CN1344586A - Composite loading nano-titania carrier and its prepn - Google Patents

Composite loading nano-titania carrier and its prepn Download PDF

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CN1344586A
CN1344586A CN 01134330 CN01134330A CN1344586A CN 1344586 A CN1344586 A CN 1344586A CN 01134330 CN01134330 CN 01134330 CN 01134330 A CN01134330 A CN 01134330A CN 1344586 A CN1344586 A CN 1344586A
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tio
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nanometer
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CN1103246C (en
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李伟
胡见波
张明慧
陶克毅
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Nankai University
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Nankai University
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Abstract

A loading type of nanometer titania composite carrier is constituted by loading 5-20 nm TiO2 in 10-40 wt% onto gamma-Al2O3. Titania sol is first prepared through sol-gel process and then dropped into pseudo-then diaspore pulp of different solution; and the product is finally processed through drying, calcination successively at 200, 300, 400 and 500 deg.c for 2 hr each. The present invention loads nanometer Tio2 onto macroporous Al2O3 to form the composite nanometer carrier. This can utilize the superority of nanometer TiO2 while overcoming the demerits. By means of the micro design, surface acidity regulation of loaded TiO2 and loading active component, the hydrorefining activity of catalyst may be raised effectively.

Description

Composite loading nano-titania carrier and preparation method thereof
Technical field
The invention belongs to the preparation method of composite loading nano-titania carrier.At γ-Al 2O 3The controlled nano-TiO of last load grain size 2Thereby, can be to supported titanium 2Complex carrier carries out microcosmic design, surface acidity modulation, makes to carry out catalyzed reaction become possibility on the controlled carrier of surface micro-structure.By further load active component on complex carrier,, can improve the hydrofining catalytic activity of catalyzer effectively as CoMo, NiW etc.
Background technology:
As everyone knows, nano material has very special structure effects such as volume effect, surface effects, quantum effect and macro quanta tunnel effect.The new function material made from nano material manifests the huge pushing effect to the future science technology and the development of the national economy gradually.Along with the expansion to every field of nano material and nanotechnology, at chemical industry and petrochemical industry, the nanometer of catalyzer research and using develops rapidly.The development of nano material and nanotechnology makes catalyzer develop into inevitable outcome towards nanometer.A large amount of practices show that many catalyzed reactions adopt nanocatalyst can obtain to be significantly higher than the effect of conventional catalyst, and its development will be played huge pushing effect to chemical industry and petroleum chemical industry.
TiO 2Have three kinds of crystal formations: brookite, anatase octahedrite and rutile, wherein rutile-type is the most stable.TiO 2Be widely used in pigment, coating, fiber, medicine and other fields.Detitanium-ore-type TiO 2" the metal one carrier strong interaction (SMSI) ", the Ti that are had + 4Characteristics such as high-temperature reductibility, solid acid alkalescence is adjustable, make it also have purposes widely as support of the catalyst.But because TiO 2Specific surface is less, shaping carrier bad mechanical strength when using separately, and is therefore industrial separately as support applications difficulty, limited its potentiality to be exploited.
Nano-TiO 2Come out in the later stage eighties, functions such as its unique colour effect, photocatalysis and ultraviolet screener make it promptly gain great popularity once emerging, and at aspects such as automotive industry, sun care preparations, wastewater treatment, sterilization, environmental protection wide application prospect are arranged.With TiO 2Though nanometer can be given full play to the advantage of its nanostructure in theory, but its active Detitanium-ore-type is because the surface energy height, cause thermostability relatively poor, and a hole is little, make most of reactant molecules be subjected to the internal diffusion restriction, use as support of the catalyst, its catalytic activity not necessarily is higher than conventional TiO 2Therefore, how both to have overcome TiO 2The shortcoming and defect that nanometer brings, the advantage of bringing into play its nanometer simultaneously again is a key problem in technology.For this reason, with nano-TiO 2Load on other macropore carrier in firm mode, forming a kind of composite Nano novel carriers might unite the two.In addition, the particle of different nano-scales, behind its load active component to the impact effect difference (transformation efficiency and selectivity) of catalyzed reaction.Therefore, the nanoparticle size of particles that control generates in preparation process is very crucial technology.
Nano-TiO 2Generally can inorganic salt (Ti (SO 4) 2, TiCl 4) be raw material, prepare by liquid phase method, but the TiO of this method preparation 2Foreign matter content is many, influences activity of such catalysts.
Summary of the invention
The purpose of this invention is to provide a kind of composite loading nano-titania carrier and preparation method thereof, at γ-Al 2O 3The controlled nano-TiO of last load grain size 2Thereby, can be to supported titanium 2Complex carrier carries out microcosmic design, surface acidity modulation, makes on the controlled carrier of surface micro-structure and carries out catalyzed reaction.
The present invention is at γ-Al 2O 3The TiO of last load 5-20 nanometer 2, TiO 2Weight content 10～40%.
The present invention adopts butyl (tetra) titanate to be raw material, to prepare nano-TiO by sol-gel processing 2, and load on Al 2O 3Last preparation complex carrier is controlled TiO by different methods 2The size of crystal grain.
Concrete preparation method of the present invention comprises the following steps:
1. pseudo-boehmite is mixed making beating with water or dehydrated alcohol.2. prepare titanium colloidal sol, concrete grammar is as follows: butyl (tetra) titanate is mixed with nitric acid with ethanol, water, and mol ratio is a butyl (tetra) titanate: dehydrated alcohol: water: nitric acid=1: 9: 3: 0.3, prepare colloidal sol.3. under agitation, by load TiO 210～40% ratio adds titanium colloidal sol in the above-mentioned made pseudo-boehmite slurries, makes nano-TiO through thermal treatment again 2Complex carrier.Heat treatment mode: sample was positioned in the air seasoning 24 hours, 60 ℃ dry 12 hours down, 120 ℃ of dryings 4 hours were calcined under 200,300,400,550 ℃ 2 hours more successively.
With nano-TiO 2Load on macropore Al in firm mode 2O 3On, form a kind of composite Nano novel carriers, not only can overcome TiO 2The shortcoming and defect that nanometer brings, the while is brought into play the advantage of its nanometer again.By to supported titanium 2Complex carrier carries out microcosmic design, surface acidity modulation, and load active component thereon again can improve the hydrofining catalytic activity of catalyzer effectively.
Description of drawings Fig. 1, content are the nano-TiO of 20wt% 2Complex carrier XRD spectra (other content identical) with it, a:TiO 2Crystal grain is between 5～10nm; B:TiO 2Crystal grain is between 15～20nm.; Fig. 2,5～10nm nano-TiO 2Complex carrier transmission electron microscope photo (TiO 2Content is 20wt%); Fig. 3,15～20nm nano-TiO 2Complex carrier transmission electron microscope photo (TiO 2Content is 20wt%).
Embodiment
The present invention can be illustrated more clearly in from following embodiment, but it is not the restriction that the present invention is made.
Embodiment 1 (γ-Al 2O 2Load 5～10nm (1nm=10 -9M) content is the TiO of 10wt% 2)
The preparation method:
With the pseudo-boehmite 2 hours (consumptions of water: (pseudo-boehmite water-intake rate (ml/g)+0.5) of in suitable quantity of water, pulling an oar *The consumption of pseudo-boehmite (g)).
By butyl (tetra) titanate: dehydrated alcohol: water: nitric acid is 1: 9: 3: 0.3 (mol ratio) preparation titanium glue.
Under violent stirring, by load TiO 2The ratio of 10wt% splashes into an amount of titanium glue in the slurries that pseudo-boehmite and water pulls an oar, and is positioned in the air seasoning then 24 hours, 60 ℃ of dryings 12 hours, and 120 ℃ of dryings 4 hours were calcined under 200,300,400,550 ℃ 2 hours more successively.
Can find supported titanium by XRD spectra 2Be Detitanium-ore-type.Calculate TiO by XRD diffraction broadening method 2Median size be 9nm.By tem observation, TiO 2Particle diameter is between 5～10nm.
Embodiment 2 (γ-Al 2O 3Load 5～10nm content is 20wt%TiO 2)
The preparation method presses TiO with embodiment 1 2Charge capacity be the ratio of 20wt% prepare titanium glue and splash into pseudo-boehmite and the slurries of water making beating in, be positioned in the air seasoning then 24 hours, 60 ℃ of dryings 12 hours, 120 ℃ of dryings 4 hours were calcined under 200,300,400,550 ℃ 2 hours more successively.
By XRD experiment (the results are shown in Figure 1a), supported titanium 2Be Detitanium-ore-type, median size is 7.9nm.By tem observation (the results are shown in Figure 2), TiO 2Particle diameter is between 5～10nm.
Embodiment 3 (γ-Al 2O 3Load 15～20nm content is 10wt%TiO 2)
The preparation method:
With pseudo-boehmite 2 hours (consumptions of dehydrated alcohol: (pseudo-boehmite is inhaled ethanol rate (ml/g)+0.5) of dipping in an amount of dehydrated alcohol *The amount of pseudo-boehmite (g)).
By butyl (tetra) titanate: dehydrated alcohol: water: nitric acid is 1: 9: 3: 0.3 (mol ratio) preparation titanium glue.
Under violent stirring, by load TiO 2The ratio of 10wt% splashes into an amount of titanium glue in the slurries of pseudo-boehmite and dehydrated alcohol making beating.Be positioned in the air seasoning then 24 hours, 60 ℃ of dryings 12 hours, 120 ℃ of dryings 4 hours.Under 200,300,400,550 ℃, calcined successively 2 hours again.
Can find supported titanium by XRD spectra 2Be Detitanium-ore-type.Calculate TiO by XRD diffraction broadening method 2Median size be 18.8nm.By tem observation, TiO 2Particle diameter is between 15～20nm.
Embodiment 4 (γ-Al 2O 3Load 15～20nm content is 20wt%TiO 2)
The preparation method presses TiO with embodiment 3 2Charge capacity be the ratio of 20wt% prepare titanium glue and splash into pseudo-boehmite and the slurries of dehydrated alcohol making beating in, be positioned in the air seasoning then 24 hours, 60 ℃ of dryings 12 hours, 120 ℃ of dryings 4 hours were calcined under 200,300,400,550 ℃ 2 hours more successively.
By XRD experiment (the results are shown in Figure 1b), supported titanium 2Be Detitanium-ore-type, median size is 17.5nm.By tem observation (the results are shown in Figure 3), TiO 2Particle diameter is between 15～20nm.
Embodiment 5 (γ-Al 2O 3Load 15～20nm content is 30wt%TiO 2)
The preparation method presses TiO with embodiment 3 2Charge capacity be the ratio of 30wt% prepare titanium glue and splash into pseudo-boehmite and the slurries of dehydrated alcohol making beating in, be positioned in the air seasoning then 24 hours, 60 ℃ of dryings 12 hours, 120 ℃ of dryings 4 hours were calcined under 200,300,400,550 ℃ 2 hours more successively.
By XRD experiment, supported titanium 2Be Detitanium-ore-type, median size is 16.3nm.By tem observation, TiO 2Particle diameter is between 15～20nm.
Embodiment 6 (γ-Al 2O 3Load 15～20nm content is 40wt%TiO 2)
The preparation method presses TiO with embodiment 3 2Charge capacity be the ratio of 40wt% prepare titanium glue and splash into pseudo-boehmite and the slurries of dehydrated alcohol making beating in, be positioned in the air seasoning then 24 hours, 60 ℃ of dryings 12 hours, 120 ℃ of dryings 4 hours were calcined under 200,300,400,550 ℃ 2 hours more successively.
By XRD experiment, supported titanium 2Be Detitanium-ore-type, median size is 17.4nm.By tem observation, TiO 2Particle diameter is between 15～20nm.
The prepared complex carrier of embodiment 7 usefulness embodiment 2 flooded Xiao Suangu and ammonium molybdate 2 hours simultaneously by equi-volume impregnating, filters, and 120 ℃ of oven dry 4 hours, load C oO (2wt%), MoO are prepared in 450 ℃ of calcinings 2 hours 3Catalyzer (8wt%).Institute's controlling catalyst and industrial Hydrobon catalyst T205 (1.52wt%CoO, 8.83wt%MoO 3) the hydrogenating desulfurization catalytic activity of thiophene is contrasted, embodiment is significantly higher than the activity of Comparative Examples to the hydrodesulfurization activity of thiophene.The results are shown in Table 1: table 1 temperature of reaction (K) 473 498 523 543 563 583 thiophene transformation efficiency embodiment 20.28 37.30 61.20 75.25 93.72 100 (%) Comparative Examples 15.48 28.31 52.91 65.47 79.61 95.59

Claims (3)

1, a kind of composite loading nano-titania carrier is characterized in that it is at γ-Al 2O 3The TiO of last load 5-20 nanometer 2Constitute, wherein TiO 2Weight content be 10～40%.
2, the said composite loading nano-titania carrier preparation method of claim 1 is characterized in that it comprises the following steps:
(1) pseudo-boehmite is mixed making beating with water or dehydrated alcohol;
(2) butyl (tetra) titanate and ethanol, water and nitric acid are mixed with out colloidal sol, mol ratio is a butyl (tetra) titanate: anhydrous second
Alcohol: water: nitric acid=1: 9: 3: 0.3;
(3) under agitation, by load TiO 210～40% ratio adds above-mentioned made pseudo-boehmite to titanium colloidal sol
In the slurries;
(4) be positioned in the air seasoning 24 hours, 60 ℃ dry 12 hours down, 120 ℃ of dryings 4 hours are calcined successively under 200,300,400,550 ℃ and were got final product in 2 hours.
3, the application of the said composite loading nano-titania carrier of claim 1 is characterized in that being applied to the hydrogenation catalyst reaction behind its load active component.
CN 01134330 2001-10-31 2001-10-31 Composite loading nano-titania carrier and its prepn Expired - Fee Related CN1103246C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244381B (en) * 2008-03-07 2010-06-09 东南大学 Process for producing TiO2-Al2O3composite nano-powder body material
CN101791578A (en) * 2010-03-23 2010-08-04 华东理工大学 Ordered double porosity Al203-TiO2 and preparation method thereof and application thereof
CN103301824A (en) * 2013-04-28 2013-09-18 西安紫云环保科技集团有限公司 Carrier with attached nano titanium dioxide and preparation method thereof
CN103360939A (en) * 2012-03-31 2013-10-23 江南大学 Preparation method of supported nano-doped photocuring water-based antifogging self-cleaning paint
CN103566942A (en) * 2012-08-06 2014-02-12 中国石油化工股份有限公司 Selective hydrogenation catalyst
CN108047739A (en) * 2017-12-28 2018-05-18 林雀萍 The preparation method of nano metal composite particle wood plastic composite
CN108165038A (en) * 2017-12-28 2018-06-15 林雀萍 The preparation method of high-intensity wood plastic composite

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100444952C (en) * 2006-04-30 2008-12-24 天津南开戈德集团有限公司 Supported nanometer crystalline titania photocatalyst and its prepn process

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244381B (en) * 2008-03-07 2010-06-09 东南大学 Process for producing TiO2-Al2O3composite nano-powder body material
CN101791578A (en) * 2010-03-23 2010-08-04 华东理工大学 Ordered double porosity Al203-TiO2 and preparation method thereof and application thereof
CN103360939A (en) * 2012-03-31 2013-10-23 江南大学 Preparation method of supported nano-doped photocuring water-based antifogging self-cleaning paint
CN103360939B (en) * 2012-03-31 2015-09-30 江南大学 A kind of preparation method of loaded nano doping photocuring water-based antifogging self-cleaning coating
CN103566942A (en) * 2012-08-06 2014-02-12 中国石油化工股份有限公司 Selective hydrogenation catalyst
CN103566942B (en) * 2012-08-06 2016-03-30 中国石油化工股份有限公司 A kind of selective hydrogenation catalyst
CN103301824A (en) * 2013-04-28 2013-09-18 西安紫云环保科技集团有限公司 Carrier with attached nano titanium dioxide and preparation method thereof
CN103301824B (en) * 2013-04-28 2015-03-04 西安紫云环保科技集团有限公司 Carrier with attached nano titanium dioxide and preparation method thereof
CN108047739A (en) * 2017-12-28 2018-05-18 林雀萍 The preparation method of nano metal composite particle wood plastic composite
CN108165038A (en) * 2017-12-28 2018-06-15 林雀萍 The preparation method of high-intensity wood plastic composite

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