CN107188195A - A kind of preparation method and application of the molecular sieves of multi-stage porous HZSM 5 - Google Patents
A kind of preparation method and application of the molecular sieves of multi-stage porous HZSM 5 Download PDFInfo
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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 method and application of the molecular sieves of multi-stage porous HZSM 5, comprise the following steps：1) silicon source is dissolved in water, and adds TPAOH solution, then added silicon source, be mixed to get molecular sieve precursor；2) molecular sieve precursor is subjected to pre- crystallization；3) sucrose mixing is added into the molecular sieve precursor Jing Guo pre- crystallization, hydrothermal crystallizing reaction is carried out；4) separating, washing, drying, with after roasting, obtains the molecular sieves of multi-stage porous ZSM 5 after the completion of crystallization；5) molecular sieves of multi-stage porous ZSM 5 are carried out after ion exchange, separating, washing, drying and roasting with ammonium salt solution, obtain the molecular sieves of multi-stage porous HZSM 5.The molecular sieves of multi-stage porous HZSM 5 obtained by the preparation method can improve its aromatizing capacity and anti-coking performance during catalytic pyrolysis of biomass.
Description
Technical field
The invention belongs to biomass energy utilization technologies field, and in particular to a kind of preparation side of multi-stage porous HZSM-5 molecular sieves
Method and application.
Background technology
The production of aromatic hydrocarbons relies primarily on petroleum resources both at home and abroad at present, by adding under conditions of catalyst and HTHP
The processes such as hydrogen, reformation, aromatic hydrocarbons conversion, separation obtain benzene,toluene,xylene, complex process, and discharge large quantity of exhaust gas, pollute ring
Border.With the increasingly growth of the increasingly deficient and aromatic hydrocarbons market demand of fossil resource, traditional Petroleum Production aromatic hydrocarbons route
It is faced with formidable challenges, exploitation green, the Aromatics Production Technology of environment-friendly type gradually draw attention.
Biomass source is extensive and renewable, and the annual biomass reserves of China are up to 5,000,000,000 tons or so according to statistics, but
The biological quality that China consumes every year only accounts for the 25% of its reserves, utilizes it as waste bio-fuel and high level chemicals
Turn into the emphasis and focus studied at present.
The exploitation of biomass aromatic hydrocarbons technology, can not only reduce dependence of the aromatics production to fossil resource, additionally it is possible to big
Amplitude reduces CO2And the discharge of pernicious gas.Aromatic hydrocarbons (including benzene,toluene,xylene etc.) is important basic organic, profit
A plurality of product chain can be derived with aromatic compound, is widely used in and prepares synthetic rubber, synthetic resin, synthetic fibers, fuel, doctor
The fields such as medicine, agricultural chemicals and fine chemicals.
Catalytic pyrolysis of biomass is a kind of efficient biomass switch technology, be using biomass as initiation material, high temperature,
In the presence of catalyst, by the series reactions such as dehydration, decarboxylation, decarbonylation, aromatisation and polymerization, generation benzene, toluene, diformazan
The products such as benzene, naphthalene, alkene, are the preferable biomass aromatics production technique of current development prospect.HZSM-5 molecular sieve catalysts
Because it has more regular and suitable pore passage structure, stronger acid and higher heat endurance, in the catalytic thermal of biomass
There is preferably aromatics yield and selectivity in solution.
For catalysis pyrolytic reaction, the yield for how improving aromatic hydrocarbons and the generation for reducing coke are to improve the technology
Key.The properties such as pore passage structure, Acidity and the distribution of HZSM-5 molecular sieves all can produce very big shadow to its catalytic performance
Ring.But existing HZSM-5 molecular sieves can produce many macromolecular substances during for catalytic pyrolysis of biomass, big point
Sub- material is difficult to enter less micropore canals, it is suppressed that the mass transfer of macromolecule reactant and product, causes in catalyst activity
The carbon distribution coking of the heart so that aromatics yield is reduced.
The content 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 preparation side of multi-stage porous HZSM-5 molecular sieves
Method and application, to improve its aromatizing capacity and anti-coking performance during catalytic pyrolysis of biomass.
Technical scheme provided by the present invention is：
A kind of preparation method of multi-stage porous HZSM-5 molecular sieves, comprises the following steps：
1) silicon source is dissolved in water, and adds TPAOH solution, then added silicon source, be mixed to get before molecular sieve
Drive body；
2) molecular sieve precursor is subjected to pre- crystallization；
3) sucrose mixing is added into the molecular sieve precursor Jing Guo pre- crystallization, hydrothermal crystallizing reaction is carried out；
4) separating, washing, drying, with after roasting, obtains multi-stage porous ZSM-5 molecular sieve after the completion of crystallization；
5) multi-stage porous ZSM-5 molecular sieve is carried out after ion exchange, separating, washing, drying and roasting with ammonium salt solution, is obtained
To multi-stage porous HZSM-5 molecular sieves.
In above-mentioned technical proposal, molecular sieve precursor passes through pre- crystallization, it is possible to reduce the size of zeolite crystal, molecular sieve
The reduction of crystallite dimension can bring molecular sieve specific surface area, the increase of external surface area and the shortening of diffusion path, then improve and divide
The carbon accumulation resisting ability of son sieve and the diffusion rate of reactant.
Secondly, sucrose is introduced in hydrothermal crystallizing reaction, sucrose introduces meso-hole structure as mesoporous template so that
Multi-stage porous HZSM-5 molecular sieves have unique pore passage structure, on the basis of a large amount of microcellular structures are retained, also with a certain amount of
Meso-hole structure, make what it had micropore concurrently to select type selectivity and highly acid, and mesoporous to the preferable mass transfer performances of macromolecular substances
Energy.The macromolecular substances produced during catalytic pyrolysis of biomass can enter the meso-hole structure of molecular sieve, promote macromolecular anti-
The rapid conversion of thing and product is answered, the generation of coke is reduced, effectively reduces the adverse effect that micropore diffusional resistance is brought to mass transfer.
In addition, the crystal structure for adding not saboteur's sieve itself of sucrose.
It is preferred that, the step 1) in silicon source be sodium metaaluminate, aluminium isopropoxide or aluminum sulfate octadecahydrate；The silicon source is just
Tetraethyl orthosilicate or Ludox.
It is preferred that, the step 1) in silicon source, silicon source, the mol ratio of TPAOH and water be 0.01~0.1:1:
0.2~0.5:20~50, wherein silicon source is with Al2O3Meter, silicon source are with SiO2Meter.More preferably 0.02~0.05:1:0.2~
0.3:20~30.
It is preferred that, the step 2) in pre- crystallization condition be 60~120 DEG C, 1~24h.
It is preferred that, the step 3) in sucrose and silicon source mol ratio be 0.075~0.3:1, wherein sucrose is in terms of C, silicon
Source is in terms of Si.More preferably 0.15:1.
It is preferred that, the step 3) in crystallization condition be 150~180 DEG C, 24~120h.
It is preferred that, the step 4) in roasting condition be 500~600 DEG C, 4~6h.
It is preferred that, the step 5) in ammonium salt solution be ammonium chloride solution；The molar concentration of the ammonium chloride solution is 0.5
~1mol/l, multi-stage porous ZSM-5 molecular sieve is with ammonium salt solution according to 1g：50~100ml ratio mixing, in 60~100 DEG C of temperature
6~12h of the lower ion exchange of degree.
It is preferred that, the step 5) intermediate ion exchange repeat 2~5 times, more preferably 3 times.
It is preferred that, the step 5) in roasting condition be 500~600 DEG C, 4~6h.
The present invention also provides a kind of application of multi-stage porous HZSM-5 molecular sieves in catalytic pyrolysis of biomass prepares aromatic hydrocarbons, institute
State the preparation method preparation method described above of multi-stage porous HZSM-5 molecular sieves.
It is preferred that, multi-stage porous HZSM-5 molecular sieves are mixed with biomass, in pyrolysis-gas chromatography-mass spectrography device
(Py-GC-MS) in, 400~700 DEG C of progress catalysis pyrolysis under inert gas shielding.Further preferably, the pyrolysis reaction temperature
For 600 DEG C.
It is preferred that, the biomass is cellulose, lignin, corncob and rice straw.
It is preferred that, the mass ratio of the multi-stage porous HZSM-5 molecular sieves and biomass is 1~30:1；More preferably
20:1。
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) mesoporous template is used as using sucrose in the present invention so that multi-stage porous HZSM-5 molecular sieves have unique hole
Road structure, on the basis of a large amount of microcellular structures are retained, also with a certain amount of meso-hole structure, selects its type of selecting for having micropore concurrently
Selecting property and highly acid, and it is mesoporous to the preferable mass-transfer performance of macromolecular substances.
(2) by controlling the addition of raw material in building-up process, silica alumina ratio, pre- crystallization condition and crystallization in the present invention
Condition etc., reaches the effect of crystallinity, pore passage structure and the acid properties of Effective Regulation molecular sieve；Keep molecular sieve crystallinity
Height, defect is few, Stability Analysis of Structures, acid strong, and aromatics yield is greatly improved, coke generation is reduced.
(3) the multi-stage porous HZSM-5 molecular sieves that the present invention is provided are used for catalyst, it is fine when reaction temperature is 600 DEG C
The optimal aromatics yield of dimension element catalysis pyrolysis reaches 39.6%, and minimum coke yield is 25.1%, with common ZSM-5 molecular sieve
Compare, aromatics yield improves 22.2%, and coke yield reduces 25.3%.
Brief description of the drawings
Fig. 1 is the XRD of catalyst prepared by embodiment 1,2 and comparative example 1,3；
Fig. 2 is the N of catalyst prepared by embodiment 1,2 and comparative example 1,32Adsorption-desorption curve map；
Fig. 3 is the graph of pore diameter distribution of catalyst prepared by embodiment 1,2 and comparative example 1,3；
Fig. 4 is the SEM figures of catalyst prepared by embodiment 1,2 and comparative example 1,3；
Fig. 5 is the TEM figures of catalyst prepared by embodiment 1,2 and comparative example 1,3；
Fig. 6 is the NH of catalyst prepared by embodiment 1,2 and comparative example 1,33- TPD schemes.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Pyrolysis-gas chromatography-mass spectrography device (Py-GC-MS) used in the present invention is by Japanese Frontier
The micro fixed-bed reactor (Rx-3050TR) of Laboratories companies production and U.S. Agilent Technologies are public
Gas chromatography-mass spectrum (GC-7890B/MS-5977A) combined apparatus composition of department's production, reaction carrier gas is helium.
Embodiment 1
1st, catalyst preparation：
0.18g sodium metaaluminates, 4.88g TPAOHs (25% aqueous solution) are dissolved in 13.5g water, are then added dropwise
Molecular sieve precursor is hybridly prepared under 6.25g tetraethyl orthosilicates, normal temperature, and stirs 3h, is then stirred under conditions of 90 DEG C
Pre- crystallization 24h under conditions of backflow, then adds 0.13g sucrose, continues to stir 4h, then the mixed liquor of gained is transferred to poly-
In the stainless steel cauldron of tetrafluoroethene liner, seal, after crystallization terminates, reactant mixture is entered by hydrothermal crystallizing 3d at 170 DEG C
Row separation of solid and liquid, and be washed with deionized fully, by the solid isolated in 110 DEG C of dry 12h, finally in Muffle furnace
6h is calcined in 550 DEG C, multi-stage porous ZSM-5 molecular sieve is obtained.
According to 1g sieve samples：The proportioning of 50ml 1mol/l ammonium chloride solution, weighs above-mentioned multi-stage porous ZSM-5
Molecular sieve is added in ammonium chloride solution, stirring 8h progress ion exchanges under the conditions of 80 DEG C, filtration washing, 110 DEG C of dry 12h,
So it is repeated 3 times, is finally calcined 5h in 550 DEG C in Muffle furnace, obtains multi-stage porous HZSM-5 molecular sieves, be designated as HZ (C/Si=
0.15)。
2nd, catalytic pyrolysis of biomass：
The multi-stage porous HZSM-5 molecular sieve catalysts of above-mentioned preparation are well mixed with cellulose, catalyst amount and raw material
The ratio of consumption is 20:1.In pyrolysis-gas chromatography-mass spectrography device (Py-GC-MS), reaction carrier gas is helium, reaction
Temperature is that 600 DEG C of progress catalysis pyrolysis prepare aromatic hydrocarbons, and yield is calculated in the carbon molar yield mode of product, and aromatics yield is
39.6%, coke yield is 25.1%.
Embodiment 2
With reference to embodiment 1, the addition for only changing sucrose is 0.26g, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (C/Si=0.3).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 38.9%, coke
Yield is 27.2%.
Embodiment 3
With reference to embodiment 1, the amount for only changing sodium metaaluminate is 0.12g, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (SiO2/Al2O3=20).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 34.8%, coke
Yield is 30.2%.
Embodiment 4
With reference to embodiment 1, the amount for only changing sodium metaaluminate is 0.3g, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (SiO2/Al2O3=50).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 36.7%, coke
Yield is 29.5%.
Embodiment 5
With reference to embodiment 1, only change pre- crystallization temperature for 60 DEG C, other conditions are constant, obtain multi-stage porous HZSM-5 molecules
Sieve, is designated as HZ (pre- 60 DEG C of crystallization).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 34.7%, coke
Yield is 30.1%.
Embodiment 6
With reference to embodiment 1, only change pre- crystallization temperature for 120 DEG C, other conditions are constant, obtain multi-stage porous HZSM-5 molecules
Sieve, is designated as HZ (pre- 120 DEG C of crystallization).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 37.7%, coke
Yield is 28.3%.
Embodiment 7
With reference to embodiment 1, only change pre- crystallization time for 12h, other conditions are constant, obtain multi-stage porous HZSM-5 molecules
Sieve, is designated as HZ (pre- crystallization 12h).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 37.1%, coke
Yield is 29.5%.
Embodiment 8
With reference to embodiment 1, only change pre- crystallization time for 16h, other conditions are constant, obtain multi-stage porous HZSM-5 molecules
Sieve, is designated as HZ (pre- crystallization 16h).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 38.9%, coke
Yield is 27.8%.
Embodiment 9
With reference to embodiment 1, it is 1d only to change the hydrothermal crystallizing time, and other conditions are constant, obtain multi-stage porous HZSM-5 molecules
Sieve, is designated as HZ (crystallization 1d).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 34.5%, coke
Yield is 31.1%.
Embodiment 10
With reference to embodiment 1, it is 2d only to change the hydrothermal crystallizing time, and other conditions are constant, obtain multi-stage porous HZSM-5 molecules
Sieve, is designated as HZ (crystallization 2d).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 37.4%, coke
Yield is 29.2%.
Embodiment 11
With reference to embodiment 1, it is 150 DEG C only to change hydrothermal crystallizing temperature, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (150 DEG C of crystallization).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 34.2%, coke
Yield is 31.3%.
Embodiment 12
With reference to embodiment 1, it is 160 DEG C only to change hydrothermal crystallizing temperature, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (160 DEG C of crystallization).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 38.3%, coke
Yield is 27.8%.
Embodiment 13
With reference to embodiment 1, it is 180 DEG C only to change hydrothermal crystallizing temperature, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (180 DEG C of crystallization).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytic cracking celluloses manufactured in the present embodiment is 37.1%, coke
Yield is 29.6%.
Embodiment 14
With reference to embodiment 1, the species for only changing silicon source is aluminium isopropoxide 0.44g, and other conditions are constant, obtain multi-stage porous
HZSM-5 molecular sieves, are designated as HZ (aluminium isopropoxide).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 37.9%, coke
Yield is 28.4%.
Embodiment 15
With reference to embodiment 1, the species for only changing silicon source is aluminum sulfate octadecahydrate 0.73g, and other conditions are constant, obtain multistage
Hole HZSM-5 molecular sieves, are designated as HZ (aluminum sulfate octadecahydrate).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose manufactured in the present embodiment is 34.1%, coke
Yield is 32.9%.
Comparative example 1
1st, the preparation of common HZSM-5 molecular sieves：
0.16g sodium metaaluminates, 4.88g TPAOHs (25% aqueous solution) are dissolved in 13.5g water, are then added dropwise
Molecular sieve precursor is hybridly prepared under 6.25g tetraethyl orthosilicates, normal temperature, and stirs 3h, then precursor water solution is transferred to
In stainless steel cauldron with polytetrafluoroethyllining lining, seal, hydrothermal crystallizing 5d at 170 DEG C, it is after crystallization terminates, reaction is mixed
Compound carries out separation of solid and liquid, and is washed with deionized fully, by the solid isolated in 110 DEG C of dry 12h, finally in Muffle
6h is calcined in 550 DEG C in stove, ZSM-5 molecular sieve is obtained.
According to 1g sieve samples：The proportioning of 50ml 1mol/l ammonium chloride solution, weighs above-mentioned ZSM-5 molecular sieve
It is added in ammonium chloride solution, 8h is stirred under the conditions of 80 DEG C and carries out ion exchange, filtration washing, so 110 DEG C of dry 12h, weight
It is multiple 3 times, 5h finally is calcined in 550 DEG C in Muffle furnace, common HZSM-5 molecular sieves is obtained, is designated as HZ-Con.
2nd, catalytic pyrolysis of biomass：
The common HZSM-5 molecular sieves of above-mentioned preparation are well mixed with cellulose, the ratio of catalyst amount and raw material dosage
Example is 20:1.In pyrolysis-gas chromatography-mass spectrography device (Py-GC-MS), reaction carrier gas is helium, and reaction temperature is
600 DEG C carry out catalysis pyrolysis and prepare aromatic hydrocarbons, and yield is calculated in the carbon molar yield mode of product, and aromatics yield is
32.4%, coke yield is 33.6%.
Comparative example 2
With reference to embodiment 1, only change pre- crystallization time for 0h, other conditions are constant, obtain multi-stage porous HZSM-5 molecular sieves,
It is designated as HZ (pre- crystallization 0h).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose prepared by this comparative example is 33.2%, coke
Yield is 32.8%.
Comparative example 3
With reference to embodiment 1, the addition for only changing sucrose is 0.51g, and other conditions are constant, obtains HZSM-5 points of multi-stage porous
Son sieve, is designated as HZ (C/Si=0.6).
The aromatics yield of multi-stage porous HZSM-5 molecular sieve catalytics pyrolysis cellulose prepared by this comparative example is 30.5%, coke
Yield is 37.3%.The reason for aromatics yield is reduced is：The addition of excessive sucrose introduces substantial amounts of mesoporous in molecular sieve
Structure, destroys the microcellular structure of molecular sieve in itself, its crystallinity and acid amount is significantly declined, and produce molecular sieve surface
More unformed material, hinders reactant to contact the activated centre of molecular sieve.
Catalyst characterization
1st, XRD signs are carried out to catalyst prepared by embodiment 1,2 and comparative example 1,3 respectively, as shown in figure 1, embodiment
1st, 2 and the multi-stage porous HZSM-5 sieve samples that prepare of comparative example 3 there is typical MFI type topological structure, and without substantially miscellaneous
The appearance of diffraction maximum, illustrates the crystal structure for adding not saboteur's sieve itself of sucrose, but the addition of excessive sucrose causes
The characteristic diffraction peak remitted its fury of molecular sieve, makes the reduction of its crystallinity.
2nd, N is carried out to catalyst prepared by embodiment 1,2 and comparative example 1,3 respectively2Adsorption-desorption is characterized, such as Fig. 2 institutes
Show, the multi-stage porous HZSM-5 sieve samples of preparation show the feature of I types and IV types, are occurred in that at higher relative pressure
Stagnant ring is significantly returned, shows to generate certain meso-hole structure.
HZ (C/Si=0.6) has highest adsorbance, occurs an obvious H3 type between P/P0=0.6~1.0
Stagnant ring is returned, from graph of pore diameter distribution (Fig. 3) it can be seen that its mesoporous pore size concentrates on 10nm or so.
The pore passage structure parameter of specific catalyst is relatively shown in Table 1, and multi-stage porous HZSM-5 molecular sieves have bigger ratio surface
Product and pore volume.With the reduction of sucrose addition, micropore specific area and Micropore volume then gradually increase, external surface area, Jie
Pore specific surface area and mesoporous pore volume are then gradually decreased.HZ (C/Si=0.6) obtains maximum specific surface area 399.3m2/ g and maximum
Pore volume 0.581cm3/g.Can be with the meso-hole structure of Effective Regulation molecular sieve sample by the addition for changing sucrose.
The parameter of the different catalysts of table 1 compares
3rd, SEM, TEM is carried out to catalyst prepared by embodiment 1,2 and comparative example 1,3 respectively to characterize, as shown in Figures 4 and 5,
Understand that multi-stage porous HZSM-5 molecular sieves have obvious meso-hole structure to generate, and produce substantial amounts of nanometer little crystal grain, these crystal grain it
Between there is obvious intercrystalline pore, this is conducive to the mass transfer of macromolecular substances in pyrolytic reaction.
4th, NH is carried out to catalyst prepared by embodiment 1,2 and comparative example 1,3 respectively3- TPD, as shown in Figure 6, it is known that with
The reduction of sucrose addition, the weak acid amount of molecular sieve gradually increases.HZ (C/Si=0.6) tools prepared by maximum sucrose addition
Substantial amounts of meso-hole structure is introduced, the micropore canals of molecular sieve in itself are destroyed, its weak acid amount and strong acid amount is significantly dropped
It is low, and offset to low temperature direction, illustrate that weak acid intensity and strong acid intensity are equally reduced.HZ (C/Si=0.3) and HZ (C/Si=
0.15) there is stronger acidity.
Claims (10)
1. a kind of preparation method of multi-stage porous HZSM-5 molecular sieves, it is characterised in that comprise the following steps：
1) silicon source is dissolved in water, and adds TPAOH solution, then added silicon source, be mixed to get molecular sieve forerunner
Body；
2) molecular sieve precursor is subjected to pre- crystallization；
3) sucrose mixing is added into the molecular sieve precursor Jing Guo pre- crystallization, hydrothermal crystallizing reaction is carried out；
4) separating, washing, drying, with after roasting, obtains multi-stage porous ZSM-5 molecular sieve after the completion of crystallization；
5) multi-stage porous ZSM-5 molecular sieve is carried out after ion exchange, separating, washing, drying and roasting with ammonium salt solution, obtains many
Level hole HZSM-5 molecular sieves.
2. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 1) in
Silicon source is sodium metaaluminate, aluminium isopropoxide or aluminum sulfate octadecahydrate；The silicon source is tetraethyl orthosilicate or Ludox.
3. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 1) in
Silicon source, silicon source, the mol ratio of TPAOH and water are 0.01~0.1:1:0.2~0.5:20~50, wherein silicon source with
Al2O3Meter, silicon source are with SiO2Meter.
4. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 2) in
The condition of pre- crystallization is 60~120 DEG C, 1~24h.
5. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 3) in
The mol ratio of sucrose and silicon source is 0.075~0.3:1, wherein sucrose in terms of C, silicon source is in terms of Si.
6. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 3) in
The condition of crystallization is 150~180 DEG C, 24~120h.
7. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 4) in
The condition of roasting is 500~600 DEG C, 4~6h.
8. the preparation method of multi-stage porous HZSM-5 molecular sieves according to claim 1, it is characterised in that the step 5) in
Ammonium salt solution is ammonium chloride solution；The molar concentration of the ammonium chloride solution is 0.5~1mol/l, multi-stage porous ZSM-5 molecular sieve
With ammonium salt solution according to 1g：50~100ml ratio mixing, 6~12h of ion exchange at a temperature of 60~100 DEG C.
9. application of a kind of multi-stage porous HZSM-5 molecular sieves in catalytic pyrolysis of biomass prepares aromatic hydrocarbons, it is characterised in that described
Preparation method of the preparation method of multi-stage porous HZSM-5 molecular sieves as described in claim 1~8 is any.
10. application of the multi-stage porous HZSM-5 molecular sieves according to claim 9 in catalytic pyrolysis of biomass prepares aromatic hydrocarbons,
Characterized in that, multi-stage porous HZSM-5 molecular sieves are mixed with biomass, it is lazy in pyrolysis-gas chromatography-mass spectrography device
Property gas shield under 400~700 DEG C progress catalysis pyrolysis.
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