CN104014362B - Synthetic method of porous inorganic materials - Google Patents
Synthetic method of porous inorganic materials Download PDFInfo
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- CN104014362B CN104014362B CN201410245099.1A CN201410245099A CN104014362B CN 104014362 B CN104014362 B CN 104014362B CN 201410245099 A CN201410245099 A CN 201410245099A CN 104014362 B CN104014362 B CN 104014362B
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Abstract
The invention discloses a synthetic method of porous inorganic materials. The synthetic method of porous inorganic materials comprises the following steps: baking natural clay for 0.5-5 hours at a temperature of 500-1000 DEG C, adding the processed clay into a silicon-containing solution, and uniformly mixing; standing the obtained size for 12-48 hours at room temperature, then adding metal ions into the size, and completely stirring; crystallizing the obtained size for 10-48 hours under the condition of sealing and at a temperature of 90-250 DEG C, and filtering so as to obtain a filter cake; and drying the obtained filter cake, so that a porous inorganic material is obtained. The method disclosed by the invention is low in raw material cost, and has a rich pore structure, and the introduction of transition metals makes up for the inadequacy of a catalytic performance. In the porous inorganic material disclosed by the invention, due to an oily crystalline aluminum silicate structure and a large number of mesoporous and macroporous structures, the pore channel distribution of a catalytic material is broader, thereby meeting the diffusion needs of raw material molecules in a catalytic reaction, and improving the approachability of an active centre in a zeolite structure; and the reaction efficiency and benefits are further improved, and negative effects caused by diffusion limits are reduced.
Description
Technical field
The invention belongs to technical field of preparation for inorganic material, more particularly, to a kind of synthetic method of porous inorganic material.
Background technology
Porous inorganic material, because of its larger specific surface, is widely used as catalysis material, in the preparation of catalyst,
For this reason, having been developed for multiple porous inorganic materials, such as, the inorganic material of zeolite type, including a type zeolite, x type zeolite, y
Type zeolite, zsm series zeolite, modenite, beta zeolite, etc..And for example, amorphous porous inorganic material, including various oxidations
Silicon, aluminium oxide and sieve and silica-sesquioxide.
Although there being so many porous inorganic material, in the face of growing society need, still cannot meet out
The needs of the excellent catalyst of volatility.
Content of the invention
The purpose of the embodiment of the present invention is to provide a kind of synthetic method of porous inorganic material it is intended to solve existing many
What the inorganic ability in hole two existed cannot meet the problem of the catalyst needs of exploitation excellent performance.
The embodiment of the present invention is achieved in that a kind of synthetic method of porous inorganic material, this porous inorganic material
Synthetic method includes:
Step one, by natural clay at 500～1000 DEG C fire 0.5～5 hour,
Step 2, in siliceous solution addition process after clay, all with mix；
Step 3, the serosity obtaining is stood 12～48 hours at room temperature, afterwards, is added thereto to metal ion, fills
Divide stirring；
Step 4, by the serosity obtaining, crystallization 10～48 hours, filtration at sealing and 90～250 DEG C, obtains filter cake；
Step 5, the filter cake obtaining is dried, that is, obtains porous inorganic material.
Further, in step one, natural clay is kaolinite, montmorillonite or illite；Kaolinite, montmorillonite and Erie
The content of stone aluminium oxide is 20%～50%；The fire condition of natural clay is preferably 700～850 DEG C, and the fire time is preferably
1-4 hour.
Further, in step 2, siliceous solution is waterglass；The modulus of waterglass is 1.0～4.0.
Further, in step 3, metal ion is ferrum, cobalt and nickel, and the ph value of serosity is more than 7.
Further, this porous inorganic material oil-containing crystalline aluminosilicate zeolite structure, crystalline aluminosilicate zeolite be y zeolite,
Zsm-5 zeolite or the mixture of y zeolite and zsm-5 zeolite；The specific surface of porous inorganic material is in 70～700m2/ g, has
Different framing structures.
Further, the synthetic method of this porous inorganic material includes: weigh 50g kaolinite, in 550 DEG C of fire 4.5 hours,
Prepare 400 milliliters of the water glass solution that modulus is 1.5, the kaolinite adding fire to cross, be thoroughly mixed uniformly, at room temperature
Standing 24 hours, serosity is put in sealing container, crystallization 32 hours at 75 DEG C, then, adds prepare in advance in serosity
Ferric Chloride Hydrated 8.2g based on iron sesquioxide, be sufficiently stirred for, make ferrum and other component mix homogeneously, then in air-proof condition
Under, crystallization 28 hours at 95 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings, obtains final product
To porous inorganic material.
Further, the synthetic method of this porous inorganic material includes: weigh 50g montmorillonite, in 750 DEG C of fire 2.5 hours,
Prepare 500 milliliters of the water glass solution that modulus is 2.0, the montmorillonite adding fire to cross, be thoroughly mixed uniformly, at room temperature
Standing 42 hours, this serosity is put in sealing container, crystallization 40 hours at 85 DEG C, then, adds join in advance in serosity
5.5 grams of the aqua oxidation cobalt of system, based on cobalt oxide, is sufficiently stirred for, and makes cobalt and other component mix homogeneously, then in air-proof condition
Under, crystallization 36 hours at 95 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings, that is, obtains
Porous inorganic material.
Further, the synthetic method of this porous inorganic material includes: weigh 50g illite, in 600 DEG C of fire 3.0 hours,
Prepare 900 milliliters of the water glass solution that modulus is 2.2, the illite adding above-mentioned fire to cross, be thoroughly mixed uniformly, in room
The lower standing of temperature 15 hours, this serosity is put in sealing container, crystallization 45 hours at 140 DEG C, then, adds pre- in serosity
The aqua oxidation nickel 3.0g first preparing, based on nickel oxide, is sufficiently stirred for, and makes nickel and other component mix homogeneously, then sealing strip again
Under part, crystallization 46 hours at 205 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings,
Obtain porous inorganic material.
Further, the synthetic method of this porous inorganic material includes: weigh 50g montmorillonite, in 750 DEG C of fire 2.5 hours,
Prepare 1000 milliliters of the water glass solution that modulus is 2.8, the montmorillonite adding fire to cross, be thoroughly mixed uniformly, in room temperature
Lower standing 38 hours, this solution is put in sealing container, crystallization 20 hours at 125 DEG C, then, adds in advance in serosity
The hydrated ferric oxide 4.5g preparing is based on ferrum oxide；It is sufficiently stirred for, make ferrum and other component mix homogeneously, then in air-proof condition
Under, crystallization 40 hours at 220 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, with washings rinse 5 times, that is,
Obtain porous inorganic material.
Further, the synthetic method of this porous inorganic material includes: weigh 50g kaolinite, in 800 DEG C of fire 2.0 hours,
Prepare 1000 milliliters of the water glass solution that modulus is 2.5, the kaolinite adding fire to cross, be thoroughly mixed uniformly, in room temperature
Lower standing 24 hours, this serosity is put in sealer, crystallization 32 hours at 95 DEG C, then, adds join in advance in serosity
The hydrated ferric oxide 4.8g of system, based on ferrum oxide, is sufficiently stirred for, and makes ferrum and other component mix homogeneously, then in air-proof condition
Under, crystallization 35 hours at 150 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, with washings rinse 5 times, that is,
Obtain porous inorganic material.
The synthetic method of the porous inorganic material that the present invention provides, cost of material is low, have abundant pore passage structure, transition
The introducing of metal compensate for the deficiency of catalytic performance, therefore, it can, for preparing catalyst, enrich and developed existing catalyst
Performance；The porous inorganic material prepared using the method that the present invention provides, oil-containing crystalline aluminosilicate zeolite structure, Ke Yiwei
Catalyst provides the surface acidity needed for catalytic reaction, due to transition metal ionss being introduced in material, the surface acidity of material
Matter is more flexibly adjustable, can better meet the demand of catalytic reaction, is needing surface acidity position and metal catalytic activity
In the catalytic process of position, more particularly suitable.Additionally, the porous inorganic material prepared using the method that the present invention provides, not only contain
Oily crystalline aluminosilicate structure, also contains substantial amounts of mesopore and macroporous structure so that the pore distribution of catalysis material is more broad, can
To meet the diffusion needs of raw molecule in catalytic reaction, improve the accessibility in zeolite structured middle active center.Carry further
High reaction efficiency and benefit, reduce the negative effect bringing because of diffusion-restricted.
Brief description
Fig. 1 is the flow chart of the synthetic method of porous inorganic material provided in an embodiment of the present invention.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
Below in conjunction with the accompanying drawings and specific embodiment is further described to the application principle of the present invention.
As shown in figure 1, the synthetic method of the porous inorganic material of the embodiment of the present invention comprises the following steps:
S101: add the natural clay that fire is processed in advance in siliceous solution, uniformly mix, form a kind of serosity；
S102: by the serosity obtaining sealing and uniform temperature under some hours of crystallization, afterwards, be added thereto to metal from
Son, is sufficiently stirred for；
S103: the further some hours of crystallization, the filtration under sealing and uniform temperature by the serosity obtaining；
Specific surface can be obtained in 70～700m using the inventive method2The porous inorganic material of/g, according to synthesis condition,
Can have different framing structures.
The present invention concretely comprises the following steps:
Step one, by natural clay at 500～1000 DEG C fire 0.5～5 hour,
Step 2, in siliceous solution addition process after clay, all with mix；
Step 3, the serosity obtaining is stood 12～48 hours at room temperature, afterwards, is added thereto to metal ion, fills
Divide stirring；
Step 4, by the serosity obtaining, crystallization 10～48 hours, filtration at sealing and 90～250 DEG C, obtains filter cake；
Step 5, the filter cake obtaining is dried, that is, obtains porous inorganic material；
In step one, natural clay is kaolinite, montmorillonite or illite；Kaolinite, montmorillonite and illite oxidation
The content of aluminum is 20%～50%；The fire condition of natural clay is preferably 700～850 DEG C, and it is little that the fire time is preferably 1-4
When；
In step 2, siliceous solution is waterglass；The modulus of waterglass is 1.0～4.0；
In step 3, metal ion is ferrum, cobalt and nickel, and the ph value of serosity is more than 7；
The porous inorganic material oil-containing crystalline aluminosilicate zeolite structure of the present invention, crystalline aluminosilicate zeolite is y zeolite, zsm-
5 zeolites or the mixture of y zeolite and zsm-5 zeolite；
The method that the present invention provides comprises the following steps:
(1), the natural claies such as kaolinite are baked and banked up with earth at 500 DEG C～1100 DEG C 0.5～5 hour, preferably 700 DEG C～
Bake and bank up with earth 1～4 hour for 850 DEG C；
(2), in siliceous solution, preferably water glass solution, the clay after adding above-mentioned (1) to process, uniformly mix, control
Slurrying liquid ph value is more than 7.0；
(3), the serosity that (2) obtain is stood 12～48 hours at room temperature, then brilliant at sealing and 90 DEG C～150 DEG C
Change 10～48 hours, afterwards, be added thereto to metal ion, preferably ferrum, cobalt, nickel ion, be sufficiently stirred for；
(4), serosity crystallization 10～48 hours, the filtration again at sealing and 90 DEG C～250 DEG C obtaining (3), obtains
Filter cake；
(5), the filter cake of (4) is dried the porous inorganic material being the present invention.
In the method that the present invention provides, the natural claies such as kaolinite are baked and banked up with earth process at high temperature, its purpose is to live
Aluminium element in change clay, so as to have solubility, departs from caly structure in process that can be subsequent again, as such, it is possible to make institute
The inorganic material obtaining has larger duct capacity, because natural clay is distinct, when determining fire activation condition, needs
Give special consideration；
Meanwhile, the active aluminium element being obtained by fire activation processing can also in subsequent crystallization process with serosity in
Element silicon combine, formed crystalline aluminosilicate zeolite structure, these crystalline aluminosilicate zeolite can be y type zeolite or
Zsm-5 zeolite, or the mixture of the two, wherein, the silica alumina ratio of y type zeolite between 4.4～6.0, the silica alumina ratio of zsm-5
Between 20～200, due to introducing transition metal in crystallization building-up process, section transitions metallic element enters boiling
The internal gutter of stone, defines the compact structural metal with zeolite, the content of these metallic elements 0%～15% it
Between；
In the method that the present invention provides, siliceous solution is waterglass, in the porous material synthesizing as needed during its concentration
Zeolite type and content determine, can in interior adjustment in a big way, if necessary to synthesis of high content zeolite porous material,
It is accomplished by adding more silicon, the concentration of waterglass is just higher, if the porous material containing zsm-5 for the synthesis is it is necessary to silicon source；Water
The concentration of glass is higher, if the porous material containing zsm-5 for the synthesis is it is also desirable to add more silicon source, the concentration of waterglass
Also higher, on the contrary, when needing, synthetic zeolite content is low, have relatively enrich big mesopore porous material when, the concentration of waterglass
Just can be lower；
In the method that the present invention provides, the metal ion of addition in the middle of crystallization, is to be added with the form of hydrous oxide
In system, these hydrous oxides, such as hydrated ferric oxide, be by under strong stirring condition to iron nitrate aqueous solution in
Add alkaline reagent, such as ammonia, be allowed to produce ultra-fine precipitates, obtained by separation, in order that metal ion, be efficiently entering boiling
Stone internal gutter, needs to make hydrated metal oxide and the serosity of poromerics be sufficiently mixed；
The method that the present invention provides, does not use directed agents, its purpose is to extend crystallization time, makes metal ion permissible
Inside more well into the micropore of aluminosilicate zeolite；
In order to meet the requirement of industrial catalyst preparation, above-mentioned porous material also needs to repeatedly wash, and removes sodium therein
Activated in ion and the other elements not participating in synthetic reaction, the such as excess metal ion of synthetic mesophase interpolation, clay
But do not form the aluminium ion of crystalline aluminosilicate.
Specific embodiment below in conjunction with the present invention is described further to the application effect of the present invention:
Embodiment 1:
Weigh 50g kaolinite (butt), as shown in table 1, in 550 DEG C of fire 4.5 hours, prepare modulus was 1.5 to its composition
400 milliliters of water glass solution, be added thereto to the kaolinite that above-mentioned fire is crossed, be thoroughly mixed uniformly, quiet at room temperature
Put 24 hours, this serosity is put in sealing container, crystallization 32 hours at 75 DEG C, then, add in serosity and prepare in advance
Ferric Chloride Hydrated 8.2g (based on iron sesquioxide), be sufficiently stirred for, make ferrum and other component mix homogeneously, then in sealing strip
Under part, crystallization 28 hours at 95 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, with washings rinse 5 times, that is,
Obtain porous inorganic material, its chemical composition and structure parameter is as shown in table 2；
Embodiment 2:
Weigh 50g montmorillonite (butt), as shown in table 1, in 750 DEG C of fire 2.5 hours, prepare modulus was 2.0 to its composition
500 milliliters of water glass solution, be added thereto to the montmorillonite that above-mentioned fire is crossed, be thoroughly mixed uniformly, quiet at room temperature
Put 42 hours, this serosity is put in sealing container, crystallization 40 hours at 85 DEG C, then, add in serosity and prepare in advance
5.5 grams of aqua oxidation cobalt (based on cobalt oxide), be sufficiently stirred for, make cobalt and other component mix homogeneously, then in air-proof condition
Under, crystallization 36 hours at 95 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings, that is, obtains
Porous inorganic material, its chemical composition and structure parameter is as shown in table 2；
Embodiment 3:
Weigh 50g illite (butt), as shown in table 1, in 600 DEG C of fire 3.0 hours, prepare modulus was 2.2 to its composition
900 milliliters of water glass solution, be added thereto to the illite that above-mentioned fire is crossed, be thoroughly mixed uniformly, quiet at room temperature
Put 15 hours, this serosity is put in sealing container, crystallization 45 hours at 140 DEG C, then, add in serosity and prepare in advance
Aqua oxidation nickel 3.0g9 (based on nickel oxide), be sufficiently stirred for, make nickel and other component mix homogeneously, then air-proof condition again
Under, crystallization 46 hours at 205 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings, obtains
To porous inorganic material, its chemical composition and structure parameter is as shown in table 2；
Embodiment 4:
Weigh 50g montmorillonite (butt), shown in its composition table 1, in 750 DEG C of fire 2.5 hours, preparing modulus is 2.8
1000 milliliters of water glass solution, is added thereto to the montmorillonite that above-mentioned fire is crossed, and is thoroughly mixed uniformly, stands at room temperature
38 hours, this solution is put in sealing container, crystallization 20 hours at 125 DEG C, then, add in serosity and prepare in advance
Hydrated ferric oxide 4.5g (based on ferrum oxide).It is sufficiently stirred for, make ferrum and other component mix homogeneously, then under air-proof condition,
Crystallization 40 hours at 220 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings, that is, obtains
Porous inorganic material, its chemical composition and structure parameter is as shown in table 2；
Embodiment 5:
Weigh 50g kaolinite (butt), as shown in table 1, in 800 DEG C of fire 2.0 hours, prepare modulus was 2.5 to its composition
1000 milliliters of water glass solution, be added thereto to the kaolinite that above-mentioned fire is crossed, be thoroughly mixed uniformly, quiet at room temperature
Put 24 hours, this serosity is put in sealer, crystallization 32 hours at 95 DEG C, then, add in serosity and to prepare in advance
Hydrated ferric oxide 4.8g (based on ferrum oxide), is sufficiently stirred for, and makes ferrum and other component mix homogeneously, then under air-proof condition,
Crystallization 35 hours at 150 DEG C, natural heat dissipation to room temperature, is opened container, serosity is filtered, and is rinsed 5 times with washings, that is, obtains
Porous inorganic material, its chemical composition and structure parameter is as shown in table 2.
Table 1 various butt composition and physical property
The chemical composition and structure parameter of table 2 porous inorganic material:
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (4)
1. a kind of synthetic method of porous inorganic material is it is characterised in that the synthetic method of this porous inorganic material includes:
Step one, by natural clay at 500～1000 DEG C fire 0.5～5 hour；
Step 2, the clay after addition is processed in siliceous solution, uniformly mix；
Step 3, the serosity obtaining is stood 12～48 hours at room temperature, this serosity is put in sealing container, 90 DEG C～
Crystallization 10 hours～48 hours at 150 DEG C, afterwards, add metal ion, are sufficiently stirred for；Step 4, by the serosity obtaining close
Crystallization 10～48 hours at envelope and 90～250 DEG C, filters, obtains filter cake；
Step 5, the filter cake obtaining is dried, that is, obtains porous inorganic material；
In step one, natural clay is kaolinite, montmorillonite or illite；Kaolinite, montmorillonite and illite aluminium oxide
Content is 20%～50%；
In step 2, siliceous solution is waterglass；The modulus of waterglass is 1.0～4.0；
In step 3, metal ion is ferrum, cobalt or nickel, and the ph value of serosity is more than 7；
This porous inorganic material contains crystalline aluminosilicate zeolite structure, and crystalline aluminosilicate zeolite is y zeolite, zsm-5 zeolite or y
Zeolite and the mixture of zsm-5 zeolite；The specific surface area of porous inorganic material is in 70～700m2/ g, has different skeleton knots
Structure.
2. the synthetic method of porous inorganic material as claimed in claim 1 is it is characterised in that the synthesis of this porous inorganic material
Method includes: weighs 50g illite, in 600 DEG C of fire 3.0 hours, prepares 900 milliliters of the water glass solution that modulus is 2.2, plus
Enter the illite that above-mentioned fire is crossed, be thoroughly mixed uniformly, stand 15 hours at room temperature, this serosity is put into sealing container
In, crystallization 45 hours at 140 DEG C, then, add the aqua oxidation nickel 3.0g preparing in advance in serosity based on nickel oxide, fill
Divide stirring, make nickel and other component mix homogeneously, then again under air-proof condition, crystallization 46 hours at 205 DEG C, natural heat dissipation is extremely
Room temperature, opens container, and serosity is filtered, and is rinsed 5 times with washings, obtains porous inorganic material.
3. the synthetic method of porous inorganic material as claimed in claim 1 is it is characterised in that the synthesis of this porous inorganic material
Method includes: weighs 50g montmorillonite, in 750 DEG C of fire 2.5 hours, prepares 1000 milliliters of the water glass solution that modulus is 2.8,
The montmorillonite adding fire to cross, is thoroughly mixed uniformly, stands 38 hours at room temperature, this solution is put into sealing container
In, crystallization 20 hours at 125 DEG C, then, add the hydrated ferric oxide 4.5g preparing in advance in serosity based on ferrum oxide；Fill
Divide stirring, make ferrum and other component mix homogeneously, then under air-proof condition, crystallization 40 hours at 220 DEG C, natural heat dissipation is extremely
Room temperature, opens container, and serosity is filtered, and is rinsed 5 times with washings, that is, obtains porous inorganic material.
4. the synthetic method of porous inorganic material as claimed in claim 1 is it is characterised in that the synthesis of this porous inorganic material
Method includes: weighs 50g kaolinite, in 800 DEG C of fire 2.0 hours, prepares 1000 milliliters of the water glass solution that modulus is 2.5,
The kaolinite adding fire to cross, is thoroughly mixed uniformly, stands 24 hours at room temperature, this serosity is put in sealer,
Crystallization 32 hours at 95 DEG C, then, add the hydrated ferric oxide 4.8g preparing in advance in serosity based on ferrum oxide, fully stir
Mix, make ferrum and other component mix homogeneously, then under air-proof condition, crystallization 35 hours at 150 DEG C, natural heat dissipation is to room
Temperature, opens container, and serosity is filtered, and is rinsed 5 times with washings, that is, obtains porous inorganic material.
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| CN201410245099.1A CN104014362B (en) | 2014-06-04 | 2014-06-04 | Synthetic method of porous inorganic materials |
| US14/685,819 US20160008797A1 (en) | 2014-06-04 | 2015-04-14 | Method for the synthesis of porous inorganic material, catalytic cracking of petroleum hydrocarbons and preparation of catalyst thereof |
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| CN201410245099.1A CN104014362B (en) | 2014-06-04 | 2014-06-04 | Synthetic method of porous inorganic materials |
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| CN1275855C (en) * | 2003-03-28 | 2006-09-20 | 中国石油化工股份有限公司 | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod |
| CN1597850A (en) * | 2003-09-15 | 2005-03-23 | 中国石油天然气股份有限公司 | Catalyst of catalyzing, cracking for reducing sulfur content in gasoline and preparation process thereof |
| CN1292051C (en) * | 2004-03-31 | 2006-12-27 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN103253683B (en) * | 2012-02-16 | 2015-04-29 | 中国石油天然气股份有限公司 | Method of in-situ crystallized synthesis of ZSM-5/mordenite compound |
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