CN107324356A - One kind is mesoporous to select type molecular sieve and preparation method thereof - Google Patents
One kind is mesoporous to select type molecular sieve and preparation method thereof Download PDFInfo
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Abstract
Mesoporous type molecular sieve and preparation method thereof is selected the invention provides one kind.The mesoporous type molecular sieve of selecting is by being obtained to silica alumina ratio for 10 14 zeolites of IM 5 progress alkali process.Above-mentioned preparation method comprises the following steps：The zeolites of IM 5 are added in alkali process solution and carry out alkali process, by filtering, washing, are dried, obtain described mesoporous selecting type molecular sieve；The alkali process solution includes one or more of combinations in NaOH solution, KOH solution, TPAOH solution and TBAOH solution.The molecular sieves of Jie's micropore IM 5 of the present invention can apply in cracking reaction, due to more rich mesoporous, in the reaction, more preferably, heavy oil macromolecular is easier access to activated centre to catalyst fluidization state, and crackate is easier diffusion, ethene and propene yield are higher, catalyst is difficult carbon distribution, therefore, and catalyst has good catalytic activity and service life.
Description
Technical field
The present invention relates to one kind it is mesoporous select type molecular sieve and preparation method thereof, belong to technical field of molecular sieve preparation.
Background technology
The processing of China's oil refining in recent years crude oil heaviness increasingly, however as the development of society, demand of the people to fuel
But it is continuously increased.Therefore heavy oil lighting is become to an important directions of catalyst research.The catalysis of heavy oil macromolecular is split
Change requires that molecular sieve has larger aperture to improve the accessibility to activated centre, and reaction intermediate small molecular
Cracking needs molecular sieve to provide stronger acid and appropriate micropore.IM-5 is used as a kind of high-silica zeolite, the hole in its duct
Footpath size is 0.53nm × 0.59nm, and being that one kind is new selects type zeolite, it is obtained widely in petrochemical industry
Using.
IM-5 molecular sieves are made up of the hole of two-dimentional ten-ring pore passage structure He some three-dimensional features.These three-dimensional skies
Cave makes it have the architectural feature different from ZSM-5, ZSM-11 equimolecular sieve before, and IM-5 not only has common poromerics
Long-range order two-dimensional channel, while the presence in hole can be contacted to reactant with activated centre, the diffusion of product with
And the generation of reduction carbon distribution plays a positive role.Because IM-5 molecular sieves have hydrothermal stability more more preferable than ZSM-5 and acid
Property, can substitute ZSM-5 is used for FCC catalytic reactions.So, the preparation of IM-5 zeolites is particularly important.
Because IM-5 molecular sieves belong to microcellular structure so that heavy oil macromolecular is difficult to be directly diffused into molecular sieve pore passage
Cracking reaction is carried out in active sites, it is therefore desirable to which its structure is adjusted, it was both selected type performance with micropore, have again
The advantage such as mesoporous diffusion is good.The preparation method on mesopore molecular sieve emerges in an endless stream at present, but these methods are present
Weak point.Mainly using chemical method and the methods such as alkali process are utilized for silica-rich zeolite molecular sieve.
Wherein, chemical method successfully can form transgranular mesoporous to silica-rich zeolite dealuminzation, and the aluminium of hydro-thermal method removing can be assembled
In zeolite cavity, chemical method need to be combined and remove the aluminium deposited in duct, but mesoporous amount and mesoporous distribution are by uncontrollable.Profit
The silicon for dissolving silica-rich zeolite with alkali process can also form mesoporous, and research is found, be carried out in alkaline medium in desiliconization processing, zeolite
Aluminium content and property have a significant impact to desiliconization process, and silica alumina ratio is to carry out alkali process in the range of 25-50 to be formed uniformly
10nm's or so is mesoporous.The silica-rich zeolite of low silica-alumina ratio, its of a relatively high aluminium content limits the extraction of silicon in zeolitic frameworks,
It is more difficult to form mesoporous；For the silica-rich zeolite of more high silica alumina ratio, alkali process can cause a large amount of desiliconizations of non-selectivity, it is possible to create
Part macropore.(the Elucidating the effect of desilication on aluminum- such as Homas C.Hoffa
rich ZSM-5zeoliteand its consequences on biomass catalytic fast pyrolysis；
Applied Catalysis A:General 529(2017)：68-78) to low silica-alumina ratio (Si/Al=12) ZSM-5 molecular sieve
Alkali process is carried out, influence of the alkali process concentration to ZSM-5 molecular sieve has been investigated, as a result found when treatment conditions are gentleer
When (0.2mol/l NaOH), mesopore volume improve only 66%；As treatment conditions harsher (1.0mol/l NaOH), it is situated between
Pore volume improves 135%, but the structure of ZSM-5 molecular sieve is destroyed than more serious.(the Alkali-treatment of such as Zhao Liang
ZSM-5zeolites with different SiO2/Al2O3ratios and light olefin production by
heavy oil cracking；Fuel Processing Technology 92 (2011) 414-420) to low silica-alumina ratio (Si/
Al=19) ZSM-5 molecular sieve has obtained mesoporous abundant ZSM-5 points in 0.2mol/l NaOH, 90 DEG C of stirred in water bath processing 6h
Son sieve, but because treatment conditions harshness causes destroyed more of microcellular structure.Qin Zhengxing (Mesoporous Y zeolite
with homogeneous aluminum distribution obtained by sequential desilication–
dealumination and its performance in the catalytic cracking of cumene and 1,
3,5-triisopropylbenzene；Journal of Catalysis 278, (2011)：266-275) to (Si/Al=2.4
And Si/Al=2.7) NaY molecular sieve is in 1.0mol/l NaOH, 90 DEG C of stirred in water bath handle 1h and carry out alkali process, XRF and BET
Characterization result shows, because higher aluminium content inhibits the removing of silicon, and causing to carry out alkali process to NaY molecular sieve to make mesoporous is
It is infeasible.
In summary, low silica-alumina ratio molecular sieve can suppress the removing of silicon because aluminium content is high so that pass through alkali treatment method
It is difficult to prepare mesoporous abundant mesopore molecular sieve.In addition, pore structure and Acidity of the IM-5 molecular sieves due to itself, shape-selective
It will be with a wide range of applications in catalytic field, and micro- composite mesoporous IM-5 molecular sieves can effectively improve macromolecule reactant
Or diffusion, mass transfer and the heat transfer problem of product, therefore with higher application value.Numerous scholars are directed to micro- mesoporous in recent years
In place of the research of composite zeolite preparation method, but the equal Shortcomings of each preparation method.The IM-5 molecular sieves of low silica-alumina ratio have more
Many acid amounts, but aluminium content height also inhibits the removing of silicon and causes the mesoporous amount generated less.At present, prepare and be situated between on post processing
The research that micropore is combined IM-5 molecular sieves is not related to.So, a kind of mesoporous amount of research and development is abundant and acid amount height, cost of material are low
And environmental protection micro- composite mesoporous IM-5 zeolites preparation method become it is necessary.
The content of the invention
In order to solve the above technical problems, mesoporous selecting type molecular sieve and its preparation side it is an object of the invention to provide one kind
Method, obtains a kind of while having micropore and mesoporous porous zeolite by carrying out alkali process to IM-5 molecular sieves.
To reach above-mentioned purpose, the invention provides one kind it is mesoporous select type molecular sieve, its be by silica alumina ratio (mole
Than) carry out alkali process for 10-14 IM-5 molecular sieves and obtain.Alkali process can be molten using NaOH solution, KOH solution, TPAOH
One or more of combinations in liquid and TBAOH solution are carried out.Preferably, when using NaOH solution, the concentration of NaOH solution
It may be controlled to 0.1-0.8mol/L, preferably 0.2-0.4mol/L.
Alkali process is carried out by the IM-5 molecular sieves to low silica-alumina ratio, the mesopore volume of IM-5 molecular sieves can be made more conventional
IM-5 molecular sieves obtain very big lifting, meanwhile, the crystallinity of molecular sieve still is able to keep, and its relative crystallinity is able to maintain that
More than 90%.The molecular sieve has preferably heat and hydrothermal stability, mesopore volume big and acid stronger, the characteristics of acid amount is more,
There is good structural stability and catalytic activity simultaneously, had great application prospect in catalytic cracking catalyst.
According to specific embodiments of the present invention, it is preferable that the mesopore volume of the molecular sieve is 0.230-0.415cm3·g-1。
According to specific embodiments of the present invention, it is preferable that the mesoporous pore size of the molecular sieve is 6-10nm.
Present invention also offers the above-mentioned mesoporous preparation method for selecting type molecular sieve, it comprises the following steps：
IM-5 zeolites are added in alkali process solution and carry out alkali process, by filtering, washing, dries, obtains being given an account of
Select type molecular sieve in hole.
In above-mentioned preparation method, it is preferable that the alkali process solution used includes NaOH solution, KOH solution, TPAOH
One or more of combinations in solution and TBAOH solution.
In above-mentioned preparation method, it is preferable that the alkali process solution used for NaOH solution, the NaOH solution it is dense
Spend for 0.1-0.8mol/L, more preferably 0.2-0.4mol/L.
In above-mentioned preparation method, it is preferable that the temperature of alkali process is 30-70 DEG C, more preferably 50-70 DEG C.
In above-mentioned preparation method, it is preferable that the solid-to-liquid ratio of IM-5 molecular sieves and NaOH solution is 1：(5-50), more preferably
For 1：(10-20).
In above-mentioned preparation method, it is preferable that the time of alkali process is 0.5-6 hours, more preferably 1-4 hours.
In above-mentioned preparation method, it is preferable that alkali process stirs progress in a water bath.
According to specific embodiments of the present invention, above-mentioned preparation method provided by the present invention can be according to side in detail below
Formula is carried out：The IM-5 zeolites of low silica-alumina ratio (Si/Al=10-14) are added to NaOH solution, stirring mixing carries out alkali process, so
Afterwards by suction filtration, washing, obtained solid is dried, mesoporous IM-5 molecular sieves are obtained.
Jie's micropore IM-5 molecular sieves provided by the present invention can apply in cracking reaction, due to being situated between with more rich
Hole, in the reaction, more preferably, heavy oil macromolecular is easier access to activated centre to catalyst fluidization state, and crackate is easier
Diffusion, ethene and propene yield are higher, and catalyst is difficult carbon distribution, and catalyst has good catalytic activity and service life.
The preparation method operating procedure for the mesoporous IM-5 molecular sieves that the present invention is provided is simple, raw material relatively low to equipment requirement
Cost is low and environmental protection, is a kind of preparation method for the mesoporous IM-5 zeolites for having broad prospect of application.
Brief description of the drawings
Fig. 1 a and Fig. 1 b are respectively the SEM figures and TEM figures of IM-5 molecular sieves.
Fig. 2 a and Fig. 2 b are respectively the SEM figures and TEM figures of alkali process IM-5D samples.
Fig. 3 for embodiment 1 IM-5A and comparative example 1 IM-5 graph of pore diameter distribution.
Fig. 4 for embodiment 2 IM-5B and comparative example 1 IM-5 graph of pore diameter distribution.
Fig. 5 for embodiment 3 IM-5C and comparative example 1 IM-5 graph of pore diameter distribution.
Fig. 6 for embodiment 4 IM-5D and comparative example 1 IM-5 graph of pore diameter distribution.
Fig. 7 for embodiment 5 IM-5E and comparative example 1 IM-5 graph of pore diameter distribution.
Embodiment
In order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
The model of X-ray diffractometer used in the thing phase of mesoporous IM-5 molecular sieves and the measure of relative crystallinity
Panalytical X ' Pert Powder diffractometers, test voltage 40kV tests electric current 40mA, 5-50 ° of test scope.
The sample of grinding distribution after drying is placed in sheet glass test window, after sample is struck off with slide, in instrument
Middle sweep test.The relative crystallinity of sample is calculated with Highscore softwares.Calculation formula is as follows：
The relative crystallinity %=(characteristic peak area of ∑ sample/mean values) of sample/(characteristic peak area of ∑ standard specimen/
Mean values) × standard specimen relative crystallinity.
Standard specimen refers to the sample before alkali process.
Specific area measuring uses the automatic physical adsorption appearance of Micromeritics companies of U.S. ASAP2020 types, uses BET method
Measurement the specific area.
Embodiment 1
A kind of preparation method of Jie's micropore IM-5 molecular sieves is present embodiments provided, it comprises the following steps：
Step one：The Na type micropores IM-5 of low silica-alumina ratio (Si/Al=10) is directly made by traditional hydrothermal synthesis method
Zeolite.
Step 2：The low silica-alumina ratio IM-5 zeolites that step one is synthesized are added to the NaOH solution that concentration is 0.2mol/L
In, the mass ratio of solid-liquid is 1:20,2h is stirred under 70 DEG C of water bath conditions, filters, wash, being dried to obtain mesoporous IM-5 zeolites,
It is designated as IM-5A samples；
Relative crystallinity through XRD ray diffraction determination products is 96%, the more conventional ZSM-5 molecules of mesopore volume of product
That sieves improves 0.149cm3g-1133% or so is improved, 0.261cm has been reached3g-1(pore volume distribution is shown in Fig. 3).
Embodiment 2
A kind of preparation method of Jie's micropore IM-5 molecular sieves is present embodiments provided, it comprises the following steps：
Step one：The Na type micropores IM-5 of low silica-alumina ratio (Si/Al=13) is directly made by traditional hydrothermal synthesis method
Zeolite.
Step 2：The low silica-alumina ratio IM-5 zeolites that step one is synthesized are added to the NaOH solution that concentration is 0.2mol/L
In, the mass ratio of solid-liquid is 1:10,2h is stirred under 70 DEG C of water bath conditions, filters, wash, being dried to obtain mesoporous IM-5 zeolites,
It is designated as IM-5B samples；
Relative crystallinity through XRD ray diffraction determination products is 94%, the more conventional ZSM-5 molecules of mesopore volume of product
That sieves improves 0.180cm3g-1161% or so is improved, 0.292cm has been reached3g-1(pore volume distribution is shown in Fig. 4).
Embodiment 3
A kind of preparation method of Jie's micropore IM-5 molecular sieves is present embodiments provided, it comprises the following steps：
Step one：The Na type micropores IM-5 of low silica-alumina ratio (Si/Al=14) is directly made by traditional hydrothermal synthesis method
Zeolite.
Step 2：The low silica-alumina ratio IM-5 zeolites that step one is synthesized are added to the NaOH solution that concentration is 0.2mol/L
In, the mass ratio of solid-liquid is 1:20,3h is stirred under 60 DEG C of water bath conditions, filters, wash, being dried to obtain mesoporous IM-5 zeolites,
It is designated as IM-5C samples；
Relative crystallinity through XRD ray diffraction determination products is 94%, the more conventional ZSM-5 molecules of mesopore volume of product
That sieves improves 0.158cm3g-1141% or so is improved, 0.270cm has been reached3g-1(pore volume distribution is shown in Fig. 5).
Embodiment 4
A kind of preparation method of Jie's micropore IM-5 molecular sieves is present embodiments provided, it comprises the following steps：
Step one：The Na type micropores IM-5 of low silica-alumina ratio (Si/Al=12) is directly made by traditional hydrothermal synthesis method
Zeolite.
Step 2：The low silica-alumina ratio IM-5 zeolites that step one is synthesized are added to the NaOH solution that concentration is 0.35mol/L
In, the mass ratio of solid-liquid is 1:10,2h is stirred under 70 DEG C of water bath conditions, filters, wash, being dried to obtain mesoporous IM-5 zeolites,
It is designated as IM-5D samples；
Relative crystallinity through XRD ray diffraction determination products is 93%, the more conventional IM-5 molecules of mesopore volume of product
That sieves improves 0.303cm3g-1271% or so is improved, 0.415cm has been reached3g-1(pore volume distribution is shown in Fig. 6).Fig. 1 a
With Fig. 1 b be respectively IM-5 molecular sieves SEM figure and TEM figure, Fig. 2 a and Fig. 2 b be respectively alkali process IM-5D samples SEM figure and
TEM schemes.Scheme from SEM it can be seen that the grain size and pattern of IM-5 molecular sieves are still complete cuboid, this explanation after alkali process
Alkali process does not produce influence to the pattern of IM-5 molecular sieves.In addition, TEM figures also demonstrate that the IM-5D samples after alkali process have greatly
The mesoporous generation of amount, but crystal morphology is still complete cuboid, this explanation：Alkali process does not destroy the knot of IM-5 molecular sieves
Structure.This matches with relative crystallinity data.
The mesoporous IM-5D zeolite products of above-mentioned gained are modified and catalytically active assessment, specifically according to following step
It is rapid to carry out：
By zeolite：1.0M NH4Cl solution=1:10 (mass ratioes) weigh NaIM-5D and NH respectively4Cl solution is made into ion
Switching architecture, is exchanged after 3h, ion exchange at 80 DEG C, filtering and washing to neutrality repeats an ammonium in the same way
Exchange, filtering and washing to neutrality, sample is stayed overnight in 120 DEG C of drying, is calcined 4h at 550 DEG C afterwards, obtains H-IM-5 molecular sieves.
According to zeolite (commercially available USY zeolite or above-mentioned H-IM-5 zeolites)：Kaolin：Binding agent=35：50：15 (butt matter
Amount ratio) ratio, zeolite, kaolin, binding agent and water are mixed after mashing, microspherical catalyst is made in spray drying.Containing USY zeolite
Microspherical catalyst be used as catalytic cracking major catalyst；And using sample after mesoporous IM-5D molecular sieves ion exchange as co-catalyst.
Above-mentioned all catalyst under the conditions of 800 DEG C after aging 4h, are screened out into particle diameter for 38-212 in 100% vapor
μm microsphere particle it is stand-by, finally 600 DEG C be calcined 6h, be stored in stand-by in drier.The catalyst of Catalytic Cracking Evaluation
It is made up of the co-catalyst mixing of 90wt% major catalyst and 10wt%, gained catalyst sample is designated as CAT-1.
With the fcc raw material of Dalian four oil for raw material, the catalytic cracking reaction of catalyst is have rated using ACE evaluating apparatus
Can, reaction evaluating data are listed in Table 1 below.
Embodiment 5
A kind of preparation method of Jie's micropore IM-5 molecular sieves is present embodiments provided, it comprises the following steps：
Step one：The Na type micropores IM-5 of low silica-alumina ratio (Si/Al=12) is directly made by traditional hydrothermal synthesis method
Zeolite.
Step 2：The low silica-alumina ratio IM-5 zeolites that step one is synthesized are added to the NaOH solution that concentration is 0.1mol/L
In, the mass ratio of solid-liquid is 1:5,4h is stirred under 65 DEG C of water bath conditions, filters, wash, being dried to obtain mesoporous IM-5 zeolites, is remembered
For IM-5E samples；
Relative crystallinity through XRD ray diffraction determination products is 95%, the more conventional ZSM-5 molecules of mesopore volume of product
That sieves improves 0.118cm3g-1105% or so is improved, 0.230cm has been reached3g-1(pore volume distribution is shown in Fig. 7).
Comparative example 1
This comparative example provides a kind of preparation method of Jie's micropore IM-5 molecular sieves, and it comprises the following steps：
Step one：The Na type micropores IM-5 of low silica-alumina ratio (Si/Al=13) is directly made by traditional hydrothermal synthesis method
Molecular sieve.
Step 2：The low silica-alumina ratio IM-5 zeolites that step one is synthesized are added to the NaOH solution that concentration is 0.05mol/L
In, the mass ratio of solid-liquid is 1:10,2h is stirred under 70 DEG C of water bath conditions, filters, wash, being dried to obtain mesoporous IM-5 zeolites,
It is designated as IM-5 samples；
Relative crystallinity through XRD ray diffraction determination products is 98%, the mesopore volume of comparative sample IM-5 molecular sieves
For 0.142cm3g-1。
According to zeolite (above-mentioned H-IM-5 zeolites)：Kaolin：Binding agent=35：50：15 (butt mass ratio) ratios, will boil
After stone, kaolin, binding agent and water mixing mashing, microspherical catalyst is made in spray drying.Microspherical catalyst containing USY zeolite is made
For catalytic cracking major catalyst；And sample is co-catalysis after the IM-5 molecular sieve ion exchanges by Material synthesis of expanded perlite
Agent.
Above-mentioned all catalyst under the conditions of 800 DEG C after aging 4h, are screened out into particle diameter for 38-212 in 100% vapor
μm microsphere particle it is stand-by, finally 600 DEG C be calcined 6h, be stored in stand-by in drier.The catalyst of Catalytic Cracking Evaluation
It is made up of the co-catalyst mixing of 90wt% major catalyst and 10wt%.Gained catalyst sample is designated as CAT-2.
With the fcc raw material of Dalian four oil for raw material, the catalytic cracking reaction of catalyst is have rated using ACE evaluating apparatus
Can, reaction evaluating data are listed in Table 1 below.
The Catalytic Cracking Performance of 1 two kinds of catalyst of table compares
| Catalyst | CAT-1 | CAT-2 |
| Product is distributed, % | ||
| Dry gas | 2.75 | 2.74 |
| Ethene | 1.27 | 0.96 |
| Propylene | 7.41 | 6.43 |
| Liquefied gas | 21.03 | 19.62 |
| Gasoline | 35.16 | 36.32 |
| Diesel oil | 24.85 | 25.13 |
| Coke | 7.53 | 8.68 |
It was found from the data of table 1, the standby catalyst of the mesoporous IM-5 system with molecular sieve for preparing that is obtained with embodiment 4, coke yield is obvious
Less than the catalyst obtained by comparative example 1, this illustrates that mesoporous presence improves the diffusion of IM-5 molecular sieves, reduces Jiao
The generation of charcoal, improves the service life of catalyst.In addition, CAT-1 is compared with CAT-2, yield of ethene improves 0.31 unit,
Propene yield improve 0.98 unit, with the standby catalyst of mesoporous IM-5D system with molecular sieve for preparing in RFCC have it is higher
Ethene and propene yield.
In summary, mesoporous IM-5 molecular sieves improve diffusion due to mesoporous presence, reduce the generation of carbon distribution,
The yield of propylene and ethene is improved, therefore with preferable catalytic performance.
Claims (10)
1. one kind is mesoporous to select type molecular sieve, it is obtained by carrying out alkali process to silica alumina ratio for 10-14 IM-5 zeolites.
2. molecular sieve according to claim 1, wherein, the alkali process uses NaOH solution, KOH solution, TPAOH solution
Carried out with one or more of combinations in TBAOH solution；
Preferably, when using NaOH solution, the concentration of the NaOH solution is 0.1-0.8mol/L, preferably 0.2-
0.4mol/L。
3. it is according to claim 1 or 2 it is mesoporous select type molecular sieve, wherein, the mesopore volume of the molecular sieve is 0.230-
0.415cm3·g-1。
4. mesoporous according to claim any one of 1-3 selects type molecular sieve, wherein, the mesoporous pore size of the molecular sieve
For 6-10nm.
5. the mesoporous preparation method for selecting type molecular sieve described in claim any one of 1-4, it comprises the following steps：
IM-5 zeolites are added in alkali process solution and carry out alkali process, by filtering, washing, dries, obtains described mesoporous select
Type molecular sieve；
The alkali process solution includes one or more of groups in NaOH solution, KOH solution, TPAOH solution and TBAOH solution
Close.
6. preparation method according to claim 5, wherein, the alkali process solution is NaOH solution, the NaOH solution
Concentration be 0.1-0.8mol/L, preferably 0.2-0.4mol/L.
7. preparation method according to claim 5, wherein, the temperature of the alkali process is 30-70 DEG C, preferably 50-70
℃。
8. the preparation method according to claim any one of 5-7, wherein, the IM-5 zeolites and the alkali process solution
Solid-to-liquid ratio is 1：(5-50), it is preferable that the solid-to-liquid ratio is 1：(10-20).
9. the preparation method according to claim any one of 5-8, wherein, the time of the alkali process is 0.5-6 hours, excellent
Elect as 1-4 hours.
10. the preparation method according to claim any one of 5-9, wherein, the alkali process stirs progress in a water bath.
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| CN113171793A (en) * | 2021-04-06 | 2021-07-27 | 广东石油化工学院 | Hydrodealkylation catalyst and preparation method thereof |
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