CN102039201A - Double microporous-mesoporous composite molecular sieve and preparation method thereof - Google Patents
Double microporous-mesoporous composite molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN102039201A CN102039201A CN2009102361681A CN200910236168A CN102039201A CN 102039201 A CN102039201 A CN 102039201A CN 2009102361681 A CN2009102361681 A CN 2009102361681A CN 200910236168 A CN200910236168 A CN 200910236168A CN 102039201 A CN102039201 A CN 102039201A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- microporous
- micropore
- mesoporous
- beta
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a double micropore-mesopore composite molecular sieve and a preparation method thereof; the zeolite is compounded by Y-type and Beta-type double microporous zeolites and an MCM-41 molecular sieve, double microporous phases are tightly wrapped on the walls of hexagonal mesoporous phases, a plurality of spherical or hemispherical hollow shell structures are presented, the spherical or hemispherical hollow shell structures are mutually connected to form a net shape, and the silicon-aluminum ratio and the micropore content of the microporous phases are adjustable; taking mixed solution of hexadecyl trimethyl ammonium bromide and alkylphenol polyoxyethylene ether as a template, respectively introducing pretreated double-micropore phase and silicon source and/or aluminum source for synthesizing mesoporous phase into the system, and obtaining the Y-Beta/MCM-41 double-micropore-mesoporous composite molecular sieve with adjustable micropore phase silicon-aluminum ratio and micropore content through hydrothermal crystallization treatment; the invention has simple operation, good reproducibility and environmental protection, combines the advantages of Y-type zeolite, Beta-type zeolite and mesoporous molecular sieve, has good catalytic reaction performance, and is used as a carrier material of a hydrocracking catalyst.
Description
Technical field
The present invention relates to catalyst carrier material that a kind of pair of micropore phase (Y type and Beta type zeolite) and mesoporous (MCM-41) mutually molecular sieve be composited and preparation method thereof.
Background technology
Micro porous molecular sieve owing to have performances such as specific area is big, hydrothermal stability is high, aperture homogeneous, surface nature is adjustable, is widely used as catalyst, adsorbent, ion-exchanger and new function material as a kind of important inorganic material.First industrial with molecular sieve be applied to catalytic field be nineteen fifty-nine U.S. combinating carbide company be applied to isomerization reaction with y-type zeolite is catalyst based, then U.S. Mobile company in 1962 is applied to catalytic cracking with X type zeolite, and Grace company had developed ultrastable (USY) catalyst in 1969.Molecular sieve catalytic was removed and was mainly used in beyond cracking and the hydrocracking at that time, at isomerization, the C of n-alkane
8Aspects such as the low temp isomerizing of aromatic hydrocarbons, the disproportionation of toluene and shape selective catalysis have realized industrialization.
Micro porous molecular sieve has the micropore and the highly acid of even prosperity, but its aperture less (less than 2nm), big molecule is difficult to enter the duct, and this has limited its industrial applicability greatly.Since Mobile company in 1992 synthesized M41S series mesopore molecular sieve, (aperture was that the problems such as synthetic technology, performance characterization and crystallization mechanism of 2nm～50nm) are the focuses of studying in the world always to mesopore molecular sieve.But, cause its faintly acid and hydrothermal stability poor because the mesopore molecular sieve hole wall is amorphous.Since the nineties in 20th century, along with the development of petrochemical industry, Fine Chemical Industry and the strictness day by day of environmental requirement, to the also constantly increase of demand of new catalytic material.Therefore the researcher wishes in conjunction with micropore, mesoporous two kinds of molecular sieves advantage separately, synthesizing new microporous-mesoporous composite molecular sieve material.Microporous-mesoporous composite molecular sieve has micropore and mesoporous dual model pore structure, combines advantages such as the highly acid of the duct advantage of mesoporous material and poromerics and high hydrothermal stability, can make two kinds of materials synergies and has complementary advantages.But and aperture and acid all modulations, promptly be optimized compoundly by two kinds of materials selecting different pore passage structures and acid matter, can prepare the composite that Different Pore Structures and acid distribute.Internationally famous molecular sieve chemist Davis points out, successful preparation and diversity mode with the multistage porous molecular sieve material that is assembled into feature will have broad application prospects in more field.
Therefore, more about the research of composite molecular screen in recent years.The researcher ins all sorts of ways to synthesize composite molecular screen.The methods of employing bimodulus plate such as Huang and two step crystallization have been synthesized ZSM-5/MCM-41 (J Phys Chem B, 2000,2817～2823) and β/MCM-41 (high chemical journal 104 (13):, 1999,20 (3): 356～358) two kinds of microporous-mesoporous composite molecular sieves have intersection but this method requires the synthesis condition of micropore and mesoporous two kinds of molecular sieves to be more or less the same or to synthesize scope.Kloetstra etc. have reported technology (the Microporous Mesoporous Mater of the mesoporous MCM-41 molecular sieve of outgrowth on Y zeolite, 1996,287～293) and MCM-41 is carried out again method (the Div Pet Chem of crystallization with the tetrapropyl ammonium ion-exchange 6 (5～6):, 1996,41 (2): 412～414).But it is unordered that arrange in the mesoporous lamella duct of the Y/MCM-41 composite molecular screen that the former synthesizes, and combined coefficient is very low, and acid matter, hydrothermal stability are all undesirable; The degree of disorder of the mesoporous wall of the ZSM-5/MCM-41 composite molecular screen that the latter synthesizes is still very high, and the part of crystallization exists only in the mesoporous wall surface, so hydrothermal stability is short of to some extent.The Pinnavaia of the U.S. etc. prepares embedded composite molecular screen by the nanometer construction from part, the crystal seed of at first prefabricated Y zeolite, and then carry out self assembly (J Am Chem Soc, 2000,122:8791～8792) with CTAB.The composite molecular screen of this method preparation has very high acidity and significant hydrothermal stability, but to prepare the crystal seed of micro porous molecular sieve earlier, and the process difficulty or ease control of preparation crystal seed, crystal seed is crossed conference influences assembling effect, and the too small acid matter that can influence material.The report that Y/MCM-41, β/MCM-41, β/MCM-48 are arranged again subsequently in succession.Microporous-mesoporous composite molecular sieve has excellent catalytic performance, as the ZSM-5/MCM-41 composite molecular screen to the catalytic activity of n-dodecane cracking reaction mechanical mixture object height than them.At present, more to the research of binary microporous-mesoporous composite molecular sieve both at home and abroad, but two the compound of microporous-mesoporous composite molecular sieve of ternary are not appeared in the newspapers as yet.We are at present in industrial Y type and the Beta type zeolite that generally uses of hydrocracking, comprehensively the two characteristic in hydrocracking: y-type zeolite heavy naphtha virtue dive high, the BMCl value is low; Beta type zeolite middle distillates oil selectivity is good, active high, but the deficiency that virtue is latent low, the BMCl value is high, invented the supermolecule self assembly effect that in alkaline system, utilizes cation, nonionic surfactant, by the method for hydro-thermal outgrowth, the two microporous-mesoporous composite molecular sieves (Y-Beta/MCM-41) of synthesizing new.This invention is the further developing to the molecular sieve catalytic material, and synthetic two microporous-mesoporous composite molecular sieves (Y-Beta/MCM-41) can be used as the novel carriers of hydrocracking catalyst, in field of petrochemical industry potential using value is arranged.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst carrier material and preparation method easy and simple to handle, favorable reproducibility that two micropore phases (Y type and Beta type zeolite) and mesoporous (MCM-41) mutually molecular sieve are composited that contain.
The of the present invention pair of microporous-mesoporous composite molecular sieve is composited by Y type and Beta type double-micropore zeolites and MCM-41 molecular sieve, two micropores closely are wrapped on the hexagonal mesoporous phase hole wall mutually, present many spheries or hemispheric hollow shell structure, commissure reticulates mutually each other, and when micro content is adjustable for micropore phase sial.
Two microporous-mesoporous composite molecular sieves (Y-Beta/MCM-41) of the present invention preparation are that micropore phase, silicon source and the aluminium source that will anticipate in alkaline system are as inorganic precursor (I
-) at cation (S
+), nonionic (S
0) under the effect of mixed surfactant, pass through S
+S
0I
-Route carries out the supermolecule self assembly, realizes mesoporously going up outgrowth mutually at micropore.
Its preparation process is as follows:
(1) micropore phase preliminary treatment: get a certain amount of Y type and Beta type zeolite, join in the deionized water after mixing in proportion, stir under specified temp, it is stand-by that note is made solution A.
(2) get certain amount of surfactant softex kw (CTAB) and APES (OP-10), join in the deionized water after mixing in proportion, and under room temperature, at the uniform velocity stir, treat the solution clarification after, it is stand-by that note is made solution B.
(3) solution A that obtains is joined in the solution B, under room temperature, stir, in mixed liquor, slowly drip silicon source and aluminium source then or only drip the silicon source, continue at room temperature to stir, in the liquid to be mixed each component uniform and stable after, with the pH value of inorganic acid or alkali regulation system, at the uniform velocity stir again, after the system for the treatment of is stable the glue that obtains packed into and have in the stainless steel cauldron of liner crystallization under specified temp.
(4) crystallization product that (3) are obtained carries out suction filtration, washing, oven dry and handles and obtain the white solid powder.With the roasting in nitrogen stream earlier of this solid product, move on to roasting in air in the Muffle furnace then, product of roasting is exchanged in proportion suction filtration, oven dry at the ammonium salt solution intermediate ion.Roasting obtains the two microporous-mesoporous composite molecular sieves of Hydrogen Y-Beta/MCM-41 in air at last.
Among the present invention, the raw material proportioning in molar ratio: CTAB/SiO
2Be 0.10～0.25, CTAB/OP-10 is 5～7, SiO
2/ H
2O is 58～78, Si/Al 〉=25; Press mass ratio (Y+Beta)/SiO
2Be 0.26～0.80, micropore phase Y type and Beta type zeolite consumption can carry out the adjusting of arbitrary proportion.
The pretreatment temperature of micropore phase is that 30 ℃～50 ℃, processing time are 25min～30min;
The pH value of synthetic system is in 10.1～12.1 scope;
Crystallization temperature≤100 ℃, crystallization time are 48h～72h;
Crystallization product roasting in nitrogen stream, its sintering temperature be at 500 ℃～550 ℃, time 1.0h; The temperature of roasting is 4.0h～6.0h at 500 ℃～600 ℃, time in air;
Ammonium salt solution concentration is 0.05mol/L～0.20mol/L, and the ratio of product of roasting and ammonium salt solution is 1g:150mol/L～300mol/L, and be 2.0h～4.0h swap time.
The inorganic acid that the present invention uses can be the mixture of any in hydrochloric acid, sulfuric acid or the nitric acid or two kinds; Inorganic base is mainly NaOH or potassium hydroxide.
Available industrial-grade sodium silicate is as the silicon source in alkaline system in the present invention, and the aluminium source can be the mixture of any in aluminium chloride, aluminum sulfate or the aluminum nitrate or two kinds.
Among the present invention, when mixed liquor added silicon source, aluminium source, the mixing time before regulation system pH value generally was advisable at 1.0h～1.5h.Regulate pH value mixing time afterwards about 0.5h.
The present invention proposes when the bakes to burn the article product is carried out ion-exchange, and used ammonium salt can be one or both the mixture in ammonium nitrate or the ammonium chloride.
The novel pair of microporous-mesoporous composite molecular sieve (Y-Beta/MCM-41) that the present invention proposes has following characteristics:
(1) from microscopic pattern, this pair microporous-mesoporous composite molecular sieve presents many spheries or hemispheric hollow shell structure, and commissure reticulates mutually each other, and micropore closely is wrapped on the mesoporous wall mutually, has significantly different with mechanical impurity.
(2) this pair microporous-mesoporous composite molecular sieve specific area can reach 829.68m
2/ g, pore volume 1.104cm
3(wherein the pore volume of micropore is 0.046cm to/g
3/ g), average pore size is 5.32nm (the maximum 2.84nm that are of a size of of wherein mesoporous distribution), mesoporous pore wall thickness is about 1.52nm.
(3) this pair microporous-mesoporous composite molecular sieve is the supermolecule assembling effect that utilizes mixed surfactant (CTAB and OP-10), adopts the synthetic method of hydro-thermal outgrowth to obtain.
(4) this pair microporous-mesoporous composite molecular sieve can synthesize the micropore phase sial adjustable two microporous-mesoporous composite molecular sieve Y-Beta/MCM-41 of micro content when in alkaline system.
(5) this pair microporous-mesoporous composite molecular sieve has good hydrothermal stability, through 550 ℃ of steam treatment 4h, still can keep good structurally ordered degree.
(6) this pair microporous-mesoporous composite molecular sieve acidity is stronger, combines Y type and Beta type zeolite separately advantage in hydrocracking, has good catalytic perfomance.
The novel pair of microporous-mesoporous composite molecular sieve (Y-Beta/MCM-41) that the present invention proposes is a kind of good catalyst carrier material, and structure and mechanical impurity are essentially different.By the control synthesis condition, introduces two kinds of zeolite structured unit, make in the composite molecular screen micropore and micropore mutually between, generation acts synergistically between micropore and the mesoporous phase, has shown better catalytic reaction activity.In the synthetic catalytic reaction of two microporous-mesoporous composite molecular sieves (Y-Beta/MCM-41) to the probe molecule alpha-methyl-naphthalene, the conversion ratio of alpha-methyl-naphthalene is more than 2 times of Y, Beta and MCM-41 mechanical impurity, so novel pair of microporous-mesoporous composite molecular sieve of this kind has bigger potential industrial application value.
Description of drawings
The XRD spectra of Fig. 1 a MY β-1
The XRD spectra of Fig. 1 b MY β-1
The low temperature N of Fig. 2 MY β-1
2Adsorption-desorption thermoisopleth and the pore volume and the aperture graph of a relation (illustration) that obtain by the BJH desorption
The SEM figure of Fig. 3 a MY β-1
The SEM figure of Fig. 3 b MY β-1
The mechanical impurity of Fig. 4 MY β-1 and Y, Beta and three kinds of materials of MCM-41 is to the comparison diagram of the catalytic performance of probe molecule alpha-methyl-naphthalene
XRD contrast spectrogram before and after Fig. 5 a MCM-41 hydrothermal treatment consists (the hydrothermal treatment consists condition: handle 4h in 550 ℃ the steam, a, b are respectively before and after the hydrothermal treatment consists)
XRD contrast spectrogram before and after Fig. 5 b MY β-1 hydrothermal treatment consists (the hydrothermal treatment consists condition: handle 4h in 550 ℃ the steam, a, b are respectively before and after the hydrothermal treatment consists)
The specific embodiment
The embodiment that the invention is further illustrated by the following examples, but the present invention is not limited to these embodiment.
With joining in the mixed solution that contains CTAB and OP-10 after 0.47g Y type and the 0.47g Beta type zeolite powder mixing preliminary treatment, in stirring at room 30min, slow Dropwise 5 ml waterglass (SiO in mixed liquor then
225.4%, Na
2O 7.4%), slowly add 0.389gAl behind the 5min
2(SO
4)
318H
2O, the feed molar proportioning is 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.02Al
2O
3: 0.28Na
2O: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.53.Regulation system pH ≈ 11.1 behind the stirring 1.0h, continue stirring behind the 30min packs glue into again is with in the reactor of liner, in 100 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting, product of roasting is exchanged 2.5h with 1: 200 ratio at the ammonium nitrate solution intermediate ion of 0.10mol/L, suction filtration, oven dry, last in air roasting promptly get the synthetic micropore that feeds intake of alkaline system to be in a ratio of 1: 1, relative amount be 53% Y-Beta/MCM-41 pair of microporous-mesoporous composite molecular sieves, this sample called after MY β-1.
By X-ray diffraction (XRD) spectrogram of Fig. 1 a, Fig. 1 b MY β-1 as can be seen, in low diffraction zone, angle, [100] locate to present stronger hexagonal mesoporous phase diffraction maximum, and the diffraction maximum of the more weak hexagonal mesoporous internal fine mutually of the representative structure of [110] and [200] equal strength is also high-visible, and two microporous-mesoporous composite molecular sieves (Y-Beta/MCM-41) that this explanation is synthesized have regularity preferably.In angle of elevation diffraction zone, [302] characteristic peak that belongs to [111] characteristic peak of Y zeolite and Beta zeolite is all high-visible.Illustrate that micropore is not destroyed fully in system.
Fig. 2 has provided the low temperature N of MY β-1
2Pore volume that adsorption-desorption thermoisopleth and BJH desorption obtain and aperture graph of a relation (illustration), its specific area is 829.68m
2/ g, pore volume 1.104cm
3(wherein the pore volume of micropore is 0.046cm to/g
3/ g), average pore size is 5.32nm (the maximum 2.84nm that are of a size of of wherein mesoporous distribution), mesoporous pore wall thickness is about 1.52nm.
SEM by Fig. 3 a, Fig. 3 b MY β-1 schemes as can be seen, and two micropore phases, the mesoporous molecular sieve that is composited mutually have many spheries or hemispheric hollow shell structure, and commissure reticulates mutually each other.
Fig. 4 has compared the catalytic performance of the mechanical impurity of MY β-1 and Y, Beta and three kinds of materials of MCM-41 to the probe molecule alpha-methyl-naphthalene, as can be seen, the two microporous-mesoporous composite molecular sieve acidity of the Y-Beta/MCM-41 that alkaline system synthesizes are stronger, in the open loop ability, take off the alkyl ability and the isomerization ability all obviously is better than mechanical impurity, have stronger catalytic activity.
In the XRD spectra after Fig. 5 b MY β-1 hydrothermal treatment consists, as can be seen, MY β-1 is after hydrothermal treatment consists, and [100] diffraction peak intensity is stronger, and [110] and [200] diffraction maximum can recognize, show that sample still is the order mesoporous structure of six sides, it is relatively good that structurally ordered degree keeps, and in the XRD spectra after Fig. 5 aMCM-41 hydrothermal treatment consists, MCM-41 is after hydrothermal treatment consists, [100] diffraction peak intensity significantly reduces, and [110] and [200] diffraction maximum disappears, and illustrates that its structurally ordered degree descends significantly.
With joining in the mixed solution that contains CTAB and OP-10 after 0.47g Y type and the 0.47g Beta type zeolite powder mixing preliminary treatment, in stirring at room 30min, slow Dropwise 5 ml waterglass (SiO in mixed liquor then
225.4%, Na
2O 7.4%), slowly add 0.156gAl behind the 5min
2(SO
4)
318H
2O, the feed molar proportioning is 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.008Al
2O
3: 0.28Na
2O: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.53.Regulation system ph ≈ 11.1 behind the stirring 1.0h, continue stirring behind the 30min packs glue into again is with in the reactor of liner, in 100 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting, product of roasting is exchanged 2.0h with 1: 300 ratio at the ammonium chloride solution intermediate ion of 0.15mol/L, suction filtration, oven dry, roasting promptly gets the two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41 that alkaline system synthesizes the Si/Al=62.5 that feeds intake, this sample called after MY β-2 in air at last.
Embodiment 3
With joining in the mixed solution that contains CTAB and OP-10 after 0.235g Y type and the 0.235g Beta type zeolite powder mixing preliminary treatment, in stirring at room 30min, slow Dropwise 5 ml waterglass (SiO in mixed liquor then
225.4%, Na
2O 7.4%), slowly add 0.389gAl behind the 5min
2(SO
4)
318H
2O, the feed molar proportioning is 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.02Al
2O
3: 0.28Na
2O: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.27.Regulation system pH ≈ 11.1 behind the stirring 1.0h, continue stirring behind the 30min packs glue into again is with in the reactor of liner, in 100 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting, product of roasting is exchanged 2.5h with 1: 200 ratio at the ammonium nitrate solution intermediate ion of 0.10mol/L, suction filtration, oven dry, roasting promptly gets the synthetic micropore that feeds intake of alkaline system to be in a ratio of 1: 1, relative amount is 27% two microporous-mesoporous composite molecular sieves of Y-Beta/MCM-41 in air at last, this sample called after MY β-3.
With joining in the mixed solution that contains CTAB and OP-10 after 0.31g Y type and the 0.62g Beta type zeolite powder mixing preliminary treatment, in stirring at room 30min, slow Dropwise 5 ml waterglass (SiO in mixed liquor then
225.4%, Na
2O 7.4%), slowly add 0.078gAl behind the 5min
2(SO
4)
318H
2O, the feed molar proportioning is 1SiO
2: 0.15CTAB: 0.025OP-10: x (Y+Beta): 0.004Al
2O
3: 0.28Na
2O: 60H
2O, wherein (Y+Beta)/SiO
2(mass ratio)=0.53.Regulation system pH ≈ 11.1 behind the stirring 1.0h, continue stirring behind the 30min packs glue into again is with in the reactor of liner, in 100 ℃ of crystallization 48h, product is through suction filtration, washing, oven dry, roasting, product of roasting is exchanged 3.0h with 1: 300 ratio at the ammonium chloride solution intermediate ion of 0.05mol/L, suction filtration, oven dry, last in air roasting promptly get the synthetic micropore that feeds intake of alkaline system and be in a ratio of that 1: 2, relative amount are 53%, the Y-Beta/MCM-41 pair of microporous-mesoporous composite molecular sieves of Si/Al=125, this sample called after MY β-4.
Claims (6)
1. two microporous-mesoporous composite molecular sieve, it is characterized in that: be composited by Y type and Beta type double-micropore zeolites and MCM-41 molecular sieve, two micropores closely are wrapped on the hexagonal mesoporous phase hole wall mutually, present many spheries or hemispheric hollow shell structure, commissure reticulates mutually each other, and when micro content is adjustable for micropore phase sial.
2. the preparation method of pair microporous-mesoporous composite molecular sieve according to claim 1 is characterized in that:
(1) micropore phase preliminary treatment: with Y type and Beta type zeolite and deionized water mixing, stir, it is stand-by that note is made mixed liquor A;
(2) surfactant softex kw, APES and deionized water are mixed, stir, it is stand-by that note is made solution B;
(3) mixed liquor A and solution B are stirred, drip silicon source and aluminium source or only drip the silicon source, stir the pH value that the inorganic acid alkali regulation system is used in the back, stirring, then crystallization, suction filtration, dry, obtain the white solid powder; With pressed powder roasting in nitrogen stream earlier, product of roasting is exchanged suction filtration, oven dry at the ammonium salt solution intermediate ion; Roasting obtains the two microporous-mesoporous composite molecular sieves of Hydrogen Y-Beta/MCM-41 in air at last;
The raw material proportioning is in molar ratio: CTAB/SiO
2Be 0.10～0.25, CTAB/OP-10 is 5～7, SiO
2/ H
2O is 58～78, Si/Al 〉=25; Press mass ratio (Y+Beta)/SiO
2Be 0.26～0.80, micropore phase Y type and Beta type zeolite consumption can carry out the adjusting of arbitrary proportion;
The pretreatment temperature of micropore phase is that 30 ℃～50 ℃, processing time are 25min～30min;
The pH value of synthetic system is in 10.1～12.1 scope;
Crystallization temperature≤100 ℃, crystallization time are 48h～72h;
Crystallization product roasting in nitrogen stream, its sintering temperature be at 500 ℃～550 ℃, time 1.0h; The temperature of roasting is 4.0h～6.0h at 500 ℃～600 ℃, time in air;
Ammonium salt solution concentration is 0.05mol/L～0.20mol/L, and the ratio of product of roasting and ammonium salt solution is 1g: 150mol/L～300mol/L, and be 2.0h～4.0h swap time.
3. the preparation method of pair microporous-mesoporous composite molecular sieve according to claim 2 is characterized in that: inorganic acid is any or any two kinds mixture in hydrochloric acid, sulfuric acid or the nitric acid; Inorganic base is NaOH or potassium hydroxide.
4. the preparation method of pair microporous-mesoporous composite molecular sieve according to claim 2 is characterized in that: the silicon source is an industrial-grade sodium silicate; The aluminium source is any in aluminium chloride, aluminum sulfate or the aluminum nitrate or two kinds mixture wherein.
5. the preparation method of pair microporous-mesoporous composite molecular sieve according to claim 2 is characterized in that: the mixing time before the regulation system pH value is regulated pH value mixing time afterwards at 0.5h generally at 1.0h～1.5h.
6. the preparation method of pair microporous-mesoporous composite molecular sieve according to claim 2 is characterized in that: in ammonium salt solution intermediate ion exchange, used ammonium salt is one or both the mixture in ammonium nitrate or the ammonium chloride with product of roasting.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102361681A CN102039201A (en) | 2009-10-22 | 2009-10-22 | Double microporous-mesoporous composite molecular sieve and preparation method thereof |
| PCT/CN2010/001368 WO2011047527A1 (en) | 2009-10-22 | 2010-09-07 | Double micro-mesoporous composite molecular sieve and preparation method thereof |
| NZ600105A NZ600105A (en) | 2009-10-22 | 2010-09-07 | A bi-microporous/mesoporous composite molecular sieve and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102361681A CN102039201A (en) | 2009-10-22 | 2009-10-22 | Double microporous-mesoporous composite molecular sieve and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102039201A true CN102039201A (en) | 2011-05-04 |
Family
ID=43899784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102361681A Pending CN102039201A (en) | 2009-10-22 | 2009-10-22 | Double microporous-mesoporous composite molecular sieve and preparation method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN102039201A (en) |
| NZ (1) | NZ600105A (en) |
| WO (1) | WO2011047527A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602955A (en) * | 2012-03-26 | 2012-07-25 | 辽宁工业大学 | Preparation method of hollow silicon-aluminum spherical molecular sieves with acidic mesoporous shell |
| CN104263526A (en) * | 2014-10-08 | 2015-01-07 | 佛山市天晟隆油脂化工有限公司 | Preparation method of biodiesel |
| CN105903487A (en) * | 2016-05-09 | 2016-08-31 | 厦门大学 | Catalyst for preparing diesel distillate through synthesis gas catalytic conversion and preparation method thereof |
| CN106694031A (en) * | 2011-11-25 | 2017-05-24 | UniZeo株式会社 | Zeolite and method for producing same, and cracking catalyst for paraffin |
| CN107519925A (en) * | 2016-06-21 | 2017-12-29 | 中国石油天然气股份有限公司 | Y/Sm2O3/SBA-3/ASA composite material and preparation method thereof |
| CN115504483A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
| CN116408142A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Diesel selective hydrogenation ring-opening cracking catalyst and preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435838B (en) * | 2015-11-05 | 2018-01-19 | 太原理工大学 | A kind of T L composite molecular screens and preparation method thereof |
| US10661260B2 (en) * | 2017-06-15 | 2020-05-26 | King Fahd University Of Petroleum And Minerals | Zeolite composite catalysts for conversion of heavy reformate to xylenes |
| CN109205636B (en) * | 2017-06-29 | 2020-02-14 | 中国石油天然气股份有限公司 | Preparation method of Y/SAPO-34/ZSM-11/ASA hierarchical pore material |
| CN114920264B (en) * | 2022-06-28 | 2023-10-20 | 安阳工学院 | Analcime molecular sieve with different morphologies and controllable preparation method of upper crystal face size of Analcime molecular sieve |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1206159C (en) * | 2001-08-20 | 2005-06-15 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| JP4818619B2 (en) * | 2005-03-03 | 2011-11-16 | 独立行政法人科学技術振興機構 | Preparation method of catalyst having nanoporous zeolite catalyst surface |
| CN101081372A (en) * | 2006-05-31 | 2007-12-05 | 中国石油大学(北京) | Kaoline/NaY/MCM-41 composite interstitial substance and method for preparing the same |
| CN101186311B (en) * | 2007-11-22 | 2012-02-22 | 复旦大学 | Y/MCM-48 composite molecular sieve and its preparation method |
-
2009
- 2009-10-22 CN CN2009102361681A patent/CN102039201A/en active Pending
-
2010
- 2010-09-07 NZ NZ600105A patent/NZ600105A/en unknown
- 2010-09-07 WO PCT/CN2010/001368 patent/WO2011047527A1/en active Application Filing
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106694031A (en) * | 2011-11-25 | 2017-05-24 | UniZeo株式会社 | Zeolite and method for producing same, and cracking catalyst for paraffin |
| CN106694031B (en) * | 2011-11-25 | 2019-06-18 | 三井金属矿业株式会社 | Zeolite, method for producing the zeolite, and catalyst for contact decomposition of paraffin |
| CN102602955A (en) * | 2012-03-26 | 2012-07-25 | 辽宁工业大学 | Preparation method of hollow silicon-aluminum spherical molecular sieves with acidic mesoporous shell |
| CN102602955B (en) * | 2012-03-26 | 2013-10-09 | 辽宁工业大学 | Preparation method of hollow silica-alumina spherical molecular sieve with acidic mesoporous shell |
| CN104263526A (en) * | 2014-10-08 | 2015-01-07 | 佛山市天晟隆油脂化工有限公司 | Preparation method of biodiesel |
| CN105903487A (en) * | 2016-05-09 | 2016-08-31 | 厦门大学 | Catalyst for preparing diesel distillate through synthesis gas catalytic conversion and preparation method thereof |
| CN105903487B (en) * | 2016-05-09 | 2019-04-16 | 厦门大学 | A kind of catalyst and preparation method thereof of syngas catalytic conversion diesel oil distillate |
| CN107519925A (en) * | 2016-06-21 | 2017-12-29 | 中国石油天然气股份有限公司 | Y/Sm2O3/SBA-3/ASA composite material and preparation method thereof |
| CN107519925B (en) * | 2016-06-21 | 2019-10-11 | 中国石油天然气股份有限公司 | Y/Sm2O3/SBA-3/ASA composite material and preparation method thereof |
| CN115504483A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
| CN115504483B (en) * | 2021-06-23 | 2024-02-02 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
| CN116408142A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Diesel selective hydrogenation ring-opening cracking catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011047527A1 (en) | 2011-04-28 |
| NZ600105A (en) | 2013-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102039201A (en) | Double microporous-mesoporous composite molecular sieve and preparation method thereof | |
| CN102039200B (en) | Y-beta/MCM-41 double microporous-mesoporous composite molecular sieve and preparation method thereof | |
| CN101186311B (en) | Y/MCM-48 composite molecular sieve and its preparation method | |
| He et al. | Research progress on green synthesis of various high-purity zeolites from natural material-kaolin | |
| CN100567152C (en) | Magadiite/ZSM-5 coexisting material and synthetic method thereof | |
| Zhang et al. | Facile fabrication of mesopore-containing ZSM-5 zeolite from spent zeolite catalyst for methanol to propylene reaction | |
| CN101795968B (en) | Crystallised material containing silicon with hierarchised and organised porosity | |
| CN1803613A (en) | ZSM-5 type molecular sieve and method for preparing the same | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN108862309A (en) | A kind of NaY molecular sieve aggregation and preparation method thereof with nano-micro structure | |
| CN101795969A (en) | Amorphous silicon-containing materials with graded and organized porosity | |
| Zhao et al. | Fabrication of mesoporous zeolite microspheres by a one-pot dual-functional templating approach | |
| CN106830003A (en) | SSZ-13/SCM-9 composite molecular screens and its synthetic method | |
| CN107244677A (en) | A kind of preparation method of mesoporous micropore hierarchical pore MFI type molecular sieve | |
| CN101306380A (en) | A preparation method of a material with in-situ large-medium-micro composite pores and high hydrothermal stability | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN112939017B (en) | Synthesis method of MTW type molecular sieve | |
| CN1654330A (en) | A method for preparing aluminum-containing MCM-41 mesoporous molecular sieve using metakaolin as raw material | |
| CN104107719B (en) | Complex type molecular sieve containing metallic element and preparation method thereof | |
| CN103121688B (en) | Synthesis method of MOR (Mordenite)-BEA (Beta Zeolite) core-shell zeolite | |
| CN101514008B (en) | Mordenite/Y zeolite coexisting molecular sieve and method for synthesizing same | |
| CN100390060C (en) | High-silica octagonal zeolite and synthesizing method thereof | |
| CN104549460B (en) | Composite molecular sieve, as well as preparation method and application thereof | |
| CN107055566A (en) | A kind of 3A molecular sieves and its processing technology | |
| Jiao et al. | Nanocrystal zeolite Y assembly synthesized with CTAB under low gelling and aging temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110504 |