CN105417553B - A kind of NaY molecular sieve and preparation method thereof - Google Patents
A kind of NaY molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN105417553B CN105417553B CN201410474786.0A CN201410474786A CN105417553B CN 105417553 B CN105417553 B CN 105417553B CN 201410474786 A CN201410474786 A CN 201410474786A CN 105417553 B CN105417553 B CN 105417553B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- filtrate
- siliceous
- nay molecular
- weight
- 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.)
- Active
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 140
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 105
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 92
- 239000010703 silicon Substances 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 35
- 230000008025 crystallization Effects 0.000 claims abstract description 35
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 33
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- 239000004411 aluminium Substances 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 238000011065 in-situ storage Methods 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910000632 Alusil Inorganic materials 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 235000019795 sodium metasilicate Nutrition 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000012797 qualification Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- -1 molecular sieves compound Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation method of NaY molecular sieve, this method includes：Kaolin is roasted, and the product after roasting and silicon source, directed agents are subjected to crystallization, it is characterized in that, the silicon source contains siliceous filtrate, the siliceous filtrate is obtained by the way that the siliceous filtrate of NaY molecular sieve is contacted with alkali compounds, and the contact is so that the NaY molecular sieve crystallite in the siliceous filtrate is below 0.005 weight %.The invention also discloses NaY molecular sieve is planted made from the above method.By using the method for the present invention, the siliceous filtrate after the contact is used to prepare NaY molecular sieve as silicon source, improving the utilization rate of silicon reduces production cost, it is thus also avoided that the outer row of substantial amounts of siliceous filtrate and the pollution to environment.
Description
Technical field
The present invention relates to a kind of NaY molecular sieve and preparation method thereof.
Background technology
NSY molecular sieves are a kind of novel Y-shaped molecular sieves compound materials with double-pore structure, it is handled with high-temperature roasting
Kaolin offer is partly " silicon source " and whole " silicon source ", hydrothermal crystallizing is carried out in alkaline system Extra Section silicon source, in the original position
During crystallization, the part SiO in kaolin2Into people's liquid phase, abundant macropore, NaY molecules are formed in kaolin surface
Crystal growth is sieved in kaolinic outer surface and inner surfaces of pores, so as to form the Y types using kaolin as the double-pore structure of carrier
Molecular sieve (also into NSY molecular sieves), adds catalyst to reactant accessibility and catalytic activity.In actual production process
In, in order to improve the silica alumina ratio of product, the silica alumina ratio often to feed intake is higher than the silica alumina ratio of product, therefore, at qualified NaY points
When son sieve carries out filtering washing, the siliceous filtrate of substantial amounts of NaY molecular sieve will be produced, direct blowdown, can both cause silicon to be lost in, into
This rise, and environmental pollution can be caused.Conventional NaY molecular sieve prepares the siliceous filtrate produced, typically using the siliceous filter of reuse
Liquid first prepares Alusil, and using the Alusil as part " silicon source " and " silicon source " for synthesizing NaY molecular sieve, so as to NaY
Si in the siliceous filtrate of molecular sieve carries out reuse.But this siliceous filtrate recycle mode of NaY molecular sieve both increased and was produced into
This, and since technique feature itself limits, can not realize the fully recovering of filtrate silicon.
The content of the invention
The purpose of the present invention overcomes production cost and difficulty present in the reuse mode of the siliceous filtrate of existing NaY molecular sieve
The defects of to realize silicon fully recovering in the filtrate, there is provided a kind of cost is relatively low, and can realize NaY molecular sieve is siliceous
The method of the preparation NaY molecular sieve of the silicon fully recovering of filtrate, and NaY molecular sieve obtained by this method.
The present inventor is had found by furtheing investigate, due to containing substantial amounts of NaY points in the siliceous filtrate of NaY molecular sieve
Son sieve crystallite, if directly carrying out reuse using the siliceous filtrate of NaY molecular sieve as the silicon source of synthesis NaY molecular sieve, it will serious
Influence the synthesis of NaY molecular sieve, and the structure and poor-performing of gained NaY molecular sieve.Based on the discovery, the present inventor
By the way that the siliceous filtrate of NaY molecular sieve and alkali compounds are contacted, and to be practically free of in the siliceous filtrate of NaY molecular sieve
There is NaY molecular sieve crystallite, so that the siliceous filtrate of NaY molecular sieve after contact can not only be effective as to silicon source prepares NaY
Molecular sieve, realizes the fully recovering of silicon source, and obtained NaY molecular sieve with crystallinity it is high, with diplopore, high silica alumina ratio
Etc. excellent performance.
To achieve these goals, the present invention provides a kind of preparation method of NaY molecular sieve, and this method includes：By kaolinite
Soil is roasted, and the product after roasting and silicon source, directed agents are carried out crystallization, wherein, the silicon source contains siliceous filter
Liquid, the siliceous filtrate are obtained by the way that the siliceous filtrate of NaY molecular sieve is contacted with alkali compounds, and the contact makes
The NaY molecular sieve crystallite obtained in the siliceous filtrate is below 0.005 weight %.
Present invention also offers the NaY molecular sieve as made from the above method.
By using the method for the present invention, the siliceous filtrate after the contact is used to prepare NaY molecular sieve as silicon source,
Improving the utilization rate of silicon reduces production cost, it is thus also avoided that the outer row of substantial amounts of siliceous filtrate and the pollution to environment.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of NaY molecular sieve, and this method includes：Kaolin is roasted, and will roasting
Product after burning carries out crystallization with silicon source, directed agents, wherein, the silicon source contains siliceous filtrate, and the siliceous filtrate is led to
Cross and the siliceous filtrate of NaY molecular sieve is contacted with alkali compounds and is obtained, the contact is so that in the siliceous filtrate
NaY molecular sieve crystallite is below 0.005 weight %.
According to the present invention, in order to obtain the NaY molecular sieve of function admirable, the kaolin can usually roasted
Before, kaolin microsphere is prepared into using the method for this area routine, such as slurry first is made in kaolin and water, then spray
Microballoon (granularity of microballoon is, for example, 1-100 μm) is shaped to, the present invention is not particularly limited the kaolin, Ke Yiwei
Commercially available various conventional kaolin products, under preferable case, with SiO in the kaolin microsphere2The content of the element silicon of meter
For 45-55 weight %, with Al2O3The content of the aluminium element of meter is 42-48 weight %.
According to the present invention, the roasting condition of the kaolin microsphere is not particularly limited, can uses and prepare
The kaolin method of roasting of this area routine during NaY molecular sieve, in order to enable the kaolinic active higher after roasting, preferably feelings
Under condition, the condition of the roasting includes：Temperature is 600-900 DEG C, time 2.5-3.5h.
According to the present invention, the product after roasting and silicon source, directed agents are subjected to crystallization, you can obtain the present invention's
NaY molecular sieve.The crystallization can carry out in water, and under preferable case, the condition of the crystallization includes：PH is
12-13, temperature are 90-96 DEG C, time 30-45h.It is highly preferred that the condition of the crystallization includes：PH is 12-12.5,
Temperature is 92-96 DEG C, time 30-40h.Wherein, the alkaline condition that pH is 12-13 (be preferably 12-12.5) by sodium hydroxide,
The collective effect of waterglass and directed agents is adjusted.
According to the present invention, in order to obtain excellent NaY type molecular sieves, under preferable case, the kaolin microsphere and described
The dosage of silicon source make it that the molar ratio of element silicon and aluminium element is 5-6：1, more preferably 5.2-5.8：1.
According to the present invention, in order to enable the more preferable in-situ crystallization of kaolin obtains NaY molecular sieve, under preferable case, in institute
In the reaction system for stating crystallization, the dosage of the kaolin and the silicon source causes with SiO2The content of the element silicon of meter is
18-30 weight %, with Al2O3The content of the aluminium element of meter is 2-6 weight %.Here the content (or aluminium element) of element silicon
Content refers in the reaction system of crystallization in the original location that element silicon (or aluminium element) accounts for the material in whole reaction system
The percetage by weight of total amount.
In the present invention, the silicon source contains siliceous filtrate, and the siliceous filtrate is by by the siliceous filtrate of NaY molecular sieve
Contacted and obtained with alkali compounds.The silicon source can be with all siliceous filtrate, or part is siliceous filtrate, preferably
Ground, on the basis of the mole of the element silicon in the silicon source, in the silicon source containing 0.5-80 moles of % in terms of element silicon
Siliceous filtrate.The siliceous filtrate in terms of element silicon containing 0.6-20 moles of % in more preferably described silicon source.When the silicon source
Part when being siliceous filtrate, remaining part silicon source can use the silicon source of this area routine, such as sodium metasilicate, Alusil
Deng.
In the present invention, the siliceous filtrate can directly contact the siliceous filtrate of NaY molecular sieve with alkali compounds
Solution afterwards, the content of element silicon and aluminium element in the siliceous filtrate by the element silicon in the siliceous filtrate of NaY molecular sieve and
The content of aluminium element is determined, and those skilled in the art are it will be obvious that the silicon usually in the siliceous filtrate of NaY molecular sieve is first
The content of element and aluminium element is relatively low, and therefore, solution after directly the siliceous filtrate of NaY molecular sieve is contacted with alkali compounds is made
When being used for for the siliceous filtrate as part silicon source, element silicon when it can not meet to prepare the NaY molecular sieve of the present invention
With the needs of the molar ratio of aluminium element, therefore, under normal circumstances, it is necessary to will using this area routine silicon source as feed silicon
Source, such as sodium metasilicate, Alusil etc..But in this case, due to directly by the siliceous filtrate of NaY molecular sieve and alkaline chemical combination
Solution after thing contact is used to, as the part silicon source for preparing NaY molecular sieve, particularly carry out as the siliceous filtrate
On a large scale, can be by the siliceous filtrate of substantial amounts of NaY molecular sieve into enforcement in the industrialized production of multiple retort simultaneous reactions
With being handled without devoting a tremendous amount of time it, siliceous filter can be reduced while the utilization rate of increased silicon
The discharge capacity of liquid waste water, has unexpected economic benefit for large-scale industrial production.
As described above, the siliceous filtrate of above-mentioned NaY molecular sieve of the present invention can after being contacted with the alkali compounds
To be used directly as the siliceous filtrate as the part silicon source for preparing NaY molecular sieve, but can also be in above-mentioned NaY
The siliceous filtrate of molecular sieve with the alkali compounds after being contacted, then carries out content and aluminium that heating concentration obtains element silicon
The all or part of silicon source that the siliceous filtrate of the content higher of element is re-used as preparing NaY molecular sieve is used, but is gone out
From the aspect of saving the energy and reducing cost, preferably directly the siliceous filtrate of NaY molecular sieve is carried out with the alkali compounds
Solution after contact is used as the part silicon source for preparing NaY molecular sieve to be used as the siliceous filtrate.
Due to containing a certain amount of NaY molecular sieve crystallite in the siliceous filtrate of NaY molecular sieve, the present invention is used as silicon source
Siliceous filtrate be as obtained from the siliceous filtrate of the NaY molecular sieve is contacted with alkali compounds liquid.Pass through
The siliceous filtrate of NaY molecular sieve is contacted with alkali compounds, the NaY molecular sieve crystallite contained in filtrate is almost molten
Solution, is below 0.005 weight %.Preferably, the contact is so as to be entirely free of NaY molecular sieve micro- in the siliceous filtrate
It is brilliant.Undesirable influence is caused on NaY molecular sieve synthesis so as to avoid due to the NaY molecular sieve crystallite contained in siliceous filtrate.
Contained NaY molecular sieve crystallite is due to after crystallization is washed with water in the siliceous filtrate of NaY molecular sieve
During product part crystallite eluted from microballoon and can be into the crystallite of people's filtrate, such as the granularity of the NaY molecular sieve crystallite
It can be below 500nm, be preferably 500-200nm.The present invention does not also limit the amount of the NaY molecular sieve crystallite particularly
Fixed, its content is determined by situation about filtering, such as the amount of the NaY molecular sieve crystallite is 1-5 weight %.
Why the siliceous filtrate of NaY molecular sieve can be used after being contacted with alkali compounds as silicon source, be to be that it contains
There are a certain amount of element silicon and aluminium element, and be to be filtered by crystallization and obtained, other impurity elements will not be substituted into again, this
The element silicon and the amount of aluminium element that contain in the siliceous filtrate of NaY molecular sieve are not particularly limited in invention, as long as can
It is to prepare the content of the element silicon contained in NaY molecular sieve, such as the siliceous filtrate of the NaY molecular sieve as silicon source
0.09-0.15 weight %, the content of aluminium element is 0.025-0.04 weight %.
In the case of, according to the invention it is preferred to, bar that the siliceous filtrate of NaY molecular sieve is contacted with alkali compounds
Part includes：Temperature is 90-96 DEG C, time 2-4.Preferably, the alkali compounds is sodium hydroxide and/or sodium methoxide, more
Preferably sodium hydroxide.
According to the present invention, to the alkalescence when the siliceous filtrate of the NaY molecular sieve is contacted with the alkali compounds
The dosage of compound is not particularly limited, as long as it is 0.005 to enable to the NaY molecular sieve crystallite in the siliceous filtrate
Below weight % (very micro, it is believed that not contain).Under preferable case, the NaY molecular sieve in terms of element silicon is siliceous
The weight ratio of NaY molecular sieve crystallite and the alkali compounds in filtrate is 1：0.08-0.1, more preferably 1：0.08-0.09.
According to the present invention, the crystallization reacts for kaolin in-situ crystallization., wherein it is desired to add directed agents.This hair
It is bright that the directed agents are not particularly limited, as long as the progress of crystallization can be induced as the crystal seed of NaY molecular sieve
, under preferable case, the chemical expression of the directed agents in mol is：(12-16)SiO2·Al2O3·(14-18)
Na2O·(300-350)H2O。
Can be the routine of this area in addition, in the present invention, also being had no particular limits to the dosage of the directed agents
Dosage.Under preferable case, the product after roasting for 100 parts by weight, the dosage of the directed agents is 40-60 parts by weight.
In the case of, according to the invention it is preferred to, this method further includes：The product after the crystallization and solid-liquid is washed with water
Separation, and liquid phase obtained by separation of solid and liquid is used as the siliceous filtrate of the NaY molecular sieve.That is, siliceous filtrate will be employed to make
After the above-mentioned crystallization of silicon source (part or all of) carry out, the product of crystallization with water wash and solid-liquid divides
From liquid phase obtained by separation of solid and liquid is also a kind of siliceous filtrate of NaY molecular sieve, can be equally used for making after contacting with alkali compounds
Reused for silicon source.
Present invention also offers the NaY molecular sieve being prepared by the above method.
The present invention will be described in detail by way of examples below.
In following preparation example, embodiment and comparative example,
NaY molecular sieve content in solids product and siliceous filtrate according to RIPP146-90 standard methods (see《Petrochemical industry
Analysis method》(RIPP test methods), Yang Cui delimits the organizational structure, Science Press, and nineteen ninety publishes) measure, wherein, it is less than test limit
It is considered as 0 weight % less than 0.005 weight %；
The product quality situation of NaY molecular sieve in solids product is by measuring NaY molecular sieve crystalline substance according to X-ray diffractometer
The distribution situation of body is analyzed.
Preparation example 1
This preparation example is used for the preparation method for illustrating the siliceous filtrate of the present invention.
Kaolin is made kaolin microsphere, and (granularity is 2 μm, with SiO2The content of the element silicon of meter is 50 weight %, with
Al2O3The content of the aluminium element of meter is 45 weight %), 3h then is roasted at 700 DEG C, the product, 453g after 100g is roasted
Directed agents (the 14SiO of sodium metasilicate, 50g2·1Al2O3·17Na2O·300H2O) and 54g 24 weight % sodium hydrate aqueous solutions
(so that pH is 12.2) is added in the water of 500mL, and in-situ crystallization reacts 28h at 93 DEG C；With 500ml water washing crystallizations
Product afterwards and separation of solid and liquid, gained solid phase 556g, the wherein content of NaY molecular sieve are 74.5 weight %, and according to X-ray diffraction
Instrument is qualification by measuring the distribution situation of NaY molecular sieve crystal, its product quality；Gained liquid phase is NaY for 1000g
The siliceous filtrate of molecular sieve, the wherein content of NaY molecular sieve crystallite are 1.3 weight %, and granularity is below 500nm, and element silicon contains
Measure as 0.99 weight %, the content of aluminium element is 0.31 weight %.
1.07g sodium hydroxides, the haptoreaction 3h at 95 DEG C so that NaY are added into the siliceous filtrate of above-mentioned NaY molecular sieve
The content of NaY molecular sieve crystallite in the siliceous filtrate of molecular sieve is 0 weight %, so as to obtain siliceous filtrate A1.
Embodiment 1
The present embodiment is used to illustrating that the kaolin in-situ crystallization of the present invention to prepare the method for NaY molecular sieve and its obtained
NaY molecular sieve.
Kaolin is made kaolin microsphere, and (granularity is 2 μm, with SiO2The content of the element silicon of meter is 50 weight %, with
Al2O3The content of the aluminium element of meter is 45 weight %), 3h then is roasted at 700 DEG C, product, 100g systems after 100g is roasted
Sodium metasilicate, the directed agents (14SiO of 50g of siliceous filtrate A1,450g of the standby gained of example 12·1Al2O3·17Na2O·300H2O)
(so that pH is 12.5) is added in the water of 350mL with the 20 weight % sodium hydrate aqueous solutions of 5.8g, it is in situ brilliant at 93 DEG C
Change reaction 28h；With the product after 400ml water washing crystallizations and separation of solid and liquid, wherein gained solid phase 557g, NaY molecular sieve
Content be 73.6 weight %, and according to X-ray diffractometer by measuring the distribution situation of NaY molecular sieve crystal, its product
Quality is qualification；Gained liquid phase (820g) is the siliceous filtrate of NaY molecular sieve, and wherein the content of NaY molecular sieve crystallite is 1.5 weights
% is measured, granularity is below 500nm, and the content of element silicon is 0.97 weight %, and the content of aluminium element is 0.3 weight %.
1g sodium hydroxides, the haptoreaction 2.5h at 96 DEG C are added into the siliceous filtrate of the NaY molecular sieve so that NaY points
The content that son sieves the NaY molecular sieve crystallite in siliceous filtrate is 0 weight %, so as to obtain siliceous filtrate A2.
Embodiment 2
The present embodiment is used to illustrating that the kaolin in-situ crystallization of the present invention to prepare the method for NaY molecular sieve and its obtained
NaY molecular sieve.
Kaolin is made kaolin microsphere, and (granularity is 10 μm, with SiO2The content of the element silicon of meter is 50 weight %, with
Al2O3The content of the aluminium element of meter is 45 weight %), 2.5h then is roasted at 800 DEG C, product, 200g after 100g is roasted
Sodium metasilicate, the directed agents (15SiO of 50g of siliceous filtrate A2,445g of the gained of embodiment 12·Al2O3·15Na2O·350H2O)
(so that pH is 12) is added in the water of 200mL with the 30 weight % sodium hydrate aqueous solutions of 4g, and in-situ crystallization is anti-at 95 DEG C
Answer 25h；With the product after 500ml water washing crystallizations and separation of solid and liquid, obtained solid 561g's, wherein NaY molecular sieve
Content is 73.2 weight %, and according to X-ray diffractometer by measuring the distribution situation of NaY molecular sieve crystal, its product matter
Measure as qualification；Gained liquid phase (840g) is the siliceous filtrate of NaY molecular sieve, and wherein the content of NaY molecular sieve crystallite is 1.43 weights
% is measured, granularity is below 500nm, and the content of element silicon is 0.98 weight %, and the content of aluminium element is 0.33 weight %.
Embodiment 3
The present embodiment is used to illustrating that the kaolin in-situ crystallization of the present invention to prepare the method for NaY molecular sieve and its obtained
NaY molecular sieve.
Kaolin is made kaolin microsphere, and (granularity is 8 μm, with SiO2The content of the element silicon of meter is 50 weight %, with
Al2O3The content of the aluminium element of meter is 45 weight %), 3h then is roasted at 850 DEG C, the product, 100g after 100g is roasted
Siliceous filtrate A1 (by heating concentration so that the content of element silicon is 12 weight %, and the content of aluminium element is 3.5 weight %),
430g sodium metasilicate, 60g directed agents (16SiO2·Al2O3·16Na2O·340H2O) and 6g 25 weight % sodium hydrate aqueous solutions
(so that pH is 12.3) is added in 400mL water, and in-situ crystallization reacts 30h at 94 DEG C；After 500ml water washing crystallizations
Product and separation of solid and liquid, gained solid phase is that the content of NaY molecular sieve in 547g is 75.1 weight %, and according to X-ray diffractometer
By measuring the distribution situation of NaY molecular sieve crystal, its product quality is qualification；Gained liquid phase (950g) is NaY points
Son sieves siliceous filtrate, and the wherein content of NaY molecular sieve crystallite is 1.37 weight %, and granularity is below 500nm, the content of element silicon
For 0.92 weight %, the content of aluminium element is 0.27 weight %.
1.1g sodium hydroxides, the haptoreaction 4h at 90 DEG C so that NaY are added into the siliceous filtrate of above-mentioned NaY molecular sieve
The content of NaY molecular sieve crystallite in the siliceous filtrate of molecular sieve is 0 weight %, so as to obtain siliceous filtrate A3.
Comparative example 1
According to the method described in embodiment 1, the difference is that adding the 9 of 2g into the siliceous filtrate of NaY molecular sieve of 100g
Weight % aluminum sulfate solutions, are made the Alusil of 1.2g, and the content of element silicon is 0.75 weight % in residual solution, aluminium element
Content is 1.5 weight %；Crystallization, gained solid phase are carried out using the Alusil as the siliceous filtrate of replacement as part silicon source
The content of 548g, wherein NaY molecular sieve are 73.5 weight %, and according to X-ray diffractometer by measuring dividing for NaY molecular sieve crystal
Cloth situation understands that its product quality is qualification；Gained liquid phase (750g) is the siliceous filtrate of NaY molecular sieve, wherein NaY molecular sieve
The content of crystallite is 2.3 weight %, and granularity is below 500nm, and the content of element silicon is 1.34 weight %, and the content of aluminium element is
0.6 weight %.
Comparative example 2
According to the method described in embodiment 1, the difference is that directly using the siliceous filtrate of the NaY molecular sieve of 100g as silicon
Source carries out crystallization, and the content of NaY molecular sieve be 72.5 weight % in gained solid phase (545g), but product caking is seriously,
Uneven dispersion body is presented, it is off quality；Gained liquid phase (825g) is the siliceous filtrate of NaY molecular sieve, wherein NaY molecular sieve
The content of crystallite is 1.8 weight %, and granularity is below 500nm, and the content of element silicon is 1.1 weight %, and the content of aluminium element is
0.37 weight %.
By above-described embodiment, method using the present invention carries out preparation NaY molecular sieve, can improve siliceous filtrate
In silicon and aluminium utilization rate.
In addition, when method using the present invention carries out preparation NaY molecular sieve, fresh water can be saved by producing molecular sieve per ton
More than 5 tons, reduce more than 5 tons of externally discharged waste water.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of preparation method of NaY molecular sieve, this method include：Kaolin is roasted, and by the product after roasting with
Silicon source, directed agents carry out crystallization, it is characterised in that the silicon source contains siliceous filtrate, and the siliceous filtrate is by by NaY
The siliceous filtrate of molecular sieve is contacted and is obtained with alkali compounds, and the contact is so that the NaY in the siliceous filtrate divides
Son sieve crystallite is below 0.005 weight %；The alkali compounds is sodium hydroxide and/or sodium methoxide, and the NaY molecular sieve contains
The weight ratio of NaY molecular sieve crystallite and the alkali compounds in silicon filtrate is 1：0.08-0.1.
2. according to the method described in claim 1, wherein, on the basis of the mole of the element silicon in the silicon source, the silicon
The siliceous filtrate in terms of element silicon containing 0.5-80 moles of % in source.
3. according to the method described in claim 1, wherein, the dosage of the kaolin and the silicon source causes element silicon and aluminium member
The molar ratio of element is 5-6：1.
4. according to the method described in claim 3, wherein, the dosage of the kaolin and the silicon source causes element silicon and aluminium member
The molar ratio of element is 5.2-5.8：1.
5. according to the method described in claim 1,3 or 4, wherein, in the reaction system of the crystallization, the kaolin
Cause with the dosage of the silicon source with SiO2The content of the element silicon of meter is 18-30 weight %, with Al2O3The aluminium element of meter contains
Measure as 2-6 weight %.
6. according to the method described in claim 1, wherein, NaY molecular sieve crystallite and institute in the siliceous filtrate of NaY molecular sieve
The weight ratio for stating alkali compounds is 1：0.08-0.09.
7. according to the method described in claim 1, wherein, the chemical expression of the directed agents in mol is：(12-16)
SiO2·Al2O3·(14-18)Na2O·(300-350)H2O。
8. according to the method described in claim 1, wherein, relative to the product after the roasting of 100 parts by weight, the directed agents
Dosage is 40-60 parts by weight.
9. according to the method described in any one in claim 1-4 and 7-8, wherein, in the siliceous filtrate of NaY molecular sieve
The content of element silicon is 0.09-0.15 weight %, and the content of aluminium element is 0.025-0.04 weight %.
10. according to the method described in claim 1, wherein, the condition of the crystallization includes：PH is 12-13, and temperature is
90-96 DEG C, time 30-45h.
11. according to the method described in claim 1, wherein, by the siliceous filtrate of the NaY molecular sieve and the alkali compounds into
The condition of row contact includes：Temperature is 90-96 DEG C, time 2-4h.
12. according to the method described in claim 1, wherein, the condition of the roasting includes：Temperature is 600-900 DEG C, and the time is
2.5-3.5h。
13. according to the method described in claim 1, wherein, this method further includes：The product after the crystallization is washed with water
And separation of solid and liquid, and liquid phase obtained by separation of solid and liquid is used as the siliceous filtrate of the NaY molecular sieve.
14. the NaY molecular sieve being prepared as the method described in any one in claim 1-13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410474786.0A CN105417553B (en) | 2014-09-17 | 2014-09-17 | A kind of NaY molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410474786.0A CN105417553B (en) | 2014-09-17 | 2014-09-17 | A kind of NaY molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105417553A CN105417553A (en) | 2016-03-23 |
| CN105417553B true CN105417553B (en) | 2018-04-13 |
Family
ID=55496175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410474786.0A Active CN105417553B (en) | 2014-09-17 | 2014-09-17 | A kind of NaY molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105417553B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114715909B (en) * | 2021-01-06 | 2023-05-26 | 中国石油天然气股份有限公司 | Kaolin in-situ synthesized small-grain NaY molecular sieve and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | A kind of synthetic method of Y-type zeolite composite material |
| CN102050468A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing NaY molecular sieve by using crystallized mother liquor of molecular sieve |
-
2014
- 2014-09-17 CN CN201410474786.0A patent/CN105417553B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | A kind of synthetic method of Y-type zeolite composite material |
| CN102050468A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing NaY molecular sieve by using crystallized mother liquor of molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| 合成分子筛母液及其利用研究;周继红;《现代化工》;20100228;第30卷(第2期);22页第2栏第15行至第20行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105417553A (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI66298B (en) | FOERFARANDE FOER FRAMSTAELLNING AV KRISTALLINA ALKALIMETALLALUMOSILIKATBASBYTARMATERIAL | |
| CN104229818B (en) | Synthesis method of beta molecular sieve | |
| CN108264057B (en) | Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite | |
| CN105032478B (en) | A kind of catalyst and its dedicated core-shell structure compound molecular sieve for the oily isomerization-visbreaking of F-T synthetic middle distillates point | |
| CN100389067C (en) | The preparation method of ZSM-5 type molecular sieve | |
| CN104671265A (en) | A method of preparing pseudoboehmite | |
| US9758677B2 (en) | Plate-like aluminum oxide and preparation method therefor | |
| CN102951656B (en) | Method for synthesizing even-grained ZSM-5 molecular sieves | |
| CN104229826A (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN101439863B (en) | Preparation of Beta molecular sieve | |
| CN105271300A (en) | Molecular sieve catalyst, and preparation method and application thereof | |
| CN105417553B (en) | A kind of NaY molecular sieve and preparation method thereof | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN105621449B (en) | A kind of NaY types molecular sieve and preparation method thereof | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN102701232B (en) | Preparation method of NaY molecular sieve | |
| CN107108475B (en) | The manufacturing method of acetonitrile | |
| JPH05310415A (en) | Production of zeolite fine particle | |
| CN106115733A (en) | A kind of preparation method of multi-stage porous mordenite molecular sieve | |
| CN116371459B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN110526259B (en) | Method for in-situ synthesis of ZSM-5 by kaolin microspheres | |
| CN100469695C (en) | Molecular sieve with core-shell structure and its preparation method and application | |
| CN107519927B (en) | Y/ZSM-22/SAPO-34/ASA/MOF composite material and preparation method thereof | |
| CN101830479B (en) | A kind of fluorine-containing T-type zeolite molecular sieve and preparation method thereof | |
| CN101559963B (en) | Method using microemulsion to prepare three-dimensional netty activated aluminium oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |