CN107235497A - 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, and mol ratio composition is：SiO2：Al2O3=4.6 982, molecular sieve contains TON and MTT matrix topologies, ZSM 22：The mol ratios of ZSM 23 are 10 90：90 10, BET are than the m of surface 253.2 283.72/ g, particle is length≤1 μm, the 30nm clubs of external diameter 20.The features such as composite molecular screen of the present invention has multistage acid, duct, and the distribution of TON/MTT ratios is adjustable, and can in relative broad range modulation silica alumina ratio.
Description
Art
The present invention relates to adjustable multistage pore canal composite molecular screen of a kind of acid distribution and preparation method thereof.
Background technology
The increasingly strict and auto industry that is required with environmental regulation is developed rapidly, the novel mechanical equipment of emergence
Demand to high-quality lubricating oil gradually increases, quality requirement also more and more higher.Therefore, quality of lubrication oil is to low nitrogen, low-sulfur, low
Ash content, high antioxidant, high detergency, dispersiveness, low volatility, the II of good viscosity-temperature characteristics and low temperature flow, Group III fry dried food ingredients
Exhibition is imperative, so that the base oil manufacturing process based on solvent refining and catalytic dewaxing is gradually by isomerization dewaxing technique
Substituted.Isomerization dewaxing reaction is that the long side chain of wax molecule and cycloalkane is changed into branched alkane, both reduces product
Pour point, higher Viscosity Index and yield is remained again, therefore, Isodewaxing Technology is referred to as petroleum refining field in recent years
Important Techmical Progress, its technological core is hydroisomerization catalyst, and is even more isomery as the zeolite molecular sieve of acid centre
The most important thing in catalyst.
Compared with the zeolite molecular sieve such as ZSM-5, modenite, Beta, SAPO, ZSM-22, ZSM-23 molecular screen are used as master
Acid centre is wanted, it is not only acid more suitable, and with excellent shape-selective effect, isomerisation selectivity can be significantly improved.
ZSM-22, ZSM-23 molecular screen are that a class has one-dimensional straight type, the Si-Al molecular sieve of ten-ring pore passage structure, respectively with TON,
MTT matrix topologies, a diameter of 0.56 × 0.45nm of ZSM-22 molecular sieve pore passages, ZSM-23 molecular screen channel diameter is 0.52
× 0.45nm, this two molecular sieve analogs synthesis technique is ripe, and 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 more than 200), and its pour point is high, low temperature
Poor mobile performance.N-alkane is converted into by branched paraffin by hydroisomerization reaction, these performances can be improved, height is obtained
The lube base oil of quality.However, for the longer chain n-alkane in wax, being only extremely difficult to reason by hydro-isomerization process
The pour point thought, it is desirable to which part carbochain is broken, that is, require that appropriate cracking reaction 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, pore passage structure is needed
Son sieves to meet this requirement.
Composite molecular screen is typically the composite crystal formed by two or more molecular sieve by chemical method.In knot
Both there is the characteristic of one-component on structure, itself unique architectural feature and multistage Acidity, the table in catalytic reaction are taken into account again
Reveal the exclusive cooperative effect and special reactivity worth different from pure phase molecular sieve.Micropore-mesoporous-microporous composite molecular sieve is come
Say, it has relatively low synthesis cost, higher hydrothermal stability and adjustable acid energy and micro-structural performance, so that 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, its method are to add ZSM-23 in ZSM-22 molecular sieves (or ZSM-23) Primogel
Molecular sieve (or ZSM-22) seed, obtained mixture carries out hydrothermal crystallizing and obtains ZSM-23/ZSM-22 composite molecular screens.It is such
There is composition skewness in the composite molecular screen product obtained by method, pore passage structure distributes irregular shortcoming, it is impossible to fully
Play the compound concerted catalysis performance of ZSM-23 molecular screen and ZSM-22 molecular sieves.It is different from such patent preparation method, China
Patent of invention CN103964460 discloses a kind of micropore and is combined Si-Al molecular sieve and preparation method thereof, utilizes conventional sol-gel
Si-Al molecular sieve of the template hydrothermal crystallizing synthesis with the microcosmic Compound Topology structures of TON/MTT.But what such method was obtained
ZSM-22 and ZSM-23 relative amounts randomness is larger in composite molecular screen, changes such as the change of reaction condition, nothing
Method carries out control accurate by preparation means, and adaptability is poor.
The content of the invention
Have the shortcomings that to prepare and microstructure Controllability for current ZSM-22/ZSM-23 composite molecular screens,
It is an object of the invention to provide a kind of ZSM-22 and ZSM-23 relative amounts are 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 for hydro-refining isomery reaction process, the cracking process being often associated with while isomery occurs for carbochain, fits
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 features such as molecular sieve of TON/MTT Compound Topology structures has multistage acidity, pore passage structure, pass through
The ratio between the adjustable two kinds of structures of various parameters is adjusted, so that the depth regulation and control to course of reaction are reached, therefore the present invention
The composite molecular screen of offer is hydrocracked in petrochemical industry and has great potential using value in terms of isomerization.
The present invention provides a kind of adjustable multistage pore canal composite molecular screen of acid distribution, based on oxide, mol ratio composition
For：SiO2：Al2O3=4.6-982, molecular sieve contains TON (ZSM-22) and MTT (ZSM-23) matrix topology, ZSM-22：
ZSM-23 mol ratios are 10-90：90-10, BET are than surface 253.2-283.7m2/ g, particle is length≤1 μm, external diameter 20-
30nm clubs.
Method preparation is prepared as follows in the composite molecular screen that the present invention is provided：
(1) inorganic alkali source is added in deionized water, stirring successively adds template A, silicon source after being completely dissolved, and continues to stir
Mix to mixture to after being completely dissolved, add template B and silicon source, 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-：Go
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 that step (1) is obtained 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, the initial former powder of Si-Al molecular sieve must be combined after drying；
(3) inorganic alkali source is added in deionized water again by material identical with step (1), priority after stirring is completely dissolved
Template A, silicon source are added, continues to stir to mixture to after being completely dissolved, template B and silicon source is added, formation has 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 former powder of compound Si-Al molecular sieve that step (2) is obtained is added in second part of Primogel, and it is added
Measure the SiO to be combined in the initial former powder of Si-Al molecular sieve2Weight：SiO in second part of Primogel2Weight=1：99-10：90,
Ultrasonic unit is placed in, at 25-100 DEG C, ultrasonic frequency 40-60kHz is carried out under the conditions of ultrasonic power 100-2500W
Sonic oscillation 10-180 minutes, obtains mixture；
(4) mixture for obtaining step (3) is placed in 140-200 DEG C, crystallization 12-240h, after the completion for the treatment of crystallization, by solid
Product is separated by filtration, and is washed with deionized to neutrality, is dried and be calcined 1-72h after 400-600 DEG C, that is, obtains comprehensive silicon aluminium point
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 diamines, N- isopropyls diethylenetriamine, 1- methyl
In butylamine, one or two kinds of mixing of ethylenediamine.
Silicon source as described above is one kind in boehmite, aluminium chloride, aluminum sulfate, aluminum nitrate, aluminium isopropoxide, sodium aluminate
Or any several combination.
During silicon source as described above is Ludox, Silica hydrogel, methyl silicate, tetraethyl orthosilicate, sodium metasilicate, white carbon
A kind of or any several combination.
Template B as described above is dimethylamine, dimethylformamide, n-propylamine, isopropylamine, n-butylamine, isobutyl amine, new
One or both of amylamine, trimethylamine, N- isopropyl -1,3- propane diamine and N, N, N', N',-tetramethyl dipropylenetriamine etc.
Mixing.
The mode of crystallization can be static crystallization or dynamic crystalline substance under pressure itself in step (2) as described above
Change.
The mode of crystallization can be static crystallization or dynamic crystalline substance under pressure itself in step (4) as described above
Change.
TON/MTT of the present invention is combined Si-Al molecular sieve and the preparation method provided and existing similar compound point
Son sieve is compared with method, is had the following advantages that：
(1) the features such as there is multistage acidity, duct the present invention relates to the molecular sieve with TON/MTT Compound Topology structures,
And distribution can carry out modulation by the relative amounts and preparation parameter of double template, reach to the proportional amount of standards of TON/MTT
Really regulation and control.
(2) composite molecular screen of the present invention can in wider range modulation silica alumina ratio (5-1000), therefore especially
It is adapted 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, is being hydrocracked and is having great potential using value in terms of isomerization.
(3) using the synthetic method that provides of the present invention, because template is not yet calcined point in the nucleus of a crystallization
The use of template can be reduced during solution, secondary crystallization, the synthesis cost of molecular sieve and the influence to environment is reduced.
(4) on the one hand the synthetic method provided using the present invention, sonic oscillation auxiliary can make the nucleus of a crystallization uniform
It is scattered, on the other hand can rapid induction gel solution condense secondary Cheng Jing in the nucleating surface of a crystallization, be prevented effectively from
The appearance of stray crystal in follow-up hydrothermal crystallization process, therefore compared with existing synthetic method, the composite molecular screen obtained is without stray crystal
Phase, granularity is small and uniform, prepares favorable reproducibility.
Brief description of the drawings
Fig. 1 is the 2-in-1 XRD spectra into TON/MTT Compound Topology structure molecular screens of embodiment.
Fig. 2 is the XRD spectra that embodiment 6 synthesizes TON/MTT Compound Topology structure molecular screens.
Fig. 3 is that the 2-in-1 SEM into TON/MTT Compound Topology structure molecular screens of embodiment schemes.
Embodiment
The present invention is described in detail below by embodiment, but the invention is not limited in these embodiments.
Embodiment 1：
Potassium hydroxide is added in deionized water, stirring successively adds second methylamine, sodium aluminate after being completely dissolved, continue to stir
After being completely dissolved to mixture, dimethylamine and Ludox are sequentially added into, first part with following mol ratio of formation is 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 of deionized water：0.2：0.05：5.0：0.005：10.0；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 initial former powder of Si-Al molecular sieve must be combined after drying；By raw material SiO2：Al2O3：Template A：Template B：OH-：Deionization
Mol ratio=1 of water：0.2：0.025：2.5：0.005：10.0 prepare second part of initial gel mixture (material and the again
A Primogel is identical), the initial former powder of molecular sieve obtained above is added in second part of Primogel, addition is first
SiO in the original that begins powder2Weight：SiO in second part of Primogel2Weight=1：99, ultrasonic unit is placed in, at 25 DEG C, is surpassed
Sonic oscillation is carried out under the conditions of frequency of sound wave 40kHz, ultrasonic power 100W 180 minutes；Obtained mixture is placed in 140
DEG C, crystallization 240h under self-generated pressure；Treat after the completion of crystallization, solid product is separated by filtration, be washed with deionized to neutrality, do
It is dry to be calcined 72h after 400 DEG C, that is, obtain the Si-Al molecular sieve with TON/MTT Compound Topology structures.Icp analysis SiO2/Al2O3
Mol ratio=4.6, BET is than surface 283.7m2/ g, XRD characterize ZSM-22 in composite molecular screen：ZSM-23 mol ratio=10：90,
Particle is 0.2~0.4 μm of length, 20~25nm of external diameter.
Embodiment 2：
Potassium hydroxide is added in deionized water, stirring successively adds diethylamine, boehmite after being completely dissolved, and continues
After stirring is completely dissolved to mixture, dimethylformamide, n-propylamine and Silica hydrogel are sequentially added into, being formed has following mole
(silicon source is with SiO for first part of initial gel mixture of proportioning2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2：Al2O3：
Diethylamine：Dimethylformamide+n-propylamine：OH-：Mol ratio=1 of deionized water：0.1：0.1：4.0 (dimethyl formyls
Amine：Mol ratio=1 of n-propylamine：1)：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 drying
Close the initial former powder of Si-Al molecular sieve；By raw material proportioning SiO2：Al2O3：Diethylamine：Dimethylformamide+n-propylamine：OH-：Go from
Mol ratio=1 of sub- water：0.1：0.05：2.0 (dimethylformamides：Mol ratio=1 of n-propylamine：1)：0.01：30.0 weights
Second part of initial gel mixture (material is identical with first part of Primogel) is newly prepared, molecular sieve obtained above is initially former
Powder is added in second part of Primogel, and addition is the SiO in initial former powder2Weight：SiO in second part of Primogel2Weight
Amount=2：98, ultrasonic unit is placed in, at 25 DEG C, ultrasonic frequency 50kHz carries out ultrasound under the conditions of ultrasonic power 500W
Vibration 120 minutes；Obtained mixture is placed in 150 DEG C, crystallization 120h under self-generated pressure；Treat after the completion of crystallization, solid is produced
Thing is separated by filtration, and is washed with deionized to neutrality, is dried and be calcined 36h after 450 DEG C, that is, obtains opening up with TON/MTT is compound
Flutter the Si-Al molecular sieve of structure.Icp analysis SiO2/Al2O3Mol ratio=8.5, BET is than surface 271.4m2/ g, XRD characterize compound
ZSM-22 in molecular sieve：ZSM-23 mol ratio=30：70, particle is 0.3~0.5 μm of length, 20~25nm of external diameter.
Embodiment 3：
Potassium hydroxide is added in deionized water, stirring successively adds 1,6- hexamethylene diamines, aluminium chloride after being completely dissolved, and continues
After stirring is completely dissolved to mixture, isopropylamine, methyl silicate and tetraethyl orthosilicate are sequentially added into, is formed to have and rubbed as follows
(silicon source is with SiO for your first part of initial gel mixture of proportioning2Meter, silicon source is with Al2O3Meter, alkali source is with OH-Meter), SiO2：
Al2O3：1,6- hexamethylene diamines：Isopropylamine：OH-：Mol ratio=1 (the methyl silicate of deionized water：Tetraethyl orthosilicate=1：1,
With SiO2Count mol 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 after crystallization 24h, solid product is separated by filtration, is washed with deionized to neutrality, after drying
The initial former powder of Si-Al molecular sieve must be combined；By raw material SiO2：Al2O3：Template A：Template B：OH-：Deionized water mole is matched somebody with somebody
Than=1 (methyl silicate：Tetraethyl orthosilicate=1：1, with SiO2Count mol ratio)：0.05：0.1：1.5：0.02：20.0 match somebody with somebody again
Second part of initial gel mixture (material is identical with first part of Primogel) is made, the initial former powder of molecular sieve obtained above is added
It is added in second part of Primogel, addition is the SiO in initial former powder2Weight：SiO in second part of Primogel2Weight=
5：95, ultrasonic unit is placed in, at 50 DEG C, ultrasonic frequency 50kHz carries out ultrasound under the conditions of ultrasonic power 1000W and shaken
Swing 60 minutes；The initial gel mixture of gained is placed in 150 DEG C, crystallization 64h under self-generated pressure；Treat after the completion of crystallization, will consolidate
Body product is separated by filtration, and is washed with deionized to neutrality, is dried and be calcined 24h after 500 DEG C, that is, obtains multiple with TON/MTT
Close the Si-Al molecular sieve of topological structure.Icp analysis SiO2/Al2O3Mol ratio=18.5, BET is than surface 279.2m2/ g, XRD table
Levy ZSM-22 in composite molecular screen：ZSM-23 mol ratio=25：75, particle is 0.2~0.5 μm of length, 20~25nm of external diameter.
Embodiment 4：
Potassium hydroxide and sodium hydroxide are added in deionized water, stirring successively adds N- isopropyl diethyls after being completely dissolved
Alkene triamine, aluminum sulfate and aluminum nitrate, after continuing to stir and being completely dissolved to mixture, are sequentially added into n-butylamine, isobutyl amine and just
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 diethylenetriamines：N-butylamine+isobutyl amine：OH-：Mole of deionized water
Proportioning=1：0.02 (aluminum sulfate：Aluminum nitrate=1：2, mol ratio, with Al2O3Meter)：0.5：2.5 (n-butylamines：Isobutyl amine=1：4,
Mol ratio)：0.05 (potassium hydroxide：Sodium hydroxide=2：3, mol 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, must be combined the initial former powder of Si-Al molecular sieve after drying；By raw material SiO2：Al2O3：N- isopropyl diethylenetriamines：N-butylamine
+ isobutyl amine：OH-：Mol ratio=1 of deionized water：0.02 (aluminum sulfate：Aluminum nitrate=1：2, mol ratio, with Al2O3Meter)：
0.25：1.25 (n-butylamine：Isobutyl amine=1：4, mol ratio)：0.05 (potassium hydroxide：Sodium hydroxide=2：3, mol ratio)：50.0
Again second part of initial gel mixture (material is identical with first part of Primogel) is prepared, molecular sieve obtained above is initial
Former powder is added in second part of Primogel, and addition is the SiO in initial former powder2Weight：SiO in second part of Primogel2
Weight=5：95, ultrasonic unit is placed in, at 50 DEG C, ultrasonic frequency 60kHz is carried out under the conditions of ultrasonic power 1000W
Sonic oscillation 60 minutes；Obtained mixture is placed in 160 DEG C, crystallization 48h under self-generated pressure；After the completion for the treatment of crystallization, by solid
Product is separated by filtration, and is washed with deionized to neutrality, is dried and be calcined 12h after 500 DEG C, that is, obtains compound with TON/MTT
The Si-Al molecular sieve of topological structure.Icp analysis SiO2/Al2O3Mol ratio=45, BET is than surface 253.2m2/ g, XRD characterize multiple
Close ZSM-22 in molecular sieve：ZSM-23 mol ratio=40：60, particle is 0.6~1 μm of length, 25~30nm of external diameter.
Embodiment 5：
Potassium hydroxide and sodium hydroxide are added in deionized water, stirring successively added after being completely dissolved 1- methylbutylamines,
Aluminum nitrate, after continuation stirring is completely dissolved to mixture, is sequentially added into special amylamine and white carbon, is formed and matched somebody with somebody with following mole
(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 of deionized water：0.01：1.0：1.0：0.1 (potassium hydroxide：Sodium hydroxide
=1：1, mol 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 must being combined Si-Al molecular sieve after drying
Begin former powder；By raw material proportioning SiO2：Al2O3：Template A：Template B：OH-：Mol ratio=1 of deionized water：0.01：
0.5：0.5：0.1 (potassium hydroxide：Sodium hydroxide=1：1, mol ratio)：70.0 prepare second part of initial gel mixture again
(material is identical with first part of Primogel), the initial former powder of molecular sieve obtained above is added in second part of Primogel,
Addition is the SiO in initial former powder2Weight：SiO in second part of Primogel2Weight=7.5：92.5, it is placed in ultrasonic wave
Device, at 100 DEG C, ultrasonic frequency 60kHz carries out sonic oscillation 30 minutes under the conditions of ultrasonic power 2000W；By what is obtained
Mixture is placed in 170 DEG C, crystallization 36h under self-generated pressure；Treat after the completion of crystallization, solid product is separated by filtration, use deionized water
Washing is dried to neutrality and is calcined 6h after 550 DEG C, that is, obtain the Si-Al molecular sieve with TON/MTT Compound Topology structures.ICP
Analyze SiO2/Al2O3Mol ratio=84, BET is than surface 266.7m2/ g, XRD characterize ZSM-22 in composite molecular screen：ZSM-23 rubs
That ratio=55：45, particle is 0.3~0.6 μm of length, 25~30nm of external diameter.
Embodiment 6：
Sodium hydroxide is added in deionized water, stirring successively adds ethylenediamine, aluminium isopropoxide after being completely dissolved, and continues to stir
Mix to mixture after being completely dissolved, be sequentially added into trimethylamine and white carbon, at the beginning of forming 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 of deionized water：0.005：2.0：0.5：0.2：100.0；Obtain first part of Primogel is mixed
Thing 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, must be combined the initial former powder of Si-Al molecular sieve after drying；By raw material proportioning SiO2：Al2O3：Template A：Template B：OH-：
Mol ratio=1 of deionized water：0.005：1.0：0.25：0.2：100.0 prepare second part of initial gel mixture (thing again
Material is identical with first part of Primogel), the initial former powder of molecular sieve obtained above is added in second part of Primogel, added
Measure as the SiO in initial former powder2Weight：SiO in second part of Primogel2Weight=10：90, ultrasonic unit is placed in,
100 DEG C, ultrasonic frequency 60kHz carries out sonic oscillation under the conditions of ultrasonic power 2500W 10 minutes；By obtained mixture
Be placed in 180 DEG C, crystallization 24h under self-generated pressure；Treat after the completion of crystallization, solid product be separated by filtration, be washed with deionized to
Neutrality, dries and is calcined 6h after 550 DEG C, that is, obtain the Si-Al molecular sieve with TON/MTT Compound Topology structures.Icp analysis
SiO2/Al2O3Mol ratio=181, BET is than surface 264.5m2/ g, XRD characterize ZSM-22 in composite molecular screen：ZSM-23 moles
Than=75：25, particle is 0.3~0.6 μm of length, 25~30nm of external diameter.
Embodiment 7：
Sodium hydroxide is added in deionized water, stirring successively adds ethylenediamine, N- isopropyl divinyls after being completely dissolved
Triamine, boehmite, aluminum sulfate, after continuing to stir and being completely dissolved to mixture, are sequentially added into N- isopropyls -1,3- the third two
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 diethylenetriamines：N- isopropyl -1,3- propane diamine：OH-：Go
Mol ratio=1 of ionized water：0.002 (boehmite：Aluminum sulfate=1：1, mol ratio, with Al2O3Meter)：5.0 (ethylenediamines：
N- isopropyls diethylenetriamine=4：1, mol 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 initial former powder of Si-Al molecular sieve must be combined after drying；By raw material proportioning SiO2：Al2O3：Ethylenediamine+N- isopropyls divinyl three
Amine：N- isopropyl -1,3- propane diamine：OH-：Mol ratio=1 of deionized water：0.002 (boehmite：Aluminum sulfate=1：
1, mol ratio, with Al2O3Meter)：2.5 (ethylenediamines：N- isopropyls diethylenetriamine=4：1, mol ratio)：0.05：0.5：100.0
Again second part of initial gel mixture (material is identical with first part of Primogel) is prepared, molecular sieve obtained above is initial
Former powder is added in second part of Primogel, and addition is the SiO in initial former powder2Weight：SiO in second part of Primogel2
Weight=5：95, ultrasonic unit is placed in, at 75 DEG C, ultrasonic frequency 40kHz is surpassed under the conditions of ultrasonic power 500W
Sound oscillation 60 minutes；The mixture mixture of gained is placed in 200 DEG C, crystallization 12h under self-generated pressure；Treat after the completion of crystallization, incite somebody to action
Solid product is separated by filtration, and is washed with deionized to neutrality, is dried and be calcined 2h after 600 DEG C, that is, obtains multiple with TON/MTT
Close the Si-Al molecular sieve of topological structure.Icp analysis SiO2/Al2O3Mol ratio=463, BET is than surface 268.0m2/ g, XRD are characterized
ZSM-22 in composite molecular screen：ZSM-23 mol ratio=65：35, particle is 0.3~0.6 μm of length, 25~30nm of external diameter.
Embodiment 8：
Sodium hydroxide is added in deionized water, stirring successively adds diethylamine, 1- methylbutylamines, aluminic acid after being completely dissolved
Sodium, continue stir be completely dissolved to mixture after, be sequentially added into N, N, N', N' ,-tetramethyl dipropylenetriamine, sodium metasilicate and
Ludox, 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- methylbutylamines：N, N, N', N' ,-tetramethyl dipropylenetriamine：OH-：Go from
Mol ratio=1 (the sodium metasilicate of sub- water：Ludox=1：1, mol ratio, with SiO2Meter)：0.001：1.0 (diethylamine：1- methyl
Butylamine=1：1, mol 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 after crystallization 24h, solid product is separated by filtration, is washed with deionized to neutrality, must be answered after drying
Close the initial former powder of Si-Al molecular sieve；By raw material SiO2：Al2O3：Diethylamine+1- methylbutylamines：N, N, N', N' ,-tetramethyl dipropyl
Alkene triamine：OH-：Mol ratio=1 (the sodium metasilicate of deionized water：Ludox=1：1, mol ratio, with SiO2Meter)：0.001：0.5
(diethylamine：1- methylbutylamine=1：1, mol ratio)：0.025：1.0：200.0 prepare second part of initial gel mixture again
(material is identical with first part of Primogel), the initial former powder of molecular sieve obtained above is added in second part of Primogel,
Addition is the SiO in initial former powder2Weight：SiO in second part of Primogel2Weight=10：90, it is placed in ultrasonic wave dress
Put, at 75 DEG C, ultrasonic frequency 50kHz carries out sonic oscillation 60 minutes under the conditions of ultrasonic power 1000W；It is mixed by what is obtained
Compound is placed in 170 DEG C, crystallization 64h under self-generated pressure；Treat after the completion of crystallization, solid product is separated by filtration, be washed with deionized water
Wash to neutrality, dry and be calcined 1h after 600 DEG C, that is, obtain the Si-Al molecular sieve with TON/MTT Compound Topology structures.ICP points
Analyse SiO2/Al2O3Mol ratio=982, BET is than surface 264.7m2/ g, XRD characterize ZSM-22 in composite molecular screen：ZSM-23 rubs
That ratio=90：10, particle is 0.3~0.6 μm of length, 25~30nm of external diameter.
Embodiment 9：
Sodium hydroxide is added in deionized water, stirring successively adds ethylenediamine, aluminum sulfate after being completely dissolved, continue to stir
After being completely dissolved to mixture, ethamine and white carbon are sequentially added into, first part with following mol ratio is formed and initially coagulates
(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 of sub- water：0.005：1.0：2.0：2.0：75.0；Obtain first part of initial gel mixture is transferred to crystallization
In kettle, under 170 DEG C, self-generated pressure after crystallization 24h, solid product is separated by filtration, is washed with deionized to neutrality, dries
After must be combined the initial former powder of 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 prepare second part of initial gel mixture (material and first part of Primogel phase again
Together), the initial former powder of molecular sieve obtained above is added in second part of Primogel, addition is the SiO in initial former powder2
Weight：SiO in second part of Primogel2Weight=2：98, ultrasonic unit is placed in, in 25 DEG C, ultrasonic frequency
Sonic oscillation is carried out under the conditions of 50kHz, ultrasonic power 1000W 30 minutes；Obtained mixture is placed in 160 DEG C, spontaneous pressure
Crystallization 64h under power；Treat after the completion of crystallization, solid product is separated by filtration, be washed with deionized to neutrality, dry after 500
DEG C roasting 3h, that is, obtain the Si-Al molecular sieve with TON/MTT Compound Topology structures.Icp analysis SiO2/Al2O3Mol ratio=
171, BET than surface 256.5m2/ g, XRD characterize ZSM-22 in composite molecular screen：ZSM-23 mol ratio=50：50, particle is length
0.4~0.8 μm of degree, 25~30nm of external diameter.
Embodiment 10
Noble metal is impregnated after the composite molecular screen being performed as described above obtained by example is switched into ammonium type, drying and roasting through ion exchange
Pt, load capacity is the 0.5wt.% of molecular sieve, and composite molecular screen carried noble metal Pt hydroisomerizing is obtained after drying and roasting
Catalyst, carries out hydrogenation reaction, 350 DEG C of reaction temperature, pressure under hydro condition by model reaction thing of hexadecane
4.0MPa, liquid air speed 1.5h-1, H2/C16=700 (volume ratios), it is 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
Go out excellent isomerization performance, under the preferred conditions, i-C16 yields can reach 80.4%.
Claims (9)
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 bones
Frame topological structure, wherein oxide mol ratio are constituted：SiO2：Al2O3=4.6-982, ZSM-22：ZSM-23 mol ratios are 10-
90：90-10, BET are than surface 253.2-283.7 m2/ g, particle is length≤1 μm, external diameter 20-30nm.
2. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 1, its feature
It is to comprise the following steps：
（1）Inorganic alkali source is added in deionized water, stirring successively adds template A, silicon source after being completely dissolved, continue to stir extremely
Mixture adds template B and silicon source to after being completely dissolved, and forms first part of Primogel with following mol ratio and mixes
Thing, 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；
（2）By step（1）First part of obtained initial gel mixture is transferred in crystallizing kettle, in 140-200 DEG C, crystallization 6-48h
Afterwards, solid product is separated by filtration, be washed with deionized to neutrality, the initial former powder of Si-Al molecular sieve must be combined after drying；
（3）Press and step（1）Identical material again adds inorganic alkali source in deionized water, and stirring is successively added after being completely dissolved
Template A, silicon source, continue to stir to mixture to after being completely dissolved, add template B and silicon source, being formed has following mole
Second part of initial gel mixture of proportioning, 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；By step（2）The obtained initial former powder of molecular sieve is added in second part of Primogel, and addition is in initial former powder
SiO2Amount：SiO in second part of Primogel2Amount=1：99-10：90, ultrasonic unit is placed in, at 25-100 DEG C, ultrasound
Sonic oscillation is carried out under the conditions of wave frequency rate 40-60kHz, ultrasonic power 100-2500W 10-180 minutes, obtain mixture；
（4）By step（3）Obtained mixture is placed in 140-200 DEG C, crystallization 12-240h, after the completion for the treatment of crystallization, by solid product
It is separated by filtration, is washed with deionized to neutrality, dries and be calcined 1-72h after 400-600 DEG C, that is, obtain comprehensive silicon aluminium molecule
Sieve.
3. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
It is the combination of one or both of sodium hydroxide, potassium hydroxide to be described alkali source.
4. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
In being described template A and being second methylamine, diethylamine, 1,6- hexamethylene diamines, N- isopropyls diethylenetriamine, 1- methylbutylamines,
One or two kinds of mixing of ethylenediamine.
5. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
It is a kind of or any several in boehmite, aluminium chloride, aluminum sulfate, aluminum nitrate, aluminium isopropoxide, sodium aluminate to be described silicon source
The combination planted.
6. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
It is that described silicon source is one kind in Ludox, Silica hydrogel, methyl silicate, tetraethyl orthosilicate, sodium metasilicate, white carbon or appointed
Several combination of meaning.
7. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
It is that described template B is dimethylamine, dimethylformamide, n-propylamine, isopropylamine, n-butylamine, isobutyl amine, neopentyl amine, three
Methylamine, N- isopropyl -1,3- propane diamine and N, N, N', N', the mixing of one or both of-tetramethyl dipropylenetriamine etc..
8. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
It is described step（2）The mode of middle crystallization is static crystallization or dynamic crystallization under pressure itself.
9. a kind of preparation method of the adjustable multistage pore canal composite molecular screen of acid distribution as claimed in claim 2, its feature
It is described step（4）The mode of middle crystallization is static crystallization or dynamic crystallization under pressure itself.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110237857A (en) * | 2019-04-22 | 2019-09-17 | 中国科学院山西煤炭化学研究所 | A kind of acid regulation method of TON molecular sieve |
| CN113830780A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | MTT molecular sieve and synthetic method and application thereof |
| CN114655964A (en) * | 2022-04-20 | 2022-06-24 | 太原理工大学 | TON/MRE double-topology structure composite molecular sieve and preparation thereof |
| WO2022148416A1 (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 |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0220893A2 (en) * | 1985-10-21 | 1987-05-06 | Mobil Oil Corporation | Synthesis of zeolites ZSM-22 and ZSM-23 |
| US6676923B1 (en) * | 2002-06-28 | 2004-01-13 | Chevron U.S.A. Inc. | Zeolite SSZ-54 composition of matter and synthesis thereof |
| CN1686800A (en) * | 2005-04-25 | 2005-10-26 | 中国科学院大连化学物理研究所 | ZSM-22/ZSM-23 composite molecular sieve and preparation method |
| CN1686799A (en) * | 2005-04-25 | 2005-10-26 | 中国科学院大连化学物理研究所 | ZSM-23/ZSM-22 composite molecular sieve and preparation method |
| CN1762807A (en) * | 2005-09-22 | 2006-04-26 | 中国科学院大连化学物理研究所 | ZSM-23/ZSM-22 composite molecular screen and preparation method thereof |
| 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 |
-
2017
- 2017-07-25 CN CN201710609605.4A patent/CN107235497B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0220893A2 (en) * | 1985-10-21 | 1987-05-06 | Mobil Oil Corporation | Synthesis of zeolites ZSM-22 and ZSM-23 |
| US6676923B1 (en) * | 2002-06-28 | 2004-01-13 | Chevron U.S.A. Inc. | Zeolite SSZ-54 composition of matter and synthesis thereof |
| CN1686800A (en) * | 2005-04-25 | 2005-10-26 | 中国科学院大连化学物理研究所 | ZSM-22/ZSM-23 composite molecular sieve and preparation method |
| CN1686799A (en) * | 2005-04-25 | 2005-10-26 | 中国科学院大连化学物理研究所 | ZSM-23/ZSM-22 composite molecular sieve and preparation method |
| CN1762807A (en) * | 2005-09-22 | 2006-04-26 | 中国科学院大连化学物理研究所 | ZSM-23/ZSM-22 composite molecular screen and preparation method thereof |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110237857A (en) * | 2019-04-22 | 2019-09-17 | 中国科学院山西煤炭化学研究所 | A kind of acid regulation method of TON molecular sieve |
| CN110237857B (en) * | 2019-04-22 | 2021-07-27 | 中国科学院山西煤炭化学研究所 | Acidity regulation and control method of TON molecular sieve |
| CN113830780A (en) * | 2020-06-08 | 2021-12-24 | 中国石油化工股份有限公司 | MTT molecular sieve and synthetic method and application thereof |
| 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 |
| WO2022148416A1 (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 |
| 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 |
| CN114655964A (en) * | 2022-04-20 | 2022-06-24 | 太原理工大学 | TON/MRE double-topology structure composite molecular sieve and preparation thereof |
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