CN104370292A - ZSM-22 and Me-ZSM-22 molecular sieve synthesis methods - Google Patents
ZSM-22 and Me-ZSM-22 molecular sieve synthesis methods Download PDFInfo
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- CN104370292A CN104370292A CN201310353621.3A CN201310353621A CN104370292A CN 104370292 A CN104370292 A CN 104370292A CN 201310353621 A CN201310353621 A CN 201310353621A CN 104370292 A CN104370292 A CN 104370292A
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention relates to ZSM-22 and Me-ZSM-22 molecular sieve synthesis methods; and the synthesis methods are characterized in that, ZSM-22 molecular sieve is used as a seed crystal for hydro-thermal synthesis of ZSM-22 and Me-ZSM-22 molecular sieves under alkaline conditions without use of an organic template agent.
Description
Technical field
The present invention relates to the synthetic method of a kind of ZSM-22 molecular sieve and Me-ZSM-22 molecular sieve.
The invention still further relates to the acid catalyzed reaction catalyzer of ZSM-22 and the Me-ZSM-22 molecular sieve using aforesaid method synthesis.
Background technology
Porous material, due to its specific pore passage structure and homogeneous aperture size, is widely used in the numerous areas such as absorption, separation, ion-exchange and catalysis.ZSM-22 molecular sieve is a kind of molecular screen material with TON feature topology developed the eighties in 20th century by Mobil company of the U.S., belongs to rhombic system, and spacer is Cmcm.Topological framework comprises five-ring, six-ring and ten-ring, and main aperture road is the one-dimensional channels with ten-ring opening, duct is parallel to (001) direction, without intersecting duct, has the oval-shaped passageway that port size is 0.45*0.55nm.Its topological framework is similar to Theta-1, Nu-10, ISI-1, KZ-2 molecular sieve [zeolites, 1985,5 (6), 349].ZSM-22 molecular sieve has excellent absorption property, thermostability, acidity and shape selective catalysis performance, is the very distinctive new catalytic material of one.Alkane aromatization, hydrocracking, alkylbenzene selection alkylation, alkene and isomerization of paraffins etc. can be widely used in.
Up to the present, many organic formwork agents can be used for synthesizing ZSM-22 zeolite, as 1,6-hexanediamine [US49022406US5707600US5783168], N-ethylpyridine, quadrol [US4556477], three (ethylidene) tetramine, diethylamine, 1-butylamine, thanomin, imidazoles bi-quaternary ammonium salt etc.These template are not only expensive, improve synthesis cost, and synthesis and drive away template process in also can produce a large amount of waste liquids and toxic gas.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, a kind of method without template crystal seed Induced synthesis pure phase ZSM-22 molecular sieve of more inexpensive environmental protection is provided.
Synthesis step is as follows:
A) by silicon source, aluminium source, mineral alkali and water mixing, the initial gel mixture with following mol ratio is formed:
Al
2O
3∶SiO
2＝0.003～0.05∶1
OH
-∶SiO
2＝0.1～0.5∶1
H
2O∶SiO
2＝10～60∶1；
B) ZSM-22 crystal seed is joined step a) in gained initial gel mixture, stir, wherein SiO in the add-on of ZSM-22 crystal seed and initial gel mixture
2mass ratio be 0.01 ~ 0.1: 1;
C) by described step b) mixture that obtains in 120 ~ 200 DEG C, crystallization 4 ~ 144h under autogenous pressure;
D) after crystallization completes, by solid product filtering separation, with deionized water wash to neutral, after drying, ZSM-22 molecular sieve is namely obtained.
The present invention also provides a kind of crystal seed to synthesize the method for Me-ZSM-22 molecular sieve, and synthesis step is as follows:
A) by silicon source, aluminium source, sodium hydroxide and water mixing, the initial gel mixture with following mol ratio is formed:
Al
2O
3∶SiO
2＝0.003～0.05∶1
OH
-∶SiO
2＝0.1～0.5∶1
H
2O∶SiO
2＝10～60∶1；
B) ZSM-22 crystal seed is joined step a) in gained initial gel mixture, after stirring, add the salt that certain proportion contains Me metal ion, wherein SiO in the add-on of ZSM-22 crystal seed and initial gel mixture
2mass ratio be 0.01 ~ 0.1: 1;
C) by described step b) mixture that obtains in 120 ~ 200 DEG C, crystallization 4 ~ 144h under autogenous pressure;
D) after crystallization completes, by solid product filtering separation, with deionized water wash to neutral, after drying, Me-ZSM-22 molecular sieve is namely obtained.
Described aluminium source is mixture a kind of or several arbitrarily in aluminum isopropylate, aluminum oxide, aluminium hydroxide, aluminum chloride, Tai-Ace S 150, aluminum nitrate, sodium aluminate; Described silicon source is a kind of or several arbitrarily mixture in silicon sol, Silica hydrogel, methyl silicate, tetraethoxy, white carbon black; Described alkali source is one or both the mixture in sodium hydroxide, potassium hydroxide; Described ZSM-22 molecular sieve crystal seed can be former powder before roasting, also can be Na type, H type or NH after roasting
4type sample, buys or self-control from commerical prod.
Described step is SiO in initial gel mixture a)
2: Al
2o
3mol ratio be 20 ~ 300: 1, preferably 30 ~ 150: 1, more preferably 40 ~ 140: 1.
Described step b) in SiO in the add-on of ZSM-22 crystal seed and initial gel mixture
2mass ratio be 0.01 ~ 0.1: 1, preferably 0.03 ~ 0.1: 1.
Described step c) in crystallization temperature be 120 ~ 200 DEG C, preferably 150 ~ 180 DEG C; Time is 4 ~ 144h preferably 8 ~ 72h.
Described step c) in crystal pattern can be static crystallization or dynamic crystallization.
In the technical scheme of synthesis Me-ZSM-22 molecular sieve, step b) described in salt containing Me metal ion can be inorganic salt and/or organic salt; Me metal ion can be Zn
2+, Cu
2+, Mg
2+, Mn
2+, Ga
3+, Ca
2+in a kind of or several arbitrarily mixing; Salt containing Me metal ion can be Zn
2+, Cu
2+, Mg
2+, Mn
2+, Ga
3+, Ca
2+nitrate, hydrochloride, a kind of or several arbitrarily mixture in vitriol or acetate, SiO in add-on and Primogel
2molar ratio be SiO
2: Me=50 ~ 300: 1.
Synthesized ZSM-22 and Me-ZSM-22, removes sodium ion through ion-exchange, in 400 ~ 700 DEG C of air after roasting, can be used as the catalyzer of acid catalyzed reaction.
Present invention also offers a kind of acid catalyzed reaction catalyzer, comprise ZSM-22 and the Me-ZSM-22 molecular sieve will synthesized according to aforesaid method, remove sodium ion through ion-exchange, obtain after roasting in 400 ~ 700 DEG C of air.
The beneficial effect that the present invention can produce comprises:
Compared with prior art, do not use organic formwork agent by the whole production process of technical solution of the present invention, production cost significantly reduces, more environmental friendliness, and obtain product degree of crystallinity and purity high, there is good catalytic reaction activity.Gained ZSM-22 and Me-ZSM-22 product have larger specific surface area, have potential using value for some important catalyzed reactions, produce the inorganic raw material environmental friendliness adopted, cheap, significant in actual chemical production field.
Accompanying drawing explanation
The XRD figure of the ZSM-22 sample of Fig. 1 synthesized by embodiment 1.
Fig. 2 is the XRD spectra of the Mg-ZSM-22 synthesized by embodiment 21.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
Embodiment 1:
Take ZSM-22 as crystal seed synthesis ZSM-22 molecular sieve
First 0.033g aluminum oxide and 0.33g sodium hydroxide are dissolved in deionized water, after settled solution to be formed, add 5.62g silicon sol (SiO
2content is 28.5%), at room temperature continuing to stir until form uniform silica-alumina gel, finally adding 0.048g (for adding SiO
23% of quality) ZSM-22 molecular sieve stirring; Transferred to by mixing raw material in the stainless steel cauldron of band polytetrafluoro liner, 170 DEG C of dynamic crystallization 18h, the mol ratio of reaction raw materials is as follows: 140SiO
2: 1.0Al
2o
3: 43.8NaOH: 3035H
2o, product suction filtration, dries and namely obtains ZSM-22 molecular sieve.
Fig. 1 is the XRD figure of sample, can find out, sample has the structure of typical ZSM-22 zeolite molecular sieve, and has very high purity and degree of crystallinity
Table 1 Zeolite synthesis batching and crystallization condition table
Embodiment 2-20
Concrete proportion scale and crystallization condition are in table 1, and concrete blending process is with embodiment 1.
Synthetic sample does XRD analysis, data results and Fig. 1 close, namely diffraction peak position is identical with shape, and the change relative peak intensities according to synthesis condition fluctuates in ± 5% scope, shows that synthetic product has the feature of ZSM-22 structure.
Embodiment 21
First 0.033g aluminum oxide and 0.33g sodium hydroxide are dissolved in deionized water, after settled solution to be formed, add 5.62g silicon sol (SiO
2content is 28.5%), at room temperature continuing to stir until form uniform silica-alumina gel, finally adding 0.048g (for adding SiO
23% of quality) ZSM-22 molecular sieve stirring; Finally add and include 0.033g Mg (NO
3)
26H
2the aqueous solution of O also stirs, and transferred to by mixing raw material in the stainless steel cauldron of band polytetrafluoro liner, 170 DEG C of dynamic crystallization 18h, the mol ratio of reaction raw materials is as follows: 140SiO
2: 1.0Al
2o
3: 43.8NaOH: 0.67Mg (NO
3)
2: 3035H
2o, product suction filtration, dries and namely obtains Mg-ZSM-22 molecular sieve.Fig. 2 is the XRD figure of sample, can find out, sample has the structure of typical ZSM-22 zeolite molecular sieve.
Embodiment 22-24
Concrete proportion scale, blending process and crystallization condition with embodiment 21, by Mg (NO
3)
26H
2o is replaced by the manganous sulfate of identical mole number, cupric chloride, zinc sulfate, calcium chloride or gallium nitrate.Synthetic sample does XRD analysis, data results and accompanying drawing 1 close, namely peak position is identical with shape, and the change relative peak intensities according to synthesis condition fluctuates in ± 5% scope, shows that synthetic product has the feature of Me-ZSM-22 structure.
Embodiment 25
Sample embodiment 1 obtained is through NH
4nO
3sodium ion is removed in ion-exchange, in 400 ~ 600 DEG C of air after roasting 4h, compressing tablet, is crushed to 20 ~ 40 orders.Take 0.5g sample and load fixed-bed reactor, carry out n-heptane isomerization reaction evaluating.At 550 DEG C, lead to nitrogen activation 2h before reaction starts, be then cooled to 400 DEG C and react.The mol ratio of normal heptane hydrogen is 2, and reaction pressure is 0.1Mpa, and the mass space velocity of normal heptane is 10h
-1.Reaction liquid product composition adopts U.S. Agilent company 6890GC type gas chromatograph to analyze, and chromatographic column is Agilent company HP-5 capillary column.With this understanding, the transformation efficiency of normal heptane and isomerisation selectivity reach 16.7% and 91.5% respectively.
Embodiment 26
Sample embodiment 21 obtained is through NH
4nO
3sodium ion is removed in ion-exchange, in 400 ~ 600 DEG C of air after roasting 4h, compressing tablet, is crushed to 40 ~ 60 orders.Take 0.6g sample and load fixed-bed reactor, carry out 1-butylene isomerization reaction evaluation.At 550 DEG C, lead to nitrogen activation 2h when reaction starts, be then cooled to 450 DEG C and react.1-butylene mass space velocity is for measuring as 6h
-1reaction pressure is normal pressure, reaction product adopts U.S. Agilent company 6890GC type gas chromatograph to analyze, chromatographic column is Agilent company HP-5 capillary column. result shows, under the reaction conditions, 1-butylene transformation efficiency be 90%, the selectivity of iso-butylene is about 40%, in the 12h of initial reaction, the yield of iso-butylene all maintains more than 35%.
The above, only several embodiments of the present invention, not any type of restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, not departing from the scope of technical solution of the present invention, make a little variation when the technology contents of above-mentioned announcement can be utilized or modify and be all equal to equivalent case study on implementation, all belong within the scope of technical scheme.
Claims (10)
1. a synthetic method for ZSM-22 molecular sieve, is characterized in that, synthesis step is as follows:
A) by silicon source, aluminium source, inorganic alkali source and water mixing, the initial gel mixture with following mol ratio is formed:
Al
2O
3∶SiO
2＝0.003～0.05∶1
OH
-∶SiO
2＝0.1～0.5∶1
H
2O∶SiO
2＝10～60∶1；
B) ZSM-22 molecular sieve crystal seed is joined step a) in gained initial gel mixture, stir, wherein SiO in the add-on of ZSM-22 crystal seed and initial gel mixture
2mass ratio be 0.01 ~ 0.1: 1;
C) by described step b) mixture that obtains in 120 ~ 200 DEG C, crystallization 4 ~ 144h under autogenous pressure;
D) after crystallization completes, by solid product filtering separation, with deionized water wash to neutral, after drying, ZSM-22 molecular sieve is namely obtained.
2. a synthetic method for Me-ZSM-22 molecular sieve, is characterized in that, synthesis step is as follows:
A) by silicon source, aluminium source, alkali source and water mixing, the initial gel mixture with following mol ratio is formed:
Al
2O
3∶SiO
2＝0.003～0.05∶1
OH
-∶SiO
2＝0.1～0.5∶1
H
2O∶SiO
2＝10～60∶1；
B) a certain proportion of ZSM-22 crystal seed is joined step a) in gained initial gel mixture, after stirring, add the salt that certain proportion contains Me metal ion, wherein SiO in the add-on of ZSM-22 crystal seed and initial gel mixture
2mass ratio be 0.01 ~ 0.1: 1;
C) by described step b) mixture that obtains in 120 ~ 200 DEG C, crystallization 4 ~ 144h under autogenous pressure;
D) after crystallization completes, by solid product filtering separation, with deionized water wash to neutral, after drying, Me-ZSM-22 molecular sieve is namely obtained.
3. method according to claim 1 and 2, is characterized in that, described aluminium source is mixture a kind of or several arbitrarily in aluminum isopropylate, aluminum oxide, aluminium hydroxide, aluminum chloride, Tai-Ace S 150, aluminum nitrate, sodium aluminate; Described silicon source is a kind of or several arbitrarily mixture in silicon sol, Silica hydrogel, methyl silicate, tetraethoxy, white carbon black; Described alkali source is one or both the mixture in sodium hydroxide, potassium hydroxide; Described ZSM-22 molecular sieve crystal seed is former powder before roasting, or Na type, H type or NH after roasting
4type sample.
4. method according to claim 1 and 2, is characterized in that, step b) in SiO in the add-on of ZSM-22 crystal seed and initial gel mixture
2mass ratio be 0.03 ~ 0.1: 1.
5. method according to claim 1 and 2, is characterized in that, step is SiO in initial gel mixture a)
2: Al
2o
3mol ratio be 30 ~ 150: 1, be preferably 40 ~ 120: 1.
6. method according to claim 1 and 2, is characterized in that, described step c) in crystallization temperature be 150 ~ 180 DEG C, the time is 8 ~ 72h.
7. method according to claim 1 and 2, is characterized in that, described step c) in crystal pattern be static crystallization or dynamic crystallization.
8. method according to claim 2, is characterized in that, step b) described in be Zn containing the salt of Me metal ion
2+, Cu
2+, Mg
2+, Mn
2+, Ga
3+, Ca
2+a kind of or several arbitrarily mixture in the inorganic salt of ion or organic salt, SiO in add-on and Primogel
2molar ratio be SiO
2: Me=50 ~ 300: 1.
9. method according to claim 2, is characterized in that, step b) described in containing the salt Zn of Me metal
2+, Cu
2+, Mg
2+, Mn
2+, Ga
3+, Ca
2+the mixture of one or more of the nitrate of ion, hydrochloride, vitriol or acetate, SiO in add-on and Primogel
2molar ratio be SiO
2: Me=50 ~ 300: 1.
10. an acid catalyzed reaction catalyzer, is characterized in that, by ZSM-22 and the Me-ZSM-22 molecular sieve that method according to claim 1 or 2 is synthesized, removes sodium ion, obtain in 400 ~ 700 DEG C of air after roasting through ion-exchange.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105129814A (en) * | 2015-09-06 | 2015-12-09 | 太原理工大学 | Preparation method for ZSM-22 molecular sieve |
| CN105293516A (en) * | 2015-10-27 | 2016-02-03 | 北京化工大学 | Method for rapidly preparing ZSM-22 molecular sieve by means of seed crystal |
| CN106483155A (en) * | 2015-08-25 | 2017-03-08 | 中国石油天然气股份有限公司 | A kind of method of mensure ZSM-22 molecular sieve relative crystallinity |
| CN108706607A (en) * | 2018-07-02 | 2018-10-26 | 南京工业大学 | A kind of zeolite molecular sieve, preparation method and applications |
Citations (2)
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| CN1083021A (en) * | 1992-06-05 | 1994-03-02 | 埃克森化学专利公司 | Improved zeolite |
| CN103101924A (en) * | 2013-02-01 | 2013-05-15 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
-
2013
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Patent Citations (2)
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|---|---|---|---|---|
| CN1083021A (en) * | 1992-06-05 | 1994-03-02 | 埃克森化学专利公司 | Improved zeolite |
| CN103101924A (en) * | 2013-02-01 | 2013-05-15 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
Non-Patent Citations (2)
| Title |
|---|
| A.P. SINGH ET AL: "Synthesis, characterization, and catalytic activity of gallosilicate analogs of zeolite ZSM-22", 《ZEOLITES》 * |
| A.P. SINGH ET AL: "Synthesis, characterization, and catalytic activity of gallosilicate analogs of zeolite ZSM-22", 《ZEOLITES》, vol. 14, 31 May 1994 (1994-05-31), pages 290 - 294 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106483155A (en) * | 2015-08-25 | 2017-03-08 | 中国石油天然气股份有限公司 | A kind of method of mensure ZSM-22 molecular sieve relative crystallinity |
| CN106483155B (en) * | 2015-08-25 | 2019-07-05 | 中国石油天然气股份有限公司 | A method of measurement ZSM-22 molecular sieve relative crystallinity |
| CN105129814A (en) * | 2015-09-06 | 2015-12-09 | 太原理工大学 | Preparation method for ZSM-22 molecular sieve |
| CN105129814B (en) * | 2015-09-06 | 2017-05-10 | 太原理工大学 | Preparation method for ZSM-22 molecular sieve |
| CN105293516A (en) * | 2015-10-27 | 2016-02-03 | 北京化工大学 | Method for rapidly preparing ZSM-22 molecular sieve by means of seed crystal |
| CN108706607A (en) * | 2018-07-02 | 2018-10-26 | 南京工业大学 | A kind of zeolite molecular sieve, preparation method and applications |
| CN108706607B (en) * | 2018-07-02 | 2021-12-03 | 南京工业大学 | Zeolite molecular sieve, preparation method and application thereof |
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| CN104370292B (en) | 2016-06-15 |
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