CN107089669A - A kind of synthetic method of the molecular sieves of c axle orientating type Zn ZSM 5 under externally-applied magnetic field effect - Google Patents
A kind of synthetic method of the molecular sieves of c axle orientating type Zn ZSM 5 under externally-applied magnetic field effect Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
A kind of synthetic method of the molecular sieves of c axle orientating type Zn ZSM 5 under externally-applied magnetic field effect, belongs to the synthetic method of the molecular sieves of Zn ZSM 5.Acted on by specific externally-applied magnetic field, solution ZSM 5 is in crystal growing process the problem of appearance structure orientation preferential growth.Synthetic method is：The prefabricated crystal seeds of silicalite 1 are added to doping Zn2+Mixed gel in, be aged under the externally-applied magnetic field effect of certain strength, then carry out crystallization, drying, roasting, c axle orientating type Zn ZSM 5 are made.The characteristics of technology is that the guide effect that is grown to zeolite crystal of externally-applied magnetic field of certain strength is obvious, the horizontal magnetic induction line position synthesis molecular sieve monomer of its placement had into c axle orientation textures, the molecular sieve new materials of zinc-type ZSM 5 of c direction of principal axis preferential growths just can be successfully synthesized by once adulterating simultaneously, synthesis technique is simple, it is reproducible, and new material specific surface area is larger, excellent methanol conversion and aromatics yield, anti-carbon performance and stability are shown in being reacted applied to aromatization of methanol.
Description
Technical field
The present invention relates to a kind of synthetic method of Zn-ZSM-5 molecular sieves, the c- axles under particularly a kind of externally-applied magnetic field effect
The synthetic method of orientating type Zn-ZSM-5 molecular sieves.
Background technology
ZSM-5 belongs to MFI-type molecular sieve, and by the straight tube shape a axis holes road of ellipsoidal cross section, (pore size is pore passage structure
0.54nm × 0.56nm) and section be approximately circular Z-shaped b axis holes road (pore size be 0.52nm × 0.58nm) intersection institute
Composition；The otherness of co-axial orientation ZSM-5 molecular sieve nanoscale pore passage structure does not cause chemical molecular in molecular sieve pore passage
There are greatest differences in mass transfer characteristic, characterization of adsorption and response characteristic.Due to benzene (B), toluene (T) and dimethylbenzene (X) molecular size
Close with ZSM-5 molecular sieve channel diameter size, load Zn or Ga ZSM-5 molecular sieve is applied to methanol aromatic hydrocarbons (MTA) instead
Good shape selective catalysis performance should be demonstrated by.Research finds the huge difference that the structure of different duct orientation ZSM-5 molecular sieves is present
It is different, catalytic performance of the molecular sieve in aromatization of methanol reaction can be had a strong impact on.Because BTX is in conventional ZSM-5 molecular sieve duct
Middle diffusional resistance is larger, easily the coking carbon distribution in duct, reduces zeolite-catalyzed reaction performance.And it is orientated duct with c-axis
The ZSM-5 molecular sieve of structure can make reactant molecule easily reach catalytic active site, and the product generated can quickly from
Spread in duct.
In recent years, people pay close attention to the synthesis of orientating type molecular sieve always, are done for synthesizing the HZSM-5 with orientating type
Many trials.For example：Ryoo etc. (Nature, 461 (2009) 246) uses the hexamethylene diamine derivative for having hydrophobicity long-chain to replace
For organic formwork agent, formed using MFI structure on the space orientation effect guiding ac faces of two amino of organic formwork, using another
One section of hydrophobic long-chain for 22 carbon of length suppresses MFI structure along b axial growths, and it is nanometer to successfully synthesize on b direction of principal axis
The ZSM-5 zeolite of yardstick.Shan etc. (Chem.Commun, 47 (2011) 1048) adds urea in synthesis starting silicon-titanium gel
With fluorine-containing surfactant FC-4, synthesize the sheet or chain TS-1 molecular sieves of b- axle oriented growths.Liu etc.
(J.Am.Chem.Soc., 134 (2012) 4557) are using cationic polymer copolymer polystyrene-co-4-
Polyvinylpyridine (PSt-co-P4VP) is that mesoporous template is prepared for containing orderly transgranular mesoporous ZSM-5 zeolite monocrystalline,
Wherein aperture grows in the mesoporous of 10-50nm along zeolite b direction of principal axis.As fully visible, current orientating type ZSM-5 molecular sieve is more
Synthesize, and needed method using expensive organic formwork agent production cost very more for b- axle orientating types molecular screen material
Height, does not meet demand of industrial production.
Wait (Yin's chess Asia Materials Science and Engineering journals, 2007,25 (5) in Yin's chess Asia：788-804).Point out, under magnetic field
Particle it is more orderly than the particle for being not added with magnetic field, this is due to charged particle such as electronics and ion etc. and some polar molecules
Essence change can occur in magnetic field particularly high-intensity magnetic field for motion, and catalyst can be enable to be easy to separation, increased operation rate.
(OhgakiK, ChemEngSci, 1994,9 (6) such as Ohgakik：Bond energy can be changed by 911-913) thinking the effect in magnetic field, so that
Change interfacial structure, influence crystal growing process, crystal is grown along a direction.(the Chao K Jet al.Adv such as Chao
Mater, 1996,8 (12)：1008-1012) taking for AFI molecular sieve crystals is limited using the vertical channel of anodized aluminum support
To growth, respectively obtain along duct direction c- axles orientation, compact arranged VAPO4- 5 and AlPO4- 5 crystal layers.In building-up process
In, nucleus penetrates into carrier duct first, then grows the crystal of c- axles orientation along duct direction and stretches out duct.
The content of the invention
The invention aims to provide a kind of conjunction of the c- axle orientating type Zn-ZSM-5 molecular sieves under externally-applied magnetic field effect
Into method, solve that template consumption present in existing synthesis nano-ZSM-5 molecular sieve hydrothermal synthesis method is excessive and c- axles
The problem of ZSM-5 crystalline phase growth and anti-carbon deposit, methanol conversion.
In order to solve the above technical problems, the object of the present invention is achieved like this：
The technical solution adopted by the present invention is as follows：
First, prepared by silicalite-1 crystal seeds：A, silicon source, template and deionized water be well mixed, being formed has such as
The mixture of lower mol ratio, template：SiO2：H2O=1：(20~40)：(70~100), aging is carried out to mixture；B, general
Gel in step a after aging is transferred to crystallizing kettle and carries out crystallization, obtains prefabricated crystal seed suspension；
2nd, prepared by mixed gel：Silicon source, silicon source, alkali source, zinc source and deionized water are well mixed, formed with as follows
The initial gel mixture of mol ratio, SiO2：Al2O3：Na2O：ZnO：H2O=(100~150)：(2~4)：6：1：(900~
1500)；Prefabricated crystal seed suspension is added into initial gel mixture, is stirred；
3rd, aging：The mixture glass container that step 2 is obtained is placed in thermostatic bath, and template is added into mixture
Agent, the additional externally-applied magnetic field of thermostatic bath, and continuously it is slowly stirred lower aging 24-36h；
4th, crystallization：Mixture after aging is transferred in crystallizing kettle and carries out crystallization, room temperature is naturally cooled to, then carried out
Filtering, washing, are dried, calcining obtains the Zn-ZSM-5 molecular sieves with c- axial arrangements.
In step one, crystallization condition, crystallization temperature is 80~120 DEG C, and crystallization time is 4~8h, and crystallization temperature is can not
Higher than 120 DEG C, its crystallization time should shorten when crystallization temperature chooses higher, to control the crystal seed grain in obtained crystal seed suspension
Degree is less than 30nm.
In step one and step 2, silicon source is a kind of or several in Ludox, Silica hydrogel, tetraethyl orthosilicate, methyl silicate
Kind；Template is one or more in TPAOH, 4-propyl bromide, 1,6- hexamethylene diamines, n-butylamine；In step 2
Silicon source is one or more in aluminium isopropoxide, aluminum nitrate, sodium metaaluminate and aluminum sulfate；Zinc source is zinc nitrate, zinc chloride or sulfuric acid
One kind in zinc.
In step 2, seed load is 1%~10%, crystal seed suspension quality and SiO in initial gel mixture2's
Mass ratio.
In step 3, the intensity of externally-applied magnetic field is 30mT~60mT.
In step 3, continuously it is slowly stirred with 20-60 revs/min.
In step 4, crystallization condition is that crystallization temperature is 140~170 DEG C, and crystallization time is 10~24h；Wherein, crystallization temperature
Degree is no more than 170 DEG C.
Beneficial effect, as a result of such scheme, the c- axles orientating type ZSM-5 molecular sieve materials synthesis under magnetic fields
Method, is acted on by specific externally-applied magnetic field, and efficiently solving ZSM-5, appearance structure orientation is preferentially in crystal growing process
The problem of growth.The characteristics of technology be the guide effect that is grown to zeolite crystal of externally-applied magnetic field of certain strength substantially, will
The horizontal magnetic induction line position synthesis molecular sieve monomer of its placement has c- axle orientation textures, without the need for after-treatment, passes through one
Secondary doping just can successfully synthesize the zinc-type ZSM-5 molecular sieve new material with c- axle orientation textures, and synthesis technique is simple, repeats
Property it is good, and new material specific surface area is larger, applied to showing excellent methanol conversion and aromatic hydrocarbons in aromatization of methanol reaction
Yield, anti-carbon performance and stability.Solve mould present in prior art synthesis nano-ZSM-5 molecular sieve hydrothermal synthesis method
Plate agent consumption is excessive and the problem of the growth of crystalline phase of c- axles ZSM-5 and anti-carbon deposit, methanol conversion, reached the present invention's
Purpose.
Advantage：Synthesis technique of the present invention is simple, reproducible, and new material specific surface area is larger, applied to methanol aromatization
Change and excellent methanol conversion and aromatics yield, anti-carbon performance and stability are shown in reaction.
Brief description of the drawings：
Fig. 1 is the SEM structure charts with c- axle orientating type Zn-ZSM-5 molecular sieves prepared under the conditions of present example 1.
Fig. 2 is the TEM structure charts with c- axle orientating type Zn-ZSM-5 molecular sieves prepared under the conditions of present example 1.
Fig. 3 is the XRD with c- axle orientating type Zn-ZSM-5 molecular sieves for preparing under the conditions of present example 1.
Fig. 4 has c- axles orientating type Zn-ZSM-5 molecular sieves and routine Zn/ for what is prepared under conditions of present example
The methanol conversion and aromatics yield comparison diagram of ZSM-5 molecular sieve (Zn is loaded using infusion process).
Embodiment
The technical solution adopted by the present invention is as follows：
First, prepared by silicalite-1 crystal seeds, and described silicalite-1 crystal seeds are a kind of total silicon type crystal seed：A, by silicon
Source, template and deionized water are well mixed, form the mixture with following mol ratio, template：SiO2：H2O=1：
(20~40)：(70~100), aging is carried out to mixture；B, the gel after aging in step a is transferred to crystallizing kettle carry out it is brilliant
Change, obtain prefabricated crystal seed suspension；
2nd, prepared by mixed gel：Silicon source, silicon source, alkali source, zinc source and deionized water are well mixed, formed with as follows
The initial gel mixture of mol ratio, SiO2：Al2O3：Na2O：ZnO：H2O=(100~150)：(2~4)：6：1：(900~
1500)；Prefabricated crystal seed suspension is added into initial gel mixture, is stirred；
3rd, aging：The mixture glass container that step 2 is obtained is placed in thermostatic bath, and template is added into mixture
Agent, the additional externally-applied magnetic field of thermostatic bath, and continuously it is slowly stirred lower aging 24-36h；
4th, crystallization：Mixture after aging is transferred in crystallizing kettle and carries out crystallization, room temperature is naturally cooled to, then carried out
Filtering, washing, are dried, calcining obtains the Zn-ZSM-5 molecular sieves with c- axial arrangements.
In step one, crystallization condition, crystallization temperature is 80~120 DEG C, and crystallization time is 4~8h, and crystallization temperature is can not
Higher than 120 DEG C, its crystallization time should shorten when crystallization temperature chooses higher, to control the crystal seed grain in obtained crystal seed suspension
Degree is less than 30nm.
In step one and step 2, silicon source is a kind of or several in Ludox, Silica hydrogel, tetraethyl orthosilicate, methyl silicate
Kind；Template is one or more in TPAOH, 4-propyl bromide, 1,6- hexamethylene diamines, n-butylamine；In step 2
Silicon source is one or more in aluminium isopropoxide, aluminum nitrate, sodium metaaluminate and aluminum sulfate；Zinc source is zinc nitrate, zinc chloride or sulfuric acid
One kind in zinc.
In step 2, seed load is 1%~10%, crystal seed suspension quality and SiO in initial gel mixture2's
Mass ratio.
In step 3, the intensity of externally-applied magnetic field is 30mT~60mT.MT is unit of magnetic field strength：Milli tesla.
In step 3, continuously it is slowly stirred with 20-60 revs/min.
In step 4, crystallization condition is that crystallization temperature is 140~170 DEG C, and crystallization time is 10~24h；Wherein, crystallization temperature
Degree is no more than 170 DEG C.
Here is embodiments of the invention, but the invention is not limited in these embodiments.
Embodiment 1：
(1) 15ml absolute ethyl alcohols, 30ml deionized waters and 25ml tetraethyl orthosilicates are mixed evenly at room temperature.
(2) 4.4ml TPAOHs are slowly added dropwise in the solution obtained to step (1), 4h is stirred at room temperature.
(3) step (2) is obtained into solution to be transferred in the reactor of the bushing pipe containing polytetrafluoroethylene (PTFE), aging 24h at 80 DEG C, then
The crystallization 4h at 120 DEG C, obtains crystal seed suspension.
(4) by 6ml 1mol/L Al (NO3)31mol/L Zn (the NO of solution, 6ml3)2The 2mol/L of solution, 36ml
NaOH solution and 78ml deionized waters are mixed evenly.
(5) agitation and dropping 72g Ludox (50%SiO in the solution obtained to step (4)2)。
(6) 10% crystal seed suspension is slowly added dropwise in the solution obtained to step (5).
(7) 3ml 1,6- hexamethylene diamines are added in the solution obtained to step (6), are stirred.
(8) solution for obtaining step (7) is in the externally-applied magnetic field that thermostatic bath is placed in 50.3mT intensity, with 20 revs/min
Clock stir speed (S.S.) is slowly stirred aging 30h.
(9) solution for obtaining step (8) is added in the synthesis reactor of polytetrafluoroethyllining lining, in 160 DEG C of crystallization 24h.
(10) solid sample for the sample centrifugal filtration for obtaining step (9)
(11) solid sample for obtaining step (10) is calcined 6h at 12h, 550 DEG C through being dried at 110 DEG C in air atmosphere,
C- axle orientating type Zn-ZSM-5 molecular sieves are made.
Embodiment 2：Present embodiment and crystallization 6h in step (3) unlike specific embodiment 1 100 DEG C.Other steps
Rapid and parameter is identical with specific embodiment 1.
Embodiment 3：Present embodiment suspends from 5% crystal seed is slowly added dropwise in step (6) unlike specific embodiment 1
Liquid.Other steps and parameter are identical with specific embodiment 1.
Embodiment 4：The present embodiment and the applied field strengths 55mT in step (8) unlike specific embodiment 1, stirring
Speed is 30 revs/min.Other steps and parameter are identical with specific embodiment 1.
Embodiment 5：The present embodiment and 170 DEG C of crystallization 15h in step (9) unlike specific embodiment 1.Other steps and
Parameter is identical with specific embodiment 1.
Claims (7)
1. a kind of synthetic method of the c- axle orientating type Zn-ZSM-5 molecular sieves under externally-applied magnetic field effect, it is characterized in that：
First, prepared by silicalite-1 crystal seeds：A, silicon source, template and deionized water be well mixed, formed to have and rubbed as follows
The mixture of your proportioning, template：SiO2：H2O=1：(20~40)：(70~100), aging is carried out to mixture；B, by step
Gel in a after aging is transferred to crystallizing kettle and carries out crystallization, obtains prefabricated crystal seed suspension；
2nd, prepared by mixed gel：Silicon source, silicon source, alkali source, zinc source and deionized water are well mixed, being formed has following mole
The initial gel mixture of proportioning, SiO2：Al2O3：Na2O：ZnO：H2O=(100~150)：(2~4)：6：1：(900~
1500)；Prefabricated crystal seed suspension is added into initial gel mixture, is stirred；
3rd, aging：The mixture glass container that step 2 is obtained is placed in thermostatic bath, and template is added into mixture,
The additional externally-applied magnetic field of thermostatic bath, and continuously it is slowly stirred lower aging 24-36h；
4th, crystallization：Mixture after aging is transferred in crystallizing kettle and carries out crystallization, room temperature is naturally cooled to, then filtered,
Washing, is dried, calcining obtains the Zn-ZSM-5 molecular sieves with c- axial arrangements.
2. the synthesis side of the c- axle orientating type Zn-ZSM-5 molecular sieves under a kind of externally-applied magnetic field effect according to claim 1
Method, it is characterized in that：In step one, crystallization condition, crystallization temperature is 80~120 DEG C, and crystallization time is 4~8h, and crystallization temperature is
Not above 120 DEG C, its crystallization time should shorten when crystallization temperature chooses higher, to control the crystalline substance in obtained crystal seed suspension
Plant granularity and be less than 30nm.
3. the synthesis side of the c- axle orientating type Zn-ZSM-5 molecular sieves under a kind of externally-applied magnetic field effect according to claim 1
Method, it is characterized in that：In step one and step 2, silicon source is one kind in Ludox, Silica hydrogel, tetraethyl orthosilicate, methyl silicate
Or it is several；Template is one or more in TPAOH, 4-propyl bromide, 1,6- hexamethylene diamines, n-butylamine；Step
Silicon source is one or more in aluminium isopropoxide, aluminum nitrate, sodium metaaluminate and aluminum sulfate in two；Zinc source be zinc nitrate, zinc chloride or
One kind in zinc sulfate.
4. the synthesis side of the c- axle orientating type Zn-ZSM-5 molecular sieves under a kind of externally-applied magnetic field effect according to claim 1
Method, it is characterized in that：In step 2, seed load is 1%~10%, in crystal seed suspension quality and initial gel mixture
SiO2Mass ratio.
5. the synthesis side of the c- axle orientating type Zn-ZSM-5 molecular sieves under a kind of externally-applied magnetic field effect according to claim 1
Method, it is characterized in that：In step 3, the intensity of externally-applied magnetic field is 30mT~60mT.
6. the synthesis side of the c- axle orientating type Zn-ZSM-5 molecular sieves under a kind of externally-applied magnetic field effect according to claim 1
Method, it is characterized in that：In step 3, continuously it is slowly stirred with 20-60 revs/min.
7. the synthesis side of the c- axle orientating type Zn-ZSM-5 molecular sieves under a kind of externally-applied magnetic field effect according to claim 1
Method, it is characterized in that：In step 4, crystallization condition is that crystallization temperature is 140~170 DEG C, and crystallization time is 10~24h；Wherein, it is brilliant
Change temperature no more than 170 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921677A (en) * | 2019-12-04 | 2020-03-27 | 广东石油化工学院 | Method for preparing 4A zeolite from kaolin |
| CN111056559A (en) * | 2019-12-30 | 2020-04-24 | 大连理工大学 | Preparation method of flaky Zn/ZSM-5 molecular sieve for methanol aromatization |
| CN112408419A (en) * | 2020-12-17 | 2021-02-26 | 河南科技大学 | Preparation method of hierarchical porous ZSM-5 nano zeolite |
| CN115646538A (en) * | 2022-11-08 | 2023-01-31 | 中国矿业大学 | Bi-metal-packaged construction b-axial ZSM-5 molecular sieve and application thereof in catalyzing MTA reaction |
| CN115672264A (en) * | 2021-07-30 | 2023-02-03 | 中国石油化工股份有限公司 | Preparation method of pressure swing adsorbent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098108A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Rectangular-morphology ZSM-5 molecular sieve and preparation method thereof |
| CN106185978A (en) * | 2016-07-06 | 2016-12-07 | 华东师范大学 | A kind of synthetic method of high silicon b orientation ZSM 5 nanometer sheet |
-
2017
- 2017-05-26 CN CN201710384153.4A patent/CN107089669B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098108A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Rectangular-morphology ZSM-5 molecular sieve and preparation method thereof |
| CN106185978A (en) * | 2016-07-06 | 2016-12-07 | 华东师范大学 | A kind of synthetic method of high silicon b orientation ZSM 5 nanometer sheet |
Non-Patent Citations (3)
| Title |
|---|
| RUIZHI CHU ET AL: "Improved Catalytic Performance of C-axis Oriented HZSM-5 Nanobunches Synthesized by Re-aging", 《CATALYSIS LETTERS》 * |
| 程婷婷: "取向型ZSM-5粉体材料的制备及其性能评价", 《中国优秀硕士学位论文数据库•工程科技I辑》 * |
| 董维阳等: "蒸汽相中c轴取向连续完美单层B-Al-ZSM-5沸石膜的原位制备", 《化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921677A (en) * | 2019-12-04 | 2020-03-27 | 广东石油化工学院 | Method for preparing 4A zeolite from kaolin |
| CN111056559A (en) * | 2019-12-30 | 2020-04-24 | 大连理工大学 | Preparation method of flaky Zn/ZSM-5 molecular sieve for methanol aromatization |
| CN112408419A (en) * | 2020-12-17 | 2021-02-26 | 河南科技大学 | Preparation method of hierarchical porous ZSM-5 nano zeolite |
| CN115672264A (en) * | 2021-07-30 | 2023-02-03 | 中国石油化工股份有限公司 | Preparation method of pressure swing adsorbent |
| CN115672264B (en) * | 2021-07-30 | 2024-02-02 | 中国石油化工股份有限公司 | Preparation method of pressure swing adsorbent |
| CN115646538A (en) * | 2022-11-08 | 2023-01-31 | 中国矿业大学 | Bi-metal-packaged construction b-axial ZSM-5 molecular sieve and application thereof in catalyzing MTA reaction |
| CN115646538B (en) * | 2022-11-08 | 2024-04-16 | 中国矿业大学 | Encapsulation bimetal constructed b-axial ZSM-5 molecular sieve and application thereof in catalyzing MTA reaction |
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