CN107235497B - A kind of adjustable multistage pore canal composite molecular screen of acid distribution and preparation method thereof - Google Patents
A kind of adjustable multistage pore canal composite molecular screen of acid distribution and preparation method thereof Download PDFInfo
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Abstract
A kind of adjustable multistage pore canal composite molecular screen of acid distribution is based on oxide, molar ratio composition are as follows: SiO2: Al2O3=4.6-982, molecular sieve contain TON and MTT matrix topology, and ZSM-22:ZSM-23 molar ratio is 10-90:90-10, BET specific surface 253.2-283.7 m2/ g, particle are length≤1 μm, outer diameter 20-30nm club.Composite molecular screen of the present invention has the characteristics that multistage acid, duct, and the distribution of TON/MTT ratio is adjustable, and can modulation silica alumina ratio in a wider range.
Description
Fields
The present invention relates to adjustable multistage pore canal composite molecular screens of a kind of acid distribution and preparation method thereof.
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.It is such
Composite molecular screen product obtained by method is unevenly distributed in the presence of composition, and cellular structure distributes irregular disadvantage, is unable to fully
Play the compound concerted catalysis performance of ZSM-23 molecular screen and ZSM-22 molecular sieve.It is different from such patent preparation method, China
Patent of invention CN103964460 discloses a kind of compound Si-Al molecular sieve of micropore and preparation method thereof, utilizes conventional sol-gel
The synthesis of template hydrothermal crystallizing has the Si-Al molecular sieve of the microcosmic Compound Topology structure of TON/MTT.But what such method obtained
ZSM-22 and ZSM-23 relative amount randomness is larger in composite molecular screen, may change, nothing with the variation of reaction condition
Method carries out control accurate by preparation means, and adaptability is poor.
Summary of the invention
For current ZSM-22/ZSM-23 composite molecular screen have the shortcomings that preparation on and microstructure Controllability,
The object of the present invention is to provide a kind of ZSM-22 and ZSM-23 relative amount is controllable, a kind of excellent acid distribution of catalytic performance can
Multistage pore canal composite molecular screen of tune and preparation method thereof.
It is well known that the cracking process being often associated with while isomery occurs for carbochain for hydro-refining isomery reaction process, fit
When crack favorable in adjustment carbon chain lengths and optimized product physical index, improve properties of product.The present invention provides a kind of compound
Molecular sieve and preparation method, the molecular sieve of TON/MTT Compound Topology structure have the characteristics that multistage acid, cellular structure, pass through
The ratio that various parameters are adjusted between two kinds of structures is adjusted, to reach the depth regulation to reaction process, therefore the present invention
The composite molecular screen of offer petrochemical industry be hydrocracked in terms of have great potential using value.
The present invention provides a kind of adjustable multistage pore canal composite molecular screen of acid distribution, based on oxide, molar ratio composition
Are as follows: SiO2: Al2O3=4.6-982, molecular sieve contain TON (ZSM-22) and MTT (ZSM-23) matrix topology, ZSM-22:
ZSM-23 molar ratio is 10-90:90-10, BET specific surface 253.2-283.7m2/ g, particle are length≤1 μm, outer diameter 20-
30nm club.
Method preparation is prepared as follows in composite molecular screen provided by the invention:
(1) inorganic alkali source is added in deionized water, template A, silicon source is successively added after being completely dissolved in stirring, continues to stir
It mixes to mixture to after being completely dissolved, template B and silicon source is added, form first part of Primogel with following mol ratio
Mixture, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter, SiO2: Al2O3: template A: template B:OH-: it goes
Ionized water=1:0.2-0.001:0.05-5.0:0.05-5.0:0.005-2.0:10.0-200.0；
(2) first part of initial gel mixture for obtaining step (1) is transferred in crystallizing kettle, in 140-200 DEG C, crystallization 6-
After 48h, solid product is separated by filtration, is washed with deionized to neutrality, obtains the compound initial original powder of Si-Al molecular sieve after dry；
(3) inorganic alkali source is added in deionized water again by material identical as step (1), stirring is successive after being completely dissolved
Template A, silicon source is added, continues stirring to mixture to after being completely dissolved, addition template B and silicon source are formed with as follows
Second part of initial gel mixture of mol ratio, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter, SiO2:
Al2O3: template A: template B:OH-: deionized water=1:0.2-0.001:0.025-2.5:0.025-2.5:0.005-2.0:
10.0-200.0；The initial original powder of compound Si-Al molecular sieve that step (2) obtains is added in second part of Primogel, is added
Amount is the SiO in the initial original powder of compound Si-Al molecular sieve2Weight: the SiO in second part of Primogel2Weight=1:99-10:90,
It is placed in ultrasonic unit, is carried out under the conditions of 25-100 DEG C, ultrasonic frequency 40-60kHz, ultrasonic power 100-2500W
Sonic oscillation 10-180 minutes, obtain mixture；
(4) mixture that step (3) obtains is placed in 140-200 DEG C, crystallization 12-240h, after the completion of crystallization, by solid
Product is separated by filtration, and is washed with deionized to neutrality, is divided after dry in 400-600 DEG C of roasting 1-72h to get to compound sial
Son sieve.
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.
Silicon source as described above is boehmite, aluminium chloride, aluminum sulfate, aluminum nitrate, aluminium isopropoxide, a kind of in sodium aluminate
Or any several combination.
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.
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.
The mode of crystallization can be static crystallization under pressure itself in step (2) as described above, and it is brilliant to be also possible to dynamic
Change.
The mode of crystallization can be static crystallization under pressure itself in step (4) as described above, and it is brilliant to be also possible to dynamic
Change.
The compound Si-Al molecular sieve of TON/MTT of the present invention and provided preparation method with existing similar compound point
Son sieve is compared with method, is had the advantages that
(1) the present invention relates to the molecular sieves with TON/MTT Compound Topology structure to have multistage acid, duct,
And distribution can carry out modulation by the relative amounts and preparation parameter of double template, reach to the proportional amount of standard of TON/MTT
Really regulation.
(2) composite molecular screen of the present invention can in wider range modulation silica alumina ratio (5-1000), therefore especially
It is suitble to requirement of the wax containing long chain hydrocarbons to molecular sieve, there is excellent catalytic for the hydro-isomerization pour-point depressing process of long chain hydrocarbons
Can, adaptability is high, be hydrocracked in terms of have great potential using value.
(3) synthetic method provided by the invention is used, template, which not yet roasts, in the nucleus as made of a crystallization divides
Solution, secondary crystallization can reduce the use of template in the process, reduce the synthesis cost of molecular sieve and the influence to environment.
(4) synthetic method provided by the invention is used, on the one hand sonic oscillation auxiliary can make the nucleus of a crystallization uniform
Dispersion, on the other hand can rapid induction gel solution nucleating surface made of a crystallization agglomerate secondary Cheng Jing, effectively avoid
The appearance of stray crystal in follow-up hydrothermal crystallization process, therefore compared with existing synthetic method, composite molecular screen obtained is without stray crystal
Phase, granularity is small and uniform, prepares favorable reproducibility.
Detailed description of the invention
Fig. 1 is the XRD spectra that embodiment 2 synthesizes TON/MTT Compound Topology structure molecular screen.
Fig. 2 is the XRD spectra that embodiment 6 synthesizes TON/MTT Compound Topology structure molecular screen.
Fig. 3 is the SEM figure that embodiment 2 synthesizes TON/MTT Compound Topology structure molecular screen.
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, sodium aluminate 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, first part with following mol ratio of formation initial
(silicon source is with SiO for gel mixture2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2: Al2O3: second methylamine: dimethylamine: OH-:
Mol ratio=1:0.2:0.05:5.0:0.005:10.0 of deionized water；Obtain first part of initial gel mixture is turned
Enter in crystallizing kettle, under 140 DEG C, self-generated pressure after crystallization 48h, solid product is separated by filtration, is washed with deionized into
Property, the compound initial original powder of Si-Al molecular sieve is obtained after dry；By raw material SiO2: Al2O3: template A: template B:OH-: deionization
Mol ratio=1:0.2:0.025:2.5:0.005:10.0 of water prepares second part of initial gel mixture (material and again
A Primogel is identical), the initial original powder of molecular sieve obtained above is added in second part of Primogel, additive amount is first
SiO in beginning original powder2Weight: the SiO in second part of Primogel2Weight=1:99, is placed in ultrasonic unit, at 25 DEG C, surpasses
It is carried out sonic oscillation 180 minutes under the conditions of frequency of sound wave 40kHz, ultrasonic power 100W；Obtained mixture is placed in 140
DEG C, crystallization 240h under self-generated pressure；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, is done
72h is roasted to get the Si-Al molecular sieve with TON/MTT Compound Topology structure is arrived in 400 DEG C after dry.Icp analysis SiO2/Al2O3
Molar ratio=4.6, BET specific surface 283.7m2/ g, ZSM-22:ZSM-23 molar ratio=10:90 in XRD characterization composite molecular screen,
Particle is 0.2~0.4 μm of length, 20~25nm of outer diameter.
Embodiment 2:
Potassium hydroxide is added in deionized water, diethylamine, boehmite is successively added after being completely dissolved in stirring, continues
After stirring is completely dissolved to mixture, it is sequentially added into dimethylformamide, n-propylamine and Silica hydrogel, being formed has following mole
(silicon source is with SiO for first part of initial gel mixture of proportion2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2: Al2O3:
Diethylamine: dimethylformamide+n-propylamine: OH-: mol ratio=1:0.1:0.1:4.0 (dimethyl formyl of deionized water
Amine: molar ratio=1:1 of n-propylamine): 0.01:30.0；Obtain first part of initial gel mixture is transferred in crystallizing kettle,
145 DEG C, under self-generated pressure after crystallization 48h, solid product is separated by filtration, is washed with deionized to neutrality, must be answered after dry
Close the initial original powder of Si-Al molecular sieve；By raw material proportioning SiO2: Al2O3: diethylamine: dimethylformamide+n-propylamine: OH-: go from
Mol ratio=1:0.1:0.05:2.0 (dimethylformamide: molar ratio=1:1 of n-propylamine): 0.01:30.0 weight of sub- water
Second part of initial gel mixture (material is identical as first part of Primogel) is newly prepared, molecular sieve obtained above is initially former
Powder is added in second part of Primogel, and additive amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2Weight
Amount=2:98, is placed in ultrasonic unit, and ultrasound is carried out under the conditions of 25 DEG C, ultrasonic frequency 50kHz, ultrasonic power 500W
Oscillation 120 minutes；Obtained mixture is placed in 150 DEG C, crystallization 120h under self-generated pressure；After the completion of crystallization, solid is produced
Object is separated by filtration, and is washed with deionized to neutrality, in 450 DEG C of roasting 36h to get to having, TON/MTT is compound to be opened up after drying
Flutter the Si-Al molecular sieve of structure.Icp analysis SiO2/Al2O3Molar ratio=8.5, BET specific surface 271.4m2/ g, XRD characterization are compound
ZSM-22:ZSM-23 molar ratio=30:70 in molecular sieve, particle are 0.3~0.5 μm of length, 20~25nm of outer diameter.
Embodiment 3:
Potassium hydroxide is added in deionized water, 1,6- hexamethylene diamine, aluminium chloride 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 first part of initial gel mixture of proportion2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2:
Al2O3: 1,6- hexamethylene diamine: isopropylamine: OH-: deionized water mol ratio=1 (methyl orthosilicate: ethyl orthosilicate=1:1,
With SiO2Count molar ratio): 0.05:0.2:3.0:0.02:20.0；Obtain first part of initial gel mixture is transferred to crystallizing kettle
In, under 150 DEG C, self-generated pressure crystallization for 24 hours after, solid product is separated by filtration, is washed with deionized to neutrality, after dry
Obtain the compound initial original powder of Si-Al molecular sieve；By raw material SiO2: Al2O3: template A: template B:OH-: deionized water mole is matched
Than=1 (methyl orthosilicate: ethyl orthosilicate=1:1, with SiO2Count molar ratio): 0.05:0.1:1.5:0.02:20.0 matches again
Second part of initial gel mixture (material is identical as first part of Primogel) is made, the initial original powder of molecular sieve obtained above is added
It is added in second part of Primogel, additive amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2Weight=
5:95 is placed in ultrasonic unit, and ultrasonic vibration is carried out under the conditions of 50 DEG C, ultrasonic frequency 50kHz, ultrasonic power 1000W
It swings 60 minutes；Resulting initial gel mixture is placed in 150 DEG C, crystallization 64h under self-generated pressure；After the completion of crystallization, it will consolidate
Body product is separated by filtration, and is washed with deionized to neutrality, is answered for 24 hours to get to TON/MTT after dry in 500 DEG C of roastings
Close the Si-Al molecular sieve of topological structure.Icp analysis SiO2/Al2O3Molar ratio=18.5, BET specific surface 279.2m2/ g, XRD table
ZSM-22:ZSM-23 molar ratio=25:75 in composite molecular screen is levied, particle is 0.2~0.5 μm of length, 20~25nm 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, aluminum sulfate and aluminum nitrate continue to be sequentially added into n-butylamine, isobutyl amine and just after stirring is completely dissolved to mixture
Silester, forming first part of initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, silicon source is with Al2O3
Meter, alkali source is with OH-Meter), SiO2: Al2O3: N- isopropyl diethylenetriamine: n-butylamine+isobutyl amine: OH-: mole of deionized water
Proportion=1:0.02 (aluminum sulfate: aluminum nitrate=1:2, molar ratio, with Al2O3Meter): 0.5:2.5 (n-butylamine: isobutyl amine=1:4,
Molar ratio): 0.05 (potassium hydroxide: sodium hydroxide=2:3, molar ratio): 50.0；By obtain first part of initial gel mixture
Be transferred in crystallizing kettle, under 160 DEG C, self-generated pressure after crystallization 12h, solid product be separated by filtration, be washed with deionized to
Neutrality obtains the compound initial original powder of Si-Al molecular sieve after dry；By raw material SiO2: Al2O3: N- isopropyl diethylenetriamine: n-butylamine
+ isobutyl amine: OH-: mol ratio=1:0.02 (aluminum sulfate: aluminum nitrate=1:2, molar ratio, with Al of deionized water2O3Meter):
0.25:1.25 (n-butylamine: isobutyl amine=1:4, molar ratio): 0.05 (potassium hydroxide: sodium hydroxide=2:3, molar ratio): 50.0
Again second part of initial gel mixture (material is identical as first part of Primogel) is prepared, molecular sieve obtained above is initial
Original powder is added in second part of Primogel, and additive amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2
Weight=5:95, is placed in ultrasonic unit, carries out under the conditions of 50 DEG C, ultrasonic frequency 60kHz, ultrasonic power 1000W
Sonic oscillation 60 minutes；Obtained mixture is placed in 160 DEG C, crystallization 48h under self-generated pressure；After the completion of crystallization, by solid
Product is separated by filtration, and is washed with deionized to neutrality, compound with TON/MTT to get arriving in 500 DEG C of roasting 12h after dry
The Si-Al molecular sieve of topological structure.Icp analysis SiO2/Al2O3Molar ratio=45, BET specific surface 253.2m2/ g, XRD characterization are multiple
ZSM-22:ZSM-23 molar ratio=40:60 in molecular sieve is closed, particle is 0.6~1 μm of length, 25~30nm 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,
Aluminum nitrate continues to be sequentially added into special amylamine and white carbon black, being formed, which has following mole, matches after stirring is completely dissolved to mixture
(silicon source is with SiO for first part of initial gel mixture of ratio2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2: Al2O3: 1-
Methylbutylamine: special amylamine: OH-: mol ratio=1:0.01:1.0:1.0:0.1 (potassium hydroxide: sodium hydroxide of deionized water
=1:1, molar ratio): 70.0；Obtain first part of initial gel mixture is transferred in crystallizing kettle, in 170 DEG C, self-generated pressure
After lower crystallization 12h, solid product is separated by filtration, is washed with deionized to neutrality, at the beginning of obtaining compound Si-Al molecular sieve after dry
Beginning original powder；By raw material proportioning SiO2: Al2O3: template A: template B:OH-: mol ratio=1:0.01 of deionized water:
0.5:0.5:0.1 (potassium hydroxide: sodium hydroxide=1:1, molar ratio): 70.0 prepare second part of initial gel mixture again
(material is identical as first part of Primogel), the initial original powder of molecular sieve obtained above is added in second part of Primogel,
Additive amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2Weight=7.5:92.5, is placed in ultrasonic wave
Device carries out sonic oscillation 30 minutes under the conditions of 100 DEG C, ultrasonic frequency 60kHz, ultrasonic power 2000W；By what is obtained
Mixture is placed in 170 DEG C, crystallization 36h under self-generated pressure；After the completion of crystallization, solid product is separated by filtration, uses deionized water
Washing roasts 6h in 550 DEG C to neutrality to get the Si-Al molecular sieve with TON/MTT Compound Topology structure is arrived after dry.ICP
Analyze SiO2/Al2O3Molar ratio=84, BET specific surface 266.7m2/ g, ZSM-22:ZSM-23 rubs in XRD characterization composite molecular screen
You are ratio=55:45, and particle is 0.3~0.6 μm of length, 25~30nm of outer diameter.
Embodiment 6:
Sodium hydroxide is added in deionized water, ethylenediamine, aluminium isopropoxide is successively added after being completely dissolved in stirring, continues to stir
It mixes to mixture after being completely dissolved, is sequentially added into trimethylamine and white carbon black, formed at the beginning of first part with following mol ratio
(silicon source is with SiO for beginning gel mixture2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2: Al2O3: ethylenediamine: trimethylamine:
OH-: mol ratio=1:0.005:2.0:0.5:0.2:100.0 of deionized water；Obtain first part of Primogel is mixed
Object is transferred in crystallizing kettle, and under 180 DEG C, self-generated pressure after crystallization 9h, solid product is separated by filtration, be washed with deionized to
Neutrality obtains the compound initial original powder of Si-Al molecular sieve after dry；By raw material proportioning SiO2: Al2O3: template A: template B:OH-:
Mol ratio=1:0.005:1.0:0.25:0.2:100.0 of deionized water prepares second part of initial gel mixture (object again
Expect identical as first part of Primogel), the initial original powder of molecular sieve obtained above is added in second part of Primogel, is added
Amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2Weight=10:90, is placed in ultrasonic unit,
It is carried out sonic oscillation 10 minutes under the conditions of 100 DEG C, ultrasonic frequency 60kHz, ultrasonic power 2500W；The mixture that will be obtained
It is placed in 180 DEG C, crystallization is for 24 hours under self-generated pressure；After the completion of crystallization, solid product is separated by filtration, be washed with deionized to
Neutrality roasts 6h in 550 DEG C to get the Si-Al molecular sieve with TON/MTT Compound Topology structure is arrived after dry.Icp analysis
SiO2/Al2O3Molar ratio=181, BET specific surface 264.5m2/ g, ZSM-22:ZSM-23 moles in XRD characterization composite molecular screen
Than=75:25, particle is 0.3~0.6 μm of length, 25~30nm of outer diameter.
Embodiment 7:
Sodium hydroxide is added in deionized water, ethylenediamine, N- isopropyl divinyl is successively added after being completely dissolved in stirring
Triamine, boehmite, aluminum sulfate 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 first part of initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, silicon source is with Al2O3
Meter, alkali source is with OH-Meter), SiO2: Al2O3: ethylenediamine+N- isopropyl diethylenetriamine: N- isopropyl -1,3- propane diamine: OH-: it goes
Mol ratio=1:0.002 (boehmite: aluminum sulfate=1:1, molar ratio, with Al of ionized water2O3Meter): 5.0 (ethylenediamine:
N- isopropyl diethylenetriamine=4:1, molar ratio): 0.1:0.5:100.0；Obtain first part of initial gel mixture is turned
Enter in crystallizing kettle, under 200 DEG C, self-generated pressure after crystallization 6h, solid product is separated by filtration, is washed with deionized into
Property, the compound initial original powder of Si-Al molecular sieve is obtained after dry；By raw material proportioning SiO2: Al2O3: ethylenediamine+N- isopropyl divinyl three
Amine: N- isopropyl -1,3- propane diamine: OH-: deionized water mol ratio=1:0.002 (boehmite: aluminum sulfate=1:
1, molar ratio, with Al2O3Meter): 2.5 (ethylenediamines: N- isopropyl diethylenetriamine=4:1, molar ratio): 0.05:0.5:100.0
Again second part of initial gel mixture (material is identical as first part of Primogel) is prepared, molecular sieve obtained above is initial
Original powder is added in second part of Primogel, and additive amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2
Weight=5:95, is placed in ultrasonic unit, is surpassed under the conditions of 75 DEG C, ultrasonic frequency 40kHz, ultrasonic power 500W
Sound oscillation 60 minutes；Resulting mixture mixture is placed in 200 DEG C, crystallization 12h under self-generated pressure；It, will after the completion of crystallization
Solid product is separated by filtration, and is washed with deionized to neutrality, is answered after dry in 600 DEG C of roasting 2h to get to TON/MTT
Close the Si-Al molecular sieve of topological structure.Icp analysis SiO2/Al2O3Molar ratio=463, BET specific surface 268.0m2/ g, XRD characterization
ZSM-22:ZSM-23 molar ratio=65:35 in composite molecular screen, particle are 0.3~0.6 μm of length, 25~30nm of outer diameter.
Embodiment 8:
Sodium hydroxide is added in deionized water, diethylamine, 1- methylbutylamine, aluminic acid is successively added after being completely dissolved in stirring
Sodium, continue stirring be completely dissolved to mixture after, be sequentially added into N, N, N', N' ,-tetramethyl dipropylenetriamine, sodium metasilicate and
Silica solution, forming first part of initial gel mixture with following mol ratio, (silicon source is with SiO2Meter, silicon source is with Al2O3Meter,
Alkali source is with OH-Meter), SiO2: Al2O3: diethylamine+1- methylbutylamine: N, N, N', N' ,-tetramethyl dipropylenetriamine: OH-: go from
Mol ratio=1 (the sodium metasilicate: silica solution=1:1, molar ratio, with SiO of sub- water2Meter): 0.001:1.0 (diethylamine: 1- methyl
Butylamine=1:1, molar ratio): 0.05:1.0:200.0；Obtain first part of initial gel mixture is transferred in crystallizing kettle,
175 DEG C, under self-generated pressure crystallization for 24 hours after, solid product is separated by filtration, is washed with deionized to neutrality, must be answered after dry
Close the initial original powder of Si-Al molecular sieve；By raw material SiO2: Al2O3: diethylamine+1- methylbutylamine: N, N, N', N' ,-tetramethyl dipropyl
Alkene triamine: OH-: the mol ratio=1 (sodium metasilicate: silica solution=1:1, molar ratio, with SiO of deionized water2Meter): 0.001:0.5
(diethylamine: 1- methylbutylamine=1:1, molar ratio): 0.025:1.0:200.0 prepares second part of initial gel mixture again
(material is identical as first part of Primogel), the initial original powder of molecular sieve obtained above is added in second part of Primogel,
Additive amount is the SiO in initial original powder2Weight: the SiO in second part of Primogel2Weight=10:90 is placed in ultrasonic wave dress
It sets, is carried out sonic oscillation 60 minutes under the conditions of 75 DEG C, ultrasonic frequency 50kHz, ultrasonic power 1000W；It is mixed by what is obtained
Close object be placed in 170 DEG C, crystallization 64h under self-generated pressure；After the completion of crystallization, solid product is separated by filtration, is washed with deionized water
It washs to neutrality, 1h is roasted after dry in 600 DEG C to get the Si-Al molecular sieve with TON/MTT Compound Topology structure is arrived.ICP points
Analyse SiO2/Al2O3Molar ratio=982, BET specific surface 264.7m2/ g, ZSM-22:ZSM-23 rubs in XRD characterization composite molecular screen
You are ratio=90:10, and particle is 0.3~0.6 μm of length, 25~30nm of outer diameter.
Embodiment 9:
Sodium hydroxide is added in deionized water, ethylenediamine, aluminum sulfate is successively added after being completely dissolved in stirring, continues to stir
After being completely dissolved to mixture, it is sequentially added into ethamine and white carbon black, being formed, there is first part of following mol ratio initially to be coagulated
(silicon source is with SiO for glue mixture2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2: Al2O3: ethylenediamine: ethamine: OH-: go from
Mol ratio=1:0.005:1.0:2.0:2.0:75.0 of sub- water；Obtain first part of initial gel mixture is transferred to crystallization
In kettle, under 170 DEG C, self-generated pressure crystallization for 24 hours after, solid product is separated by filtration, is washed with deionized to neutrality, it is dry
Afterwards the initial original powder of compound Si-Al molecular sieve；By raw material SiO2: Al2O3: ethylenediamine: ethamine: OH-: the mol ratio of deionized water
=1:0.005:0.5:1.0:2.0:75.0 prepares second part of initial gel mixture (material and first part of Primogel phase again
Together), the initial original powder of molecular sieve obtained above is added in second part of Primogel, additive amount is the SiO in initial original powder2
Weight: the SiO in second part of Primogel2Weight=2:98, is placed in ultrasonic unit, at 25 DEG C, ultrasonic frequency
It is carried out sonic oscillation 30 minutes under the conditions of 50kHz, ultrasonic power 1000W；Obtained mixture is placed in 160 DEG C, spontaneous pressure
Crystallization 64h under power；After the completion of crystallization, solid product is separated by filtration, is washed with deionized to neutrality, in 500 after drying
DEG C roasting 3h to get to TON/MTT Compound Topology structure Si-Al molecular sieve.Icp analysis SiO2/Al2O3Molar ratio=
171, BET specific surface 256.5m2/ g, ZSM-22:ZSM-23 molar ratio=50:50 in XRD characterization composite molecular screen, particle are length
0.4~0.8 μm of degree, 25~30nm of outer diameter.
Embodiment 10
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 80.4%.
Claims (7)
1. a kind of adjustable multistage pore canal composite molecular screen of acid distribution, it is characterised in that composite molecular screen contains TON and MTT bone
Frame topological structure, wherein oxide mol ratio forms are as follows: SiO2: Al2O3=4.6-982, ZSM-22:ZSM-23 molar ratio are 10-
90:90-10, BET specific surface 253.2-283.7 m2/ g, particle are length≤1 μm, outer diameter 20-30nm.
2. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as described in claim 1, feature
It is to include the following steps:
(1) inorganic alkali source is added in deionized water, template A, silicon source is successively added after being completely dissolved in stirring, continues stirring extremely
Template B and silicon source is added to after being completely dissolved in mixture, and being formed, there is first part of Primogel of following mol ratio to mix
Object, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter, SiO2: Al2O3: template A: template B:OH-: deionization
Water=1:0.2-0.001:0.05-5.0:0.05-5.0:0.005-2.0:10.0-200.0；The template A be second methylamine,
Diethylamine, 1,6- hexamethylene diamine, N- isopropyl diethylenetriamine, in 1- methylbutylamine, one or two kinds of mixing of ethylenediamine, institute
The template B stated is dimethylamine, dimethylformamide, n-propylamine, isopropylamine, n-butylamine, isobutyl amine, neopentyl amine, trimethylamine, N-
Isopropyl -1,3- propane diamine and N, N, N', N', the mixing of one or both of-tetramethyl dipropylenetriamine；
(2) first part of initial gel mixture for obtaining step (1) is transferred in crystallizing kettle, in 140-200 DEG C, crystallization 6-48h
Afterwards, solid product is separated by filtration, is washed with deionized to neutrality, obtain the compound initial original powder of Si-Al molecular sieve after dry；
(3) inorganic alkali source is added in deionized water again by material identical as step (1), stirring is successively added after being completely dissolved
Template A, silicon source continue stirring to mixture to after being completely dissolved, and addition template B and silicon source, being formed has following mole
Second part of initial gel mixture of proportion, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter, SiO2: Al2O3: mould
Plate agent A: template B:OH-: deionized water=1:0.2-0.001:0.025-2.5:0.025-2.5:0.005-2.0:10.0-
200.0；The initial original powder of molecular sieve that step (2) obtains is added in second part of Primogel, additive amount is in initial original powder
SiO2Amount: the SiO in second part of Primogel2Amount=1:99-10:90, is placed in ultrasonic unit, at 25-100 DEG C, ultrasound
It is carried out sonic oscillation 10-180 minutes under the conditions of wave frequency rate 40-60kHz, ultrasonic power 100-2500W, obtains mixture；
(4) mixture that step (3) obtains is placed in 140-200 DEG C, crystallization 12-240h, after the completion of crystallization, by solid product
Be separated by filtration, be washed with deionized to neutrality, it is dry after in 400-600 DEG C of roasting 1-72h to get to compound silicoaluminophosphate molecular
Sieve.
3. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, feature
It 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 adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, feature
Be the silicon source be boehmite, it is aluminium chloride, aluminum sulfate, aluminum nitrate, aluminium isopropoxide, a kind of or any several in sodium aluminate
The combination of kind.
5. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, feature
It is that the silicon source is one of silica solution, Silica hydrogel, methyl orthosilicate, ethyl orthosilicate, sodium metasilicate, white carbon black or appoints
It anticipates several combinations.
6. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, feature
The mode for being crystallization in the step (2) is static crystallization or dynamic crystallization under pressure itself.
7. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, feature
The mode for being crystallization in the step (4) is static crystallization or dynamic crystallization under pressure itself.
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| 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 |
| WO2022148424A1 (en) | 2021-01-07 | 2022-07-14 | 中国石油化工股份有限公司 | Zsm-23 molecular sieve and preparation method therefor |
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