CN103950951A - Method for synthesizing heteroatomic ZSM-5 molecular sieve and application thereof - Google Patents
Method for synthesizing heteroatomic ZSM-5 molecular sieve and application thereof Download PDFInfo
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Abstract
The invention provides a method for synthesizing a heteroatomic ZSM-5 molecular sieve. The method comprises the steps of (a) adding a gallium source and an aluminum source into a templating agent, then adding sodium hydroxide, and then mixing with a silicon source to form a sol-gel system; (2) crystallizing for 48-80 hours; (3) filtering, drying and roasting to remove the organic templating agent; and (4) carrying out ion exchange on molecular sieve powder by using an ammonium hydroxide solution to obtain the hydrogen-type molecular sieve. According to the synthesis method provided by the invention, the molecular sieve, which is synthesized directly from the inexpensive silicon source, gallium source, aluminum source, mineralizer and organic templating agent, is unnecessary to be subjected to subsequent micropore aperture adjustment. The synthesized heteroatomic ZSM-5 molecular sieve belongs to an MFI structure and no heterophase crystal systems appear. Compared with a conventional ZSM-5 molecular sieve, the heteroatomic ZSM-5 molecular sieve synthesized by the method provided by the invention has the advantages that biomass and polyethylene are rapidly pyrolyzed under the catalytic action of the heteroatomic ZSM-5 molecular sieve, the yield of monocyclic aromatic hydrocarbon is not reduced and the selectivity of benzene, toluene and p-xylene in aromatic hydrocarbon is improved by about 80%.
Description
Technical field
The invention belongs to petrochemical industry, be specifically related to a kind of preparation method and application thereof of the molecular sieve for the reaction of catalysis fast pyrogenation.
Background technology
At present, the fossil oil reserves in the whole world sharply reduce, and research emphasis is turned to non-oil circuit combination liquid fuel by people, to alleviate the shortage of crude oil, Sweet natural gas.As utilize catalysis fast pyrolysis technology (Catalytic fast pyrolysis, CFP) technology, biomass or plastic waste are changed into liquid fuel.Lignocellulose biomass or plastic waste are through fast pyrogenation, generate the organic compound of small molecules amount, then further on molecular sieve, there is the reactions such as alkene aromizing, hydrogen transference, alkylation, finally generate the organic chemicals such as aromatic hydrocarbons, low-carbon alkene alkane and charcoal.Test by catalytically active assessment, investigator find ZSM-5 molecular sieve biomass [
1-4] or plastic waste [
5-7] catalytic pyrolysis in demonstrate high aromatics yield, be the molecular sieve catalyst of tool application prospect.ZSM-5 molecular sieve belongs to the MFI zeolite catalyst of high silica alumina ratio, and has good heat-resisting and hydrothermal stability, and strong anti-carbon deposition ability.
But biomass or plastic waste carry out catalytic cracking reaction at ZSM-5 molecular sieve, the aromatic product of high added value as the yield of toluene, p-Xylol and selectivity low.This is due to ZSM-5 molecular sieve aperture bigger (～0.56nm), polyalkylbenzene, indenes, the naphthalene with large-molecular dynamics diameter easily diffuse out from duct, and the economic worth of these organic compound is low and further have influence on the quality of liquid fuel.In order to improve the yield of p-Xylol, investigator adopts many method for subsequent processing regulation and control ZSM-5 molecular sieve aperture conventionally: chemical vapour deposition (CVD), the alkali liquor desiliconization processing etc. of impregnating metal salt, silicon gel.But the shortcoming of above method is subsequent processes complexity, be difficult to accurately control aperture control, easily blocking portion micropore canals reduces catalytic activity.
In addition, patent CN1169953A reacts for aromatization of methanol about silicon gallium MFI Zeolite synthesis, does not improve the selectivity of p-Xylol in product; Patent CN101722033A uses the molecular sieve of multistep crystallization method synthetic kernel shell structure, and Hydrothermal Synthesis process is comparatively complicated.Therefore, select that Direct Hydrothermal method is synthetic, heteroatoms MFI molecular sieve that must not subsequent processes, be directly used in biomass or plastic waste catalyse pyrolysis is prepared toluene, p-Xylol and gaseous olefin, have more application prospect.
Reference:
1.Jae,J.,et?al.,Investigation?into?the?shape?selectivity?of?zeolite?catalysts?for?biomass?conversion.Journal?of?Catalysis,2011.279(2):p.257-268.
2.Jackson,M.A.,D.L.Compton,and?A.A.Boateng,Screening?heterogeneous?catalysts?for?the?pyrolysis?of?lignin.Journal?of?Analytical?and?Applied?Pyrolysis,2009.85(1-2):p.226-230.
3.Rinaldi,R.and?F.Schuth,Design?of?solid?catalysts?for?the?conversion?of?biomass.Energy&Environmental?Science,2009.2(6):p.610-626.
4.Stocker,M.,Biofuels?and?Biomass-To-Liquid?Fuels?in?the?Biorefinery:Catalytic?Conversion?of?Lignocellulosic?Biomass?using?Porous?Materials.Angewandte?Chemie-International?Edition,2008.47(48):p.9200-9211.
5.Takuma,K.,Y.Uemichi,and?A.Ayame,Product?distribution?from?catalytic?degradation?of?polyethylene?over?H-gallosilicate.Applied?Catalysis?a-General,2000.192(2):p.273-280.
6.Marcilla,A.,A.Gómez-Siurana,and?F.J.Valdés,Evolution?of?the?deactivation?mode?and?nature?of?coke?of?HZSM-5and?USY?zeolites?in?the?catalytic?cracking?of?low-density?polyethylene?during?successive?cracking?runs.Applied?Catalysis?A:General,2009.352(1-2):p.152-158.
7.Aguado,J.,D.P.Serrano,and?J.M.Escola,Fuels?from?Waste?Plastics?by?Thermal?and?Catalytic?Processes:A?Review.Industrial&Engineering?Chemistry?Research,2008.47(21):p.7982-7992.
Summary of the invention
For the selectivity of product restricted problem of ZSM-5 molecular sieve in prior art, the object of this invention is to provide a kind of preparation method with the less heteroatoms ZSM-5 molecular sieve in aperture.
Another object of the present invention is to propose the application of described heteroatoms ZSM-5 molecular sieve in catalyse pyrolysis reaction.
For achieving the above object, technical scheme of the present invention is:
A synthetic method for heteroatoms ZSM-5 molecular sieve, comprises step:
(1) taking one or more in tetraethoxy, silicic acid, water glass or silicon sol as silicon source; One or more in Tai-Ace S 150, pseudo-boehmite, aluminum isopropylate or aluminium hydroxide are aluminium source; Taking gallium sulfate or gallium nitrate as gallium source; Taking sodium-chlor or sodium hydroxide as mineralizer; Taking TPAOH (TPAOH) as organic formwork agent;
The proportioning raw materials SiO of synthesis of molecular sieve collosol and gel
2: Al
2o
3: Ga
2o
3: NaOH:TPAOH:H
2o is 25:x:y:1:(3-10): (1000-3000), and x+y=0.5-3, x/y=0-5.
Gallium source, aluminium source are added in template, then add sodium hydroxide, then mix with silicon source, form sol-gel system;
(2) step (1) gained sol gel precursor is tied up to crystallization 48-80 hour at 160-200 DEG C, after crystallization, obtain molecular screen primary powder;
(3) molecular screen primary powder is put into 110 DEG C of oven dry of baking oven after separating, filter, washing, and removes organic formwork agent at 500-600 DEG C of roasting temperature 4-8 hour, obtains molecular sieve powder;
(4) the solution of ammonium hydroxide ion-exchange of 1M 1 hour for molecular sieve powder, repeated exchanged 3 times after filtering, then through 110 DEG C of oven dry of spending the night, obtain Hydrogen heteroatoms ZSM-5 molecular sieve at 500-600 DEG C of roasting temperature 4-8 hour.
In step (1), all convert as oxide compound in the silicon source in raw material, aluminium source, gallium source, and example drops in molar ratio.
Described crystallization can carry out in the popular response equipment of this area, such as homogeneous reactor, reactor etc.
Preferably, x+y=0.625-1.5 in the proportioning raw materials of synthesis of molecular sieve collosol and gel, x/y=0.1-5.
Preferably, in described step (1), gallium source, aluminium source being added to strength of solution is in the template solution of 1-2mol/L, stirs 20-40 minute; Add again sodium hydroxide, stir 20-40 minute; Above-mentioned solution is moved in the aqueous solution in silicon source, continue to stir 100-150 minute, form the sol-gel system of homogeneous.
The aqueous solution in described silicon source can be the aqueous solution containing silica 1 0-50%.
Water in water, the silicon source aqueous solution in template agent removing solution, in proportioning raw materials, remaining water can join in sol-gel system by making the aqueous solution with Huo Lv source, gallium source.
Wherein, in described step (2), after the material after crystallization is taken out, centrifugation goes out molecular screen primary powder, adds deionized water wash, filters 2-5 time.
The roasting of step (3) can be carried out in the roasting apparatus of any routine, for example retort furnace, resistance furnace or roasting kiln.
Preferably, in described step (4), the solution of ammonium hydroxide ion-exchange 1-2 hour of 0.5-3M for molecular sieve powder, repeated exchanged 2-3 time after filtering.Ion-exchange after product need be dried moisture, can at 110 DEG C of temperature, dry 10-20 hour.
Further, step (4) also comprises: by for subsequent use the gained Hydrogen hetero-atom molecular-sieve 40-140 order that sieves.
The heteroatoms ZSM-5 molecular sieve that synthetic method of the present invention obtains.
The application of described heteroatoms ZSM-5 molecular sieve is the application in catalysis fast pyrogenation prepare liquid fuel and liquefied petroleum solid/liquid/gas reactions;
The reaction raw materials of described catalysis fast pyrogenation is lignocellulose and/or plastic waste; Described lignocellulose is generally biomass, includes but not limited to Mierocrystalline cellulose, hemicellulose, stalk, wood chip etc., and described plastic waste is the waste or used plastics that industrial or agricultural and urban life produce, and composition is mainly polyethylene or polypropylene.
Described catalysis fast pyrogenation reaction is used heteroatoms ZSM-5 molecular sieve as catalyzer, and the product of described catalysis fast pyrogenation mainly comprises aromatic hydrocarbons (benzene, toluene, p-Xylol) and liquefied petroleum gas (LPG).
Further, the reaction of described catalysis fast pyrogenation is carried out in a reactor.
Beneficial effect of the present invention is:
(1) heteroatoms ZSM-5 molecular sieve adopts cheap silicon source, gallium source, aluminium source, mineralizer and organic formwork agent directly synthetic, and molecular sieve needn't carry out follow-up micropore size adjustment.
(2) the heteroatoms ZSM-5 molecular sieve of Hydrothermal Synthesis belongs to MFI structure, does not have dephasign crystallographic system to occur.
(3) compared with conventional ZSM-5 molecular sieve, biomass are carried out catalyse pyrolysis at heteroatoms ZSM-5 molecular sieve, and mononuclear aromatics total recovery does not reduce, and benzene, toluene, the p-Xylol selectivity in aromatic hydrocarbons is brought up to 80% left and right.
(4) compared with conventional ZSM-5 molecular sieve, plastic waste carries out catalyse pyrolysis at heteroatoms ZSM-5 molecular sieve, and mononuclear aromatics total recovery brings up to 36% by 19%, and benzene, toluene, the overall selectivity of p-Xylol in aromatic hydrocarbons bring up to 90%.
(5) compared with conventional ZSM-5 molecular sieve, biomass and plastic waste carry out common catalyse pyrolysis at heteroatoms ZSM-5 molecular sieve, and mononuclear aromatics total recovery slightly increases, and benzene, toluene, the overall selectivity of p-Xylol in aromatic hydrocarbons bring up to 86%.
(6) use heteroatoms ZSM-5 molecular sieve, in hydrocarbon product, the selectivity of p-Xylol in dimethylbenzene is at 70-90%.
To sum up, heteroatoms ZSM-5 molecular sieve is a kind of efficient catalyst of the synthetic high added value organic chemicals of Non oil-based route, has good development prospect.
Brief description of the drawings
Fig. 1 molecular sieve XRD figure;
Fig. 2 biomass are reacted schematic diagram with the catalysis fast pyrogenation of plastic waste.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1 molecular sieve
(1) silicon sol is that silicon source, Tai-Ace S 150 are that aluminium source, gallium sulfate are that gallium source, sodium hydroxide are mineralizer, and organic formwork agent is TPAOH (TPAOH), and the molar ratio that raw material conversion is oxide compound is:
SiO
2:Al
2O
3:Ga
2O
3:NaOH:TPAOH:H
2O＝25:0.7:0.7:1:5:2000
(2) gallium source, aluminium source are added in template solution (concentration 2mol/L), stir 30 minutes; Add again sodium hydroxide, stir 30 minutes; Above-mentioned solution is moved in the aqueous solution (commercial silicon sol, 25% silicon-dioxide) in silicon source, continue to stir 120 minutes, form the sol-gel system of homogeneous.In proportioning raw materials, remaining water and gallium sulfate are made the aqueous solution and are added.
(3) above-mentioned collosol and gel is moved in the reactor that is lined with tetrafluoroethylene, then put at 180 DEG C of homogeneous reactors crystallization 48 hours, obtain molecular screen primary powder.Material after crystallization is taken out, and centrifugation goes out molecular screen primary powder, adds deionized water wash, filter 23.
(4) molecular screen primary powder after filtering is put into the oven dry of spending the night of 110 DEG C, baking oven, and in retort furnace, 550 DEG C of roastings are removed organic formwork agent in 5 hours, obtain molecular sieve powder.
(5) by the solution of ammonium hydroxide ion-exchange of the molecular sieve powder use 1M obtaining 1 hour, repeated exchanged 3 times after filtering, then through 110 DEG C of oven dry of spending the night, in retort furnace, 550 DEG C of roastings obtain Hydrogen heteroatoms ZSM-5 molecular sieve for 5 hours.
Embodiment 2: molecular sieve
(1) tetraethoxy is that silicon source, Tai-Ace S 150 are that aluminium source, gallium sulfate are that gallium source, sodium hydroxide are mineralizer, and organic formwork agent is TPAOH (TPAOH), and the molar ratio that raw material conversion is oxide compound is:
SiO
2:Al
2O
3:Ga
2O
3:NaOH:TPAOH:H
2O＝25:0.4:0.9:1:5:2000
(2) gallium source, aluminium source are added in template solution (strength of solution 1mol/L), stir 30 minutes; Add again sodium hydroxide, stir 30 minutes; Above-mentioned solution is moved in the aqueous solution (commercial teos solution, 28.4% silicon oxide) in silicon source, continue to stir 120 minutes, form the sol-gel system of homogeneous.In proportioning raw materials, remaining water and gallium sulfate are made the aqueous solution and are added.
(3) above-mentioned collosol and gel is moved in the reactor that is lined with tetrafluoroethylene, then put at 180 DEG C of homogeneous reactors crystallization 48 hours, obtain molecular screen primary powder.Material after crystallization is taken out, and centrifugation goes out molecular screen primary powder, adds deionized water wash, filter 23.
Subsequent step is with embodiment 1.
Embodiment 3 molecular sieves
(1) positive silicic acid is that silicon source, gallium nitrate are that gallium source, sodium hydroxide are mineralizer, and organic formwork agent is TPAOH (TPAOH), and the molar ratio that raw material conversion is oxide compound is:
SiO
2:Ga
2O
3:NaOH:TPAOH:H
2O＝25：1.3：1：5：2000
(2) gallium source is added in template solution (concentration 2mol/L), stir 30 minutes; Add again sodium hydroxide, stir 30 minutes; Above-mentioned solution is moved in the aqueous solution (commercial teos solution, 28.4% silicon-dioxide) in silicon source, continue to stir 120 minutes, form the sol-gel system of homogeneous.In proportioning raw materials, remaining water and gallium nitrate are made the aqueous solution and are added.
(3) above-mentioned collosol and gel is moved in the reactor that is lined with tetrafluoroethylene, then put at 180 DEG C of homogeneous reactors crystallization 60 hours, obtain molecular screen primary powder.Material after crystallization is taken out, and centrifugation goes out molecular screen primary powder, adds deionized water wash, filter 23.
Subsequent step is with embodiment 1.
Embodiment 4 molecular sieves
(1) tetraethoxy is that silicon source, gallium sulfate are that gallium source, sodium hydroxide are mineralizer, and organic formwork agent is TPAOH (TPAOH), and the molar ratio that raw material conversion is oxide compound is:
SiO
2:Ga
2O
3:NaOH:TPAOH:H
2O＝25：0.6：1：5：2000
(2) gallium source is added in template solution (concentration 2mol/L), stir 30 minutes; Add again sodium hydroxide, stir 30 minutes; Above-mentioned solution is moved in the aqueous solution (commercial teos solution, 28.4% silicon-dioxide) in silicon source, continue to stir 120 minutes, form the sol-gel system of homogeneous.In proportioning raw materials, remaining water and gallium sulfate are made the aqueous solution and are added.
(3) above-mentioned collosol and gel is moved in the reactor that is lined with tetrafluoroethylene, then put at 180 DEG C of homogeneous reactors crystallization 60 hours, obtain molecular screen primary powder.Material after crystallization is taken out, and centrifugation goes out molecular screen primary powder, adds deionized water wash, filter 23.
Subsequent step is with embodiment 1.
Molecular sieve prepared by embodiment 1-4 is labeled as respectively SGA1, SGA2, SG30, SG40, and the ZSM-5 molecular sieve (SiO of industrial routine
2/ Al
2o
3=25, be labeled as 25H), the XRD figure spectrum of molecular sieve is shown in Fig. 1.As seen from the figure, the XRD diffraction peak of SGA, SG Series Molecules sieve is the characteristic diffraction peak of HZSM-5, and does not occur dephasign peak or belong to the diffraction peak of large crystal grain gallium oxide.As can be seen here, adopt synthetic method of the present invention, can obtain the molecular sieve of pure MFI crystal formation.Table 1 has provided the elementary composition and texture characteristic of molecular sieve.The silicon oxide of SGA, SG Series Molecules sieve and the ratio of gallium aluminum oxide are between 20-50.Due to the difference of synthesis of molecular sieve grain size, total specific surface and the micropore specific surface of SGA, SG Series Molecules sieve decrease than little crystal grain 25H molecular sieve.
Elementary composition and the texture characteristic of table 1. molecular sieve
Embodiment 5 catalysis fast pyrogenation reactions
Experimental raw: used catalyst is chosen SGA synthetic in embodiment 1-4, SG Series Molecules sieve; Reactant adopts common pine wood chip in biomass.Biomass and molecular sieve mass ratio are 1:15, after mixing, pack quartz tube reactor into, and clog with silica wool at two ends.Then, silica tube is inserted in the probe of the quick cracking instrument of CDS and carry out catalyzed reaction.
The quick cracking instrument of reaction unit: CDS (Pyroprobe5200analytical pyrolyzer)
Temperature of reaction: 550 DEG C
Reaction pressure: normal pressure
Product analysis: Agilent 7890A gas-chromatography, Agilent 5975C MSD mass spectrograph.
Reaction carrier gas is helium; Yield calculates in a mole carbon yield mode for product, the results are shown in Table 2.
Table 2 pine CFP distribution of reaction products
A comprises the isomer of a p-Xylol, ethylbenzene, ethyl methyl benzene and trimethylbenzene.
B comprises indenes and hydrogenation indenes.
C comprises naphthalene, methylnaphthalene and ethyl naphthalene.
As seen from Table 2, the reaction product of pine CFP is mainly by aromatic hydrocarbons, gaseous hydrocarbons, CO/CO
2form with charcoal.Compared with 25H, the mononuclear aromatics yield of SGA, SG molecular sieve slightly reduces, but polycyclic aromatic hydrocarbons, low-carbon alkanes, CO, CO
2yield significantly reduce.This is because the acidity of SGA, SG is weaker than, and channel diameter diminishes, and the aldehydes matter in the elementary pyrolysis product of pine is difficult to diffuse into deoxidation, scission reaction occur in molecular sieve pore passage.
Although mononuclear aromatics yield declines, the benzene of SGA, SG30, toluene, the selectivity of p-Xylol in total aromatic hydrocarbons significantly increase.For example, the toluene of SGA2, the p-Xylol selectivity in aromatic hydrocarbons is increased to 64.6%, and the selectivity of p-Xylol in xylene compounds is increased to 95.7%.Result shows, gallium inserts MFI framework of molecular sieve, can dwindle channel diameter, is beneficial to the raising of Selectivity for paraxylene.
Embodiment 6 catalysis fast pyrogenation reactions
Experimental raw: used catalyst is chosen SGA synthetic in embodiment 1-4, SG Series Molecules sieve; Reactant adopts polyethylene (LDPE).
Other reaction conditionss, with embodiment 5, the results are shown in Table 3.
Table 3 polyethylene CFP distribution of reaction products
A comprises the isomer of a p-Xylol, ethylbenzene, ethyl methyl benzene and trimethylbenzene.
B comprises indenes and hydrogenation indenes.
C comprises naphthalene, methylnaphthalene and ethyl naphthalene.
As seen from Table 3, the reaction product of polyethylene CFP is mainly made up of aromatic hydrocarbons, gaseous hydrocarbons and charcoal.Compared with biomass (as pine), polyethylene at high temperature straight chain carbon bond easily ruptures, and its elementary pyrolysis intermediate diffusion enters and in molecular sieve pore passage, carries out catalyzed reaction, and the aromatic hydrocarbons obtaining, gaseous hydrocarbons yield are high.
Compared with 25H, acid weak SGA, SG30 molecular sieve aromatics yield are brought up to 27.7-35.8%, and this is because the acidic site effectively reduces second pyrolysis, the reforming reaction of reaction product.Meanwhile, the gallium on skeleton has stronger dehydrogenation, and in product, low-carbon alkanes yield obviously declines.
In addition, benzene, toluene, the selectivity of p-Xylol in aromatic product of SGA Series Molecules sieve are brought up to 66.4-87.0%.Contained gallium in molecular sieve, by regulation and control channel diameter, has improved the selection of p-Xylol in dimethylbenzene.
Embodiment 7 catalysis fast pyrogenation reactions
Experimental raw: used catalyst is chosen SGA synthetic in embodiment 1-4, SG Series Molecules sieve; Reactant adopts biomass (pine wood chip) and the polyethylene mixture that mass ratio is 2:1.
Other reaction conditionss, with embodiment 5, the results are shown in Table 4.
Table 4 pine and polyethylene CFP distribution of reaction products
A comprises the isomer of a p-Xylol, ethylbenzene, ethyl methyl benzene and trimethylbenzene.
B comprises indenes and hydrogenation indenes.
C comprises naphthalene, methylnaphthalene and ethyl naphthalene.
Available hydrogen content in biomass is low and oxygen level is high.Waste or used plastics (polyethylene) can be used as New Hydrogen source material and biomass catalyse pyrolysis altogether, improves aromatic product yield.Table 4 has provided pine and the polyethylene products distribution of catalysis fast pyrogenation altogether.Can find out, SGA and SG30, in improving mononuclear aromatics yield, effectively suppress the generation of polycyclic aromatic hydrocarbons, low-carbon alkanes, and yield of light olefins has increase to a certain degree.
The selectivity of benzene on hetero-atom molecular-sieve, toluene, p-Xylol also significantly increases.Therefore, heteroatoms MFI molecular sieve has high catalytic activity in biomass, plastic waste and the two common catalyse pyrolysis reaction, significantly improves the yield of the high added value petroleum productss such as toluene, p-Xylol, low-carbon alkene.
Below be only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a synthetic method for heteroatoms ZSM-5 molecular sieve, is characterized in that, comprises step:
(1) taking one or more in tetraethoxy, silicic acid, water glass or silicon sol as silicon source; One or more in Tai-Ace S 150, pseudo-boehmite, aluminum isopropylate or aluminium hydroxide are aluminium source; Taking gallium sulfate or gallium nitrate as gallium source; Taking sodium-chlor or sodium hydroxide as mineralizer; Taking TPAOH as organic formwork agent;
The raw material of synthesis of molecular sieve collosol and gel is according to a mole proportioning SiO
2: Al
2o
3: Ga
2o
3: NaOH:TPAOH:H
2o is 25:x:
y: 1:(3-10): (1000-3000), and x+y=0.5-3, x/y=0-5;
Gallium source, aluminium source are added in template, then add sodium hydroxide, then mix with silicon source, form sol-gel system;
(2) step (1) gained sol gel precursor is tied up to crystallization 48-80 hour at 160-200 DEG C, after crystallization, obtain molecular screen primary powder;
(3) molecular screen primary powder washs, filters and dry, and removes organic formwork agent at 500-600 DEG C of roasting temperature 4-8 hour, obtains molecular sieve powder;
(4) molecular sieve powder is carried out ion-exchange with solution of ammonium hydroxide, then through 110 DEG C of oven dry, obtains Hydrogen heteroatoms ZSM-5 molecular sieve at 500-600 DEG C of roasting temperature 4-8 hour.
2. synthetic method according to claim 1, is characterized in that, x+y=0.625-1.5 in the proportioning raw materials of synthesis of molecular sieve collosol and gel, x/y=0.5-1.
3. synthetic method according to claim 1, is characterized in that, in described step (1), gallium source, aluminium source being added to concentration is in the template solution of 1-2mol/L, stirs 20-40 minute; Add again sodium hydroxide, stir 20-40 minute; Above-mentioned solution is moved in the aqueous solution in silicon source, continue to stir 100-150 minute, form the sol-gel system of homogeneous.
4. synthetic method according to claim 1, is characterized in that, in described step (2), after the material after crystallization is taken out, centrifugation goes out molecular screen primary powder, adds deionized water wash, filters 2-5 time.
5. synthetic method according to claim 1, is characterized in that, in described step (4), and the solution of ammonium hydroxide ion-exchange 1-2 hour of 0.5-3M for molecular sieve powder, repeated exchanged 2-3 time after filtering.
6. synthetic method according to claim 1, is characterized in that, described step (5) also comprises: by for subsequent use the gained Hydrogen ZSM-5 hetero-atom molecular-sieve 40-140 order that sieves.
7. the heteroatoms ZSM-5 molecular sieve that the arbitrary described synthetic method of claim 1-6 obtains.
8. the application of heteroatoms ZSM-5 molecular sieve claimed in claim 7, is characterized in that, is the application in catalysis fast pyrogenation prepare liquid fuel and liquefied petroleum gas (LPG);
The reaction raw materials of described catalysis fast pyrogenation is lignocellulose biomass, and/or plastic waste;
The reaction of described catalysis fast pyrogenation is used heteroatoms ZSM-5 molecular sieve as catalyzer; The product of described catalysis fast pyrogenation mainly comprises aromatic hydrocarbons and liquefied petroleum gas (LPG).
9. the application of molecular sieve according to claim 8, is characterized in that, the reaction of described catalysis fast pyrogenation is carried out in a reactor.
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