CN105621447B - A kind of method of synthesis NaY type molecular sieves - Google Patents
A kind of method of synthesis NaY type molecular sieves Download PDFInfo
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Abstract
The invention discloses a kind of method of synthesis NaY type molecular sieves, including following content：（1）Sodium hydroxide, silicon source, waterglass and water are well mixed, is aged, obtains directed agents；（2）Kaolin starting material is subjected to the modified kaolin that hydro-thermal process is obtained；（3）By step（1）Obtain directed agents, step（2）Obtained modified kaolin, sodium hydroxide, water and waterglass is well mixed, and obtains gel rubber system, then through low temperature crystallized, high temperature crystallization, cooling, separation of solid and liquid and drying, obtains NaY type molecular sieves.This method is using the kaolin of hydrothermal modification as raw material, and building-up process is simple, and product crystallinity is high and the features such as good hydrothermally stable.
Description
Technical field
The invention belongs to Zeolite synthesis field, a kind of method of synthesis NaY type molecular sieves is related in particular to.
Background technology
The method for generally preparing NaY type molecular sieves is using alkaline silica-alumina gel system synthesis.The raw material typically used for
Sodium hydroxide, waterglass, water, aluminum sulfate and sodium metaaluminate, are eventually adding a certain amount of directed agents, the NaY types point so synthesized
Sub- sifter device has the characteristics of molecular sieve content is high, silica alumina ratio is high, using different method of modifying, can make modified NaY type molecules
Sifter device has a variety of reaction characteristicses.
Kaolin in-situ synthetic method is the standby important method of NaY type system with molecular sieve for preparing.USP3506594, USP3503900,
The method that USP3647718 prepares active constituent and the in-situ crystallization zeolite of matrix simultaneously by raw material of kaolin, uses in-situ crystallization
The FCC catalyst that method is obtained is referred to as kaolin type catalyst, also known as full clay catalyst.The Y type molecules synthesized with gel method
Sieve as active component, the FCC catalyst prepared using semi-synthesizing technology is compared, and full clay catalyst has preventing from heavy metal pollution energy
Power is strong, and activity index is high, and the advantages of hydrothermal stability, structural stability are good has the disadvantage the adjustable denaturation of active component and matrix
Be not as flexible as semi-synthesis method.
When early stage synthesizes NaY type molecular sieves with kaolin, typically using metakaolin (hereinafter referred to as partially native) microballoon.
UK1271450 is described is fired into metakaolin by kaolin below 704 DEG C, then with the reaction synthesis NaY types point such as sodium metasilicate
Son sieve；USP3377006 discloses one kind with special thin partially native powder to synthesize NaY type molecular sieves.
USP3367886, USP3367887, USP3506594, USP3647718, USP3657154, USP3663165,
USP3932268 etc. uses NaY in the in-situ crystallization product of 900 DEG C of high temperature above roasting kaolins (hereinafter referred to as high soil) preparations
The silica alumina ratio of type molecular sieve is higher, but crystallinity is general between 20%-30%.
USP4493902 discloses one kind in same microballoon simultaneously containing soil partially, high soil and crystal seed synthesis high zeolite content
The method of crystallization product, crystallization product crystallinity is higher than 40%, but this method is very high to the ingredient requirement used in spray shaping, makes
With the high soil of fine and fine original soil ASP ~ 600, this ultra-fine soil is expensive, and in the market is difficult purchase.
In the above method, the synthesis of NaY type molecular sieves be all in kaolin spray shaping, as what is carried out after microballoon,
The NaY type molecular sieve crystallinities of preparation are low, modulation very flexible.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of method of synthesis NaY type molecular sieves, and this method is changed with hydro-thermal
Property kaolin be raw material, building-up process is simple, and product crystallinity is high and the features such as good hydrothermally stable.
The method of the synthesis NaY type molecular sieves of the present invention, including following content：（1）By sodium hydroxide, silicon source, waterglass
Well mixed with water, ageing obtains directed agents；（2）Kaolin starting material is subjected to the modified kaolin that hydro-thermal process is obtained；（3）
By step（1）Obtain directed agents, step（2）Obtained modified kaolin, sodium hydroxide, water and waterglass is well mixed, and is obtained
Gel rubber system, then through low temperature crystallized, high temperature crystallization, cooling, separation of solid and liquid and drying obtain NaY type molecular sieves.
In the inventive method, step（1）Described silicon source is one kind in aluminium chloride, aluminum sulfate, aluminum nitrate or sodium aluminate
Or several, preferred sodium aluminate.
In the inventive method, step（1）The mol ratio that described material is counted using following material is Na2O: Al2O3:SiO2:
H2O=15~20:1:15~22:300~400。
In the inventive method, step（1）Described aging condition is：Aging Temperature be 50 ~ 110 DEG C, preferably 60 ~ 110 DEG C,
Digestion time is 1 ~ 24 hour, preferably 2 ~ 12 hours.
In the inventive method, step（2）Described hydrothermal conditions are：Hydro-thermal process temperature is 500 ~ 850 DEG C, preferably
600 ~ 800 DEG C, hydrothermal conditions be 1 ~ 8 hour, preferably 2 ~ 6 hours, hydro-thermal process pressure be 0 ~ 0.5MPa, preferably 0.05 ~
0.3MPa；Above-mentioned hydrothermal treatment process is carried out preferably under the conditions of water filling, wherein water injection rate be 20 ~ 800ml/h, preferably 50 ~
600ml/h。
In the inventive method, step（2）Described kaolin starting material is commercially available prod, with following property：Silica alumina ratio（Institute
The silica alumina ratio stated is the mol ratio of silica and aluminum oxide, similarly hereinafter）For 1.8 ~ 2.6, preferably 2.1 ~ 2.4；Potassium oxide and sodium oxide molybdena
Total content is less than 0.8wt%, preferably smaller than 0.6 wt%.
In the inventive method, step（3）Mol ratio of each material in terms of following material is in gel rubber system（Do not include wherein
The modified kaolin and directed agents of addition）： NaOH: SiO2:H2O=14~17: 8~18:450 ~ 700, preferably NaOH:SiO2:
H2O=14.5~16.5:10~16:480~680。
In the inventive method, step（3）The quality of the modified kaolin of middle addition account for the 2wt% of gel rubber system gross mass ~
14wt%, preferably 4wt% ~ 12wt%.
In the inventive method, step（3）The quality of the directed agents of middle addition accounts for 1wt% ~ 10wt% of gel rubber system gross mass,
It is preferred that 3wt% ~ 8wt%.
In the inventive method, step（3）Described low temperature crystallized condition is：Crystallization temperature is 50 ~ 80 DEG C, preferably 60 ~ 70
DEG C, crystallization time is 4 ~ 24 hours, preferably 8 ~ 12 hours.
In the inventive method, step（3）Described high temperature crystallization condition is：Crystallization temperature be 85 ~ 120 DEG C, preferably 90 ~
110 DEG C, crystallization time is 12 ~ 72 hours, preferably 24 ~ 60 hours.
In the inventive method, step（3）Described drying temperature is 80 ~ 100 DEG C, and drying time is 8 ~ 16 hours.
The inventive method to kaolin by carrying out hydro-thermal process modification, the then height using modified kaolin fabricated in situ
The NaY type molecular sieves of crystallinity.Kaolinic hydrothermal treatment process is by the kaolin component in protokaolin in the inventive method
In silica and the connecting key of aluminum oxide completely open, kaolin is fully converted to unformed silica and aluminum oxide,
NaY type molecular sieves for synthesis high-crystallinity lay the foundation.The method that tradition passes through high-temperature roasting active oxidation silicon and aluminum oxide
The chemical bond for aoxidizing sial can not completely be opened, make the molecular sieve defect of preparation more, in molecular sieve modified process reclaimed water
Stability is not high in heat treatment process.The NaY prepared relative to traditional method, the present invention using the kaolin after hydro-thermal process
The characteristics of type molecular sieve has crystallinity height and good hydrothermal stability.
Brief description of the drawings
Fig. 1 is the XRD diffraction spectrograms of the sintetics of the embodiment of the present invention 6.
Embodiment
The preparation process of the present invention is further illustrated with reference to embodiment, but and is not so limited the present invention.
Embodiment 1
By 500g kaolin, incubation water heating handles 3h under the conditions of 600 DEG C, and hydro-thermal process pressure is 0.3MPa, and water injection rate is
100ml/h, obtains modified kaolin 1.Kaolinic silica alumina ratio is 2.2, and potassium oxide is 0.58 wt% with sodium oxide molybdena total content.
Embodiment 2
By 500g kaolin, incubation water heating handles 2h under the conditions of 650 DEG C, and hydro-thermal process pressure is 0.1MPa, is modified
Kaolin 2.Kaolinic silica alumina ratio is 2.3, and potassium oxide is 0.52 wt% with sodium oxide molybdena total content.
Embodiment 3
By 500g kaolin, incubation water heating handles 5h under the conditions of 700 DEG C, and hydro-thermal process pressure is 0.2MPa, and water injection rate is
400ml/h, obtains modified kaolin 3.Kaolinic silica alumina ratio is 2.1, and potassium oxide is 0.56 wt% with sodium oxide molybdena total content.
Embodiment 4
By 500g kaolin, incubation water heating handles 4h under the conditions of 750 DEG C, and hydro-thermal process pressure is 0.2MPa, and water injection rate is
300ml/h, obtains modified kaolin 4.Kaolinic silica alumina ratio is 2.3, and potassium oxide is 0.50wt% with sodium oxide molybdena total content.
Embodiment 5
（1）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=18:1:16:360, under stirring,
Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker formation mixed liquor, is then aged 2 days at 35 DEG C, is made and leads
To agent.
（2）Under conditions of stirring, by modified kaolin 1, sodium hydroxide, water, waterglass and step（1）It is obtained to be oriented to
Agent, which is added in beaker, forms gel rubber system, by first thermostatic crystallization 12 hours under the conditions of 60 DEG C of gel, then in 95 DEG C of conditions
Lower thermostatic crystallization 60 hours, then through cooling, washing, suction filtration, then at 100 DEG C, NaY type molecules are obtained after drying 12 hours
Sieve.In gel rubber system（Remove the modified kaolin added and directed agents）The mol ratio of each material isn(NaOH):n(SiO2):n
(H2O)=15.5:12:570, the quality of the modified kaolin of addition accounts for the 6wt% of gel rubber system gross mass, the directed agents of addition
Quality accounts for the 5wt% of gel rubber system gross mass.
Embodiment 6
（1）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:18:320, under stirring,
Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker formation mixed liquor, is then aged 1 day at 35 DEG C, is made and leads
To agent.
（2）Under conditions of stirring, by modified kaolin 2, sodium hydroxide, water, waterglass and step（1）It is obtained to be oriented to
Agent, which is added in beaker, forms gel rubber system, by first thermostatic crystallization 10 hours under the conditions of 60 DEG C of gel, then in 100 DEG C of conditions
Lower thermostatic crystallization 48 hours, then through cooling, washing, suction filtration, then at 90 DEG C, NaY type molecular sieves are obtained after drying 10 hours.
In gel rubber system（Remove the modified kaolin added and directed agents）The mol ratio of each material isn(NaOH):n(SiO2):n(H2O)
=15:13:620, the quality of the modified kaolin of addition accounts for the 5wt% of gel rubber system gross mass, and the quality of the directed agents of addition is accounted for
The 4wt% of gel rubber system gross mass.
Embodiment 7
（1）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16:1:20:380, under stirring,
Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker formation mixed liquor, is then aged 1 day at 35 DEG C, is made and leads
To agent.
（2）Under conditions of stirring, by modified kaolin 3, sodium hydroxide, water, waterglass and step（1）It is obtained to be oriented to
Agent, which is added in beaker, forms gel rubber system, by first thermostatic crystallization 10 hours under the conditions of 65 DEG C of gel, then in 105 DEG C of conditions
Lower thermostatic crystallization 36 hours, then through cooling, washing, suction filtration, then at 80 DEG C, NaY type molecular sieves are obtained after drying 16 hours.
In gel rubber system（Remove the modified kaolin added and directed agents）The mol ratio of each material isn(NaOH):n(SiO2):n(H2O)
=15.6:12:520, the quality of the modified kaolin of addition accounts for the 5wt% of gel rubber system gross mass, the quality of the directed agents of addition
Account for the 7wt% of gel rubber system gross mass.The property of molecular sieve is as shown in table 1.
Embodiment 8
（1）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=17:1:17:400, under stirring,
Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker formation mixed liquor, is then aged 1 day at 35 DEG C, is made and leads
To agent.
（2）Under conditions of stirring, by modified kaolin 4, sodium hydroxide, water, waterglass and step（1）It is obtained to be oriented to
Agent, which is added in beaker, forms gel rubber system, by first thermostatic crystallization 9 hours under the conditions of 68 DEG C of gel, then under the conditions of 95 DEG C
Thermostatic crystallization 52 hours, then through cooling, washing, suction filtration, then at 100 DEG C, NaY type molecular sieves are obtained after drying 8 hours.It is solidifying
In colloid system（Remove the modified kaolin added and directed agents）The mol ratio of each material isn(NaOH):n(SiO2):n(H2O)=
15.8:13:500, the quality of the modified kaolin of addition accounts for the 10wt% of gel rubber system gross mass, the quality of the directed agents of addition
Account for the 8wt% of gel rubber system gross mass.
Comparative example 1
（1）According to mol ration(Na2O):n(Al2O3):n(SiO2):n(H2O)= 16:1:20:380, under stirring,
Sodium aluminate, water, sodium hydroxide and waterglass are sequentially added into beaker formation mixed liquor, is then aged 1 day at 35 DEG C, is made and leads
To agent.
（2）Under conditions of stirring, by the kaolin of roasting, sodium hydroxide, water, waterglass and step（1）It is obtained to lead
It is added to agent in beaker and forms gel rubber system, by first thermostatic crystallization 10 hours under the conditions of 65 DEG C of gel, then in 105 DEG C of bars
Thermostatic crystallization 36 hours under part, then through cooling, washing, suction filtration, then at 80 DEG C, NaY type molecules are obtained after drying 16 hours
Sieve.In gel rubber system（Remove the roasting kaolin added and directed agents）The mol ratio of each material isn(NaOH):n(SiO2):n
(H2O)=15.6:12:520, the quality of the roasting kaolin of addition accounts for the 5wt% of gel rubber system gross mass, the directed agents of addition
Quality accounts for the 7wt% of gel rubber system gross mass.Roasting kaolin is kaolin constant temperature calcining 5h under the conditions of 700 DEG C.Molecular sieve
Property is as shown in table 1.
Hydrothermal stability is investigated
NaY types molecular sieve prepared by embodiment 7 and comparative example 1 carries out secondary ammonium exchange.Exchange temperature is 95 DEG C；It is used
Ammonium salt be ammonium nitrate, the concentration of ammonium salt is 2mol/L；The liquid-solid ratio of exchange process（ml/g）For 8；Each swap time is 1.5
Hour.
The molecular sieve that ammonium has been exchanged is handled under hydrothermal conditions.Hydro-thermal process temperature is at 600 DEG C；During hydro-thermal process
Between be 3 hours；Hydro-thermal process pressure is 0.2MPa；Hydrothermal treatment process water injection rate is 200ml/h.
The property of molecular sieve after hydro-thermal process is as shown in table 1.
The physico-chemical property of the molecular sieve of table 1.
The property data of molecular sieve shows, after hydro-thermal process is carried out to molecular sieve by identical hydrothermal conditions,
The destructiveness of molecular sieve prepared by the inventive method is smaller, remains more crystal structures, crystallinity is higher.Absolutely prove
The hydrothermal stability of molecular sieve prepared by the inventive method is more preferable.
Claims (14)
1. a kind of method of synthesis NaY type molecular sieves, it is characterised in that including following content：（1）By sodium hydroxide, silicon source, water
Glass and water are well mixed, and ageing obtains directed agents；（2）Kaolin starting material is subjected to the modified kaolin that hydro-thermal process is obtained；
（3）By step（1）Obtain directed agents, step（2）Obtained modified kaolin, sodium hydroxide, water and waterglass is well mixed, and is obtained
To gel rubber system, then through low temperature crystallized, high temperature crystallization, cooling, separation of solid and liquid and drying obtain NaY type molecular sieves；Step
（2）Described hydrothermal conditions are：Hydro-thermal process temperature is 500 ~ 850 DEG C, and hydrothermal conditions are 1 ~ 8 hour, at hydro-thermal
Reason pressure is 0.05 ~ 0.3MPa.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described silicon source is aluminium chloride, aluminum sulfate, nitre
One or more in sour aluminium or sodium aluminate.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）In mol ratio of the material in terms of following material
For Na2O: Al2O3:SiO2: H2O=15~20:1:15~22:300~400。
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Described aging condition is：Aging Temperature is 50
~ 110 DEG C, digestion time is 1 ~ 24 hour.
5. in accordance with the method for claim 1, it is characterised in that：Step（2）Described hydrothermal conditions are：Hydro-thermal process
Temperature is 600 ~ 800 DEG C, and hydrothermal conditions are 2 ~ 6 hours, and hydro-thermal process pressure is 0.05 ~ 0.3MPa.
6. according to the method described in claim 1 or 5, it is characterised in that：Hydrothermal treatment process is carried out under the conditions of water filling, wherein
Water injection rate is 20 ~ 800ml/h.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described kaolin starting material is commercially available prod, tool
There is following property：The mol ratio of silica and aluminum oxide is 1.8 ~ 2.6, and potassium oxide is less than 0.8wt% with sodium oxide molybdena total content.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）Each material is in terms of following material in gel rubber system
Mol ratio be NaOH: SiO2:H2O=14~17: 8~18:450 ~ 700, wherein not including modified kaolin and the guiding added
Agent.
9. according to the method described in claim 1 or 8, it is characterised in that：Step（3）Each material is with following material in gel rubber system
The mol ratio of meter is NaOH:SiO2:H2O=14.5~16.5:10~16:480 ~ 680, wherein not include add modified kaolin and
Directed agents.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）The quality of the modified kaolin of middle addition accounts for solidifying
2wt% ~ 14wt% of colloid system gross mass.
11. in accordance with the method for claim 1, it is characterised in that：Step（3）The quality of the directed agents of middle addition accounts for gelinite
It is 1wt% ~ 10wt% of gross mass.
12. in accordance with the method for claim 1, it is characterised in that：Step（3）Described low temperature crystallized condition is：Crystallization temperature
Spend for 50 ~ 80 DEG C, crystallization time is 4 ~ 24 hours.
13. in accordance with the method for claim 1, it is characterised in that：Step（3）Described high temperature crystallization condition is：Crystallization temperature
Spend for 85 ~ 120 DEG C, crystallization time is 12 ~ 72 hours.
14. in accordance with the method for claim 1, it is characterised in that：Step（3）Described drying temperature is 80 ~ 100 DEG C, is done
The dry time is 8 ~ 16 hours.
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| US3506594A (en) * | 1968-06-20 | 1970-04-14 | Engelhard Min & Chem | Microspherical zeolitic molecular sieve composite catalyst and preparation thereof |
| US6004527A (en) * | 1997-09-29 | 1999-12-21 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
| CN1163301C (en) * | 2000-07-19 | 2004-08-25 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
| CN101618882B (en) * | 2008-07-04 | 2012-01-25 | 中国石油化工股份有限公司 | Method for in-situ synthesis of Y-type molecular sieve |
| CN102764670A (en) * | 2012-07-31 | 2012-11-07 | 海南出入境检验检疫局检验检疫技术中心 | In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst |
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