CN105692628A - Method for preparing mesoporous silica material from kaolin through calcination-free template-free method - Google Patents

Method for preparing mesoporous silica material from kaolin through calcination-free template-free method Download PDF

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CN105692628A
CN105692628A CN201610033520.1A CN201610033520A CN105692628A CN 105692628 A CN105692628 A CN 105692628A CN 201610033520 A CN201610033520 A CN 201610033520A CN 105692628 A CN105692628 A CN 105692628A
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zeolite
template
kaolin
silicon oxide
acid solution
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CN105692628B (en
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舒杼
李天天
周俊
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China University of Geosciences
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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
    • 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
    • B01J20/12—Naturally occurring clays or bleaching earth
    • 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
    • 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
    • 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
    • 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
    • C01P2006/16—Pore diameter

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to the field of preparation of disorderly mesoporous materials and particularly provides a method for preparing a mesoporous silica material from kaolin through a calcination-free template-free method. The method includes the following steps that 1, zeolite is synthesized, wherein the kaolin is prepared into the silicon-aluminum zeolite; 2, the zeolite prepared in the step 1 reacts with an acid solution, the crystal structure of the zeolite is completely damaged through acid treatment, metal elements in components of the zeolite are leached, then solid-liquid separation is conducted, a solid phase is washed and dried, and the mesoporous silica material is obtained, wherein the specific surface area of the obtained mesoporous silica material can reach 650-710 m<2>/g, and the most probable hole diameter ranges from 3.5 nm to 4.2 nm. The method is low in production cost, the related process is simple and feasible, and the obtained mesoporous silica material has the high specific surface area.

Description

Kaolin is utilized to pass through not calcine the method that template-free method prepares meso pore silicon oxide material
Technical field
The present invention relates to meso pore silicon oxide material preparation and kaolin mineral utilization of resources field, be specifically related to a kind of utilize Kaolin to pass through not calcine template-free method to prepare the technique with high specific surface area meso pore silicon oxide material。
Background technology
Mesoporous material with the pore-size distribution (2～50nm) of its excellence and bigger specific surface area, absorption, separate, catalysis and medicine embedding and conveying etc. many in have and be increasingly widely applied。
At present, the preparation of mesoporous material mainly adopts template。Template refers to and utilizes surfactant (soft template) or some mesoporous materials (hard template) to form intermediate for pore creating material or framing structure and industrial chemicals, then passes through a kind of method removing template composition and obtain meso-hole structure。But, in order to ensure stable formation and the high-sequential of soft template, in purity with kind, there is significantly high requirement for template, raw material and solvent etc.。These template, raw material and solvent etc. not only involve great expense, and part (such as silester, methanol, benzene) even poisonous and harmful。Technique is removed in follow-up organic formwork calcining then can increase the complexity of technique, and causes the waste of environmental pollution and template。Hard template rule utilizes the Ordered Materials (ordered meso-porous silicon oxide or mesoporous carbon) that soft template method synthesizes to be hard template mostly, then removes the method for hard template to prepare target mesoporous material。Obviously, hard template method has higher cost。High cost limits the industrial applications of template。
Obviously, without template and mould material the technique of preparing mesoporous material for raw material with mineral material cheap and easy to get, namely mineral material template-free method is utilized to prepare mesoporous material technique, can reduce the production cost of mesoporous material, promote the commercial application of mesoporous material and provide new research direction for the comprehensive utilization of the natural mineral material being easy to get。
Kaolin is prepared mesoporous material by numerous researcheres for template-free method as a kind of natural minerals cheap and easy to get。Existing research is mainly acid leaching process after first calcining: kaolin starting material calcining and activating at a certain temperature is become metakaolin by (1)；(2) at hydrothermal reaction condition, strong acid is utilized the activated aluminum composition in metakaolin to be performed etching thus obtaining the meso pore silicon oxide material with high specific surface area。But, the achievement in research of many researchers shows that the silica material specific surface area utilizing calcining acid leaching process to obtain is less than 350m2/ g, and it mostly is poromerics。Easypro reeds etc. are on the working foundation of forefathers, on the impact of the mesoporous material of preparation, the parameters such as the calcining heat (750～1200 DEG C) in calcining acid leaching process, acidleach temperature (60～120 DEG C), etching agent concentration (2～9mol/L) and response time (0.5～24h) are carried out system comprehensively study, found that utilize its specific surface area of material prepared by calcining acid leaching process to reach as high as 430m2/ g, and still there is more micropore canals structure (AppliedClayScience, 2014,102:33-40)。Subsequently, after Li Tiantian etc. propose calcining, alkali activates the technique of acid treatment again, namely Kaolin first carries out calcining and activating and obtains metakaolin, again through water hot alkali treatment, metakaolin carries out original position alkali activation, then carry out acid treatment again, be prepared for specific surface area up to 604m2/ g, most probable pore size is the meso pore silicon oxide material of 4.41nm, further increases the specific surface area (AppliedClayScience, 2015,107:182-187) of the mesoporous material utilizing Kaolin template-free method to prepare。
It is obvious that there is the silica material relatively low (< 650m of its specific surface area utilizing Kaolin template-free method to prepare of bibliographical information at present2/ g), with the specific surface area of template synthesis up to 700～1000m2The ordered mesoporous material of/g is compared or has a certain distance。
It is noted that at present bibliographical information utilize the method that Kaolin template-free method prepares meso pore silicon oxide material Kaolin will be carried out calcining and activating to become metakaolin。And under normal circumstances, Kaolin needs calcining under the high temperature of 650～900 DEG C can be converted into metakaolin in more than 2 hours。Undoubtedly, kaolinic calcine technology not only increases energy consumption cost, and adds the complexity of technique process。Therefore, utilize Kaolin to pass through not calcine template-free method to prepare the technique with more Mesoporous Materials With High Specific and will have bigger advantage。
Summary of the invention
It is an object of the invention to provide and a kind of utilize Kaolin to pass through not calcine template-free method to prepare the method with high specific surface area and mesoporous silica material。
To achieve these goals, the technical scheme is that
Utilize Kaolin to pass through not calcine the method that template-free method prepares meso pore silicon oxide material, comprise the following steps:
(1) synthetic zeolite: directly utilize Kaolin synthesizing Si-Al zeolite；
(2) acid treatment: by the zeolite obtained in step (1) and acid solution reaction, the crystal structure of zeolite is thoroughly destroyed by acid treatment, leach the metallic element in its composition, then solid-liquid separation, solid-phase is washed and dries, namely obtaining meso pore silicon oxide material, obtained meso pore silicon oxide material specific surface area is 650～710m2/ g, most probable pore size is 3.5～4.2nm。
In step (2), the main purpose of acid treatment process is thoroughly to destroy the crystal structure of zeolite, leaches the metallic element in its composition, obtains meso pore silicon oxide material。Its acid solution adopted should be able to, for destroying the crystal structure of zeolite, can be that strong acid is (such as HCl, HNO3、H2SO4Deng) one or two or more kinds in solution by the mixture of any proportioning, or strong acid solution (one or more) with other weak acid (such as acetic acid, HNO2) by the mixture of suitable proportion。
In step (2), Si-Al zeolite is after acid etch, its crystal structure is totally disrupted, aluminium component therein is etched and is dissolved in acid solution, and then can separate with the silicon oxide composition not dissolving in acid, therefore aluminium element be can extract from the acid solution containing aluminum, metal aluminium or meso-porous alumina prepared。
In step (2), acid solution is the HCl solution of 1～10mol/L, and zeolite and HCl solution react 2～12h when 40～100 DEG C, and solid-to-liquid ratio is 1kg:4～50L。
In the art, zeolite is a kind of common poromerics (aperture, duct is less than 2nm), and in crystal structure, it is by [SiO4] tetrahedron and [AlO4] top, four angles of tetrahedron is shared and connects along three dimensions, eventually becomes the crystal of rack-like。Different from other rack-like aluminium silicate salts, zeolite has secondary structure unit, these secondary units form the polyhedron space of definite shape in zeolite crystal structure, i.e. so-called cage (e.g., α-cage, β-cage, γ-cage)。Therefore, zeolite has higher specific surface area (400～800m2/ g), in fields such as absorption, catalysis, separation, ion exchanges, there is relatively broad application。But, development along with science, the application of conventional mineral type Si-Al zeolite has become increasingly limited, and its main defect has: the duct of (1) zeolite is the chemical reaction that pore size (great majority are less than 1nm) is not particularly suited for comprising macromole；(2) although most of mineral type Si-Al zeolite has comparatively perfect crystal structure, but because its composition has more aluminum, its absolute acid stability and thermally-stabilised very low。Therefore, the mesoporous material of research and development and exploitation high stability is one, inorganic material field important branch。Mesoporous material (especially mesopore silicon oxide and mesoporous carbon) has significantly high specific surface area, abundant pore passage structure, comparatively homogeneous mesoporous pore size distribution (2～50nm) and significantly high heat stability and absolute acid stability, the absorption of macromole that has been difficult at a lot of micro-pore zeolite molecular sieves, separation, especially have in catalytic reaction and more act on widely。Additionally, irrefragable, zeolite is just because of its special crystal framework, thus having abundant pore passage structure, once the crystal structure of zeolite suffers to destroy completely, the micropore canals structure within zeolite will be collapsed, thus causing the forfeiture of its using value。It is true that researcher had been carried out the work that Si-Al zeolite is structurally-modified before for a long time, but it is all carry out under the premise ensureing zeolite crystal skeleton, namely Si-Al zeolite molecular sieve is carried out suitable dealuminzation so that zeolitic frameworks situ produces mesopore orbit。These mesopore orbits produce hole due to framework of molecular sieve local dealuminzation, original position and obtain, and its pore size and quantity are relevant with dealuminzation condition, are difficult to control。In brief, at present not about thoroughly destroying zeolite crystal structure, wherein aluminium component is etched, thus obtaining research and the report of meso pore silicon oxide material。The application very not harsh requirement for the taste of Si-Al zeolite, and the various methods of existing bibliographical information therefore can be adopted to prepare Si-Al zeolite。The main purpose of acid treatment process is thoroughly to destroy the crystal structure of zeolite, leaches the metallic element in its composition, obtains mesoporous material。Its acid solution adopted should be able to for destroying the crystal structure of zeolite, can be one or two or more kinds in strong acid solution by the mixture of any proportioning, or strong acid solution and other weak acid press the mixture of suitable proportion。
Compared with prior art, the invention have the advantages that
1, mesoporous material is prepared with natural minerals Kaolin cheap and easy to get for unique raw material, and preparation technology does not use template or the mould material (such as hexamethylene diamine, cetyl trimethylammonium bromide etc.) of costliness, without introducing any poisonous and hazardous organic solvent (such as benzene, methanol, ether etc.), production technology is simple, with low cost, is suitable for industrialized production。
2, the technique that this technique prepares meso pore silicon oxide material for traditional direct acidleach of metakaolin, propose in a creative way and utilize Kaolin directly to prepare the technique of acid treatment after Si-Al zeolite without calcination process, namely first by simple process preparation, Kaolin is become Si-Al zeolite to carry out acid treatment again and obtain mesopore silicon oxide, be that a kind of thinking breaks through and technological innovation；And in view of the similarity of the structure of mineral and composition, this technique should have certain practicality for other raw mineral materials；The specific surface area of meso pore silicon oxide material prepared by this technique may be up to 710m simultaneously2/ g, its most probable pore size is 3.5～4.2nm, close to mesoporous material prepared by segment template method。
3, this technique directly utilizes Kaolin and prepares mesoporous material, it is not necessary to Kaolin is carried out calcining and activating process, and relatively traditional handicraft has advantage in energy consumption with technique process。
4, porous material prepared by the present invention when room temperature and pH=10 for the saturated extent of adsorption of methylene blue up to 700mg/g, as the adsorbing material of a kind of function admirable, can have relatively broad application prospect。
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption-desorption isotherm figure of example 1 intermediary hole silicon oxide
Fig. 2 is the graph of pore diameter distribution that example 1 intermediary hole silicon oxide uses BJH model analysis。
Detailed description of the invention
For making those skilled in the art be more fully understood that technical scheme, below in conjunction with accompanying drawing, the present invention is described in further detail。
Embodiment 1
Utilizing the method that Kaolin template-free method prepares meso pore silicon oxide material, it comprises the steps:
(1) zeolite is prepared: mixed with the ratio of 1kg:20L with the sodium hydroxide solution of 6mol/L by Kaolin, stir when 100 DEG C and react 6h, then the solid product extremely neutrality filtered and obtain with deionized water wash, then through 110 DEG C of dry removal moisture, obtains zeolite；
(2) acid treatment: mix obtaining zeolite in step (1) with the ratio of 1kg:20L with the HCl solution of 5mol/L, stir when 80 DEG C and react 6h, then the solid product extremely neutrality filtered and obtain with deionized water wash, then through 110 DEG C of dry removal moisture, obtain meso pore silicon oxide material prepared by template-free method。The acid solution containing aluminum being filtrated to get after acid treatment can be used to carry aluminum, prepares metal aluminium or meso-porous alumina。
The specific surface area of the meso pore silicon oxide material obtained in the present embodiment is 713m2/ g, its most probable pore size is 4.0nm。Its nitrogen adsorption-desorption isotherm as it is shown in figure 1, its pore-size distribution obtained according to BJH model as shown in Figure 2。

Claims (3)

1. utilize Kaolin to pass through not calcine the method that template-free method prepares meso pore silicon oxide material, it is characterised in that to comprise the following steps:
(1) synthetic zeolite: directly utilize Kaolin and prepare Si-Al zeolite；
(2) acid treatment: by the zeolite obtained in step (1) and acid solution reaction, the crystal structure of zeolite is thoroughly destroyed by acid treatment, leach the metallic element in its composition, then solid-liquid separation, solid-phase is washed and dries, namely obtaining meso pore silicon oxide material, obtained meso pore silicon oxide material specific surface area is 650～710m2/ g, most probable pore size is 3.8～4.2nm。
2. according to claim 1 utilize Kaolin to pass through not calcine the method that template-free method prepares meso pore silicon oxide material, it is characterized in that: in step (2), acid solution is can for destroying the acid solution of the crystal structure of zeolite, be specially one or two or more kinds in strong acid solution by the mixture of any proportioning, or for mixture that strong acid solution and weak acid solution are made into。
3. according to claim 1 utilize Kaolin to pass through not calcine the method that template-free method prepares meso pore silicon oxide material, it is characterized in that: in step (2), acid solution is the HCl solution of 1～10mol/L, zeolite and HCl solution react 2～12h when 40～100 DEG C, and solid-to-liquid ratio is 1kg:4～50L。
CN201610033520.1A 2016-01-18 2016-01-18 The method for preparing meso pore silicon oxide material by not calcining template-free method using kaolin Expired - Fee Related CN105692628B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109354029A (en) * 2018-11-22 2019-02-19 山西大学 A method of by coal ash for manufacturing for mesopore silicon oxide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1559900A (en) * 2004-02-26 2005-01-05 南开大学 Process of preparing velence pore molecular siever by natural kaolinite
CN102167352A (en) * 2011-03-14 2011-08-31 浙江师范大学 Method for preparing 4A zeolite by kaolin alkali fusion one-step method
CN104557130A (en) * 2015-01-20 2015-04-29 中国地质大学（武汉） Preparation method of kaolin-based mesoporous silica material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1559900A (en) * 2004-02-26 2005-01-05 南开大学 Process of preparing velence pore molecular siever by natural kaolinite
CN102167352A (en) * 2011-03-14 2011-08-31 浙江师范大学 Method for preparing 4A zeolite by kaolin alkali fusion one-step method
CN104557130A (en) * 2015-01-20 2015-04-29 中国地质大学（武汉） Preparation method of kaolin-based mesoporous silica material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109354029A (en) * 2018-11-22 2019-02-19 山西大学 A method of by coal ash for manufacturing for mesopore silicon oxide
CN109354029B (en) * 2018-11-22 2022-03-18 山西大学 Method for preparing mesoporous silicon oxide from fly ash

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