CN109704360A - A kind of ZSM-35 and preparation method thereof of petal spherical shape looks - Google Patents
A kind of ZSM-35 and preparation method thereof of petal spherical shape looks Download PDFInfo
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- CN109704360A CN109704360A CN201910140571.8A CN201910140571A CN109704360A CN 109704360 A CN109704360 A CN 109704360A CN 201910140571 A CN201910140571 A CN 201910140571A CN 109704360 A CN109704360 A CN 109704360A
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Abstract
The present invention relates to a kind of method for preparing ZSM-35 molecular sieve, the ZSM-35 molecular sieve which obtains not only has unique pattern, can be used for wider array of catalytic applications；And synthesized using crystal seed, it greatly reduced the use of the template containing amine, greatly reduce pollution of the production process for environment.The present invention is using steps are as follows: step A: preparation SZR crystal seed: directed agents mol ratio: 1Al2O3: (10~50): SiO2: (1~20) KOH:(1~50) TEAOH:(50~3000) H2O, crystallization obtain SZR crystal seed；Step B: SZR crystal seed is added in silica-alumina gel, and crystallization obtains the spherical ZSM-35 molecular sieve of petal.
Description
Technical field
The invention belongs to silicon, the technical fields of aluminum oxide molecular sieve, and in particular to prepare petal ball to using SZR crystal seed
The ZSM-35. of pattern
Technical background
US4016245, the 1970s middle and later periods, U.S. Mobil company, which developed, a kind of has FER topological structure
It possesses the two-dimensional channel system of square crossing with molecular sieve, wherein be in parallel 0.42 with the ten-ring duct size in [001] face ×
0.54nm；The octatomic ring duct size for being parallel to [010] face is 0.35 × 0.48nm.ZSM-35 is widely used in the hydrocarbon conversion
In catalysis reaction, such as isomerization, polymerization, aromatisation and cracking catalysis reaction of linear alkene etc..
US4016245 is disclosed or pyrrolidines or ethylenediamine as template synthesize ZSM-35 molecular sieve.
US4795623 discloses a kind of side for preparing ZSM-35 molecular sieve and synthesizing ZSM-35 molecular sieve using piperidines as template
Method.
US4146584 disclose using butanediamine as template synthesize ZSM-35 molecular sieve, than using traditional ethylenediamine,
Pyrrolidine template agent prepares higher purity, the molecular sieve of more preferable performance.
US4795623, which is disclosed, synthesizes ZSM-35 molecular sieve by template of piperidines.
US5174980 discloses 4- aminocyclohexanol as template and synthesizes ZSM-35 molecular sieve.
US5190736 discloses Isosorbide-5-Nitrae-cyclohexanediamine as template and synthesizes ZSM-35 molecular sieve.
US5288475 discloses Isosorbide-5-Nitrae-lupetazin as template and synthesizes ZSM-35 molecular sieve.
In conclusion most of the Zeolite synthesis of early stage has using organic formwork agent, a large amount of organic formwork is used
Agent causes the waste of cost first, secondly also can cause environmental pollution.
Summary of the invention
The present invention provides the molecular sieve of the ZSM-35 of petal spherical shape looks using the preparation of SZR crystal seed a kind of, such hairs
The bright use substantially reduced in conventional molecular sieve synthesis for organic formwork agent, while the cost of synthesis can be made to subtract significantly
It is few, reduce the discharge of amine template in waste water.
The present invention provides a kind of spherical ZSM-35 molecular sieve of petal the preparation method is as follows:
(1) by silicon source, silicon source, alkali source, template and water mixing crystallization prepare SZR crystal seed, wherein silicon source: silicon source: alkali source:
Template: the mol ratio of water are as follows: 1:(10~50): (1~20): (1~50): (50~3000) are 130 in crystallization temperature
It is reacted at DEG C -170 DEG C, while crystallization time is 2 days -5 days, is prepared into SZR crystal seed.
(2) by silicon source, silicon source, alkali source and water mixing, prepare silica-alumina gel, wherein silicon source: silicon source: alkali source: water mole is matched
Than are as follows: 1:(10~60): (1~20): (50~3000).
(3) the SZR crystal seed of step (1) preparation sial is added to the ratio of silica-alumina gel weight ratio 1%~20% to coagulate
Glue, the crystallization at 130 DEG C -170 DEG C, crystallization time are 3 days -8 days；For gained sample by washing, 120 DEG C of dryings are final to obtain
To ZSM-35 molecular sieve.
Preferably, silicon source are as follows: one of aluminium powder, boehmite, aluminium hydroxide, aluminium isopropoxide, aluminum nitrate, aluminum sulfate
Or arbitrary proportion mixing；Silicon source are as follows: one of silica solution, waterglass, white carbon black or arbitrary proportion mixing；Alkali source are as follows:
KOH；Template are as follows: one of tetraethyl ammonium hydroxide, ethylenediamine, ring amine or arbitrary proportion mixing.
Preferably, crystallization temperature is 130 DEG C -170 DEG C in step (1), and crystallization time is 2 days -5 days.
Preferably, SZR crystal seed amount is the 5%~10% of silica-alumina gel quality in step (3).
Preferably, crystallization temperature is 130 DEG C -170 DEG C in step (3), and crystallization time is 3 days -8 days.Gained sample is logical
Cross washing, 120 DEG C of dryings.
It is highly preferred that the mol ratio of step (1): Al2O3:SiO2: KOH:TEAOH:H2O is 1:(10~50): (1~
20): (1~50): (50~3000).
It is highly preferred that the silica-alumina gel mol ratio of step (2) are as follows: Al2O3:SiO2: KOH:H2O is 1:(10~60): (1
~20): (50~3000).
Detailed description of the invention:
Fig. 1 is the XRD spectra of 1 synthetic sample of embodiment.
Fig. 2 is the XRD spectra of 5 synthetic sample of embodiment.
Fig. 3 is the scanning electron microscope (SEM) photograph of 5 synthetic sample of embodiment.
Implementation method of the invention:
Embodiment 1 (synthesis SZR crystal seed)
37.24g deionized water wiring solution-forming A is added in 3.71g aluminium isopropoxide and 4.69gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.28.66g silica solution (40%), 9.85g tetraethyl ammonium hydroxide are added 20g deionized water and be mixed
It is formed uniformly solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is transferred to
In 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample is by washing
It washs, 120 DEG C of dryings, obtains SZR crystal seed, attached drawing 1 gives the XRD spectra of sample obtained by this example.
Primogel mole composition: 21.2SiO2:Al2O3:7.9KOH:2.6TEAOH:498H2O
Embodiment 2 (synthesis SZR crystal seed)
36.77g deionized water wiring solution-forming A is added in 1.39g boehmite and 4.69gKOH (85%), stirs 0.5h
It is completely dissolved silicon source.The mixing of 20g deionized water is added in 28.66g silica solution (40%), 9.85g tetraethyl ammonium hydroxide to stir
It mixes and is formed uniformly solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is transferred to
In 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample is by washing
It washs, 120 DEG C of dryings, obtains SZR crystal seed, the XRD spectra of sample obtained by this example is the same as attached drawing 1.
Primogel mole composition: 21.2SiO2:Al2O3:7.9KOH:2.6TEAOH:498H2O
Embodiment 3 (synthesis SZR crystal seed)
27.69g deionized water wiring solution-forming A is added in 3.71g aluminium isopropoxide and 4.69gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.38.21g silica solution (30%), 9.85g tetraethyl ammonium hydroxide are added 20g deionized water and be mixed
It is formed uniformly solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is transferred to
In 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample is by washing
It washs, 120 DEG C of dryings, obtains SZR crystal seed, the XRD spectra of sample obtained by this example is the same as attached drawing 1.
Primogel mole composition: 21.2SiO2:Al2O3:7.9KOH:2.6TEAOH:498H2O
Embodiment 4 (synthesis SZR crystal seed)
37.96g deionized water wiring solution-forming A is added in 2.48g aluminium isopropoxide and 5.82gKOH (85%), stirring 0.5h makes
Silicon source is completely dissolved.30.01g silica solution (40%), 2.19g ethylenediamine, 6.01g cyclohexylamine are added 30g deionized water and mixed
It stirs evenly to form solution B.Then 1h is mixed in solution A and B solution, forms white gels.The gel of formation is shifted
Into 170ml ptfe autoclave, dynamically rotated with the revolving speed of 20r/min, in 150 DEG C crystallization 4 days.Gained sample passes through
Washing, 120 DEG C of dryings obtain SZR crystal seed, and the XRD spectra of sample obtained by this example is the same as attached drawing 1.
Primogel mole composition: 33.3SiO2:Al2O3:14.7KOH:6EDA:10CHA:798H2O
Embodiment 5 (prepares ZSM-35 molecular sieve)
38.16g deionized water is added in 2.48g aluminium isopropoxide and 3.13gKOH (85%), stirring 0.5h keeps silicon source complete
Dissolution adds the crystal seed 5g of 19.11g silica solution (40%) and [embodiment 1] preparation, is mixed evenly to form white coagulate
Glue.The gel of formation is transferred in 100ml ptfe autoclave, is dynamically rotated with the revolving speed of 20r/min, in 150 DEG C
Crystallization 6 days.Gained sample is obtained ZSM-35 molecular sieve, and is analyzed by X-ray fluorescence spectra by washing, 120 DEG C of dryings
It is 16.4 that instrument, which measures Si/Al, and attached drawing 2 gives the XRD spectra of sample obtained by this example, and the SEM figure of sample obtained by this example is
Attached drawing 3.
Embodiment 6 (prepares ZSM-35 molecular sieve)
38.16g deionized water is added in 2.48g aluminium isopropoxide and 3.13gKOH (85%), stirring 0.5h keeps silicon source complete
Dissolution adds the crystal seed 5g of 19.11g silica solution (40%) and [embodiment 2] preparation, is mixed evenly to form white coagulate
Glue.The gel of formation is transferred in 100ml ptfe autoclave, is dynamically rotated with the revolving speed of 20r/min, in 150 DEG C
Crystallization 6 days.Gained sample is obtained ZSM-35 molecular sieve, and is analyzed by X-ray fluorescence spectra by washing, 120 DEG C of dryings
It is 10.2 that instrument, which measures Si/Al, and discovery crystallization degree is not so good.The XRD spectra of sample obtained by this example is such as attached drawing 2.
Embodiment 7 (prepares ZSM-35 molecular sieve)
It repeats embodiment 6 and changes aluminium isopropoxide into 1.23g boehmite, measured by X-ray fluorescence spectrometer
Si/Al is 14.8.
Embodiment 8 (prepares ZSM-35 molecular sieve)
Embodiment 5 is repeated, the crystal seed of addition changes into what [embodiment 3] be prepared, and it is that 8g is penetrated by X that grain weight, which is added,
It is 17.0 that line fluorescence spectrum analyzer, which measures Si/Al,.
Embodiment 9 (prepares ZSM-35 molecular sieve)
Embodiment 5 is repeated, the crystal seed of addition changes into what [embodiment 4] be prepared, and it is that 8g is penetrated by X that grain weight, which is added,
It is 12.5 that line fluorescence spectrum analyzer, which measures Si/Al,.
Embodiment 10 (prepares ZSM-35 molecular sieve)
Embodiment 5 is repeated, changing crystallization time is 5 days, and 160 DEG C of crystallization temperature, obtained result and example 5 be not poor
Not.
Claims (8)
1. a kind of ZSM-35 molecular sieve synthesis step of petal spherical shape looks, comprising the following steps:
(1) by silicon source, silicon source, alkali source, template and water mixing crystallization prepare SZR crystal seed, wherein silicon source: silicon source: alkali source: template
Agent: the mol ratio of water are as follows: 1:(10~50): (1~20): (1~50): (50~3000), crystallization temperature be 130 DEG C-
It is reacted at 170 DEG C, while crystallization time is 2 days -5 days, is prepared into SZR crystal seed；
(2) by silicon source, silicon source, alkali source and water mixing, silica-alumina gel is prepared, wherein silicon source: silicon source: alkali source: water mol ratio are as follows:
1:(10~60): (1~20): (50~3000)；
(3) SZR crystal seed prepared by step (1) is added to silica-alumina gel with the ratio of silica-alumina gel weight ratio 1%~20%,
Crystallization at 130 DEG C -170 DEG C, crystallization time are 3 days -8 days；Gained sample finally obtains ZSM- by washing, 120 DEG C of dryings
35 molecular sieves.
2. synthesis step described in claim 1, it is characterised in that: silicon source are as follows: aluminium powder, boehmite, aluminium hydroxide, isopropyl
One of aluminium alcoholates, aluminum nitrate, aluminum sulfate or arbitrary proportion mixing；Silicon source are as follows: silica solution, waterglass, one in white carbon black
Kind or arbitrary proportion mixing；Alkali source are as follows: KOH；Template are as follows: one of tetraethyl ammonium hydroxide, ethylenediamine, ring amine or
The mixing of person's arbitrary proportion.
3. synthesis step of any of claims 1 or 2, it is characterised in that: crystallization temperature is 130 DEG C -170 DEG C in step (1),
Crystallization time is 2 days -5 days.
4. synthesis step of any of claims 1 or 2, it is characterised in that: SZR crystal seed amount is silica-alumina gel quality in step (3)
5%~10%.
5. synthesis step described in claim 1 or 3, it is characterised in that: crystallization temperature is 130 DEG C -170 DEG C in step (3),
Crystallization time is 3 days -8 days.Gained sample passes through washing, 120 DEG C of dryings.
6. synthesis step of any of claims 1 or 2, it is characterised in that: the mol ratio of step (1): Al2O3:SiO2: KOH:
TEAOH:H2O is 1:(10~50): (1~20): (1~50): (50~3000).
7. synthesis step of any of claims 1 or 2, it is characterised in that: the silica-alumina gel mol ratio of step (2) are as follows: Al2O3:
SiO2: KOH:H2O is 1:(10~60): (1~20): (50~3000).
8. a kind of ZSM-35 molecular sieve that petal is spherical, it is characterised in that: synthesized using any the method for claim 1-7
It arrives.
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| CN102249257A (en) * | 2011-05-13 | 2011-11-23 | 大连理工大学 | Method for recycling crystallization mother liquor from SUZ-4 molecular sieve production for producing SUZ-4 molecular sieve |
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