CN100562361C - A kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier - Google Patents

A kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier Download PDF

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CN100562361C
CN100562361C CNB2008100600912A CN200810060091A CN100562361C CN 100562361 C CN100562361 C CN 100562361C CN B2008100600912 A CNB2008100600912 A CN B2008100600912A CN 200810060091 A CN200810060091 A CN 200810060091A CN 100562361 C CN100562361 C CN 100562361C
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tio
complex carrier
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ticl
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CN101234358A (en
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蒋晓原
林辉
李惠娟
郑小明
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Zhejiang University ZJU
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Abstract

A kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier, TiO in the chemical composition of complex carrier 2Mass percent be 15%, with titanium tetrachloride (TiCl 4) and aluminum nitrate (Al (NO 3) 39H 2O) presoma is raw material, adopts the co-precipitation legal system standby.The gained precipitation is behind 110 ℃ of dry 24h of baking oven and 500 ℃ of roasting 2h of muffle furnace, and the acquisition specific area is 292.6m 2The TiO of/g 2/ γ-Al 2O 3Complex carrier.Technology of the present invention is simple, and is easy to operate, and component is even, and its specific area is than the big 50-100m of common aluminum titanium composite oxide 2/ g can be used as the carrier of catalyst, also is specially adapted to the carrier that plasma-catalyzing cooperation takes off the NO catalyst.

Description

A kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier
Technical field
The invention provides a kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier, its specific area (292.6m 2/ g) than single TiO 2And γ-Al 2O 3And aluminum titanium composite oxide is much larger, Heat stability is good, can be used as the carrier of catalyst, also is specially adapted to the carrier that plasma-catalyzing cooperation takes off the NO catalyst.
Background technology
Nitrogen oxide (NO x) be one of major pollutants that cause atmosphere pollution.NO xDischarging brought serious harm to global environment.Tradition improvement method has the methods such as liquid absorption method, active carbon adsorption, catalytic oxidation, but all exists a lot of not enough.Explore with research and find, with TiO 2For the catalyst of carrier has active high, the advantages such as selectively good, anti-Poisoning is strong, low temperature active good, surface acidity is adjustable, high temperature reducibility.But also have the specific area less, acid amount is lower, for high pressure and the disadvantageous shortcoming of macromolecular reaction; And γ-Al 2O 3Carrier then can overcome these deficiencies well.Therefore, TiO 2/ γ-Al 2O 3Single TiO has been gathered in the development of complex carrier 2And γ-Al 2O 3The advantage of carrier, and overcome shortcoming each other, so, more and more receive researcher's concern.Vargas, A.; Montoya, J, A.; Maldonado, C.et al.Micropor.Mater, 2004,74 (1): 9., adopt sol-gel process to prepare TiO 2/ γ-Al 2O 3Composite oxides are found TiO 2/ γ-Al 2O 3Have good heat endurance, after 900 ℃ of roastings of high temperature, its structure and composition is constant.Guti é rrez-Alejandre, A.; Gonz á lez-Cruz, M.; Trombetta, M.et al.Micropor.and Mesopor.Mater., 1998,23 (5-6): 265, adopt sol-gal process and coprecipitation to prepare TiO 2/ γ-Al 2O 3Complex carrier, and, find prepared titanium aluminium complex carrier behind 500 ℃ of roasting 24h by characterization methods such as XRD, UV, FTIR, BET and Raman, its specific area is at 180m 2About/g; Also find TiO simultaneously 2Though load on γ-Al 2O 3On, but can not detect Ti 4+Exist, show Ti 4+May enter γ-Al 2O 3Octahedral interstices, form Al 2TiO 5Orthohormbic structure.Macleod, N., Cropley, R., Keel, J.et al.J.Catal., 2004,221 (1): 29, the Pd/TiO that adopted the technical research such as original position XRD, XPS, HREM and DRIFS 2/ Al 2O 3To H 2/ CO/NO/O 2Reaction, find when 150 ℃ of reaction temperatures, can to make NO under the excess oxygen xConversion ratio reaches 100%, and points out TiO 2And Al 2O 3Between the complex surface reaction that takes place promoted NO xRemove.Huang, H.Y.; Long, R.Q.; Yang, R.T.Appl.Catal.B:Environ., 2001,33:127 is with Pd-Rh/TiO 2/ Al 2O 3For catalyst has been studied NO by oxygen deprivation-oxygen enrichment circulating system xConversion.This catalyst is at 100ppmSO 2, 2.3%H 2O, T=250 ℃, GHSV=30,000h -1The time, behind the reaction 5h, NO xRemoval efficiency be 90%.This has illustrated Pd-Rh/TiO 2/ Al 2O 3Catalyst is removing NO xHas good sulfur resistance in the process.Neuman, S.D.R.; Eon, J.G.; Schmal, M.J.Catal., 1999,183:6-13 is with the Pt/18%TiO of immersion process for preparing 2/ Al 2O 3Catalyst, behind 500 ℃ of roasting 4h, its specific area is 147m 2/ g., prepared the TiO of different loads amount with gas phase adsorption method 2/ Al 2O 3Carrier, behind 600 ℃ of roasting 8h, the specific area of its carrier is at 95-137m 2Between/the g.Y.; Wei, Z.B.; Feng, Z.C.et al.J.Catal., 2004,202:200-204 adopts butyl titanate modification γ-Al 2O 3, having prepared titanium aluminium complex carrier, behind 500 ℃ of roasting 4h, its specific area is 118m 2/ g.Liu X; Liu Y; Li XH, et al.ChineseJournal of Catalysis, 2004,22 (4): 319-320, adopt four butyl ester metatitanic acids to γ-Al 2O 3Carry out modification, carry out alcoholysis in ethanolic solution, through stirring and drying, behind 500 ℃ of roasting 4h, recording its specific area is 210m 2/ g, and with this carrier loaded CuO, be used for catalyzing and synthesizing cyclopropane, find that productive rate is up to 93.5%.I.M.Low Materials Research Bulletin, 1998,33 (10): 1475-1482, three kinds of methods such as employing sol-gel, mechanical mixture and co-precipitation have prepared aluminum titanium composite oxide respectively and have examined or check their sintering character, discover sample behind 1100 ℃ of roasting 10min, the aluminum titanium composite oxide that detects the sol-gel process preparation through XRD has generated single Al at 1100 ℃ 2TiO 5The composite oxides phase; And the aluminum titanium composite oxide of mechanical mixture and coprecipitation preparation has generated α-Al 2O 3, rutile mutually and Al 2TiO 5The composite oxides coexisting phase; And point out sample after 1300 ℃ of roastings, the aluminum titanium composite oxide of three kinds of method preparations all is converted into Al fully 2TiO 5Composite oxides.Huang, Y.X.; Senos, A.M.R.Materials Research Bulletin 2002,37:99-111, adopt alkoxide hydrolysis and coprecipitation, and add 2.5wt.%MgO, prepared aluminum titanium composite oxide, by the sign of TEM, TG-DTA, XRD and IR, studied TiO 2And Al 2O 3Pyroreaction, find that both begin pyroreaction about 1220 ℃, generate Al simultaneously 2TiO 5Composite oxides.Liu, S.Q.; Tao, W.H.; Li.J.et al.Powder Technology 2005,155:187-192 has studied Al 2TiO 5Synthetic reaction, the result shows that XRD has detected α-Al in the time of 1150 ℃ 2O 3With rutile mutually, faint Al is arranged simultaneously 2TiO 5Diffraction maximum occurs, and this explanation in above-mentioned reaction temperature Al has taken place 2TiO 5Synthetic reaction.
Chinese patent 200610050304.4 discloses a kind of preparation method of aluminum titanium composite oxide with high specific surface, and its chemical composition is TiO 2/ Al 2O 3, described component TiO 2Mass percent be 15%, take titanium tetrachloride and aluminum nitrate as raw material, with the coprecipitation preparation, having obtained specific area is 265.7m 2The aluminum titanium composite oxide of/g.But because the reaction condition of the preparation of employing coprecipitation and selection is not best, the complex carrier component that makes is not enough consistent, and is not enough even, and the carrier specific area of acquisition is also not enough big.
Summary of the invention
The present invention seeks to provides a kind of TiO on Chinese patent 200610050304.4 bases 2/ γ-Al 2O 3The system of complex carrier
Preparation Method obtains to have higher specific area TiO 2/ γ-Al 2O 3Complex carrier.
The invention provides TiO 2/ γ-Al 2O 3The preparation method of complex carrier, described TiO 2/ γ-Al 2O 3Complex carrier consists of TiO 2And γ-Al 2O 3, component TiO 2Mass percent be 15%, be with titanium tetrachloride (TiCl 4) and the presoma (Al (NO of aluminum nitrate 3) 39H 2O) be raw material, adopt the co-precipitation legal system standby.Preparation process is:
A) with pure TiCl 4Solution dropwise is added drop-wise in the hydrochloric acid solution of pH＜1, stirs 1h in ice-water bath, is mixed with the TiCl of 0.35mol/L 4Solution (A);
B) with Al (NO 3) 39H 2The O crystal adds in the distilled water of respective volume, and it is fully dissolved, and is mixed with the Al (NO of 2.08mol/L 3) 3Solution (B);
C) by described component TiO 2Mass percent is the corresponding titanium tetrachloride TiCl of 15% calculating 4With the aluminum nitrate quality, after with solution (A) and (B) evenly mixing, obtain containing the mixed solution (C) of Ti and Al;
D) adopt the co-precipitation method, in 40 ℃ water bath with thermostatic control, under magnetic agitation, drip (NH 4) 2CO 3Solution and the mixed solution that contains Ti and Al (C) of preparing, the rate of addition of mixed solution (C) is 60～80/min, (NH 4) 2CO 3Rate of addition be that 40～60/min is that 1: 1 ammoniacal liquor is regulated sedimentary acid-base value to pH=9 with volume ratio at last, solution (C) is formed homogeneous precipitation;
E) with white precipitation of hydroxide ageing under room temperature in its mother liquor of gained, suction filtration washs to there not being Cl with deionized water -, put into the baking oven inner drying, 500 ℃ of roasting temperatures 2 hours, the acquisition specific area was 292.6m 2The TiO of/g 2/ γ-Al 2O 3Complex carrier.
Ageing is 24 hours under the room temperature of the present invention, uses 0.1mol/L AgNO 3Solution detects no Cl -1There are 110 ℃ of dry 24h.
The present invention passes through TiCl 4Splash in pH＜1 hydrochloric acid solution and to suppress its hydrolysis, adopt the co-precipitation method to make TiCl 4And Al (NO 3) 3Solution fully mixes, and the complex carrier component that makes is consistent, and the complex carrier component is even, with single TiO 2And Al 2O 3Compare and have bigger specific area.Work as TiO 2Load capacity be 15% o'clock, its specific area is 292.6m behind 500 ℃ of roasting 2h 2/ g, its total pore volume are 0.554mL/g, and average pore size is 14.41nm.
TiO in described carrier 2Mass fraction be 15% o'clock, have largest specific surface area, best catalytic performance, oxidation-reduction quality and good low temperature active, can be used as and remove NO xThe carrier of catalyst.Also be specially adapted to plasma-catalyzing cooperation and take off the carrier of NO catalyst.
Technical process of the present invention is simple, but each step all needs to control through strictness.The new Ti O that makes 2/ γ-Al 2O 3Complex carrier is through N 2Suction-desorption experiment, find that suctions-desorption isotherm type belongs to the VI class in the BDDT classification, because the precipitating reagent of employing is (NH 4) 2CO 3, the presoma of the complex carrier of generation can produce a large amount of CO when roasting 2Gas has reaming, the effect of supported hole structure, by experiment, this carrier behind 1000 ℃ of lower roasting 2h its specific area still up to 51.6m 2/ g.So it is big that the complex carrier that adopts this preparation method to synthesize has the aperture, and advantage such as easy-sintering not.
The specific embodiment
Embodiment 1
(1) TiO 2/ γ-Al 2O 3Complex carrier is with titanium tetrachloride (TiCl 4) and the presoma (Al (NO of aluminum nitrate 3) 39H 2O) be raw material, by described component TiO 2And Al 2O 3Mass percent be TiO 2: Al 2O 3Calculate corresponding titanium tetrachloride (TiCl at=3: 17 4) and Al (NO 3) 39H 2The quality of O is dissolved in water.
(2) compound concentration is the TiCl of 0.35mol/L 4Solution (A): a certain amount of hydrochloric acid is added in an amount of water, and stirring makes and mixes, and makes pH＜1 of solution.Under ice-water bath and strong agitation with pure TiCl 4Be added drop-wise in this hydrochloric acid solution, after stirring, solution placed ice-water bath, and constantly stir 1h, be mixed with the TiCl of 0.35mol/L 4Solution (A).
(3) take by weighing the Al (NO of amount of calculation 3) 39H 2The O crystal adds deionized water and stirring and makes its dissolving evenly, is mixed with the Al (NO of 2.08mol/L 3) 3Solution (B).After solution temperature is upgraded to room temperature, TiCl 4Solution is slowly poured Al (NO into 3) 3In the solution (B), obtain TiCl 4And Al (NO 3) 3Mixed solution (C).
(4) take by weighing (NH of amount of calculation 4) 2CO 3Solid adds a certain amount of deionized water dissolving, is mixed with (the NH of 2.95mol/L 4) 2CO 3Solution.
(5) in 40 ℃ water bath with thermostatic control, under the condition of magnetic agitation with (NH 4) 2CO 3Drip together in the beaker rate of addition (NH in solution and the mixed solution that contains Ti and Al (C) prepared 4) 2CO 3Solution is 40～60d/min, and mixed salt solution is 60～80d/min.Dripping rear is that 1: 1 ammoniacal liquor is regulated sedimentary acid-base value to pH=9 with volume ratio; Gained is deposited in the 24h that wears out in its mother liquor under room temperature.Suction filtration, deionized water is washed to there not being Cl -(use AgNO till the existence 3The no Cl of solution check -Exist), 110 ℃ of dry 24h change muffle furnace over to then, and 500 ℃ of roasting 2h naturally cool to room temperature, namely get new Ti O 2/ γ-Al 2O 3Complex carrier.
Embodiment 2:
● take by weighing Al (NO 3) 39H 2O 63.17g adds the 100mL deionized water in the 500mL beaker, stir to make fully dissolving, and being mixed with concentration is 2.08mol/L Al (NO 3) 3The aqueous solution.
● in another clean beaker, add deionized water 20mL, add the 5mL concentrated hydrochloric acid, stir evenly; Under ice-water bath and strong agitation with pure TiCl 4Be added drop-wise in this hydrochloric acid solution, after stirring, in beaker, add the 30ml deionized water again, solution is placed ice-water bath, and constantly stir 1h, be mixed with the TiCl of 0.35mol/L 4Solution.
● treat Al (NO 3) 3After solution temperature is upgraded to room temperature, TiCl 4Solution is slowly poured Al (NO into 3) 3In the solution (B), obtain TiCl 4And Al (NO 3) 3Mixed solution.
● take by weighing (NH 4) 2CO 3Solid 28.34g adds the deionized water dissolving of 100ml, is mixed with (the NH of 2.95mol/L 4) 2CO 3Solution.
● 40 ℃ water bath with thermostatic control, under the magnetic agitation condition with (NH 4) 2CO 3Drip together in the beaker rate of addition (NH in solution and the mixed solution that contains Ti and Al (C) prepared 4) 2CO 3Solution is 40～60d/min, and mixed salt solution is 60～80d/min.Treat that it is that 1: 1 ammoniacal liquor is regulated sedimentary acid-base value to pH=9 with volume ratio that solution all drips the back; Gained is deposited in the 24h that wears out in its mother liquor under room temperature.Suction filtration, deionized water is washed to there not being Cl -(use AgNO till the existence 3The no Cl of solution check -Exist), 110 ℃ of dry 24h change muffle furnace over to then, and 500 ℃ of roasting 2h naturally cool to room temperature, namely get new Ti O 2/ γ-Al 2O 3Complex carrier.
Embodiment 3
Impact sees Table 1 to different preparation methods to the product specific surface
The preparation method Specific area
The co-precipitation method 292.6m 2/ g
Along addition 242.7m 2/ g
Contrary addition 206.5m 2/ g
The TiO that the co-precipitation method is prepared 2/ γ-Al 2O 3The specific area maximum of complex carrier.
Embodiment 4
Influence sees Table 2 to pH value during titration end-point to the product specific surface
The pH value Specific area
7 199.8m 2/ g
9 292.6m 2/ g
10 234.7m 2/ g
PH value when changing titration end-point, the pH value as with titration end-point the time is transferred to 7 and 10, but the specific area of gained carrier is respectively 199.8m 2/ g, 234.7m 2/ g, the specific area of gained carrier during equally less than titration end-point pH=9.
Embodiment 5
Influence sees Table 3 to reaction temperature to the product specific surface
Reaction temperature Specific area
0 ℃ 224.1m 2/ g
25 ℃ 279.6m 2/ g
40 ℃ 292.6m 2/ g
60 ℃ 281.0m 2/ g
80 ℃ 249.5m 2/ g
Carrier prepared under 40 ℃ the condition has the highest specific area.
Embodiment 6
Impact sees Table 3 to different precipitating reagents to the product specific surface
Precipitating reagent Specific area
Ammoniacal liquor (1: 1) 288.6m 2/ g
NH 4HCO 3 224.8m 2/ g
(NH 4) 2CO 3With pure concentrated ammonia liquor 260.0m 2/ g
(NH 4) 2CO 3 292.6m 2/ g
With (NH 4) 2CO 3The specific area of the carrier that solution is prepared is the highest.

Claims (2)

1, a kind of TiO 2/ γ-Al 2O 3The preparation method of complex carrier is characterized in that: TiO in the chemical composition of described complex carrier 2Mass percent be 15%, take the presoma of titanium tetrachloride and aluminum nitrate as raw material, adopt the co-precipitation method, preparation process is:
● with pure TiCl 4Dropwise be added drop-wise in the hydrochloric acid solution of pH＜1, after stirring, hydrolysis 1h in ice-water bath is mixed with the TiCl of 0.35mol/L 4Solution (A);
● with Al (NO 3) 39H 2The O crystal adds in the distilled water of respective volume, and it is fully dissolved, and is mixed with the Al (NO of 2.08mol/L 3) 3Solution (B);
● by described component TiO 2Mass percent is the corresponding titanium tetrachloride TiCl of 15% calculating 4With the aluminum nitrate quality, after with solution (A) and (B) evenly mixing, obtain containing the mixed solution (C) of Ti and Al;
● adopt the co-precipitation method, in 40 ℃ water bath with thermostatic control, under magnetic agitation, drip (NH 4) 2CO 3Solution and the mixed solution that contains Ti and Al (C) of preparing, the rate of addition of mixed solution (C) is 60～80/min, (NH 4) 2CO 3Rate of addition be 40～60/min; Be that 1: 1 ammoniacal liquor is regulated sedimentary acid-base value to pH=9 with volume ratio at last, solution (C) is formed homogeneous precipitation;
● with white precipitation of hydroxide ageing under room temperature in its mother liquor of gained, suction filtration washs to there not being Cl with deionized water -, put into the baking oven inner drying, 500 ℃ of roasting temperatures 2 hours, the acquisition specific area was 292.6m 2The TiO of/g 2/ γ-Al 2O 3Complex carrier.
2, TiO according to claim 1 2/ γ-Al 2O 3The preparation method of complex carrier is characterized in that resulting white depositions ageing 24h at room temperature, and suction filtration spends deionised water then, to cleaning solution 0.1mol/L AgNO 3Solution detects no Cl -1There are 110 ℃ of dry 24h.
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CN101869852B (en) * 2009-04-24 2014-10-01 中国石油化工股份有限公司 Titanium modified carrier and preparation method thereof
CN103100379B (en) * 2011-11-14 2015-04-15 中国石油化工股份有限公司 Production method of titanium oxide-alumina composite
CN108767221A (en) * 2018-05-24 2018-11-06 北方奥钛纳米技术有限公司 modified anode material of lithium battery, preparation method and lithium ion battery
CN113979471B (en) * 2021-12-02 2023-06-23 西安元创化工科技股份有限公司 Synthetic method of rutile type titanium dioxide nano-composite

Non-Patent Citations (2)

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Title
Al2O3-TiO2二元氧化物地制备条件对酸性的影响. 朱建飞等.无机化学学报，第15卷第4期. 1999
Al2O3-TiO2二元氧化物地制备条件对酸性的影响. 朱建飞等.无机化学学报，第15卷第4期. 1999 *

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