CN105692627A - Method for preparing mesoporous silica material from kaolin through template-free method - Google Patents
Method for preparing mesoporous silica material from kaolin through template-free method Download PDFInfo
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- CN105692627A CN105692627A CN201610032397.1A CN201610032397A CN105692627A CN 105692627 A CN105692627 A CN 105692627A CN 201610032397 A CN201610032397 A CN 201610032397A CN 105692627 A CN105692627 A CN 105692627A
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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
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- C01P2006/12—Surface area
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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 template-free method.The method includes the following steps that 1, calcined activation is conducted, wherein the kaolin is subjected to a calcination process to obtain amorphous metakaolin; 2, zeolite is synthesized, wherein the metakaolin obtained in the step 1 is prepared into the silicon-aluminum zeolite; 3, the zeolite obtained in the step 2 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 680-760 m<2>/g, and the most probable hole diameter ranges from 3.8 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
Technical field
The present invention relates to mesoporous materials field, be specifically related to a kind of utilize Kaolin pass through template-free method prepare there is high specific surface area meso pore silicon oxide material technique。
Background technology
Mesoporous material with the pore-size distribution (2～50nm) of its excellence and bigger specific surface area, absorption, separate, many fields such as catalysis and medicine embedding and conveying have and are 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 nano 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, utilize strong acid that the activated aluminum composition in metakaolin is performed etching thus obtaining the nano oxidized silicon materials 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, the impact of the parameter mesoporous material on utilizing Kaolin to prepare 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) is carried out system comprehensively study, found that utilize its specific surface area of material prepared by calcining acid leaching process the highest only up to 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。
Summary of the invention
It is an object of the invention to provide the Kaolin that utilizes of a kind of low production cost and pass through the method that template-free method preparation has high specific surface area and mesoporous silica material。
To achieve these goals, the technical scheme is that
The method utilizing Kaolin to prepare meso pore silicon oxide material by template-free method, comprises the following steps:
(1) calcining: Kaolin is obtained metakaolin by calcining；
(2) synthetic zeolite: the metakaolin obtained in step (1) is prepared for Si-Al zeolite；
(3) acid treatment: by the zeolite obtained in step (2) 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 680～760m2/ g, most probable pore size is 3.8～4.2nm。
In step (1), calcine technology is 600～900 DEG C of calcining 1～24h。
In step (3), 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 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 (3), 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 step (3), Si-Al zeolite is acid treated, and its crystal structure is entirely destroyed, and the aluminium element in its composition is dissolved, and enters acid solution, separates with the silicon oxide not dissolving in acid, such that it is able to be extracted, is used for preparing metal aluminium or meso-porous alumina。
Kaolinic in the present invention it is mainly composed of kaolinite (Al2O3·2SiO2·2H2O), through step 1) occur decarboxylation reaction to be activated, finally it is changed into amorphous metakaolin (Al with greater activity2O3·2SiO2)。In practical operation can according to different kaolinic types and the place of production etc., in calcining heat with carry out suitable process optimization in the time。
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。Present application has been thinking to break through and technological innovation, creatively propose and first prepare the technique of acid treatment after Si-Al zeolite, namely first pass through simple process and prepare into and only there is microcellular structure not there is the Si-Al zeolite of meso-hole structure, then carry out acid treatment。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 technical scheme that the application provides has the advantage that
1, the application prepares meso pore silicon oxide material 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 application proposes in a creative way and first prepares the technique of acid treatment after Si-Al zeolite, is 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 750m simultaneously2/ g, its most probable pore size is up to 4nm, close to meso pore silicon oxide material prepared by segment template method。Porous material prepared by the present invention when room temperature and pH=10 for the saturated extent of adsorption of methylene blue up to 760mg/g, as the adsorbing material of a kind of function admirable, can have relatively broad application prospect。
3, the present invention can obtain the acid solution containing aluminum while preparing mesopore silicon oxide, can be used for carrying aluminum, prepares metal aluminium or meso-porous alumina。
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption-desorption isotherm figure of embodiment 1 intermediary hole silicon oxide；
Fig. 2 is the graph of pore diameter distribution that embodiment 1 intermediary hole silicon oxide uses BJH model analysis；
Fig. 3 is the transmission electron microscope photo of example 1 intermediary hole silicon oxide。
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) calcining and activating: Kaolin is placed in calciner under 850 DEG C of conditions calcining 2h after, until equipment cool down after take out, obtain unbodied metakaolin；
(2) zeolite is prepared: adopt hydro-thermal alkalization method to prepare Si-Al zeolite (zeoliteLTA) metakaolin of step (1) gained；
(3) acid treatment: mix obtaining zeolite in step (2) with the ratio of 1kg:20L with the HCl solution of 5mol/L, 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, obtain meso pore silicon oxide material prepared by template-free method。The acid solution containing aluminum being filtrated to get 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 751.5m2/ g, its most probable pore size is 3.88nm。Its nitrogen adsorption-desorption isotherm and the pore-size distribution that obtains according to BJH model are as depicted in figs. 1 and 2。Fig. 3 is its transmission electron microscope observing photo。
Embodiment 2
Utilizing the method that Kaolin template-free method prepares meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: Kaolin is placed in calciner under 600 DEG C of conditions calcining 12h after high temperature direct sample, obtain unbodied metakaolin；
(2) it is 5.3Na by calcined kaolin, sodium hydroxide, Ludox and its ionized water by molar ratio2O:1.0Al2O3:4.0SiO2:240H2O carries out mix and blend, then adds the 13X molecular sieve crystal seed of 2% in solution, quickly stirs 5h, then reaction mixture is put into crystallization 80min in the microwave oven of 700W, obtain 13X zeolite molecular sieve。
(3) acid treatment: by the H of the zeolite obtained in step (2) and 1mol/L2SO4Solution mixes with the ratio of 1kg:50L, stirs when 40 DEG C and reacts 2h, the solid product extremely neutrality then filtering and obtaining with deionized water wash, then through 110 DEG C of dry removal moisture, obtains meso pore silicon oxide material prepared by template-free method。The acid solution containing aluminum being filtrated to get 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 760m2/ g, its most probable pore size is 3.9nm。
Embodiment 3
Utilizing the method that Kaolin template-free method prepares meso pore silicon oxide material, it comprises the steps:
(1) calcining and activating: Kaolin is placed in calciner under 900 DEG C of conditions calcining 1h after high temperature direct sample, obtain unbodied metakaolin；
(2) zeolite is prepared: the metakaolin of step (1) gained is prepared into Si-Al zeolite；
(3) acid treatment: the zeolite obtained in step (2) is mixed with the ratio of 1kg:10L with the mixed solution containing 2mol/LHNO3 and 1mol/LHCl, stir when 60 DEG C and react 10h, 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 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 750m2/g, and its most probable pore size is 4.1nm。
Claims (4)
1. utilize the method that Kaolin prepares meso pore silicon oxide material by template-free method, it is characterised in that comprise the following steps:
(1) calcining: Kaolin is obtained metakaolin by calcining；
(2) synthetic zeolite: the metakaolin obtained in step (1) is prepared for Si-Al zeolite；
(3) acid treatment: by the zeolite obtained in step (2) 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 680～760m2/ g, most probable pore size is 3.8～4.2nm。
2. the method utilizing Kaolin to prepare meso pore silicon oxide material by template-free method according to claim 1, it is characterised in that: in step (1), calcine technology is 600～900 DEG C of calcining 1～24h。
3. the method utilizing Kaolin to prepare meso pore silicon oxide material by template-free method according to claim 1, it is characterized in that: in step (3), 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。
4. utilize, according to claim 1 or 3, the method that Kaolin prepares meso pore silicon oxide material by template-free method, it is characterized in that: in step (3), 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。
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Cited By (6)
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| CN108341416A (en) * | 2018-01-09 | 2018-07-31 | 浙江工业大学 | It is a kind of to utilize the acicular nanometer zeolitic material and its method of metakaolin preparation and application |
| 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 |
| CN110508235A (en) * | 2019-08-23 | 2019-11-29 | 南京理工大学 | A method of porous oxidation silicon materials are prepared using chlorite |
| CN111822057A (en) * | 2019-04-23 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of spherical alumina carrier |
| CN111821986A (en) * | 2019-04-23 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of hydrogenation carbon residue removal catalyst |
| CN113924272A (en) * | 2019-06-05 | 2022-01-11 | 雷奥技术公司 | Synthesis of adsorbent Material |
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| CN104557130A (en) * | 2015-01-20 | 2015-04-29 | 中国地质大学（武汉） | Preparation method of kaolin-based mesoporous silica material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN111822057A (en) * | 2019-04-23 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of spherical alumina carrier |
| CN111821986A (en) * | 2019-04-23 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of hydrogenation carbon residue removal catalyst |
| 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 |
| CN111821986B (en) * | 2019-04-23 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation carbon residue removal catalyst |
| CN113924272A (en) * | 2019-06-05 | 2022-01-11 | 雷奥技术公司 | Synthesis of adsorbent Material |
| CN110508235A (en) * | 2019-08-23 | 2019-11-29 | 南京理工大学 | A method of porous oxidation silicon materials are prepared using chlorite |
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