CN1205122C - Process for synthesizing ZSM-5 molecular sieve - Google Patents
Process for synthesizing ZSM-5 molecular sieve Download PDFInfo
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- CN1205122C CN1205122C CN 02153377 CN02153377A CN1205122C CN 1205122 C CN1205122 C CN 1205122C CN 02153377 CN02153377 CN 02153377 CN 02153377 A CN02153377 A CN 02153377A CN 1205122 C CN1205122 C CN 1205122C
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Abstract
The present invention discloses a method for synthesizing ZSM-5. The present invention is characterized in that diatomite is used as silicon sources, whole or partial aluminum sources are mixed with other aluminum sources, NaOH and water, 0 to 10 weight% of molecular sieves are added to be used as crystal seeds, reaction mixture slurry with the mole proportion of 20 to 80 of SiO2/Al2O3, 0.05 to 0.20 of Na2 O/SiO2 and 4 to 30 of H2 O/SiO2 is prepared, and hydrothermal crystallization is carried out according to conventional conditions. The method has the advantages of reduced generation of gelatin, enhanced solid content and reduced cost.
Description
Technical field
The invention relates to a kind of method of synthetic ZSM-5 molecular sieve.
Background technology
The ZSM-5 molecular sieve belongs to high silicon five-element circular type (Pentasil) zeolite, at first succeeds in developing (USP3702886) by Mobil company.Because pore passage structure and excellent heat and hydrothermal stability that it has higher silica alumina ratio, uniqueness are widely used in numerous chemical processes and other field.The synthetic method of ZSM-5 molecular sieve is also made organic method of template by the employing organic ammonium of classics, it is synthetic to develop into no ammonium method.The silicon source of mainly using when synthetic is mainly water glass and solid silicone.When being raw material with water glass, because of gelation process is arranged into, must add big yield and guarantee heat and mass, reduced the long-pending production efficiency of unit kettle; And be though that raw material can reduce water silicon ratio with the solid silicone, the silica gel price is more expensive, has increased the production cost of molecular sieve.
Summary of the invention
The purpose of this invention is to provide a kind of minimizing gel and generate, improve solid content, the method for the synthetic ZSM-5 molecular sieve that reduces cost.
Diatomite is natural mineral, generally is to be formed by the dead later silicate remains of the unicellular algae that is referred to as diatom, does not contain quartz or only contains a spot of quartzy impurity, mainly by unformed SiO
2Form, and contain a spot of Fe
2O
3, Al
2O
3, CaO, MgO, Na
2O, K
2O and organic impurity.Its igloss is between 30～85%, and appearance luster is white in color or oyster white or yellow or brown or grey or greyish-green.
ZSM-5 molecular sieve synthetic method provided by the present invention, be with the aluminium source of diatomite as silicon source and part, mix with aluminium source and NaOH and water, adding is selected from one or more mixture in faujusite (X type or y-type zeolite), A type zeolite, β zeolite or the ZSM-5 zeolite as crystal seed in the heavy %'s of diatomite butt 0～10, and making mole proportioning is SiO
2/ Al
2O
3=20～80, Na
2O/SiO
2=0.05～0.20, H
2O/SiO
2=4～30, preferred SiO
2/ Al
2O
3=30～55, Na
2O/SiO
2=0.07～0.12, H
2O/SiO
2=5～15 reaction mixture slurry forms through hydrothermal crystallizing.
In synthetic method provided by the invention, though natural diatomaceous earth can use without anticipating also, but we preferably will and be broken into and be narrower than 40 purpose particles through screening, more preferably again with this particle more than 90 ℃, the acid solution except hydrofluoric acid is handled the smart soil particle that obtains.
In the method provided by the invention, said aluminium source is the used aluminium commonly used source of synthesis of molecular sieve, as aluminum oxide, aluminium hydroxide, aluminium colloidal sol, sodium metaaluminate etc.
In the method provided by the invention, said amount of seed is in 0～10 weight % of diatomite butt, and said crystal seed is selected from one or more the mixture in faujusite (X type or y-type zeolite), A type zeolite, β zeolite or the ZSM-5 zeolite.
In the method provided by the invention, said hydrothermal crystallizing is meant reaction mixture slurry in pressurized vessel, thermostatic crystallization or variable temperature crystallization.Wherein, the condition of said thermostatic crystallization is 120～220 ℃ of following crystallization 8 hours to 6 days; The condition of said variable temperature crystallization is 80～140 ℃ of following crystallization 0.5 hour to 2 days, again 140～220 ℃ of following crystallization 4 hours to 6 days, preferably 100～130 ℃ of following crystallization 2 hours to 10 hours, again 160～200 ℃ of following crystallization 6 hours to 3 days.
After molecular sieve is synthetic, generally also will be through overcooling, filtration, washing, oven dry to obtain the molecular sieve finished product.
The synthetic method of ZSM-5 molecular sieve provided by the invention has following characteristics:
(1) diatomite that use cost is cheap has been developed new approach as silicon source and aluminium source for diatomaceous utilization, has also reduced raw materials cost.
(2) in building-up process, the diatomaceous nucleation crystallization that depolymerizes to glue and molecular sieve is progressively to take place simultaneously, can not produce a large amount of gels, stirs difficulty, the drawback that the mass-and heat-transfer effect is bad thereby avoided ordinary method because the appearance of a large amount of gels makes.
(3) remove to dilute gel owing to need not a large amount of water, the water silicon ratio that feeds intake in synthetic system can significantly reduce, in general, and in the prior art, when being the silicon source with water glass, the water silicon that feeds intake ratio is usually greater than 20, and in the method provided by the invention, the water silicon ratio that feeds intake can be reduced to 5～15, like this, because the reduction of the water yield can improve single still molecular sieve output greatly, reduces production costs.
Description of drawings
Accompanying drawing is the X-ray diffraction spectrogram of embodiment 1 synthetic molecular sieve.
Embodiment
In an embodiment, said relative crystallinity be with product and standard specimen separately the ratio of the peak height sum of five characteristic diffraction peaks of 2 θ between 22.5～25.0 of X-ray powder diffraction (XRD) represent with percentage ratio.The standard specimen that adopts is the ZSM-5 Industrial products that dying of Shanghai seven factories produce, and its degree of crystallinity is decided to be 100%.
Diatomaceous chemical constitution adopts the X-fluorescence spectrometry.
The molecular sieve specific surface adopts the BET method to measure.
Embodiment 1
Diatomite original soil is that produce the Changbai, is crushed to and is narrower than 40 orders, and igloss is 16.6%, and its weight percent composition sees Table 1.
Table 1
| SiO 2 | Al 2O 3 | Na 2O | K 2O | MgO | CaO | Fe 2O 3 |
| 94 | 1.7 | 0.13 | 0.62 | 0.19 | 0.36 | 1.4 |
With NaOH, high alkali deflection aluminium acid sodium (consists of Al
2O
3=44.4g/l, Na
2O=291.8g/l), NaY (Qilu Petrochemical company catalyst plant is produced) adds in the entry, stirs.Add above-mentioned diatomite original soil, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.1, H
2O/SiO
2=10, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.Cooled and filtered, washing, oven dry, the X-ray diffraction spectrogram of gained sample is shown in the accompanying drawing, illustrates that it is the ZSM-5 molecular sieve, degree of crystallinity 86%.Specific surface 332m
2/ g.
Embodiment 2
Diatomite original soil among the embodiment 1 was handled 6 hours at 90 ℃ with 30% sulfuric acid, filtration, washing, oven dry, this diatomite is hereinafter to be referred as smart soil, and igloss is 8.2%, and the weight percent composition sees Table 2:
Table 2
| SiO 2 | Al 2O 3 | Na 2O | K 2O | MgO | CaO | Fe 2O 3 |
| 96 | 1.2 | 0.11 | 0.60 | 0.17 | 0.22 | 0.9 |
Other conditions are identical with embodiment 1, and gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 94%.
Embodiment 3
With NaOH, high alkali deflection aluminium acid sodium adds in the entry, stirs.Add smart soil, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.1, H
2O/SiO
2=10 system continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.Cooled and filtered, washing, oven dry, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 54%.
Embodiment 4
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.1, H
2O/SiO
2=10, the system of NaY/ diatomite=0.10 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 92%.
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, be configured to molar fraction SiO
2/ Al
2O
3=25, Na
2O/SiO
2=0.1, H
2O/SiO
2=10, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 110 ℃ in pressurized vessel, constant temperature 2 hours is warming up to 200 ℃ again, constant temperature 6 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 62%.
Embodiment 6
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=50, Na
2O/SiO
2=0.1, H
2O/SiO
2=10, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 77%.
Embodiment 7
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.07, H
2O/SiO
2=10, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 130 ℃ in pressurized vessel, constant temperature 6 hours is warming up to 170 ℃ again, constant temperature 48 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 54%.
Embodiment 8
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.15, H
2O/SiO
2=10, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 51%.
Embodiment 9
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.1, H
2O/SiO
2=8, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 72%.
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart soil of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.1, H
2O/SiO
2=15, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, and degree of crystallinity is 51%.
Embodiment 11
With NaOH, (the Qilu Petrochemical catalyst plant produces pseudo-boehmite, Al
2O
3=64.5%) add in the entry, stir, add diatomaceous original soil, being configured to molar fraction is SiO
2/ Al
2O
3=40, Na
2O/SiO
2=0.1, H
2O/SiO
2=15, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.In pressurized vessel, stir crystallization and be warming up to 180 ℃, constant temperature 18 hours.The cooled and filtered washing and drying, gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 55%.
Embodiment 12
With NaOH, high alkali deflection aluminium acid sodium, NaY add in the entry, stir.Add the smart earth sample (composition sees Table 3) of diatomite, being configured to molar fraction is SiO
2/ Al
2O
3=39.5, Na
2O/SiO
2=0.1, H
2O/SiO
2=10, the system of NaY/ diatomite=0.05 (weight fraction) continues to stir.Stir crystallization and be warming up to 120 ℃ in pressurized vessel, constant temperature 4 hours is warming up to 180 ℃ again, constant temperature 16 hours.Cooled and filtered washing and drying gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 84%.
Table 3
| Na 2O | MgO | Al 2O 3 | SiO 2 | P 2O 5 | SO 3 | K 2O | CaO | Fe 2O 3 | Cl |
| 0.088 | 0.24 | 4.0 | 93 | 0.014 | 0.10 | 0.58 | 0.38 | 1.2 | 0.085 |
Embodiment 13
Change the crystallization intensification condition among the embodiment 2 into stirring and be warming up to 110 ℃, constant temperature 2 hours is warming up to 190 ℃ again, constant temperature 48 hours, and other conditions are identical.Gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 67%.
Embodiment 14
NaY among the embodiment 2 is substituted with NaA (Zhengzhou Aluminium Plant produces, igloss 12%) and Na type ZSM-5 (Chang Ling petrochemical industry catalyst plant produces, igloss 10%), and consumption is respectively NaY/ diatomite=0.025 and Na-ZSM-5/ diatomite=0.025, and other conditions are identical.Gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 86%.
Change the stirring crystallization among the embodiment 2 into static crystallization, other conditions are identical.Gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 31%.
Embodiment 16
NaY among the embodiment 2 is substituted with NaA (Zhengzhou Aluminium Plant produces, igloss 12%), and other conditions are identical.Gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 80%.
Embodiment 17
NaY among the embodiment 2 is substituted with Na type ZSM-5 (Chang Ling petrochemical industry catalyst plant produces, igloss 10%), and other conditions are identical.Gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 85%.
Embodiment 18
NaY among the embodiment 2 is substituted with Na type beta-molecular sieve (Fushun No.3 Petroleum Factory produces, igloss 12%), and other conditions are identical.Gained sample x-ray diffraction spectrogram has the accompanying drawing feature, is the ZSM-5 molecular sieve, degree of crystallinity 77%.
Claims (8)
1, a kind of method of synthetic ZSM-5 molecular sieve, it is characterized in that this method is that diatomite is mixed with aluminium source, NaOH and water as silicon source and part aluminium source, as crystal seed, making mole proportioning is SiO in one or more the mixture in the A type that is selected from, X type, Y type, β and the ZSM-5 zeolite of the heavy % of diatomite butt 0～10 in adding
2/ Al
2O
3=20～80, Na
2O/SiO
2=0.05～0.20, H
2O/SiO
2=4～30 reaction mixture slurry is carried out hydrothermal crystallizing.
2, in accordance with the method for claim 1, wherein said reaction mixture slurry has SiO
2/ Al
2O
3=30～55, Na
2O/SiO
2=0.07～0.12, H
2O/SiO
2=5～15 mole proportioning.
3, in accordance with the method for claim 1, wherein said aluminium source is selected from aluminium colloidal sol, sodium metaaluminate, aluminum oxide or aluminium hydroxide.
4, in accordance with the method for claim 1, wherein said diatomite is natural diatomaceous earth original soil or native through the essence of acid elution processing.
5, in accordance with the method for claim 1, said hydrothermal crystallizing be with reaction mixture slurry in pressurized vessel, thermostatic crystallization or variable temperature crystallization.
6, in accordance with the method for claim 5, said thermostatic crystallization, its condition is 120～220 ℃ of following crystallization 8 hours to 6 days.
7, in accordance with the method for claim 5, said variable temperature crystallization, its condition is 80～140 ℃ of following crystallization 0.5 hour to 2 days, again 140～220 ℃ of following crystallization 4 hours to 6 days.
8, according to the said method of claim 7, wherein said variable temperature crystallization condition is 100～130 ℃ of following crystallization 2 hours to 10 hours, again 160～200 ℃ of following crystallization 6 hours to 3 days.
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|---|---|---|---|
| CN 02153377 CN1205122C (en) | 2002-11-29 | 2002-11-29 | Process for synthesizing ZSM-5 molecular sieve |
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|---|---|---|---|
| CN 02153377 CN1205122C (en) | 2002-11-29 | 2002-11-29 | Process for synthesizing ZSM-5 molecular sieve |
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| CN1504410A CN1504410A (en) | 2004-06-16 |
| CN1205122C true CN1205122C (en) | 2005-06-08 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384735C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain without bonding agent |
| CN100389067C (en) * | 2005-12-30 | 2008-05-21 | 中国石油大学(北京) | ZSM-5 type molecular sieve and method for preparing the same |
| CN101462740B (en) * | 2007-12-20 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite by in situ crystallization |
| CN101462741B (en) * | 2007-12-20 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite by in situ crystallization |
| JP5351216B2 (en) * | 2010-07-01 | 2013-11-27 | 日本化学工業株式会社 | Method for producing zeolite |
| CN102963908B (en) * | 2012-11-29 | 2015-02-18 | 中国科学院过程工程研究所 | Method for preparing ZSM-5 molecular sieve without template agent |
| CN104150505A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Method for preparing nano ZSM-5 zeolite by taking diatomite as raw material |
| CN104709922B (en) * | 2013-12-12 | 2017-11-24 | 中国石油天然气集团公司 | A kind of molecular sieves of mesoporous ZSM 5 and preparation method thereof |
| CN105084390A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparation of spherical ZSM-5 zeolite from diatomite |
| CN104016370A (en) * | 2014-06-05 | 2014-09-03 | 诺威尔（天津）能源装备股份有限公司 | Method for preparing 5A molecular sieve from diatomite |
| CN105731492A (en) * | 2016-01-28 | 2016-07-06 | 中国石油大学(华东) | Low-cost green method for synthesizing Fe-ZSM-5 molecular sieve |
| CN106185977B (en) * | 2016-06-30 | 2018-11-27 | 福州大学 | A kind of method of green syt ZSM-5 molecular sieve |
| CN106829998A (en) * | 2017-01-06 | 2017-06-13 | 鲁西催化剂有限公司 | A kind of preparation method of zeolite molecular sieve crystal seed |
-
2002
- 2002-11-29 CN CN 02153377 patent/CN1205122C/en not_active Expired - Lifetime
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| CN1504410A (en) | 2004-06-16 |
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