CN110078093A - A kind of NaY molecular sieve and its preparation method and application - Google Patents
A kind of NaY molecular sieve and its preparation method and application Download PDFInfo
- Publication number
- CN110078093A CN110078093A CN201810071617.0A CN201810071617A CN110078093A CN 110078093 A CN110078093 A CN 110078093A CN 201810071617 A CN201810071617 A CN 201810071617A CN 110078093 A CN110078093 A CN 110078093A
- Authority
- CN
- China
- Prior art keywords
- silicon source
- molecular sieve
- preparation
- nay molecular
- reaction gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention provides a kind of NaY molecular sieves and its preparation method and application.Preparation method are as follows: the first silicon source, the first silicon source, alkali source and water are mixed and are aged to obtain directed agents；Second silicon source, the second silicon source, directed agents and water are mixed and adds regulator and stirs to get reaction gel；Reaction gel is subjected to crystallization, obtains NaY molecular sieve after filtration washing is dry.The preparation method operating procedure of NaY molecular sieve provided by the invention is simple, cost of material is low, the requirement to process equipment is low, has very strong application；It can synthesize the NaY molecular sieve with high-crystallinity, and silicon source utilization rate can reach 65%-75%, and one-pot yield can be improved 20%-30%, and single-autoclave yield rate reaches twice of traditional handicraft or more；The product grains size uniformity that is finally prepared, silica alumina ratio are high, stability is good；Moreover, this method solves the problems, such as that industrial waterglass system exists in the case where not increasing cost.
Description
Technical field
The invention belongs to catalyst technical field, it is related to a kind of NaY molecular sieve and its preparation method and application.
Background technique
Y type molecular sieve is widely used in petrochemical industry, especially catalytic cracking process.The preparation of catalyst occupies refining
The important a part of oily process costs, oil price significantly fluctuated in recent years, therefore, improves catalyst yield, simplifies synthesis step
Suddenly, shorten the cost that oil refining process can be effectively reduced in preparation time, preferably cope with the fluctuation of oil price.
Currently, industrially the silicon source of production NaY molecular sieve often uses waterglass, since waterglass system raw material is liquid, this
Body contains a large amount of water and silicon content is lower, SiO2Mass fraction there was only 18%-29% so that this method solid content is lower,
Cause the product yield for preparing Y type molecular sieve in reaction process not high, one-pot yield is often lower than 10%.Further, since silicon source is sharp
Low with rate, so that silicon source is lost seriously, and the lye containing a large amount of silicon in mother liquor can also cause adverse effect to environment.It is reported that
Many techniques are recycled the mother liquor for preparing Y type molecular sieve, this compensates for the stream of silicon source in technique to a certain extent
Vector, but also will increase the cost of the preparation process.
It is the product crystallinity for directly obtaining solid silicon and aluminum source ground and mixed that solid phase transformation method, which prepares NaY molecular sieve,
It is low, and there is stirring difficulty in synthesis process, be unfavorable for the problems such as industrialized production.
Therefore, for energy-efficient, environmentally protective angle, the synthesis technology of NaY molecular sieve is being continuously improved, how
The Y type molecular sieve for synthesizing high-quality under conditions of raising product yield, reduction process flow and reduction pollutant emission becomes
One of the direction that researchers make great efforts；Meanwhile exploitation efficiently synthesizes system, preparation has complete crystal phase, high silica alumina ratio, high stable
The high-performance Y type molecular sieve of property has become a hot topic of research.
Summary of the invention
In order to which the crystallinity for solving to prepare NaY molecular sieve in the prior art is low, silicon source utilization rate, product yield is low, mother liquor
The problems such as exhaust emission, the purpose of the present invention is to provide a kind of NaY molecular sieves and its preparation method and application.The preparation method
Without using any template or additive, operating procedure is simple, raw material production cost is low, the requirement to process equipment is low, product
High income has very strong application.Finally obtained product has high-crystallinity, high silica alumina ratio, high stability, and crystal grain ruler
The advantages that very little uniform.
The purpose of the present invention is achieved by the following technical programs:
On the one hand, the present invention provides a kind of preparation method of NaY molecular sieve, comprising the following steps:
According to Na2O:Al2O3: SiO2: H2O=(8-25): 1:(8-25): the molar ratio meter of (150-450), by first
Silicon source, the first silicon source, alkali source and water mixing are aged to obtain directed agents；
According to Na2O:Al2O3: SiO2: H2O=(3-6): 1:(6-12): total molar ratio meter of (50-150), by second
Silicon source, the second silicon source, directed agents and water, which mix and adds regulator, stirs to get reaction gel；
Reaction gel is subjected to crystallization, obtains NaY molecular sieve after filtration washing is dry.
In above-mentioned preparation method, the molal quantity in " total molar ratio " refers to that directed agents and preparation reaction gel are all thrown
The total mole number of material.
In above-mentioned preparation method, it is preferable that first silicon source may include waterglass and/or silica solution etc..
In above-mentioned preparation method, it is preferable that first silicon source may include sodium metaaluminate, aluminum sulfate, aluminum nitrate and
One of aluminium chloride etc. or a variety of combinations.
In above-mentioned preparation method, it is preferable that the alkali source may include sodium hydroxide etc..
In above-mentioned preparation method, it is preferable that the water may include deionized water etc..
In above-mentioned preparation method, it is preferable that according to Na2O:Al2O3: SiO2: H2O=(3.5-5): 1:(6.5-9.5):
Second silicon source, the second silicon source, directed agents and water are mixed and add regulator and stirred by total molar ratio meter of (85-120)
To reaction gel.
In above-mentioned preparation method, it is preferable that second silicon source includes one of sodium metasilicate of different moduluses or more
The combination of kind, the modulus of the sodium metasilicate includes 1.9-2.1,2.2-2.4,2.7-2.9,2.9-3.1 and 3.1-3.3；Preferably,
Second silicon source includes the sodium metasilicate that modulus is 2.2-3.3.
In above-mentioned preparation method, it is preferable that second silicon source may include sodium metaaluminate, aluminum sulfate, aluminum nitrate and
One of aluminium chloride etc. or a variety of combinations.
In above-mentioned preparation method, it is preferable that second silicon source may include sodium metaaluminate and/or aluminum sulfate etc..
In above-mentioned preparation method, it is preferable that the regulator may include the concentrated sulfuric acid or aluminum sulfate.
In above-mentioned preparation method, it is preferable that the pH value that the regulator adjusts reaction gel is 12-14.
In above-mentioned preparation method, it is preferable that the pH value that the regulator adjusts reaction gel is 13-14.
In above-mentioned preparation method, when regulator selects the concentrated sulfuric acid, n (concentrated sulfuric acid)/n (SiO2)=0.2-1.5, it is more excellent
Choosing, be 0.5-1.0；When regulator selects aluminum sulfate, n (NaAlO2)/n(Al2(SO4)3)=0.2-4.5, it is furthermore preferred that
For 0.5-3.5.
In above-mentioned preparation method, it is preferable that when preparing reaction gel, first located the second silicon source in advance in water
Reason obtains active aqueous silica sol, and the second silicon source and directed agents are then added, and is eventually adding the pH that regulator adjusts reaction system
Value.
In above-mentioned preparation method, it is preferable that pretreated temperature is 0-60 DEG C, and the pretreated time is 2-6h.
In above-mentioned preparation method, it is preferable that introduce H by addition water2The weight of O accounts for the reaction gel total weight
30%-80%.
In above-mentioned preparation method, it is preferable that introduce H by addition water2The weight of O accounts for the reaction gel total weight
30%-50%.
In above-mentioned preparation method, it is preferable that the Al introduced by addition directed agents2O3Weight account for the reaction gel
Middle Al2O3The 5%-20% of total weight.
In above-mentioned preparation method, it is preferable that the Aging Temperature is 10-35 DEG C, digestion time 5-100h.
In above-mentioned preparation method, it is preferable that digestion time 20-80h；
In above-mentioned preparation method, it is preferable that the temperature that the reaction gel carries out crystallization is 90-110 DEG C, crystallization when
Between be 20-120h.
In above-mentioned preparation method, it is preferable that the time of crystallization is 24-72h.
On the other hand, the present invention also provides the NaY molecular sieves that above-mentioned preparation method is prepared.
In the NaY molecular sieve that above-mentioned preparation method is prepared, it is preferable that the silica alumina ratio of the NaY molecular sieve is 5.0-
6.0, relative crystallinity 95%-105%；The partial size of crystal grain is 350-500nm.
In the NaY molecular sieve that above-mentioned preparation method is prepared, it is preferable that the partial size of crystal grain is 400-500nm.
In another aspect, the present invention also provides above-mentioned NaY molecular sieve as catalyst active component in catalytic cracking, plus hydrogen
Application in cracking or alkylation oil refining process.
In above-mentioned preparation method, the second silicon source is solid silicon source, and is located in advance during preparing reaction gel
Active silicon source is formed after reason.
Technical solution provided by the invention is added without any template or additive in reaction gel, and it is solidifying that reaction is only added
Al in glue2O3The directed agents of the 5-20% of weight percent, cost of material are low.
For technical solution provided by the invention during preparing reaction gel, the aluminium salts such as the concentrated sulfuric acid or aluminum sulfate are added can
With the pH value of regulation system, the proportion for being optimal system and crystallization state.
For technical solution provided by the invention during preparing reaction gel, stirring is good, is suitable for industrial metaplasia
It produces.
Technical solution provided by the invention is during preparing reaction gel, silicon source, silicon source, water, acid solution (regulator)
Sequencing is not emphasized in addition with directed agents, and water and acid solution can first be added, quickly stirring while be added silicon source and
Silicon source is stirring evenly and then adding into directed agents, can also quickly stir down the elder generation according to water, acid solution, silicon source, silicon source and directed agents
Sequentially feed intake afterwards, perhaps feed intake under fast stirring according to the sequencing of water, acid solution, silicon source, silicon source and directed agents or
Quickly feed intake under stirring according to the sequencing of silicon source, water, acid solution, directed agents and silicon source.
Solid silicon source sodium metasilicate is used in technical solution provided by the invention, is considerably reduced raw material and is occupied in kettle
Volume；Solid silicon source is the sodium metasilicate of different moduluses, and synthetic reaction gel is without additional addition sodium hydroxide；Simultaneously using dense
The aluminium salts such as sulfuric acid or aluminum sulfate adjust the pH value of synthesized gel rubber system, and the crystallization state for being optimal system utilizes dense sulphur
After the pH value of sour regulation system, SO4 2-Without being further processed, simplify processing step.It is solidifying that synthesis is adjusted using aluminium salts such as aluminum sulfate
The pH value of colloid system, while can function as silicon source, in addition, the system solid content of the invented technology can be adjusted in a certain range
It is whole, enhance the flexibility of technique.
In the technical solution provided by the present invention, waterglass can use commercially available conventional reagent, can for example use SiO2
Content is 23.05wt%, Na2O content is the commercial water glass product of 7.83wt%；Sodium metasilicate can be using commercially available conventional examination
Agent can for example use SiO2Content is 60.00wt%, Na2O content is the commercially available sodium metasilicate product of 19.00wt%；Silica solution
Commercially available conventional reagent can be used, SiO can be for example used2Content is 30.00wt%, Na2O content is 0.40wt%, average ruler
The very little commercially available silica solution product for 10-20nm；Sodium metaaluminate Al2O3Content is 45.00wt%, Na2O content is 41.00wt%'s
Commercially available sodium metaaluminate product；Aluminum sulfate can use commercially available conventional reagent, can for example use Al2(SO4)3·18H2O content is
99% aluminum sulfate product；The concentrated sulfuric acid can use commercially available conventional reagent, can for example use H2SO4Content is 98.00wt%'s
Commercially available concentrated sulfuric acid product.
The preparation method operating procedure of NaY molecular sieve provided by the invention is simple, cost of material is low, wants to process equipment
It asks low, there is very strong application；It can synthesize the NaY molecular sieve with high-crystallinity, improve silicon source utilization rate and list
Kettle yield, silicon source utilization rate can reach 65%-75%, and one-pot yield can be improved 20%-30%, and single-autoclave yield rate reaches tradition
Twice or more of technique；The product grains size uniformity that is finally prepared, silica alumina ratio are high, stability is good；Moreover, this method exists
Solve the problems, such as that industrial waterglass system exists in the case where not increasing cost.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram for the NaY molecular sieve that the embodiment of the present invention 1 provides；
Fig. 2 is scanning electron microscope (SEM) figure for the NaY molecular sieve that the embodiment of the present invention 1 provides.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
In each embodiment and comparative example:
The lattice constant and relative crystallinity of molecular sieve are measured with x-ray powder diffraction, using RIPP145-90 standard
Method (referring to " petrochemical analysis method ", Yang Cui is surely equal to be compiled, Science Press, nineteen ninety version)；
Framework si-al ratio is calculated according to following formula: SiO2/Al2O3(SiO2/Al2O3Molar ratio)=2*
(25.8575-α0)/(α0-24.191)；
The average grain size of molecular sieve is using scanning projection microscope measurement.
Embodiment 1
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) the NaOH solid (Beijing Century Red Star Chemical Co., Ltd., analysis is pure, similarly hereinafter) for weighing 8.32g is placed in beaker
In, then weigh the deionized water of 25.48g and be placed in a beaker, the two is mixed evenly, and stir 1h at room temperature, is prepared
Obtain sodium hydroxide solution；
Sequentially add the NaAlO of 2.46g2(Tianjin saliva section chemical institute, Al2O3Content be 45wt%, Na2O's
Content is 41wt%, similarly hereinafter), the waterglass of 60.20g (SiO in waterglass2Content be 23.05wt%, Na2The content of O is
7.83wt%, similarly hereinafter), it is uniformly mixed, is transferred to biochemical cultivation case, 48h is aged at 25 DEG C, directed agents are prepared, led
It is the colloidal sol of homogeneous transparent to agent.
2) concentrated sulfuric acid (Beijing Chemical Plant, the H of 6.76g are added in the deionized water of 75.24g2SO4Content is 98wt%, under
Together), 1h is stirred under constant temperature to be cooled to room temperature；Add the solid NaSiO of 18.76g3(Shanghai fine chemistry industry research institute, modulus
2.2-2.4, SiO2Content be 53.0-55.0wt%, Na2The content of O is 23.0-25.0wt%), stirs 1h under constant temperature, is prepared
The aqueous silica sol of high activity is obtained, 6.20g NaAlO is then weighed2It is added in the aqueous silica sol of high activity, stirs evenly
Afterwards, the above-mentioned directed agents of 12.88g are added, stir evenly obtained reaction gel, the pH value of reaction gel is 12.5 at this time.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 103%, silica alumina ratio 5.22, and crystallite dimension is
400-500nm。
The XRD spectra of NaY molecular sieve product provided in this embodiment is as shown in Figure 1, scanning electron microscope (SEM) spectrogram such as Fig. 2
It is shown.The NaY molecular sieve product of the present embodiment shows apparent Y molecular sieve characteristic peak it can be seen from XRD spectra, and does not have
Miscellaneous peak is occurred, by eight 2 θ=15.7 ° ± 0.2 of characteristic peak of Y type molecular sieve, 18.7 ° ± 0.2,20.4 ° ± 0.2,23.7 °
± 0.2,27.1 ° ± 0.2,30.8 ° ± 0.2,31.5 ° ± 0.2 and 34.2 ° ± 0.2 of calculated by peak area its crystallinity, can obtain this
The crystallinity of embodiment NaY molecular sieve is 103%.The NaY molecular sieve of the present embodiment shows octahedral it can be seen from SEM figure
The pattern of body, and dispersion is more uniform, apparent agglomeration does not occur, zeolite crystal size range is 400-500nm.
Relevant test characterization is carried out to NaY molecular sieve provided in this embodiment, the results are shown in tables 1.
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 2
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) concentrated sulfuric acid of 5.25g is added in the deionized water of 70.20g, stirring 1h is cooled to room temperature under constant temperature；It adds
15.42g solid NaSiO3(modulus 1.9-2.1, SiO2Content be 51.0-53.0wt%, Na2The content of O is 26.0-
28.0wt%), 1h is stirred under constant temperature, the aqueous silica sol of high activity is prepared, then weigh the NaAlO of 5.45g2It is added high
In active aqueous silica sol, after mixing evenly, the above-mentioned directed agents of 11.47g is added, stir evenly obtained reaction gel, this
When reaction gel pH value be 13.2.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 102%, silica alumina ratio 5.17, and crystallite dimension is
400-500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 3
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) concentrated sulfuric acid of 9.25g is added in the deionized water of 93.50g, stirring 1h is cooled to room temperature under constant temperature；It adds
25.20g solid NaSiO3(modulus 2.7-2.9, SiO2Content be 56.0-58.0wt%, Na2The content of O is 20.0-
22.0wt%), 1h is stirred under constant temperature, the aqueous silica sol of high activity is prepared, then weigh the NaAlO of 7.70g2It is added high
In active aqueous silica sol, after mixing evenly, the above-mentioned directed agents of 24.25g is added, stir evenly obtained reaction gel, this
When reaction gel pH value be 12.8.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 104%, silica alumina ratio 5.28, and crystallite dimension is
400-500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 4
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) concentrated sulfuric acid of 10.87g is added in the deionized water of 102.34g, stirring 1h is cooled to room temperature under constant temperature；It adds
29.68g solid NaSiO3(modulus 2.9-3.1, SiO2Content be 57.0-59.0wt%, Na2The content of O is 19.0-
21.0wt%), 1h is stirred under constant temperature, the aqueous silica sol of high activity is prepared, then weigh the NaAlO of 8.45g2It is added high
In active aqueous silica sol, after mixing evenly, the above-mentioned directed agents of 35.07g is added, stir evenly obtained reaction gel, this
When reaction gel pH value be 13.5.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 93%, silica alumina ratio 5.30, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 5
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) concentrated sulfuric acid for weighing 12.56g is added in the deionized water of 111.02g, and 1h is stirred under constant temperature and is cooled to room temperature；
Add the solid NaSiO of 34.46g3(modulus 3.1-3.3, SiO2Content be 59.0-61.0wt%, Na2The content of O is
18.0-20.0wt%), 1h is stirred under constant temperature, the aqueous silica sol of high activity is prepared, then weigh the NaAlO of 9.20g2
It is added in the aqueous silica sol of high activity, after mixing evenly, the above-mentioned directed agents of 45.38g is added, stir evenly to be made and react solidifying
Glue, the pH value of reaction gel is 12.4 at this time.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 94%, silica alumina ratio 5.84, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 6
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) the solid NaSiO of 23.40g is weighed3(Shanghai fine chemistry industry research institute, modulus 2.2-2.4, SiO2Content be
53.0-55.0wt%, Na2The content of O is 23.0-25.0wt%) it is added in the deionized water of 100.20g, it is stirred under constant temperature
The aqueous silica sol of high activity is prepared in 1h；Then the NaAlO of 3.95g is weighed2(Tianjin saliva section chemical institute, Al2O3's
Content is 45wt%, Na2The content of O be 41wt%) and 11.35g Al2(SO4)3(the limited public affairs of development in science and technology are recovered in Tianjin
Department, Al2SO4·18H2The content of O is 99%) to be dissolved in the aqueous silica sol of high activity, continues after mixing evenly, to be added
The above-mentioned directed agents of 19.55g, stir evenly obtained reaction gel, and the pH value of reaction gel is 13.8 at this time.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 98%, silica alumina ratio 5.23, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 7
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) the solid NaSiO of 21.39g is weighed3(modulus 1.9-2.1, SiO2Content be 51.0-53.0wt%, Na2O's
Content is 26.0-28.0wt%) it is added in the deionized water of 85.56g, 1h is stirred under constant temperature, the water of high activity is prepared
Close silica solution；Then the NaAlO of 3.36g is weighed2With the Al of 9.70g2(SO4)3(Science and Technology Ltd. is recovered in Tianjin,
Al2SO4·18H2The content of O is 99%, similarly hereinafter) it is dissolved in the aqueous silica sol of high activity, continue after mixing evenly, to be added
The above-mentioned directed agents of 16.91g, stir evenly obtained reaction gel, and the pH value of reaction gel is 12.6 at this time.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 93%, silica alumina ratio 5.15, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 8
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) the solid NaSiO of 27.70g is weighed3(modulus 2.7-2.9, SiO2Content be 56.0-58.0wt%, Na2O's
Content is 20.0-22.0wt%) it is added in the deionized water of 110.2g, 1h is stirred under constant temperature, the water of high activity is prepared
Close silica solution；Then the NaAlO of 4.33g is weighed2With the Al of 12.47g2(SO4)3It is dissolved in the aqueous silica sol of high activity, continues
After mixing evenly, the above-mentioned directed agents of 30.78g are added, stir evenly obtained reaction gel, the pH value of reaction gel is at this time
12.9。
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 95%, silica alumina ratio 5.31, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 9
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) the solid NaSiO of 32.36g is weighed3(modulus 2.9-3.1, SiO2Content be 57.0-59.0wt%, Na2O's
Content is 19.0-21.0wt%) it is added in the deionized water of 120.20g, 1h is stirred under constant temperature, the water of high activity is prepared
Close silica solution；Then the NaAlO of 4.70g is weighed2With the Al of 13.58g2(SO4)3It is dissolved in the aqueous silica sol of high activity, continues
After mixing evenly, the above-mentioned directed agents of 38.24g are added, stir evenly obtained reaction gel, the pH value of reaction gel is at this time
13.3。
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 92%, silica alumina ratio 5.36, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Embodiment 10
Present embodiments provide a kind of NaY molecular sieve and preparation method thereof comprising following steps:
1) preparation method of directed agents and raw material sources are the same as embodiment 1.
2) the solid NaSiO of 37.32g is weighed3(modulus 3.1-3.3, SiO2Content be 59.0-61.0wt%, Na2O's
Content is 18.0-20.0wt%) it is added in the deionized water of 130.20g, 1h is stirred under constant temperature, the water of high activity is prepared
Close silica solution；Then the NaAlO of 5.08g is weighed2With the Al of 14.70g2(SO4)3It is dissolved in the aqueous silica sol of high activity, continues
After mixing evenly, the above-mentioned directed agents of 49.15g are added, stir evenly obtained reaction gel, the pH value of reaction gel is at this time
13.1。
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After 48h, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity of NaY molecular sieve provided in this embodiment is 90%, silica alumina ratio 5.85, crystallite dimension 400-
500nm。
This implementation also provide above-mentioned NaY molecular sieve as the active component of catalyst in catalytic cracking, be hydrocracked or alkane
Application in base oil refining process.
Comparative example 1
This comparative example provides a kind of synthetic method of NaY molecular sieve comprising following steps:
1) waterglass (Chang Ling oil-refining chemical factory catalyst plant, the specific gravity 1.252, SiO of 7.7mL are weighed2Content 227g/L,
Modulus 2.9) it is placed in a beaker, then weigh the high sodium aluminate solution of 5.0mL (producer is same as above, Al2O3Content 40g/L, Na2O is dense
Spend 281.5g/L, specific gravity 1.36) it is placed in a beaker, the two is mixed evenly, is transferred in biochemical cultivation case, it is old at 20 DEG C
Directed agents are prepared in change for 24 hours, and mole group becomes Na2O:Al2O3:SiO2:H2O=16.7:1:14.9:345.
2) concentrated sodium silicate solution (the inorganization factory in Nanjing, the specific gravity 1.38, SiO of 138g are weighed2Content 26.7wt%, mould
Number 3.13) it is placed in a beaker, after being heated to 95 DEG C, stop heating, the low NaAlO of 53.00g is added thereto2Solution (Chang Ling oil refining
Chemical plant catalyst plant, Al2O3Content 106g/L, Na2O concentration 157g/L, specific gravity 1.25), the Al of 43.62g2(SO4)3Solution
(Chang Ling oil-refining chemical factory catalyst plant, Al2O3Content 92.6g/L, specific gravity 1.283) and above-mentioned directed agents, stirring 1h is obtained under constant temperature
To silica-alumina gel mixture, above-mentioned directed agents are then added in silica-alumina gel mixture, continue after mixing evenly, reaction to be made
Gel.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After for 24 hours, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity for the NaY molecular sieve that this comparative example provides is 90%, silica alumina ratio 5.30.
Relevant test characterization is carried out to the Y type molecular sieve that this comparative example obtains, the results are shown in tables 1.
Comparative example 2
1) preparation method of directed agents and raw material sources are the same as comparative example 1.
2) waterglass (Chang Ling oil-refining chemical factory catalyst plant, the specific gravity 1.252, SiO of 102.5mL are weighed2Content 227g/
L, modulus 2.9) it is placed in a beaker, the low NaAlO of 33.25g is added2The Al of solution (with comparative example 1), 28.61g2(SO4)3Solution
(with comparative example 1), the deionized water of 31.1g and the above-mentioned directed agents of 11.3g are uniformly mixed, and 4-6h are stirred under constant temperature, reaction is made
Gel.
3) above-mentioned reaction gel is fitted into the stainless steel cauldron with politef liner, static crystallization at 100 DEG C
After for 24 hours, reaction kettle is cooled to room temperature, is filtered, washed products obtained therefrom to the close neutrality of pH value.Filter cake is placed in oven and dried
12h obtains NaY molecular sieve.
The relative crystallinity for the NaY molecular sieve that this comparative example provides is 91%, silica alumina ratio 5.10.
Relevant test characterization is carried out to the Y type molecular sieve that this comparative example obtains, the results are shown in tables 1.
Table 1: the comparison of different NaY molecular sieve synthetic methods
| Experimental comparison's content | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| SiO in reaction gel2Quality/g | 19.79 | 24.29 | 24.50 |
| Product NaY molecular sieve quality/g | 18 | 18 | 18 |
| SiO in NaY molecular sieve2Quality/g | 13.61 | 13.41 | 13.6 |
| Product silicon source utilization rate/% | 69 | 55 | 56 |
| Product crystallinity/% | 103 | 90 | 91 |
| Feed intake silica alumina ratio | 7.0 | 8.4 | 8.3 |
| Product silica alumina ratio | 5.2 | 5.3 | 5.1 |
| n(Na2O)/n(SiO2) | 0.65 | 0.51 | 0.54 |
By 1 experimental data of table it can be seen that when synthesizing the NaY molecular sieve of phase homogenous quantities (18g), the silicon source benefit of embodiment 1
It is 69% with rate, compared with comparative example 1 (55%) and comparative example 2 (56%), is higher by 25.5% and 23.2% respectively；Three kinds of synthesis
The product crystallinity of method is higher, 90% or more；The product silica alumina ratio of three kinds of synthetic methods is similar (5.1-5.3), but
The silica alumina ratio that feeds intake of embodiment 1 is only 7.0, is lower than the silica alumina ratio that feeds intake of comparative example 1 (8.4) and comparative example 2 (8.3)；Three kinds of conjunctions
At the n (Na of method2O)/n(SiO2) in, it is 0.65 that embodiment 1 is higher, because the second silicon source selects sodium silicate solid, raw material sheet
Body contains a certain amount of Na2O, so that the basicity of synthetic system is higher, and point of comparative example 1 (0.51) and comparative example 2 (0.54)
Son sieve can synthesize at lower basicities.
In conclusion the preparation method operating procedure of NaY molecular sieve provided by the invention is simple, cost of material is low, to work
The requirement of skill equipment is low, has very strong application；It can synthesize the NaY molecular sieve with high-crystallinity, improve silicon source
Utilization rate and one-pot yield, silicon source utilization rate can reach 65%-75%, and one-pot yield can be improved 20%-30%, and one-pot produces
Rate reaches twice of traditional handicraft or more；The product grains size uniformity that is finally prepared, silica alumina ratio are high, stability is good；And
And this method solves the problems, such as that industrial waterglass system exists in the case where not increasing cost.
Claims (10)
1. a kind of preparation method of NaY molecular sieve, which comprises the following steps:
According to Na2O:Al2O3: SiO2: H2O=(8-25): 1:(8-25): the molar ratio meter of (150-450), by the first silicon
Source, the first silicon source, alkali source and water mixing are aged to obtain directed agents；
According to Na2O:Al2O3: SiO2: H2O=(3-6): 1:(6-12): total molar ratio meter of (50-150), by the second silicon
Source, the second silicon source, directed agents and water, which mix and adds regulator, stirs to get reaction gel；
Reaction gel is subjected to crystallization, obtains NaY molecular sieve after filtration washing is dry.
2. preparation method according to claim 1, it is characterised in that: first silicon source includes that waterglass and/or silicon are molten
Glue；
Preferably, first silicon source includes one of sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminium chloride or a variety of groups
It closes；
Preferably, the alkali source includes sodium hydroxide；
Preferably, the water includes deionized water.
3. preparation method according to claim 1, it is characterised in that: according to Na2O:Al2O3: SiO2: H2O=(3.5-5):
1:(6.5-9.5): the second silicon source, the second silicon source, directed agents and water are mixed and are added by total molar ratio meter of (85-120)
Regulator stirs to get reaction gel.
4. preparation method according to claim 1 or 3, it is characterised in that: second silicon source includes the silicon of different moduluses
One of sour sodium or a variety of combinations, the modulus of the sodium metasilicate include 1.9-2.1,2.2-2.4,2.7-2.9,2.9-3.1
And 3.1-3.3；Preferably, second silicon source includes the sodium metasilicate that modulus is 2.2-3.3；
Preferably, second silicon source includes one of sodium metaaluminate, aluminum sulfate, aluminum nitrate and aluminium chloride or a variety of groups
It closes；It is further preferred that second silicon source includes sodium metaaluminate and/or aluminum sulfate.
5. preparation method according to claim 1 or 3, it is characterised in that: the regulator includes the concentrated sulfuric acid or aluminum sulfate；
Preferably, it is 12-14 that the regulator, which adjusts the pH value of reaction gel,；It is further preferred that the regulator adjusts reaction gel
PH value be 13-14.
6. preparation method according to claim 1 or 3, it is characterised in that: when preparing reaction gel, first by the second silicon
Pretreatment is carried out in water and obtains active aqueous silica sol, and the second silicon source and directed agents are then added, are eventually adding regulator
Adjust the pH value of reaction system；
Preferably, pretreated temperature is 0-60 DEG C, and the pretreated time is 2-6h.
7. preparation method according to claim 1, it is characterised in that: introduce H by addition water2The weight of O accounts for the reaction
The 30%-80% of gel total weight；Preferably, H is introduced by addition water2The weight of O accounts for the reaction gel total weight
30%-50%；
Preferably, the Al introduced by addition directed agents2O3Weight account for Al in the reaction gel2O3The 5%- of total weight
20%.
8. preparation method according to claim 1, it is characterised in that: the Aging Temperature is 10-35 DEG C, and digestion time is
5-100h；Preferably, digestion time 20-80h；
Preferably, it is 90-110 DEG C that the reaction gel, which carries out the temperature of crystallization, and the time of crystallization is 20-120h；Preferably, brilliant
The time of change is 24-72h.
9. the NaY molecular sieve that any one of the claim 1-8 preparation method is prepared；
Preferably, the silica alumina ratio of the NaY molecular sieve is 5.0-6.0, relative crystallinity 95%-105%；The partial size of crystal grain is
350-500nm；It is further preferred that the partial size of crystal grain is 400-500nm.
10. NaY molecular sieve described in claim 9 as catalyst active component in catalytic cracking, be hydrocracked or be alkylated
Application in oil refining process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810071617.0A CN110078093B (en) | 2018-01-25 | 2018-01-25 | NaY molecular sieve and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810071617.0A CN110078093B (en) | 2018-01-25 | 2018-01-25 | NaY molecular sieve and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110078093A true CN110078093A (en) | 2019-08-02 |
| CN110078093B CN110078093B (en) | 2022-02-01 |
Family
ID=67411890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810071617.0A Active CN110078093B (en) | 2018-01-25 | 2018-01-25 | NaY molecular sieve and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078093B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110803957A (en) * | 2019-10-25 | 2020-02-18 | 新疆红旗坡农业发展集团有限公司 | Apple sugar core anti-digestion physiological regulator and treatment technology |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160676A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Preparation process of fine-grain NaY zeolite |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN104118884A (en) * | 2013-04-23 | 2014-10-29 | 中国石油大学(北京) | Preparation method for NaY molecular sieve |
| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
| CN104826651A (en) * | 2014-02-08 | 2015-08-12 | 中国石油化工股份有限公司 | Preparation method for hydrocracking catalyst |
-
2018
- 2018-01-25 CN CN201810071617.0A patent/CN110078093B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160676A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司 | Preparation process of fine-grain NaY zeolite |
| CN1789125A (en) * | 2004-12-15 | 2006-06-21 | 中国石油化工股份有限公司 | Small crystal grain molecular sieve preparation method |
| CN101722023A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | NaY-type molecular sieves and preparation method thereof |
| CN104118884A (en) * | 2013-04-23 | 2014-10-29 | 中国石油大学(北京) | Preparation method for NaY molecular sieve |
| CN104692412A (en) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve |
| CN104826651A (en) * | 2014-02-08 | 2015-08-12 | 中国石油化工股份有限公司 | Preparation method for hydrocracking catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110803957A (en) * | 2019-10-25 | 2020-02-18 | 新疆红旗坡农业发展集团有限公司 | Apple sugar core anti-digestion physiological regulator and treatment technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110078093B (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107758691B (en) | The preparation method of high silicon CHA types SSZ-13 molecular sieves | |
| CN101643219B (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN102452666B (en) | Method for synthesizing IM-5 molecular sieve | |
| CN105000574B (en) | HZSM-5 molecular sieve with special appearance and preparation method and application thereof | |
| CN101733143A (en) | ZSM-5 molecular sieve with small crystal grains and application thereof | |
| CN104692412A (en) | A method of synthesizing a NaY molecular sieve and the synthesized NaY molecular sieve | |
| CN103043680A (en) | NaY molecular sieve/natural mineral composite material having multistage pore structure and preparation method thereof | |
| CN109775723B (en) | Application of pretreated raw material in preparation of SSZ-13 molecular sieve | |
| CN109701619A (en) | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method | |
| CN1785808A (en) | Preparation method of high silicon aluminium ratio small crystal NaY molecular sieve | |
| CN113044853A (en) | Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio | |
| CN1083021A (en) | Improved zeolite | |
| CN102198950B (en) | Method for preparing NaY molecular sieve with high aluminum-silicon ratio | |
| CN1785807A (en) | High silicon aluminium ratio small crystal NaY molecular sieve | |
| CN100575258C (en) | Adopt solid phase to transform the method for preparing the NaY molecular sieve | |
| CN107285330A (en) | A kind of preparation method of NU-88 molecular sieves | |
| CN102452667B (en) | Method of synthesizing IM-5 molecular sieve by using composite template | |
| CN106276950B (en) | A method of preparing NU-88 molecular sieve | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN106745053A (en) | Microwave synthesizes the method for high selectivity preparing propylene from methanol molecular sieve of Nano zeolite | |
| CN110078093A (en) | A kind of NaY molecular sieve and its preparation method and application | |
| CN103964466B (en) | 5 molecular sieves of a kind of ZSM and preparation method thereof | |
| CN105314651B (en) | A kind of preparation method of small crystal grain NaY molecular sieve | |
| CN103723740B (en) | Synthesis method of IM-5 molecular sieve | |
| CN102701232A (en) | Preparation method of NaY molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |