CN105692627B - The method for preparing meso pore silicon oxide material by template-free method using kaolin - Google Patents
The method for preparing meso pore silicon oxide material by template-free method using kaolin Download PDFInfo
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention relates to unordered meso pore silicon oxide material preparation field, specifically provides a kind of method for preparing meso pore silicon oxide material by template-free method using kaolin, comprises the following steps：(1) calcining and activating：Kaolin is obtained into amorphous metakaolin by calcine technology；(2) synthetic zeolite：The metakaolin obtained in step (1) is prepared as Si-Al zeolite；(3) zeolite and acid solution reaction that will be obtained in step (2), the crystal structure of zeolite is thoroughly destroyed by acid treatment, leach the metallic element in its composition, then separation of solid and liquid, solid phase is washed and dried, meso pore silicon oxide material is obtained, resulting meso pore silicon oxide material specific surface area is up to 680~760m2/ g, most probable pore size is in 3.8~4.2nm.This method production cost is low, is related to technique simple possible, and resulting meso pore silicon oxide material has high-specific surface area.
Description
Technical field
The present invention relates to mesoporous materials field, and in particular to one kind is prepared with higher using kaolin by template-free method
The technique of specific surface area meso pore silicon oxide material.
Background technology
Mesoporous material is with its excellent pore-size distribution (2~50nm) and larger specific surface area, in absorption, separation, catalysis
Embedded with medicine has more and more extensive application with many fields such as conveyings.
At present, the preparation of mesoporous material mainly uses template.Template refer to using surfactant (soft template) or
Some mesoporous materials (hard template) are that pore creating material or skeleton structure form intermediate with industrial chemicals, then by remove template into
Divide and obtain a kind of method of meso-hole structure.However, in order to ensure the stable formation of soft template and high-sequential, for template
Agent, raw material and solvent etc. have very high requirement in terms of purity and species.The not only cost such as these templates, raw material and solvent
Costliness, and part is (such as silester, methanol, benzene) or even poisonous and harmful.And follow-up organic formwork calcining removes technique and then can
Increase the complexity of technique, and cause environmental pollution and the waste of template.Hard template rule is synthesized using soft template method mostly
Ordered Materials (ordered meso-porous silicon oxide or mesoporous carbon) be hard template, then remove hard template method it is mesoporous to prepare target
Material.Obviously, hard template method has higher cost.High cost limits the industrial applications of template.
It is clear that without template and mould material and mesoporous material is prepared as raw material using mineral material cheap and easy to get
Technique, i.e., prepare mesoporous material technique using mineral material template-free method, the production cost of mesoporous material can be reduced, promote
The comprehensive utilization of the commercial application of mesoporous material and the mineral material to be naturally easy to get provides new research direction.
Kaolin has been prepared by numerous researchers for template-free method as a kind of natural minerals cheap and easy to get
Nano material.Acid leaching process after existing research is predominantly first calcined：(1) by kaolin starting material calcining and activating at a certain temperature
As metakaolin；(2) in hydrothermal reaction condition, the active aluminium component in metakaolin is performed etching using strong acid so as to obtain
To the nano oxidized silicon materials with high specific surface area.However, the achievement in research of many researchers shows to utilize calcining
The silica material specific surface area that acid leaching process obtains is no more than 350m2/ g, and mostly poromerics.The work in forefathers such as easypro reed
It is dense to the calcining heat (750~1200 DEG C) in calcining acid leaching process, acidleach temperature (60~120 DEG C), etching agent on the basis of work
The influence of mesoporous material of the degree parameter such as (2~9mol/L) and reaction time (0.5~24h) to being prepared using kaolin is carried out
System is comprehensively studied, and as a result finds to utilize its specific surface area highest of the material only up to 430m for calcining acid leaching process preparation2/ g,
And still have more micropore canals structure (Applied Clay Science, 2014,102:33-40).Then, Li Tiantian
Etc. the technique for proposing alkali activation acid treatment again after calcining, i.e., calcining and activating is first carried out to kaolin and obtains metakaolin, then is led to
Cross hydro-thermal alkali process and alkali activation in situ is carried out to metakaolin, then carry out acid treatment again, be prepared for specific surface area and be up to
604m2/ g, most probable pore size are 4.41nm meso pore silicon oxide material, further increase and are prepared using kaolin template-free method
Mesoporous material specific surface area (Applied Clay Science, 2015,107:182-187).
It is obvious that have at present document report using kaolin template-free method prepare silica material its compare surface
Product it is relatively low (<650m2/ g), the specific surface area prepared with template is up to 700~1000m2/ g ordered mesoporous material is compared to still
There is a certain distance.
The content of the invention
Being prepared it is an object of the invention to provide a kind of low production cost using kaolin by template-free method has height
The method of specific surface area meso pore silicon oxide material.
To achieve these goals, the technical scheme is that：
The method for being prepared meso pore silicon oxide material by template-free method using kaolin, is comprised the following steps：
(1) calcine：Kaolin is obtained into metakaolin by calcining；
(2) synthetic zeolite：The metakaolin obtained in step (1) is prepared as Si-Al zeolite；
(3) acid treatment：The zeolite and acid solution reaction that will be obtained in step (2), zeolite is thoroughly destroyed by acid treatment
Crystal structure, the metallic element in its composition is leached, then separation of solid and liquid, solid phase is washed and dried, that is, obtains mesoporous oxygen
Silicon nitride material, resulting meso pore silicon oxide material specific surface area are 680~760m2/ g, most probable pore size are 3.8~4.2nm.
Calcine technology is 600~900 DEG C of 1~24h of calcining in step (1).
The main purpose of acid treatment process is the thorough crystal structure for destroying zeolite in step (3), is leached in its composition
Metallic element, obtain mesoporous material.Its acid solution used should be able to be used for destroying the crystal structure of zeolite, can be for strong acid (such as
HCl、HNO3、H2SO4Deng) one or two or more kinds in solution press the mixture of any proportioning, or strong acid solution (it is a kind of or
It is a variety of) and other weak acid (such as acetic acid, HNO2) by the mixture of suitable proportion.
Acid solution is 1~10mol/L HCl solution in step (3), and zeolite is with HCl solution under conditions of 40~100 DEG C
React 2~12h, solid-to-liquid ratio 1kg：4~50L.
Si-Al zeolite is acid treated in step (3), and its crystal structure is entirely destroyed, and the aluminium element in its composition is molten
Go out, into acid solution, separated with the silica insoluble in acid, so as to be extracted, for preparing metal aluminium or mesoporous oxygen
Change aluminium.
Kaolinic main component is kaolinite (Al in the present invention2O3·2SiO2·2H2O), deshydroxy occurs through step 1)
Base reaction is activated, and is finally changed into amorphous metakaolin (Al with greater activity2O3·2SiO2).In practical operation
In appropriate process optimization can be carried out in calcining heat and in terms of the time according to different kaolinic types and place of production etc..
In the art, zeolite is a kind of common poromerics (duct aperture is less than 2nm), in terms of crystal structure,
It is by [SiO4] tetrahedron and [AlO4] four angles of tetrahedron top is shared and is connected along three dimensions, eventually become the crystal of rack-like.
It is different from other rack-like aluminium silicate salts, there is secondary structure unit, these secondary units group in zeolite crystal structure in zeolite
Into the polyhedron space of definite shape, i.e., so-called cage (e.g., α-cage, β-cage, γ-cage).Therefore, zeolite has higher ratio table
Area (400~800m2/ g), there is relatively broad application in fields such as absorption, catalysis, separation, ion exchanges.However, with
The continuous development of science, the defects of application of conventional mineral type Si-Al zeolite has become increasingly limited, and its is main has：
(1) duct of zeolite is that pore size (most of to be less than 1nm) is not particularly suited for including the chemical reaction of macromolecular；(2) although
Most of mineral type Si-Al zeolites have more perfect crystal structure, but because having more aluminium in its composition, its acid is stable
Property and thermostabilization are very low.Therefore, the mesoporous material for researching and developing and developing high stability is one important point of inorganic material field
Branch.Mesoporous material (especially mesopore silicon oxide and mesoporous carbon) has very high specific surface area, abundant pore passage structure, more equal
One mesoporous pore size distribution (2~50nm) and very high heat endurance and absolute acid stability, it is difficult in many micro-pore zeolite molecular sieves
With the absorption of the macromolecular of completion, separation, there is more extensive effect especially in catalytic reaction.It is in addition, irrefragable
That zeolite is just because of its special crystal framework, so as to abundant pore passage structure, once the crystal structure of zeolite by
Destroy completely, the micropore canals structure inside zeolite will collapse, so as to cause the forfeiture of its application value.In fact, scientific research
Worker has been carried out the structurally-modified work of Si-Al zeolite before for a long time, but is all to ensure the premise of zeolite crystal skeleton
Lower progress, i.e., appropriate dealuminzation is carried out to Si-Al zeolite molecular sieve so that zeolitic frameworks situ produces mesopore orbit.These are situated between
Hole duct is due to its pore size and quantity and dealuminzation obtained from framework of molecular sieve part dealuminzation, generation hole in situ
Condition is relevant, it is difficult to control.In brief, at present not on thoroughly destroy zeolite crystal structure, etch wherein aluminium into
Point, so as to obtain the research of meso pore silicon oxide material and report.The application has carried out thinking breakthrough and technological innovation, creatively
The technique for first preparing acid treatment after Si-Al zeolite is proposed, that is, first passes through simple process and is prepared into and only do not have with microcellular structure
The Si-Al zeolite of meso-hole structure, then carry out acid treatment.The very not harsh requirement of taste of the application for Si-Al zeolite,
Therefore Si-Al zeolite can be prepared using the various methods that existing literature is reported.The main purpose of acid treatment process is thoroughly broken
The crystal structure of bad zeolite, the metallic element in its composition is leached, obtains mesoporous material.Its acid solution used should be able to be used for
The crystal structure of zeolite is destroyed, the mixture of any proportioning, or strong acid can be pressed for the one or two or more kinds in strong acid solution
Solution presses the mixture of suitable proportion with other weak acid.
Compared with prior art, the technical scheme that the application provides has advantages below：
1st, meso pore silicon oxide material is prepared by unique raw material of natural minerals kaolin cheap and easy to get in the application, and made
In standby technique without using expensive template or mould material (such as：Hexamethylene diamine, cetyl trimethylammonium bromide etc.), without
Introduce any poisonous and hazardous organic solvent (such as：Benzene, methanol, ether etc.), simple production process, cost are cheap, are suitable for work
Industry metaplasia is produced.
2nd, the application proposes the technique for first preparing acid treatment after Si-Al zeolite in a creative way, is that a kind of thinking breaks through and skill
Art is innovated；And in view of the structure of mineral and the similitude of composition, this technique should have certain reality for other raw mineral materials
The property used；The specific surface area of meso pore silicon oxide material prepared by this technique may be up to 750m simultaneously2/ g, its most probable pore size are reachable
4nm, the meso pore silicon oxide material prepared close to segment template method.Porous material prepared by the present invention is in normal temperature and pH=10
Under the conditions of for methylene blue saturated extent of adsorption up to 760mg/g, can as a kind of sorbing material of function admirable, have compared with
To be widely applied prospect.
3rd, the present invention can obtain the acid solution containing aluminium while mesopore silicon oxide is prepared, and available for aluminium is carried, prepare gold
Belong to aluminium or meso-porous alumina.
Brief description of the drawings
Fig. 1 is nitrogen adsorption-desorption isotherm figure of the intermediary hole silica of embodiment 1；
Fig. 2 is the graph of pore diameter distribution that the intermediary hole silica of embodiment 1 uses BJH model analysis；
Fig. 3 is the transmission electron microscope photo of the intermediary hole silica of example 1.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
The method that meso pore silicon oxide material is prepared using kaolin template-free method, it comprises the following steps：
(1) calcining and activating：Kaolin is placed in calciner under the conditions of 850 DEG C after calcining 2h, after equipment cooling
Take out, obtain unbodied metakaolin；
(2) zeolite is prepared：Si-Al zeolite (zeolite is made using hydro-thermal alkalization method in metakaolin obtained by step (1)
LTA)；
(3) acid treatment：Zeolite and 5mol/L HCl solution will be obtained with 1kg in step (2)：20L ratio mixing,
Stirred under conditions of 100 DEG C and react 6h, the solid product for then filtering and being washed with deionized to obtain is to neutrality, then passes through
Moisture removal is removed in 110 DEG C of dryings, obtains the meso pore silicon oxide material of template-free method preparation.The acid solution containing aluminium being filtrated to get can use
To carry aluminium, metal aluminium or meso-porous alumina are prepared.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 751.5m2/ g, its most probable pore size are
3.88nm.Its nitrogen adsorption-desorption isotherm and the pore-size distribution that is obtained according to BJH models are as depicted in figs. 1 and 2.Fig. 3 is
Its transmission electron microscope observing photo.
Embodiment 2
The method that meso pore silicon oxide material is prepared using kaolin template-free method, it comprises the following steps：
(1) calcining and activating：Kaolin is placed in calciner the high temperature direct sample after calcining 12h under the conditions of 600 DEG C,
Obtain unbodied metakaolin；
(2) it is 5.3Na by molar ratio by calcined kaolin, sodium hydroxide, Ludox and its ionized water2O：
1.0Al2O3:4.0SiO2:240H2O is mixed, and 2% 13X molecular sieve seeds are then added into solution, are quickly stirred
5h is mixed, then reaction mixture is put into crystallization 80min in 700W micro-wave oven, obtain 13X zeolite molecular sieves.
(3) acid treatment：The zeolite and 1mol/L H that will be obtained in step (2)2SO4Solution is with 1kg：50L ratio mixing,
Stirred under conditions of 40 DEG C and react 2h, the solid product for then filtering and being washed with deionized to obtain is to neutrality, then passes through
Moisture removal is removed in 110 DEG C of dryings, obtains the meso pore silicon oxide material of template-free method preparation.The acid solution containing aluminium being filtrated to get can use
To carry aluminium, metal aluminium or meso-porous alumina are prepared.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 760m2/ g, its most probable pore size are
3.9nm。
Embodiment 3
The method that meso pore silicon oxide material is prepared using kaolin template-free method, it comprises the following steps：
(1) calcining and activating：Kaolin is placed in calciner the high temperature direct sample after calcining 1h under the conditions of 900 DEG C,
Obtain unbodied metakaolin；
(2) zeolite is prepared：Metakaolin obtained by step (1) is prepared into Si-Al zeolite；
(3) acid treatment：The zeolite obtained in step (2) and the mixing containing 2mol/L HNO3 and 1mol/L HCl is molten
Liquid is with 1kg：10L ratio mixing, stirs under conditions of 60 DEG C and reacts 10h, then filter and be washed with deionized
The solid product arrived removes moisture removal to neutrality, then through 110 DEG C of dryings, obtains the meso pore silicon oxide material of template-free method preparation.Cross
Filter the obtained acid solution containing aluminium to can be used to carry aluminium, prepare metal aluminium or meso-porous alumina.
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 750m2/g, and its most probable pore size is
4.1nm。
Claims (4)
1. the method for meso pore silicon oxide material is prepared by template-free method using kaolin, it is characterised in that comprise the following steps：
(1) calcine：Kaolin is obtained into metakaolin by calcining；
(2) synthetic zeolite：The metakaolin obtained in step (1) is prepared as Si-Al zeolite；
Specifically, preparing Si-Al zeolite using hydro-thermal alkalization method or crystal seed method, the technique of wherein crystal seed method is as follows：Will calcining
Kaolin, sodium hydroxide, Ludox and its ionized water are 5.3Na by molar ratio2O：1.0Al2O3:4.0SiO2:240H2O enters
Row is mixed, and 2% 13X molecular sieve seeds are then added into solution, 5h is stirred, reaction mixture then is put into 700W
Micro-wave oven in crystallization 80min, obtain 13X zeolite molecular sieves；
(3) acid treatment：The zeolite and acid solution reaction that will be obtained in step (2), the crystal of zeolite is thoroughly destroyed by acid treatment
Structure, the metallic element in its composition is leached, then separation of solid and liquid, solid phase is washed and dried, that is, obtains mesopore silicon oxide
Material, resulting meso pore silicon oxide material specific surface area are 680~760m2/ g, most probable pore size are 3.8~4.2nm.
2. the method according to claim 1 for preparing meso pore silicon oxide material by template-free method using kaolin, it is special
Sign is：Calcine technology is 600~900 DEG C of 1~24h of calcining in step (1).
3. the method according to claim 1 for preparing meso pore silicon oxide material by template-free method using kaolin, it is special
Sign is：Acid solution is can be used for destroying the acid solution of the crystal structure of zeolite in step (3), specially in strong acid solution
One or two or more kinds press the mixture of any proportioning, or the mixture being made into for strong acid solution with weak acid solution.
4. the method for preparing meso pore silicon oxide material by template-free method using kaolin according to claim 1 or 3, its
It is characterised by：Acid solution is 1~10mol/L HCl solution, zeolite and condition of the HCl solution at 40~100 DEG C in step (3)
Lower reaction 2~12h, solid-to-liquid ratio 1kg：4~50L.
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| CN108435228A (en) * | 2018-03-14 | 2018-08-24 | 中国地质大学（武汉） | One kind preparing g-C based on hard template method3N4The technique of nanotube |
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| CN111822057B (en) * | 2019-04-23 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of spherical alumina carrier |
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| CN1220631C (en) * | 2004-02-26 | 2005-09-28 | 南开大学 | Process of preparing velence pore molecular siever by natural kaolinite |
| CN102167352B (en) * | 2011-03-14 | 2013-08-28 | 浙江师范大学 | Method for preparing 4A zeolite by kaolin alkali fusion one-step method |
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