CN101941718A - Synthesis method of molecular sieve of TON structure - Google Patents
Synthesis method of molecular sieve of TON structure Download PDFInfo
- Publication number
- CN101941718A CN101941718A CN2009100124732A CN200910012473A CN101941718A CN 101941718 A CN101941718 A CN 101941718A CN 2009100124732 A CN2009100124732 A CN 2009100124732A CN 200910012473 A CN200910012473 A CN 200910012473A CN 101941718 A CN101941718 A CN 101941718A
- Authority
- CN
- China
- Prior art keywords
- crystallization
- agent
- molecular sieve
- structure directing
- directing agent
- 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.)
- Granted
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a synthesis method of a molecular sieve of a TON structure. The method comprises the following steps: firstly preparing a structure-directing agent which consists of an IIIA element compound and an IVA element compound in a periodic table of elements, an inorganic alkaline substance, an organic template agent and water; and preparing uniform gel for synthesizing the TON molecular sieve by a silicon source, an aluminum source, alkali, an organic template agent and the structure-directing agent, and then crystallizing the gel under an appropriate condition to obtain the TON-type molecular sieve through aftertreatment. The synthesis method is mainly characterized by adding the structure-directing agent to the gel; and compared with the prior art, the method has the advantages of low crystallization temperature, short crystallization time, high product yield, high product quality and the like.
Description
Technical field
The present invention relates to a kind of method of synthetic TON structure molecular screen.
Background technology
Molecular sieve is the crystalline material with homogeneous aperture, regular pore canal shape and trend, and it comprises natural and two big classes synthetic, and having found has so far had hundreds of with synthetic molecular sieve kind.Wherein many as sorbent material, catalyzer etc.On catalytic material, demonstrate advantages of high activity and selectivity, particularly particularly outstanding in hydrocarbon conversion reactions.Being used as sorbent material and catalyst molecule sieve aperture degree of lip-rounding shape size and duct trend all has considerable influence to reactivity worth, then particularly evident to selecting the type reaction.Molecular sieve can be divided into the mesoporous molecular sieve of the small pore molecular sieve less than 8 Yuans rings, 10 Yuans rings and the large pore molecular sieve of 12 Yuans rings by the aperture size.The aperture is big again then belongs to mesoporous molecular sieve analog.
At present molecular sieve has developed and multiple series, and as SAPO, ZSM, SSZ, M41S etc., what wherein belong to the TON structure has ZSM-22, Theta-1, ISI-1, KZ-2 and a NU-10 etc.The TON structure molecular screen has 10 Yuans non-intersection one-dimensional channels of ring, what belong to this structure molecular screen has: USP4481177 discloses a kind of employing N-ethyl bromination pyrroles and has been template, is the method for synthesizing ZSM-22 under the condition of 400r/min at 160 ℃ with stirring velocity, in this preparation process, the subtle change of crystallization parameter all can cause the variation of product crystalline phase.If obtain purified ZSM-22, must carry out accurate control to raw material composition and crystallization condition, the repeated difficulty of product is bigger.USP4900528 discloses a kind of synthetic method of called after NU-10 molecular sieve, employing be L
1-(CH
2)
n-L
2The organic formwork agent of structure, the L here
1, L
2For hydroxyl or/and amido.USP4483835 discloses the molecular sieve of a kind of called after ISI-I, is that to adopt a kind of salt of derivative of nitrogen-containing heterocycle compound be template, under 150 ℃, the condition of 30r/min, and crystallization 6 days and obtaining; USP5342596 discloses the molecular sieve preparation method of a kind of called after THETA-1, and it is template that this process is to use a kind of halo derivatives of nitrogen-containing heterocycle compound, in the rotation voltage-resistant reactor, and crystallization 144h under 170 ℃ of conditions and obtaining.Chinese patent CN1565969 and CN1565971 disclose a kind of preparation method of TON type molecular sieve, and this process is to use double template, and general crystallization temperature is that 160 ℃ of crystallization times obtained above 48 hours.
The XRD of the molecular sieve of the disclosed TON of having structure the results are shown in Table 1 in the prior art document.
The XRD result of table 1ZSM-22 molecular sieve
The represented relative intensity of symbol is worth as follows in the form: VS, 60%-100%; S, 40%～60%; M, 20%-40%; W,＜20%; Down together.
Existing technical literature preparation has the method for TON structure, is that the single organism of employing is template and auxiliary template agent mostly, and the crystallization that directly heats up generally exists crystallization time length, product purity and the low problem of yield.
Summary of the invention
At the deficiency of existing patent, this patent provides a kind of method of synthetic ZSM-22 type molecular sieve, and the inventive method has characteristics such as crystallization temperature is low, crystallization time weak point, product yield height.
The main preparation process of TON type molecular sieve provided by the invention comprises:
(a) preparation structure directing agent, structure directing agent is made up of IIIA element compound, IVA element compound, inorganic base substance, organic formwork agent and water in the periodic table of elements; Wherein the IIIA element is boron, aluminium or gallium, and the IVA element is silicon or germanium, and organic formwork agent is selected from one or more in the nitrogen-containing heterocycle compound;
(b) the synthetic material of preparation TON type molecular sieve crystallization, the synthetic material of crystallization is the even gel of being made up of silicon source, aluminium source, alkali and organic formwork agent and water, contains in steps the structure directing agent of (a) preparation in this gel simultaneously;
(c) the synthetic TON type molecular sieve of crystallization, the gel of heating steps (b) preparation makes the gel crystallization under the condition of crystallization, obtain TON type molecular sieve through aftertreatment.
In the step (a) in the preparation structure directing agent, the mixture that is selected from IIIA in the periodic table of elements, IVA element compound, inorganic base substance, organic formwork agent and water obtains structure directing agent through 100 ℃～180 ℃, 10～30 hours processing.The structure directing agent mole is formed and is about: (5～80) RN1: Al
2O
3: (50～500) SiO
2: (5～80) MOH: (2000～10000) H
2O is preferably (10～70) RN1: Al
2O
3: (80～300) SiO
2: (10～50) MOH: (3000～8000) H
2O, wherein RN1 represents organic formwork agent, and M represents metal.Organic formwork agent is generally nitrogenous hybrid compounds, is preferably pyrrole derivative, more preferably tetramethyleneimine.
The mole composition of the synthetic material gel of TON type molecular sieve crystallization is about in the step (b): (10～100) RN2: Al
2O
3: (20～800) SiO
2: (10～100) MOH: (2000～10000) H
2O is preferably (20～80) RN2: Al
2O
3: (50～500) SiO
2: (20～80) MOH: (3000～8000) H
2O, structure directing agent account for 1%～50% of the synthetic weight of material of crystallization, are preferably 5%～20%.The consumption of structure directing agent is represented with its shared weight percent in the synthetic material of crystallization.Wherein RN2 represents organic formwork agent, and M represents metal.Template is a diamine compounds, can be C
2～C
10Diamines, be preferably C
5～C
8Diamines.
The crystallization of step (c) is carried out in the high-pressure reactor of autogenous pressure, and general crystallization temperature is 110 ℃～170 ℃, is preferably 120 ℃～150 ℃, and crystallization time is 8h～96h, is preferably 20h～48h.
In the TON type molecular sieve synthetic method of the present invention, other content can be undertaken by the conventional knowledge in this area.
The inventive method synthetic TON type molecular sieve silica alumina ratio (SiO
2/ Al
2O
3, mol) 30～300, be generally 40～100, be needle crystal, the XRD result of molecular sieve provided by the invention has table 2 feature, belongs to TON type molecular sieve.
The XRD result of table 2 TON molecular sieve of the present invention
Compare with the correlation technique document, the method that the present invention prepares molecular sieve has crystallization temperature low (generally than low about 30 ℃ of existing method), crystallization time short (generally reducing about 10h than existing method) has product purity and degree of crystallinity height and product yield advantages of higher simultaneously.
Embodiment
The present invention prepares the method for TON structure molecular screen, and its principal feature is for adding structure directing agent, and the selection and the prior art of other condition and various raw materials are similar.
Usually IVA element compound in the related periodic table of elements in the described structure directing agent of step (a), can be selected from the compound of silicon or germanium one or more, be preferably the compound of silicon, can be all silicon-containing compounds that can be used in other molecular sieve of preparation, for example silica-gel powder, active silica, silicate, vaporific silicon, white carbon black, silicon sol and siliceous organism etc. are preferably silicon sol.Described IIIA element can be boron, aluminium, sow, indium etc., is preferably aluminium.The aluminium source can be to be selected from activated alumina and precursor, aluminum soluble salt and the organic aluminum contained compound one or more, for example clay, hydrous oxide, aluminium colloidal sol, aluminate, aluminium salt and aluminiferous organism, be preferably aluminate and aluminium salt, more preferably aluminium salt, for example AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3Deng.Described mineral alkali is can be all alkaline matters, and the oxyhydroxide of for example alkali-metal oxyhydroxide, carbonate, alkaline-earth metal etc. and ammoniacal liquor etc. are preferably alkali-metal oxyhydroxide, more preferably potassium hydroxide.Described template is generally nitrogenous hybrid compounds, is preferably pyrrole derivative, more preferably tetramethyleneimine.
The preparation method of the described gel of step b) carries out thorough mixing with required silicon source, aluminium source, mineral alkali and organic formwork agent material, obtains the homogeneous phase colloidal mixture.Wherein said template is a diamine compounds, can be C
2～C
10Diamines, be preferably C
5～C
8Diamines, hexanediamine more preferably, described silicon source can be silica-gel powder, active silica, silicate, vaporific silicon, white carbon black, silicon sol and siliceous organism etc., be preferably silicate, silicon sol and silica-gel powder, silica-gel powder more preferably, described aluminium source can be clay, hydrous oxide, aluminium colloidal sol, aluminate, aluminium salt and aluminiferous organism, is preferably aluminate and aluminium salt, more preferably aluminium salt, for example AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3Deng.Said mineral alkali can be all inorganic base substances, and the oxyhydroxide of for example alkali-metal oxyhydroxide, carbonate, alkaline-earth metal and ammoniacal liquor etc. are preferably alkali-metal oxyhydroxide, more preferably potassium hydroxide.
Treatment condition described in the step (a) are that temperature is 100 ℃～180 ℃, and the time is 10h～30h.Said crystallization is to carry out in the high-pressure reactor of autogenous pressure in the step (c), general crystallization temperature is 110 ℃～170 ℃, be preferably 120 ℃～150 ℃, crystallization time is 8h～96h, is preferably 20h～48h, and said aftertreatment refers to through processing such as collection, washing and dryings, can adopt method commonly used at present to carry out, for example collect and use method of pumping filtration, use deionized water wash, make the sample thorough drying at 100 ℃～250 ℃ then.
Give further instruction below by embodiment to technology of the present invention.
Embodiment 1
The preparation structure directing agent
In a beaker, add silicon source, aluminium source, alkali, organic formwork agent and water successively, behind the thorough mixing, obtain white gels, its mole composition is about: (5～80) RN becomes: Al
2O
3: (50～500) SiO
2: (5～80) MOH: (2000～10000) H
2O is preferably (10～70) RN1: Al
2O
3: (80～300) SiO
2: (10～50) MOH: (3000～8000) H
2O, wherein RN1 represents organic formwork agent, and M represents metal.Through 100 ℃～180 ℃ of excess temperatures, after time 10～24h handled, the mixture that obtains was structure directing agent CL with gel.The preparation condition and the composition of structure directing agent see Table 3.
Table 3 structure directing agent preparation condition and composition
CL-1 silicon source: silicon sol, aluminium source: AlCl
3, alkali: KOH, template: tetramethyleneimine;
CL-2 silicon source: silicon sol, aluminium source: Al
2(SO
4)
3, alkali: KOH, template: N-crassitude;
CL-3 silicon source: silica-gel powder, aluminium source: Al (OH)
3, alkali: NaOH, template: tetramethyleneimine;
CL-4 silicon source: Na
2SiO
3, aluminium source: NaAlO
2, alkali: KOH, template: tetramethyleneimine;
CL-5 silicon source: silicon sol, aluminium source: aluminium colloidal sol, alkali: KOH, template: N-ethyl pyrrolidine;
Embodiment 2～4
Get quantitative water and place beaker, add silicon source, aluminium source and alkali successively, thorough mixing, add template and structure directing agent more successively, together add after also these materials can being mixed, behind the thorough mixing, move into autoclave and carry out crystallization, wherein the consumption of structure directing agent is represented with the mass percent that it is occupied in the crystallization material.The gel of each embodiment is formed and crystallization condition sees Table 4, and the XRD of product shows that product is a TON type structure molecular screen, the results are shown in Table 4.
The gel of each embodiment of table 4 is formed and crystallization condition
Annotate: 1. silicon source: silicon sol, aluminium source: AlCl
3, alkali: KOH, template: hexanediamine, structure directing agent: CL-1;
2. silicon source: tetraethoxy, aluminium source: NaAlO
2, alkali: KOH, template: heptamethylene diamine, structure directing agent: CL-3;
3. silicon source: Na
2SiO
3, aluminium source: Al (OH)
3, alkali: NaOH, template: octamethylenediamine, structure directing agent: CL-5.
The comparative example raw material is identical with embodiment 2 and 3 respectively, just the template in the structure directing agent (tetramethyleneimine) is directly added in the gel of molecular sieve synthesis material.
From embodiment as can be seen, the method for the TON of preparation structure molecular screen provided by the invention is compared with correlation technique, and crystallization time obviously shortens, and crystallization temperature reduces, and product yield and degree of crystallinity are improved.
The XRD result of table 5 embodiment 1 product
The XRD result of table 6 embodiment 2 products
Claims (10)
1. the method for a synthetic TON structure molecular screen, step is following to be comprised:
(a) preparation structure directing agent, structure directing agent is made up of IIIA element compound, IVA element compound, inorganic base substance, organic formwork agent and water in the periodic table of elements; Wherein the IIIA element is boron, aluminium or gallium, and the IVA element is silicon or germanium, and organic formwork agent is selected from one or more in the nitrogen-containing heterocycle compound;
(b) the synthetic material of preparation TON type molecular sieve crystallization, the synthetic material of crystallization is the even gel of being made up of silicon source, aluminium source, mineral alkali and organic formwork agent and water, contains in steps the structure directing agent of (a) preparation in this gel;
(c) the synthetic TON type molecular sieve of crystallization, the gel of heating steps (b) preparation makes the gel crystallization under the condition of crystallization, obtain TON type molecular sieve through aftertreatment.
2. in accordance with the method for claim 1, it is characterized in that: in the preparation structure directing agent, the mixture that is selected from IIIA in the periodic table of elements, IVA element compound, inorganic base substance, organic formwork agent and water carries out 100 ℃～180 ℃, 10～30 hours processing in the step (a).
3. it is characterized in that in accordance with the method for claim 1: the structure directing agent mole described in the step (a) consists of: (5～80) RN1: Al
2O
3: (50～500) SiO
2: (5～80) MOH: (2000～10000) H
2O, wherein RN1 represents organic formwork agent, and M represents metal, and organic formwork agent is a pyrrole derivative.
4. it is characterized in that in accordance with the method for claim 3: the structure directing agent mole consists of: (10～70) RN1: Al
2O
3: (80～300) SiO
2: (10～50) MOH: (3000～8000) H
2O.
5. according to claim 1 or 3 described methods, it is characterized in that: the organic formwork agent in the structure directing agent is a tetramethyleneimine.
6. it is characterized in that in accordance with the method for claim 1: the mole of the synthetic material of TON type molecular sieve crystallization consists of in the step (b): (10～100) RN2: Al
2O
3: (20～800) SiO
2: (10～100) MOH: (2000～10000) H
2O, structure directing agent account for 1%～50% of the synthetic weight of material of crystallization, and wherein RN2 represents organic formwork agent, and M represents metal, and organic formwork agent is a diamine compounds.
7. according to claim 1 or 6 described methods, it is characterized in that: the mole of the synthetic material of TON type molecular sieve crystallization consists of in the step (b): (20～80) RN2: Al
2O
3: (50～500) SiO
2: (20～80) MOH: (3000～8000) H
2O, structure directing agent account for 5%～20% of synthetic weight of material.
8. according to claim 1 or 6 described methods, it is characterized in that: the organic formwork agent that uses in the step (b) is C
2～C
10Diamines.
9. in accordance with the method for claim 1, it is characterized in that: the crystallization of step (c) is carried out in the high-pressure reactor of autogenous pressure, and crystallization temperature is 110 ℃～170 ℃, and crystallization time is 8h～96h.
10. in accordance with the method for claim 1, it is characterized in that: the crystallization of step (c) is carried out in the high-pressure reactor of autogenous pressure, and crystallization temperature is 120 ℃～150 ℃, and crystallization time is 20h～48h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100124732A CN101941718B (en) | 2009-07-09 | 2009-07-09 | Synthesis method of molecular sieve of TON structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100124732A CN101941718B (en) | 2009-07-09 | 2009-07-09 | Synthesis method of molecular sieve of TON structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101941718A true CN101941718A (en) | 2011-01-12 |
| CN101941718B CN101941718B (en) | 2012-05-30 |
Family
ID=43433961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100124732A Active CN101941718B (en) | 2009-07-09 | 2009-07-09 | Synthesis method of molecular sieve of TON structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101941718B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106853972A (en) * | 2015-12-09 | 2017-06-16 | 中国石油天然气股份有限公司 | A kind of stable synthetic method of TON zeolites |
| CN108298553A (en) * | 2017-01-11 | 2018-07-20 | 中国科学院上海高等研究院 | A method of preparing molecular sieve |
| CN111232999A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Synthesis method of TON type molecular sieve with low silicon-aluminum ratio |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242919C (en) * | 2003-06-25 | 2006-02-22 | 温州市双华石化三剂制造厂 | Molecular sieve with TON structure and preparation method thereof |
-
2009
- 2009-07-09 CN CN2009100124732A patent/CN101941718B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106853972A (en) * | 2015-12-09 | 2017-06-16 | 中国石油天然气股份有限公司 | A kind of stable synthetic method of TON zeolites |
| CN106853972B (en) * | 2015-12-09 | 2019-11-08 | 中国石油天然气股份有限公司 | A kind of stabilization synthetic method of TON zeolite |
| CN108298553A (en) * | 2017-01-11 | 2018-07-20 | 中国科学院上海高等研究院 | A method of preparing molecular sieve |
| CN108298553B (en) * | 2017-01-11 | 2021-07-23 | 中国科学院上海高等研究院 | Method for preparing molecular sieve |
| CN111232999A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Synthesis method of TON type molecular sieve with low silicon-aluminum ratio |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101941718B (en) | 2012-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101249968B (en) | Method for synthesizing Beta molecular sieve by organic-free template | |
| CN103848439B (en) | Synthetic method of ZSM-5 type molecular sieve | |
| CN101723402B (en) | Method for synthesizing core-shell type zeolite molecular sieve | |
| AU2020101871A4 (en) | A Method for Preparing ZSM-5 Zeolite by Using Solid wastes | |
| KR101098495B1 (en) | - Process for the manufacture of catalysts used for producing para-xylene by toluene shape selective alkylation | |
| CN106938849A (en) | The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst | |
| CN102040229B (en) | Synthetic method of MCM-22 (Multiple Chip Module 22) molecular sieve | |
| CN102040228A (en) | Method for synthesizing MCM-22 molecular sieve | |
| CN101723401A (en) | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve | |
| CN108217683B (en) | Method for synthesizing silicon-rich ZSM-23 zeolite molecular sieve by adopting seed crystal guiding method | |
| CN101941718B (en) | Synthesis method of molecular sieve of TON structure | |
| CN102464326B (en) | Method for synthesizing high-silicon mordenite | |
| CN103058222B (en) | Method for synthesizing ZSM-35 molecular sieve | |
| CN109592696B (en) | Preparation method of nano-sheet clinoptilolite molecular sieve | |
| CN101941717A (en) | Method for synthesizing molecular sieve with TON structure | |
| CN112174164B (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN1020039C (en) | Synthesis of mercerized zeolite with high silicon content | |
| CN1121979C (en) | Process for preparing ZSM-5 molecular sieve | |
| CN110817899B (en) | Method for promoting synthesis of ZSM-11 molecular sieve | |
| CN110615445A (en) | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive | |
| CN104649290B (en) | Organic-template-free [beta]-molecular sieve synthesizing method | |
| CN104556105B (en) | Aerosol-assisted synthesis method of Beta molecular sieve | |
| CN1242919C (en) | Molecular sieve with TON structure and preparation method thereof | |
| CN111186846B (en) | ITH structure silicon-aluminum molecular sieve and preparation method thereof | |
| CN110615442B (en) | ZSM-5/MOR composite zeolite monolith for synthesizing 5-hydroxymethylfurfural and preparation method thereof |
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 |