CN100503040C - Method for preparing tetragonal phase mesoporous sulphuric acid zirconia solid superacid - Google Patents
Method for preparing tetragonal phase mesoporous sulphuric acid zirconia solid superacid Download PDFInfo
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- CN100503040C CN100503040C CNB2007100381037A CN200710038103A CN100503040C CN 100503040 C CN100503040 C CN 100503040C CN B2007100381037 A CNB2007100381037 A CN B2007100381037A CN 200710038103 A CN200710038103 A CN 200710038103A CN 100503040 C CN100503040 C CN 100503040C
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Abstract
The invention relates to a preparing method for tetragonal mesoporous sulfated zirconia solid super-acid, belonging to the solid acid preparing technology field. The method makes use of sol-gel technology, adopts block nonionic surfactant Pl23 as template agent and Zr(OC3H7)4 as zirconium source. There is no need of alkali catalyst and under the room temperature the air with saturated vapor is poured in to carry hydrolysis reaction out to obtain solid gel. After the template agent is eliminated by ethanol extraction and it is treated by sulfuric acid acidation, the tetragonal mesoporous sulfated zirconia solid super-acid with high specific surface and shallow pore diameter distribution is obtained by baking under 740-760deg.C. It has a wide applicable prospect in many acid catalytic reactions.
Description
Technical field
The invention belongs to the solid acid preparing technical field, be specifically related to a kind of preparation method of tetragonal phase region sulphuric acid zirconia solid superacid.
Background technology
Mesoporous silicon based material has high specific area, narrow pore-size distribution and good heat endurance, but owing to lack active sites, its application in catalytic field is restricted.Transition metal oxide occupies an important position aspect Industrial Catalysis, but because the specific surface of block materials is low, active sites is few, usually need load, the preparation of metal oxide and composite oxides mesoporous material can greatly improve specific surface, as tungsten oxide (Small, 2006,2,1203), iron oxide (Angew.Chem.Int.Ed.2004,43,5958), (Science 1997,276 for manganese oxide, 926), tantalum oxide (Chem.Mater.2001,13,1194), vanadium oxide (Catal.Lett.2004,94,217), the preparation of zirconia (CN Patent:1067393,1992) etc. has caused extensive concern.
Zirconia (CN Patent:1524794,2004; CN Patent:1524795,2004; CN Patent:1267568,2003) have acid and basic surface activated centre, good ion-exchange performance.Mesoporous zircite also has special fluorescent emission phenomenon, the two photoluminescent bands of purple light and blue light at room temperature can occur.Therefore zirconia is being with a wide range of applications aspect catalytic field, the multifunctional material.Zirconium dioxide has three kinds of crystalline state: monocline phase, four directions mutually with cube mutually.Cubic phase sulfated zirconia through oversulfated processing is a kind of super acids, can be used as the catalyst of hydrocarbon conversion reactions such as cracking, isomerization, alkylation.Usually can produce more micropore in the preparation of tradition sulfated zirconia, microcellular structure caves in easily and forms the macroporous structure of being piled into by intracrystalline pore when high-temperature roasting, and pore-size distribution is generally very wide.In order to obtain big molecule is had the super acidic catalyst of shape selective catalysis function, people once attempted preparing mesoporous sulfated zirconia with several different methods, as adopted charged template agent softex kw n-C
16H
33(CH
3)
3NBr, sodium cetanesulfonate n-C
16H
33SO
3Na etc., but remove in the process of template agent in roasting or extraction, the hole of material can subside for stablizing the pore structure of mesoporous zirconia material, phosphoric acid is handled and is made it be stabilized in (Angew.Chem.Int.Ed.1996 below 500 ℃, 35,541), but the nitrogen adsorption curve show and to have many microcellular structures; Make template agent (J.Mater.Chem.1996 with softex kw, 6,89), the mesoporous zircite pore-size distribution that obtains very wide (half-peak breadth is greater than 2.0nm), and do the synthesising mesoporous zirconia of template agent with nonionic surface active agent, such as chain alkyl amine, remove the template agent by the mode of ethanol extraction, can obtain the zirconia (Catal.Lett.1996 of stratiform (lamellarphase), 38,219), Sachtler once obtains mesoporous cubic phase sulfated zirconia with octadecylamine (US Patent:5 786 294,1998; Appl.Catal.A:Gen.1996,148,135), specific surface is not very big, and the aperture can not modulation.
Summary of the invention
The object of the present invention is to provide a kind of new method that the soda acid agent prepares the Large ratio surface tetragonal phase region sulphuric acid zirconia solid superacid that need not of simple and easy to control, economical rationality.
The preparation method of the mutually mesoporous sulfated zirconia in four directions that the present invention proposes, concrete steps are: P123 is dissolved into the anhydrous C of 10-30g with the agent of 1-2g template
2H
5Among the OH, the room temperature lower magnetic force stirs 2-4h; Put into the logical high purity nitrogen 1-2h of glove box, make and be in water-less environment in the case, normal propyl alcohol solution (content of zirconium-n-propylate the is 74.4wt%) 4.4-8.8g that adds zirconium-n-propylate, room temperature magnetic agitation 6-12h, feed the air 4-24h that contains saturated steam simultaneously, make the zirconium-n-propylate complete hydrolysis become solid gel; With the solid gel that obtains after hydrolysis apparatus,Soxhlet's ethanol extraction 18-36h, remove the template agent, after drying, room temperature gets solid; With every gram powder 10-15mL0.5M H
2SO
4Solution at room temperature magnetic agitation handle 3-6h, 740-760 ℃ of roasting obtains the mesoporous sulfated zirconia of cubic phase under air atmosphere then, its specific surface can reach 120m
2/ g.
The present invention utilizes the synthesising mesoporous sulfated zirconia of sol-gel technique, with blocked non-ionic surface active agent P123 (vinyl ethylene glycol-acrylic ethylene glycol-vinyl ethylene glycol block copolymer) is the template agent, zirconium-n-propylate is the zirconium source, ethanol is solvent, utilize steam control hydrolysis rate, no acid base catalysator.Synthetic product is through nitrogen absorption, XRD, and signs such as transmission electron microscope illustrate that the sulfated zirconia that obtains is cubic phase meso-hole structure, and pore-size distribution is narrower.
When changing synthesis condition, along with the prolongation of hydrolysis time, pore-size distribution narrows down, and illustrates that hydrolysis rate has very big influence (Fig. 1, Fig. 2) to the aperture of product; Increase the time that sulfuric acid acidation is handled, it is big that the particle of end product becomes; Template agent consumption more for a long time, the sample specific surface that obtains is bigger; Sintering temperature is very big to the influence of sample crystalline phase, during roasting at a lower temperature, can only obtain the monocline phase, along with the phase of monocline four directions mixed crystal appears in the rising of temperature, when reaching suitable temperature (740-760 ℃, the best is 750 ℃), product is cubic phase (Fig. 3) substantially, and when sintering temperature surpassed this temperature, the four directions was mutually destroyed, the TEM of Fig. 4 and HRTEM photo explanation products therefrom contains abundant mesoporous, these mesoporous its specific areas that increased; The influence on sintering temperature contrast surface is also very big, and the specific surface of sample is 326m before roasting
2/ g, specific surface is 156m after 650 ℃ of roastings
2/ g, specific surface has only 121m after 750 ℃ of roastings
2/ g, sintering temperature high-ratio surface more are more little; Same acids handle and roasting condition under the also difference to some extent of specific surface of the sample that synthesizes of different hydrolysis times.
Through 0.5M H
2SO
4After handling 6h and 750 ℃ of roastings, the resulting sample specific surface of 4h complete hydrolysis is 78m
2/ g, 12h complete hydrolysis gained sample specific surface is 107m
2/ g, the sample specific surface of 24h complete hydrolysis is 120m
2/ g, hydrolysis rate help the increase of narrowing of sample pore-size distribution and specific surface slowly.
Therefore, utilize sol-gel process, can synthesising mesoporous zirconia under the situation of no acid base catalysator, also can be applied to the system that gelation reaction can take place for other.
The advantage that the present invention synthesizes is: by the control hydrolysis rate, can obtain the big and narrow mesoporous sulfated zirconia of pore-size distribution of specific area.Product can be used as catalyst, catalyst carrier and luminescent material etc. and is applied to a plurality of fields.
The inventive method is compared with conventional method, and is simple and easy to control, do not need to add acid base catalysator, the preparation efficiency height, and product quality and yield rate can both be guaranteed.
Description of drawings
Fig. 1 is the influence of hydrolysis rate to nitrogen adsorption/desorption curve, and wherein the used time of (a) complete hydrolysis is 12h, and (b) the used time of complete hydrolysis is 24h.
Fig. 2 is the pore-size distribution of Fig. 1 counter sample, reaches the influence of hydrolysis rate to pore-size distribution, and (a) the used time of complete hydrolysis is 12h, and (b) the used time of complete hydrolysis is 24h.
The influence that Fig. 3 generates the four directions mutually for sintering temperature.Wherein, T----four directions phase, M----monocline phase.
Fig. 4 is the TEM photo of mesoporous sulfuric acid zirconium dioxide.
The specific embodiment
Embodiment 1:
4g P123 is dissolved into the anhydrous C of 20g
2H
5Among the OH, the room temperature lower magnetic force stirs 4h, put into the logical high purity nitrogen 2h of glove box, make and be in anhydrous environment in the case, normal propyl alcohol solution (content of zirconium-n-propylate the is 74.4wt%) 8.7g that adds zirconium-n-propylate, room temperature magnetic agitation 12h, feed the air that contains saturated steam then in the solution system under magnetic agitation, by the adjustments of gas flow, make zirconium-n-propylate all-hydrolytic in different time become solid gel, hydrolysis rate is narrower favourable to pore-size distribution slowly, and when the used time of hydrolysis was 24h, the pore-size distribution that obtains sample was best.
Embodiment 2:
2g P123 is dissolved into the anhydrous C of 10g
2H
5Among the OH, the room temperature lower magnetic force stirs 4h, put into the logical high purity nitrogen 2h of glove box, make and be in anhydrous environment in the case, normal propyl alcohol solution (content of zirconium-n-propylate the is 74.4wt%) 4.4g that adds zirconium-n-propylate, room temperature magnetic agitation 12h feeds the air that contains saturated steam then in the solution system under magnetic agitation, making the zirconium-n-propylate complete hydrolysis become the used time of solid gel is 12h; With the apparatus,Soxhlet's ethanol extraction 36h of the solid gel after the hydrolysis, room temperature is dried and is promptly got unformed mesoporous zircite; Should unformed mesoporous zircite 0.5MH
2SO
4With 15mL/g magnetic agitation processing at room temperature 3h, under air atmosphere, when 750 ℃ of roastings, obtain being substantially the sulfated zirconia of cubic phase.
Embodiment 3:
1-2g P123 is dissolved into the anhydrous C of 10g
2H
5Among the OH, the room temperature lower magnetic force stirs 4h, put into the logical high purity nitrogen 2h of glove box, make and be in anhydrous environment in the case, normal propyl alcohol solution (content of zirconium-n-propylate the is 74.4wt%) 5.6g that adds zirconium-n-propylate, room temperature magnetic agitation 12h feeds the air that contains saturated steam then in the solution system under magnetic agitation, making the zirconium-n-propylate complete hydrolysis become the used time of solid gel is 12h; With the apparatus,Soxhlet's ethanol extraction 36h of the solid gel after the hydrolysis, the many more specific surfaces of amount adding of template agent are big more.
Embodiment 4:
1gP123 is dissolved into the anhydrous C of 5g
2H
5Among the OH, the room temperature lower magnetic force stirs 4h, put into the logical high purity nitrogen 2h of glove box, make and be in anhydrous environment in the case, normal propyl alcohol solution (content of zirconium-n-propylate the is 74.4wt%) 4.8g that adds zirconium-n-propylate, room temperature magnetic agitation 12h feeds the air vapor that contains saturated steam then in the solution system under magnetic agitation, making the zirconium-n-propylate complete hydrolysis become the used time of solid gel is 12h; With the apparatus,Soxhlet's ethanol extraction 36h of the solid gel after the hydrolysis, room temperature is dried and is promptly got unformed mesoporous zircite; Should unformed mesoporous zircite 0.5M H
2SO
4With 15mL/g at room temperature magnetic agitation handle 3h, 760 ℃ of roastings under air atmosphere then, what obtain is the sulfated zirconia of cubic phase substantially.
Claims (1)
1, a kind of preparation method of tetragonal phase region sulphuric acid zirconia solid superacid is characterized in that concrete steps are: 1-2g template agent vinyl ethylene glycol-acrylic ethylene glycol-vinyl ethylene glycol block copolymer is dissolved into the anhydrous C of 10-30g
2H
5Among the OH, the room temperature lower magnetic force stirs 2-4h; Put into glove box, logical high purity nitrogen 1-2h, make and be in water-less environment in the case, add the normal propyl alcohol solution 4.4-8.8g that contains the 10-20mmol zirconium-n-propylate, the content of zirconium-n-propylate is 74.4wt%, room temperature magnetic agitation 6-12h feeds the air 4-24h that contains saturated steam simultaneously, makes the zirconium-n-propylate complete hydrolysis become solid gel; With the solid gel that obtains after hydrolysis apparatus,Soxhlet's ethanol extraction 18-36h, remove the template agent, after drying, room temperature gets solid; Add 10-15mL0.5MH with every gram pressed powder
2SO
4The ratio of solution, at room temperature magnetic agitation is handled 3-24h, and 740-760 ℃ of roasting obtains tetragonal phase region sulphuric acid zirconia solid superacid under air atmosphere then.
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| CN101530788B (en) * | 2009-04-03 | 2011-06-01 | 中国科学院上海硅酸盐研究所 | Multilevel porous structure solid super acidic catalyst and preparation method thereof |
| CN104817109B (en) * | 2015-05-11 | 2016-04-13 | 太原理工大学 | Based on the zirconic preparation method of rich sulfur vulcanization of Tetragonal |
| CN112295557A (en) * | 2020-11-27 | 2021-02-02 | 安庆医药高等专科学校 | Nano compound for acid catalytic reaction and preparation method thereof |
| CN114602513A (en) * | 2022-03-29 | 2022-06-10 | 江南大学 | Mesoporous solid acid catalyst for esterification reaction and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| Alumina-promoted mesoporous sulfated zirconia: A catalystfor n-butane isomerization. Jung-Hui Wang, Chung-Yuan Mou.Applied Catalysis A: General,Vol.286 . 2005 |
| Alumina-promoted mesoporous sulfated zirconia: A catalystfor n-butane isomerization. Jung-Hui Wang, Chung-Yuan Mou.Applied Catalysis A: General,Vol.286. 2005 * |
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