CN103253682A - Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source - Google Patents
Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source Download PDFInfo
- Publication number
- CN103253682A CN103253682A CN2013101861427A CN201310186142A CN103253682A CN 103253682 A CN103253682 A CN 103253682A CN 2013101861427 A CN2013101861427 A CN 2013101861427A CN 201310186142 A CN201310186142 A CN 201310186142A CN 103253682 A CN103253682 A CN 103253682A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- source
- beta
- sio
- add
- 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
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a method for synthesizing a beta molecular sieve by using crystalline-state aluminum phosphate as an aluminum source. The method comprises the following steps of: uniformly mixing an alkali metal oxide source, an aluminum source, a silicon source, water and an organic template to obtain initial gel; stirring under the room temperature until the gel is uniform; adding the uniform gel to a reaction kettle for carrying out crystallization for 60-120 hours under the pressure at the temperature of 140 DEG C-170 DEG C; and washing and drying to obtain the beta molecular sieve, wherein the molar ratio of the materials for preparing the initial gel is as follows: SiO2/Al2O3 being 20-80, Na2O/SiO2 being 0.10-0.15, H2O/SiO2 being 6-10, organic template/SiO2 being 0.10-0.20. The aluminum source is crystalline-state aluminum phosphate with a chemical formula of [Al2 (HPO3)3(H2O)3].H2O. The method for synthesizing a beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source can be used for greatly improving the yield of the beta molecular sieve.
Description
Technical field
The method of a kind of beta-molecular sieve of the present invention is exactly that a kind of usefulness has the crystal form aluminum phosphite NKX-5 of special three-dimensional structure (chemical formula is [Al specifically
2(HPO
3)
3(H
2O)
3] H
2O) be the method for the synthetic beta-molecular sieve in aluminium source.
Background technology
The β zeolite is by the at first research and development in 1967 of U.S. Mobil oil company, has three-dimensional staggered twelve-ring channel architecture and stronger acidity, in refining of petroleum and petrochemical industry, be widely used, in heterogeneous catalytic reactions such as benzene and propylene alkylation, show good catalytic performance.The β zeolite grain relatively disperses tiny, small crystal grain molecular sieve is owing to have bigger external surface area and short the evolving path, reactant molecule easily arrives catalytic active site, and the product that generates can spread out from the duct very soon, therefore can improve the utilising efficiency of catalyzer, strengthen macromolecular conversion capability, reduce catalyzer coking and deactivation speed.But the little crystal grain that disperses is because crystal grain careful and disperse very difficultly to separate by common filter method, in industrial production, the productive rate of β zeolite is all lower, under the situation that does not add the coagulation agent, generally only have 60%～70%, add the coagulation agent and also only risen to more than 80%, caused waste and loss.So improve the productive rate of β zeolite its industrial production application had vital role.
CN200310113488.0 discloses a kind of phosphorous β prepare zeolite method, be that aluminium source, alkali source and tetraethylammonium cation solution are made into working solution in water, be that 20-300 purpose silica gel is the silicon source with the granularity, silica gel and this working solution are mixed, make silica gel particle surface wetting by this working solution, keep making in 20-80 hour crystal seed glue down in 80-140 ℃; In the above-mentioned crystal seed glue that is prepared into, add the feed intake aluminum phosphate of weight 5-30% of crystal seed glue again, mix the back at 140-170 ℃ of following crystallization 50-100 hour, isolate solid product, wash to Na
2O content gets final product after the drying less than 0.1 weight %.This method makes molecular sieve contain phosphoric by adding aluminum phosphate in the reaction stage casing, but does not still mention the low problem of beta-molecular sieve productive rate.This method adopts the synthetic beta-molecular sieve of the method for fractional steps in addition, exists generated time long, complicated operation, energy consumption height, shortcomings such as reinforced difficulty.
CN100384731C discloses a kind of preparation method of beta zeolite in small crystal grain, is the SiO with high-content
2Silicon sol be the silicon source, sodium aluminate is the aluminium source, tetraethyl ammonium hydroxide is that template is 80-160 ℃ of following hydrothermal crystallizing 1～8 day in temperature, filtering and washing obtains the β zeolite, though this method has reduced template agent, but the template consumption is still very high, and the preferred proportion of template is organic formwork agent/SiO
2=0.20～0.40, and the water yield reduces and added the difficulty that stirs, and the shortcoming that in washing process, exists alkali lye to clean, causing product loss, productive rate is only about 70～80%.
The invention provides the method that adopts a kind of aluminum phosphite with three-dimensional structure to synthesize beta-molecular sieve as aluminium source direct method.This aluminum phosphite abbreviates NKX-5 as, and it consists of ([Al
2(HPO
3)
3(H
2O)
3] H
2O), it belongs to oblique system, P2
1Spacer, unit cell parameters a=0.7609 (4) nm, b=0.9900 (5) nm, c=0.8073 (4) nm, β=111.934 (7) °, V=0.5641 (5) nm
3By HPO
3 2-Distortion tetrahedron and AlO
6Octahedra strict alternately the connection constitutes skeleton structure, and formed the octatomic ring pore canal system (petroleum journal (refining of petroleum)) 2006 of three dimensional intersection, (B10), and 79-81).During the reactant mixing, becoming glue, it is stable that this aluminum phosphite structure keeps, and makes that the state in aluminium source is single, stable, even in β zeolite crystallization process, is conducive to improve the productive rate of β zeolite.The PO that introduces in the while system
4 3-Ion can greatly accelerate the generation of β nucleus and the reunion of crystal grain (Nature, 1996,381:298).The PO that the aluminium source itself has
3 3-Under the condition of high temperature hydro-thermal, be oxidized to PO easily
4 3-, having promoted generation and the reunion of crystal grain, bigger particle makes that filtration is very efficient, makes the productive rate of β zeolite greatly improve.And the phosphorus because of in the aluminum phosphite of synthetic β zeolite makes its modification.
Summary of the invention
The invention provides a kind of synthetic method of beta-molecular sieve, use a kind of crystal form aluminum phosphite (NKX-5) as the aluminium source, it consists of ([Al
2(HPO
3)
3(H
2O)
3] H
2O), by HPO
3 2-Distortion tetrahedron and AlO
6Octahedra strictness alternately constitutes skeleton structure, contains 10 membered ring channels, two 8 yuan three dimensional intersection pore canal system of going back the duct in the skeleton structure of crystal.
The synthetic method of beta-molecular sieve disclosed in this invention, concrete steps are: alkalimetal oxide source, aluminium source, silicon source, water and organic formwork agent are uniformly mixed into initial gel; Stir under the room temperature, in the reactor of packing into, crystallization is 60～120 hours under 140～170 ℃ of temperature self pressure, and washing, drying obtain beta-molecular sieve; The mol ratio for preparing the various raw materials of initial gel is: SiO
2/ Al
2O
3=20～80, Na
2O/SiO
2=0.10～0.15, H
2O/SiO
2=5～10, organic formwork agent/SiO
2=0.10～0.20;
The synthetic method of beta-molecular sieve disclosed in this invention preferably will be synthesized colloid 150 ℃ and autogenous pressure hydrothermal crystallizing 4～5 days, and the washing drying obtains beta-molecular sieve.
The synthetic method of beta-molecular sieve disclosed in this invention, silicon source and organic formwork agent are that those skilled in the art are known, described silicon source can be one or both in tlc silica gel, the white carbon black, the alkali metal hydroxide source is sodium hydroxide, organic formwork agent is tetraethyl ammonium hydroxide, and water is deionized water.
The invention has the beneficial effects as follows: utilize and use a kind of crystal form aluminum phosphite (NKX-5) as the synthetic beta-molecular sieve productive rate height that obtains in aluminium source, waste and loss have been reduced, remove the use of coagulation agent in filtering simultaneously, provided cost savings, had vast market prospect.
Description of drawings
The ten-ring duct of Fig. 1 NKX-5.
The XRD figure of Fig. 2 NKX-5.
The β X zeolite RD figure that Fig. 3 embodiment 1 is synthesized, wherein 2 θ angles are 7.74 °, 21.42 ° and 22.46 ° of characteristic diffraction peaks that the peak of locating is the β zeolite.
Embodiment
Embodiment 1
At 25 ℃, get 3.68 milliliters of the sodium hydroxide solutions of 4.25mol/L, add NKX-5 solid 1.30 grams, add 6.15 gram white carbon blacks again, stirred 40 minutes rapidly, add 7.15 milliliter of 25% tetraethyl ammonium hydroxide then, add 1.25 milliliters of deionized waters again, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 165 ℃ of crystallization 120 hours, collect then, wash, drying, namely get product, obtain product quality 6.65 grams, productive rate is 89.26%.
Embodiment 2
At 25 ℃, get 2.41 milliliters of the sodium hydroxide solutions of 4.25mol/L, add NKX-5 solid 1.30 grams, add 6.15 gram white carbon blacks again, stirred 40 minutes rapidly, add 7.15 milliliter of 25% tetraethyl ammonium hydroxide then, add 3.30 milliliters of deionized waters again, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 170 ℃ of crystallization 85 hours, collect then, wash, drying, namely get product, obtain quality 6.61 grams, productive rate is 88.67%.
Embodiment 3
At 25 ℃, get 2.06 milliliters of the sodium hydroxide solutions of 4.25mol/L, add NKX-5 solid 0.47 gram, add 6.15 gram white carbon blacks again, stirred 40 minutes rapidly, add 7.15 milliliter of 25% tetraethyl ammonium hydroxide then, add 3.64 milliliters of deionized waters again, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 150 ℃ of crystallization 85 hours, collect then, wash, drying, namely get product, obtain quality 5.85 grams, productive rate is 88.32%.
Embodiment 4
At 25 ℃, get 2.06 milliliters of the sodium hydroxide solutions of 4.25mol/L, add NKX-5 solid 1.30 grams, add 6.15 gram white carbon blacks again, stirred 40 minutes rapidly, add 7.15 milliliter of 25% tetraethyl ammonium hydroxide then, add 3.64 milliliters of deionized waters again, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 140 ℃ of crystallization 85 hours, collect then, wash, drying, namely get product, obtain product quality 6.78 grams, productive rate is 91.02%.
At 25 ℃, get 4.82 milliliters of the sodium hydroxide solutions of 4.25mol/L, add NKX-5 solid 1.87 grams, add 6.15 gram white carbon blacks again, stirred rapidly 40 minutes, add 14.76 milliliter of 25% tetraethyl ammonium hydroxide then, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 150 ℃ of crystallization 60 hours, collect then, wash, drying, namely get product, obtain product quality 7.24 grams, productive rate is 90.32%.
Embodiment 6
At 25 ℃, get 1.002 milliliters of the sodium hydroxide solutions of 6.5816mol/L, add 1.45 milliliters in water, add NKX-5 solid 0.4183 gram, add 2.403 gram tlc silica gels again, stirred 40 minutes rapidly, add 3.00 milliliter of 25% tetraethyl ammonium hydroxide then, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 150 ℃ of crystallization 100 hours, collect then, wash, drying, namely get product, obtain product quality 2.5188 grams, productive rate is 89.27%.
Embodiment 7
At 25 ℃, get 0.802 milliliter of the sodium hydroxide solution of 6.5816mol/L, add 1.22 milliliters in water, add NKX-5 solid 0.4183 gram, add 2.403 gram tlc silica gels again, stirred 40 minutes rapidly, add 3.00 milliliter of 25% tetraethyl ammonium hydroxide then, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 150 ℃ of crystallization 100 hours, collect then, wash, drying, namely get product, obtain product quality 2.6050 grams, productive rate is 93.92%.
Embodiment 8
At 25 ℃, get 0.912 milliliter of the sodium hydroxide solution of 6.5816mol/L, add 4.00 milliliters in water, add NKX-5 solid 0.4183 gram, add 2.403 gram tlc silica gels again, stirred 40 minutes rapidly, add 3.00 milliliter of 25% tetraethyl ammonium hydroxide then, stir then and moved into to even back in 1 hour in the stainless steel cauldron in 150 ℃ of crystallization 100 hours, collect then, wash, drying, namely get product, obtain product quality 2.6227 grams, productive rate is 92.95%.
Claims (2)
1. with the method for a kind of crystal form aluminum phosphite for the synthetic beta-molecular sieve in aluminium source, it is characterized in that alkali metal hydroxide source, aluminium source, silicon source, water and organic formwork agent are stirred synthetic initial gel; Be stirred under the room temperature evenly, in the reactor of packing into, 140～170 ℃ of following crystallization of temperature 60～120 hours, washing, drying obtained beta-molecular sieve; The mol ratio for preparing the various raw materials of initial gel is: SiO
2/ Al
2O
3=20～80, Na
2O/SiO
2=0.10～0.15, H
2O/SiO
2=6～10, organic formwork agent/SiO
2=0.10～0.20.
2. the synthetic method of beta-molecular sieve according to claim 1 is characterized in that the aluminium source is a kind of crystal micropore aluminum phosphite with three-dimensional structure, by HPO
3 2-Distortion tetrahedron and AlO
6Octahedra strict alternately the connection constitutes skeleton structure, and its chemical formula is [Al
2(HPO
3)
3(H
2O)
3] H
2O, the silicon source is tlc silica gel, or white carbon black, and alkalimetal oxide is sodium hydroxide, and organic formwork agent is tetraethyl ammonium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101861427A CN103253682A (en) | 2013-05-20 | 2013-05-20 | Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101861427A CN103253682A (en) | 2013-05-20 | 2013-05-20 | Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103253682A true CN103253682A (en) | 2013-08-21 |
Family
ID=48957964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101861427A Pending CN103253682A (en) | 2013-05-20 | 2013-05-20 | Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103253682A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthesis method of beta molecular sieve |
| CN104445254A (en) * | 2013-09-25 | 2015-03-25 | 天津神能科技有限公司 | Synthesis method of agglomerated Beta zeolite molecular sieve |
| CN104512908A (en) * | 2013-09-26 | 2015-04-15 | 天津神能科技有限公司 | Synthesis method of ZSM-5 zeolite molecular sieve in small crystal grains |
| CN106044792A (en) * | 2016-05-31 | 2016-10-26 | 南开大学 | SAPO-34 molecular-sieve preparing method simultaneously using crystal microporous aluminum phosphite NKX-6 as phosphorus source and aluminum source |
| CN106082266A (en) * | 2016-05-31 | 2016-11-09 | 南开大学 | The method that two kinds of microporous crystals coordinate conversion to prepare SAPO 34 molecular sieve |
| CN109279623A (en) * | 2018-10-12 | 2019-01-29 | 南开大学 | A method of it with micropore aluminium phosphite NKX-12 is silicon source synthesizing high-silicon aluminium than modenite |
| JP2022068842A (en) * | 2020-10-22 | 2022-05-10 | ジィァンスー リースーデェァ ニュー マテリアル カンパニー リミテッド | Crystalline aluminum phosphite, preparation method and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249271A (en) * | 1998-09-25 | 2000-04-05 | 北京燕山石油化工公司研究院 | Process for synthesizing beta-zeolite |
-
2013
- 2013-05-20 CN CN2013101861427A patent/CN103253682A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249271A (en) * | 1998-09-25 | 2000-04-05 | 北京燕山石油化工公司研究院 | Process for synthesizing beta-zeolite |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229818A (en) * | 2013-06-18 | 2014-12-24 | 中国石油天然气股份有限公司 | Synthesis method of beta molecular sieve |
| CN104229818B (en) * | 2013-06-18 | 2016-04-06 | 中国石油天然气股份有限公司 | Synthesis method of beta molecular sieve |
| CN104445254A (en) * | 2013-09-25 | 2015-03-25 | 天津神能科技有限公司 | Synthesis method of agglomerated Beta zeolite molecular sieve |
| CN104512908A (en) * | 2013-09-26 | 2015-04-15 | 天津神能科技有限公司 | Synthesis method of ZSM-5 zeolite molecular sieve in small crystal grains |
| CN104512908B (en) * | 2013-09-26 | 2017-02-08 | 天津神能科技有限公司 | Synthesis method of ZSM-5 zeolite molecular sieve in small crystal grains |
| CN106044792A (en) * | 2016-05-31 | 2016-10-26 | 南开大学 | SAPO-34 molecular-sieve preparing method simultaneously using crystal microporous aluminum phosphite NKX-6 as phosphorus source and aluminum source |
| CN106082266A (en) * | 2016-05-31 | 2016-11-09 | 南开大学 | The method that two kinds of microporous crystals coordinate conversion to prepare SAPO 34 molecular sieve |
| CN106044792B (en) * | 2016-05-31 | 2018-03-09 | 南开大学 | A kind of crystalline microporous aluminium phosphite NKX 6 prepares the molecular sieve methods of SAPO 34 as phosphorus source and silicon source simultaneously |
| CN109279623A (en) * | 2018-10-12 | 2019-01-29 | 南开大学 | A method of it with micropore aluminium phosphite NKX-12 is silicon source synthesizing high-silicon aluminium than modenite |
| JP2022068842A (en) * | 2020-10-22 | 2022-05-10 | ジィァンスー リースーデェァ ニュー マテリアル カンパニー リミテッド | Crystalline aluminum phosphite, preparation method and use thereof |
| JP7258295B2 (en) | 2020-10-22 | 2023-04-17 | ジィァンスー リースーデェァ ニュー マテリアル カンパニー リミテッド | Crystalline aluminum phosphite and method for producing and using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103253682A (en) | Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source | |
| CN101643219B (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN100540471C (en) | The method of preparing molecular sieve with EUO structure from silicon aluminum oxide powder | |
| CN102502687B (en) | Method for greenly synthesizing Ti-Si molecular sieve | |
| CN101973563B (en) | Method for synthetizing ZSM-35 molecular sieve by seed crystal process | |
| CN102452666B (en) | Method for synthesizing IM-5 molecular sieve | |
| CN102241407B (en) | Preparation method of SUZ-4 molecular sieve | |
| CN104229818B (en) | Synthesis method of beta molecular sieve | |
| AU2020101871A4 (en) | A Method for Preparing ZSM-5 Zeolite by Using Solid wastes | |
| CN102249258A (en) | Method for synthesizing heteroatom Sn-beta zeolite | |
| CN104923293B (en) | Orthoresol isomerization catalyst, its preparation method and the method that M-and P-cresols is catalyzed and synthesized using it | |
| CN102211779B (en) | Preparation method of beta zeolite | |
| CN102649574B (en) | Preparation method for mesoporous ZSM-11 zeolite | |
| CN103880036B (en) | Method for synthesizing mesoporous mordenite | |
| CN104418357A (en) | ZSM-35 molecular sieve preparation method | |
| CN102730712B (en) | Preparation method of nano GaZSM-5 molecular sieve | |
| CN103058208B (en) | Preparation method of SAPO-56 molecular sieve | |
| CN101870478A (en) | Method for synthesizing nano Y-type molecular sieve | |
| CN103708491B (en) | The method of synthesis IM-5 molecular sieve | |
| CN101412522A (en) | Preparation of silicoaluminophosphate molecular sieve | |
| CN102198950A (en) | Preparation method of NaY molecular sieve with high silicon-aluminum ratio | |
| CN1156395C (en) | Process for synthesizing beta molecular sieve | |
| CN102757066B (en) | Method for synthesizing B-beta-heteroatom molecular sieve | |
| CN104671252A (en) | Method for synthesizing and preparing ZSM-22 molecular sieve under conditions of no organic template and no crystal seed | |
| CN106467309A (en) | A kind of method of temperature programming synthesizing methanol propylene nano-ZSM-5 molecular sieve |
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: 20130821 |