CN105565339A - Preparation method of small-crystalline-grain ZSM-22 (Zeolite Socony Mobil-22) molecular sieve - Google Patents
Preparation method of small-crystalline-grain ZSM-22 (Zeolite Socony Mobil-22) molecular sieve Download PDFInfo
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- CN105565339A CN105565339A CN201610119519.0A CN201610119519A CN105565339A CN 105565339 A CN105565339 A CN 105565339A CN 201610119519 A CN201610119519 A CN 201610119519A CN 105565339 A CN105565339 A CN 105565339A
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The invention discloses a preparation method of a small-crystalline-grain ZSM-22 (Zeolite Socony Mobil-22) molecular sieve. The preparation method comprises the following steps of uniformly mixing a silicon source, a aluminum source, an alkali source, a templating agent and deionized water, to form an initial gel mixture, and then adding one or several of active carbon, graphite, graphene, black carbon, a starch microsphere, chitosan and a polylactic acid microsphere into the initial gel mixture, uniformly agitating an obtained mixture, and then crystallizing the agitated mixture, filtering to separate a solid product, washing the solid product to be neutral by using the deionized water, and drying and roasting the washed solid product, to obtain the small-crystalline-grain ZSM-22 molecular sieve. The preparation method has the advantages that the activity of a catalyst is high; the large-scale industrial production can be realized; the operation charge is low.
Description
Affiliated field
The present invention relates to a kind of preparation method of fine grain ZSM-5-22 Si-Al molecular sieve.
Background technology
ZSM-22 molecular sieve is Mobil company of the U.S. in a kind of micropore, the high-silica zeolite of eighties of last century exploitation the late nineteen eighties, belongs to TON topological framework.It only has the duct of the one dimension of ten-ring opening, and port size is 0.44nm × 0.55nm, and port size is smaller, and without intersection duct.Because ZSM-22 molecular sieve has the pore passage structure and acidic nature be comparatively applicable to, in normal alkane isomerization reaction, have good catalytic performance, at petrochemical industry, particularly the aspect such as lubricant base isomerization dewaxing has been widely applied.
In lubricant base, the main component of wax is high-melting-point long-chain n-praaffin, and its pour point is high, and low temperature flowability is poor.By hydroisomerization reaction, normal paraffin is converted into branched paraffin, these performances can be improved.The isomerization of long chain alkane is reacted in the aperture of ZSM-22 molecular sieve by aperture catalysis and key lock catalytic mechanism.But the pattern of ZSM-22 molecular sieve is club shaped structure, and its length generally can reach 1 ~ 3 μm.Therefore, being only positioned at the activity of the active centre near molecular sieve aperture to catalyzer has contribution, and high catalyst activity requires that catalyzer has the aperture of more exposures.Improve the effective ways exposing aperture number and have two kinds: the mesopore orbit (2 ~ 50nm) that 1, manufacturing dimension is larger in zeolite crystal, form hierarchical porous structure; 2, the grain-size of molecular sieve is reduced.
At present, by preparing multi-stage porous ZSM-22 molecular sieve, to improve the report of catalyst performance more.Sinopec Group discloses the method that three kinds (CN102464325B, CN102874829B and CN102874830B) prepare mesopore-micropore zeolite molecular sieve material.First method CN102464325B is: in the enclosed system containing lower molecular weight organic solvent, first processes micro-pore zeolite (as ZSM-22) with alkaline solution; Then, with acid solution, micro-pore zeolite is processed, through being separated, washing and drying, finally obtain mesoporous-microporous zeolite.Second method CN102874829B introduces ultrasonication method, and detailed process is: first, is mixed by micro-pore zeolite (as ZSM-22), carry out ultrasonication with alkaline solution; Then, in the presence of an organic, in enclosed system, micro-pore zeolite is heat-treated; With acid solution, micro-pore zeolite is processed again, finally obtain mesoporous-microporous zeolite molecular sieve.The third method CN102874830B introduces microwave treatment method, detailed process is: micro-pore zeolite (as ZSM-22), alkaline solution and organic solvent are mixed, and carry out microwave treatment, and then carry out acid treatment, through being separated, washing and drying, finally obtain mesoporous-microporous zeolite.Although these three kinds of methods effectively can both prepare mesoporous-microporous zeolite molecular sieve, but the use of organic solvent and acid-base solution has increased considerably operation and the difficulty of liquid waste disposal, make its processing costs high, ultrasonic wave and microwave treatment have some limitations in large-scale industrial production in addition.
The ZSM-22 molecular sieve of synthesizing small-grain can obtain the aperture of more exposures, and catalyst activity is increased, and has no relevant report through retrieval.
Summary of the invention
The object of the present invention is to provide a kind of catalyst activity high, can large-scale industrial production, fine grain ZSM-5-22 molecular sieve preparation method that process cost is low.
The present invention is in ZSM-22 building-up process, by adding Graphene, spherex, chitosan, polylactic acid microsphere, gac, carbon black, graphite etc., there is the material being easily adsorbed in ZSM-22 molecular sieve aperture place feature, reaching and suppressing ZSM-22 grain growing thus the object obtaining small crystal grain molecular sieve.
Preparation method's concrete steps of the present invention are as follows:
(1) silicon source, aluminium source, alkali source, template and deionized water are mixed, form the initial gel mixture with following mol ratio, silicon source is with SiO
2meter, aluminium source is with Al
2o
3meter, alkali source is with OH
-meter, SiO
2: Al
2o
3: template: OH
-: deionized water=1:0.003-0.05:0.005-1.0:0.005-1.0:1-100;
(2) in step (1) gained initial gel mixture, add one or more in gac, graphite, Graphene, carbon black, spherex, chitosan, polylactic acid microsphere, and stir, wherein, SiO in the add-on of these materials and initial gel mixture
2mass ratio be: 0.001-2.0:1;
(3) mixture step (2) obtained in 120-200 DEG C, crystallization 4-144h under autogenous pressure;
(4) after crystallization completes, by solid product filtering separation, with deionized water wash to neutral, fine grain ZSM-5-22 molecular sieve after drying and roasting, is namely obtained; Wherein, maturing temperature is 400-600 DEG C, and roasting time is 5-40h.
Silicon source described above is a kind of or several arbitrarily mixture in silicon sol, Silica hydrogel, methyl silicate, tetraethoxy, white carbon black; Described aluminium source is mixture a kind of or several arbitrarily in pseudo-boehmite, aluminum chloride, Tai-Ace S 150, aluminum nitrate, aluminum isopropylate, sodium aluminate; The template adopted is one or more in diamines, N-methylimidazole bi-quaternary ammonium salt, diethylamine, n-Butyl Amine 99,1,8-diamino-octane of 1-ethylpyridine bromide, 1,6-; Described alkali source is one or both the mixture in sodium hydroxide, potassium hydroxide.
The present invention can also add crystal seed in step (1) starting sol, and crystal seed is filtered, washing, the dry stoste containing ZSM-22 crystal seed, also can be the former powder of ZSM-22.The addition of crystal seed is SiO
2the 0.1-10% of quality.
In step described above (3), crystal pattern is static under pressure itself or dynamic crystallization.
The crystal particle diameter of ZSM-22 molecular sieve prepared by method described above can be contracted to <300nm.Relative to traditional long particle diameter ZSM-22, there is higher catalytic activity.Such as: in n-dodecane hydroisomerization process, under the same reaction conditions, when n-dodecane transformation efficiency all reaches 90%, on traditional Pt/ZSM-22 molecular sieve, isomerisation selectivity is 63.1%, and on the Pt/ZSM-22 small crystal grain molecular sieve that the inventive method obtains, isomerisation selectivity can reach 75.1%.
Compared with prior art, the technology of the present invention can realize the synthesis of fine grain ZSM-5-22 in ZSM-22 molecular sieve process, without the need to adding acid-base solution again and organic solvent carries out pore-creating aftertreatment after ZSM-22 synthesis.Process of the present invention has the features such as simple to operate, with low cost, environmental friendliness, and gained ZSM-22 zeolite product has the advantages that crystal grain is little, catalytic activity is high, has good catalytic applications prospect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of comparative example product.
Fig. 2 is that the SEM of comparative example product is according to figure.
Fig. 3 is the XRD spectra of embodiment 1 product.
Fig. 4 is that the SEM of embodiment 1 product is according to figure.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
Comparative example 1:
First, mixed by following mol ratio by raw material, silicon sol is (with SiO
2meter): Tai-Ace S 150 is (with Al
2o
3meter): 1,6-is diamines: potassium hydroxide: deionized water=1:0.011:0.30:0.29:40.Then, mixing raw material is transferred in stainless steel cauldron, 160 DEG C of dynamic crystallization 48h, product is through filtration, washing, dry, 550 DEG C of roasting 16h, namely obtain conventional ZSM-22 molecular sieve, crystal grain length ~ 2 μm, Fig. 1 is shown in by XRD spectra and the SEM photo of product.
Embodiment 1:
First, mixed by following mol ratio by raw material, silicon sol is (with SiO
2meter): Tai-Ace S 150 is (with Al
2o
3meter): 1,6-is diamines: potassium hydroxide: deionized water=1:0.011:0.005:0.29:40.Then, add 0.5g gac (with add SiO
2mass ratio be 0.06:1), add the former powder of ZSM-22 (addition is 10% of SiO2 quality).Stir.Finally, mixing raw material is transferred in stainless steel cauldron, 160 DEG C of dynamic crystallization 48h, product is through filtration, washing, dry, 550 DEG C of roasting 16h, namely obtain the ZSM-22 molecular sieve of little crystal grain, crystal grain length ~ 200nm, XRD and the SEM spectrogram of product is shown in Fig. 2.
Embodiment 2-8:
Concrete proportion scale and crystallization condition are in table 1, and concrete preparation process is with embodiment 1.Wherein, the crystal seed that embodiment 2 adds is the stoste containing ZSM-22 crystal seed, and addition is SiO
20.1% of quality.The crystal seed that embodiment 3 adds is the former powder of ZSM-22, and addition is SiO
210% of quality.Embodiment 4-9, does not add crystal seed.
Synthetic sample does XRD analysis, data results and Fig. 1 close, show that synthetic product is high purity ZSM-22 molecular sieve.Synthetic sample does sem analysis, can find out that product is small crystal grain molecular sieve, Chang Du≤220nm.
Table 1 Zeolite synthesis batching and crystallization, roasting condition
Claims (8)
1. a preparation method for fine grain ZSM-5-22 molecular sieve, is characterized in that comprising the steps:
Silicon source, aluminium source, alkali source, template and deionized water are mixed, form the initial gel mixture with following mol ratio, silicon source is with SiO
2meter, aluminium source is with Al
2o
3meter, alkali source is with OH
-meter, SiO
2: Al
2o
3: template: OH
-: deionized water=1:0.003-0.05:0.005-1.0:0.005-1.0:1-100;
To in step (1) gained initial gel mixture, add one or more in gac, graphite, Graphene, carbon black, spherex, chitosan, polylactic acid microsphere, and stir, wherein, SiO in the add-on of these materials and initial gel mixture
2mass ratio be: 0.001-2.0:1;
Mixture step (2) obtained is in 120-200
oc, crystallization 4-144h under autogenous pressure;
After crystallization completes, by solid product filtering separation, with deionized water wash to neutral, after drying and roasting, namely obtain fine grain ZSM-5-22 molecular sieve; Wherein, maturing temperature is 400-600
oc, roasting time is 5-40h.
2. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as claimed in claim 1, is characterized in that adding crystal seed in step (1) starting sol, and crystal seed is filtered, washing, the dry stoste containing ZSM-22 crystal seed, or the former powder of ZSM-22.
3. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as claimed in claim 2, is characterized in that described seed load is SiO
2the 0.1-10% of quality.
4. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as described in any one of claim 1-3, is characterized in that described silicon source is a kind of or several arbitrarily mixture in silicon sol, Silica hydrogel, methyl silicate, tetraethoxy, white carbon black.
5. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as described in any one of claim 1-3, is characterized in that described aluminium source is mixture a kind of or several arbitrarily in pseudo-boehmite, aluminum chloride, Tai-Ace S 150, aluminum nitrate, aluminum isopropylate, sodium aluminate.
6. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as described in any one of claim 1-3, it is characterized in that described template is 1-ethylpyridine bromide, 1, one or more in diamines, N-methylimidazole bi-quaternary ammonium salt, diethylamine, n-Butyl Amine 99,1,8-diamino-octane of 6-.
7. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as described in any one of claim 1-3, is characterized in that described alkali source is one or both the mixture in sodium hydroxide, potassium hydroxide.
8. the preparation method of a kind of fine grain ZSM-5-22 molecular sieve as described in any one of claim 1-3, is characterized in that in described step (3), crystal pattern is static or dynamic crystallization.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115733A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of multi-stage porous mordenite molecular sieve |
| CN106475131A (en) * | 2016-10-11 | 2017-03-08 | 中国科学院山西煤炭化学研究所 | A kind of Graphene/molecular sieve composite catalyst and preparation method thereof |
| CN106587100A (en) * | 2016-10-25 | 2017-04-26 | 浙江大学 | Method for synthesizing laminar ZSM-5 zeolite molecular sieve with single micro-molecule organic template |
| CN108470594A (en) * | 2018-03-14 | 2018-08-31 | 清华大学 | A method of it is added dropwise and prepares simulation pollucite source core |
| CN111410207A (en) * | 2020-03-12 | 2020-07-14 | 青岛科技大学 | Normal-pressure synthesis method of SAPO-11 molecular sieve |
| CN111422881A (en) * | 2020-04-10 | 2020-07-17 | 吉林大学 | TON type zeolite molecular sieve and preparation method thereof |
| CN113023747A (en) * | 2021-03-31 | 2021-06-25 | 南京工业大学 | TON zeolite with fractal structure and preparation method thereof |
| CN113233472A (en) * | 2021-06-11 | 2021-08-10 | 福州大学 | Synthesis method of nano small-grain ZSM-22 molecular sieve |
| CN114160193A (en) * | 2021-12-06 | 2022-03-11 | 厦门大学 | CoAPO-11 molecular sieve, preparation method and application thereof, alkane hydroisomerization catalyst and application thereof |
| CN116212961A (en) * | 2023-02-15 | 2023-06-06 | 南宁师范大学 | Preparation method for forming mesoporous structure by adjusting and controlling ZIF-67 through ZSM-5 seed crystal |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106115733A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of multi-stage porous mordenite molecular sieve |
| CN106475131A (en) * | 2016-10-11 | 2017-03-08 | 中国科学院山西煤炭化学研究所 | A kind of Graphene/molecular sieve composite catalyst and preparation method thereof |
| CN106475131B (en) * | 2016-10-11 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of graphene/molecular sieve composite catalyst and preparation method thereof |
| CN106587100A (en) * | 2016-10-25 | 2017-04-26 | 浙江大学 | Method for synthesizing laminar ZSM-5 zeolite molecular sieve with single micro-molecule organic template |
| CN106587100B (en) * | 2016-10-25 | 2018-09-21 | 浙江大学 | The method for synthesizing laminar ZSM-5 zeolite molecular sieve with single small molecule organic formwork agent |
| CN108470594A (en) * | 2018-03-14 | 2018-08-31 | 清华大学 | A method of it is added dropwise and prepares simulation pollucite source core |
| CN111410207A (en) * | 2020-03-12 | 2020-07-14 | 青岛科技大学 | Normal-pressure synthesis method of SAPO-11 molecular sieve |
| CN111410207B (en) * | 2020-03-12 | 2022-11-25 | 青岛科技大学 | Normal-pressure synthesis method of SAPO-11 molecular sieve |
| CN111422881B (en) * | 2020-04-10 | 2021-11-05 | 吉林大学 | TON type zeolite molecular sieve and preparation method thereof |
| CN111422881A (en) * | 2020-04-10 | 2020-07-17 | 吉林大学 | TON type zeolite molecular sieve and preparation method thereof |
| CN113023747A (en) * | 2021-03-31 | 2021-06-25 | 南京工业大学 | TON zeolite with fractal structure and preparation method thereof |
| CN113233472B (en) * | 2021-06-11 | 2022-06-07 | 福州大学 | Synthesis method of nano small-grain ZSM-22 molecular sieve |
| CN113233472A (en) * | 2021-06-11 | 2021-08-10 | 福州大学 | Synthesis method of nano small-grain ZSM-22 molecular sieve |
| CN114160193A (en) * | 2021-12-06 | 2022-03-11 | 厦门大学 | CoAPO-11 molecular sieve, preparation method and application thereof, alkane hydroisomerization catalyst and application thereof |
| CN114160193B (en) * | 2021-12-06 | 2023-04-07 | 厦门大学 | CoAPO-11 molecular sieve, preparation method and application thereof, alkane hydroisomerization catalyst and application thereof |
| CN116212961A (en) * | 2023-02-15 | 2023-06-06 | 南宁师范大学 | Preparation method for forming mesoporous structure by adjusting and controlling ZIF-67 through ZSM-5 seed crystal |
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