CN103877928A - Method for synthesizing SiO2-Al2O3 material with macropores and large specific area - Google Patents

Method for synthesizing SiO2-Al2O3 material with macropores and large specific area Download PDF

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CN103877928A
CN103877928A CN201410051125.7A CN201410051125A CN103877928A CN 103877928 A CN103877928 A CN 103877928A CN 201410051125 A CN201410051125 A CN 201410051125A CN 103877928 A CN103877928 A CN 103877928A
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aqueous solution
filter cake
sio
inorganic salt
solution
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CN103877928B (en
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姚楠
李小年
王其刚
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a method for synthesizing a SiO2-Al2O3 material with macropores and large specific area. The method for synthesizing the SiO2-Al2O3 material with macropores and large specific area comprises the following steps: (a) mixing and reacting a silicon-contained inorganic salt aqueous solution and an aluminum-contained inorganic salt aqueous solution according to the mole ratio of 7 to 8 of Si/Al so as to obtain suspension containing precipitate, wherein the silicon-contained inorganic salt aqueous solution is a potassium metasilicate aqueous solution or water glass of K or Na, and the aluminum-contained inorganic salt aqueous solution is an aluminum nitrate aqueous solution or an aluminum sulfate aqueous solution; (b) adjusting the pH value of the suspension containing precipitate to be between 5 and 8, and filtering so as to obtain a filter cake I; (c) pulping and filtering the filter cake I in an alkaline solution to remove impurities so as to obtain a filter cake II, wherein the alkaline solution is an ammonium carbonate aqueous solution, ammonium hydroxide or an ammonium bicarbonate aqueous solution with the mole ratio of 0.5-1.5 mol.L<1->; (d) soaking the filter cake II obtained in the step (c) into an organic alcohol solvent, and then recycling the solvent to obtain a filter cake III; (e) roasting the filter cake III under an air atmosphere of 300-600 DEG C so as to obtain the SiO2-Al2O3 material.

Description

A kind of SiO with macropore, bigger serface 2-Al 2o 3the synthetic method of material
(1) technical field
The present invention relates to a kind of SiO 2-Al 2o 3the preparation method of material, especially relates to a kind of synthetic SiO simultaneously with bigger serface, large aperture structure 2-Al 2o 3the preparation method of material.
(2) background technology
SiO 2-Al 2o 3material is the acid carrier that a class is widely used in the various load type metal catalysts of preparation.With SiO 2-Al 2o 3material is that loaded catalyst prepared by carrier is widely used in all kinds of catalytic reactions such as PETROLEUM PROCESSING, catalytic hydrogenation.For can by metal active constituent (for example: Pt, Pd, Au, Ru) evenly, high degree of dispersion is to time carrier surface, the diffusion in raising catalytic reaction process, in the urgent need to SiO 2-Al 2o 3carrier has higher specific area and larger aperture simultaneously.But, in the synthetic porous material of conventional method, exist the problem (A.Mart í nez, G.Prieto, J.Roll á n, J.Catal.263 (2009) 292-305) of " specific area-aperture restricts mutually ", along with SiO 2-Al 2o 3material specific area ground increases, and its aperture is but constantly reducing.
Therefore, be difficult to the synthetic SiO simultaneously with bigger serface, large aperture structure by conventional method 2-Al 2o 3material.Meanwhile, in order to increase and to control SiO 2-Al 2o 3the aperture of material and pore structure, at SiO 2-Al 2o 3in the building-up process of material, often use all kinds of organic formwork agents, pore regulator.This has not only increased preparation cost, and can damage environment, does not meet the environmental protection of current increasingly stringent and the requirement of energy-saving and emission-reduction.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic SiO with bigger serface, large aperture characteristic 2-Al 2o 3the new method of material, the method is easy, raw material is cheap and easy to get, economy, environmental protection.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of SiO 2-Al 2o 3the synthetic method of material, comprises the steps:
(a) be 7～8 hybrid reactions by siliceous inorganic salt solution and the inorganic salt containing aluminium aqueous solution according to Si/Al mol ratio, obtain the suspension that contains precipitation; Described siliceous inorganic salt solution is potassium silicate aqueous solution or the waterglass containing K or Na, and the mass percent concentration of siliceous inorganic salts is 15-25%; The described inorganic salt containing aluminium aqueous solution is aluminum nitrate or aluminum sulfate aqueous solution, and wherein the mass percent concentration of inorganic salt containing aluminium is 10-30%;
(b) regulate the pH value of the suspension that contains precipitation being obtained by step (a) between 5-8, filter and obtain filter cake I;
(c) filter cake step (b) being obtained by pulling an oar, removing by filter impurity, obtains filter cake II in alkaline solution; Described alkaline solution is that molar concentration is at 0.5-1.5mol L -1the amine carbonate aqueous solution, ammoniacal liquor or the Ammonium bicarbonate food grade aqueous solution;
(d) the filter cake II being made by step (c) is immersed in organic alcohol solvent, and then recovery solvent obtains filter cake III; Described organic alcohol solvent is selected from following a kind of or several combination arbitrarily: methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, butanediol, propane diols, glycerine, polyethylene glycol;
(e) filter cake III is carried out to calcination process in 300-600 DEG C under air atmosphere condition and obtain SiO 2-Al 2o 3material.
In step of the present invention (a), using cheap potassium silicate or waterglass is raw material, because Na, K ion have the SiO of making 2-Al 2o 3material is densified and significantly reduce the shortcoming of material acidity, therefore needs to use above-mentioned steps (b) that Na, K ion in precipitation are thoroughly washed away, to avoid affecting gained SiO 2-Al 2o 3the specific area of material and acidity.But, due to SiO 2-Al 2o 3al in material can enter SiO 2skeleton structure forms electronegative cellular construction, so part Na, K ion are used to the electronegative cellular construction of balance, to maintain its structural stability.So this part Na, K ion is more difficult removes up hill and dale by common washing methods.Therefore, in step of the present invention (c), process filter cake with alkaline solution, contain decomposable NH by introducing 4 +ion is replaced Na, K ion, under the prerequisite that maintains cation, has removed again Na, K ion, thereby makes the SiO of preparation 2-Al 2o 3material has higher specific area and aperture.In step of the present invention (d), use Organic Alcohol to carry out replacement Treatment to the water in filter cake, to reduce the impact of surface tension on pore structure in roasting process.
Further, in step (a), the preferred aluminum nitrate of described inorganic salt containing aluminium, in the inorganic salt containing aluminium aqueous solution, the mass percent concentration of inorganic salt containing aluminium is preferably 22～25%; The described preferred potassium silicate of siliceous inorganic salts, the mass percent concentration of siliceous inorganic salts preferably 15～20% in siliceous inorganic salt solution.
Further, siliceous inorganic salts and inorganic salt containing aluminium are 7.65 to feed intake according to Si/Al mol ratio.
Further, in step (b), preferably adjust the pH value of the suspension that contains precipitation 6～7, more preferably adjust pH value to 7.In this step, can regulate pH value with sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor, amine carbonate solution or nitric acid.
Further, in step (c), described alkaline solution is preferably ammonium carbonate solution, and preferably the molar concentration of alkaline solution is 1molL -1.
Further, in step (d), Organic Alcohol preferred alcohol.
Further, in step (e), roasting time was at 4～6 hours.
Further, sintering temperature is 400 DEG C, and roasting time is 5 hours.
The concrete preferred described SiO of the present invention 2-Al 2o 3the synthetic method of material is carried out in accordance with the following steps:
(a) be 7.65 hybrid reactions by potassium silicate aqueous solution and aluminum nitrate aqueous solution according to Si/Al mol ratio, obtain the suspension that contains precipitation; Wherein in aluminum nitrate aqueous solution, the mass percent of aluminum nitrate is 22～25%; The mass percent of potassium silicate aqueous solution mesosilicic acid potassium is 15～20%;
(b) the pH value of adjusting the suspension that contains precipitation being obtained by step (a), between 6-7, is filtered and is obtained filter cake I;
(c) filter cake step (b) being obtained is at 1mol L -1in ammonium carbonate solution, by pulling an oar, removing by filter impurity, obtain filter cake II;
(d) the filter cake II being made by step (c) is immersed in alcohol solvent, and then recovery solvent obtains filter cake III;
(e) filter cake III is processed and obtains SiO in 400 DEG C of roastings under air atmosphere condition for 5 hours 2-Al 2o 3material.
The SiO being made by the present invention 2-Al 2o 3material, its specific area is 350-400m 2g -1; Aperture is 12-15nm; Compared with the prior art, the present invention has the following advantages:
(1) new method that the present invention reports is conducive to formation to be had compared with the SiO of bigger serface and aperture structure simultaneously 2-Al 2o 3material;
(2) the preparation process environmental friendliness of the present invention's report, is used cheap raw material, and preparation process does not need complex apparatus, is convenient to suitability for industrialized production;
(4) detailed description of the invention
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not subject to the restriction of the following example.
Embodiment (1)
By 23.14 grams of K 2siO 3join 100cm 3in deionized water, also form siliceous A solution by stirring.By 7.36 grams of Al (NO 3) 39H 2o joins 10cm 3in deionized water and by stirring, form the B solution containing aluminium.By A and B solution hybrid reaction 30min.The pH=7 of the suspension that adjusting contains precipitation.Obtain filter cake by filtration, this filter cake working concentration is 1molL -1(NH 4) 2cO 3solution repeatedly washs.To be immersed in ethanol through the filter cake of washing, after filtering, in air atmosphere, within 5 hours, obtain SiO through 400 DEG C of roastings again 2-Al 2o 3material.The specific area of this material and pore volume are to adopt N 2adsorption method is measured.According to Brunauer, the theoretical specific area from adsorption isotherm calculation sample of Emmett and Teller (BET).Through measuring, the specific area of this material is～391m 2g- 1, bore dia is～13.7nm.
Comparative example (1)
By 23.14 grams of K 2siO 3join 100cm 3in deionized water, also form siliceous A solution by stirring.By 7.36 grams of Al (NO 3) 39H 2o joins 10cm 3in deionized water and by stirring, form the B solution containing aluminium.By A and B solution hybrid reaction 30min.Regulate the pH=7 of suspension.Obtain filter cake by filtration, by 200cm 3deionized water joins in filter cake carries out agitator treating 30 minutes, then filters and obtains filter cake.Repeat above washing 10 times.In air atmosphere, within 5 hours, obtain SiO through 400 DEG C of roastings again 2-Al 2o 3material.Pass through N 2the specific area of the material that adsorption method obtains is～282m 2g -1, bore dia is～8.0nm.By relatively can clearly finding with embodiment (1), adopt traditional preparation method cannot obtain bigger serface, wide-aperture SiO 2-Al 2o 3material.
Comparative example (2)
By 23.14 grams of K 2siO 3join 100cm 3in deionized water, also form siliceous A solution by stirring.By 7.36 grams of Al (NO 3) 39H 2o joins 10cm 3in deionized water and by stirring, form the B solution containing aluminium.By A and B solution hybrid reaction 30min.Regulate the pH=7 of suspension.Obtain filter cake by filtration, this filter cake working concentration is 1mol L -1(NH 4) 2cO 3solution repeatedly washs.The filter cake obtaining is obtained to SiO for 5 hours through 400 DEG C of roastings in air atmosphere 2-Al 2o 3material.Through N 2adsorption method is measured, and the specific area of this material is～344m 2g -1, bore dia is～7.0nm.By relatively can clearly finding with embodiment (1), only have by adopting the preparation method who is reported by this patent to obtain and there is high surface area (350-400m simultaneously 2g -1), the SiO of large aperture (12-15nm) characteristic 2-Al 2o 3material.

Claims (9)

1. a SiO 2-Al 2o 3the synthetic method of material, comprises the steps:
(a) be 7～8 hybrid reactions by siliceous inorganic salt solution and the inorganic salt containing aluminium aqueous solution according to Si/Al mol ratio, obtain the suspension that contains precipitation; Described siliceous inorganic salt solution is potassium silicate aqueous solution or the waterglass containing K or Na, and the mass percent concentration of siliceous inorganic salts is 15-25%; The described inorganic salt containing aluminium aqueous solution is aluminum nitrate or aluminum sulfate aqueous solution, and wherein the mass percent concentration of inorganic salt containing aluminium is 10-30%;
(b) regulate the pH value of the suspension that contains precipitation being obtained by step (a) between 5-8, filter and obtain filter cake I;
(c) filter cake step (b) being obtained by pulling an oar, removing by filter impurity, obtains filter cake II in alkaline solution; Described alkaline solution is that molar concentration is at 0.5-1.5molL -1the amine carbonate aqueous solution, ammoniacal liquor or the Ammonium bicarbonate food grade aqueous solution;
(d) the filter cake II being made by step (c) is immersed in organic alcohol solvent, and then recovery solvent obtains filter cake III; Described organic alcohol solvent is selected from following a kind of or several combination arbitrarily: methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, butanediol, propane diols, glycerine, polyethylene glycol;
(e) filter cake III is carried out to calcination process in 300-600 DEG C under air atmosphere condition and obtain SiO 2-Al 2o 3material.
2. SiO as claimed in claim 1 2-Al 2o 3the synthetic method of material, is characterized in that: the described inorganic salt containing aluminium aqueous solution is that mass percent concentration is 22～25% aluminum nitrate aqueous solution; Described siliceous inorganic salt solution is that mass percent concentration is 15～20% potassium silicate aqueous solution.
3. SiO as claimed in claim 1 or 2 2-Al 2o 3the synthetic method of material, is characterized in that: in step (a), siliceous inorganic salt solution and the inorganic salt containing aluminium aqueous solution are 7.65 mixing according to Si/Al mol ratio.
4. SiO as claimed in claim 1 or 2 2-Al 2o 3the synthetic method of material, is characterized in that: in step (b), regulate the pH value of the suspension that contains precipitation 6～7.
5. SiO as claimed in claim 1 or 2 2-Al 2o 3the synthetic method of material, is characterized in that: in step (c), described alkaline solution is 1molL -1ammonium carbonate solution.
6. SiO as claimed in claim 1 or 2 2-Al 2o 3the synthetic method of material, is characterized in that: in step (d), Organic Alcohol is ethanol.
7. SiO as claimed in claim 1 or 2 2-Al 2o 3the synthetic method of material, is characterized in that: in step (e), roasting time was at 4～6 hours.
8. SiO as claimed in claim 7 2-Al 2o 3the synthetic method of material, is characterized in that: sintering temperature is 400 DEG C, and roasting time is 5 hours.
9. SiO as claimed in claim 1 2-Al 2o 3the synthetic method of material, is characterized in that described synthetic method carries out in accordance with the following steps:
(a) be 7.65 hybrid reactions by potassium silicate aqueous solution and aluminum nitrate aqueous solution according to Si/Al mol ratio, obtain the suspension that contains precipitation; Wherein in aluminum nitrate aqueous solution, the mass percent of aluminum nitrate is 22～25%; The mass percent of potassium silicate aqueous solution mesosilicic acid potassium is 15～20%;
(b) the pH value of adjusting the suspension that contains precipitation being obtained by step (a), between 6-7, is filtered and is obtained filter cake I;
(c) filter cake step (b) being obtained is at 1molL -1in ammonium carbonate solution, by pulling an oar, removing by filter impurity, obtain filter cake II;
(d) the filter cake II being made by step (c) is immersed in alcohol solvent, and then recovery solvent obtains filter cake III;
(e) filter cake III is processed and obtains SiO in 400 DEG C of roastings under air atmosphere condition for 5 hours 2-Al 2o 3material.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107185463A (en) * 2017-06-26 2017-09-22 浙江工业大学 A kind of SiO2‑Al2O3The synthetic method of mixed oxide aerogel material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1210755A (en) * 1997-09-10 1999-03-17 中国石油化工总公司 Amorphous silica-alumina and its preparing method
CN1393425A (en) * 2001-06-28 2003-01-29 山西大学 Process for preparing composite SiO2-Al2O2 oxide with high specific surface area
CN101723393A (en) * 2008-10-28 2010-06-09 中国石油化工股份有限公司 Method for preparing silicon-aluminum oxide material with mesopore/macropore combined porous structure
CN101850244A (en) * 2010-06-08 2010-10-06 浙江大学 Preparation method of Al2O3-SiO3 solid acid catalyst in nuclear shell structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1210755A (en) * 1997-09-10 1999-03-17 中国石油化工总公司 Amorphous silica-alumina and its preparing method
CN1393425A (en) * 2001-06-28 2003-01-29 山西大学 Process for preparing composite SiO2-Al2O2 oxide with high specific surface area
CN101723393A (en) * 2008-10-28 2010-06-09 中国石油化工股份有限公司 Method for preparing silicon-aluminum oxide material with mesopore/macropore combined porous structure
CN101850244A (en) * 2010-06-08 2010-10-06 浙江大学 Preparation method of Al2O3-SiO3 solid acid catalyst in nuclear shell structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107185463A (en) * 2017-06-26 2017-09-22 浙江工业大学 A kind of SiO2‑Al2O3The synthetic method of mixed oxide aerogel material
CN107185463B (en) * 2017-06-26 2019-10-18 浙江工业大学 A kind of SiO2-Al2O3The synthetic method of mixed oxide aerogel material

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