CN108821306A - A kind of preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve - Google Patents
A kind of preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
The present invention relates to a kind of preparation methods of metal-modified multi-stage porous HZSM-5 molecular sieve, include the following steps：1) metal-organic framework materials (MOFs), which are placed in atmosphere of inert gases, roasts, and prepares the mesoporous template of Metal Supported porous carbon；2) silicon source is dissolved in microcellular structure directed agents, deionized water is added, dissolution is stirred at room temperature, then adds silicon source, obtains molecular sieve precursor；3) porous carbon template obtained in step 1) is added in molecular sieve precursor, carries out pre- crystallization；4) after the completion of pre- crystallization, mixture is transferred in water heating kettle and carries out hydrothermal crystallizing；5) after the completion of crystallization, metal-modified multi-stage porous HZSM-5 molecular sieve is obtained by centrifugation, washing, drying, roasting.The HZSM-5 molecular sieve of this method preparation introduces active metal and multi-stage artery structure simultaneously by one-step method, can improve the catalytic activity and stability of molecular sieve simultaneously.
Description
Technical field
The invention belongs to field of catalyst preparation, are related to a kind of preparation side of metal-modified multi-stage porous HZSM-5 molecular sieve
Method.
Background technique
HZSM-5 molecular sieve is a kind of microporous molecular with extensive use that 1970s are developed by Mobil company
Sieve.Since HZSM-5 molecular sieve has the characteristics that good thermal stability, higher specific surface area and suitable acid strength, thus
Receive the extensive favor of academia and business circles.But the single micropore canals of HZSM-5 molecular sieve are unfavorable in macromolecular
The diffusion of mesosome and reaction product is easy to cause the macromoleculars such as high molecular polymer product to be stranded in molecular sieve pore passage for a long time
In, so as to cause catalyst coking and deactivation.In addition, catalytic activity of the HZSM-5 molecular sieve in the reaction such as aromatisation, alkylation
Also not high enough, it is not able to satisfy the requirement of industrialized production still.Therefore, it develops while there is good catalytic activity and stability
HZSM-5 molecular sieve is significant.
In recent years, research of the researchers at home and abroad in terms of the preparation of HZSM-5 molecular sieve and modification is very active.But
These researchs are mostly focused on the catalytic activity or stability for individually changing molecular sieve, and the catalysis that can change simultaneously molecular sieve is living
The research of property and stability is relatively fewer.Zn, Ag, Ni, Ga etc. that Chinese patent CN 105949019A is disclosed with various concentration
Dehydrogenation metal modified HZSM-5 molecular sieve, and make its high oxide containing metals such as V, Ce, Fe, Cr simultaneously, in weak oxide
Property gas and other inert dilution gas mixing atmosphere under, catalysis methanol aromatization.The result shows that due to dehydrogenation metal
It is introduced with high oxide, the catalytic activity of molecular sieve is improved.But the metal introduced in the patented method can not
Improve the stability of catalyst.Chinese patent CN 107188195A provides a kind of preparation side of multi-stage porous HZSM-5 molecular sieve
Sucrose is added as mesoporous template in method, this method in molecular sieve precursor crystallization process, and gained multistage porous molecular sieve can
Its anti-coking performance during catalytic pyrolysis of biomass prepares aromatic hydrocarbons is improved, therefore can be improved the steady of molecular sieve catalyst
It is qualitative.But influence of the patented method without reference to reactive metal modified to HZSM-5 molecular sieve catalytic active.In in addition,
State patent CN 107118793A provides a kind of preparation method of Metal Supported multistage porous molecular sieve.This method first will preparation
HZSM-5 molecular sieve carry out alkali process obtain multi-stage porous HZSM-5；Then source metal is deposited to using atomic layer deposition method more
On grade hole HZSM-5, Metal Supported multi-stage porous HZSM-5 molecular sieve is obtained.This method successively introduces multi-stage porous and active metal
It has arrived in molecular sieve, it is thus possible to improve the stability and catalytic activity of molecular sieve.But the patented method is needed in preparation point
It is additional to add the last handling processes such as alkali process and atomic layer deposition on the basis of son sieve, make this method is cumbersome, cost compared with
It is high.
Summary of the invention
Technical problem：In order to solve the problems, such as that existing HZSM-5 molecular sieve is difficult to improve catalytic activity and stability simultaneously,
Provide a kind of preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve.This method is situated between by the way that Metal Supported porous carbon is added
Hole template introduces active metal and multi-stage artery structure simultaneously in molecular sieve, to obtained while had by one-step method
There is the HZSM-5 molecular sieve of good catalytic activity and stability.
Technical solution：The preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve of the invention, includes the following steps：
1) metal-organic framework materials are placed in atmosphere of inert gases and are roasted, prepare the mesoporous template of Metal Supported porous carbon
Agent；
2) silicon source is dissolved in microcellular structure directed agents, deionized water is added, dissolution is stirred at room temperature, then adds silicon source, obtains
To molecular sieve precursor；
3) the mesoporous template of Metal Supported porous carbon obtained in step 1) is added in molecular sieve precursor, is carried out pre-
Crystallization；
4) mixture that pre- crystallization obtains is transferred in water heating kettle and carries out hydrothermal crystallizing；
5) product after hydrothermal crystallizing is obtained metal-modified multi-stage porous HZSM-5 points by centrifugation, washing, dry, roasting
Son sieve.
Further, in the method for the present invention, metal-organic framework materials described in step 1) are that zinc salt/2-methylimidazole is matched
Close object, cobalt salt/2-methylimidazole complex, chromic salts/terephthalic acid (TPA) complex or zinc salt/terephthalic acid (TPA) complex；It is described
Inert gas is nitrogen, argon gas or helium；The roasting condition is 300~800 DEG C, 0.5~5h.
Further, in the method for the present invention, the zinc salt/2-methylimidazole complex is ZIF-8 type metal organic framework
Material, the cobalt salt/2-methylimidazole complex are ZIF-67 type metal-organic framework materials, the chromic salts/terephthalic acid (TPA)
Complex is MIL-101 type metal-organic framework materials, and the zinc salt/terephthalic acid (TPA) complex is that MOF-5 type metal is organic
Framework material.
Further, in the method for the present invention, silicon source is aluminium isopropoxide, ANN aluminium nitrate nonahydrate or 18 water sulfuric acid in step 2)
Aluminium；The microcellular structure directed agents are tetrapropylammonium hydroxide or 4-propyl bromide；The silicon source is tetraethyl orthosilicate, silicon
Colloidal sol or fumed silica；Source of aluminium, silicon source, microcellular structure directed agents, the molar ratio of water are (0.01~0.08): 1:
(0.1~0.5): (5~50), wherein silicon source molal quantity is with Al2O3Meter, silicon source molal quantity are with SiO2Meter.
Further, in the method for the present invention, the mesoporous template of Metal Supported porous carbon and molecular sieve precursor in step 3)
The molar ratio of middle silicon source is (0.05~0.6): 1；Pre- crystallization condition is 20~80 DEG C, 10~48h.
Further, in the method for the present invention, the crystallization condition in step 4) is 120~240 DEG C, 24~120h.
Further, in the method for the present invention, drying condition in step 5) is 80~120 DEG C, 5~for 24 hours, roasting condition be
500~700 DEG C, 3~8h.
In the present invention, the synthesis step of ZIF-8 type metal-organic framework materials is：Six are weighed respectively in molar ratio for 1: 8
Nitric hydrate zinc and 2-methylimidazole, are dissolved in methanol, are stirred at room temperature for 24 hours.It is centrifuged, washs, being dried to obtain ZIF-8 type metal and have
Machine framework material.
The synthesis step of the ZIF-67 type metal-organic framework materials is：Six hydrations are weighed respectively in molar ratio for 1: 8
Cobalt nitrate and 2-methylimidazole, are dissolved in methanol, and 2h is stirred at room temperature.It is centrifuged, washs, being dried to obtain the organic bone of ZIF-67 type metal
Frame material.
The synthesis step of the MIL-101 type metal-organic framework materials is：Nine hydrations are weighed respectively in molar ratio for 1: 1
Deionized water is added in chromic nitrate and terephthalic acid (TPA).Above-mentioned mixed liquor is placed in water heating kettle in 220 DEG C of heating 18h.Filtering,
It washs, be dried to obtain MIL-101 type metal-organic framework materials.
The synthesis step of the MOF-5 type metal-organic framework materials is：It is weighed respectively for 1: 2: 8 to benzene two in molar ratio
Formic acid, zinc nitrate hexahydrate and triethylamine, are dissolved in n,N-Dimethylformamide, and 4h is stirred at room temperature.It is centrifugation, washing, dry
To MOF-5 type metal-organic framework materials.The present invention is by being added the mesoporous template of Metal Supported porous carbon simultaneously in molecular sieve
In introduce active metal and multi-stage artery structure, the molecular sieve not only catalytic activity with higher prepared by this method,
It is with good stability simultaneously.
Beneficial effect：Compared with prior art, the present invention having the following advantages that：
(1) present invention is prepared using the Metal Supported porous carbon based on MOFs material as mesoporous template metal-modified more
Grade hole HZSM-5 molecular sieve.Due to Metal Supported porous carbon simultaneously active metal and meso-hole structure, the method for the present invention by its
The preparation process of molecular sieve is introduced into as mesoporous template, to introduce active gold simultaneously in molecular sieve by one-step method
Category and multi-stage artery structure, and then obtained while having had the HZSM-5 molecular sieve of high catalytic activity and stability.With document report
The modified molecular screen preparation method by simple introduction active metal or meso-hole structure in road is compared, and the method for the present invention is drawn simultaneously
Into active metal and meso-hole structure, so as to improve the catalytic activity and stability of molecular sieve simultaneously.In addition, with document report
The multistep processes in road prepares modified molecular screen and compares, and this method makes without post-processing steps such as additional alkali process and Metal Supported
Easy to operate, cost reduces.
(2) the method for the present invention can also pass through the type of MOFs material in control synthesis process, the roasting item of MOFs material
Part, the dosage of Metal Supported porous carbon, Crystallization of Zeolite condition etc. reach effective modulation molecular sieve active site, cellular structure
Effect, so as to simultaneously regulatory molecule sieve catalytic activity and stability.
Specific embodiment
Below by embodiment, the present invention is further elaborated, it should be noted that following instance is merely to illustrate this hair
It is bright rather than limit the scope of the invention.
Embodiment 1
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.0g is obtained.
Embodiment 2
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-67 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.8g metallic cobalt.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.2g is obtained.
Embodiment 3
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 300 DEG C of roasting 0.5h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 5.3g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.3g is obtained.
Embodiment 4
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 800 DEG C of roasting 5h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.3g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.3g is obtained.
Embodiment 5
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.84g ANN aluminium nitrate nonahydrate is dissolved in 24.80g 4 third
In base ammonium hydroxide (25w%), 36.30g deionized water is added, stirs 2h.Then, the positive silicic acid tetrem of 25.42g is added dropwise
Ester is stirred at room temperature 3h and obtains molecular sieve precursor.Metal Supported porous carbon obtained in 0.54g step 1) is added into presoma
Template is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to in polytetrafluoroethylene (PTFE)
In the closed water heating kettle of lining, 170 DEG C of standing 48h carry out hydrothermal crystallizing.After crystallization, mixture is centrifugated, gained is solid
Body is washed with deionized to neutrality, 110 DEG C of dry 12h in baking oven is placed in, then in Muffle furnace 550 DEG C under air atmosphere
It roasts 6h and removes template, obtain the metal-modified multi-stage porous HZSM-5 molecular sieve of 4.3g.
Embodiment 6
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：4.0g aluminium isopropoxide is dissolved in 49.6g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 108.9g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.4g is obtained.
Embodiment 7
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：0.5g aluminium isopropoxide is dissolved in 9.92g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 11.0g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate is added dropwise, room temperature is stirred
It mixes 3h and obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma, rises
Temperature for 24 hours, carries out pre- crystallization to 40 DEG C of stirrings.Then, resulting mixed liquor is transferred to the closed of polytetrafluoroethyllining lining
In water heating kettle, 170 DEG C of standing 48h carry out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid spend from
Sub- water washing is placed in 110 DEG C of dry 12h in baking oven, then 550 DEG C of roasting 6h are removed under air atmosphere in Muffle furnace to neutrality
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 3.6g is obtained.
Embodiment 8
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 24.43g silica solution (30w%), room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 6.1g is obtained.
Embodiment 9
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 2.37g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.4g is obtained.
Embodiment 10
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.2g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 4.3g is obtained.
Embodiment 11
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
20 DEG C of stirring 10h are warming up to, pre- crystallization is carried out.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 3.4g is obtained.
Embodiment 12
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
80 DEG C of stirring 48h are warming up to, pre- crystallization is carried out.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 4.7g is obtained.
Embodiment 13
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 120 DEG C stand for 24 hours, carry out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 110 DEG C of dry 12h in baking oven to neutrality, then in Muffle furnace under air atmosphere 550 DEG C of roasting 6h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 2.6g is obtained.
Embodiment 14
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 240 DEG C of standing 120h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is used
Deionized water is washed to neutrality, and 110 DEG C of dry 12h in baking oven are placed in, then 550 DEG C of roastings under air atmosphere in Muffle furnace
6h removes template, obtains the metal-modified multi-stage porous HZSM-5 molecular sieve of 4.5g.
Embodiment 15
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in 80 DEG C of dry 5h in baking oven, then 500 DEG C of roasting 3h are removed under air atmosphere in Muffle furnace to neutrality
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 5.1g is obtained.
Embodiment 16
1) preparation of the mesoporous template of Metal Supported porous carbon：6.0g ZIF-8 is placed in the tube furnace under nitrogen atmosphere
In, 600 DEG C of roasting 3h are down to room temperature and obtain the mesoporous template of the supported porous carbon of 4.7g metallic zinc.
2) preparation of metal-modified multi-stage porous HZSM-5 catalyst：1.0g aluminium isopropoxide is dissolved in 24.80g tetrapropyl hydrogen-oxygen
Change in ammonium (25w%), 36.30g deionized water is added, stirs 2h.Then, 25.42g tetraethyl orthosilicate, room temperature is added dropwise
Stirring 3h obtains molecular sieve precursor.Metal Supported porous carbon template obtained in 0.54g step 1) is added into presoma,
It is warming up to 40 DEG C of stirrings for 24 hours, carries out pre- crystallization.Then, resulting mixed liquor is transferred to the close of polytetrafluoroethyllining lining
It closes in water heating kettle, 170 DEG C of standing 48h, carries out hydrothermal crystallizing.After crystallization, mixture is centrifugated, obtained solid is spent
Ion water washing is placed in baking oven 120 DEG C of dryings for 24 hours to neutrality, then in Muffle furnace under air atmosphere 700 DEG C of roasting 8h
Template is removed, the metal-modified multi-stage porous HZSM-5 molecular sieve of 4.1g is obtained.
Claims (7)
1. a kind of preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve, which is characterized in that this approach includes the following steps：
1) metal-organic framework materials are placed in atmosphere of inert gases and are roasted, prepare the mesoporous template of Metal Supported porous carbon；
2) silicon source is dissolved in microcellular structure directed agents, deionized water is added, dissolution is stirred at room temperature, then adds silicon source, is divided
Son sieve presoma；
3) the mesoporous template of Metal Supported porous carbon obtained in step 1) is added in molecular sieve precursor, carries out pre- crystalline substance
Change；
4) mixture that pre- crystallization obtains is transferred in water heating kettle and carries out hydrothermal crystallizing；
5) product after hydrothermal crystallizing is obtained into metal-modified multi-stage porous HZSM-5 molecule by centrifugation, washing, dry, roasting
Sieve.
2. the preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve according to claim 1, which is characterized in that institute
State in step 1) metal-organic framework materials be zinc salt/2-methylimidazole complex, cobalt salt/2-methylimidazole complex, chromic salts/
Terephthalic acid (TPA) complex or zinc salt/terephthalic acid (TPA) complex；Inert gas is nitrogen, argon gas or helium；Roasting condition is
300~800 DEG C, 0.5~5h.
3. the preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve according to claim 2, which is characterized in that institute
Stating zinc salt/2-methylimidazole complex is ZIF-8 type metal-organic framework materials, and the cobalt salt/2-methylimidazole complex is
ZIF-67 type metal-organic framework materials, the chromic salts/terephthalic acid (TPA) complex are MIL-101 type metal organic framework material
Material, the zinc salt/terephthalic acid (TPA) complex are MOF-5 type metal-organic framework materials.
4. the preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve according to claim 1, which is characterized in that institute
Stating silicon source in step 2) is aluminium isopropoxide, ANN aluminium nitrate nonahydrate or aluminum sulfate octadecahydrate；The microcellular structure directed agents are 4 third
Base ammonium hydroxide or 4-propyl bromide；The silicon source is tetraethyl orthosilicate, silica solution or fumed silica；The aluminium
Source, silicon source, microcellular structure directed agents, the molar ratio of water are (0.01~0.08): 1: (0.1~0.5): (5~50), wherein silicon source
Molal quantity is with Al2O3Meter, silicon source molal quantity are with SiO2Meter.
5. the according to claim 1, preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve described in 2,3 or 4, feature
It is, the molar ratio of the mesoporous template of Metal Supported porous carbon and silicon source in molecular sieve precursor is (0.05 in the step 3)
~0.6): 1；Pre- crystallization condition is 20~80 DEG C, 10~48h.
6. the according to claim 1, preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve described in 2,3 or 4, feature
It is, the crystallization condition in the step 4) is 120~240 DEG C, 24~120h.
7. the according to claim 1, preparation method of metal-modified multi-stage porous HZSM-5 molecular sieve described in 2,3 or 4, feature
Be, the drying condition in the step 5) be 80~120 DEG C, 5~for 24 hours, roasting condition be 500~700 DEG C, 3~8h.
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