CN108751219A - A kind of multi-stage porous EU-1 molecular sieves and its synthetic method - Google Patents
A kind of multi-stage porous EU-1 molecular sieves and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of multi-stage porous EU-1 molecular sieves and its synthetic methods, and the EU-1 molecular screen primary powders that silica/alumina molar ratio is 20~200 are placed in inorganic base and pyroles organo-alkali compound mixed-alkali solution, press solid-liquid mass ratio 1 at room temperature:(10~50) 10~60min is handled, then plus acid for adjusting pH value is to neutrality, after filtration, washing and drying sample and a concentration of 0.01~0.5mol/L acid solutions in mass ratio 1:(10~50), in 80~120 DEG C of 0.5~12h of reflow treatment, using filter, washing, it is dry after obtain the EU-1 molecular sieves of multi-stage porous.There is good reaction molecular diffusion on multi-stage porous EU-1 molecular sieves provided by the invention, there is good application prospect as catalyst carrier.
Description
Technical field
The present invention relates to a kind of multi-stage porous EU-1 molecular sieves and its synthetic methods, are a kind of post-processing sides of EU-1 molecular sieves
Method belongs to inorganic material synthesis field.
Background technology
There is one-dimensional ten-ring 0.54nm × 0.41nm in [100] direction in EUO type topological structure crystal structure of molecular sieve
Duct also has depth 0.81nm twelve-ring 0.68nm × 0.58nm side pockets in the both sides in ten-ring duct.EU-1, ZSM-50 and
TPZ-3 molecular sieves all have EUO type topological structure, and wherein EU-1 molecular sieves are the more extensive molecular sieves of Recent study, by
In its special pore passage structure and acidic character, prepared as isomerization of C-8 aromatics acidity of catalyst constituent element difunctional
Catalyst shows good activity and selectivity, quilt in the isopropylation catalysis reaction of C8 aronmatic hysomer, benzene
It is described as the first choice of the xylene isomerization catalysis material of a new generation.
US4537754 discloses a kind of hydrothermal crystallizing synthetic method of EU-1 types molecular sieve, with polymethylene α-ω-diamines
The alkyl derivative of ion or its precursor are template, after mixing by silicon and aluminum source, alkali metal, template and crystal seed etc.
It is made through hydrothermal crystallizing.US65144479 discloses a kind of method of hydrothermal synthesis EUO type molecular sieve, by silicon and aluminum source, alkali metal,
Hydro-thermal process, the method simultaneously reduce crystallite dimension, gained crystal grain ruler using ultrasonication after mixing for template and crystal seed etc.
It is very little within 5 μm.(same, hetero-seeds effect in EU-1 Zeolite synthesis, the petroleum journal (PETROLEUM PROCESSING) such as Li Xiaofeng
Supplementary issue in 2006：Same, hetero-seeds effect in EU-1 Zeolite synthesis 93-95) is investigated.Product can be improved in addition homogeneity crystal seed
Crystallinity, and crystallization time is foreshortened to 1~2 day.Gained EU-1 molecular sieves are oval, and size is 1.0 μm of 2.0 μ m.Lee
(Fast back-projection algorithm and characterization of EU-1 molecular sieves, petrochemical industry, 2007,36 (8) such as Xiao Feng:It 794-798) reports using solid phase
In situ conversion process is in HMBr2-Na2O-Al2O3-SiO2-H2The method of Fast back-projection algorithm high-crystallinity EU-1 molecular sieves, water in O systems
The thermal synthesis time can foreshorten to 28 hours.The aggregate that EU-1 molecular sieves are 1~5 μm obtained by the method, by 0.3~0.8 μm of Asia
Particle aggregation forms.US6377063 patents disclose a kind of synthetic method of EUO structure molecular screens, using at least one more existing
There is the alkyl derivative of template disclosed in technology or the safer cheap methylene diamine ion of template precursor as knot
Structure directed agents can reduce production cost, safer environmental protection.
EUO structure molecular screens preparation method disclosed in document above mainly has conventional hydrothermal method and solid phase in-situ method, but
Molecular sieve structure is almost the same, and grain size is generally larger, in the micron-scale, and stray crystal is susceptible to, for molecular sieve catalytic
Service life has serious limitation, product yield to be improved.Multistage pore canal EUO structure molecular screens will shorten molecule diffusion away from
From so that reaction product is easier to be diffused into outer surface from active sites, it is suppressed that the formation of coking increases the longevity of catalyst
Life.
In view of the deficiencies of the prior art, the present invention proposes a kind of EU-1 molecular sieves under alkaline condition desiliconization and combination acidity
Dealumination process obtains hierarchical porous structure and restores silicon/aluminium ratio to previous level, to meet the mass transfer and water of molecular sieve catalyst
The requirement of thermal stability.
Invention content
That present invention aim to address reactant molecule diffuser efficiencies on EU-1 molecular sieves is low, hydrothermal stability is bad, leads
The problem for causing catalysis reaction deactivation rate fast, provides a kind of multi-stage porous EU-1 molecular screen material preparation methods.
Usually by " from top to bottom " mode obtain multistage porous molecular sieve createed using Si in alkali soluble solution skeleton structure it is mesoporous,
This mode is easy to operate, cheap, but may make when the molecular sieve of the high sial of processing unstable under structure hydrothermal condition
Fixed or even structural breakdown.When inorganic alkali process molecular sieve, yield is low, mesoporous big；And it is yield when using organic alkali process
It is high, mesoporous small.The present invention proposes that pyridines monocyclic compound organic base is added simultaneously in inorganic alkali process, can occupy at inorganic base
The silicone hydroxyl vacancy left after reason forms steric effect and slows down Si-O structures excessive dissolution in molecular sieve, improves molecular sieve phase
To crystallinity reservation degree, and suitable meso-hole structure can be generated.
The present invention proposes EU-1 molecular sieve silica alumina ratios between 20~200, and this range silica alumina ratio makes desiliconization method obtain
Transgranular mesoporous and retain the most suitable range in the centers Al, for the EU-1 zeolites of more high silica alumina ratio, alkali process can lead to no selection
A large amount of desiliconizations of property, generate the part macropore of impalpable structure, greatly reduce the relative crystallinity of molecular sieve.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of synthetic method of multi-stage porous EU-1 molecular sieves, includes the following steps：By what is be prepared by conventional method
Silica：Alumina molar ratio is that the EU-1 molecular screen primary powders of 20-200 are placed in inorganic alkali solution and pyroles organo-alkali compound
In the mixed-alkali solution of formation, alkali process 10-60min at room temperature；Then add acid for adjusting pH to neutrality into system, filter out
Solid, solid are dried after deionized water is washed to neutrality；Solid after drying, which is placed in again in acid solution, to carry out at reflux
Reason, then filters out solid product, and solid product is dried after deionization is washed to neutrality, obtains EU-1 points of multi-stage porous
Son sieve.
In above-mentioned technical proposal, the inorganic alkali solution is the aqueous solution of inorganic base, inorganic base NaOH, Na2CO3、
NaHCO3、LiOH、KOH、K2CO3、KHCO3In any one, two kinds or more the mixtures mixed with arbitrary proportion.
In above-mentioned technical proposal, the inorganic alkali solution, wherein a concentration of 0.05~5.0mol/L of inorganic base, preferably
0.05~1.0mol/L.
In above-mentioned technical proposal, the pyroles organo-alkali compound is pyrroles, nafoxidine, N- ethenyl pyrrolidones
Ketone, N- methylpyrroles, 1- crassitudes, 2,5- dimethyl pyrroles, 2,4- dimethyl pyrroles, 2- crassitudes, 1- butyl
Pyrrolidines, 2- methylpyrrolines, N-Methyl pyrrolidone, 2,5- dimethyl pyrrolidines, N- ethyl-2-aminomethylpentazaneands, 3-
Crassitude, 3- pyrrolidinols, (R) -2- crassitudes, (S) -2- crassitudes, (R) -3- crassitudes, (S) -
In 3- crassitudes, N- methylpyrrolidin- 3- amine any one, two kinds or more the mixing mixed with arbitrary proportion
Object.
In above-mentioned technical proposal, the solid-liquid mass ratio of EU-1 molecular screen primary powders and mixed-alkali solution is 1：(10-50), pyrrole
Cough up class organo-alkali compound and the SiO in EU-1 molecular screen primary powders2Molar ratio be (0.01~0.06)：1.
In above-mentioned technical proposal, adjust pH acid be citric acid, oxalic acid, succinic acid, glutaric acid, acetic acid, formic acid, propionic acid,
In nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid, succinic acid any one, two kinds or more mixed with arbitrary proportion
Made of mixture, sour a concentration of 0.01-0.5mol/L.
In above-mentioned technical proposal, solid is dried after deionized water is washed to neutrality, drying temperature 100-130
DEG C, drying time 12-48h.
In above-mentioned technical proposal, the acid solution of reflux is the aqueous solution of acid, and acid is citric acid, oxalic acid, succinic acid, penta 2
In acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid, succinic acid any one, two kinds and
The mixture mixed above with arbitrary proportion, sour a concentration of 0.01-0.5mol/L in acid solution.
In above-mentioned technical proposal, it is dry after solid be placed in again in acid solution and carry out reflow treatment, solid and acid solution
Solid-liquid mass ratio is 1：(10-50).
In above-mentioned technical proposal, the temperature of reflow treatment is 80~120 DEG C, and processing time is 0.5~12h.
In above-mentioned technical proposal, solid product is dried after deionization is washed to neutrality, drying temperature 100-130
DEG C, drying time 12-48h.
Compared with existing EU-1 Zeolite synthesis method, the method for the present invention has the characteristics that：
(1) the EUO molecular sieves that the present invention synthesizes have the multi-stage artery structure of micropore-mesopore, are conducive to reactant molecule
It is spread on its catalyst activity position, increases external surface area, improve Activation Diffusion in Zeolites, further increased catalysis and live
Property.
(2) in the method for the present invention EU-1 molecular sieves by inorganic alkali process obtain it is mesoporous can be by pyroles monocycle chemical combination
Object is filled, and the rate of molten silicon is effectively relieved as protective agent, to produce the mesoporous of size uniform, can also increase substantially production
Product solid yields, generation two level is mesoporous and increases mesopore volume, and can greatly retain micro pore volume.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of molecular sieve prepared by comparative example 1 of the present invention.
Fig. 2 is X-ray diffraction (XRD) spectrogram of molecular sieve prepared by the embodiment of the present invention 1.
Fig. 3 is scanning electron microscope (SEM) photo of molecular sieve prepared by comparative example 1 of the present invention.
Fig. 4 is scanning electron microscope (SEM) photo of molecular sieve prepared by the embodiment of the present invention 2.
Specific implementation mode
The specific implementation mode of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold：
Product in the embodiment of the present invention and comparative example is inhaled using 2020 type nitrogen physisorptions of Micromeritics ASAP
Attached instrument carries out phenetic analysis specific surface area, pore volume and average pore size.The preprocess method of sample is as follows before analysis：In room temperature
It is lower by sieve sample vacuumize process, after reaching vacuum condition, at 130 DEG C handle 2h, later at 350 DEG C handle 2h.
Comparative example 1：
EU-1 molecular sieves are synthesized according to patent CN201610102491 embodiments：Take 393.3g deionized waters and 0.18g hydrogen
Sodium oxide molybdena (NaOH：96%), 82.32g hexamethylene bromides (HMBr2：99%), 97.96g white carbons (SiO2：92%),
9.09g sodium metaaluminates (Al2O3:37.4wt%, Na2O%：29.22%) it mixes, stirs 2h, be placed in reaction kettle and be aged：
80 DEG C of Aging Temperature, digestion time is for 24 hours.170 DEG C of crystallization 60h filter, wash simultaneously 120 DEG C of dry 12h, are warming up to 550 DEG C of roastings
4h obtains sample and is shown to be EU-1 object phases by XRD (Fig. 1) phenetic analysis, and relative crystallinity 95%, XRF analysis measures silicon
Aluminium ratio is 45, and crystallite dimension analysis is 2~4 μm.Fig. 3 explanations conventionally obtain large scale grain morphology.
Embodiment 1：
Using the EU-1 molecular sieves in comparative example 1 as original powder, original powder is placed in the NaOH of 0.08mol/L and mixing for pyrroles's formation
It closes in alkaline solution, alkali process 10min at room temperature, solid-liquid mass ratio 1:20, the SiO in pyrroles and EU-1 molecular screen primary powders2
Molar ratio be 0.02：1.Then add a concentration of 0.4mol/L first acid for adjusting pH to neutrality into system, filter out solid, solid
12h is dried at 120 DEG C after deionized water is washed to neutrality；Solid after drying is placed in the citric acid solution of 0.5mol/L again
In at 120 DEG C reflow treatment 10h, solid-liquid mass ratio 1:10；Then solid product is filtered out, solid product is washed through deionization
12h is dried after washing to neutrality at 120 DEG C, obtains the EU-1 molecular sieves of multi-stage porous.Fig. 2 illustrates that obtained product is opened up for EUO
Works phase is flutterred, Fig. 4 illustrates multi-stage porous Molecular Sieve Morphology.
Embodiment 2-8：
The preparation method of embodiment 2-8 is substantially same as Example 1, uses inorganic lye type, piperidines
Type, molecular sieve processing time, sour type, acid concentration, solid and acid solution mass ratio, reflux temperature and time etc. in lye are each
A parameter is different, as Table 1 and Table 2 below；Nitrogen physisorption the result shows that, the sample that embodiment 1-8 is obtained contains
There are meso-hole structure, mesoporous pore size distribution, average pore size and mesoporous hole to hold as shown in table 3：
Table 1
Table 2
*：Product solid yields %=multi-stage porous EU-1 zeolite products quality/initial EU-1 molecular sieve quality × 100%
Table 3
There are two types of various sizes of meso-hole structures for the molecular sieve synthesized by the embodiment of the present invention as shown in Table 3, with molecule
Sieve the EU-1 molecular sieves that original micropore forms hierarchical porous structure.In addition, embodiment sample can keep larger micro pore volume,
And big mesopore volume more notable than comparative example is obtained, this illustrates that the present invention has excellent hierarchical porous structure feature, fits
For reducing reaction molecular diffusional resistance, increases kinetic reaction rate, reduce such molecular sieve catalyst carbon distribution inactivation probability
Deng.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of synthetic method of multi-stage porous EU-1 molecular sieves, which is characterized in that include the following steps：Conventional method system will be passed through
Silica made of standby：Alumina molar ratio is that the EU-1 molecular screen primary powders of 20-200 are placed in inorganic alkali solution and pyroles are organic
In the mixed-alkali solution that alkali cpd is formed, alkali process 10-60min at room temperature；Then add acid for adjusting pH into system
Property, solid is filtered out, solid is dried after deionized water is washed to neutrality；Solid after drying be placed in again in acid solution into
Then row reflow treatment filters out solid product, solid product is dried after deionization is washed to neutrality, obtains multi-stage porous
EU-1 molecular sieves；
The pyroles organo-alkali compound is pyrroles, nafoxidine, n-vinyl pyrrolidone, N- methylpyrroles, 1- first
Base pyrrolidines, 2,5- dimethyl pyrroles, 2,4- dimethyl pyrroles, 2- crassitudes, 1- butyl pyrrolidines, 2- methylpyrroles
Quinoline, N-Methyl pyrrolidone, 2,5- dimethyl pyrrolidines, N- ethyl-2-aminomethylpentazaneands, 3- crassitudes, 3- pyrroles
Alkanol, (R) -2- crassitudes, (S) -2- crassitudes, (R) -3- crassitudes, (S) -3- crassitudes, N- first
In base pyrrolidines -3- amine any one, two kinds or more the mixtures mixed with arbitrary proportion.
2. synthetic method according to claim 1, which is characterized in that the inorganic alkali solution is the water-soluble of inorganic base
Liquid, inorganic base NaOH, Na2CO3、NaHCO3、LiOH、KOH、K2CO3、KHCO3In any one, two kinds or more with arbitrary
The mixture that ratio mixes.
3. synthetic method according to claim 1, which is characterized in that the inorganic alkali solution, wherein inorganic base is dense
Degree is 0.05~5.0mol/L.
4. synthetic method according to claim 1, which is characterized in that EU-1 molecular screen primary powders are consolidated with mixed-alkali solution
Liquid mass ratio is 1：(10-50), piperidines organo-alkali compound and the SiO in EU-1 molecular screen primary powders2Molar ratio be (0.01
~0.06)：1.
5. synthetic method according to claim 1, which is characterized in that adjust pH acid be citric acid, oxalic acid, succinic acid,
In glutaric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid, succinic acid any one, two
Kind or more the mixture that is mixed with arbitrary proportion, sour a concentration of 0.01-0.5mol/L.
6. synthetic method according to claim 1, which is characterized in that solid is done after deionized water is washed to neutrality
Dry, drying temperature is 100-130 DEG C, drying time 12-48h.
7. synthetic method according to claim 1, which is characterized in that the acid solution of reflux is the aqueous solution of acid, and acid is
Citric acid, oxalic acid, succinic acid, glutaric acid, acetic acid, formic acid, propionic acid, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, tartaric acid, malic acid, amber
In amber acid any one, two kinds or more the mixtures mixed with arbitrary proportion, sour a concentration of 0.01- in acid solution
0.5mol/L。
8. synthetic method according to claim 1, which is characterized in that the solid after dry is placed in acid solution again to be returned
The solid-liquid mass ratio of stream process, solid and acid solution is 1：(10-50).
9. synthetic method according to claim 1, which is characterized in that the temperature of reflow treatment is 80~120 DEG C, when processing
Between be 0.5~12h.
10. synthetic method according to claim 1, which is characterized in that solid product is washed through deionization to neutral laggard
Row drying, drying temperature are 100-130 DEG C, drying time 12-48h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109626390A (en) * | 2019-01-15 | 2019-04-16 | 太原理工大学 | A kind of preparation method of multi-stage pore zeolite molecular sieve |
| CN112978750A (en) * | 2021-01-26 | 2021-06-18 | 青岛科技大学 | Molecular sieve modification post-treatment method |
| CN114180594A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Preparation method of ITH molecular sieve |
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| CN103183354A (en) * | 2011-12-31 | 2013-07-03 | 上海欣年石化助剂有限公司 | Method for preparing EUO structural zeolite |
| CN104918886A (en) * | 2012-11-13 | 2015-09-16 | 巴斯夫欧洲公司 | Production and use of a zeolitic material in a process for the conversion of oxygenates to olefins |
| CN104936898A (en) * | 2012-12-18 | 2015-09-23 | 环球油品公司 | UZM-43 an EUO-NES-NON zeolite |
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| CN102464335A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of ZSM-11 molecular sieve |
| CN103183354A (en) * | 2011-12-31 | 2013-07-03 | 上海欣年石化助剂有限公司 | Method for preparing EUO structural zeolite |
| CN104918886A (en) * | 2012-11-13 | 2015-09-16 | 巴斯夫欧洲公司 | Production and use of a zeolitic material in a process for the conversion of oxygenates to olefins |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109626390A (en) * | 2019-01-15 | 2019-04-16 | 太原理工大学 | A kind of preparation method of multi-stage pore zeolite molecular sieve |
| CN109626390B (en) * | 2019-01-15 | 2021-12-21 | 太原理工大学 | Preparation method of hierarchical pore zeolite molecular sieve |
| CN114180594A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Preparation method of ITH molecular sieve |
| CN112978750A (en) * | 2021-01-26 | 2021-06-18 | 青岛科技大学 | Molecular sieve modification post-treatment method |
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