CN108069437A - A kind of Beta molecular sieves and its synthetic method and application - Google Patents
A kind of Beta molecular sieves and its synthetic method and application 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention discloses a kind of Beta molecular sieves and its synthetic method and application.The Beta molecular sieves intermediary hole pore volume accounts for the 40 60% of total pore volume, and 2 ~ 6nm is mesoporous to account for the 20 ~ 75% of mesoporous total volume, and 15 ~ 20nm is mesoporous to account for the 10 ~ 60% of mesoporous total volume, described 700 DEG C of hydro-thermal process 4h of Beta molecular sieves, relative crystallinity conservation rate 85 ~ 97%.The preparation method of the Beta molecular sieves, including following content：Water, template, silicon source, alkali source, silicon source are mixed to form gel, Beta molecular sieves are made after crystallization, washing, drying, roasting.The Beta molecular sieves have multistage pore canal and high hydrothermal stability.
Description
Technical field
The present invention relates to a kind of Beta molecular sieves and its synthetic method and applications, relate in particular to a kind of high hydrothermally stable
The multi-stage pore channel beta molecular screen and its synthetic method of property and application.
Background technology
β zeolites be the U.S. succeed in developing in the Mobil companies sixties with three-dimensional open-framework silica-rich zeolite (US3,
308,069), the late nineteen eighties, scholars are to the research Showed Very Brisks of β zeolites, due to the pore passage structure of β zeolites uniqueness
With excellent catalytic performance, it is with a wide range of applications in oil and chemical field.In practical application, micropore canals are due to hole
Road diameter (< 2nm）The smaller mass transfer diffusion for often influencing catalytic process reactant and product in its duct, causes activity
It is reduced with conversion ratio, reduces the efficiency of zeolite molecular sieve application.Therefore mesoporous and macropore is introduced in zeolite and combines the two respectively
From advantage, it is one of popular domain studied at present to prepare a kind of new multistage porous molecular sieve.
CN104353484A by the methods of commercially available Beta molecular sieves calcining, alkali process, ammonium nitrate processing by having obtained highly acid
Multi-stage porous Beta zeolites, but this method is being further processed to the molecular sieve that has synthesized.
CN1769169A uses the hydrothermal synthesis method of optimal conditions, obtains pore volume as 0.35-0.50ml/g, aperture is concentrated
It is distributed in 0.1~1.7nm, 1.7~6.0nm, the β zeolite products of tri- sections of 10.0~90.0nm.The invention is needed in building-up process
Ammonium salt processing procedure is first carried out afterwards, obtains acid treatment and hydro-thermal process that zeolite carries out suitable condition.CN103964458A will
Raw material Beta zeolites carry out acid treatment twice and double roasting has obtained the Beta zeolites of high silica alumina ratio multistage pore canal.
CN102826565A is divided in the case of without the second template by " plan solid phase " alumino-silicate one-step synthesis multistage pore canal Beta
Son sieve, but need to be evaporated gel to obtain " plan solid phase " dry glue, energy consumption is big, and TEAOH dosages are big, do not provide product sial
Than.CN103318911A discloses a kind of preparation method of beta zeolite with multilevel pore canals：By silicon source, tetraethyl ammonium hydroxide solution, hydrogen
Sodium oxide molybdena and the silicon source that is completely dissolved after mixing constant temperature stirring at a certain temperature until forming xerogel；Gained xerogel
120 ~ 180 DEG C of progress first time hydro-thermals, suitable silane coupling agent is added in after cooling, grinding；120 ~ 180 ° DEG C carry out second
Hydro-thermal can obtain the β zeolites of multistage pore canal after cooling, filtering, roasting, hydro-thermal and gel were evaporated this method needs twice
Journey.CN101538049 discloses a kind of preparation method of beta zeolite with multilevel pore canals, belongs to the preparation and application technology neck of zeolite
Domain.It is characterized in that the charcoal particle for constraining lower generation using ordered mesoporous pore canals adds small molecule organic ammonium as hard template
The mesoporous Si-Al converted in-situ for wrapping up charcoal particle is micropore β zeolites by soft template, and roasting can must contain multistage after removing soft or hard template
The β zeolites in duct.CN101003378A discloses a kind of preparation method of the Beta zeolite molecular sieve of hierarchical porous structure, is to use sugarcane
Sugar juice impregnates monolithic silica column, and dry, polymerization, charing obtain charcoal silicon compound, by charcoal silicon compound with by silicon source, inorganic
After alkali, organic amine, the mixed solution of water composition soak, crystallization and recovery product.CN102745707A is lured by using phase separation
It leads agent polyethylene glycol, polyoxyethylene etc. and structure directing agent citric acid, tartaric acid etc. obtains hierarchical pore structure sliicon-aluminum zeolite material.
CN102826564A discloses a kind of preparation method of the Beta zeolite molecular sieve of hierarchical porous structure, using ethyl orthosilicate as silicon
Source, using sodium metaaluminate as silicon source, using six ammonium cation type quaternary surfactants as template, in alkaline conditions
The multi-stage pore zeolite molecular sieve containing mesoporous and Beta zeolite micropores is prepared by hydrothermal synthesis method.CN103073020A provides one
Kind is template using cationic surfactant, assembles silanization zeolite seed crystal under hydrothermal conditions, synthesizes hierarchical zeolite
The method of molecular sieve.CN104418348A discloses a kind of Beta molecular sieves and its synthetic method with multistage pore canal.Contain
The II grades that I grades that aperture is 2 ~ 4.8nm are mesoporous and aperture is 4.9 ~ 13nm are mesoporous, in the synthesis process using polyquaternium -6,
Polyquaternium -7, Merquat 280, quaternary ammonium salt -39 are simultaneously as micropore and mesoporous directed agents.CN104261423A is with N- first
Base -2-Pyrrolidone has synthesized multi-stage porous Beta zeolites for mesoporous pore-foaming agent.
Up to the present, people employ many methods to prepare multi-stage artery structure zeolite molecular sieve, can generally divide
Into two methods.A kind of is that the zeolite molecular sieve synthesized is modified, using alkali desiliconization, sour dealuminzation or steam treatment etc.
Mesoporous passage can be formed in microporous molecular sieve duct.Another method is direct under the conditions of template and Template-free method
The multistage porous molecular sieve of synthesis.Prepared by the prior art has mesoporous and/or macropore multi-stage artery structure zeolite molecular sieve, although
Be conducive to the absorption and diffusion of macromolecular in reaction process, but its hydrothermal stability, mechanical strength and catalytic activity are poor, fail
Reach the requirement of commercial Application.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of multi-stage pore channel beta molecular screen with high hydrothermal stability
And its preparation method and application.
A kind of Beta molecular sieves, the Beta molecular sieves intermediary hole pore volume account for the 40-60% of total pore volume, preferably 45-
55%, 2 ~ 6nm be mesoporous to account for the 20 ~ 75% of mesoporous total volume, preferably 30 ~ 55%, and further preferred 45 ~ 55%, 15 ~ 20nm is mesoporous to be accounted for
The 10 ~ 60% of mesoporous total volume, preferably 20 ~ 60%, further preferred 40 ~ 60%, described 700 DEG C of hydro-thermal process 4h of Beta molecular sieves,
Relative crystallinity conservation rate 85 ~ 97%, preferably 90 ~ 97%.
SiO in above-mentioned Beta molecular sieves2/Al2O3（Molar ratio）For 25-100, preferably 30-50；Relative crystallinity is 80-
120, preferably 100-120；Grain size is 100 ~ 700 nm, is preferably 200 ~ 400 nm；BET specific surface area is 500 ~ 750m2/
G is preferably 650 ~ 750m2/g；Infrared total acid content is 0.1 ~ 1.0mmol/g, is preferably 0.15 ~ 0.85mmol/g；Na2The weight of O
Content is below 0.15wt%.
A kind of preparation method of Beta molecular sieves, including following content：Water, template, silicon source, alkali source, silicon source are mixed
Gel is formed, Beta molecular sieves are made after crystallization, washing, drying, roasting, the template includes two kinds, the first is to have
Machine amine (CnH2n+1)4One or more of NX, wherein n=1-22；X=OH, Br or Cl are denoted as (TEA)2O；Second
EHL is denoted as enzymolysis xylogen, and the molar ratio of each raw material is SiO in the gel2 : Al2O3 : H2O : Na2O :
(TEA)2O =30~60 : 1 : 140~300 : 3~6 :2.5 ~ 5, the EHL and SiO of addition2Mass ratio be 1:10~300.
In the above method, the water, template, silicon source, alkali source, silicon source mixed process are as follows：First by water, the first mould
Plate agent organic amine (CnH2n+1)4One or more of NX, silicon source, alkali source are mixed in a certain ratio, 10 ~ 35oC stirs 5-
It dissolves within 20 minutes, then adds in second of template enzymolysis xylogen, be eventually adding silicon source.
In the above method, the alkali source is NaOH, KOH and NH4The mixture of one or more of OH.The silicon
Source is the mixing of one or more of Ludox, waterglass, Silica hydrogel, tetraethyl orthosilicate and positive silicic acid propyl ester.The aluminium
Source is the mixing of one or more of sodium aluminate, aluminum sulfate, aluminium isopropoxide and tertiary butyl aluminium.
In the above method, the crystallization process preferably carries out segmentation crystallization, further preferred two sections of crystallization, first in 80-
120oWhen the low temperature crystallized 10-20 of C are small, temperature is then raised to 130-150oC continues crystallization 20-70 h.Crystallization process is segmented, is had
Beneficial to enzymolysis xylogen with the interaction of silicon.
In the above method, the drying temperature be 10 DEG C -120 DEG C, drying time be 6 ~ 12h, calcination temperature 450
DEG C -600 DEG C, roasting time is 7 ~ 10h.
In the method for the present invention, further containing the third template in the gel rubber system, the third described template is
One or more of the lignin monomers such as guaiacol, lilac phenol or glucose, fructose, the third template of addition
With SiO2Mass ratio be 1:10~300.The addition of the third template can increase by 2 ~ 6 nm ducts volumes.
Above-mentioned Beta molecular sieves react for diesel oil pour point depression, and reaction condition is as follows：React stagnation pressure 5-10MPa, hydrogen oil volume
Compare 400-800：1,1 h of volume space velocity during liquid-1-3h-1。
The reduction of hydrothermal stability mostlys come from partial collapse caused by the removing of Al in zeolite-water heat treatment process,
And-Si-OH is subject to OH in water-Attack avalanche.In the above method, micropore template agent tetraethyl ammonium hydroxide is remained, from
And it ensure that higher product silica alumina ratio（SiO2:Al2O3>25）, reduce low hydrothermal stability caused by de- Al；And it synthesizes
The monomer reaction that the hydrolysis of part-Si-OH and enzymolysis xylogen generates in the process generates specific structure, organic in roasting process
Structure removes, and connected silicon species condensation reconstruct forms Si-O-Si, and then hydrothermal stability of molecular sieve gets a promotion.
The present invention provide it is a kind of it is simple for process using cheap biological material for mesoporous template synthesizing high-silicon aluminium than multistage
The method of duct Beta molecular sieves.The molecular sieve has two level mesopore orbit, and diffusion is good, the distribution of special mesopore orbit
Make it that there is special selectivity in macromolecular reaction field.
Using one-step synthesis, a kind of single enzymolysis xylogen just can form multistage mesoporous the present invention, be not required to additional
Any unbodied carrier, simple for process, reduction water, crystallization time is short, and temperature is low, and production cost is low, and high income is suitable for
Industrialized production.Prepared multi-stage pore canal molecular sieve is active, good hydrothermal stability, high mechanical strength.Available for petrochemical industry,
The fields such as fine chemicals preparation and environmental catalysis.
Description of the drawings
Fig. 1 is the XRD spectra of 10 product of embodiment.
Fig. 2 is N2 adsorption-desorption isotherm figure of 10 product of embodiment.
Fig. 3 is 10 product of embodiment by the pore volume that BJH is adsorbed and aperture relational graph.
Specific embodiment
The functions and effects of method are further illustrated the present invention with reference to embodiment and comparative example, but following embodiment is not
Form the limitation to the method for the present invention.Enzymolysis xylogen prepares fuel second from wheat straw, maize straw enzymolysis in following embodiment
The by-product of alcohol, is derived from Shandong Longli Biology Science and Technology Co., Ltd, is a kind of phenol polymer of complexity.
Using Rigaku Co., Ltd. D/max-2500 type full-automatic rotating target X-ray diffractions instrument analyze it is dry and
Sample object phase composition after roasting configures graphite monochromator, and Cu targets, K α radiation source, 40 kV of tube voltage, 80 mA of tube current are swept
2 θ of scope is retouched as 5 °~40 °.
The ratio table of determination of nitrogen adsorption sample is used on 2420 type physical adsorption appearances of Micromeritics companies ASAP
Area and pore volume.
Comparative example 1
According to the method that CN102826564A is provided, by 0.25g NaOH（Top pure grade, >=98%）, 0.075g sodium metaaluminates（Change
Learn pure, content is with Al2O3Meter >=41.0%）, six amino quaternary surfactants of 1.2g and 21ml water stir to get settled solution.
Under 50 DEG C of stirrings, 3.6ml ethyl orthosilicates are added dropwise into obtained settled solution（98%）With the alcohol mixed solution of 3.8ml
Obtain silica-alumina gel；Obtained silica-alumina gel, which is maintained at 50 DEG C, to be continued to stir 6h, continues, in 30 DEG C of still aging 16h, then will
It is fitted into the stainless steel cauldron of sealing, the crystallization 120h at 145 DEG C, and the solid after crystallization is through filtering, washing and do
After dry, then 550 DEG C of calcining 5h remove organic formwork agent in air, obtain Beta-0.Obtained molecular sieve is placed in reaction tube
It is placed in hydro-thermal process stove, 700 DEG C of constant temperature processing 4h, flow rates 0.07 under 100% water vapor conditions of normal pressure.Compare
With the crystallization situation of before processing molecular sieve after processing, crystallinity retention rate is calculated.
Crystallinity retention rate=×100%
Embodiment 1
By 2.05 g NaAlO2（Chemistry is pure, and content is with Al2O3Meter >=41.0%）、0.5 g NaOH（Top pure grade, >=98%） 、
20.4g water and 14.7g tetraethyl ammonium hydroxides（Mass fraction 25%）Mixing, 20oAfter C stirs 20 min, add in thereto
22.5 g silica gel and 0.5g EHL, continue to stir 30 min, obtain gel mixture, which is moved into polytetrafluoroethylene (PTFE)
It is sealed in synthesis reactor, 80oAfter 10 h of C crystallization, 130 are warming up too20 h of C crystallization is cooled down, and is washed, dry, calcine to get
To multi-stage porous Beta molecular sieves Beta-1.Obtained molecular sieve, which is placed in reaction tube, to be placed in hydro-thermal process stove, in normal pressure 100%
The lower 700 DEG C of constant temperature processing 4h of water vapor conditions, flow rates 0.07.Compare the crystallization feelings with before processing molecular sieve after handling
Condition calculates crystallinity retention rate.
Embodiment 2-6
Using the method for embodiment 1, silicon source, silicon source, alkali source, the addition of water and mesoporous template are identical with comparative example, but
Amount EHL and guaiacol as shown in Table 1 are added in simultaneously when silica gel is added in building-up process（It analyzes pure）.And adjust crystallization time
And crystallization temperature（As shown in table 1）, respectively obtain Beta-2, Beta-3, Beta-4, Beta-5, Beta-6, property such as table 2
It is shown.
Embodiment 7
By 2.05 g NaAlO2（Chemistry is pure, and content is with Al2O3Meter >=41.0%）、2.0 g NaOH（Top pure grade, >=98%） 、
40.0g water and 36.8g tetraethyl ammonium hydroxides（Mass fraction 25%）Mixing, 20oAfter C stirs 20 min, add in thereto
45.0 g silica gel and 2.0g EHL, continue to stir 30 min, obtain gel mixture, which is moved into polytetrafluoroethylene (PTFE)
It is sealed in synthesis reactor, 120oAfter 20 h of C crystallization, 150 are warming up too20 h of C crystallization is cooled down, and is washed, dry, calcine to get
To multi-stage porous Beta molecular sieves Beta-7.Obtained molecular sieve, which is placed in reaction tube, to be placed in hydro-thermal process stove, in normal pressure 100%
The lower 700 DEG C of constant temperature processing 4h of water vapor conditions, flow rates 0.07.Compare the crystallization feelings with before processing molecular sieve after handling
Condition calculates crystallinity retention rate.
The method that embodiment 8-14 uses embodiment 1, silicon source, silicon source, alkali source, water and mesoporous template addition with it is right
Ratio is identical, but in the synthesis process add in silica gel when add in amount EHL and guaiacol as shown in Table 1 simultaneously（It analyzes pure）.
And adjust crystallization time and crystallization temperature（As shown in table 1）, respectively obtain Beta-8, Beta-9, Beta-10, Beta-11,
Beta-12, Beta-13, Beta-14, property are as shown in table 2.
1 embodiment key reaction condition of table
Note：Wherein T1 represents one section of crystallization temperature, and T2 represents two sections of crystallization temperatures, and t1 represents one section of crystallization time, and t2 represents two
Section crystallization time
2 comparative example of table and 1 ~ 11 products molecule of embodiment sieve property
Comparative example 2
Beta-0 molecular sieves on fixed bed hydrogenation experimental rig are evaluated, technique stream is once passed through using one-stage serial
Journey, operating condition are：React stagnation pressure 7.0MPa, hydrogen to oil volume ratio 500：1, volume space velocity 1.5h during liquid-1, use high freezing point diesel fuel
As feedstock oil, raw material oil nature is listed in table 3, and evaluation result is listed in table 4.
Embodiment 15
Beta-7 molecular sieves on fixed bed hydrogenation experimental rig are evaluated, technique stream is once passed through using one-stage serial
Journey, operating condition are：React stagnation pressure 7.0MPa, hydrogen to oil volume ratio 500：1, volume space velocity 1.5h during liquid-1, use high freezing point diesel fuel
As feedstock oil, raw material oil nature is listed in table 3, and evaluation result is listed in table 4.
3 raw material oil nature of table
4 comparative evaluation's result of table
Molecular sieve of the present invention, selectivity, yield and the product of low-coagulation diesel oil product are used it can be seen from the evaluation result of table 4
Quality is superior to using comparative example.
The above is only several case study on implementation of the present invention, and limitation in any form is not done to the present invention.
Protection scope of the present invention is without being limited thereto.
Claims (12)
1. a kind of Beta molecular sieves, it is characterised in that：The Beta molecular sieves intermediary hole pore volume accounts for the 40-60% of total pore volume,
2 ~ 6nm is mesoporous to account for the 20 ~ 75% of mesoporous total volume, and 15 ~ 20nm is mesoporous to account for the 10 ~ 60% of mesoporous total volume, the Beta molecular sieves
700 DEG C of hydro-thermal process 4h, relative crystallinity conservation rate 85 ~ 97%.
2. molecular sieve according to claim 1, it is characterised in that：The Beta molecular sieves intermediary hole pore volume accounts for total hole
The 45-55% of volume, 2 ~ 6nm are mesoporous to account for the 30 ~ 55% of mesoporous total volume, and 15 ~ 20nm is mesoporous to account for the 20 ~ 60% of mesoporous total volume,
Described 700 DEG C of hydro-thermal process 4h of Beta molecular sieves, relative crystallinity conservation rate 90 ~ 97%.
3. molecular sieve according to claim 2, it is characterised in that：In the Beta molecular sieves 2 ~ 6nm it is mesoporous account for it is mesoporous total
The 45 ~ 55% of volume, 15 ~ 20nm is mesoporous to account for the 40 ~ 60% of mesoporous total volume.
4. molecular sieve according to claim 1, it is characterised in that：SiO in Beta molecular sieves2/Al2O3（Molar ratio）For
25-100；Relative crystallinity is 80-120；Grain size is 100 ~ 700 nm；BET specific surface area is 500 ~ 750m2/g；It is infrared total
Acid amount is 0.1 ~ 1.0mmol/g；Na2The weight content of O is below 0.15wt%.
5. molecular sieve according to claim 4, it is characterised in that：SiO in Beta molecular sieves2/Al2O3（Molar ratio）For
30-50；Relative crystallinity is 100-120；Grain size is 200 ~ 400 nm；BET specific surface area is 650 ~ 750m2/g；It is infrared total
Acid amount is 0.15 ~ 0.85mmol/g.
6. the preparation method of any molecular sieve of claim 1 to 5, it is characterised in that：Including following content：By water, template
Agent, silicon source, alkali source, silicon source are mixed to form gel, and Beta molecular sieves, the template are made after crystallization, washing, drying, roasting
Agent includes two kinds, the first is organic amine (CnH2n+1)4One or more of NX, wherein n=1-22；X=OH, Br or
Cl is denoted as (TEA)2O；EHL is denoted as enzymolysis xylogen second, the molar ratio of each raw material is SiO in the gel2 :
Al2O3 : H2O : Na2O : (TEA)2O =30~60 : 1 : 140~300 : 3~6 :2.5 ~ 5, the EHL and SiO of addition2
Mass ratio be 1:10~300.
7. according to the method described in claim 6, it is characterized in that：The water, template, silicon source, alkali source, silicon source mixed
Journey is as follows：First by water, the first template organic amine (CnH2n+1)4One or more of NX, silicon source, alkali source are by certain ratio
Example mixing, 10 ~ 35oC, which is stirred 5-20 minutes, to be dissolved, and is then added in second of template enzymolysis xylogen, is eventually adding silicon
Source.
8. according to the method described in claim 6, it is characterized in that：The alkali source is NaOH, KOH and NH4One kind in OH or
Several mixtures, the silicon source are one in Ludox, waterglass, Silica hydrogel, tetraethyl orthosilicate and positive silicic acid propyl ester
Kind or several mixing, the silicon source are the mixing of one or more of sodium aluminate, aluminum sulfate, aluminium isopropoxide and tertiary butyl aluminium.
9. according to the method described in claim 6, it is characterized in that：Two sections of crystallization of the crystallization process point, first in 80-
120oWhen the low temperature crystallized 10-20 of C are small, temperature is then raised to 130-150oC continues crystallization 20-70 h.
10. according to the method described in claim 6, it is characterized in that：The drying temperature is 100 DEG C -120 DEG C, when dry
Between for 6 ~ 12h, calcination temperature is 450 DEG C -600 DEG C, and roasting time is 7 ~ 10h.
11. according to the method described in claim 6, it is characterized in that：Further contain the third template in the gel rubber system
Agent, the third described template are guaiacol, lilac phenol lignin monomer or one kind or several in glucose, fructose
Kind, the third template and SiO of addition2Mass ratio be 1:10~300.
12. any Beta molecular sieves of claim 1 to 5 react for diesel oil pour point depression, it is characterised in that：Reaction condition is as follows：Instead
Answer stagnation pressure 5-10MPa, hydrogen to oil volume ratio 400-800：1,1 h of volume space velocity during liquid-1-3h-1。
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| CN112250087A (en) * | 2020-11-08 | 2021-01-22 | 江西苏克尔新材料有限公司 | Preparation method and application of metal modified SAPO-34 molecular sieve |
| CN112844465A (en) * | 2021-01-25 | 2021-05-28 | 中国石油天然气股份有限公司 | Hydrocracking catalyst and application thereof |
| CN114074946A (en) * | 2020-08-13 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of Beta molecular sieve |
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| WO2022165912A1 (en) * | 2021-02-05 | 2022-08-11 | 福州大学 | Neutral polymer-directed beta molecular sieve having hierarchical pores, and green preparation method therefor |
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