CN103145163A - Method for preparing aluminum-silicon composite oxide with mesoporous hollow microsphere structure - Google Patents
Method for preparing aluminum-silicon composite oxide with mesoporous hollow microsphere structure Download PDFInfo
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- CN103145163A CN103145163A CN201310083085XA CN201310083085A CN103145163A CN 103145163 A CN103145163 A CN 103145163A CN 201310083085X A CN201310083085X A CN 201310083085XA CN 201310083085 A CN201310083085 A CN 201310083085A CN 103145163 A CN103145163 A CN 103145163A
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Abstract
The invention discloses a method for preparing aluminum-silicon composite oxide with a mesoporous hollow microsphere structure. The method is characterized by comprising the steps of adding a pore-foaming agent into water to evenly disperse, orderly adding silicate ester and acid, adding an aluminum source to react for a period of time after reacting for a period of time, drying the obtained sol in a spraying manner to obtain a white product, baking and firing the product at high temperature to obtain the aluminum-silicon composite oxide. The composite oxide is solid acid, is strong in acidity, abundant in L acid site, good in micromolecule trafficability characteristic, and displays the mesoporous hollow microsphere structure; and the specific surface area is greater than 1000m<2>/g.
Description
Technical field
The invention belongs to field of inorganic material preparing technology, relate to specifically a kind of preparation method of aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
Background technology
Acid catalysis is modal catalytic process, occupies critical role in refining of petroleum, petrochemical complex.Traditional catalyzer is the Lewis acids such as liquid acid sulfuric acid, phosphoric acid, hydrofluoric acid, aluminum chloride, zinc chloride.These processes all exist equipment corrosion, spent acid to reclaim, the environmental problems such as discharging.Eco-friendly solid acid catalyst advantage is there is no the equipment corrosion problem, product is easy to separate with catalyzer, the catalytic activity high, thereby synthesize fields such as (a plurality of products such as tetrahydrofuran (THF), dioxane, alkyl pyrazine, alkyl pyridine) at softening agent (a plurality of products such as DOA, DOP), lubricating oil (a plurality of products such as tricarboxymethyl propane oleate, PETO), biofuel, petroleum cracking, heterocycle and more and more used.The aluminium Si composite oxide is as solid acid catalyst or the existing some reports of carrier.201110358027.4 reported a kind of Al
2O
3-SiO
2Ceramic membrane and preparation method thereof, membrane pore size is even, membranous wall is thin, the large and conservation of permeation flux, be easy to realize the separating device miniaturization, the characteristics such as simplify the structure.But existing aluminium Si composite oxide specific surface area is less, and the small molecules trafficability characteristic is bad.
Summary of the invention
Purpose of the present invention provides a kind of preparation method of aluminium Si composite oxide of meso-porous hollow micro-sphere structure just for existing weak point in above-mentioned prior art.
The present invention is added to the water silicon source and pore-creating agent successively, then add acid, reaction adds the aluminium source after for some time, continue reaction, controlling level of response makes system remain on collosol state, then colloidal sol is carried out spraying drying, products therefrom is removed the aluminium Si composite oxide that can obtain the meso-porous hollow micro-sphere structure after pore-creating agent by solution extracting or high temperature sintering.
Purpose of the present invention can realize by following technique measures:
The preparation method of the aluminium Si composite oxide of meso-porous hollow micro-sphere structure of the present invention comprises the steps:
A. pore-creating agent is added to the water 20 ~ 80 ℃ of stirring and dissolving, the weight/volume of wherein said pore-creating agent and water is 1:10～100, be cooled to 5 ~ 30 ℃, then under agitation silicon ester is added in mentioned solution, wherein the weight ratio of silicon ester and pore-creating agent is 1:0.2 ~ 10, then add acid, hierarchy of control pH value was reacted under 5 ~ 60 ℃ 5～120 minutes 2 ~ 4.
B. add the aluminium source in a solution, in the aluminium source in aluminum oxide and silicon ester the weight ratio of silicon-dioxide be 1:2.5～40, continue to stir 15～120 minutes under 5 ~ 60 ℃.
C. b colloidal sol is carried out spraying drying, 160～220 ℃ of vapo(u)rizing temperatures, 110～130 ℃ of detected temperatures obtain white powder.Prepared white powder was dried under 80～100 ℃ 2～8 hours, then 400～600 ℃ of lower calcinations 1～2 hour, then 800～1000 ℃ of lower thermal treatments 30～120 minutes, can obtain the aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
Pore-creating agent of the present invention is any one in hexadecyl benzene sulfonic acid sodium salt, cetyl trimethylammonium bromide, cetyltriethylammonium bromide, palmityl trimethyl ammonium chloride, hexadecyl triethyl ammonium chloride, lauryl amine, hexadecylamine, octadecylamine, epoxy polyethylene, oxyethylene-propylene oxide copolymer or oxyethylene-propylene oxide-oxyethylene terpolymer.
Silicon ester of the present invention is any one in positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four isopropyl esters or positive silicic acid four butyl esters.
Aluminium of the present invention source is any one in aluminum nitrate, Tai-Ace S 150, aluminum chloride, aluminic acid trimethyl, aluminic acid three isopropyl esters or aluminic acid three benzyl esters.
Acid of the present invention is any one in hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, acetic acid or carbonic acid.
Beneficial effect of the present invention is as follows:
1. the aluminium Si composite oxide of gained is a kind of solid acid, and is acid strong, and L acid position is abundant.
2. the aluminium Si composite oxide of gained presents the meso-porous hollow micro-sphere structure, and the small molecules trafficability characteristic is good, and specific surface area is higher than 1000m
2/ g.
Embodiment
The present invention is described in further detail below with reference to embodiment.Be necessary to be pointed out that at this following examples only are used for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1. is added to the water cetyl trimethylammonium bromide 50 ℃ of stirring and dissolving, wherein the weight/volume of cetyl trimethylammonium bromide and water is 1:30, be cooled to 25 ℃, then under agitation tetraethoxy is added in mentioned solution, wherein the weight/volume of tetraethoxy and cetyl trimethylammonium bromide is 1:2, then add hydrochloric acid, hierarchy of control pH value is 4, and reaction is 30 minutes under 40 ℃.Then adding aluminum nitrate, the weight/volume of aluminum nitrate and tetraethoxy in mentioned solution is 1:1, continues to stir 30 minutes under 40 ℃.Then above-mentioned colloidal sol is carried out spraying drying, 180 ℃ of vapo(u)rizing temperatures, 120 ℃ of detected temperatures obtain white powder.Prepared white powder was dried 2 hours under 100 ℃, then 500 ℃ of lower calcinations 1 hour, can obtain the aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
Embodiment 2. is added to the water the hexadecyl benzene sulfonic acid sodium salt 60 ℃ of stirring and dissolving, wherein the weight/volume of hexadecyl benzene sulfonic acid sodium salt and water is 1:30, be cooled to 25 ℃, then under agitation tetraethoxy is added in mentioned solution, wherein the weight/volume of tetraethoxy and hexadecyl benzene sulfonic acid sodium salt is 2:3, then add hydrochloric acid, hierarchy of control pH value is 4, and reaction is 30 minutes under 40 ℃.Then adding Aluminium chloride hexahydrate, the weightmeasurement ratio of Aluminium chloride hexahydrate and tetraethoxy in mentioned solution is 2:1, continues to stir 30 minutes under 40 ℃.Then above-mentioned colloidal sol is carried out spraying drying, 180 ℃ of vapo(u)rizing temperatures, 120 ℃ of detected temperatures obtain white powder.Prepared white powder was dried 2 hours under 100 ℃, then 500 ℃ of lower calcinations 1 hour, can obtain the aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
Embodiment 3. is added to the water lauryl amine 60 ℃ of stirring and dissolving, wherein the weight/volume of lauryl amine and water is 1:30, be cooled to 25 ℃, then under agitation positive silicic acid four butyl esters are added in mentioned solution, wherein the weight/volume of positive silicic acid four butyl esters and lauryl amine is 1:3, then add hydrochloric acid, hierarchy of control pH value is 4, and reaction is 30 minutes under 40 ℃.Then add Tai-Ace S 150 in mentioned solution, the weightmeasurement ratio of Tai-Ace S 150 and positive silicic acid four butyl esters is 1:2, continues to stir 30 minutes under 40 ℃.Then above-mentioned colloidal sol is carried out spraying drying, 180 ℃ of vapo(u)rizing temperatures, 120 ℃ of detected temperatures obtain white powder.Prepared white powder was dried 2 hours under 100 ℃, then 500 ℃ of lower calcinations 1 hour, can obtain the aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
Oxyethylene-propylene oxide-oxyethylene terpolymer is added to the water 60 ℃ of stirring and dissolving, wherein the weight/volume of oxyethylene-propylene oxide-oxyethylene terpolymer and water is 1:10, be cooled to 25 ℃, then under agitation tetraethoxy is added in mentioned solution, wherein the weight/volume of tetraethoxy and oxyethylene-propylene oxide-oxyethylene terpolymer is 1:8, then add sulfuric acid, hierarchy of control pH value is 4, and reaction is 30 minutes under 40 ℃.Then add aluminic acid three isopropyl esters in mentioned solution, the weightmeasurement ratio of aluminic acid three isopropyl esters and tetraethoxy is 1:1, continues to stir 30 minutes under 40 ℃.Then above-mentioned colloidal sol is carried out spraying drying, 180 ℃ of vapo(u)rizing temperatures, 120 ℃ of detected temperatures obtain white powder.Prepared white powder was dried 2 hours under 100 ℃, then 500 ℃ of lower calcinations 1 hour, can obtain the aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
Claims (5)
1. the preparation method of the aluminium Si composite oxide of a meso-porous hollow micro-sphere structure, it is characterized in that: described method comprises the steps:
A. pore-creating agent is added to the water 20 ~ 80 ℃ of stirring and dissolving, the weight/volume of wherein said pore-creating agent and water is 1:10～100, be cooled to 5 ~ 30 ℃, then under agitation silicon ester is added in mentioned solution, wherein the weight ratio of silicon ester and pore-creating agent is 1:0.2 ~ 10, then add acid, hierarchy of control pH value was reacted under 5 ~ 60 ℃ 5～120 minutes 2 ~ 4;
B. add the aluminium source in a solution, in the aluminium source in aluminum oxide and silicon ester the weight ratio of silicon-dioxide be 1:2.5～40, continue to stir 15～120 minutes under 5 ~ 60 ℃;
C. b colloidal sol is carried out spraying drying, 160～220 ℃ of vapo(u)rizing temperatures, 110～130 ℃ of detected temperatures, obtain white powder, prepared white powder was dried under 80～100 ℃ 2～8 hours, then 400～600 ℃ of lower calcinations 1～2 hour, at last 800～1000 ℃ of lower thermal treatments 30～120 minutes, can obtain the aluminium Si composite oxide of meso-porous hollow micro-sphere structure.
2. method according to claim 1, it is characterized in that: described pore-creating agent is any one in hexadecyl benzene sulfonic acid sodium salt, cetyl trimethylammonium bromide, cetyltriethylammonium bromide, palmityl trimethyl ammonium chloride, hexadecyl triethyl ammonium chloride, lauryl amine, hexadecylamine, octadecylamine, epoxy polyethylene, oxyethylene-propylene oxide copolymer or oxyethylene-propylene oxide-oxyethylene terpolymer.
3. method according to claim 1 is characterized in that: silicon ester is any one in positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four isopropyl esters or positive silicic acid four butyl esters.
4. method according to claim 1 is characterized in that: the aluminium source is any one in aluminum nitrate, Tai-Ace S 150, aluminum chloride, aluminic acid trimethyl, aluminic acid three isopropyl esters or aluminic acid three benzyl esters.
5. method according to claim 1, it is characterized in that: described acid is any one in hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, acetic acid or carbonic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186007A (en) * | 2016-07-07 | 2016-12-07 | 安徽省含山县锦华氧化锌厂 | A kind of MgO granule with micron/nano composite construction and preparation method thereof |
| CN106179493A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of hydrophobic solid acid catalyst and preparation and the application in aromatic acid is esterified |
| CN107398263A (en) * | 2017-09-20 | 2017-11-28 | 钦州学院 | A kind of pillared layered sial composite oxides and preparation method thereof |
-
2013
- 2013-03-15 CN CN201310083085XA patent/CN103145163A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 吴俊升等: ""介孔/大孔Al2O3-SiO2复合氧化物的制备与表征"", 《催化学报》 * |
| 程文喜等: ""CTAB含量对介孔空心微球结构的影响"", 《河南化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179493A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of hydrophobic solid acid catalyst and preparation and the application in aromatic acid is esterified |
| CN106179493B (en) * | 2015-05-06 | 2018-11-13 | 中国科学院大连化学物理研究所 | A kind of hydrophobic solid acid catalyst and preparation and the application in aromatic acid esterification |
| CN106186007A (en) * | 2016-07-07 | 2016-12-07 | 安徽省含山县锦华氧化锌厂 | A kind of MgO granule with micron/nano composite construction and preparation method thereof |
| CN107398263A (en) * | 2017-09-20 | 2017-11-28 | 钦州学院 | A kind of pillared layered sial composite oxides and preparation method thereof |
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Application publication date: 20130612 |