CN106807324A - A kind of compound modulating method of acidic zeolite and pore structure - Google Patents
A kind of compound modulating method of acidic zeolite and pore structure Download PDFInfo
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- CN106807324A CN106807324A CN201510873822.5A CN201510873822A CN106807324A CN 106807324 A CN106807324 A CN 106807324A CN 201510873822 A CN201510873822 A CN 201510873822A CN 106807324 A CN106807324 A CN 106807324A
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Abstract
The present invention provides the compound modulating method of a kind of acidic zeolite and pore structure, belongs to molecular sieve modified, sorbing material preparation and field of catalyst preparation.The method is to introduce aluminium salt in high-silica zeolite or treatment medium in a certain way, then heated, filtration washing is to neutrality, hydrogen type molecular sieve is exchanged into by ion exchange, roasting process after drying, the method is simple to operate, with low cost, and the product yield of modified molecular screen material can be effectively improved, gained modified molecular screen material microcellular structure keeps good, and produces abundant secondary pore pore structure, while acid occur：The acid distribution feature that strong acid center density is kept completely, weak acid is improved with middle strong acid center density.
Description
Technical field
Prepared the invention belongs to molecular sieve modified, sorbing material and field of catalyst preparation, and in particular to a kind of
The compound modulating method of acidic zeolite and pore structure.
Background technology
Since molecular sieve comes out, because it has abundant microcellular structure, good hydrothermal stability and strong acid
Property the features such as, as catalysis, adsorption and separation material have been widely used for PETROLEUM PROCESSING, Coal Chemical Industry, environment
The catalytic field such as protection and fine chemistry industry.Especially ZSM-5, the sieve extensive use of modenite equimolecular
In cracking, isomery is alkylated, in the reaction such as aromatisation.Because microporous molecular mesh size is smaller, in reaction
In there are problems that absorption, diffusion limitation, it is easy, improve its pore structure and Acidity distribution turn into
Solve the effective ways of these problems.
At present, the method for industrially being improved to Molecular Sieve Pore and Acidity predominantly chemical after-treatment logos.
US5118482 disclose it is a kind of using alkaline solution (NaOH, KOH or ammonia spirit) to L, FER,
Modenite equimolecular sieve carries out immersion treatment, the method to improve Al content in molecular sieve.US5118482
Disclose US6184167 and disclose a kind of using NaOH or sodium carbonate (Na2CO3) ZSM-5 is carried out
The method for the treatment of.US5952259 discloses one kind using alkaline solution treatment-acid solution reprocessing to molecule
The method that sieve is modified treatment.Javier P é rez-Ram í rez et al. detailed examination is existed using NaOH solution
Micro porous molecular sieve under uniform temperature to Si/Al ratio example in the range of 25-50 carries out immersion treatment, is formed secondary
, at 8nm (Chem.Eur.J.2005,11,4983-4994), the total acid content of molecular sieve is for pore size distribution$
Rise, but the strong acid quantity of molecular sieve has declined.Javier P é rez-Ram í rez et al. also investigate pure silicon MFI
Molecular sieve (Si/Al=∞) in NaOH solution pore structure situation of change (Chem.Eur.J.2011,17,
1137-1147), find to add a small amount of metal (Al in NaOH solution3+, Ga3+) salt, can keep away
Exempt from unordered and a large amount of dissolvings of pure silicon MFI molecular sieves, but this processing method cannot produce strong acid in molecular sieve
Center.The characteristic of alkali treatment method is in above-mentioned molecular sieve post-processing approach：Because alkaline medium is to molecular sieve
Middle four-coordination skeleton Al is (strongSour position) structure removing effect so that the strong acid center of molecular sieve
Certain loss is subject to after the treatment；Additionally, the regulation to the secondary pore structure of molecular sieve places one's entire reliance upon
The temperature (60-90 DEG C) and concentration (0.2-5.0 mol/Ls) of alkali process process, but high pure alkali is risen merely
The treatment temperature of liquid and the concentration for the treatment of alkali lye cause secondary pore aperture to become big, while high concentration basic solution pole
It is easily caused a large amount of dissolvings and microcellular structure destruction (Chem.Eur.J.2005,11,4983-4994) of molecular sieve.
It is above-mentioned not enough so that obtaining structure and obtaining certain modulation but molecular sieve by above-mentioned basic treatment method
Acid strong acid center quantity is necessarily weakened, and is restricted its application.
The content of the invention
Regarding to the issue above, the purpose of the present invention is adjusted by using the basic treatment medium of aluminum contained compound
Become the acidity and pore structure of Si-Al molecular sieve, by this method treatment institute acquisition molecular sieve secondary pore structure with
It is acid, hence it is evident that the secondary pore structure and acidity of alkali lye media processes gained molecular sieve different from the past.
The invention provides a kind of acidic zeolite and the compound modulating method of pore structure, the method specific steps
It is as follows：During molecular sieve to put into the alkaline medium solution of aluminium-containing substance in proportion, by molecular sieve with containing aluminium alkalescence
The suspension of medium is stirred, and is warming up to 50-90 DEG C, the duration of heat -70 minutes 15 minutes it
Between.Sample filtering after above-mentioned treatment is washed to neutral, dry, then 3-6h is calcined at 350-600 DEG C,
Carry out ammonium exchange, roasting again afterwards, be finally changed into Na2Hydrogen type molecular sieve of the O content less than 0.05wt%.
The molecular sieve includes：
Topological structure is MFI, Si/Al atomic ratio between 25-60, Na2The ZSM-5 of O content 0-0.5wt%
Molecular sieve；
Topological structure is MEL, Si/Al atomic ratio between 25-70, Na2The ZSM-5 of O content 0-1.5wt%
Molecular sieve；
Topological structure is MOR, Si/Al atomic ratio between 35-55, Na2O content 0.05-1.0wt%
Modenite；
Or above-mentioned three kinds of molecular sieves include the state of aluminium compound in advance.
Described alkaline medium is NaOH, KOH, Na2CO3, K2CO3, in one or more, alkali
Property medium substance withdrawl syndrome is with anion (OH-, CO3 2-) concentration calculate between 0.15-0.50mol/L；
The aluminium-containing substance is the mixed of one or more in aluminum nitrate, aluminum fluoride, aluminium isopropoxide, aluminum sulfate
Zoarium system, the amount concentration containing Al elemental substances is calculated between 0.003-0.200mol/L with Al ion concentrations；
The ratio of the amount of the alkaline medium material and the amount of aluminium element material is 20-250.
The ratio (volume/mass) of the alkaline medium containing aluminium and molecular sieve is between 5-40.
The state comprising aluminium compound can be by dipping or dry-mixed, the Ran Hou of machinery in advance for the molecular sieve
The 250-600 DEG C of method of roasting is obtained.
The present invention suppresses alkaline medium to molecular sieve four-coordination bone by introducing material containing Al in alkaline medium
Frame Al is (strongSour position) skeleton removing effect；Change dissolving of the alkaline medium to molecular sieve simultaneously
Ability, while molecular sieve strong acid center quantity is kept, increased a number of weak acid with middle strong acid number
Amount, and realize the regulation to the secondary pore structure of molecular sieve.
The inventive method is simple to operate, with low cost, and can effectively improve the product receipts of modified molecular screen material
Rate, gained modified molecular screen material microcellular structure keeps good, and produces abundant secondary pore pore structure, together
When acid occur：The acid distribution that strong acid center density is kept completely, weak acid is improved with middle strong acid center density
Feature.With good industrial applications prospect.
Brief description of the drawings
Fig. 1 is the secondary pore point of the treatment ZSM-5 molecular sieve sample of alkaline medium containing aluminium in the embodiment of the present invention 1
Cloth curve.
Fig. 2 is the secondary pore point of sample after the alkaline medium containing aluminium of the embodiment of the present invention 2 treatment ZSM-5 molecular sieve
Cloth curve.
Fig. 3 is the secondary pore of sample after the treatment of alkaline medium containing aluminium ZSM-5 molecular sieve in the embodiment of the present invention 5
Distribution curve.
Fig. 4 is to be processed without aluminium alkaline medium in original ZSM-5 samples and comparative example of the present invention in embodiment 1
After ZSM-5 molecular sieve sample secondary pore distribution curve (▲ be original ZSM-5 in embodiment 1；Δ is contrast
Sample is processed without aluminium alkaline medium) in example.
Fig. 5 is to be processed without aluminium alkaline medium in original ZSM-5 samples and comparative example of the present invention in embodiment 1
ZSM-5 molecular sieve and the treatment of alkaline medium containing aluminium ZSM-5 molecular sieve sample in the embodiment of the present invention 1
NH3- TPD contrasts (solid line：Original ZSM-5 samples；Imaginary point line：ZSM-5 is processed without aluminium alkaline medium
Molecular sieve；Empty short-term：The treatment ZSM-5 molecular sieve of alkaline medium containing aluminium sample).
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Embodiment 1
Take 10g ZSM-5 molecular sieves (Si/Al=35, Na2O content<0.02wt%) 300ml is added to contain
There are 0.20mol/L NaOH-0.008mol/L Al (NO3)3In solution, magnetic agitation 35 minutes at 65 DEG C,
Then filtration washing is to neutrality, is calcined 3 hours at 550 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours.
Eligible molecule sieve is added in the ammonium nitrate solution of 0.8mol/L, solid-to-liquid ratio is 1:Magnetic force at 10,85 DEG C
Stirring 2 hours, then filtration washing, dries 12 hours, afterwards 550 DEG C in Muffle furnace at 120 DEG C
Lower roasting 6 hours, is designated as A.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 1.
The secondary pore distribution curve of the treatment of alkaline medium containing aluminium ZSM-5 molecular sieve sample is as shown in Figure 1 in the present embodiment.
Embodiment 2
Take 15g ZSM-5 molecular sieves (Si/Al=38, Na2O content 0.15wt%) it is added to 200ml and contains
There are 0.25mol/L KOH-0.005mol/L AlF3Mixed solution in, magnetic agitation 60 minutes at 65 DEG C,
Then filtration washing is to neutrality, is calcined 3 hours at 540 DEG C in the Muffle furnace after 110 DEG C of dryings 12 hours.
Eligible molecule sieve is added in the ammonium nitrate solution of 1.0mol/L, solid-to-liquid ratio is 1:Magnetic force at 20,85 DEG C
Stirring 2 hours, then filtration washing, dries 12h at 120 DEG C, afterwards in the Muffle furnace at 550 DEG C
Roasting 6 hours, is designated as B.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 1.
The secondary pore distribution curve of sample is as shown in Figure 2 after the present embodiment alkaline medium containing aluminium treatment ZSM-5 molecular sieve.
Embodiment 3
Take 10g ZSM-5 molecular sieves (Si/Al=34, Na2O content 0.15wt%) it is added to 200ml and contains
In having a mixed solution of 0.25mol/L NaOH-0.009mol/L aluminium isopropoxides, 55 points of magnetic agitation at 75 DEG C
Clock, then filtration washing is to neutrality, and 3 are calcined at 540 DEG C in the Muffle furnace after 110 DEG C of dryings 12 hours
Hour.Eligible molecule sieve is added in the ammonium nitrate solution of 1.0mol/L, solid-to-liquid ratio is 1:20,85 DEG C
Lower magnetic agitation 2 hours, then filtration washing, dries 12h at 120 DEG C, afterwards 550 in Muffle furnace
It is calcined 6 hours at DEG C, is designated as C.The aluminum contained compound alkaline medium treatment molecular sieve structure data such as institute of table 1
Show.
Embodiment 4
Take 50g ZSM-5 molecular sieves (Si/Al=30, Na2O content 0.09wt%) it is added to 1200ml and contains
There are 0.20mol/L NaOH-0.009mol/L Al (NO3)3Mixed solution in, 60 points of magnetic agitation at 65 DEG C
Clock, then filtration washing is to neutrality, and 3 are calcined at 530 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours
Hour.Eligible molecule sieve is added in the ammonium nitrate solution of 1.0mol/L, solid-to-liquid ratio is 1:10,80 DEG C
Lower magnetic agitation 2 hours, then filtration washing, dries 12 hours, afterwards in Muffle furnace at 120 DEG C
In be calcined 6 hours at 530 DEG C, be designated as D.Aluminum contained compound alkaline medium treatment molecular sieve structure data are such as
Shown in table 1.
Embodiment 5
Take 20g ZSM-5 molecular sieves (Si/Al=45, Na2O content<0.02wt%) 600ml is added to contain
There are 0.25mol/L NaOH-0.010mol/L Al2(SO4)3Mixed solution in, magnetic agitation 40 at 65 DEG C
Minute, then filtration washing is to neutrality, and 3 are calcined at 510 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours
Hour.Eligible molecule sieve is added in the ammonium nitrate solution of 1.0mol/L, solid-to-liquid ratio is 1:20,90 DEG C
Lower magnetic agitation 2 hours, then filtration washing, dries 12 hours, afterwards in Muffle furnace at 120 DEG C
It is calcined 6 hours at 530 DEG C, is designated as E.Aluminum contained compound alkaline medium processes molecular sieve structure data such as table
Shown in 2.In the present embodiment alkaline medium containing aluminium treatment ZSM-5 molecular sieve after sample secondary pore distribution curve such as
Shown in Fig. 3.
Embodiment 6
Take 40g ZSM-5 molecular sieves (Si/Al=30, Na2O content<0.02wt%), 3.0g is added
Al(NO3)3·9H2After O, 40ml deionized water dissolvings are added, then room temperature magnetic agitation 8 hours, 120 DEG C
It is calcined 3 hours at 500 DEG C in the Muffle furnace after drying 12 hours.Molecular sieve after roasting is added to 1200ml
Contain 0.40mol/L Na2CO3-0.002mol/L Al(NO3)3In solution, magnetic agitation 35 minutes at 85 DEG C,
Then filtration washing is to neutrality, is calcined 3 hours at 550 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours.
Eligible molecule sieve is added in the ammonium nitrate solution of 0.90mol/L, solid-to-liquid ratio is 1:Magnetic force at 30,90 DEG C
Stirring 2 hours, then filtration washing, dries 12 hours, afterwards 510 DEG C in Muffle furnace at 120 DEG C
Lower roasting 6 hours, is designated as F.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 2.
Embodiment 7
Take 20g ZSM-5 molecular sieves (Si/Al=35, Na2O content 0.6wt%), add 2.6g
Al(NO3)3·9H2After O, it is calcined 3 hours at 400 DEG C in the Muffle furnace after mechanical mixture is uniform.After being calcined
Molecular sieve is added to during 600ml contains 0.30mol/L NaOH solutions, magnetic agitation 30 minutes at 85 DEG C,
Then filtration washing is to neutrality, is calcined 3 hours at 550 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours.
Eligible molecule sieve is added in the ammonium nitrate solution of 0.90mol/L, solid-to-liquid ratio is 1:Magnetic force at 30,90 DEG C
Stirring 2 hours, then filtration washing, dries 12 hours, afterwards 510 DEG C in Muffle furnace at 120 DEG C
Lower roasting 6 hours, is designated as G.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 2.
Embodiment 8
Take 40g ZSM-5 molecular sieves (Si/Al=30, Na2O content 0.2wt%) it is added to 500ml and contains
There are 0.25mol/L NaOH-0.004mol/L Al (NO3)3In solution, magnetic agitation 45 minutes at 70 DEG C, so
Filtration washing is to neutrality afterwards, is calcined 3 hours at 550 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours.
Eligible molecule sieve is added in the ammonium nitrate solution of 0.9mol/L, solid-to-liquid ratio is 1:Magnetic force at 20,85 DEG C
Stirring 2 hours, then filtration washing, dries 12 hours, afterwards 530 DEG C in Muffle furnace at 120 DEG C
Lower roasting 6 hours, is designated as H.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 2.
Embodiment 9
Take 33g ZSM-11 molecular sieves (Si/Al=50, Na2O content<0.02wt%) it is added to 660ml
Containing in 0.25mol/L NaOH-0.015mol/L aluminium isopropoxide solution, magnetic agitation 35 minutes at 70 DEG C,
Then filtration washing is to neutrality, is calcined 3 hours at 550 DEG C in the Muffle furnace after 120 DEG C of dryings 12 hours.
Eligible molecule sieve is added in the ammonium nitrate solution of 0.8mol/L, solid-to-liquid ratio is 1:Magnetic force at 20,90 DEG C
Stirring 2 hours, then filtration washing, dries 12 hours, afterwards 550 DEG C in Muffle furnace at 120 DEG C
Lower roasting 6 hours, is designated as I.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 3.
Embodiment 10
Take 40g modenites (Si/Al=45, Na2O content 0.6wt%), add 1500ml to contain 0.35
mol/L NaOH-0.004mol/L Al(NO3)3In solution, magnetic agitation 50 minutes, are then centrifuged at 80 DEG C
Washing is calcined 3 hours in the Muffle furnace after 120 DEG C of dryings 12 hours to neutrality at 550 DEG C.To obtain point
Son sieve is added in the ammonium nitrate solution of 1.3mol/L, and solid-to-liquid ratio is 1:Magnetic agitation 1.5 at 30,85 DEG C
Hour, then filtration washing dries 12 hours at 120 DEG C, is roasted at 530 DEG C in the Muffle furnace afterwards
Burn 6 hours, be designated as J.Aluminum contained compound alkaline medium treatment molecular sieve structure data are as shown in table 3.
Comparative example 1
Take 10g ZSM-5 molecular sieves (Si/Al=35, Na2O content<0.02wt%) 300ml is added to contain
In 0.20mol/L NaOH solutions, magnetic agitation 30 minutes at 65 DEG C, then filtration washing is to neutrality, and 120
After DEG C drying 12 hours, it is calcined 3 hours at 550 DEG C in the Muffle furnace.Eligible molecule sieve is added to 0.8
In the ammonium nitrate solution of mol/L, solid-to-liquid ratio is 1:Magnetic agitation 2 hours at 10,85 DEG C, then cross diafiltration
Wash, dried at 120 DEG C 12 hours, be calcined 6 hours at 550 DEG C in the Muffle furnace afterwards.
In embodiment 1 ZSM-5 molecular sieve is processed in original ZSM-5 samples and this comparative example without aluminium alkaline medium
Afterwards the secondary pore distribution curve of sample as shown in Figure 4 (▲ be original ZSM-5 in embodiment 1；Δ is comparative example
It is middle to process sample without aluminium alkaline medium).
Divide without aluminium alkaline medium treatment ZSM-5 in original ZSM-5 samples and comparative example of the present invention in embodiment 1
Son sieve processes the NH of ZSM-5 molecular sieve sample with alkaline medium containing aluminium in the embodiment of the present invention 13- TPD is contrasted
(solid line as shown in Figure 5：Original ZSM-5 samples；Imaginary point line：ZSM-5 molecules are processed without aluminium alkaline medium
Sieve；Empty short-term：The treatment ZSM-5 molecular sieve of alkaline medium containing aluminium sample).
The aluminum contained compound alkaline medium of table 1 treatment molecular sieve structure data 1
The aluminum contained compound alkaline medium of table 2 treatment molecular sieve structure data 2
The aluminum contained compound alkaline medium of table 3 treatment molecular sieve structure data 3
Claims (6)
1. the compound modulating method of a kind of acidic zeolite and pore structure, it is characterised in that follow the steps below：Will
Molecular sieve is put into the alkaline medium solution of aluminium-containing substance in proportion, and the alkalescence of molecular sieve and aluminium-containing substance is situated between
Matter suspension is stirred, and is warming up to 50~-90 DEG C, and the duration of heat was at 15~70 minutes；Will be above-mentioned
Sample filtering after treatment is washed to neutral, dry, is then calcined 3~-6h, Zhi Houzai at 350~-600 DEG C
Ammonium exchange, roasting are carried out, is finally changed into Na2Hydrogen type molecular sieve of the O content less than 0.05wt%.
2. according to a kind of acidic zeolite and the compound modulating method of pore structure described in claim 1, it is characterised in that
The molecular sieve is：
Topological structure is MFI, Si/Al atomic ratio between 25-60, Na2The ZSM-5 of O content 0-0.5wt%
Molecular sieve；
Topological structure is MEL, Si/Al atomic ratio between 25-70, Na2The ZSM-5 of O content 0-1.5wt%
Molecular sieve；
Topological structure is MOR, Si/Al atomic ratio between 35-55, Na2O content 0.05-1.0wt%
Modenite；
Or above-mentioned three kinds of molecular sieves include the state of aluminium compound in advance.
3., according to a kind of acidic zeolite and the compound modulating method of pore structure described in claim 1, its feature exists
In the alkaline medium solution of the aluminium-containing substance：
Described alkaline medium is NaOH, KOH, Na2CO3, K2CO3, in one or more, alkali
Property medium substance withdrawl syndrome is with anion (OH-, CO3 2-) concentration calculate between 0.15-0.50mol/L；
The aluminium-containing substance is the mixed of one or more in aluminum nitrate, aluminum fluoride, aluminium isopropoxide, aluminum sulfate
Zoarium system；The amount concentration containing Al elemental substances is calculated in 0.003-0.200 with Al ion concentrations in aluminium-containing substance
Between mol/L；
The ratio of the amount of aluminium element material is in 20-250 in the amount and aluminium-containing substance of the alkaline medium material：1
Between.
4. according to a kind of acidic zeolite described in claim 1 and the compound modulating method of pore structure, it is characterised in that
The volume containing Al alkaline mediums and molecular sieve quality ratio are in 5-40ml/g.
5. according to a kind of acidic zeolite described in claim 2 and the compound modulating method of pore structure, it is characterised in that：
The molecular sieve includes the state of aluminium compound in advance, and the previously-introduced Al in part can be by dipping or machinery
It is dry-mixed, then it is obtained in the 250-600 DEG C of method of roasting.
6. according to a kind of acidic zeolite described in claim 1 and the compound modulating method of pore structure, it is characterised in that
The aluminium-containing substance is one or more in aluminum nitrate, aluminum fluoride, aluminum sulfate, aluminium isopropoxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112934254A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Bifunctional catalyst for catalyzing n-heptane conversion and preparation method thereof |
| WO2022089338A1 (en) * | 2020-10-26 | 2022-05-05 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve catalyst, and preparation and application thereof |
| CN114471685A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Binderless Beta molecular sieve catalyst and preparation method and application thereof |
| CN114471673A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Phosphorus-containing binder-free ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN116621191A (en) * | 2023-06-02 | 2023-08-22 | 深圳鼎诚环境科学有限公司 | Molecular sieve adsorbent for removing benzene series in VOCs and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972664A (en) * | 2010-10-13 | 2011-02-16 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of propane for preparing propylene and preparation method thereof |
| CN102049308A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
-
2015
- 2015-12-02 CN CN201510873822.5A patent/CN106807324A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049308A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
| CN101972664A (en) * | 2010-10-13 | 2011-02-16 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of propane for preparing propylene and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LILI YU ET AL.: ""A Facile Top-Down Protocol for Postsynthesis Modification of Hierarchical Aluminum-Rich MFI Zeolites"", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
| 谢在库 等: "《新结构高性能多孔催化材料》", 31 January 2010, 中国石化出版社 * |
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| CN112934254A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Bifunctional catalyst for catalyzing n-heptane conversion and preparation method thereof |
| CN112934254B (en) * | 2019-12-11 | 2023-06-20 | 中国科学院大连化学物理研究所 | Dual-function catalyst for catalyzing n-heptane conversion and preparation method thereof |
| WO2022089338A1 (en) * | 2020-10-26 | 2022-05-05 | 中国石油化工股份有限公司 | Silicon-aluminum molecular sieve catalyst, and preparation and application thereof |
| CN114471685A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Binderless Beta molecular sieve catalyst and preparation method and application thereof |
| CN114471673A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Phosphorus-containing binder-free ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN114471685B (en) * | 2020-10-26 | 2023-08-29 | 中国石油化工股份有限公司 | Binder-free Beta molecular sieve catalyst and preparation method and application thereof |
| CN114471673B (en) * | 2020-10-26 | 2023-08-29 | 中国石油化工股份有限公司 | Phosphorus-containing non-binder ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN116621191A (en) * | 2023-06-02 | 2023-08-22 | 深圳鼎诚环境科学有限公司 | Molecular sieve adsorbent for removing benzene series in VOCs and preparation method thereof |
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Application publication date: 20170609 |