after aging, and controlling various raw materials make the mol ratio of each substance in synthetic system
For 0.01 ~ 0.25 Na2O: 1 SiO2: 0.01~0.5 Al2O3: 10~80 H2O；Product that crystallization obtains is cooling, cross and filter out
Mother liquor is removed, gained filter cake is washed with water to neutrality and obtains ZSM-5 molecular sieve after drying.
Step（1）The silica alumina ratio of the low silica-alumina ratio mineral is 10 hereinafter, the sial mole of high silica alumina ratio mineral
Than 30 or more.
Further, the low silica-alumina ratio mineral are in rectorite, montmorillonite, bentonite, concave convex rod and kaolin
One or more, the high silica alumina ratio mineral are diatomite and/or white carbon black.
Step（1）Described in sub-molten salt medium be NaOH-H2O system；When low silica-alumina ratio mineral activation, low silica-alumina ratio mine
Object and NaOH-H2The mass ratio of O sub-molten salt medium is 1:1 ~ 10, activation temperature is 100 ~ 400 DEG C.
Step（1）The maturing temperature of the activation processing of middle high silica alumina ratio mineral is 500 ~ 1000 DEG C, and calcining time is 1 ~ 10
h。
Step（2）Described in crystal seed be：The SiO produced with Catalyst Factory, Nankai Univ is used when synthesizing for the first time2With
Al2O3Molar ratio be 38 ZSM-5 molecular sieve product be ZSM-5 molecular sieve product made from crystal seed；In subsequent all experiments
In be using the ZSM-5 molecular sieve product for preparing for the first time of the present invention as crystal seed；The additive amount of crystal seed is SiO in synthetic system2Always
The 1 ~ 15% of quality.
Preferably, step（2）Described in synthetic system in each substance mol ratio be 0.05 ~ 0.20 Na2O: 1
SiO2: 0.02~0.05 Al2O3: 10~60 H2O。
Step（2）Described in aging be to be carried out at 50 ~ 80 DEG C, ageing time be 2 ~ 24 h.
Step（2）Described in crystallization be to be carried out at 130 ~ 210 DEG C, crystallization time be 18 ~ 72 h.
Preferably, step（2）Described in crystallization be to be carried out at 150 ~ 200 DEG C.
The beneficial effects of the present invention are：
1）The present invention whole silicon sources and silicon source required for being synthesized by natural minerals offer, do not need addition other forms
Chemical silicon source and silicon source obtain ZSM-5 molecular sieve through hydrothermal crystallizing under conditions of Template-free method；This method not only can be big
Width reduces the production cost of Zeolite synthesis, and can greatly improve the green of synthesis process；
2）The ZSM-5 molecular sieve with different crystallinity, different silica alumina ratios can be obtained using the method for the present invention, it is opposite to tie
Brilliant degree is 60 ~ 100%, and mole silica alumina ratio is 2.0 to 48.0.
Detailed description of the invention
Fig. 1-Fig. 8 is XRD spectra of the embodiment of the present invention 1 to 8 gained type ZSM 5 molecular sieve of embodiment.
Specific embodiment
Specifically, the method for green syt ZSM-5 molecular sieve provided by the invention includes the following steps：
（1）The activation of low silica-alumina ratio mineral：By low silica-alumina ratio mineral and NaOH-H2O sub-molten salt medium is according to 1:1~1:10
Mass ratio mixing, then at 100 ~ 400 DEG C dry after as synthesis ZSM-5 molecular sieve raw material, wherein described in
NaOH-H2It according to mass ratio is 10 that O sub-molten salt medium, which is by sodium hydrate solid and deionized water,:1~1:5 prepare；
（2）The activation of high silica alumina ratio mineral：After high silica alumina ratio mineral are roasted 1 ~ 10 h at 500 ~ 1000 DEG C, as
Synthesize the raw material of ZSM-5 molecular sieve；
（3）To step（2）Deionized water, crystal seed, step are added in the synthesis material of acquisition（1）The synthesis material of acquisition,
The mol ratio for adjusting each substance in synthetic system is 0.01 ~ 0.25 Na2O: 1 SiO2: 0.01~0.5 Al2O3: 10~80
H2O；Wherein the additive amount of crystal seed is SiO in synthetic system2The 1 ~ 15% of gross mass, obtained mixture is old at 50 ~ 80 DEG C
After changing 2 ~ 24 h, in 130 ~ 210 DEG C of 18 ~ 72 h of crystallization, crystallization product is obtained；
（4）By step（3）The crystallization product of acquisition is cooling, is filtered to remove mother liquor, filter cake be washed with deionized to it is neutral,
It is dried to obtain type ZSM 5 molecular sieve.
The present invention provides whole silicon source and silicon source required for synthesis of molecular sieve as natural mineral raw, does not need to add it
The chemical silicon source or silicon source of his form, have widened the application field of natural minerals and the raw material sources of synthesis of molecular sieve；And not
Using any organic formwork agent, the synthesis cost of molecular sieve is reduced, disposal of pollutants is reduced.
Heretofore described low silica-alumina ratio mineral refer to silica alumina ratio in 10 natural minerals below；The high sial
Refer to natural minerals of the silica alumina ratio 30 or more than mineral.Therefore, in method of the present invention, the day of low silica-alumina ratio
Right mineral can also select the natural minerals such as montmorillonite, bentonite, attapulgite, kaolin in addition to rectorite；High silicon mineral removes
Outside diatomite, the white carbon black prepared with natural minerals also can be selected.
Crystal seed employed in the present invention：It is produced when synthesizing for the first time with the ZSM-5 molecular sieve of Catalyst Factory, Nankai Univ production
Product (SiO2With Al2O3Molar ratio be 38) be the obtained ZSM-5 molecular sieve product of crystal seed；And it is in subsequent all experiments
The ZSM-5 molecular sieve product prepared for the first time using the present invention is crystal seed.
Below by way of the beneficial effect of the specific embodiment implementation process that the present invention will be described in detail and generation, it is intended to which help is read
Reader more fully understands essence and feature of the invention, does not limit the scope of the present invention.
Described relative crystallinity is according to ASTM D 5758-01 standard, with products therefrom and molecular sieve mark in embodiment
2 angles θ are 22.5 ~ 25.0 in the XRD spectra of sampleoBetween the sum of characteristic peak area ratio, be expressed as a percentage, standard specimen be with
Conventional chemical reagent is the ZSM-5 molecular sieve (Catalyst Factory, Nankai Univ production, silica alumina ratio 38) of Material synthesis, will
Its crystallinity is defined as 100%.
Product silica alumina ratio is characterized by x-ray fluorescence (XRF) method, using Rigaku ZSX-100e4580 type X
The silica alumina ratio of ray fluorescence spectrometer, molecular sieve described in the present invention refers to SiO2With Al2O3Molar ratio.
The selection of each embodiment Minerals and crystal seed：Diatomite, rectorite, kaolin and montmorillonite used is commercially available
Product.The main component of diatomite is：SiO2Content be 93.2 wt.%, Al2O3Content be 3.31 wt.%；Rectorite
Main component is：SiO2Content be 43.2 wt.%, Al2O3Content be 37.2 wt.%；Kaolinic main component is：
SiO2Content be 50.5 wt.%, Al2O3Content be 44.6 wt.%；The main component of montmorillonite is：SiO2Content be
60.0 wt.%, Al2O3Content be 16.5 wt.%；Crystal seed used in embodiment 1 is the ZSM- of Catalyst Factory, Nankai Univ production
5 zeolite product (SiO2With Al2O3Molar ratio be 38), crystal seed used in 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, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 700 DEG C of roasting 6 h, it is spare；Weigh the tired support of 6.00 g
Native powder, 9.00 g sodium hydrate solids and 45.00 g deionized waters after mixing, are dried at 250 DEG C, spare；
2）System with molecular sieve for preparing is standby：10.40 g of diatomite powder after weighing above-mentioned roasting, 1.35 g sodium hydroxides of addition,
The above-mentioned processed rectorite powder of 0.75 g, 0.20 g crystal seed and 60.20 g deionized waters adjust mole matching for synthetic system
Than for 0.137 Na2O: 1 SiO2: 0.0273 Al2O3: 20.4 H2O；8 h are mixed at 60 DEG C；By the mixture
It moves into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 180 DEG C of static 48 h of crystallization；It is cold after crystallization
But, it is filtered to remove mother liquor, solid product is washed to neutrality, the drying to obtain crystallization product at 120 DEG C.Through XRD determining,
Object mutually belongs to ZSM-5 molecular sieve, and the relative crystallinity of type ZSM 5 molecular sieve is 97% in product, and product silica alumina ratio is 35, XRD
Spectrogram is shown in Fig. 1.
Embodiment 2
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：10.00 g diatomite powders are weighed in 500 DEG C of roasting 10 h, it is spare；It is tired to weigh 6.00 g
It holds in the palm native powder, 12.00 g sodium hydrate solids and 12.00 g deionized waters after mixing, is dried at 350 DEG C, it is spare；
2）System with molecular sieve for preparing is standby：7.92 g of diatomite powder after weighing above-mentioned roasting, 0.68 g sodium hydrate solid of addition,
The above-mentioned processed rectorite powder of 2.10 g, 1.15 g crystal seeds and 46.50 g deionized waters adjust mole matching for synthetic system
Than for 0.2 Na2O: 1 SiO2: 0.04 Al2O3: 20 H2O；4 h are mixed at 70 DEG C.The mixture is moved into band
In the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, it is warming up to 200 DEG C of static 18 h of crystallization.After crystallization, cooling, filtering
Removing mother liquor, solid product are washed to neutrality, dry at 120 DEG C, obtain crystallization product.Through XRD determining, object mutually belongs to
ZSM-5 molecular sieve, the relative crystallinity of type ZSM 5 molecular sieve is 65% in product, and product silica alumina ratio is 23, and XRD spectra is shown in figure
2。
Embodiment 3
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 800 DEG C of roasting 4 h, it is spare；Weigh the tired support of 5.00 g
Native powder, 5.00 g sodium hydrate solids and 2.00 g deionized waters after mixing, are dried at 150 DEG C, spare；
2）System with molecular sieve for preparing is standby：4.00 g of diatomite powder after weighing above-mentioned roasting, 0.44 g sodium hydrate solid of addition,
The above-mentioned processed rectorite powder of 1.0 g, 0.20 g crystal seed and 59.16 g deionized waters adjust mole matching for synthetic system
Than for 0.18 Na2O: 1 SiO2: 0.047 Al2O3: 50 H2O；6 h are mixed at 80 DEG C.The mixture is moved into
In stainless steel crystallizing kettle with polytetrafluoroethyllining lining, it is warming up to 170 DEG C of static 60 h of crystallization.After crystallization, cooling, mistake
Filter out mother liquor, solid product is washed to neutrality, dry at 120 DEG C, obtain crystallization product.Through XRD determining, object mutually belongs to
The relative crystallinity of type ZSM 5 molecular sieve is 92% in ZSM-5 molecular sieve, product, and product silica alumina ratio is 20, and XRD spectra is shown in
Fig. 3.
Embodiment 4
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 600 DEG C of roasting 5 h, it is spare；Weigh the tired support of 5.00 g
Native powder, 10.00 g sodium hydrate solids and 20.00 g deionized waters after mixing, are dried at 300 DEG C, spare；
2）System with molecular sieve for preparing is standby：6.65 g of diatomite powder after weighing above-mentioned roasting, 0.56 g sodium hydrate solid of addition,
The above-mentioned processed rectorite powder of 1.05 g, 0.10 g crystal seed and 57.40 g deionized waters adjust mole matching for synthetic system
Than for 0.15 Na2O: 1 SiO2: 0.032 Al2O3: 30 H2O；20 h are mixed at 50 DEG C.The mixture is moved into
In stainless steel crystallizing kettle with polytetrafluoroethyllining lining, it is warming up to 160 DEG C of static 72 h of crystallization.After crystallization, cooling, mistake
Filter out mother liquor, solid product is washed to neutrality, dry at 120 DEG C, obtain crystallization product.Through XRD determining, object mutually belongs to
The relative crystallinity of type ZSM 5 molecular sieve is 73% in ZSM-5 molecular sieve, product, and product silica alumina ratio is 30, and XRD spectra is shown in
Fig. 4.
Embodiment 5
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 1000 DEG C of roasting 2 h, it is spare；It is tired to weigh 8.00 g
It holds in the palm native powder, 10.00 g sodium hydrate solids and 30.00 g deionized waters after mixing, is dried at 280 DEG C, it is spare；
2）System with molecular sieve for preparing is standby：5.40 g of diatomite powder after weighing above-mentioned roasting, 0.28 g sodium hydrate solid of addition,
The above-mentioned processed rectorite powder of 0.23 g, 0.40 g crystal seed and 61.00 g deionized waters adjust mole matching for synthetic system
Than for 0.06 Na2O: 1 SiO2: 0.025 Al2O3: 40 H2O；12 h are mixed at 70 DEG C.The mixture is moved into
In stainless steel crystallizing kettle with polytetrafluoroethyllining lining, it is warming up to 175 DEG C of static 36 h of crystallization.After crystallization, cooling, mistake
Filter out mother liquor, solid product is washed to neutrality, dry at 120 DEG C, obtain crystallization product.Through XRD determining, object mutually belongs to
The relative crystallinity of type ZSM 5 molecular sieve is 77% in ZSM-5 molecular sieve, product, and product silica alumina ratio is 38, and XRD spectra is shown in
Fig. 5.
Embodiment 6
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 750 DEG C of roasting 8 h, it is spare.It is tired to weigh 20.00 g
It holds in the palm native powder, 20.00 g sodium hydrate solids and 10.00 g deionized waters after mixing, is dried at 380 DEG C, it is spare；
2）System with molecular sieve for preparing is standby：It is solid that 1.10 g sodium hydroxides are added in 12.50 g of diatomite powder after weighing above-mentioned roasting
The above-mentioned processed rectorite powder of body, 1.00 g, 0.30 g crystal seed and 53.50 g deionized waters, adjust rubbing for synthetic system
Your proportion is 0.10 Na2O: 1 SiO2: 0.3 Al2O3: 15 H2O；16 h are mixed at 65 DEG C.The mixture is moved
Enter in the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 165 DEG C of static 24 h of crystallization.After crystallization, cooling,
Be filtered to remove mother liquor, solid product is washed to neutrality, dry at 120 DEG C, obtain crystallization product.Through XRD determining, object phase
Belong to ZSM-5 molecular sieve, the relative crystallinity of type ZSM 5 molecular sieve is 85% in product, and product silica alumina ratio is 32, XRD spectra
See Fig. 6.
Embodiment 7
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 800 DEG C of roasting 4 h, it is spare；Weigh 9.00 g kaolinites
Native powder, 9.00 g sodium hydrate solids and 45.00 g deionized waters after mixing, are dried at 250 DEG C, spare；
2）System with molecular sieve for preparing is standby：10.18 g of diatomite powder after weighing above-mentioned roasting, 1.14 g sodium hydroxides of addition,
The above-mentioned processed kaolin powder of 0.84 g, 0.10 g crystal seed and 60.20 g deionized waters adjust mole matching for synthetic system
Than for 0.12 Na2O: 1 SiO2: 0.032 Al2O3: 20 H2O；8 h are mixed at 70 DEG C；The mixture is moved into
In stainless steel crystallizing kettle with polytetrafluoroethyllining lining, it is warming up to 170 DEG C of static 24 h of crystallization；After crystallization, cooling, mistake
Filter out mother liquor, solid product is washed to neutrality, the drying to obtain crystallization product at 120 DEG C.Through XRD determining, object mutually belongs to
The relative crystallinity of type ZSM 5 molecular sieve is 88% in ZSM-5 molecular sieve, product, and product silica alumina ratio is 30, and XRD spectra is shown in
Fig. 7.
Embodiment 8
A kind of method of green syt ZSM-5 molecular sieve, the specific steps are：
1）The activation of mineral：20.00 g diatomite powders are weighed in 600 DEG C of roasting 6 h, it is spare；It weighs 9.00 g and covers and take off
Native powder, 9.00 g sodium hydrate solids and 45.00 g deionized waters after mixing, are dried at 200 DEG C, spare；
2）System with molecular sieve for preparing is standby：0.50 g sodium hydroxide, 0.90 is added in 4.00 g of diatomite powder after weighing above-mentioned roasting
The above-mentioned processed montmorillonite powder of g, 0.15 g crystal seed and 66.00 g deionized waters, the mol ratio for adjusting synthetic system are
0.18 Na2O: 1 SiO2: 0.03 Al2O3: 55 H2O；6 h are mixed at 65 DEG C；The mixture is moved into poly- four
In the stainless steel crystallizing kettle of vinyl fluoride liner, it is warming up to 180 DEG C of static 36 h of crystallization；After crystallization, cooling is filtered to remove
Mother liquor, solid product are washed to neutrality, the drying to obtain crystallization product at 120 DEG C.Through XRD determining, object mutually belongs to ZSM-
5 molecular sieves, the relative crystallinity of type ZSM 5 molecular sieve is 90% in product, and product silica alumina ratio is 30, and XRD spectra is shown in Fig. 8.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (8)
1. a kind of method of green syt ZSM-5 molecular sieve, it is characterised in that：Zeolite synthesis institute is provided with natural clay mineral
The whole silicon sources and silicon source needed, and any template is not used, ZSM-5 molecular sieve is made through hydrothermal crystallization method；Including following
Step：
（1）The activation of mineral：Low silica-alumina ratio mineral, high silica alumina ratio mineral are activated respectively, wherein low silica-alumina ratio mineral are adopted
It is activated with sub-molten salt medium, high silica alumina ratio mineral are activated using high-temperature roasting mode；
（2）Crystallization：By step（1）Low silica-alumina ratio mineral, high silica alumina ratio mineral and sodium hydroxide, water and crystal seed after activation are mixed
It closes, the crystal seed is the SiO first produced with Catalyst Factory, Nankai Univ2With Al2O3Molar ratio be 38 ZSM-5 molecular sieve
Product is crystal seed；Then using the ZSM-5 molecular sieve product prepared for the first time as crystal seed synthesis of molecular sieve；The additive amount of crystal seed is synthesis
SiO in system2The 1 ~ 15% of gross mass carries out hydrothermal crystallizing after aging, and the inventory for controlling various raw materials makes synthetic system
In the mol ratio of each substance be：0.01~0.25 Na2O: 1 SiO2: 0.01~0.5 Al2O3: 10~80 H2O；Crystallization is obtained
The product arrived is cooling, is filtered to remove mother liquor, and gained filter cake is washed with water to neutrality and obtains ZSM-5 molecular sieve after drying；It is described
The ZSM-5 molecular sieve product prepared for the first time prepare according to the following steps：
1）The activation of mineral：20.00 g diatomite powders are weighed in 700 DEG C of roasting 6 h, it is spare；Weigh 6.00 g rectorite powder
End, 9.00 g sodium hydrate solids and 45.00 g deionized waters after mixing, are dried at 250 DEG C, spare；
2）System with molecular sieve for preparing is standby：1.35 g sodium hydroxides, 0.75 g are added in 10.40 g of diatomite powder after weighing above-mentioned roasting
Above-mentioned processed rectorite powder, 0.20 g crystal seed and 60.20 g deionized waters, the mol ratio for adjusting synthetic system are
0.137 Na2O: 1 SiO2: 0.0273 Al2O3: 20.4 H2O；8 h are mixed at 60 DEG C；The mixture is moved into
In stainless steel crystallizing kettle with polytetrafluoroethyllining lining, it is warming up to 180 DEG C of static 48 h of crystallization；After crystallization, cooling, mistake
Mother liquor is filtered out, solid product is washed to neutrality, the drying to obtain crystallization product at 120 DEG C.
2. the method for green syt ZSM-5 molecular sieve according to claim 1, it is characterised in that：Step（1）Described is low
The silica alumina ratio of silica alumina ratio mineral is 10 hereinafter, the silica alumina ratio of high silica alumina ratio mineral is 30 or more.
3. the method for green syt ZSM-5 molecular sieve according to claim 1 or 2, it is characterised in that：The low sial
It is one of rectorite, montmorillonite, bentonite, concave convex rod and kaolin or a variety of, described high silica alumina ratio mineral than mineral
For diatomite and/or white carbon black.
4. the method for green syt ZSM-5 molecular sieve according to claim 1, it is characterised in that：Step（1）Described in
Sub-molten salt medium is NaOH-H2O system；When low silica-alumina ratio mineral activation, low silica-alumina ratio mineral and NaOH-H2O sub-molten salt medium
Mass ratio is 1:1 ~ 10, activation temperature is 100 ~ 400 DEG C.
5. the method for green syt ZSM-5 molecular sieve according to claim 1, it is characterised in that：Step（1）Middle high sial
Maturing temperature than the activation processing of mineral is 500 ~ 1000 DEG C, and calcining time is 1 ~ 10 h.
6. the method for green syt ZSM-5 molecular sieve according to claim 1, it is characterised in that：Step（2）Described in
The mol ratio of each substance is in synthetic system：0.05~0.20 Na2O: 1 SiO2: 0.02~0.05 Al2O3: 10~60
H2O。
7. the method for green syt ZSM-5 molecular sieve according to claim 1, it is characterised in that：Step（2）Described in
Aging is carried out at 50 ~ 80 DEG C, and ageing time is 2 ~ 24 h.
8. the method for green syt ZSM-5 molecular sieve according to claim 1, it is characterised in that：Step（2）Described in
Crystallization is carried out at 130 ~ 210 DEG C, and crystallization time is 18 ~ 72 h.
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| CN103848439B (en) * | 2012-11-29 | 2015-07-01 | 中国石油大学(北京) | Synthetic method of ZSM-5 type molecular sieve |
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| CN115340104A (en) * | 2022-08-22 | 2022-11-15 | 淮安六元环新材料有限公司 | Method for synthesizing all-silicon ZSM-5 zeolite molecular sieve by using crystal seed-oriented sodium-free method |
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