CN108114740A - Level hzsm-5 catalyst - Google Patents
Level hzsm-5 catalyst Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
5 catalyst of level HZSM prepares mixed liquor with silicon source and template, and silicon source is passed through with gaseous form, is stood high temperature high pressure enclosed reaction after aging, then is dipped in NH4Ion exchange is carried out in Cl solution, is prepared by washing the processing procedures such as drying and roasting.5 catalyst silica alumina ratios of level HZSM prepared by the present invention are 25 ~ 40：1, specific surface area is 350 ~ 450m2/ g, pore volume are 0.25 ~ 0.40cm3/ g, intermediary hole pore volume account for 50 ~ 80%.The present invention is prepared in 5 catalyst process of level HZSM, and molecular sieve silica alumina ratio easy-regulating, catalyst silica alumina ratio is high, and mesoporous quantity is more, and pore-size distribution is good, and preparing aromatic hydrocarbons reaction for biomass catalyzing uses, and aromatics yield improves a lot.
Description
Technical field
The present invention relates to a kind of by level catalyst of the HZSM-5 molecular sieves for raw material preparation more particularly to a kind of biomass
The catalyst of catalytic pyrolysis aromatic hydrocarbons.
Background technology
Aromatic hydrocarbons is the general name of the hydrocarbon containing benzene ring structure, is the important source material of organic chemical industry.Wherein mononuclear aromatics
It is more prominent.Benzene, dimethylbenzene are a variety of synthetic resin of manufacture, synthetic rubber, the raw material of synthetic fibers.Toluene can be converted into diformazan
Benzene and benzene.Senior alkyl benzene is the important source material for manufacturing surfactant.Biphenyl is used as the heat load of chemical process in polycyclic aromatic hydrocarbon
Body.Naphthalene is the important source material for manufacturing dyestuff and plasticizer in condensed-nuclei aromatics.Some aromatic hydrocarbons or its mixture such as benzene, dimethylbenzene, first
Benzene etc. can make solvent, and aromatic hydrocarbons (such as isopropylbenzene) octane number is higher, be contained with the aromatic hydrocarbons in light fraction oil is increased the methods of reformation
Amount, it is significant to improving quality of gasoline.
Document " Investigation into the shape selectivity of zeolite catalysts
For biomass conversion " are open to be reported HZSM-5 molecular sieves to be that wood fiber element catalytic pyrolysis is most effective urges
Agent.Since it is with suitable acidity, pore passage structure, good hydrothermal stability and carbon accumulation resisting ability etc., urged in cellulose
Change thermal cracking aromatics yield and be up to 30% or so.But HZSM-5 ducts are single, average pore size only has 0.55 nm, in cellulose
During catalytic pyrolysis, some polycyclic aromatic hydrocarbons of formation etc. easily block duct, form a large amount of coke, catalyst is caused to lose
Living, aromatics yield is difficult to improve.
Document " Catalytic fast pyrolysis of biomass with mesoporous ZSM-5
Zeolites prepared by desilication with NaOH solutions " are open to be reported using after NaOH
Reason HZSM-5 is prepared in cellulose catalytic thermal cracking to be used on aromatic hydrocarbons.NaOH post-processes HZSM-5, can remove the bone on HZMS-5
Frame Si, so as to form mesopore orbit, and aromatics yield also from 31.1% be increased to the mesoporous pore volumes of 32.1%, HZSM-5 also from
0.058 ml/g has been increased to 0.127 ml/g, illustrates to introduce the mesoporous HZSM-5 that can improve in right amount in cellulose catalytic thermal cracking
Catalytic activity.
Document " Synthesis of Ni/mesoporous ZSM-5 for direct catalytic conversion
of cellulose to hexitols:modulating the pore structure and acidic sites via a
Nanocrystalline cellulose template " are reported using nano-cellulose and directly to be synthesized multistage as hard template
Hole HZSM-5.The mesoporous pore volumes of multi-stage porous HZSM-5 being synthesized in this way are up to 0.9ml/g, and mesoporous pore size distribution is main
In 9.5nm or so.Domestic patent CN104445261A also synthesizes multi-stage porous ZSM-5 by the use of cellulose as hard template.Mesoporous pore size
It is distributed in 4-10 nm.
Patent CN103484142A reports biomass and is total to the method that catalytic pyrolysis prepares aromatic hydrocarbons with plastics.With this side
Method prepares aromatic hydrocarbons, and aromatics yield is more taller than the aromatic hydrocarbons that simple biomass and simple plastics catalytic pyrolysis generate.Patent
CN105195066A prepares aromatic hydrocarbons using fluid unit, can effectively convert biomass, efficient to prepare biological aromatic hydrocarbons.
The problems such as aromatics yield is not high, and the mesoporous quantity of molecular sieve is few, and pore-size distribution is bad exists in the prior art above, this
Invention uses brand-new synthetic method, and the level hole ZSM-5 synthesized, mesoporous quantity is more, and with preferable mesoporous pore size point
Cloth, while the more conventional molecular sieve of aromatics yield improves a lot.
The content of the invention
Few to solve the mesoporous number of HZSM-5 molecular sieve catalysts in the prior art, mesoporous pore size distribution is not concentrated, fiber
The problem of plain catalytic pyrolysis aromatics yield is low, the present invention intend providing the catalyst that a kind of biomass catalyzing cracking prepares aromatic hydrocarbons,
Its mesoporous quantity is more, and concentration is compared in mesoporous pore size distribution, and cellulose catalytic thermal cracking aromatics yield is high.
To realize above-mentioned technical purpose, first aspect present invention provides a kind of preparation side of level HZSM-5 catalyst
Method comprises the following steps：
The first step, by organic formwork agent, silicon source, water, hard mould agent according to mass ratio be 1 ~ 6：0.1~1.0：50~150：0.1~
1.0 mixing, stirring form mixed liquor, and gaseous state ethyl orthosilicate is passed through into above-mentioned mixed liquor, and temperature is 170 ~ 250 DEG C, is led to
The angle of incidence is 1 ~ 12h；
Second step, the liquid agitation after first step reaction, stands aging, is transferred in autoclave, closed in 120 ~ 200 DEG C
Reaction 1 ~ 8 day；Solid product washing after reaction, dry, roasting；
The product of second step is placed in 50 ~ 90 DEG C, the NH of 0.1 ~ 2.0mol/L by the 3rd step48 ~ 12h is impregnated in Cl solution, is washed,
It is dry, repeat it is above impregnate, washing, dry process 2 ~ 4 times, roasting.
The technical purpose of second aspect of the present invention is to provide the level HZSM-5 catalyst prepared by above method.
Level HZSM-5 catalyst prepared by the invention described above, silica alumina ratio are 25 ~ 40：1, it is preferably 28 ~ 36：1, ratio
Surface area is 350 ~ 450m2/ g, pore volume are 0.25 ~ 0.40cm3/ g, intermediary hole pore volume account for 50 ~ 80%.
The technical purpose of third aspect present invention is to provide a kind of method that aromatic hydrocarbons is prepared by catalytically cracking biomass, with above-mentioned layer
Grade HZSM-5 catalyst and biomass haptoreaction.
During the present invention prepares level HZSM-5 catalyst process, silicon source is passed through with gaseous form in reaction system, it can be with
By controlling the condition that is passed through of silicon source gas phase, increase the contact area of silicon source and silicon source, strengthen heterogeneous mass transfer, improve silicon source and exist
Dissolution degree in reaction solution makes more silicon participate in reaction, changes molecular sieve silica alumina ratio, so as to regulate and control catalytic activity；In addition
The mesoporous quantity of level HZSM-5 catalyst prepared by method using the present invention is more, and pore-size distribution is good, biomass catalyzing hot tearing
Solution aromatics yield improves a lot.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
3 width of attached drawing of the present invention,
The transmission electron microscope picture of level HZSM-5 catalyst C1 prepared by Fig. 1 embodiments 1；
The nitrogen adsorption isotherm of level HZSM-5 catalyst C1 prepared by Fig. 2 embodiments 1；
Level HZSM-5 catalyst C1BJH mesoporous pore size distribution maps prepared by Fig. 3 embodiments 1.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
First aspect present invention provides a kind of preparation method of level HZSM-5 catalyst, comprises the following steps：
The first step, by organic formwork agent, silicon source, water, hard mould agent according to mass ratio be 1 ~ 6：0.1~1.0：50~150：0.1~
1.0 mixing, stirring form mixed liquor, and gaseous state ethyl orthosilicate is passed through into above-mentioned mixed liquor, and temperature is 170 ~ 250 DEG C, is led to
The angle of incidence is 1 ~ 12h；
Second step, the liquid agitation after first step reaction, stands aging, is transferred in autoclave, closed in 120 ~ 200 DEG C
Reaction 1 ~ 8 day；Solid product washing after reaction, dry, roasting；
The product of second step is placed in 50 ~ 90 DEG C, the NH of 0.1 ~ 2.0mol/L by the 3rd step48 ~ 12h is impregnated in Cl solution, is washed,
It is dry, repeat it is above impregnate, washing, dry process 2 ~ 4 times, roasting.
In above-mentioned preparation method, the flow velocity for the gaseous state ethyl orthosilicate being passed through in the first step is 100 ~ 400mL/min, excellent
Elect 150 ~ 300mL/min as, more preferably 180 ~ 250mL/min；Temperature is preferably 190 ~ 220 DEG C；Be passed through the time be preferably 5 ~
7h.With N2Or inert gas is passed through for carrier gas, the flow velocity of carrier gas is 100 ~ 400mL/min.
In above-mentioned preparation method, stirred after organic formwork agent described in the first step, silicon source, water, hard mould agent mixing mixed
1 ~ 6h is closed, is 3 ~ 6 preferably according to mass ratio：0.3~0.6：80~120：0.5 ~ 1.0 mixing, wherein by aluminium element in mixed solution
Gauge, concentration be 0.03 ~ 0.06mol/L.
In above-mentioned preparation method, organic formwork agent described in the first step be selected from tetrapropylammonium hydroxide, 4 third ammonium bromides,
One kind in diethylamine, wherein preferably tetrapropylammonium hydroxide；Source of aluminium in sodium metaaluminate and aluminium isopropoxide one
Kind, wherein preferably sodium metaaluminate；The hard mould agent is selected from nano-cellulose, general fibre element, carbon nanotubes, carbon Nanowire
At least one of dimension, wherein preferably nano-cellulose.
In above-mentioned preparation method, time for being stirred described in second step is 1 ~ 4h, stand the time of aging for 3 ~ for 24 hours.
In above-mentioned preparation method, dry temperature described in second step is 80 ~ 150 DEG C, and the time is 8 ~ 12h；The roasting
The temperature of burning is 400 ~ 600 DEG C, and the time is 2 ~ 6h.
In above-mentioned preparation method, solid product is placed in NH in the 3rd step4It impregnates, wash in Cl solution, dry mistake
Journey preferred operations 3 times.
In above-mentioned preparation method, the temperature roasted described in the 3rd step is 400 ~ 600 DEG C, and the time is 2 ~ 6h.
The technical purpose of second aspect of the present invention is to provide the level HZSM-5 catalyst prepared by above method.
Level HZSM-5 catalyst prepared by the invention described above, silica alumina ratio are 25 ~ 40：1, it is preferably 28 ~ 36：1, ratio
Surface area is 350 ~ 450m2/ g, pore volume are 0.25 ~ 0.40cm3/ g, intermediary hole pore volume account for 50 ~ 80%.
The technical purpose of third aspect present invention is to provide a kind of method that aromatic hydrocarbons is prepared by catalytically cracking biomass, with above-mentioned layer
Grade HZSM-5 catalyst and biomass haptoreaction.
In the method for aromatic hydrocarbons is prepared by catalytically cracking biomass above, the catalyst is according to mass ratio with biomass
10~25：1 hybrid junction touches, and is reacted at 400 ~ 700 DEG C.
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.In following embodiment and comparative example, unless otherwise instructed, raw material used can be obtained by commercially available
.
Embodiment 1
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.3g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 200 DEG C, TEOS gas
The flow velocity of body is 200mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C1.
Fig. 1 is the transmission electron microscope picture of catalyst C1, and can be seen that in Fig. 1 has many small ZSM-5 crystal to reunite together,
The zeolite catalyst for having intergranular mesoporous formed.Fig. 2 is the nitrogen adsorption isotherm of catalyst C1, be can see in Fig. 2 bright
Aobvious hysteresis loop illustrates there are a large amount of mesoporous presence.Fig. 3 is the BJH mesoporous pore size distribution maps of catalyst C1, can from figure
Go out, there is preferable distribution in aperture in 4~10nm in catalyst C1.
The silica alumina ratio of catalyst C1 is 31.3, specific surface area 415m2/ g, total pore volume 0.46cm3/ g, mesoporous pore volume are
0.36cm3/ g, Micropore volume 0.10cm3/g。
By catalyst C1 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 600 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 45.8%.
Embodiment 2
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.3g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 180 DEG C, TEOS gas
The flow velocity of body is 200mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C2.
By catalyst C2 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 700 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 45.5%.
Embodiment 3
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.3g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 200 DEG C, TEOS gas
The flow velocity of body is 200mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C3.
By catalyst C3 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 400 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 41.1%.
Embodiment 4
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.3g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 220 DEG C, TEOS gas
The flow velocity of body is 100mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C4.
The silica alumina ratio of catalyst C4 is 25.7, specific surface area 358m2/ g, total pore volume 0.34cm3/ g, mesoporous pore volume are
0.21cm3/ g, Micropore volume 0.11cm3/g。
By catalyst C4 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 600 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 44.6%.
Embodiment 5
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.3g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 200 DEG C, TEOS gas
The flow velocity of body is 300mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C5.
The silica alumina ratio of catalyst C5 is 35.1, specific surface area 403m2/ g, total pore volume 0.38cm3/ g, mesoporous pore volume are
0.26cm3/ g, Micropore volume 0.09cm3/g。
By catalyst C5 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 600 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 40.6%.
Embodiment 6
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.2g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 240 DEG C, TEOS gas
The flow velocity of body is 200mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C6.
The silica alumina ratio of catalyst C6 is 36.8, specific surface area 388m2/ g, total pore volume 0.39cm3/ g, mesoporous pore volume are
0.26cm3/ g, Micropore volume 0.11cm3/g。
By catalyst C6 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 600 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 41.3%.
Embodiment 7
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.1g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 200 DEG C, TEOS gas
The flow velocity of body is 200mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C7.
The silica alumina ratio of catalyst C7 is 39.7, specific surface area 407m2/ g, total pore volume 0.36cm3/ g, mesoporous pore volume are
0.23cm3/ g, Micropore volume 0.11cm3/g。
By catalyst C7 and cellulose according to mass ratio 20:1 ratio ground and mixed is uniform, is catalyzed at 600 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 39.6%.
Embodiment 8
（1）Magnetic force at room temperature after 10g tetrapropylammonium hydroxide, 27g water, 0.3g sodium metaaluminates, 0.3g nano-celluloses are mixed
3h is stirred, mixed liquor is formed, TEOS vapor is passed through thereto, with N2For carrier, the temperature of TEOS vapor is 200 DEG C, TEOS gas
The flow velocity of body is 200mL/min, N2Flow velocity is 200mL/min, is passed through the time as 6h；
（2）It will（1）Liquid agitation after reaction stands aging 12h, is transferred in autoclave in 170 DEG C of crystallization 5 days, instead
Solid product washing after answering, dry, 550 DEG C of roasting 10h；
（3）It will（2）Obtained solid product is placed in 80 DEG C, the NH of 1.0mol/L48h in Cl solution carries out ion exchange, filter,
Washing, drying, repeat above procedure twice, and 550 DEG C of roasting 6h obtain level HZSM-5 catalyst C8.
By catalyst C8 and cellulose according to mass ratio 10:1 ratio ground and mixed is uniform, is catalyzed at 600 DEG C
Cracking reaction is done cellulose catalytic thermal cracking with Py-GCMS and is analyzed, aromatics yield 38.1%.
Comparative example
The silica alumina ratio that Catalyst Factory, Nankai Univ is bought（SiO2/Al2O3）For 38 ZSM-5 catalyst and cellulose according to matter
Measure ratio 20:1 ratio ground and mixed is uniform, and catalytic cracking reaction is carried out at 600 DEG C, and cellulose catalytic heat is done with Py-GCMS
Cracking analysis, aromatics yield 33.6%.
Claims (11)
1. a kind of preparation method of level HZSM-5 catalyst, comprises the following steps：
The first step, by organic formwork agent, silicon source, water, hard mould agent according to mass ratio be 1 ~ 6：0.1~1.0：50~150：0.1~
1.0 mixing, stirring form mixed liquor, and gaseous state ethyl orthosilicate is passed through into above-mentioned mixed liquor, and temperature is 170 ~ 250 DEG C, is led to
The angle of incidence is 1 ~ 12h；
Second step, the liquid agitation after first step reaction, stands aging, is transferred in autoclave, closed in 120 ~ 200 DEG C
Reaction 1 ~ 8 day；Solid product washing after reaction, dry, roasting；
The product of second step is placed in 50 ~ 90 DEG C, the NH of 0.1 ~ 2.0mol/L by the 3rd step48 ~ 12h is impregnated in Cl solution, is washed,
It is dry, repeat it is above impregnate, washing, dry process 2 ~ 4 times, roasting.
2. preparation method according to claim 1, which is characterized in that gaseous state ethyl orthosilicate described in the first step was passed through
Flow velocity is 100 ~ 400mL/min, is preferably 150 ~ 300mL/min, more preferably 180 ~ 250mL/min.
3. preparation method according to claim 1, which is characterized in that the temperature for the gaseous state ethyl orthosilicate being passed through in the first step
It spends for 190 ~ 220 DEG C, the time is 5 ~ 7h.
4. preparation method according to claim 1, which is characterized in that organic formwork agent described in the first step, silicon source, water,
Hard mould agent is 3 ~ 6 according to mass ratio：0.3~0.6：80~120：0.5 ~ 1.0 mixing, wherein the amount by aluminium element in mixed solution
Meter, concentration are 0.03 ~ 0.06mol/L.
5. preparation method according to claim 1, which is characterized in that organic formwork agent described in the first step is selected from tetrapropyl
One kind in ammonium hydroxide, 4 third ammonium bromides, diethylamine；The one kind of source of aluminium in sodium metaaluminate and aluminium isopropoxide；Institute
It states hard mould agent and is selected from least one of nano-cellulose, general fibre element, carbon nanotubes, carbon nano-fiber.
6. preparation method according to claim 5, which is characterized in that the organic formwork agent is tetrapropylammonium hydroxide,
Source of aluminium is sodium metaaluminate；The hard mould agent is nano-cellulose.
7. preparation method according to claim 1, which is characterized in that the time stirred described in second step is 1 ~ 4h, quiet
Put time of aging for 3 ~ for 24 hours.
8. preparation method according to claim 1, which is characterized in that dry temperature described in second step is 80 ~ 150
DEG C, the time is 8 ~ 12h；The temperature of the roasting is 400 ~ 600 DEG C, and the time is 2 ~ 6h.
9. level HZSM-5 catalyst prepared by the preparation method described in claim 1 ~ 8 any one.
10. the method for aromatic hydrocarbons is prepared by catalytically cracking biomass, which is characterized in that with the catalyst described in claim 9 and life
Substance haptoreaction.
11. according to the method described in claim 10, it is characterized in that, the catalyst and biomass according to mass ratio for 10 ~
25：1 is mixed, and is reacted at 400 ~ 700 DEG C.
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| CN102125866A (en) * | 2010-12-16 | 2011-07-20 | 神华集团有限责任公司 | H-ZSM-5 zeolite catalyst for preparing propylene from methanol and application thereof |
| CN103480411A (en) * | 2013-09-28 | 2014-01-01 | 复旦大学 | Molecular sieve catalyst containing mesoporous ZSM-5 and preparation method and application of molecular sieve catalyst |
| CN104437602A (en) * | 2014-12-16 | 2015-03-25 | 湖南科技大学 | Multistage meso-porous ZSM-5 catalyst as well as preparation method and application method thereof |
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| CN102125866A (en) * | 2010-12-16 | 2011-07-20 | 神华集团有限责任公司 | H-ZSM-5 zeolite catalyst for preparing propylene from methanol and application thereof |
| CN103480411A (en) * | 2013-09-28 | 2014-01-01 | 复旦大学 | Molecular sieve catalyst containing mesoporous ZSM-5 and preparation method and application of molecular sieve catalyst |
| CN104437602A (en) * | 2014-12-16 | 2015-03-25 | 湖南科技大学 | Multistage meso-porous ZSM-5 catalyst as well as preparation method and application method thereof |
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| CN110252391A (en) * | 2019-07-02 | 2019-09-20 | 中国天辰工程有限公司 | A kind of preparation method and application of catalyst |
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