CN106809859A - The synthetic method and ZSM-5 molecular sieve of a kind of ZSM-5 molecular sieve - Google Patents
The synthetic method and ZSM-5 molecular sieve of a kind of ZSM-5 molecular sieve Download PDFInfo
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- CN106809859A CN106809859A CN201510861727.3A CN201510861727A CN106809859A CN 106809859 A CN106809859 A CN 106809859A CN 201510861727 A CN201510861727 A CN 201510861727A CN 106809859 A CN106809859 A CN 106809859A
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- zsm
- molecular sieve
- synthetic method
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Abstract
The present invention is interlocked the synthetic method of self supporting structure nano-ZSM-5 molecular sieve for a kind of sheet, belongs to Inorganic synthese and catalyst preparation technical field.It is silicon source and silicon source that the method uses Ludox, sodium metaaluminate, one or more organic matters in piperazine, morpholine, triethylene diamine, piperidines are added in synthesis, raw material mixing after 20-50 DEG C gel 0.5-10 hours, it is then transferred into carrying out crystallization at 120-180 DEG C in autoclave, there is sheet staggeredly self supporting structure after the ZSM-5 molecular sieve for obtaining is fired.
Description
Technical field
The invention belongs to Inorganic synthese and catalyst preparation technical field, it is related to a kind of sheet staggeredly self supporting structure
The synthetic method of nano-ZSM-5 molecular sieve.
Background technology
Mobil companies in 1972 report first use quaternary ammonium salt be template synthesize ZSM-5 molecular sieve side
Method (USP3702886).ZSM-5 is a kind of high silica alumina ratio molecular sieve with MFI structure, in its structure
There is no cage, and there is 3-dimensional to intersect pore passage structure, therefore show unique selecting property catalytic performance, while ZSM-5
There is stronger acid and excellent hydrothermal stability, in catalytic cracking, synthesis paraxylene, methyl alcohol conversion system
The aspect such as alkene and gasoline is widely used.Conventional ZSM-5 crystal is generally micron order, because its aperture is small
(about), it is unfavorable for molecule diffusion and mass transfer, the acidic site in duct is difficult to make full use of, on the other hand
Cause the easy carbon distribution of catalyst to inactivate, influence its life-span.Meanwhile, the less outer surfaces of micron order ZSM-5 are not yet
Beneficial to its application in bulky molecular catalysis reaction (such as heavy oil pyrolysis).And nano molecular sieve is due to crystal grain chi
Very little small, orifice throat length is short, shortens the diffusion path of molecule, is conducive to molecule to spread and mass transfer, Ke Yiti
The activity of height reaction, regulation selectivity, particularly improve catalyst stability.Additionally, the nanometer of little crystal grain
Molecular sieve exposes more outer surface acidity positions, also there is the advantage of uniqueness in the catalytic reaction of macromolecular.Closely
Nian Lai, the growth kinetics of crystal is sieved by regulatory molecule, controls the appearance structure of molecular sieve crystal, new hair
The nano molecular sieve with two-dimensional sheet or 1 dimension wire and column structure is opened up, it is had in one direction
There are nano-scale structures, and other directions are identical with common micro molecular sieve structure.Some needs are utilized and is divided
The reaction of type selectivity is realized selecting in son sieve duct long, and this molecular sieve analog may play the advantage of uniqueness, is keeping
Promote reactant and product molecule in the diffusion in molecular sieve nanoscale direction while molecular sieve intrinsic property and
Mass transfer.
In current open report, realize that it has in specific direction by controlling ZSM-5 molecular sieve crystal morphology
There is the method for nano-scale structures, mainly realized by bi-quaternary ammonium salt template of the design with special construction
's.Ryoo etc. has 22 long chain alkane structure Cs of C long using one end22-6-6Br2Bi-quaternary ammonium salt template
Agent, with tetraethyl orthosilicate and aluminum sulfate as silicon source and silicon source, raw material composition is 30Na2O/1Al2O3/100
SiO2/10C22-6-6Br2/18H2SO4/4000H2O, 150 DEG C of dynamic crystallizations 5 days, synthesizes in b direction of principal axis
Thickness is the ZSM-5 nanometer sheets (Nature, 2009,41,246) of 2nm.Okubo etc. is with N, N, N, N, N, N-
The ammonium of Hexaethyl penta 2 (diquat-C5) is that the selfing paraplasia of template control molecular sieve crystal is long, with positive silicic acid
Ethyl ester and aluminium hydroxide are silicon source and silicon source, and synthesis material composition is
8SiO2/xAl2O3/1.55diquat-C5/3KOH/1600H2O/32EtOH (x=0-0.4), 150 DEG C of crystallization 216
Hour, obtained sheet from the ZSM-5 molecular sieve of staggeredly supporting construction (Angew.Chem.Int.Ed.2013,
52,3355).Additionally, Che etc. is with C6H5-C6H4-O-C10H20-N+(CH3)2-C6H13(Br-) it is template,
Being interacted using the π-π of phenyl ring in template structure makes template carry out self assembly, has synthesized thickness and has been about
The ZSM-5 nanometer sheets (Nat.Commun., 2014,5,4262) of 2.7nm；Zhang etc. is with tetrapropyl hydrogen-oxygen
Change the ZSM-5 molecular sieve of ammonium and the TBAH laminated structure of interlocking for double template synthesizes.
The content of the invention
Interlock self supporting structure nano-ZSM-5 molecular sieve it is an object of the invention to provide a kind of new sheet
Synthetic method.
The present invention is provided in a kind of use piperazine, piperidines, triethylene diamine, morpholine and Isosorbide-5-Nitrae-dioxane
One or more organic matters are template, and synthesizing flaky interlocks self supporting structure nano-ZSM-5 molecular sieve
Method, its step is successively including the mixing of raw material, gel, hydrothermal crystallizing and filtration washing and roasting.
Comprise the following steps that：
(1) mixing of raw material：Weigh a certain amount of NaOH and NaAlO2It is placed in the beaker of polypropylene material
It is interior, add deionized water and under agitation be allowed to dissolving after, under agitation addition piperazine, piperidines, triethylene
One or more organic matters in diamines, morpholine and Isosorbide-5-Nitrae-dioxane, thing mixed above stir to
Instill a certain amount of LUDOX AS-40 silicon dioxide gels after to homogeneous solution under agitation again.
(2) gel：The mixture of above-mentioned gained raw material, (600 revs/min) are in a constant temperature under stirring
(20-50 DEG C) carries out gel/pre- crystallization under degree, and the time is 0.5-10 hours.
(3) mixture is transferred to autoclaves of the 100ml equipped with polytetrafluoroethyllining lining after the completion of gel
In carry out dynamic crystallization, crystallization temperature is 120-180 DEG C, and crystallization temperature is 2-10 days.So-called dynamic crystallization is
Be fixed on reactor on the support that motor is rotated by finger, and reactor is spun upside down during revolution,
Reaction mass in kettle can borrow the upset disturbance of kettle to be well mixed.
(4) after the completion of crystallization, reactor is placed in and room temperature is quickly cooled in cold water, filters and with deionized water
Then washing, gained sediment was calcined in Muffle furnace in air atmosphere in 110 DEG C of dryings 12 hours,
Roasting process is：2 DEG C/min are warming up to 350 DEG C, and constant temperature is after 3 hours again with 1 DEG C/min of heating rate liter
Temperature is to 550 DEG C, and constant temperature 12 hours, obtains the sheet staggeredly self supporting structure nano-ZSM-5 molecular sieve.
Brief description of the drawings
Fig. 1 is that the sheet of embodiment 7 is interlocked the powder x-ray diffraction of self supporting structure nano-ZSM-5 molecular sieve
(XRD) figure.
Fig. 2 is that the sheet of embodiment 6 is interlocked the SEM of self supporting structure nano-ZSM-5 molecular sieve
(SEM) figure.
Specific embodiment
Embodiment 1：NaOH 0.3g, NaAlO20.437g is placed in 250ml polypropylene material beakers, plus
Deionized water 30g, being stirred at room temperature 5 minutes makes NaOH and NaAlO2Dissolving, adds in above-mentioned solution
Piperidinyl-1 0g, stirring obtains homogeneous solution in 10 minutes, and 20g LUDOX AS-40 silicon dioxide gels are existed
It is slowly dropped under stirring in above-mentioned solution.Gained mixture (600 revs/min) under 30 DEG C of magnetic agitations
Placing 4h carries out gel/pre- crystallization, is then transferred into autoclaves of the 100ml with polytetrafluoroethyllining lining
(mode of operation taken is that reactor is placed on rotation motor to 145 DEG C of dynamic crystallizations, and motor rotary speed is within 5 days
60 revs/min).Crystallization terminate rear reactor be placed in cold water it is quick be down to room temperature after, suction filtration, and with 1L
Deionized water carries out cyclic washing, and gained is deposited in 110 DEG C of dryings 12 hours.Then horse in air atmosphere
Not it is calcined in stove, roasting process is：2 DEG C/min are warming up to 350 DEG C, constant temperature after 3 hours again with 1 DEG C/
Minute heating rate be warming up to 550 DEG C, and constant temperature 12 hours obtains the sheet staggeredly self supporting structure
Nano-ZSM-5 molecular sieve.
Embodiment 2：With embodiment 1, the addition of piperidines is 5.677g for operation.XRD shows, gained sample
It is ZSM-5 molecular sieve.
Embodiment 3：NaOH 0.32g, NaAlO20.656g is placed in 250ml polypropylene material beakers, plus
Deionized water 36g, being stirred at room temperature 5 minutes makes NaOH and NaAlO2Dissolving, adds in above-mentioned solution
Piperazine 8.52g, stirring obtains homogeneous solution in 10 minutes, by 20g LUDOX AS-40 silicon dioxide gels
It is slowly dropped under agitation in above-mentioned solution.Gained mixture (600 revs/min) under 25 DEG C of magnetic agitations
Placing 3h carries out gel/pre- crystallization, is then transferred into autoclaves of the 100ml with polytetrafluoroethyllining lining
(mode of operation taken is that reactor is placed on rotation motor to 150 DEG C of dynamic crystallizations, and motor rotary speed is within 5 days
40 revs/min).Crystallization terminate rear reactor be placed in cold water it is quick be down to room temperature after, suction filtration, and with 1L
Deionized water carries out cyclic washing, and gained is deposited in 110 DEG C of dryings 12 hours.Then horse in air atmosphere
Not it is calcined in stove, roasting process is：2 DEG C/min are warming up to 350 DEG C, constant temperature after 3 hours again with 1 DEG C/
Minute heating rate be warming up to 550 DEG C, and constant temperature 12 hours obtains the sheet staggeredly self supporting structure
Nano-ZSM-5 molecular sieve.
Embodiment 4：Operation is with embodiment 3, NaOH 0.4g, NaAlO20.874g, morpholine is changed into by piperazine
5.677g, unclassified stores addition is constant.XRD shows that gained sample is ZSM-5 molecular sieve.
Embodiment 5：Operation is with embodiment 4, NaOH 0.32g, NaAlO20.437g, morpholine 14.2g, its
His material addition is constant.XRD shows that gained sample is ZSM-5 molecular sieve
Embodiment 6：Operation is with embodiment 3, NaOH0.35g, NaAlO20.72g, three second are changed into by piperazine
Alkene diamines 25g, unclassified stores addition is constant, and crystallization temperature is changed into 155 DEG C.XRD shows, gained sample
Product are mainly ZSM-5, containing micro modenite.
Embodiment 7：Operation is with embodiment 6, NaOH 0.32g, NaAlO20.656g, deionized water 24g,
Triethylene diamine 20g, unclassified stores addition is constant, and crystallization temperature is changed into 160 DEG C, crystallization time 4 days.
XRD shows that gained sample is ZSM-5 molecular sieve.
Claims (8)
1. a kind of synthetic method of ZSM-5 molecular sieve, it is characterised in that：
With Ludox, sodium metaaluminate as silicon source and silicon source；Add piperazine, piperidines, triethylene diamine, morpholine
And one or more organic matters in Isosorbide-5-Nitrae-dioxane；
20-50 DEG C under agitation after the mixing of synthesis material Ludox, sodium metaaluminate, NaOH, water and organic matter
Gel 0.5-10 hours；
Raw material is transferred in the autoclave with tetrafluoroethene liner after gel, at 120-180 DEG C, moves
State crystallization 2-10 days；
After the completion of crystallization, be cooled to room temperature, filter and simultaneously washed with deionized water, gained sediment in drying,
Then it is calcined in Muffle furnace in air atmosphere, roasting process is：1-10 DEG C/min is warming up to from constant temperature
250-400 DEG C, during constant temperature 2-8 after be warming up to 450-650 DEG C with 0.2-5 DEG C/min of heating rate again, it is and permanent
It is warm 5-30 hours, obtain the sheet staggeredly self supporting structure nano-ZSM-5 molecular sieve.
2. according to the synthetic method described in claim 1, it is characterised in that：
The composition of synthesis material is：NaOH 0.15-1g, NaAlO20.1-1g, water 20-75g, Ludox 10-40g,
Organic matter 5-30g.
3. according to the synthetic method described in claim 1, it is characterised in that：The composition of optimum synthesis raw material is
NaOH 0.25-0.75g, NaAlO20.2-0.75g, water 30-60g, LUDOX AS-4015-30g, PEI 10-20
g。
4. according to the synthetic method described in claim 1,2 or 3, it is characterised in that：Described Ludox is
LUDOX AS-40。
5. according to the synthetic method described in claim 1, it is characterised in that：Need to enter under agitation after raw material mixing
Row gel, the gelatinization temperature of optimization is 25-40 DEG C；The gel time of optimization is 2-6 hours.
6. according to the synthetic method described in claim 1, it is characterised in that：The crystallization temperature of the optimization is
130-170℃；The crystallization time of the optimization is 3-8 days.
7. according to the synthetic method described in claim 1, it is characterised in that：Described dynamic crystallization method refers to
Crystallization is completed under shake state, and the mode of operation taken is that reactor is placed on rotation motor, and motor turns
Speed is 20-100 revs/min, and optimization rotating speed is 40-80 revs/min.
8. the ZSM-5 molecular sieve that a kind of any synthetic methods of claim 1-7 are obtained, it is characterised in that：
Described ZSM-5 molecular sieve has sheet staggeredly self supporting structure, lamellar spacing about 50-500nm；
The self supporting structure goes out cluster ZSM-5 sheets for ZSM-5 each vertical-growth of flat crystal upper and lower surface
Structure, forms size and is about 0.5-5 μm of lamella staggeredly self-supporting nanostructured.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902668A (en) * | 2017-11-20 | 2018-04-13 | 中国科学院山西煤炭化学研究所 | A kind of self-supporting film shape MFI molecular sieves and preparation method |
| CN111977666A (en) * | 2019-05-21 | 2020-11-24 | 中石化南京化工研究院有限公司 | Preparation method and application of ZSM-5 zeolite molecular sieve |
| CN112299442A (en) * | 2020-11-23 | 2021-02-02 | 中国科学院过程工程研究所 | Preparation method of ZSM-5 molecular sieve nanosheet based on bi-quaternary phosphonium ionic liquid |
| CN114804140A (en) * | 2021-01-22 | 2022-07-29 | 中国科学院大连化学物理研究所 | Synthesis method of mordenite molecular sieve with sheet-shaped staggered structure and molecular sieve |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902668A (en) * | 2017-11-20 | 2018-04-13 | 中国科学院山西煤炭化学研究所 | A kind of self-supporting film shape MFI molecular sieves and preparation method |
| CN107902668B (en) * | 2017-11-20 | 2019-09-10 | 中国科学院山西煤炭化学研究所 | A kind of self-supporting film shape MFI molecular sieve and preparation method |
| CN111977666A (en) * | 2019-05-21 | 2020-11-24 | 中石化南京化工研究院有限公司 | Preparation method and application of ZSM-5 zeolite molecular sieve |
| CN112299442A (en) * | 2020-11-23 | 2021-02-02 | 中国科学院过程工程研究所 | Preparation method of ZSM-5 molecular sieve nanosheet based on bi-quaternary phosphonium ionic liquid |
| CN112299442B (en) * | 2020-11-23 | 2022-07-12 | 中国科学院过程工程研究所 | Preparation method of ZSM-5 molecular sieve nanosheet based on bi-quaternary phosphonium ionic liquid |
| CN114804140A (en) * | 2021-01-22 | 2022-07-29 | 中国科学院大连化学物理研究所 | Synthesis method of mordenite molecular sieve with sheet-shaped staggered structure and molecular sieve |
| CN114804140B (en) * | 2021-01-22 | 2024-03-22 | 中国科学院大连化学物理研究所 | Synthesis method of mordenite molecular sieve with flaky staggered structure and molecular sieve |
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