CN107416860B - A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology - Google Patents
A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology Download PDFInfo
- Publication number
- CN107416860B CN107416860B CN201710609648.2A CN201710609648A CN107416860B CN 107416860 B CN107416860 B CN 107416860B CN 201710609648 A CN201710609648 A CN 201710609648A CN 107416860 B CN107416860 B CN 107416860B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- source
- zeolite molecular
- meter
- zsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/082—Gallosilicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/087—Ferrosilicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of non-aluminum zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology.Template A is added after inorganic alkali source is spent ionized water dissolution, template B and silicon source is added in boron source, source of iron or gallium source after being completely dissolved, total silicon ZSM-22 molecular sieve is added into resulting Primogel as progress ultrasound after crystal seed；The mixture obtained after ultrasound is heated using microwave radiation, obtains the non-aluminum zeolite molecular sieve with TON/MTT Compound Topology structure after crystallization.This method utilizes the non-aluminum zeolite molecular sieve of hetero atom substitution, and acid moderate and multistage acid distribution is adjustable；Using preparation method provided by the invention, generated time is short, and stray crystal is few, epigranular, and reproducible；This composite molecular screen be hydrocracked in terms of have great potential using value.
Description
Technical field
The present invention relates to a kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology.
Background technique
With the rapid development for the increasingly strict and auto industry that environmental regulation requires, the novel mechanical equipment of emergence
Demand to high-quality lubricating oil gradually increases, and quality requirement is also higher and higher.Therefore, quality of lubrication oil is to low nitrogen, low-sulfur, low
Ash content, high antioxidant, high detergency, dispersibility, low volatility, the II of good viscosity-temperature characteristics and low temperature flow, Group III fry dried food ingredients
It is imperative to open up, so that the base oil manufacturing process based on solvent refining and catalytic dewaxing is gradually by isomerization dewaxing technique
It is substituted.Isomerization dewaxing reaction is that the long side chain of wax molecule and cycloalkane is converted to branched alkane, both reduces product
Pour point, and remain higher Viscosity Index and yield, therefore, Isodewaxing Technology is referred to as petroleum refining field in recent years
Important Techmical Progress, technological core is hydroisomerization catalyst, and the zeolite molecular sieve as acid centre is even more isomery
The most important thing in catalyst.
Compared with the zeolite molecular sieves such as ZSM-5, modenite, Beta, SAPO, ZSM-22, ZSM-23 molecular screen are as master
Acid centre is wanted, it is not only acid to be more suitable for, and there is excellent shape-selective effect, isomerisation selectivity can be significantly improved.
ZSM-22, ZSM-23 molecular screen are a kind of Si-Al molecular sieves with one-dimensional straight type, ten-ring cellular structure, be respectively provided with TON,
MTT matrix topology, ZSM-22 molecular sieve pore passage diameter are 0.56 × 0.45nm, and ZSM-23 molecular screen channel diameter is 0.52
× 0.45nm, these two types of Zeolite synthesis technical maturities, hydro-refining isomery reaction activity is higher, is dual-functional hydrogenation heterogeneous catalyst
Appropriate acid carrier.
The main component of wax is dystectic long-chain normal paraffin (carbon number reaches as high as 200 or more), and pour point is high, low temperature
Poor mobile performance.Branched paraffin is converted by n-alkane by hydroisomerization reaction, these performances can be improved, obtain height
The lube base oil of quality.However, only being extremely difficult to manage by hydro-isomerization process for the longer chain n-alkane in wax
The pour point thought, it is desirable that part carbochain is broken, that is, requires that cracking reaction appropriate occurs while hydro-refining isomery reaction, ability
The product property of lube base oil is set to reach ideal indicator.Therefore a kind of point with multistage acidic site, cellular structure is needed
Son sieve is to meet this requirement.
Composite molecular screen is usually the composite crystal formed by two or more molecular sieve by chemical method.It is tying
Not only with the characteristic of one-component on structure, but also itself unique structure feature and multistage Acidity are taken into account, the table in catalysis reaction
Reveal the exclusive synergistic effect and special reactivity worth different from pure phase molecular sieve.Micropore-mesoporous-microporous composite molecular sieve is come
Say, with lower synthesis cost, higher hydrothermal stability and it is adjustable it is acid can and micro-structure performance, thus favorably
In the raising of selectivity of product, more potential application value is shown in the industries such as petrochemical industry.
Chinese invention patent CN1693196, CN1762807, CN1769173 and CN1772611 disclose ZSM-23/ZSM-
22 composite molecular screens and preparation method, method are that ZSM-23 is added in the Primogel of ZSM-22 molecular sieve (or ZSM-23)
Molecular sieve (or ZSM-22) seed, obtained mixture carry out hydrothermal crystallizing and obtain ZSM-23/ZSM-22 composite molecular screen.With this
Class patent preparation method is different, and Chinese invention patent CN103964460 discloses a kind of compound Si-Al molecular sieve of micropore and its system
Preparation Method has the sial point of the microcosmic Compound Topology structure of TON/MTT using the synthesis of conventional sol-gel template hydrothermal crystallizing
Son sieve.Such TON/MTT sial composite molecular screen is made a general survey of, due to leading to compound point containing considerable amount of sial ZSM-23 structure
Son sieve surface acidity is stronger, therefore often cracking is more obvious during hydroisomerizing, and catalyst yield is lower；It is conventional simultaneously
Synthetic method is difficult to be precisely controlled the relative amount of ZSM-22 and ZSM-23, and molecular sieve adaptability is poor.
Summary of the invention
For current ZSM-22/ZSM-23 sial composite molecular screen there are the shortcomings that and microstructure Controllability, this
The purpose of invention is to provide a kind of with TON/MTT Compound Topology structure and what relative amount was controllable opens up containing TON/MTT skeleton
Flutter the zeolite molecular sieve and preparation method thereof of structure.
It is well known that carbochain occurs to be often associated with while isomery cracked due to for hydro-refining isomery reaction process
Journey, crack favorable appropriate improve properties of product in adjustment carbon chain lengths and optimized product physical index.It is provided by the present invention
The requirement of process can be met completely with multistage acid non-aluminum composite molecular screen and preparation method, therefore provided by the invention multiple
Close molecular sieve petrochemical industry be hydrocracked in terms of have great potential using value.
The present invention provides a kind of zeolite molecular sieve containing TON/MTT matrix topology, and molecular sieve contains TON (ZSM-
22) it with MTT (ZSM-23) matrix topology, is formed by oxide mol ratio are as follows: SiO2: M2O3=10-200, wherein M=B,
Fe or Ga, ZSM-22:ZSM-23 molar ratio are 10-90:90-10, BET specific surface 162.7-184.2m2/ g, particle are length 1-
2 μm, outer diameter 20-50nm is uniform, slender rod shaped object.
Method preparation is prepared as follows in composite molecular screen provided by the invention:
(1) inorganic alkali source is added in deionized water, stirring sequentially adds template A after being completely dissolved, boron source, source of iron or
Stirring is continued to mixture to after being completely dissolved in gallium source, and addition template B and silicon source, being formed has the first of following mol ratio
Beginning gel mixture, silicon source is with SiO2Meter, boron source or source of iron or gallium source are with M2O3Meter, alkali source is with OH-Meter, SiO2: M2O3: template
A: template B:OH-: deionized water=1:0.1-0.01:0.05-5.0:0.05-5.0:0.005-2.0:10.0-200.0；
(2) into step (1) resulting initial gel mixture, total silicon ZSM-22 molecular sieve is added as crystal seed, with
SiO2Meter, additive amount by addition silicon source 1-10wt%, be placed in ultrasonic unit, at 25-100 DEG C, ultrasonic frequency
It is carried out sonic oscillation 10-180 minutes under the conditions of 40-60kHz, ultrasonic power 100-2500W；
(3) mixture obtained after step (2) ultrasound is placed in the high-pressure microwave reaction kettle with polytetrafluoroethyllining lining,
It is heated to 140-200 DEG C using microwave radiation, crystallization 0.5-8h under self-generated pressure；
(4) after the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, in 400- after drying
600 DEG C of roasting 1-72h to get arrive the zeolite molecular sieve containing TON/MTT matrix topology.
Alkali source as described above is the combination of one or both of sodium hydroxide, potassium hydroxide.
Template A as described above is second methylamine, diethylamine, 1,6- hexamethylene diamine, N- isopropyl diethylenetriamine, 1- methyl
In butylamine, one or two kinds of mixing of ethylenediamine.
Boron source as described above be Boratex, potassium borate, in boric acid one or any of several combination；Source of iron is sulfuric acid
The combination of one or any of several in the soluble ferric iron salts such as iron, ferric nitrate, iron chloride, ironic citrate；Gallium salt is gallium nitrate, chlorination
The combination of one or any of several in the solubility gallium salt such as gallium, gallium sulfate.
Template B as described above is dimethylamine, dimethylformamide, n-propylamine, isopropylamine, n-butylamine, isobutyl amine, new
Amylamine, trimethylamine, N- isopropyl -1,3- propane diamine and N, N, N', N', one or both of-tetramethyl dipropylenetriamine etc.
Mixing.
Silicon source as described above be silica solution, Silica hydrogel, methyl orthosilicate, ethyl orthosilicate, sodium metasilicate, in white carbon black
The combination of one or any of several.
Microwave radiation frequencies as described above are 900-4500MHz.
Compared with the prior art, the invention has the following advantages:
(1) compared with existing TON/MTT composite molecular screen, using the composite molecular screen acid of hetero atom (B, Fe, Ga) substitution
Property moderate and multistage acid distribution it is adjustable, can avoid the overcracking in catalytic hydrogenation, improve the production of hydroisomerizing process
Product yield.
(2) compared with existing preparation method, using ultrasonic wave added provided by the invention-microwave irradiation synthesis combined method,
And using total silicon ZSM-22 as synthesis crystal seed, not only generated time is short, but also is more advantageous to composite molecular screen crystallization process
It carries out, reduces the formation of stray crystal, epigranular, and it is reproducible.
(3) non-aluminum zeolite molecular sieve made from the method is particularly suitable for requirement of the wax containing long chain hydrocarbons to molecular sieve, right
Had excellent catalytic properties in the hydro-isomerization pour-point depressing process of long chain hydrocarbons, adaptability is high, therefore present invention offer prepare it is compound
Molecular sieve be hydrocracked in terms of have great potential using value.
Detailed description of the invention
Fig. 1 is the XRD spectra for the non-aluminum zeolite molecular sieve that the synthesis of embodiment 4 has TON/MTT Compound Topology structure.
Fig. 2 is the SEM figure for the non-aluminum zeolite molecular sieve that the synthesis of embodiment 4 has TON/MTT Compound Topology structure.
Specific embodiment
The present invention is described in detail below by embodiment, but the invention is not limited to these embodiments.
Embodiment 1:
Potassium hydroxide is added in deionized water, second methylamine, Boratex is successively added after being completely dissolved in stirring, continues to stir
After being completely dissolved to mixture, it is sequentially added into dimethylamine and silica solution, being formed has the Primogel of following mol ratio mixed
Closing object, (silicon source is with SiO2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter), SiO2: B2O3: second methylamine: dimethylamine: OH-: deionized water
=1:0.1:0.05:5.0:0.005:10.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, adds
Is silicon source is added (with SiO in dosage2Meter) 1wt.%, be placed in ultrasonic unit, at 25 DEG C, ultrasonic frequency 40kHz, surpass
It is carried out sonic oscillation 180 minutes under the conditions of acoustic power 100W；The mixture obtained after ultrasound is placed in band polytetrafluoroethylene (PTFE)
In the high-pressure microwave reaction kettle of lining, 140 DEG C, under self-generated pressure are heated to using microwave radiation (microwave radiation frequencies 900MHz)
Crystallization 8h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted after dry in 400 DEG C
72h has the borosilicate zeolite of TON/MTT Compound Topology structure to get arriving.Icp analysis SiO2/B2O3Molar ratio=10, BET ratio
Surface 162.7m2/ g, ZSM-22:ZSM-23 molar ratio=10:90 in XRD characterization composite molecular screen, SEM result Molecular Sieve Morphology
It is 1.6~2 μm of length, the slender rod shaped object of 40~50nm of outer diameter.
Embodiment 2:
Potassium hydroxide is added in deionized water, diethylamine, potassium borate is successively added after being completely dissolved in stirring, continues to stir
After being completely dissolved to mixture, it is sequentially added into dimethylformamide, n-propylamine and Silica hydrogel, being formed has following mol ratio
Initial gel mixture (silicon source is with SiO2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter), SiO2: B2O3: diethylamine: dimethyl
Formamide+n-propylamine: OH-: deionized water=1:0.05:0.1:4.0 (dimethylformamide: n-propylamine=3:1, molar ratio):
0.01:30.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, is silicon source is added in additive amount
(with SiO2Meter) 2wt.%, be placed in ultrasonic unit, at 25 DEG C, ultrasonic frequency 40kHz, ultrasonic power 100W condition
Lower progress sonic oscillation 180 minutes；The mixture obtained after ultrasound is placed in the reaction of the high-pressure microwave with polytetrafluoroethyllining lining
In kettle, 150 DEG C are heated to using microwave radiation (microwave radiation frequencies 1200MHz), crystallization 4h under self-generated pressure；It is complete to crystallization
Solid product is separated by filtration by Cheng Hou, is washed with deionized to neutrality, it is dry after in 450 DEG C of roasting 36h to get to having
The borosilicate zeolite of TON/MTT Compound Topology structure.Icp analysis SiO2/B2O3Molar ratio=19.5, BET specific surface 164.3m2/
G, ZSM-22:ZSM-23 molar ratio=10:90 in XRD characterization composite molecular screen, SEM result Molecular Sieve Morphology are length 1.6~2
μm, the slender rod shaped object of 40~50nm of outer diameter.
Embodiment 3:
Potassium hydroxide is added in deionized water, 1,6- hexamethylene diamine, boric acid is successively added after being completely dissolved in stirring, continues to stir
It mixes to mixture after being completely dissolved, is sequentially added into isopropylamine, methyl orthosilicate and ethyl orthosilicate, being formed has following mole
(silicon source is with SiO for the initial gel mixture of proportion2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter), SiO2: B2O3: 1,6- oneself two
Amine: isopropylamine: OH-: deionized water=1 (methyl orthosilicate: ethyl orthosilicate=1:4, molar ratio, with SiO2Meter): 0.025:
0.2:3.0:0.02:20.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, additive amount is added
Enter silicon source (with SiO2Meter) 5wt.%, be placed in ultrasonic unit, at 30 DEG C, ultrasonic frequency 50kHz, ultrasonic power
It is carried out sonic oscillation 120 minutes under the conditions of 500W；The mixture obtained after ultrasound is placed in the high pressure with polytetrafluoroethyllining lining
In microwave reaction kettle, 160 DEG C are heated to using microwave radiation (microwave radiation frequencies 1800MHz), crystallization 2h under self-generated pressure；
After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted for 24 hours, i.e., after dry in 500 DEG C
Obtain the borosilicate zeolite with TON/MTT Compound Topology structure.Icp analysis SiO2/B2O3Molar ratio=38, BET specific surface
166.6m2/ g, ZSM-22:ZSM-23 molar ratio=20:80 in XRD characterization composite molecular screen, SEM result Molecular Sieve Morphology are length
1.2~1.6 μm of degree, the slender rod shaped object of 40~45nm of outer diameter.
Embodiment 4:
Potassium hydroxide and sodium hydroxide are added in deionized water, N- isopropyl diethyl is successively added after being completely dissolved in stirring
Alkene triamine, Boratex and boric acid, continue stirring be completely dissolved to mixture after, be sequentially added into n-butylamine, isobutyl amine and positive silicon
Acetoacetic ester, forming the initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, boron source is with B2O3Meter, alkali source with
OH-Meter), SiO2: B2O3: N- isopropyl diethylenetriamine: n-butylamine+isobutyl amine: OH-: deionized water=1:0.02 (Boratex:
And boric acid=1:1, molar ratio, with B2O3Meter): 0.5:2.5 (n-butylamine: isobutyl amine=1:4, molar ratio): 0.05 (potassium hydroxide:
Sodium hydroxide=1:4, molar ratio): 50.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, adds
Is silicon source is added (with SiO in dosage2Meter) 7.5wt.%, be placed in ultrasonic unit, at 40 DEG C, ultrasonic frequency 50kHz,
It is carried out sonic oscillation 60 minutes under the conditions of ultrasonic power 500W；The mixture obtained after ultrasound is placed in band polytetrafluoroethylene (PTFE)
In the high-pressure microwave reaction kettle of lining, 165 DEG C are heated to using microwave radiation (microwave radiation frequencies 1800MHz), self-generated pressure
Lower crystallization 2h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted after dry in 500 DEG C
12h is burnt to get the borosilicate zeolite with TON/MTT Compound Topology structure is arrived.Icp analysis SiO2/B2O3Molar ratio=46.5,
BET specific surface 165.1m2/ g, ZSM-22:ZSM-23 molar ratio=20:80 in XRD characterization composite molecular screen, SEM result molecule
Sieving pattern is 1.2~1.6 μm of length, the slender rod shaped object of 20~30nm of outer diameter.
Embodiment 5:
Potassium hydroxide and sodium hydroxide are added in deionized water, stirring be successively added after being completely dissolved 1- methylbutylamine,
Potassium borate and boric acid continue to be sequentially added into special amylamine and white carbon black after stirring is completely dissolved to mixture, formed have it is as follows
(silicon source is with SiO for the initial gel mixture of mol ratio2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter), SiO2: B2O3: 1- first
Base butylamine: special amylamine: OH-: deionized water=1:0.01 (potassium borate: boric acid=3:1, molar ratio, with B2O3Meter): 1.0:1.0:
0.1 (potassium hydroxide: sodium hydroxide=1:1, molar ratio): 70.0；Total silicon ZSM- is added into resulting initial gel mixture
22 are used as crystal seed, and is silicon source is added (with SiO in additive amount2Meter) 10wt.%, be placed in ultrasonic unit, at 50 DEG C, ultrasound
It is carried out sonic oscillation 30 minutes under the conditions of wave frequency rate 60kHz, ultrasonic power 1000W；The mixture obtained after ultrasound is placed in
In high-pressure microwave reaction kettle with polytetrafluoroethyllining lining, it is heated to using microwave radiation (microwave radiation frequencies 3600MHz)
170 DEG C, crystallization 1h under self-generated pressure；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality,
6h is roasted to get the borosilicate zeolite with TON/MTT Compound Topology structure is arrived in 550 DEG C after drying.Icp analysis SiO2/B2O3
Molar ratio=94, BET specific surface 174.8m2/ g, ZSM-22:ZSM-23 molar ratio=50:50 in XRD characterization composite molecular screen,
SEM result Molecular Sieve Morphology is 1.2~1.6 μm of length, the slender rod shaped object of 30~35nm of outer diameter.
Embodiment 6:
Sodium hydroxide is added in deionized water, ethylenediamine, Boratex and potassium borate is successively added after being completely dissolved in stirring,
Continue to be sequentially added into trimethylamine and white carbon black after stirring is completely dissolved to mixture, formed have following mol ratio just
(silicon source is with SiO for beginning gel mixture2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter), SiO2: B2O3: ethylenediamine: trimethylamine: OH-:
Deionized water=1:0.005 (Boratex: potassium borate=2:3, molar ratio, with B2O3Meter): 2.0:0.5:0.2:100.0；To gained
Initial gel mixture in be added total silicon ZSM-22 as crystal seed, is silicon source is added (with SiO in additive amount2Meter)
2wt.% is placed in ultrasonic unit, and ultrasound is carried out under the conditions of 60 DEG C, ultrasonic frequency 60kHz, ultrasonic power 1500W
Oscillation 30 minutes；The mixture obtained after ultrasound is placed in the high-pressure microwave reaction kettle with polytetrafluoroethyllining lining, utilization is micro-
Wave radiation (microwave radiation frequencies 3600MHz) is heated to 175 DEG C, crystallization 1h under self-generated pressure；After the completion of crystallization, by solid
Product is separated by filtration, and is washed with deionized to neutrality, in 550 DEG C of roasting 6h to get to having, TON/MTT is compound to be opened up after drying
Flutter the borosilicate zeolite of structure.Icp analysis SiO2/B2O3Molar ratio=200, BET specific surface 184.2m2/ g, XRD characterization are compound
ZSM-22:ZSM-23 molar ratio=80:20 in molecular sieve, SEM result Molecular Sieve Morphology are 1.2~1.6 μm of length, outer diameter 20~
The slender rod shaped object of 30nm.
Embodiment 7:
Sodium hydroxide is added in deionized water, ethylenediamine, N- isopropyl divinyl is successively added after being completely dissolved in stirring
Triamine, Boratex, continue stirring be completely dissolved to mixture after, be sequentially added into N- isopropyl -1,3- propane diamine and sodium metasilicate,
Forming the initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter),
SiO2: B2O3: ethylenediamine+N- isopropyl diethylenetriamine: N- isopropyl -1,3- propane diamine: OH-: deionized water=1:0.01:
5.0 (ethylenediamines: N- isopropyl diethylenetriamine=4:1, molar ratio): 0.1:0.5:100.0；It is mixed to resulting Primogel
Total silicon ZSM-22 is added in object as crystal seed, is silicon source is added (with SiO in additive amount2Meter) 5wt.%, be placed in ultrasonic wave
Device carries out sonic oscillation 20 minutes under the conditions of 80 DEG C, ultrasonic frequency 50kHz, ultrasonic power 2000W；After ultrasound
Obtained mixture is placed in the high-pressure microwave reaction kettle with polytetrafluoroethyllining lining, utilizes microwave radiation (microwave radiation frequencies
180 DEG C are heated to for 3600MHz), crystallization 1h under self-generated pressure；After the completion of crystallization, solid product is separated by filtration, spend from
Sub- water washing roasts 2h in 600 DEG C to neutrality to get the borosilicate zeolite with TON/MTT Compound Topology structure is arrived after dry.
Icp analysis SiO2/B2O3Molar ratio=98.5, BET specific surface 179.6m2/ g, ZSM-22:ZSM- in XRD characterization composite molecular screen
23 molar ratios=90:10, SEM result Molecular Sieve Morphology are 1~1.5 μm of length, the slender rod shaped object of 25~30nm of outer diameter.
Embodiment 8:
Sodium hydroxide is added in deionized water, diethylamine, 1- methylbutylamine, boric acid is successively added after being completely dissolved in stirring
Potassium, continue stirring be completely dissolved to mixture after, be sequentially added into N, N, N', N' ,-tetramethyl dipropylenetriamine, sodium metasilicate and
Silica solution, forming the initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, boron source is with B2O3Meter, alkali source with
OH-Meter), SiO2: B2O3: diethylamine+1- methylbutylamine: N, N, N', N' ,-tetramethyl dipropylenetriamine: OH-: deionized water=1
(sodium metasilicate: silica solution=1:4, molar ratio, with SiO2Meter): 0.015:1.0 (diethylamine: 1- methylbutylamine=3:2, mole
Than): 0.5:1.0:200.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, additive amount is added
Enter silicon source (with SiO2Meter) 1wt.%, be placed in ultrasonic unit, at 100 DEG C, ultrasonic frequency 60kHz, ultrasonic power
It is carried out sonic oscillation 10 minutes under the conditions of 2500W；The mixture obtained after ultrasound is placed in the high pressure with polytetrafluoroethyllining lining
In microwave reaction kettle, 200 DEG C are heated to using microwave radiation (microwave radiation frequencies 4500MHz), crystallization under self-generated pressure
0.5h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted after dry in 600 DEG C
1h has the borosilicate zeolite of TON/MTT Compound Topology structure to get arriving.Icp analysis SiO2/B2O3Molar ratio=65, BET ratio
Surface 177.0.6m2/ g, ZSM-22:ZSM-23 molar ratio=60:40 in XRD characterization composite molecular screen, SEM result molecular sieve shape
Looks are 1.5~2 μm of length, the slender rod shaped object of 25~30nm of outer diameter.
Embodiment 9:
Sodium hydroxide is added in deionized water, ethylenediamine, boric acid is successively added after being completely dissolved in stirring, continues stirring extremely
After mixture is completely dissolved, it is sequentially added into ethamine and white carbon black, forms the initial gel mixture with following mol ratio
(silicon source is with SiO2Meter, boron source is with B2O3Meter, alkali source is with OH-Meter), SiO2: B2O3: ethylenediamine: ethamine: OH-: deionized water=1:
0.1:1.0:2.0:2.0:75.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, additive amount is
Silicon source be added is (with SiO2Meter) 1wt.%, be placed in ultrasonic unit, at 50 DEG C, ultrasonic frequency 40kHz, ultrasonic wave function
It is carried out sonic oscillation 30 minutes under the conditions of rate 1000W；The mixture obtained after ultrasound is placed in the height with polytetrafluoroethyllining lining
It presses in microwave reaction kettle, is heated to 170 DEG C of (microwave radiation frequencies 1800MHz), crystallization under self-generated pressure using microwave radiation
2h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, it is dry after in 500 DEG C of roasting 3h,
Obtain the borosilicate zeolite with TON/MTT Compound Topology structure.Icp analysis SiO2/B2O3Molar ratio=12.5, BET compares table
Face 168.1m2/ g, ZSM-22:ZSM-23 molar ratio=40:60 in XRD characterization composite molecular screen, SEM result Molecular Sieve Morphology are
1.5~2 μm of length, the slender rod shaped object of 40~45nm of outer diameter.
Embodiment 10:
Potassium hydroxide is added in deionized water, 1,6- hexamethylene diamine, ferric sulfate is successively added after being completely dissolved in stirring, continues
After stirring is completely dissolved to mixture, it is sequentially added into isopropylamine, methyl orthosilicate and ethyl orthosilicate, is formed to have and be rubbed as follows
(silicon source is with SiO for your initial gel mixture of proportion2Meter, source of iron is with Fe2O3Meter, alkali source is with OH-Meter), SiO2: Fe2O3: 1,6-
Hexamethylene diamine: isopropylamine: OH-: deionized water=1 (methyl orthosilicate: ethyl orthosilicate=2:3, molar ratio, with SiO2Meter):
0.025:0.2:3.0:0.02:20.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, additive amount
By silicon source is added (with SiO2Meter) 5wt.%, be placed in ultrasonic unit, at 30 DEG C, ultrasonic frequency 50kHz, ultrasonic wave
It is carried out sonic oscillation 120 minutes under the conditions of power 500W；The mixture obtained after ultrasound is placed in polytetrafluoroethyllining lining
In high-pressure microwave reaction kettle, 160 DEG C are heated to using microwave radiation (microwave radiation frequencies 1800MHz), it is brilliant under self-generated pressure
Change 2h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted after dry in 500 DEG C
For 24 hours to get to TON/MTT Compound Topology structure ferrosilicon molecular sieve.Icp analysis SiO2/Fe2O3Molar ratio=36.5,
BET specific surface 169.4m2/ g, ZSM-22:ZSM-23 molar ratio=10:90 in XRD characterization composite molecular screen, SEM result molecule
Sieving pattern is 1~1.2 μm of length, the slender rod shaped object of 45~50nm of outer diameter.
Embodiment 11:
Potassium hydroxide and sodium hydroxide are added in deionized water, N- isopropyl diethyl is successively added after being completely dissolved in stirring
Alkene triamine, ferric nitrate, continue stirring be completely dissolved to mixture after, be sequentially added into n-butylamine, isobutyl amine and ethyl orthosilicate,
Forming the initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, source of iron is with Fe2O3Meter, alkali source is with OH-Meter),
SiO2: Fe2O3: N- isopropyl diethylenetriamine: n-butylamine+isobutyl amine: OH-: deionized water=1:0.02:0.5:2.5 (positive fourth
Amine: isobutyl amine=1:4, molar ratio): 0.05 (potassium hydroxide: sodium hydroxide=1:4, molar ratio): 50.0；To resulting initial
Total silicon ZSM-22 is added in gel mixture as crystal seed, is silicon source is added (with SiO in additive amount2Meter) 7.5wt.%, and
It is placed in ultrasonic unit, is carried out sonic oscillation 60 minutes under the conditions of 40 DEG C, ultrasonic frequency 50kHz, ultrasonic power 500W；
The mixture obtained after ultrasound is placed in the high-pressure microwave reaction kettle with polytetrafluoroethyllining lining, microwave radiation (microwave is utilized
Radiation frequency is 1200MHz) 165 DEG C are heated to, crystallization 2h under self-generated pressure；After the completion of crystallization, by solid product filtering point
From being washed with deionized to neutrality, 12h roasted after dry in 500 DEG C to get to TON/MTT Compound Topology structure
Ferrosilicon molecular sieve.Icp analysis SiO2/Fe2O3Molar ratio=48, BET specific surface 171.5m2/ g, in XRD characterization composite molecular screen
ZSM-22:ZSM-23 molar ratio=20:80, SEM result Molecular Sieve Morphology are 1~1.2 μm of length, and 40~45nm's of outer diameter is elongated
Club.
Embodiment 12:
Sodium hydroxide is added in deionized water, ethylenediamine, N- isopropyl divinyl is successively added after being completely dissolved in stirring
Triamine, iron chloride and ironic citrate continue to be sequentially added into N- isopropyl -1,3- the third two after stirring is completely dissolved to mixture
Amine and sodium metasilicate, forming the initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, source of iron is with Fe2O3Meter, alkali
Source is with OH-Meter), SiO2: Fe2O3: ethylenediamine+N- isopropyl diethylenetriamine: N- isopropyl -1,3- propane diamine: OH-: deionization
Water=1:0.01 (iron chloride: ironic citrate=4:1, molar ratio, with Fe2O3Meter): 5.0 (ethylenediamines: N- isopropyl divinyl three
Amine=4:1, molar ratio): 0.1:0.5:100.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed,
Is silicon source is added (with SiO in additive amount2Meter) 5wt.%, be placed in ultrasonic unit, at 80 DEG C, ultrasonic frequency 50kHz,
It is carried out sonic oscillation 20 minutes under the conditions of ultrasonic power 2000W；The mixture obtained after ultrasound is placed in band polytetrafluoroethylene (PTFE)
In the high-pressure microwave reaction kettle of liner, 180 DEG C are heated to using microwave radiation (microwave radiation frequencies 4500MHz), spontaneous pressure
Crystallization 1h under power；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, in 600 DEG C after drying
2h is roasted to get the ferrosilicon molecular sieve with TON/MTT Compound Topology structure is arrived.Icp analysis SiO2/Fe2O3Molar ratio=95,
BET specific surface 180.2m2/ g, ZSM-22:ZSM-23 molar ratio=90:10 in XRD characterization composite molecular screen, SEM result molecule
Sieving pattern is 1~1.5 μm of length, the slender rod shaped object of 25~35nm of outer diameter.
Embodiment 13:
Potassium hydroxide is added in deionized water, second methylamine, gallium nitrate is successively added after being completely dissolved in stirring, continues to stir
After being completely dissolved to mixture, it is sequentially added into dimethylamine and silica solution, being formed has the Primogel of following mol ratio mixed
Closing object, (silicon source is with SiO2Meter, gallium source is with Ga2O3Meter, alkali source is with OH-Meter), SiO2: Ga2O3: second methylamine: dimethylamine: OH-: deionization
Water=1:0.1:0.05:5.0:0.005:10.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed,
Is silicon source is added (with SiO in additive amount2Meter) 1wt.%, be placed in ultrasonic unit, at 25 DEG C, ultrasonic frequency 40kHz,
It is carried out sonic oscillation 180 minutes under the conditions of ultrasonic power 100W；The mixture obtained after ultrasound is placed in band polytetrafluoroethylene (PTFE)
In the high-pressure microwave reaction kettle of liner, 140 DEG C are heated to using microwave radiation (microwave radiation frequencies 900MHz), self-generated pressure
Lower crystallization 8h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted after dry in 400 DEG C
72h is burnt to get the silicon gallium molecular sieve with TON/MTT Compound Topology structure is arrived.Icp analysis SiO2/Ga2O3Molar ratio=10,
BET specific surface 163.4m2/ g, ZSM-22:ZSM-23 molar ratio=10:90 in XRD characterization composite molecular screen, SEM result molecule
Sieving pattern is 1.5~2 μm of length, the slender rod shaped object of 20~25nm of outer diameter.
Embodiment 14:
Sodium hydroxide is added in deionized water, diethylamine, 1- methylbutylamine, chlorination is successively added after being completely dissolved in stirring
Gallium, continue stirring be completely dissolved to mixture after, be sequentially added into N, N, N', N' ,-tetramethyl dipropylenetriamine, sodium metasilicate and
Silica solution, forming the initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, gallium source is with Ga2O3Meter, alkali source with
OH-Meter), SiO2: Ga2O3: diethylamine+1- methylbutylamine: N, N, N', N' ,-tetramethyl dipropylenetriamine: OH-: deionized water=1
(sodium metasilicate: silica solution=1:1, molar ratio, with SiO2Meter): 0.015:1.0 (diethylamine: 1- methylbutylamine=4:1, mole
Than): 0.5:1.0:200.0；Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, additive amount is added
Enter silicon source (with SiO2Meter) 5wt.%, be placed in ultrasonic unit, at 100 DEG C, ultrasonic frequency 60kHz, ultrasonic power
It is carried out sonic oscillation 10 minutes under the conditions of 2500W；The mixture obtained after ultrasound is placed in the high pressure with polytetrafluoroethyllining lining
In microwave reaction kettle, 200 DEG C are heated to using microwave radiation (microwave radiation frequencies 4500MHz), crystallization under self-generated pressure
0.5h；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is roasted after dry in 600 DEG C
1h has the silicon gallium molecular sieve of TON/MTT Compound Topology structure to get arriving.Icp analysis SiO2/Ga2O3Molar ratio=62.5, BET
Specific surface 172.9m2/ g, ZSM-22:ZSM-23 molar ratio=60:40 in XRD characterization composite molecular screen, SEM result molecular sieve shape
Looks are 1.5~2 μm of length, the slender rod shaped object of 20~23nm of outer diameter.
Embodiment 15:
Sodium hydroxide is added in deionized water, ethylenediamine, gallium sulfate and gallium chloride is successively added after being completely dissolved in stirring,
Continue to be sequentially added into trimethylamine and white carbon black after stirring is completely dissolved to mixture, formed have following mol ratio just
(silicon source is with SiO for beginning gel mixture2Meter, gallium source is with Ga2O3Meter, alkali source is with OH-Meter), SiO2: Ga2O3: ethylenediamine: trimethylamine:
OH-: deionized water=1:0.005 (gallium sulfate: gallium chloride=2:3, molar ratio, with Ga2O3Meter): 2.0:0.5:0.2:100.0；
Total silicon ZSM-22 is added into resulting initial gel mixture as crystal seed, is silicon source is added (with SiO in additive amount2Meter)
2wt.% is placed in ultrasonic unit, and ultrasound is carried out under the conditions of 60 DEG C, ultrasonic frequency 60kHz, ultrasonic power 1500W
Oscillation 30 minutes；The mixture obtained after ultrasound is placed in the high-pressure microwave reaction kettle with polytetrafluoroethyllining lining, utilization is micro-
Wave radiation (microwave radiation frequencies 3600MHz) is heated to 175 DEG C, crystallization 1h under self-generated pressure；After the completion of crystallization, by solid
Product is separated by filtration, and is washed with deionized to neutrality, in 550 DEG C of roasting 6h to get to having, TON/MTT is compound to be opened up after drying
Flutter the borosilicate zeolite of structure.Icp analysis SiO2/Ga2O3Molar ratio=192, BET specific surface 181.5m2/ g, XRD characterization are compound
ZSM-22:ZSM-23 molar ratio=80:20 in molecular sieve, SEM result Molecular Sieve Morphology are 1.5~2 μm of length, outer diameter 20~
The slender rod shaped object of 23nm.
Embodiment 16:
Composite molecular screen obtained by embodiment as above is switched into ammonium type through ion exchange, impregnates noble metal after drying and roasting
Pt, load capacity are the 0.5wt.% of molecular sieve, and the hydroisomerizing of composite molecular screen carried noble metal Pt is obtained after drying and roasting
Catalyst, using hexadecane as model reaction object progress hydrogenation reaction under hydro condition, 350 DEG C of reaction temperature, pressure
4.0MPa, liquid air speed 1.5h-1, H2/C16=700 (volume ratios), as a result as shown in the table:
As shown above, hydroisomerization catalyst is prepared by acid carrier of composite molecular screen made from this method, showed
Excellent isomerization performance out, under the preferred conditions, i-C16 yield can reach 83.1%.
Claims (8)
1. a kind of zeolite molecular sieve containing TON/MTT matrix topology, it is characterised in that zeolite molecular sieve is to contain TON/
The zeolite molecular sieve of MTT matrix topology becomes SiO by oxide mol ratio group2: M2O3=10-200, wherein M=B, Fe or
Ga, ZSM-22:ZSM-23 molar ratio are 10-90:90-10, BET specific surface 162.7-184.2 m2/ g, particle are length 1-2 μ
M, outer diameter 20-50nm are uniform.
2. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as described in claim 1, special
Sign is to include the following steps:
(1) inorganic alkali source is added in deionized water, stirring sequentially adds template A, boron source, source of iron or gallium after being completely dissolved
Stirring is continued to mixture to after being completely dissolved in source, and addition template B and silicon source, being formed has the initial of following mol ratio
Gel mixture, silicon source is with SiO2Meter, boron source or source of iron or gallium source are with M2O3Meter, alkali source is with OH-Meter, SiO2: M2O3: template A:
Template B:OH-: deionized water=1:0.1-0.01:0.05-5.0:0.05-5.0:0.005-2.0:10.0-200.0, it is described
Template A is second methylamine, diethylamine, 1,6- hexamethylene diamine, N- isopropyl diethylenetriamine, 1- methylbutylamine, a kind of in ethylenediamine
Or two kinds of mixing, the template B be dimethylamine, dimethylformamide, n-propylamine, isopropylamine, n-butylamine, isobutyl amine,
Neopentyl amine, trimethylamine, N- isopropyl -1,3- propane diamine and N, N, N', N', one or both of-tetramethyl dipropylenetriamine
Mixing；
(2) into step (1) resulting initial gel mixture, total silicon ZSM-22 molecular sieve is added as crystal seed, with SiO2Meter,
Its additive amount by addition silicon source 1-10wt%, be placed in ultrasonic unit, at 25-100 DEG C, ultrasonic frequency 40-60kHz,
It is carried out sonic oscillation 10-180 minutes under the conditions of ultrasonic power 100-2500W；
(3) mixture obtained after step (2) ultrasound is placed in the high-pressure microwave reaction kettle with polytetrafluoroethyllining lining, is utilized
Microwave radiation is heated to 140-200 DEG C, crystallization 0.5-8h under self-generated pressure；
(4) after the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, in 400-600 DEG C after drying
1-72h is roasted to get the zeolite molecular sieve containing TON/MTT matrix topology is arrived.
3. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as claimed in claim 2, special
Sign is that the alkali source is the combination of one or both of sodium hydroxide, potassium hydroxide.
4. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as claimed in claim 2, special
Sign be the boron source be Boratex, potassium borate, in boric acid one or any of several combination.
5. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as claimed in claim 2, special
Sign be source of iron be ferric sulfate, ferric nitrate, iron chloride, in ironic citrate soluble ferric iron salt one or any of several combination.
6. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as claimed in claim 2, special
Sign be gallium salt be gallium nitrate, gallium chloride, in gallium sulfate solubility gallium salt one or any of several combination.
7. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as claimed in claim 2, special
Sign be the silicon source be one of silica solution, Silica hydrogel, methyl orthosilicate, ethyl orthosilicate, sodium metasilicate, white carbon black or
Any several combination.
8. a kind of preparation method of the zeolite molecular sieve containing TON/MTT matrix topology as claimed in claim 2, special
Sign is that the microwave radiation frequencies are 900-4500MHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710609648.2A CN107416860B (en) | 2017-07-25 | 2017-07-25 | A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710609648.2A CN107416860B (en) | 2017-07-25 | 2017-07-25 | A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107416860A CN107416860A (en) | 2017-12-01 |
| CN107416860B true CN107416860B (en) | 2019-11-05 |
Family
ID=60431044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710609648.2A Active CN107416860B (en) | 2017-07-25 | 2017-07-25 | A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107416860B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516472B (en) * | 2019-01-23 | 2022-03-22 | 黑龙江大学 | Synthesis method of Ga isomorphous substituted nano GaZSM-22 molecular sieve |
| CN109939726A (en) * | 2019-04-08 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | A kind of preparation and application of the catalyst of the molecular sieve of MTT containing hetero atom |
| CN113830780B (en) * | 2020-06-08 | 2023-07-04 | 中国石油化工股份有限公司 | MTT molecular sieve and synthesis method and application thereof |
| CN112322333B (en) * | 2020-10-21 | 2021-11-16 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
| CN115703071A (en) * | 2021-08-05 | 2023-02-17 | 中国石油化工股份有限公司 | Aromatic methylation catalyst and preparation method and application thereof |
| CN114655964B (en) * | 2022-04-20 | 2023-04-28 | 太原理工大学 | TON/MRE double-topological structure composite molecular sieve and preparation thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693196A (en) * | 2005-06-03 | 2005-11-09 | 中国科学院大连化学物理研究所 | Micropore crystalline aluminium silicate and its preparation process |
| CN1769173A (en) * | 2005-09-22 | 2006-05-10 | 中国科学院大连化学物理研究所 | ZSM-22/ZSM-23 composite molecular screen and its preparation method |
| CN1792451A (en) * | 2005-12-21 | 2006-06-28 | 中国科学院大连化学物理研究所 | Hydro-isomerization catalyst for paraffine, and its preparing method and application |
| CN101591560A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of diesel oil hydrofining catalyst and preparation method thereof |
| CN103964460A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Microporous composite silicon aluminum molecular sieve and preparation method thereof |
-
2017
- 2017-07-25 CN CN201710609648.2A patent/CN107416860B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693196A (en) * | 2005-06-03 | 2005-11-09 | 中国科学院大连化学物理研究所 | Micropore crystalline aluminium silicate and its preparation process |
| CN1769173A (en) * | 2005-09-22 | 2006-05-10 | 中国科学院大连化学物理研究所 | ZSM-22/ZSM-23 composite molecular screen and its preparation method |
| CN1792451A (en) * | 2005-12-21 | 2006-06-28 | 中国科学院大连化学物理研究所 | Hydro-isomerization catalyst for paraffine, and its preparing method and application |
| CN101591560A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of diesel oil hydrofining catalyst and preparation method thereof |
| CN103964460A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Microporous composite silicon aluminum molecular sieve and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Hydroisomerization performance of platinum supported on ZSM-22/ZSM-23 intergrowth zeolite catalyst;Chi Kebin et al.;《Petroleum Science》;20131231;第10卷(第2期);第242-250页 * |
| Synthesis of ZSM-23/ZSM-22 intergrowth zeolite with a novel dual-template strategy;Bingchun Wang et al.;《Materials Research Bulletin》;20090805;第44卷;第2258–2261页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107416860A (en) | 2017-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107416860B (en) | A kind of zeolite molecular sieve and preparation method thereof containing TON/MTT matrix topology | |
| CN107235497B (en) | A kind of adjustable multistage pore canal composite molecular screen of acid distribution and preparation method thereof | |
| CN107758691B (en) | The preparation method of high silicon CHA types SSZ-13 molecular sieves | |
| CN104418349B (en) | It is a kind of in, the preparation method of the compound duct Beta molecular sieve of micropore | |
| CN101935053B (en) | ZSM-5 zeolite and synthesis method thereof | |
| CN106513035A (en) | Preparation method for mesoporous-microporous composite hydroisomerization dewaxing catalyst | |
| CN104525245B (en) | Nanocrystalline accumulation meso-microporous ZSM-5 catalyst and preparation and application | |
| CN104646047A (en) | Hierarchical porous composite molecular sieve, preparation and application thereof | |
| CN103626202A (en) | Method for preparing catalyst used for methanol/dimethyl ether high selectivity propylene preparation | |
| CN105621445B (en) | A kind of NaY types molecular sieve and preparation method thereof | |
| CN100509627C (en) | ZSM-23/ZSM-22 composite molecular sieve and preparation method thereof | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN105000571A (en) | EU-1/ZMS-48 intergrowth zeolite and preparation and application thereof | |
| CN105645427B (en) | The preparation method of the molecular sieves of ZSM 22 with mesoporous micropore graded structure | |
| CN107311191A (en) | A kind of method of microwave irradiation synthesis composite molecular screen | |
| JP2017521232A (en) | Catalyst suitable for production of aircraft kerosene from synthetic oil obtained by biomass Fischer-Tropsch process and process for its preparation | |
| CN114436279B (en) | ZSM-22 molecular sieve, preparation method and application thereof, and n-dodecane isomerization reaction | |
| CN106745053A (en) | Microwave synthesizes the method for high selectivity preparing propylene from methanol molecular sieve of Nano zeolite | |
| CN106672997A (en) | Modified Y type molecular sieve and preparation method thereof | |
| CN107311202B (en) | A kind of method of low template dosage synthesis ZSM-22/ZSM-23 composite molecular screen | |
| CN108114743A (en) | A kind of solid phase synthesis process of hydroisomerization catalyst | |
| CN106517229B (en) | The method that hydrothermal synthesis method prepares nano-sheet SAPO-11 molecular sieves | |
| CN102205250B (en) | Catalyst for catalyzing and dewaxing lubricating oil and application thereof | |
| CN1769173B (en) | ZSM-22/ZSM-23 composite molecular screen and its preparation method | |
| CN105668580A (en) | Composite-structure molecular sieve and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |