CN105084389B - A kind of method of modifying of Y type molecular sieve - Google Patents
A kind of method of modifying of Y type molecular sieve Download PDFInfo
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- CN105084389B CN105084389B CN201410215065.8A CN201410215065A CN105084389B CN 105084389 B CN105084389 B CN 105084389B CN 201410215065 A CN201410215065 A CN 201410215065A CN 105084389 B CN105084389 B CN 105084389B
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Abstract
A kind of method of modifying of Y type molecular sieve, it is characterised in that include the following steps: to add water to be beaten NaY molecular sieve, sieve mass ratio (1~20) in alcohol after mixing: polyhydroxy-alcohol, 1~10h of stir-activating at 80~200 DEG C is added in 1 ratio；2) after being cooled to room temperature the Product slurries after activation in step 1), sieve mass ratio (0.1~10) in ammonium: organic ammonium template is added in 1 ratio, stirs evenly；3) silicon source is added into the slurries that step 2) obtains at room temperature~60 DEG C, added silicon source presses Al2O3The mass ratio of meter and molecular sieve is (0.1~10): 1, continue to be aged 2h at 50~80 DEG C after stirring evenly；4) slurries for obtaining step 3) are transferred in stainless steel crystallizing kettle, 5~30h of secondary crystallization and recovery product at 100~120 DEG C.This method takes into account raising activity while being conducive to molecular sieve structure stabilization.
Description
Technical field
The present invention relates to a kind of method of modifying of Y type molecular sieve.
Background technique
Y type molecular sieve with faujasite crystal structure is due to good hydrothermal stability, acid strong, the high spy of activity
It puts and becomes catalyst important in modern industry, especially in petroleum refining and process, Y type molecular sieve is answered extensively
For in catalytic cracking and hydrocracking reaction.
The Y type molecular sieve directly synthesized is not directly applicable the processes such as catalytic cracking since sodium oxide content is higher, needs
Sodium oxide molybdena is washed till reduced levels by the methods of ion exchange such as ammonium exchange, the method for rare earth ion exchanged can also be used both
Sodium oxide molybdena can be eluted to the structural stability and cracking activity that molecular sieve also can be improved.
The operating condition of catalytic cracking process is more harsh, therefore mentions to the stability of molecular sieve especially hydrothermal stability
Higher requirement is gone out.For conventional NaY molecular sieve, silica alumina ratio about 5.0 or so, aluminium content is relatively high, and Al-O
Key is unstable under high temperature hydrothermal condition, therefore easily causes framework dealumination, influences molecular sieve structure.In order to improve Y type molecular sieve
Stability, scientific research personnel has conducted extensive research work, sums up several methods for improving stability, specifically includes that high temperature
Hydro-thermal method, Coordinative Chemistry method, gas phase and liquid phase aluminium-eliminating and silicon-replenishing method etc..Several method mainly passes through in dealumination process to be filled up with silicon
Hole caused by dealuminzation achievees the purpose that avoid skeleton structure to collapse, improves molecular sieve stability, but not due to treatment conditions
Together, also different for filling up the silicon source in hole, therefore the effect reached is also not quite similar.Something in common is gained molecular sieve
Framework si-al ratio improves, and replaces molecular sieve structure cell after Al-O key to reduce by the shorter Si-O key of bond distance, stability improves, but simultaneously
Molecular sieve acid site will receive influence, and acid amount decreases, and have certain influence to cracking activity and product distribution.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of take into account to improve stability and raising molecular sieve
The method of modifying of acid and cracking activity Y type molecular sieve.
The purpose of the present invention is what is be achieved through the following technical solutions, a kind of method of modifying of Y type molecular sieve, feature exists
In including the following steps:
1) add water to be beaten NaY molecular sieve, sieve mass ratio (1~20) in alcohol after mixing: polyhydroxy is added in 1 ratio
Alcohol, 1~10h of stir-activating at 80~200 DEG C；
2) after being cooled to room temperature the Product slurries after activation in step 1), mass ratio (0.1~10) is sieved by ammonium: 1 ratio
Organic ammonium template is added in example, stirs evenly；
3) silicon source is added into the slurries that step 2) obtains at room temperature~60 DEG C, added silicon source presses Al2O3Meter and molecular sieve
Mass ratio be (0.1~10): 1, after stirring evenly continue be aged 2h at 50~80 DEG C；
4) slurries for obtaining step 3) are transferred in stainless steel crystallizing kettle, 5~30h of secondary crystallization at 100~120 DEG C
And recovery product.
NaY molecular sieve used in method provided by the invention can be the NaY molecular sieve of various conventional method preparations, right
When grain size etc. is not particularly limited sial, and crystallinity is generally 80% or more, lattice constant about 2.464-2.466nm.
For example, Y type molecule disclosed in the documents such as US3639099, US4482530, US4576807, CN1621349A, CN1840475A
Sieve is used equally for the present invention.
Described polyhydroxy-alcohol is glycerine, propylene glycol or Isopropanediol.Described alcohol sieve mass ratio preferably 3
~15:1.Described reaction temperature is preferably 100~180 DEG C, and the reaction time is preferably 2~8h.
Described organic ammonium template is in tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide and tetramethylammonium hydroxide
It is one or more.The mass ratio of the Y type molecular sieve of described organic ammonium template and step 1) is preferably 0.2~5:1.
Described silicon source is one of aluminum sulfate, aluminum nitrate, sodium metaaluminate and aluminium oxide or a variety of.Described silicon source is pressed
Al2O3The mass ratio of meter and molecular sieve is preferably 0.2~5:1.
The process of described recovery product is known to those skilled in the art, and generally includes product through suction filtration, washing, dry
After dry, then at 500-800 DEG C of roasting 2-10h step.
The present invention also provides the molecular sieves that above-mentioned method of modifying obtains.Method of modifying of the invention, by adding polyhydroxy
Base alcohol activator, organic ammonium template and additional silicon source and secondary crystallization, the molecular sieve being modified have better water
Thermal stability, and take into account catalytic cracking activity.
Specific embodiment
Following examples will further illustrate the present invention, but not thereby limiting the invention.
Embodiment 1
Weigh the industrial NaY molecular sieve (silica alumina ratio 5.0, Na of 20g (butt)2O13.1%, crystallinity 85%) in beaker,
Appropriate amount of deionized water mashing is added, about 200mL glycerine is added after stirring evenly, sonic oscillation is uniformly mixed, mixture is warming up to
160 DEG C, it is stirred to react 4h；After standing is cooled to room temperature, 80mLTPAOH solution (mass fraction 25wt%) is added and stirs evenly,
Then by 60mL sodium metaaluminate (Shandong catalyst plant, Al at 40 DEG C2O3Content 103g/L) be slowly added thereto, to silicon source plus
After entering, temperature is risen to 60 DEG C, constant temperature stirring ageing 2h.Then by above-mentioned slurries be transferred in stainless steel crystallizing kettle in
100 DEG C of static crystallization 12h after obtained product is filtered, washed, is dried, roast 3h at 750 DEG C and obtain offer of the present invention
Material.It is denoted as GYA-1.
Embodiment 2
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, about 120mL is added after stirring evenly
Glycerine, sonic oscillation are uniformly mixed, mixture are warming up to 140 DEG C, is stirred to react 4h；After standing is cooled to room temperature, it is added
40mL TEAOH solution (mass fraction 25wt%) stirs evenly, then by 60mL sodium metaaluminate and 75mL aluminum sulfate at 50 DEG C
Solution (Shandong catalyst plant, Al2O3Content 90g/L) it is slowly added thereto, after being added to silicon source, temperature is risen to 50 DEG C,
Constant temperature stirring ageing 2h.Then above-mentioned slurries are transferred in stainless steel crystallizing kettle in 100 DEG C of static crystallization 15h, by what is obtained
After product is filtered, washed, dries, 3h is roasted at 750 DEG C and obtains material provided by the invention.It is denoted as GYA-2.
Embodiment 3
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, 80mL third is added after stirring evenly
Glycol, sonic oscillation are uniformly mixed, mixture are warming up to 100 DEG C, is stirred to react 8h；After standing is cooled to room temperature, it is added
30mL TMAOH solution (mass fraction 25wt%) stirs evenly, and 50mL aluminum sulfate solution is then slowly added to it at 40 DEG C
In, after being added to silicon source, temperature is risen to 70 DEG C, constant temperature stirring ageing 2h.Above-mentioned slurries are then transferred to stainless steel
In 100 DEG C of static crystallization 20h in crystallizing kettle, after obtained product is filtered, washed, is dried, 4h is roasted at 600 DEG C and is obtained
Material provided by the invention.It is denoted as GYA-3.
Embodiment 4
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, 160mL third is added after stirring evenly
Glycol, sonic oscillation are uniformly mixed, mixture are warming up to 120 DEG C, is stirred to react 3h；After standing is cooled to room temperature, it is added
20mL TPAOH solution stirs evenly, and is then at room temperature slowly added thereto 95mL sodium aluminate solution, is added to silicon source
After, temperature is risen to 80 DEG C, constant temperature stirring ageing 2h.Then above-mentioned slurries are transferred in stainless steel crystallizing kettle in 110
DEG C static crystallization 15h, after obtained product is filtered, washed, is dried, roasted at 550 DEG C 6h obtain it is provided by the invention
Material.It is denoted as GYA-4.
Embodiment 5
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, 100mL third is added after stirring evenly
Triol, sonic oscillation are uniformly mixed, mixture are warming up to 180 DEG C, is stirred to react 2h；After standing is cooled to room temperature, it is added
40mL TPAOH solution stirs evenly, and 180mL sodium metaaluminate and 60mL aluminum sulfate solution are then slowly added to it at room temperature
In, after being added to silicon source, temperature is risen to 60 DEG C, constant temperature stirring ageing 2h.Above-mentioned slurries are then transferred to stainless steel
In 110 DEG C of static crystallization 20h in crystallizing kettle, after obtained product is filtered, washed, is dried, 5h is roasted at 550 DEG C and is obtained
Material provided by the invention.It is denoted as GYA-5.
Comparative example 1
This comparative example illustrates according to the method provided by the invention, but is added without the comparison modifying process of alcohols activator.
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, sonic oscillation is uniformly mixed
Molecular sieve pulp is obtained, 30mL TPAOH solution is then added thereto and stirs evenly, then by 50mL meta-aluminic acid at 50 DEG C
Sodium and 50mL aluminum sulfate solution are slowly added thereto, and after being added to silicon source, temperature are risen to 60 DEG C, constant temperature stirring ageing
2h.Then above-mentioned slurries are transferred in stainless steel crystallizing kettle in 110 DEG C of static crystallization 10h, by the filtering of obtained product, are washed
After washing, drying, 4h is roasted at 600 DEG C and obtains contrast material DB-1.
Comparative example 2
This comparative example illustrates according to the method provided by the invention, but the comparison for being added without organic ammonium class template agent was modified
Journey.
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, 150mL third is added after stirring evenly
Triol, sonic oscillation are uniformly mixed, mixture are warming up to 120 DEG C, is stirred to react 2h；Standing will when being cooled to 50 DEG C or so
60mL sodium aluminate solution is slowly added thereto, and after being added to silicon source, temperature is risen to 70 DEG C, constant temperature stirring ageing 2h.
Then above-mentioned slurries are transferred in stainless steel crystallizing kettle in 100 DEG C of static crystallization 20h, obtained product is filtered, washed, is done
After dry, 1h is roasted at 500 DEG C and obtains contrast material DB-2.
Comparative example 3
This comparative example illustrates according to the method provided by the invention, but is added without the comparison modifying process of silicon source.
20gNaY molecular sieve (butt) is weighed in beaker, appropriate amount of deionized water mashing is added, 100mL third is added after stirring evenly
Triol, sonic oscillation are uniformly mixed, mixture are warming up to 120 DEG C, is stirred to react 2h；After standing is cooled to room temperature, it is added
30mL TPAOH solution stirs evenly, and temperature is risen to 60 DEG C, constant temperature stirring ageing 2h.Then above-mentioned slurries are transferred to stainless
In 100 DEG C of static crystallization 12h in steel crystallizing kettle, after obtained product is filtered, washed, is dried, roast 5h at 550 DEG C to obtain the final product
To contrast material DB-3.
Test case
The sieve sample that this test case method of modifying obtains is small through aging process 17 under 800 DEG C, 100% water vapor conditions
When after stability data and light oil microactivity data.
By contrast sample DB-1~3 obtained in obtained sample GYA-1~5 above-described embodiment 1-5 and comparative example 1-3 into
After the processing of row removing sodium, by its tabletting and 20~40 mesh particles are ground into, the aging process 17 under 800 DEG C, 100% water vapor conditions
Hour, and carry out materialization characterization and measure light oil microactivity MA.
Light oil micro-reactor evaluation condition: molecular sieve loading amount 2g, feedstock oil are huge port straight distillation light diesel oil, oil inlet quantity 1.56g, reaction
460 DEG C of temperature.
It the results are shown in Table 1.
Table 1
Seen from table 1, after 800 DEG C, 17h aging process, the crystal retention (aged samples of embodiment sieve sample
Crystallinity and fresh sample crystallinity ratio) 28.2%~32.8%, hence it is evident that higher than the 24.9% of comparative example
~26.8%, illustrate method of modifying of the invention, keeps the stability of its structure more preferable；Light oil microactivity is 43~46, also high
In the 40~42 of contrast sample.This shows using method of modifying provided by the invention, is being conducive to stable same of molecular sieve structure
When, take into account the active raising of molecular sieve.
Claims (7)
1. a kind of method of modifying of Y type molecular sieve, it is characterised in that include the following steps:
1) add water to be beaten NaY molecular sieve, sieve mass ratio (1~20) in alcohol after mixing: polyhydroxy-alcohol is added in 1 ratio,
1~10h of stir-activating at 80~200 DEG C, the polyhydroxy-alcohol are glycerine, propylene glycol or Isopropanediol；
2) after being cooled to room temperature the Product slurries after activation in step 1), by the NaY molecule of organic amine template and step 1)
The mass ratio (0.1~10) of sieve: organic amine template is added in 1 ratio, stirs evenly, and the organic amine template is 4 third
One of base ammonium hydroxide, tetraethyl ammonium hydroxide and tetramethylammonium hydroxide are a variety of；
3) silicon source is added into the slurries that step 2) obtains at room temperature~60 DEG C, added silicon source presses Al2O3The matter of meter and molecular sieve
Amount is than being (0.1~10): 1, continue to be aged 2h at 50~80 DEG C after stirring evenly；
4) slurries for obtaining step 3) are transferred in stainless steel crystallizing kettle, at 100~120 DEG C 5~30h of secondary crystallization and return
Receive product.
2. method of modifying described in accordance with the claim 1, wherein it is 3~15:1 that alcohol described in step 1), which sieves mass ratio,.
3. method of modifying described in accordance with the claim 1, wherein reaction temperature described in step 1) is 100~180 DEG C, reaction
Time is 2~8h.
4. method of modifying described in accordance with the claim 1, wherein the NaY molecular sieve of the organic amine template and step 1)
0.2~5:1 of mass ratio.
5. method of modifying described in accordance with the claim 1, wherein silicon source described in step 3) is aluminum sulfate, aluminum nitrate, meta-aluminic acid
One of sodium and aluminium oxide are a variety of.
6. method of modifying described in accordance with the claim 1, wherein silicon source described in step 3) presses Al2O3The quality of meter and molecular sieve
Than 0.2~5:1.
7. the molecular screen material that method of modifying described in one of claim 1-6 obtains.
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| CN101332995A (en) * | 2008-03-25 | 2008-12-31 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing kaolin in-situ crystallization ZSM-5 molecular sieve |
| CN102951655A (en) * | 2012-11-27 | 2013-03-06 | 华东师范大学 | Modified method of Y-type molecular sieve |
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| US6756029B2 (en) * | 1999-08-11 | 2004-06-29 | Petroleo Brasileiro S.A.-Petrobras | Molecular sieves of faujasite structure |
| CN103449471B (en) * | 2012-06-01 | 2017-07-14 | 中国石油天然气股份有限公司 | A kind of phosphorous Ultra-stable rare earth Y-type molecular sieve and preparation method |
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| CN101332995A (en) * | 2008-03-25 | 2008-12-31 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing kaolin in-situ crystallization ZSM-5 molecular sieve |
| CN102951655A (en) * | 2012-11-27 | 2013-03-06 | 华东师范大学 | Modified method of Y-type molecular sieve |
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