CN110040741A - A kind of multi-stage porous ZSM-5 molecular sieve and its synthetic method - Google Patents
A kind of multi-stage porous ZSM-5 molecular sieve and its synthetic method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
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- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
The invention discloses a kind of multi-stage porous ZSM-5 molecular sieve and its synthetic methods, belong to technical field of molecular sieve.For the multi-stage porous zeolite crystal having a size of 1~2 μm, grain surface has the molecular sieve association crystal grain of 50~500nm, and molecular sieve concentrates mesopore size between 7~15nm, and specific surface area is not less than 400m2/g；Synthetic method is the following steps are included: silicon source, structure directing agent, water are uniformly mixed by (1) with ethyl alcohol, obtain crystal seed Gel Precursor, reaction cartridge kettle is cooled to room temperature in 50~180 DEG C of crystallization after stirring, obtains silica zeolite (Silicalite-1) crystal seed of liquid.(2) silicon source, silicon source and mineralizer are mixed, adds the liquid Si licalite-1 crystal seed in step (1), the mass ratio of liquid Si licate-1 crystal seed and silicon source is 2~15%.(3) by reaction mixture obtained in (2) in pressure-tight container 1~8h of rapid crystallization under 90~220 DEG C of self-generated pressures, obtain crystallization product.(4) crystallization product of recycling step (3).
Description
Technical field
The invention belongs to technical field of molecular sieve, it is related to a kind of multi-stage porous ZSM-5 molecular sieve and its synthetic method.
Background technique
The oxygen-octahedron and aluminum-oxygen tetrahedron that zeolite is connected by oxygen bridge are constituted, it is defined as micropore silicon aluminate crystal.
The exclusive crystal structure of zeolite makes it have higher thermal stability and hydrothermal stability.Due to including less than 1nm's in zeolite
Duct and hole, therefore most reaction moleculars can enter in its inside；Simultaneously because its range of micropores inner duct is uniform, therefore
Zeolite has good shape selectivity to various sizes of molecule.Aluminium ion is+trivalent in zeolite skeleton, and silicon ion is -4 valences, because
Additional cation is needed to carry out balancing charge in this zeolite skeleton, this makes zeolite have ion-exchange capacity, can be used as water
Deionization processing and one of the ingredient as washing.Structure, the difference of composition silica alumina ratio and pretreatment condition according to zeolite,
The ratio of B acid and the L acid of zeolite is adjustable in very large range, therefore it can be used as catalyst applied to petroleum refining and petrochemical industry
In many catalysis reaction of industry.Zeolite has high specific surface area and micro pore volume, can be used as the load of catalytic active component
Body.Therefore, can by ion-exchange perhaps infusion process by it is metal-doped enter zeolite skeleton prepare double acidic sites or
Bifunctional catalyst.The acidity of zeolite and plus the/bi-functional of dehydrogenation so that it is widely used in the hydrotreating of oil and is reformed anti-
Ying Zhong.
Compared with micropore ZSM-5 molecular sieve, the higher external surface area of multi-stage porous ZSM-5 molecular sieve has preferably big point
The accessibility of sub- reactant makes it have higher catalytic activity.In addition to this, multi-stage porous ZSM-5 molecular sieve pore size
Short, diffusion is good, has adjustable pore structure, and surface utilisation is high, this makes it have the advantage of many uniquenesses, to big point
The cracking ability of sub- reactant is significantly enhanced.There are many problems for the common synthetic method of multi-stage porous ZSM-5 zeolite, such as operate
Complex steps, synthesis process control are difficult, with high costs, and pore performance is difficult to modulation etc..
There are many problems, such as complex for operation step, synthesis processes to control for the common synthetic method of multi-stage porous ZSM-5 zeolite
Difficult, with high costs, pore performance is difficult to modulation etc..
Summary of the invention
The object of the present invention is to provide a kind of multi-stage porous ZSM-5 products and preparation method thereof.In order to realize mesh of the invention
, the technical solutions adopted are as follows.
A kind of multi-stage porous ZSM-5 molecular sieve, which is characterized in that having a size of 1~2 μm, grain surface has the zeolite crystal
The molecular sieve association crystal grain of 50~500nm, molecular sieve concentrate mesopore size between 7~15nm, and specific surface area is not less than 400m2/
g；The total pore volume of the molecular sieve is not less than 0.21cm3/ g, micro pore volume are not less than 0.1m2/g。
The synthetic method of aforementioned multi-stage porous ZSM-5 molecular sieve, which comprises the following steps:
(1) by silicon source, structure directing agent, alkali (NaOH or Na2CO3), water be uniformly mixed to obtain reaction mixture with ethyl alcohol,
SiO in the reaction mixture2∶R∶Na2O∶H2O: EtOH molar ratio is 1: (0.01~1.0): (0.001~0.01): (5-
400): (1~10) is prepared crystal seed Gel Precursor, stir after 2~12h reaction cartridge kettle in 50~180 DEG C of crystallization 1~
12h is cooled to room temperature, and obtains silica zeolite (Silicalite-1) crystal seed of liquid；R represents structure in reaction mixture and leads
To agent molal quantity；
(2) by silicon source, silicon source, alkali (NaOH or Na2CO3) and mineralizer be mixed to get reaction mixture, the reaction mixture
Middle SiO2∶Al2O3∶Na2O∶M∶2H2The molar ratio of O is 1: (0.01~0.1): (0.01~1): and (0~1): (5~20), then plus
Enter the liquid Si licalite-1 crystal seed in (1)；Liquid Si licate-1 crystal seed and the mass ratio of silicon source are 2~15%, M representative
The molal quantity of mineralizer in reaction mixture；
(3) by reaction mixture obtained in (2) in pressure-tight container the crystallization 1 under 90~220 DEG C of self-generated pressures
~8h, obtains crystallization product；
(4) crystallization product that recycling step (3) obtains.
In some specific embodiments, silicon source described in step (1) and step (2) is selected from methyl orthosilicate, positive silicon
At least one of sour second vinegar, the third vinegar of positive silicic acid, positive silicic acid fourth vinegar, silica gel, white carbon black and silica solution.
In some specific embodiments, silicon source described in step (2) is selected from sodium metaaluminate, aluminium isopropoxide, aluminum sulfate
At least one of.
In some specific embodiments, structure directing agent described in step (1) is selected from tetramethylammonium hydroxide, tetrem
At least one of base ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
In some specific embodiments, crystallization temperature described in step (1) is 60~160 DEG C, time of crystallization is 2~
10h。
In some specific embodiments, mineralizer described in step (2) in KCl, KBr, KF, KOH at least
It is a kind of.
In some specific embodiments, crystallization temperature described in step (2) be 80~180 DEG C, crystallization time be 2~
5h。
In some specific embodiments, this method further includes step (5): the crystallization product of step (4) recycling is carried out
Calcination process.Further, the condition of calcination process described in step (5) is: maturing temperature is 400~900 DEG C, calcining time
It is 1~16 hour.
Product synthesis process of the invention is simple, easily controllable；Due to the introducing of mesoporous, zeolite interior acidic site can
Proximity and effective rate of utilization are obviously improved, the excellent catalytic performance in corresponding catalysis reaction, can be used as catalyst and
Catalyst carrier.Preparation method of the invention can quickly prepare multi-stage porous ZSM- using hydro-thermal method controlling crystallizing dynamic process
5 zeolites, the use without mesoporous template.
Detailed description of the invention
Fig. 1 is the XRD spectra for the multi-stage porous ZSM-5 molecular sieve that embodiment 1 obtains.
Fig. 2 is the N for the multi-stage porous type ZSM 5 molecular sieve that embodiment 1 obtains2Adsorption desorption curve.
Fig. 3 is the BJH pore size distribution curve for the multi-stage porous type ZSM 5 molecular sieve that embodiment 1 obtains.
Fig. 4 is the SEM photograph for the multi-stage porous type ZSM 5 molecular sieve that embodiment 1 obtains.
Specific embodiment
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
According to the present invention, the crystalline phase figure of X-ray diffraction (XRD) is measured with Philips Panalytical X'pert
It arrives, test condition are as follows: Cu target, Ka radiation, Ni filter plate, super detector, tube voltage 30KV, tube current 40mA；Then multi-stage porous
The relative crystallinity of ZSM-5 molecular sieve can be calculated according to the size of the characteristic peak of molecular sieve in XRD spectrum.
According to the present invention, the specific surface area is the ASAP2405J static state N2 adsorption using Micromeritics company
Instrument measures the static N of sample at liquid nitrogen temperature (77.4K)2After adsorption desorption curve, to P/P0Suction in=0.05~0.35 range
Attached curve carries out BET and is fitted to obtain.
Embodiment 1
Under agitation, it is uniformly mixed silicon source, structure directing agent, alkali, water to obtain reaction mixture with ethyl alcohol, this is anti-
Answer SiO in mixture2: R:Na2O:H2O:EtOH molar ratio is 1:0.36:0.004:60:5, and crystal seed gel forerunner is prepared
Body, reaction cartridge kettle is cooled to room temperature in 100 DEG C of crystallization 12h, obtains the silica zeolite of liquid after stirring 12h
(Silicalite-1) crystal seed；
Silicon source, silicon source, alkali and mineralizer are mixed to get reaction mixture, SiO in the reaction mixture2: Al2O3:
Na2O:M:2H2The molar ratio of O is 1:0.012:0.15:0.6:8, adds liquid Si licalite-1 crystal seed.Liquid
Silicate-1 crystal seed and the mass ratio of silicon source are 12%；
By reaction mixture in pressure-tight container under 160 DEG C of self-generated pressures crystallization 2h, obtain crystallization product；To not
Rust steel pressure resistance reaction kettle is cooled to room temperature, the multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast, after 110 DEG C of dry 6h, then
Multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.XRD characterization result such as Fig. 1 of multi-stage porous ZSM-5 molecular sieve
Shown, TEM result is as shown in Fig. 2, pore size distribution figure is as shown in Figure 3.After isometric load 0.8%Pt, 200 DEG C of reduction 3h, test
Its guaiacol hydrogenation reaction, conversion ratio 92%, cyclohexanol selectivity 80%.
Embodiment 2
Under agitation, it is uniformly mixed silicon source, structure directing agent, alkali, water to obtain reaction mixture with ethyl alcohol, this is anti-
Answer SiO in mixture2: R:Na2O:H2O:EtOH molar ratio is 1:0.36:0.004:60:5, and crystal seed gel forerunner is prepared
Body, reaction cartridge kettle is cooled to room temperature in 100 DEG C of crystallization 10h, obtains the silica zeolite of liquid after stirring 12h
(Silicalite-1) crystal seed.
Silicon source, silicon source, alkali and mineralizer are mixed to get reaction mixture, SiO in the reaction mixture2: Al2O3:
Na2O:M:2H2The molar ratio of O is 1:0.012:0.15:0.6:10, adds liquid Si licalite-1 crystal seed.Liquid
Silicate-1 crystal seed and the mass ratio of silicon source are 10.5%.
By reaction mixture in pressure-tight container under 160 DEG C of self-generated pressures crystallization 2.5h, obtain crystallization product；To
Stainless steel pressure resistance reaction kettle is cooled to room temperature, the multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast, after 110 DEG C of dry 6h, then
Multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.After isometric load 0.8%Pt, 200 DEG C of reduction 3h, test
Its guaiacol hydrogenation reaction, conversion ratio 93%, cyclohexanol selectivity 83%.
Embodiment 3
Under agitation, it is uniformly mixed silicon source, structure directing agent, alkali, water to obtain reaction mixture with ethyl alcohol, this is anti-
Answer SiO in mixture2: R:Na2O:H2O:EtOH molar ratio is 1:0.36:0.004:60:5, and crystal seed gel forerunner is prepared
Body, reaction cartridge kettle is cooled to room temperature in 100 DEG C of crystallization 10h, obtains the silica zeolite of liquid after stirring 12h
(Silicalite-1) crystal seed.
Silicon source, silicon source, alkali and mineralizer are mixed to get reaction mixture, SiO in the reaction mixture2: Al2O3:
Na2O:M:2H2The molar ratio of O is 1:0.012:0.15:0.6:15, adds liquid Si licalite-1 crystal seed.Liquid
Silicate-1 crystal seed and the mass ratio of silicon source are 10.5%.
By reaction mixture in pressure-tight container under 160 DEG C of self-generated pressures crystallization 3h, obtain crystallization product；To not
Rust steel pressure resistance reaction kettle is cooled to room temperature, the multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast, after 110 DEG C of dry 6h, then
Multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.After isometric load 0.8%Pt, 200 DEG C of reduction 3h, test
Its guaiacol hydrogenation reaction, conversion ratio 99%, cyclohexanol selectivity 90%.
Embodiment 4
Under agitation, it is uniformly mixed silicon source, structure directing agent, alkali, water to obtain reaction mixture with ethyl alcohol, this is anti-
Answer SiO in mixture2: R:Na2O:H2O:EtOH molar ratio is 1:0.36:0.004:60:5, and crystal seed gel forerunner is prepared
Body, reaction cartridge kettle is cooled to room temperature in 100 DEG C of crystallization 10h, obtains the silica zeolite of liquid after stirring 12h
(Silicalite-1) crystal seed.
Silicon source, silicon source, alkali and mineralizer are mixed to get reaction mixture, SiO in the reaction mixture2: Al2O3:
Na2O:M:2H2The molar ratio of O is 1:0.012:0.15:0.6:15, adds liquid Si licalite-1 crystal seed.Liquid
Silicate-1 crystal seed and the mass ratio of silicon source are 10.5%；
By reaction mixture in pressure-tight container under 160 DEG C of self-generated pressures crystallization 3h, obtain crystallization product；To not
Rust steel pressure resistance reaction kettle is cooled to room temperature, the multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast, after 110 DEG C of dry 6h, then
Multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.After isometric load 0.8%Pt, 200 DEG C of reduction 3h, test
Its guaiacol hydrogenation reaction, conversion ratio 95%, cyclohexanol selectivity 96%.
The crystallinity and pore structure data of 1 embodiment 1-4 molecular sieve of table
Claims (10)
1. a kind of multi-stage porous ZSM-5 molecular sieve, which is characterized in that for the zeolite crystal having a size of 1~2 μm, grain surface has 50
The molecular sieve association crystal grain of~500nm, molecular sieve concentrate mesopore size between 7~15nm, and specific surface area is not less than 400m2/g；
The total pore volume of the molecular sieve is not less than 0.21cm3/ g, micro pore volume are not less than 0.1m2/g。
2. the synthetic method of multi-stage porous ZSM-5 molecular sieve according to claim 1, which comprises the following steps:
(1) it is uniformly mixed silicon source, structure directing agent, alkali, water to obtain reaction mixture with ethyl alcohol, SiO in the reaction mixture2∶
R∶Na2O∶H2O: EtOH molar ratio is 1: (0.01~1.0): (0.001~0.01): (5-400): (1~10) is prepared
Crystal seed Gel Precursor, reaction cartridge kettle is cooled to room temperature in 50~180 DEG C of 1~12h of crystallization, obtains liquid after stirring 2~12h
Silica zeolite (Silicalite-1) crystal seed；R represents structure directing agent molal quantity in reaction mixture；
(2) silicon source, silicon source, alkali and mineralizer are mixed to get reaction mixture, SiO in the reaction mixture2∶Al2O3∶Na2O∶
M∶2H2The molar ratio of O is 1: (0.01~0.1): (0.01~1): (0~1): (5~20) add the liquid in (1)
Silicalite-1 crystal seed；Liquid Si licate-1 crystal seed and the mass ratio of silicon source are that 2~15%, M is represented in reaction mixture
The molal quantity of mineralizer；
(3) by reaction mixture obtained in (2) in pressure-tight container 1~8h of crystallization under 90~220 DEG C of self-generated pressures,
Obtain crystallization product；
(4) crystallization product that recycling step (3) obtains.
3. synthetic method according to claim 2, which is characterized in that silicon source described in step (1) and step (2) is selected from
At least one of methyl orthosilicate, positive silicic acid second vinegar, the third vinegar of positive silicic acid, positive silicic acid fourth vinegar, silica gel, white carbon black and silica solution.
4. synthetic method according to claim 2, which is characterized in that silicon source described in step (2) be selected from sodium metaaluminate,
At least one of aluminium isopropoxide, aluminum sulfate.
5. synthetic method according to claim 2, which is characterized in that structure directing agent described in step (1) is selected from four
At least one of ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
6. synthetic method according to claim 2, which is characterized in that crystallization temperature described in step (1) is 60~160
DEG C, the time of crystallization is 2~10h.
7. synthetic method according to claim 2, which is characterized in that mineralizer described in step (2) be selected from KCl,
At least one of KBr, KF, KOH.
8. synthetic method according to claim 2, which is characterized in that crystallization temperature described in step (2) is 80~180
DEG C, crystallization time is 2~5h.
9. synthetic method according to claim 2, which is characterized in that this method further includes step (5): step (4) are obtained
The crystallization product arrived carries out calcination process.
10. synthetic method according to claim 9, which is characterized in that the condition of calcination process described in step (5) is:
Maturing temperature is 400~900 DEG C, and calcining time is 1~16 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112408419A (en) * | 2020-12-17 | 2021-02-26 | 河南科技大学 | Preparation method of hierarchical porous ZSM-5 nano zeolite |
| WO2021129719A1 (en) * | 2019-12-26 | 2021-07-01 | 镇江贝斯特新材料有限公司 | Hierarchical porous zsm-5 molecular sieve, preparation method therefor, hzsm-5 molecular sieve prepared therefrom, and use of molecular sieve |
| CN115805099A (en) * | 2023-02-17 | 2023-03-17 | 河北鑫鹏新材料科技有限公司 | Auxiliary agent for maximizing propylene octane number and preparation method thereof |
| CN115872415A (en) * | 2023-02-17 | 2023-03-31 | 河北鑫鹏新材料科技有限公司 | Nano ZSM-5 molecular sieve and preparation method thereof |
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2019
- 2019-05-30 CN CN201910462326.9A patent/CN110040741A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021129719A1 (en) * | 2019-12-26 | 2021-07-01 | 镇江贝斯特新材料有限公司 | Hierarchical porous zsm-5 molecular sieve, preparation method therefor, hzsm-5 molecular sieve prepared therefrom, and use of molecular sieve |
| CN112408419A (en) * | 2020-12-17 | 2021-02-26 | 河南科技大学 | Preparation method of hierarchical porous ZSM-5 nano zeolite |
| CN115805099A (en) * | 2023-02-17 | 2023-03-17 | 河北鑫鹏新材料科技有限公司 | Auxiliary agent for maximizing propylene octane number and preparation method thereof |
| CN115872415A (en) * | 2023-02-17 | 2023-03-31 | 河北鑫鹏新材料科技有限公司 | Nano ZSM-5 molecular sieve and preparation method thereof |
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Application publication date: 20190723 |