CN102774854A - Synthetic method of novel mesoporous-microporous NaY zeolite - Google Patents
Synthetic method of novel mesoporous-microporous NaY zeolite Download PDFInfo
- Publication number
- CN102774854A CN102774854A CN2011101218664A CN201110121866A CN102774854A CN 102774854 A CN102774854 A CN 102774854A CN 2011101218664 A CN2011101218664 A CN 2011101218664A CN 201110121866 A CN201110121866 A CN 201110121866A CN 102774854 A CN102774854 A CN 102774854A
- Authority
- CN
- China
- Prior art keywords
- microporous
- mesoporous
- template
- molecular sieve
- compound method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a novel mesoporous-microporous NaY zeolite and a synthetic method thereof. The method comprises a step that the mesoporous-microporous NaY zeolite is obtained by in-situ synthesis through introducing a template which is a silane modified polymer in the Y zeolite synthesis process, and has the advantages of short synthetic period and easily controlled operation conditions. The novel mesoporous-microporous NaY zeolite has a good hydrothermal stability, and has wide application prospects in the fields of petroleum catalytic cracking, hydrocracking and the like.
Description
Technical field
The present invention relates to a kind of novel mesoporous-microporous NaY molecular screen material and compound method, belong to the molecular screen material technical field.
Background technology
The supplied utilization of conventional oil resource reduces just day by day, and the processing of heavy oil and residual oil receives increasing attention.The characteristics of BO are that molecule is big, molecular structure is complicated.And in the heavy oil enrichment most sulphur, nitrogen and metallic compound in the crude oil, not only self the more difficult cracking of these compounds is easy to green coke, and is deposited on catalyst surface poisoning of catalyst is lost activity.
The These characteristics of BO has proposed special requirement to catalytic cracking catalyst; As typical micro porous molecular sieve; Y zeolite is from duct, acidity, hydrothermal stability and synthesize to become and see that originally Y zeolite still is a topmost active ingredient the modern catalytic cracking catalyst, and Y zeolite also exists some disadvantages, and the main aperture road of Y zeolite is made up of twelve-ring; Diameter is approximately 0.74nm; Catalytic cracking is carried out in the duct that makes the heavy oil molecules with big kinetic diameter can not get into Y zeolite, to form vapour (bavin) oil prodn, therefore can reduce the oily productive rate of vapour (bavin).In addition, because Y zeolite is cage structure, some components that produce in hydrocarbon compound gets into cage and when carrying out catalytic cracking are not easy to spread out, and form carbon deposit thus, thereby cause the inactivation of catalyst active center.Mesopore molecular sieve has the pore distribution of quite high specific surface and homogeneous; Not only the aperture is big; But also can select suitable template to come the adjustment aperture size according to actual needs; The key that realizes RFCC is: the first, and material has greatly-pore passage structure of Jies-microinverse distribution, carry out cracking with assurance heavy oil molecules mode with " relay race " in catalyzer; The second, mesoporous hydrothermal stability satisfies the harsh requirement of catalytic cracking process than higher.
The mesoporous-microporous molecular screen material that has of synthetic high thermal stability becomes catalytic material hot research fields in recent years, and Chinese scholars has been carried out number of research projects, has mesoporous-microporous molecular sieve in the hope of preparation.
The method of employing dual mould plate agents such as Van Bekkum has been synthesized have mesoporous-microporous molecular sieve (vanBekkum, H, et al.Chemical Communication 78:2281-2282 (1997); Van Bekkum, H, et al.Chemistry of Materials 13:683-687 (2001)), the method for dual mould plate agent can be synthesized various types of gradient porous molecular sieves.
It is with the mixture of small molecules quaternary ammonium salt and the hc-surfactant method as template synthesizing high-stability mesopore molecular sieve that CN200710055706.8 discloses a kind of.This invention (comprises triblock copolymer (EO) with small molecules quaternary ammonium salt (tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide, 4 bromide etc.) and hc-surfactant
20(PO)
70(EO)
20(P123) and (EO)
100(PO)
70(EO)
100(F127)) make mixed templates, under the high-temperature water heat condition, synthesized orderly mesopore molecular sieve, silicon species is highly condensed in its skeleton of product, has extraordinary hydrothermal stability.
CN200510017081.7 discloses and has a kind ofly mixed as composite shuttering with polyphosphazene polymer quaternary ammonium salt (polyquaternium) and organic amine (tetraethyl ammonium hydroxide, TPAOH) or organic quaternary ammonium salt; Perhaps with the polyphosphazene polymer quaternary ammonium salt as template; The molecular screen material of preparation composite pore structural; Have composite pore structural, have advantages of high catalytic activity; And can introduce multiple atoms metal.
CN200510017080.2 discloses a kind of preparation method of composite molecular screen, adopts hard template (mainly referring to rice husk or basicity styrene series ion exchange resin or inorganic carbon etc.) to mix with organic amine or organic quaternary ammonium salt and make template.The molecular sieve that makes has micropore and mesoporous composite pore structural simultaneously, and the molecular sieve hole wall is MFI or BEA or NaY or MOR crystalline structure.
Though the method for dual mould plate agent can be synthesized mesoporous-microporous molecular sieve,, improved the synthetic cost of molecular sieve owing to the use of multiple template.
CN01119907.5 discloses a kind of compound method of middle mesoporous-microporous composite molecular sieve, is the reaction mixture gel of preparing synthetic microporous molecular sieve (like Y zeolite, beta-molecular sieve) with the method for routine earlier; And then under 30～300 ℃ of conditions, carry out the crystallization of fs, and crystallization is after 3～300 hours, and the acidity-basicity ph value of adjustment reaction mixture is 9.5～12; And the synthetic used template of mesoporous molecular sieve of adding; Simultaneously also can add the silicon source---water glass, silicon sol, aluminium source---Tai-Ace S 150, sodium metaaluminate; Also can add transistion metal compound---tetrabutyl titanate, iron nitrate are introduced the heteroatoms metal; Also can add sodium-acetate, sodium-chlor auxiliary agent again, then, depress the hydrothermal crystallizing that carries out subordinate phase certainly at 30～170 ℃ again; Crystallization time is 15～480 hours, obtains the said middle mesoporous-microporous composite molecular sieve compsn of the present invention.
CN200810137042.4 discloses a kind of preparation method of microporous-mesoporous composite molecular sieve; Its composition comprises: preparation silicon and aluminum source slurries; Organic ammonium salt tensio-active agent 0.5～1.5 weight part is dissolved in heating for dissolving in 5～20 parts by weight of deionized water, and cooling mixes cooled solution with the silicon and aluminum source slurries; Violent stirring formed mixed gel in 1 hour; Described mixed gel is sealed in the stainless steel cauldron of polytetrafluoroethyllining lining pad, takes out after 24～48 hours in crystallization under 100～120 ℃ the temperature condition and be cooled to room temperature, it is 8.0～12.5 that the aqueous acetic acid of use 2.0mol/L is adjusted to the pH value; Crystallization 24～72 hours under 100～120 ℃ temperature condition again, be cooled to room temperature with product filter, washing, dry, roasting.
CN200410012548.4 discloses a kind of microporous-mesoporous composite molecular sieve and preparation method thereof; It is characterized in that making full use of intercrystalline amorphous aluminum silicide of micro-pore zeolite and appropriateness dissolving crystal edge part sial; As the silicon and aluminum source of synthesising mesoporous molecular sieve, with micro-pore zeolite molecular sieve ZSM-5, β zeolite, mordenite, zeolite L, MCM-22, ZSM-35, behind sodium hydroxide solution stirring pulping; Add the used template of synthesising mesoporous molecular sieve; After 22～26 hours, the potential of hydrogen of adjustment reaction mixture makes its pH value between 7.5～9.5, continues at 90～120 ℃ of static crystallizations and gets final product in 24～168 hours at 90～120 ℃ of static crystallizations.
On give an account of micro porous molecular sieve compound method all to belong to for two steps synthetic, all need carry out twice hydrothermal crystallizing, synthesis step is loaded down with trivial details, the action required time is long.
(Yan Y.Microporous Mesoporous Materials, 17 (15): 347-356 (2005) such as Yan; The polymkeric substance that Tatsumi T.Chemistry of Materials, 17 (15), 3913-3920 (2005)) will contain functionalized silicon group is introduced the physical and chemical performance that molecular sieve system is improved molecular sieve.
Tatsumi etc. (Aguado, Tatsumi.WO 2005026050) utilize the organosilicon polymer preparation to have the molecular sieve than bigger serface.But the molecule of the organosilicon polymer that they select for use is less, and perhaps the ratio of polymkeric substance and organosilicon modifier is improper, and molecular sieve does not produce meso-hole structure.
Pinnavaia etc. utilizes the chemical property of polymine more active in the US20070258884 patent; Adopt 3-(2.3-epoxy third oxygen) propyl trimethoxy silicane that it is carried out modification; Polymine after the modification is that template original position generation in the building-up process of ZSM-5 molecular sieve is mesoporous, and mesoporous aperture concentrates on about 3nm.
The present invention does template with the polymkeric substance and the substituted reaction product of aliphatic epoxy silanamines that contain the NH group, in the process of synthetic Y zeolite, adds the template original position and produces mesoporous-microporous structure.Innovative point of the present invention is to add a kind of new solvent in the synthetic template process, makes reaction more be prone to carry out, and in addition, in synthetic mesoporous-microporous molecular sieve process, through the control to pH, the result who obtains is superior to other bibliographical informations.The aperture of its micropore is between 0.39～0.6nm, and mesoporous aperture is between 2～4nm.
This method cost is low, simple to operate, only needs a crystallization, and the action required time is short.
Summary of the invention
The invention provides a kind of compound method of template, method is simple and easy to operate, reduces synthetic cost.
The present invention also provides a kind of mesoporous-microporous NaY molecular sieve synthetic method, through the mesoporous-microporous NaY molecular screen material of a quick synthesizing new of step.This material has regular pore structure, therefore has ideal acidity and hydrothermal stability.
The invention provides a kind of mesoporous-microporous NaY molecular sieve compound method, this compound method may further comprise the steps:
(1) preparation of template: polymine and 3-(2.3-epoxy third oxygen) propyl trimethoxy silicane (GPMS) reacted under certain solvent obtain.Temperature of reaction is 60～100 ℃, and the reaction times is 24～48h.
(2) preparation of directed agents: the proportioning of gelling system is: (1～30) Na
2O: Al
2O
3: (10-40) SiO
2: (200～500) H
2O gets at 45 ℃ of down aging 4.5-48h.
(3) preparation of mesoporous-microporous NaY type molecular sieve: with various silicon commonly used sources and aluminium source is main raw material, is solvent with water.Under vigorous stirring, add water glass successively, directed agents, alkali lye and Tai-Ace S 150, the proportioning of gelling system is: (1-500) Na
2O: Al
2O
3: (1-850) SiO
2: (10-800) H
2O: (1-10) template.Stir 1h down at 25-100 ℃, in gelation process, regulate the pH value.Mixture is transferred to crystallizing kettle then, at 100-120 ℃ of following crystallization 12-96h, and the product suction filtration, washing is to neutral, and drying is calcined.
According to above-mentioned compound method, the silicon source is selected from tetraethoxysilance in the step (3), water glass etc., and the aluminium source is selected from sodium metaaluminate, Tai-Ace S 150 etc.
This case applicant finds that utilize suitable template consumption and silicon and aluminum source, directed agents at room temperature obtains having the mesoporous-microporous molecular sieve of ordered structure according to suitable material ratio through suitable crystallization.
According to compound method provided by the invention, the proportioning of control reactant feed has material impact.Preferred synthesis condition: the top condition of synthesizing silane properties-correcting agent is: the consumption of polymine is: 10.6g, and solvent load: 8g, 3-(2.3-epoxy third oxygen) propyl trimethoxy silicane (GPMS) consumption is 3g, at 100 ℃ of reaction 24h; The top condition for preparing mesoporous-microporous NaY type molecular sieve is: water glass 72.13g, directed agents 15.83g, NaOH:8.00 and NaAlO
2: 1.00g is dissolved in 45ml water, and the consumption of silane modifier is: 6g, the consumption of solvent TMOAH is: 4.25g, Al
2(SO
4)
3: 21.88g, the pH value of colloidal sol is pH=12 before the molecular sieve crystallization, and crystallization temperature is 100 ℃, and crystallization time is 48h, the powerful stirring more than the 1h.
The present invention also provides a kind of synthetic according to the method described above mesoporous-microporous NaY molecular screen material, and this composite molecular screen micropore and meso-hole structure are obvious, has regular mesoporous-microporous structure.
In a word, enforcement of the present invention has following beneficial effect:
The present invention adopts the novel template of synthetic voluntarily, and synthetic materials is a technical grade, and synthetic cost reduces, and synthesis step is simple, and synthesis condition is gentle, and saves the running time.
The mesoporous-microporous molecular sieve of synthetic of the present invention has regular mesoporous and microvoid structure, is expected to be used for the catalyzed reaction that macromole is participated in as catalytic material.
Description of drawings
Fig. 1 is the small angle x-ray diffraction (SAXD) spectrogram of the mesoporous-microporous hexagonal mesoporous molecular sieve of embodiment 1 synthetic.
Fig. 2 is the mesoporous adsorption isothermal curve of the mesoporous-microporous molecular sieve of embodiment 1 synthetic.
Fig. 3 is the TEM figure of the embodiment 1 synthetic mesoporous-microporous molecular sieve that is.
Fig. 4 is the FFIR figure of the embodiment 1 synthetic mesoporous-microporous molecular sieve that is.
Embodiment
Below through specific embodiment the present invention is further explained, be intended to help the reader better to understand essence of the present invention and the beneficial effect that brings.But but should not be construed as any qualification to the present invention's practical range.
Embodiment one: the preparation of silane modifier MP-20000
Step 1: get 0.50g 3-(2.3-epoxy third oxygen) propyl trimethoxy silicane (GPMS) and (2.12mmol) be dissolved in the 8g solvent, at 100 ℃ of reaction 24h with 10.6g polymine (0.53mmol).
Step 2: resultant vacuumizes with revolving the steaming appearance, removes ethanol, thereby obtains silane modifier MP-20000.
Embodiment two: the preparation of mesoporous-microporous NaY molecular sieve
Step 1: take by weighing water glass 72.13g, directed agents 15.83g puts into the 250ml flask; Taking by weighing 6.00gMP-20000 is dissolved among the 4.25g TMOAH; Take by weighing NaOH:8.00g and NaAlO
2: 1.00g puts into beaker, with 45ml deionized water dissolving (alkali lye); Take by weighing Al
2(SO
4)
3: 21.88g puts into beaker, uses the 40ml deionized water dissolving;
Step 2: in flask, add the mixed solution of MP-20000 and TMOAH, add alkali lye then, regulate the pH value, drip Al at last
2(SO
4)
3Work as Al
2(SO
4)
3Be added drop-wise to half, strengthen rotating speed and make into the glue homogeneous reaction; Dropwise, keep stirring 1 hour at 25 ℃;
Step 3: stop to stir, placed 110 ℃ of still crystallization 24 hours;
Step 4: cooling, suction filtration, drying is calcined the micropore NaY type molecular sieve that obtains being situated between
Step 5: characterize: utilize XRD to characterize the structure of Jie's micropore NaY type molecular sieve.The result is as shown in Figure 1 to have tangible NaY type molecular sieve characteristic diffraction peak; Utilize BET to characterize and have mesopore orbit, result such as Fig. 2 explanation have meso-hole structure; Utilize TEM to characterize pore structure, the result is as shown in Figure 3 to know the existence of seeing micropore on mesoporous hole wall, and the duct be arranged with certain rules property, further specify template and played the reaming effect; Utilize FFIR figure to characterize the functional group of mesoporous-microporous molecular sieve, as having occurred at wave number 3450cm in Fig. 4 spectrogram
-1And 1630cm
-1The spectrum peak at place is the stretching vibration of hydroxyl and the flexural vibration peak of planar water, at 455cm
-1The flexural vibration peak of T-O (T=Si or Al) key in the corresponding tetrahedral structure of the vibration peak at place, 557cm
-1What the vibration peak of vicinity was corresponding is the vibration peak of the two six-rings of NaY type molecular sieve, and the relevant spectrum peak of silicon skeleton appears at wave number 1080cm
-1And 806cm
-1The place is respectively unsymmetrically and the symmetrical stretching vibration of siliconoxygen bond Si-O-Si, explains that forming mesoporous-microporous molecular sieve main body is the NaY molecular sieve.
Comprehensive the foregoing description can be known: the synthetic voluntarily template of the present invention, in the process of synthetic NaY molecular sieve, introduce the synthetic mesoporous-microporous NaY type molecular sieve of template original position.Compare with other mesoporous-microporous molecular sieve compound methods, the synthetic voluntarily template of the present invention, synthetic cost reduces, and synthesis step is simple, and synthesis condition is gentle, and saves the running time.Therefore, the present invention has very important use value and reference value.
Need to prove that at last above embodiment only is used to explain technical scheme of the present invention and is unrestricted.Although the present invention has been carried out detailed invention with reference to preferred embodiment; Those skilled in the art is to be understood that; Can make amendment or replacement on an equal basis to technical scheme of the present invention; And not breaking away from the spirit and the scope of technical scheme of the present invention, it all should cover in the middle of the claim scope of the present invention.
Claims (7)
1. novel mesoporous-microporous NaY molecular sieve compound method, this compound method may further comprise the steps:
(1) preparation of template: with polymkeric substance and the reaction of aliphatic epoxy silane modifier, the polymkeric substance after the modification is as template.Temperature of reaction is 80-110 ℃, and the reaction times is 24-48h.
(2) preparation of directed agents: the proportioning of gelling system is: (1～30) Na
2O: Al
2O
3: (10-40) SiO
2: (200～500) H
2O obtains at 45 ℃ of aging 4.5-24h.
(3) mesoporous-microporous NaY type molecular sieve is synthetic: with various silicon commonly used sources and aluminium source is main raw material, is solvent with water.Under vigorous stirring, add water glass successively, directed agents, template, alkali lye and Tai-Ace S 150, the proportioning of gelling system is: (1-500) Na
2O: Al
2O
3: (1-850) SiO
2: (10-800) H
2O: (1-10) template.Stirred 1 hour down at 25-45 ℃, mixture is transferred to crystallizing kettle then, at 100-120 ℃ of following crystallization 12-96h, and the product suction filtration, washing is extremely neutral, drying, calcining.
2. compound method according to claim 1 is characterized in that, in the step (1), template is the polymkeric substance and the substituted reaction product of aliphatic epoxy silanamines that have a NH group at least.Polymkeric substance and aliphatic epoxy silane covalency link here, the quality of polymkeric substance is every mole 100 gram at least in every mole of silane modifier.
3. compound method according to claim 1 is characterized in that, in the step (1), polymkeric substance comprises: Z 150PH, polyvinylamine, Vestolen PP 7052 imines, SEPIGEL 305, polymine etc.Aliphatic epoxy silane comprises: vinyltrimethoxy silane, propyl trimethoxy silicane, 3-aminopropyl trimethoxysilane, dodecyl Trimethoxy silane, methyltrimethoxy silane, 3-(2.3-epoxy third oxygen) propyl trimethoxy silicane (GPMS) etc.
4. compound method according to claim 1 is characterized in that, in the step (3), synthetic template is dissolved in a certain amount of TMAH.
5. compound method according to claim 1 is characterized in that, in the step (3), the silicon source is selected from tetraethoxysilance, water glass, and water glass etc., the aluminium source is selected from sodium metaaluminate, Tai-Ace S 150 etc.
6. compound method according to claim 1 is characterized in that, in the step (3), calcining temperature between 500-850 ℃, calcination time 4-24h.
7. novel mesoporous-microporous NaY molecular sieve, this composite molecular screen is to be prepared from according to the said compound method of claim 1-6 item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101218664A CN102774854A (en) | 2011-05-12 | 2011-05-12 | Synthetic method of novel mesoporous-microporous NaY zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101218664A CN102774854A (en) | 2011-05-12 | 2011-05-12 | Synthetic method of novel mesoporous-microporous NaY zeolite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102774854A true CN102774854A (en) | 2012-11-14 |
Family
ID=47119996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101218664A Pending CN102774854A (en) | 2011-05-12 | 2011-05-12 | Synthetic method of novel mesoporous-microporous NaY zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102774854A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112870A (en) * | 2013-01-31 | 2013-05-22 | 郑州大学 | Method for preparing ZSM-5/AlPO4-5 composite molecular sieve in polymer system |
| WO2015024380A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Beta molecular sieve having mesoporous/microporous combined channel structure, and synthesizing method thereof |
| CN106608639A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Modification method for Y type molecular sieve |
| CN106608640A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Molecular sieve obtained by NaY modification |
| CN106608641A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Method for improving stability of Y-type molecular sieve |
| CN107555446A (en) * | 2017-05-26 | 2018-01-09 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of multi-stage porous Y type molecular sieve |
| CN108249456A (en) * | 2018-01-23 | 2018-07-06 | 中国石油大学(华东) | A kind of method that grade hole Y type molecular sieve is prepared using rice husk as raw material |
| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
| WO2018205841A1 (en) * | 2017-05-08 | 2018-11-15 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing mesoporous nay-type zeolite molecular sieve |
| CN109206476A (en) * | 2018-11-20 | 2019-01-15 | 中国科学院青岛生物能源与过程研究所 | A kind of method of separation and purification of protein |
| CN109453802A (en) * | 2018-11-19 | 2019-03-12 | 内江师范学院 | Molecular sieve catalyst and preparation method thereof, the application in methanol and Benzyl Side-Chain alkylated reaction |
| CN111072045A (en) * | 2019-12-26 | 2020-04-28 | 闽南师范大学 | Hierarchical pore molecular sieve material and preparation method thereof |
| CN112850741A (en) * | 2019-11-12 | 2021-05-28 | 中国石油天然气股份有限公司 | Method for synthesizing small-grain NaY molecular sieve with intracrystalline mesopores |
| CN115678419A (en) * | 2022-07-19 | 2023-02-03 | 浙江工业大学 | Antibacterial water-repellent organic-inorganic hybrid coating of quaternary ammonium salt and synthetic method |
| CN116836748A (en) * | 2023-07-06 | 2023-10-03 | 孚迪斯石油化工科技(葫芦岛)股份有限公司 | Preparation method of high-heat-stability aviation lubricating oil |
-
2011
- 2011-05-12 CN CN2011101218664A patent/CN102774854A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112870B (en) * | 2013-01-31 | 2015-02-25 | 郑州大学 | Method for preparing ZSM-5/AlPO4-5 composite molecular sieve in polymer system |
| CN103112870A (en) * | 2013-01-31 | 2013-05-22 | 郑州大学 | Method for preparing ZSM-5/AlPO4-5 composite molecular sieve in polymer system |
| WO2015024380A1 (en) * | 2013-08-20 | 2015-02-26 | 中国科学院大连化学物理研究所 | Beta molecular sieve having mesoporous/microporous combined channel structure, and synthesizing method thereof |
| CN106608641B (en) * | 2015-10-26 | 2019-02-01 | 中国石油化工股份有限公司 | A method of improving Y type molecular sieve stability |
| CN106608639A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Modification method for Y type molecular sieve |
| CN106608640A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Molecular sieve obtained by NaY modification |
| CN106608641A (en) * | 2015-10-26 | 2017-05-03 | 中国石油化工股份有限公司 | Method for improving stability of Y-type molecular sieve |
| CN106608639B (en) * | 2015-10-26 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of method of modifying of Y type molecular sieve |
| CN106608640B (en) * | 2015-10-26 | 2019-02-01 | 中国石油化工股份有限公司 | It is a kind of that obtained molecular sieve is modified by NaY |
| WO2018205841A1 (en) * | 2017-05-08 | 2018-11-15 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing mesoporous nay-type zeolite molecular sieve |
| CN107555446A (en) * | 2017-05-26 | 2018-01-09 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of multi-stage porous Y type molecular sieve |
| CN107555446B (en) * | 2017-05-26 | 2020-09-25 | 中海油天津化工研究设计院有限公司 | Preparation method of hierarchical pore Y-type molecular sieve |
| CN108249456A (en) * | 2018-01-23 | 2018-07-06 | 中国石油大学(华东) | A kind of method that grade hole Y type molecular sieve is prepared using rice husk as raw material |
| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
| CN109453802A (en) * | 2018-11-19 | 2019-03-12 | 内江师范学院 | Molecular sieve catalyst and preparation method thereof, the application in methanol and Benzyl Side-Chain alkylated reaction |
| CN109453802B (en) * | 2018-11-19 | 2021-09-07 | 内江师范学院 | Molecular sieve catalyst, preparation method thereof and application thereof in side-chain alkylation reaction of methanol and toluene |
| CN109206476B (en) * | 2018-11-20 | 2021-08-17 | 中国科学院青岛生物能源与过程研究所 | Method for separating and purifying protein |
| CN109206476A (en) * | 2018-11-20 | 2019-01-15 | 中国科学院青岛生物能源与过程研究所 | A kind of method of separation and purification of protein |
| CN112850741A (en) * | 2019-11-12 | 2021-05-28 | 中国石油天然气股份有限公司 | Method for synthesizing small-grain NaY molecular sieve with intracrystalline mesopores |
| CN112850741B (en) * | 2019-11-12 | 2023-02-07 | 中国石油天然气股份有限公司 | Method for synthesizing small-grain NaY molecular sieve with intracrystalline mesopores |
| CN111072045A (en) * | 2019-12-26 | 2020-04-28 | 闽南师范大学 | Hierarchical pore molecular sieve material and preparation method thereof |
| CN111072045B (en) * | 2019-12-26 | 2022-12-20 | 闽南师范大学 | Hierarchical pore molecular sieve material and preparation method thereof |
| CN115678419A (en) * | 2022-07-19 | 2023-02-03 | 浙江工业大学 | Antibacterial water-repellent organic-inorganic hybrid coating of quaternary ammonium salt and synthetic method |
| CN115678419B (en) * | 2022-07-19 | 2023-11-24 | 浙江工业大学 | Water-repellent organic-inorganic hybrid coating with antibacterial quaternary ammonium salt and synthesis method |
| CN116836748A (en) * | 2023-07-06 | 2023-10-03 | 孚迪斯石油化工科技(葫芦岛)股份有限公司 | Preparation method of high-heat-stability aviation lubricating oil |
| CN116836748B (en) * | 2023-07-06 | 2024-03-26 | 孚迪斯石油化工科技(葫芦岛)股份有限公司 | Preparation method of high-heat-stability aviation lubricating oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102774854A (en) | Synthetic method of novel mesoporous-microporous NaY zeolite | |
| CN102745708B (en) | Synthetic method of mesoporous-microporous molecular sieve with improved hydrothermal stability | |
| CN103204515B (en) | Preparation method for high-dispersion zeolite molecular sieves | |
| CN101172243B (en) | Mesoporous material/micropore molecular sieve composite material and preparation method thereof | |
| US10005074B2 (en) | Molecular sieve material, its synthesis and use | |
| WO2011047528A1 (en) | Bi-microporous-mesoporous composite molecular sieve y-beta/ mcm-41 and preparing method thereof | |
| CN102689910B (en) | Synthesis method of mesoporous-microporous Y-type molecular sieve | |
| CN107555446A (en) | A kind of preparation method of multi-stage porous Y type molecular sieve | |
| Pan et al. | Direct synthesis of HZSM-5 from natural clay | |
| CN102502696A (en) | Synthetic method of ZSM-5 zeolites | |
| CN102942192A (en) | Preparation method for high-dispersion nanometer zeolite molecular sieve | |
| WO2011047527A1 (en) | Double micro-mesoporous composite molecular sieve and preparation method thereof | |
| CN100439246C (en) | Hard template synthetic composite hole zeolite molecular sieve and its preparing method | |
| CN100453460C (en) | High molecule polymer template synthetic composite hole zeolite molecular sieve and its preparing method | |
| CN102533316B (en) | Method for selective hydrocracking of light oil | |
| CN103073019B (en) | Hierarchical pore zeolite molecular sieve preparation method | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| Knyazeva et al. | Synthesis of nanoscale zeolites | |
| CN108439427A (en) | A kind of method that fabricated in situ is rich in mesoporous NaY molecular sieve | |
| CN105668580A (en) | Composite-structure molecular sieve and synthetic method thereof | |
| CN105253898A (en) | Preparation method for nanometer ZSM-5 molecular sieve aggregation | |
| CN107021504A (en) | A kind of preparation method of mesoporous IM-5 molecular sieves | |
| CN102259890B (en) | ZSM-5/ECR-1/mordenite three-phase symbiotic material and preparation method thereof | |
| CN105460952B (en) | The ZSM-5 molecular sieve material that the preparation method and this method of a kind of ZSM-5 molecular sieve material are prepared | |
| CN106946273B (en) | A kind of EU-1/ZSM-5 composite molecular screen and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| DD01 | Delivery of document by public notice |
Addressee: Xu Chunyan Document name: Notification of Publication of the Application for Invention |
|
| DD01 | Delivery of document by public notice |
Addressee: Xu Chunyan Document name: Notification of before Expiration of Request of Examination as to Substance |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121114 |
|
| DD01 | Delivery of document by public notice |
Addressee: Xu Chunyan Document name: Notification that Application Deemed to be Withdrawn |