CN108640126A - A method of preparing ZSM-5 molecular sieve with small crystal grains using filtrate - Google Patents
A method of preparing ZSM-5 molecular sieve with small crystal grains using filtrate Download PDFInfo
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- CN108640126A CN108640126A CN201810644340.6A CN201810644340A CN108640126A CN 108640126 A CN108640126 A CN 108640126A CN 201810644340 A CN201810644340 A CN 201810644340A CN 108640126 A CN108640126 A CN 108640126A
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- filtrate
- molecular sieve
- zsm
- silicon source
- crystallization
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- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
Abstract
The present invention provides a kind of methods using 5 molecular sieve of filtrate synthesizing small crystal grain ZSM-5, this method is without using template, use Ludox and white carbon for silicon source, aluminium hydroxide is silicon source, filtrate after upper 5 Crystallization of Zeolite of kettle ZSM is synthesized replaces water, part silicon source, part silicon source, part alkali, and 5 molecular sieve of fine grain ZSM-5 of 190 340nm can be obtained after hydrothermal crystallizing.This method does not prepare 5 molecular sieve of fine grain ZSM-5 only with Template-free method method, without Organic Ingredients method, and filtrate is efficiently recycled to use, and Atom economy is up to 100%.
Description
Technical field
The invention belongs to ZSM-5 molecular sieve with small crystal grains preparing technical fields, more particularly to utilize filtrate to prepare little crystal grain
The method of ZSM-5 molecular sieve.
Background technology
In liquid-solid reaction system, catalyst crystal grain is small, and reactant contacts more abundant with active sites, and resistance to mass tranfer is small,
Diffusion is fast, often active higher.Therefore, the synthesis of small-grain ZSM-5 is always the hot spot of field of catalyst preparation research.Small crystalline substance
The synthesis of grain ZSM-5 is essentially divided into two major classes method.First kind method uses organic silicon source (tetraethyl orthosilicate, organosilicon
Alkane etc.), organic silicon source (aluminium isopropoxide etc.) or organic formwork agent (4 third season ammonium hydroxide, organic amine) prepare fine grain ZSM-5-
5 molecular sieves.Organic amine is respectively adopted in CN1699173, CN1715186 and quaternary ammonium salt prepares the small crystalline substance of tens and 200nm or so
Grain ZSM-5.CN101244391 is using the organosiloxane of low molecular weight as silicon source, in the presence of template, hydrothermal crystallizing system
It is standby go out crystal grain in the small crystal grain ZSM-5 zeolite of 100-500nm, and use it for the shape-selective catalyst of selective disproportionation of toluene, obtain
Obtained high activity and selectivity.The shortcomings that such method is to need that organic formwork agent is added or use organic silicon source, system with molecular sieve for preparing
Make it is of high cost, and the later stage also need to molecular sieve carry out calcination process, seriously pollute air environment.Second class method is then to body
Suitable alkali metal salt, especially sodium salt are added in system, sodium ion can promote nucleus to generate in synthetic system, to obtain
Small crystal grain molecular sieve.The shortcomings that such method is that the sodium salt being added needs to carry out washing removing with a large amount of water in the later stage.
It can be seen that have many researchs for the preparation of small-grain ZSM-5 at present, or using organic silicon source, silicon source, or add
Enter organic formwork agent, or alkali metal salt is added, but the ZSM-5 molecular sieve that these methods are prepared is required to further rear place
Reason, increases operating procedure and cost, and can cause environmental pollution.
Invention content
The purpose of the present invention is to provide a kind of method using -5 molecular sieve of filtrate synthesizing small crystal grain ZSM-5, the mistakes of synthesis
Inorganic silicon source and silicon source are used in journey, and any template or alkali metal salt need not additionally be added, it is easy to operate, it is of low cost.
And the filtrate after Zeolite synthesis can also be efficiently used, it further reduces the cost, eliminates discharging of waste liquid, really realize green
Synthesis.
To achieve the above object, the technical solution adopted by the present invention is：
A method of ZSM-5 molecular sieve with small crystal grains being prepared using filtrate, which is by silicon source, silicon source, alkali source
It is uniformly mixed to form mixed liquor with upper level crystallization filtrate, wherein silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali source is with Na2O
It counts, each material mol ratio is Na in mixed liquor2O:SiO2:Al2O3:H2O=12:150:3:3000；By mixed liquor hydrothermal crystallizing, obtain
ZSM-5 molecular sieve slurries, be then centrifuged for washing to PH be 7-8, dry obtained ZSM-5 molecular sieve at 100 DEG C；
Wherein, it is (1-0) that silicon source, which is the molar ratio of element silicon,:The Ludox of (0-1) and the mixture of white carbon, silicon source are
Aluminium hydroxide or aluminium oxide, alkali source are sodium hydroxide.
As currently preferred, the specific step of the preparation method is：
(1) prepared by silicon source mixture：Upper level crystallization filtrate is divided into two parts, is first part of upper level crystallization filtrate and the
Ludox and white carbon are added in first part of upper level crystallization filtrate two parts of upper level crystallization filtrates, and stirring keeps its mixing equal
It is even, form A liquid；
(2) prepared by silicon source mixture：Aluminium hydroxide or aluminium oxide are added in the aqueous solution of NaOH, dissolved by heating, is generated
Sodium aluminate solution is slowly added into second part of upper level crystallization filtrate by sodium aluminate solution, and stirring makes it be uniformly mixed,
Form B liquid；NaOH can be completely dissolved by the amount of required water in the step；
(3) prepared by ZSM-5 molecular sieve：By in step (1) and (2) A liquid and B liquid be uniformly mixed, by mixed liquor after ageing
It is transferred to hydrothermal crystallizing in crystallizing kettle, ZSM-5 molecular sieve slurries is obtained, is then centrifuged for, washs, drying obtained ZSM-5 molecular sieve.
As currently preferred, the upper level crystallization filtrate is after Template-free method hydrothermal synthesis method prepares ZSM-5
The preparation process of the filtrate of separation, the crystallization filtrate of initial level-one is：Using Ludox and white carbon as silicon source, aluminium oxide is aluminium
Source, sodium hydroxide are alkali source, and Ludox and white carbon are added to the water, and form silicon source, and aluminium oxide is dissolved in sodium hydrate aqueous solution
Silicon source and silicon source are mixed, are stirred evenly by middle formation silicon source, form precursor liquid, and hydrothermal crystallizing obtains ZSM-5 molecular sieve slurries,
Products therefrom after slurries crystallization is detached, ZSM-5 molecular sieve is obtained, filtrate is the crystallization filtrate of initial level-one.
As currently preferred, the condition of the hydrothermal crystallizing is that first room temperature is aged 8-24h, 170-190 DEG C of crystallization 18-
36h。
As currently preferred, the silica particles size is 1-40nm.
As currently preferred, the silica particles size is 1-30nm.
In the present invention in the preparation process of ZSM-5 molecular sieve with small crystal grains, crystallization filtrate is substantially instead of in mixed liquor
Water, part silicon source, part silicon source, part alkali source, the small of 190-340nm is prepared using the charging process hydrothermal crystallizing of cocurrent
Grain ZSM-5 molecular sieve.The ZSM-5 molecular sieve with small crystal grains that the present invention is prepared using upper level crystallization filtrate is to be based on containing in filtrate
The particle for the molecular sieve for having some primary MFI skeleton structure units, playing the role of crystal seed in synthesis next time, therefore prepare
It is smaller.
Compared with prior art, beneficial effects of the present invention are：
1, the present invention prepares the method simplicity of ZSM-5 molecular sieve with small crystal grains using filtrate, not only reduces the input of raw material
Amount, avoids the discharge of waste liquid, solves problem of environmental pollution, gained ZSM-5 molecular sieve grain size 190-340nm it
Between.
2, preparation method of the present invention compares traditional small-grain ZSM-5 preparation method, and this method has at low cost, zero-emission
And the advantages that energy saving, it is more advantageous to commercial Application.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail.
Comparative example 1
With Ludox and particle size, for the white carbon of 7nm, (the element silicon molar ratio of two kinds of silicon sources is 1:0.5) it is silicon source,
Aluminium oxide is silicon source, and sodium hydroxide is alkali source, and water is solvent, Ludox and white carbon is added to the water to form silicon source, hydroxide
Aluminium, which is dissolved in the aqueous solution of sodium hydroxide, forms silicon source, and silicon source is uniformly mixed with silicon source, forms precursor liquid, and the PH of precursor liquid is
12-13, silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali source is with Na2O is counted, and the molar ratio of each substance is 12Na in precursor liquid2O:
150SiO2:3Al2O3:3000H2O, room temperature are aged for 24 hours, and the mixed liquor after ageing is packed into the crystallizing kettle of 2L, 180 DEG C of crystallization
36h is cooled to room temperature, and is filtered, wherein filtrate retention is spare when filtering, solid is then washed, dried, and obtains the ZSM-5 of 1um or so
Molecular sieve.It is denoted as A1.
Embodiment 1
Using Ludox and particle size, for the white carbon of 7nm, as silicon source, (the element silicon molar ratio of two kinds of silicon sources is 1:0.1),
Aluminium hydroxide is silicon source, and sodium hydroxide is alkali source, and the filtrate (120g, as upper level crystallization filtrate) in comparative example 1 is solvent,
Filtrate is divided into two parts, such as 80g and 40g can be divided into, Ludox and white carbon are added in the filtrate of 80g, is uniformly mixed,
A liquid is formed, aluminium hydroxide is added in the aqueous solution of sodium hydroxide, is dissolved by heating and be added in the filtrate of 40g, B liquid is formed,
Make A liquid and B liquid with cocurrent process while being slowly added in 500mL sky round-bottomed flasks, the molar ratio of each substance is in mixed liquor
12Na2O:150SiO2:3Al2O3:3000H2O is aged, crystallization, wherein filtrate is stayed after crystallization according to the condition of comparative example 1
It saves as to prepare next time and use, the ZSM-5 molecular sieve of 250nm or so is obtained after solid drying.It is denoted as A2.
According to the preparation method of A2, recycles be prepared into the 9th filtrate successively, the ZSM-5 molecular sieve obtained is denoted as successively
A3、A4、A5、A6、A7、A8、A9、A10。
Embodiment 2
It is that as silicon source, (the element silicon molar ratio of two kinds of silicon sources is 1 to 40nm or so white carbons using Ludox and particle size:
0.2), aluminium hydroxide is silicon source, and sodium hydroxide is alkali source, is solvent with the filtrate (120g) in comparative example 1, filtrate is divided into two
Part, such as 80g and 40g can be divided into, Ludox and white carbon are added in the filtrate of 80g, are uniformly mixed, A liquid is formed, by hydrogen
Aluminium oxide is added in the aqueous solution of sodium hydroxide, dissolves by heating and is added in the filtrate of 40g, forms B liquid, with cocurrent process by A
Liquid and B liquid are slowly added in 500mL sky round-bottomed flasks simultaneously, and it is 12Na to make the molar ratio of each substance in mixed liquor2O:150SiO2:
3Al2O3:3000H2O is aged, crystallization according to the condition of comparative example 1, and filtrate is retained wherein after crystallization makes for preparation next time
With solid obtains the ZSM-5 molecular sieve of 970nm or so after drying.It is denoted as B2.
According to the preparation method of B2, recycles be prepared into the 4th filtrate successively, the ZSM-5 molecular sieve obtained is denoted as successively
B3、B4、B5。
ZSM-5 molecular sieve achieved above is subjected to SEM and measures grain size, 1 series gained sample crystal grain of embodiment is big
It is small between 190-340nm.2 series gained sample grain size of embodiment is between 700-970nm.
The grain size result of 1 gained ZSM-5 molecular sieve of table
The condition of hydrothermal crystallizing can also be selected as first room temperature ageing 8h, 170 or 190 DEG C of crystallization 18h in the embodiment of the present invention,
As long as first room temperature is aged 8-24h, all belonged to the scope of protection of the present invention under conditions of 170-190 DEG C of crystallization 18-36h.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of method preparing ZSM-5 molecular sieve with small crystal grains using filtrate, which is characterized in that the specific step of the preparation method
For：
（1）It is prepared by silicon source mixture：Upper level crystallization filtrate is divided into two parts, is first part of upper level crystallization filtrate and second part
Ludox and white carbon are added in first part of upper level crystallization filtrate upper level crystallization filtrate, and stirring makes it be uniformly mixed, shape
At A liquid；
（2）It is prepared by silicon source mixture：Aluminium hydroxide or aluminium oxide are added in the aqueous solution of NaOH, dissolves by heating, generates inclined aluminium
Sodium aluminate solution is slowly added into second part of upper level crystallization filtrate by acid sodium solution, and stirring makes it be uniformly mixed, and is formed
B liquid；
（3）It is prepared by ZSM-5 molecular sieve：By step（1）With（2）In A liquid and B liquid be uniformly mixed, mixed liquor is shifted after ageing
Hydrothermal crystallizing in crystallizing kettle obtains ZSM-5 molecular sieve slurries, is then centrifuged for, washs, drying obtained ZSM-5 molecular sieve.
2. the method according to claim 1 for preparing ZSM-5 molecular sieve with small crystal grains using filtrate, which is characterized in that described
Upper level crystallization filtrate is that Template-free method hydrothermal synthesis method prepares the filtrate detached after ZSM-5, the crystallization filtrate of initial level-one
Preparation process be：It is with the molar ratio of element silicon（1-0）:（0-1）Ludox and white carbon be silicon source, aluminium hydroxide or oxygen
Change aluminium is silicon source, and sodium hydroxide is alkali source, and Ludox and white carbon are added to the water, and forms silicon source, aluminium hydroxide or aluminium oxide
It is dissolved in sodium hydrate aqueous solution and forms silicon source, silicon source and silicon source are mixed, stirred evenly, form precursor liquid, hydrothermal crystallizing obtains
To ZSM-5 molecular sieve slurries, products therefrom after slurries crystallization is detached, obtains ZSM-5 molecular sieve, filtrate is the most junior one
The crystallization filtrate of grade.
3. the method according to claim 1 or 2 for preparing ZSM-5 molecular sieve with small crystal grains using filtrate, which is characterized in that institute
The condition for stating hydrothermal crystallizing is that first room temperature is aged 8-24h, 170-190 DEG C of crystallization 18-36h.
4. the method according to claim 1 or 2 for preparing ZSM-5 molecular sieve with small crystal grains using filtrate, which is characterized in that institute
It is 1-40nm to state silica particles size.
5. the method according to claim 4 for preparing ZSM-5 molecular sieve with small crystal grains using filtrate, which is characterized in that described
Silica particles size is 1-30nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190312A (en) * | 2010-03-18 | 2011-09-21 | 华东师范大学 | Method for recycling molecular sieve mother solution |
| CN105329915A (en) * | 2015-12-17 | 2016-02-17 | 江苏天诺新材料科技股份有限公司 | Method for synthesizing nanometer ZSM-5 molecular sieves through crystallized mother liquor |
| CN106044793A (en) * | 2016-08-05 | 2016-10-26 | 江苏天诺新材料科技股份有限公司 | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate |
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- 2018-06-21 CN CN201810644340.6A patent/CN108640126B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190312A (en) * | 2010-03-18 | 2011-09-21 | 华东师范大学 | Method for recycling molecular sieve mother solution |
| CN105329915A (en) * | 2015-12-17 | 2016-02-17 | 江苏天诺新材料科技股份有限公司 | Method for synthesizing nanometer ZSM-5 molecular sieves through crystallized mother liquor |
| CN106044793A (en) * | 2016-08-05 | 2016-10-26 | 江苏天诺新材料科技股份有限公司 | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate |
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