CN102211780B - NU-87 molecular sieve and preparation method thereof - Google Patents
NU-87 molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN102211780B CN102211780B CN201010227460XA CN201010227460A CN102211780B CN 102211780 B CN102211780 B CN 102211780B CN 201010227460X A CN201010227460X A CN 201010227460XA CN 201010227460 A CN201010227460 A CN 201010227460A CN 102211780 B CN102211780 B CN 102211780B
- Authority
- CN
- China
- Prior art keywords
- crystallization
- molecular sieve
- sio
- preparation
- silica alumina
- 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.)
- Active
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses an NU-87 molecular sieve and a preparation method thereof. The method comprises a preparation process of a crystallization material, a crystallization process and a recovery and treatment process of a crystallization product, wherein in the preparation process of the crystallization material, an aluminum source, a silicon source, alkali, a template agent, inorganic salt, an EU-1 molecular sieve and water are mixed; and the mass ratio of the EU-1 molecular sieve fed into the crystallization material to SiO2 contained in other components is 0.1-0.4. The NU-87 molecular sieve prepared by the method has the advantages of low silicon-aluminum ratio, high pore volume, low cost, and the like.
Description
Technical field
The present invention relates to a kind of NU-87 molecular sieve and preparation method thereof.
Background technology
The NU-87 molecular sieve has NES type topological framework, is the supersiliceous zeolite molecular sieve of two-dimentional microvoid structure.It is to be that 10 yuan of 0.47nm * 0.60nm parallel ducts of ring and diameter are the two-dimentional micropore system that the twelve-ring duct of 0.53nm * 0.68nm intersects to form by diameter, and only communicates with the external world through ten-ring duct window.This particular structural makes the NU-87 molecular sieve in some catalyzed reaction, both show the characteristic of ten-ring, shows the characteristic of twelve-ring again.NES type structure molecular screen has special physical and chemical performance, in reactions such as alkylation, isomerizing, disproportionation, shows unique catalytic performance.
European patent EP 377291 has proposed NU-87 molecular sieve and preparation method thereof the earliest with U.S. Pat 5041402.Concrete compound method is following: aluminium source, alkali and inorganic salt are dissolved in process solution A in the portion water, template is dissolved in processes solution B in the portion water, the silicon source is dissolved in the water processes solution C; At first solution B is joined in the solution A, stir, then solution C is joined in the solution A, stir; At last at the synthetic NU-87 molecular sieve of 180 ℃ of following crystallization 257～451h.Each molar ratio of material that adds is SiO
2/ Al
2O
3=20～200, Na
2O/SiO
2=0.1～0.5, R/SiO
2=0.05～0.5, H
2O/SiO
2=25～75, NaL/SiO
2=0～0.25, wherein R is the template C-10, and NaL is a sodium salt.U.S. Pat 5102641 also discloses a kind of preparation method of NU-87 molecular sieve; Its compound method and U.S. Pat 5041402 not too big differences; The template that just adopts is C-10, bromination dodecyl diamine, bromination octane diamine; Enlarged the kind of template, and in building-up process, added the NU-87 molecular sieve as crystal seed, crystallization time shortens to 130～192h.Adopt the pore volume of the resulting NU-87 molecular sieve of this compound method to be generally (Corma A about 0.17ml/g; Martinez-Soria V; Schnoeveld E.Alkylation of Benzene with Short-Chain Olefins over MCM-22Zeolite:CatalyticBehaviour and Kinetic Mechanism [J] .Catal; 2000,192:163-173.).
Can know that from above method the silica alumina ratio of synthetic NU-87 molecular sieve is generally more than 20 in the prior art, high silica alumina ratio can make the acidity of molecular sieve reduce, and influences the catalytic activity of molecular sieve and the adjustable sex change of molecular sieve.In addition, the molecular sieve that synthesizes of aforesaid method also exists pore volume to be generally 0.15～0.24cm for a short time
3/ g, big, the high deficiency of cost of template consumption.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of NU-87 molecular sieve and preparation method thereof, and this method has that silica alumina ratio is low, pore volume is high, low cost and other advantages.
The preparation method of NU-87 molecular sieve of the present invention; Comprise crystallization material process for preparation, crystallization process and crystallization product recycling process; Described crystallization material process for preparation is that aluminium source, silicon source, alkali, template, inorganic salt, EU-1 molecular sieve and water are mixed, EU-1 molecular sieve that adds in the crystallization material and the contained SiO of all the other each components
2Mass ratio be 0.1～0.4, all the other each components by the mol ratio of its oxide compound or salt are:
SiO
2/Al
2O
3＝12～60；
R/SiO
2＝0.04～0.6；
Na
2O/SiO
2＝0.1～0.6；
H
2O/SiO
2＝25～60；
NaL/SiO
2＝0.1～0.4；
R is a template bromination decamethonium, and NaL is a kind of sodium salt, can be sodium-chlor, Sodium Bromide, SODIUMNITRATE, sodium-acetate, sodium oxalate, is preferably sodium-chlor.
Described all the other each components are aluminium source, silicon source, alkali, template, inorganic salt and water.
Described aluminium source can be preferably sodium aluminate for one or more the mixture in aluminium salt, aluminate, aluminum oxide, white lake or the aluminium colloidal sol; Said silicon source can be preferably silicon sol for white carbon black, silicon sol, water glass or tetraethoxy etc.
Described EU-1 molecular sieve, its silica alumina ratio (SiO
2/ Al
2O
3Mol ratio) be 20～35.The EU-1 molecular sieve can be through roasting, also can be unfired, preferably passes through the EU-1 molecular sieve of roasting.
Described crystallization process crystallization temperature is 60～200 ℃, and crystallization time is 1～10 day.Crystallization process can adopt static crystallization, also can adopt dynamic crystallization, the preferred latter.Dynamic crystallization generally adopts the mode of stirring to carry out, stirring velocity be generally 150～800rpm (rev/min).The dynamic crystallization temperature is preferably at first 70～150 ℃ of crystallization 1～2 day, then 160～190 ℃ of following crystallization 3～8 days.
The inventive method synthetic NU-87 possesses the XRD characteristic spectrogram of NU-87 molecular sieve, the silica alumina ratio (SiO of molecular sieve
2/ Al
2O
3Mol ratio) be 8～40, preferred 8～20, specific surface area is 350～420m
2/ g, pore volume are 0.3～0.37cm
3/ g.
The NU-87 molecular sieve of the inventive method preparation can be applied to field of petrochemical industry, is a kind of good catalytic material, and it is at alkylating aromatic hydrocarbon, and aspects such as aromatics isomerization and methane aromatizing and alkane hydroisomerizing all have good catalytic performance.
The EU-1 molecular sieve that the inventive method is used in crystallization material process for preparation belongs to EUO type molecular sieve.EUO type molecular sieve is structurally extremely similar with the NU-87 molecular sieve a kind of molecular sieve, and it also possesses the characteristics of nanocrystal simultaneously.The inventive method is fully used the characteristics of the nanocrystal of EUO type molecular sieve; Make it in crystallization material process for preparation, decompose, form the secondary structure unit of a large amount of EUO type molecular sieves; And these structural units also are the structural units of NU-87 molecular sieve; With these secondary structure units is directed agents, and auxiliary NU-87 molecular sieve template is incorporated into the sial in the crystallization material in the skeleton of NU-87 molecular sieve.The inventive method not only can reduce the silica alumina ratio in the molecular sieve synthesized gel rubber; The proportioning of each material, the used conventional template agent of minimizing preparation NU-87 molecular sieve in the adjustment molecular sieve crystallization material; Reduce preparation cost, and the NU-87 molecular sieve of preparing have the characteristics of high pore volume.Do not compare with not adding the EU-1 molecular sieve in the conventional compound method, the prepared NU-87 molecular sieve pore volume of the present invention is more than doubled.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 1 preparation.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 2 preparations.
Embodiment
Further specify the present invention program and effect below by embodiment.
Embodiment 1
Obtain solution 1: in beaker, successively add 9.84g sodium hydroxide, 5.23g sodium aluminate (Al
2O
3Weight content is 45%), 7.5g bromination decamethonium, 5.36g sodium-chlor and 156ml zero(ppm) water, stir, add the baked EU-1 molecular sieve of 3.6g (silica alumina ratio is 27) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 60ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 100 ℃ from room temperature, 100 ℃ of following constant temperature 1.2 days, the stirring velocity of synthesis reactor was 350rpm then.Be warming up to 180 ℃ then, 180 ℃ of following constant temperature 5 days, the stirring velocity of synthesis reactor was 250rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 9, and pore volume is 0.36ml/g, and specific surface area is 410m
2/ g.
Embodiment 2
Obtain solution 1: in beaker, successively add 10.5g sodium hydroxide, 4.2g sodium aluminate (Al
2O
3Weight content is 45%), 7.5g bromination decamethonium, 5.36g sodium-chlor and 156ml zero(ppm) water, stir, add the baked EU-1 crystal seed of 4.5g (silica alumina ratio is 27) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 40ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 80 ℃ from room temperature, 80 ℃ of following constant temperature 1.5 days, the stirring velocity of synthesis reactor was 450rpm then.Be warming up to 185 ℃ then, 185 ℃ of following constant temperature 4.5 days, the stirring velocity of synthesis reactor was 350rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 12, and pore volume is 0.34ml/g, and specific surface area is 380m
2/ g.
Embodiment 3
Obtain solution 1: in beaker, successively add 9.84g sodium hydroxide, 3.4g sodium aluminate (Al
2O
3Weight content is 45%), 13g bromination decamethonium, 4.47g sodium-chlor and 156ml zero(ppm) water, stir, add the baked EU-1 crystal seed of 5.38g (silica alumina ratio is 27) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 60ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 100 ℃ from room temperature, 100 ℃ of following constant temperature 1.2 days, the stirring velocity of synthesis reactor was 350rpm then.Be warming up to 170 ℃ then, 170 ℃ of following constant temperature 5 days, the stirring velocity of synthesis reactor was 250rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 16, and pore volume is 0.30ml/g, and specific surface area is 390m
2/ g.
Embodiment 4
Obtain solution 1: in beaker, successively add 7.87g sodium hydroxide, 2.26g sodium aluminate (Al
2O
3Weight content is 45%), 37.65g bromination decamethonium, 5.36g sodium-chlor and 169ml zero(ppm) water, stir, add the baked EU-1 crystal seed of 3.59g (silica alumina ratio is 34) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 60ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 140 ℃ from room temperature, 140 ℃ of following constant temperature 1 day, the stirring velocity of synthesis reactor was 550rpm then.Be warming up to 180 ℃ then, 180 ℃ of following constant temperature 6 days, the stirring velocity of synthesis reactor was 250rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 24, and pore volume is 0.32ml/g, and specific surface area is 390m
2/ g.
Obtain solution 1: in beaker, successively add 5.9g sodium hydroxide, 1.72g sodium aluminate (Al
2O
3Weight content is 45%), 43.93g bromination decamethonium, 7.1g sodium-chlor and 214ml zero(ppm) water, stir, add the baked EU-1 crystal seed of 2.1g (silica alumina ratio is 34) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 60ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 100 ℃ from room temperature, 100 ℃ of following constant temperature 1.2 days, the stirring velocity of synthesis reactor was 350rpm then.Be warming up to 180 ℃ then, 180 ℃ of following constant temperature 5 days, the stirring velocity of synthesis reactor was 250rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 32, and pore volume is 0.35ml/g, and specific surface area is 370m
2/ g.
Embodiment 6
Obtain solution 1: in beaker, successively add 3.93g sodium hydroxide, 1.64g sodium aluminate (Al
2O
3Weight content is 45%), 65g bromination decamethonium, 7.1g sodium-chlor and 214ml zero(ppm) water, stir, add the baked EU-1 crystal seed of 2.1g (silica alumina ratio is 34) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 60ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 75 ℃ from room temperature, 75 ℃ of following constant temperature 2 days, the stirring velocity of synthesis reactor was 350rpm then.Be warming up to 180 ℃ then, 180 ℃ of following constant temperature 5 days, the stirring velocity of synthesis reactor was 320rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 36, and pore volume is 0.29ml/g, and specific surface area is 400m
2/ g.
Embodiment 7
Obtain solution 1: in beaker, successively add 5.9g sodium hydroxide, 1.13g sodium aluminate (Al
2O
3Weight content is 45%), 55.06g bromination decamethonium, 5.36g sodium-chlor and 180ml zero(ppm) water, stir, add the baked EU-1 crystal seed of 3.4g (silica alumina ratio is 34) then.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 50ml zero(ppm) water, stir.Solution 2 is slowly joined in the solution 1, carry out dynamic hydrothermal crystallizing in the synthesis reactor of packing into after stirring.
Crystallization condition is following: be warming up to 100 ℃ from room temperature, 100 ℃ of following constant temperature 1.2 days, the stirring velocity of synthesis reactor was 350rpm then.Be warming up to 180 ℃ then, 180 ℃ of following constant temperature 5 days, the stirring velocity of synthesis reactor was 250rpm.Then room temperature is reduced in the temperature natural cooling.
After crystallization was accomplished, through filtering, wash and drying, roasting made the NU-87 molecular sieve.The silica alumina ratio of NU-87 molecular sieve is 38, and pore volume is 0.34ml/g, and specific surface area is 360m
2/ g.
Claims (9)
1. the preparation method of a NU-87 molecular sieve; Comprise crystallization material process for preparation, crystallization process and crystallization product recycling process; It is characterized in that: described crystallization material process for preparation is that aluminium source, silicon source, alkali, template, inorganic salt, EU-1 molecular sieve and water are mixed, EU-1 molecular sieve that adds in the crystallization material and the contained SiO of all the other each components
2Mass ratio be 0.1～0.4, all the other each components by the mol ratio of its oxide compound or salt are:
SiO
2/Al
2O
3＝12～60；
R/SiO
2＝0.04～0.6；
Na
2O/SiO
2＝0.1～0.6；
H
2O/SiO
2＝25～60；
NaL/SiO
2＝0.1～0.4；
R is a template bromination decamethonium, and NaL is a kind of sodium salt, and the silica alumina ratio of described EU-1 molecular sieve is 20～35, and described crystallization process crystallization temperature is 60～200 ℃, and crystallization time is 1～10 day.
2. the method for claim 1 is characterized in that: the EU-1 molecular sieve is through roasting or without roasting.
3. the method for claim 1 is characterized in that: described aluminium source is one or more the mixture in aluminium salt, aluminate, aluminum oxide, white lake or the aluminium colloidal sol.
4. the method for claim 1, it is characterized in that: said silicon source is white carbon black, silicon sol, water glass or tetraethoxy.
5. the method for claim 1, it is characterized in that: described crystallization process is static crystallization or dynamic crystallization.
6. method as claimed in claim 5 is characterized in that: described dynamic crystallization adopts the mode that stirs to carry out, and stirring velocity is 150～800 rev/mins.
7. method as claimed in claim 6 is characterized in that: the dynamic crystallization condition at first 70～150 ℃ of crystallization 1～2 day, then 160～190 ℃ of following crystallization 3～8 days.
8. NU-87 molecular sieve is characterized in that: adopt arbitrary method preparation among the claim 1-8, the silica alumina ratio of molecular sieve is 8～40, and specific surface area is 350～420m
2/ g, pore volume are 0.3～0.37cm
3/ g.
9. molecular sieve as claimed in claim 8 is characterized in that: the silica alumina ratio of molecular sieve is 8～20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010227460XA CN102211780B (en) | 2010-04-02 | 2010-07-09 | NU-87 molecular sieve and preparation method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010155250 | 2010-04-02 | ||
| CN201010155250.4 | 2010-04-02 | ||
| CN201010227460XA CN102211780B (en) | 2010-04-02 | 2010-07-09 | NU-87 molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102211780A CN102211780A (en) | 2011-10-12 |
| CN102211780B true CN102211780B (en) | 2012-10-17 |
Family
ID=44743352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010227460XA Active CN102211780B (en) | 2010-04-02 | 2010-07-09 | NU-87 molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102211780B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044052A (en) * | 1988-12-22 | 1990-07-25 | 帝国化学工业公司 | Utilize the catalyzed reaction of zeolite |
| CN1044078A (en) * | 1988-12-22 | 1990-07-25 | 帝国化学工业公司 | Zeolite |
-
2010
- 2010-07-09 CN CN201010227460XA patent/CN102211780B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044052A (en) * | 1988-12-22 | 1990-07-25 | 帝国化学工业公司 | Utilize the catalyzed reaction of zeolite |
| CN1044078A (en) * | 1988-12-22 | 1990-07-25 | 帝国化学工业公司 | Zeolite |
Non-Patent Citations (1)
| Title |
|---|
| 陈会英等.含有10元环和12元环的NU-87分子筛对甲烷脱氢芳构化的催化性能(英文).《催化学报》.2004,(第11期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102211780A (en) | 2011-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW590986B (en) | UZM-5, UZM-5P and UZM-6: crystalline alumino-silicate zeolites and processes using the same | |
| WO2018227849A1 (en) | Molecular sieve scm-14, synthesis method therefor and use thereof | |
| JP2000185913A (en) | Zeolite euo containing crystal having special particle size and crystal aggregate, and its use as catalyst for isomerizing 8c aromatic compound | |
| EP1115657A1 (en) | Preparation of high silica zeolites bound by zeolite and use thereof | |
| CN107555446A (en) | A kind of preparation method of multi-stage porous Y type molecular sieve | |
| US4300013A (en) | Isomerization of xylenes | |
| CN103787355B (en) | Beta molecular sieve synthesizing method | |
| CN103803576B (en) | A kind of low silica-alumina ratio ZSM-48 molecular sieve and preparation method thereof | |
| CN110357121A (en) | A kind of preparation method of little crystal grain nanometer hierarchical pore SSZ-13 molecular sieve | |
| CN107010636A (en) | A kind of ferrierite molecular sieve and preparation method and application | |
| CN101618884B (en) | Method for preparing Magadiite/ZSM-35 eutectic molecular sieve | |
| CN102442681B (en) | NU-85 zeolite and preparation method thereof | |
| JPS581045B2 (en) | crystalline aluminosilicate | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| JPS593932B2 (en) | Method for producing crystalline aluminosilicate | |
| CN102745709B (en) | Method for preparing EUO type molecular sieve by utilizing kaolin | |
| CN102211780B (en) | NU-87 molecular sieve and preparation method thereof | |
| CN104418341B (en) | A kind of ZSM-48/Silicalite-1 composite molecular screen and preparation method thereof | |
| CN102862996B (en) | Preparation method of low-cost NU-87 molecular sieve | |
| CN106946266B (en) | A kind of SAPO-34/ZSM-12 composite molecular screens and its synthetic method | |
| CN105621433B (en) | A kind of preparation method for having core shell structure Y Beta composite molecular screens | |
| CN1487904A (en) | Crystalline molecular sieve composition MCM-65, its synthesis and use | |
| CN113880110A (en) | Nanometer hierarchical pore MOR/MTW eutectic molecular sieve and preparation method and application thereof | |
| CN104588091B (en) | A kind of Beta and the composite molecular screens of EU 1 and its synthetic method | |
| CN106946270A (en) | A kind of Beta/EU-1 composite molecular screens and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |