CN1103246C - Composite loading nano-titania carrier and its prepn - Google Patents

Composite loading nano-titania carrier and its prepn Download PDF

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CN1103246C
CN1103246C CN 01134330 CN01134330A CN1103246C CN 1103246 C CN1103246 C CN 1103246C CN 01134330 CN01134330 CN 01134330 CN 01134330 A CN01134330 A CN 01134330A CN 1103246 C CN1103246 C CN 1103246C
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tio
hours
nanometer
tio2
supported
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CN1344586A (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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Abstract

The present invention relates to a supported nanometer TiO2 composite supporter and a preparation method thereof. The supported nanometer TiO2 composite supporter is formed by a method that 5 to 20 nanometers of TiO2 is supported on gamma-Al2O3, wherein the weight content of TiO2 is from 10 to 40%. Titanium sol is prepared by a sol-gel method and is dripped in pseudo-boehmite pulped by different solutions, and the mixtures are dried and orderly calcined for 2 hours at 200 DEG C, 300 DEG C, 400 DEG C and 550 DEG C. The nanometer TiO2 is firmly supported on the macroporous Al2O3 to form the new-type nanometer composite supporter, the disadvantages and the defects brought by the nanometer mechanism of TiO2 can be overcome, and simultaneously, the advantages of the nanometer mechanism are displayed. The hydrofining catalytic activity of catalysts can be effectively improved by microscopically designing the supported TiO2 composite supporter, regulating the acidity of surfaces and supporting active constituents on the supported TiO2 composite supporter.

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 catalytic reaction become possibility on the controlled carrier of surface micro-structure.By further load active component on complex carrier,, can improve the hydrofinishing catalytic activity of catalyst effectively as CoMo, NiW etc.
Background technology:
As everyone knows, nano material has very special structure effects such as bulk effect, skin effect, quantum effect and macro quanta tunnel effect.The new function material made from nano material manifests the huge impetus to the future science technology and the development of the national economy gradually.Along with the expansion to every field of nano material and nanometer technology, at chemical industry and petrochemical industry, the nanometer research of a catalyst and using develops rapidly.The development of nano material and nanometer technology makes catalyst develop into inevitable outcome towards nanometer.A large amount of practices show that many catalytic reactions adopt nanocatalyst can obtain to be significantly higher than the effect of conventional catalyst, and its development will be played huge impetus to chemical industry and petroleum chemical industry.
TiO 2Have three kinds of crystal formations: brockite, anatase 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" metal-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 catalyst carrier.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 auto 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 nanostructured in theory, but its active Detitanium-ore-type is because the surface can be high, cause heat endurance relatively poor, and a hole is little, make most of reactant molecules be subjected to interior diffusion-restricted, use as catalyst carrier, its catalytic activity not necessarily is higher than conventional TiO 2Therefore, how both to have overcome TiO 2The shortcoming and defect that nanometer is brought, 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 (conversion ratio and selectivity) of catalytic reaction.Therefore, the nanoparticle particle size that control generates in preparation process is very crucial technology.
Nano-TiO 2Generally can inorganic salts (Ti (SO 4) 2, TiCl 4) be raw material, prepare by liquid phase method, but the TiO of this method preparation 2Impurity 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 catalytic 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 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 distinct methods 2The size of crystal grain.
Concrete preparation method of the present invention comprises the following steps:
1. boehmite is mixed making beating with water or absolute ethyl alcohol.2. prepare titanium colloidal sol, concrete grammar is as follows: butyl titanate is mixed with nitric acid with ethanol, water, and mol ratio is a butyl titanate: absolute ethyl 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 boehmite slurries, makes nano-TiO through heat treatment again 2Complex carrier.Heat treatment mode: sample was positioned in the air air dry 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 is brought, 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 hydrofinishing catalytic activity of catalyst 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%).
The specific 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 3Load 5～10nm (1nm=10 -9M) content is the TiO of 10wt% 2)
The preparation method:
With the boehmite 2 hours (consumptions of water: (boehmite water absorption rate (ml/g)+0.5) of in suitable quantity of water, pulling an oar *The consumption of boehmite (g)).
By butyl titanate: absolute ethyl alcohol: water: nitric acid is 1: 9: 3: 0.3 (mol ratio) preparation titanium glue.
Under strong agitation, by load TiO 2The ratio of 10wt% splashes into an amount of titanium glue in the slurries that boehmite and water pulls an oar, and is positioned in the air air dry 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 2Average grain diameter 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 2Load capacity be the ratio of 20wt% prepare titanium glue and splash into boehmite and the slurries of water making beating in, be positioned in the air air dry 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, average grain diameter 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 boehmite 2 hours (consumptions of absolute ethyl alcohol: (boehmite is inhaled ethanol rate (ml/g)+0.5) of dipping in an amount of absolute ethyl alcohol *The amount of boehmite (g)).
By butyl titanate: absolute ethyl alcohol: water: nitric acid is 1: 9: 3: 0.3 (mol ratio) preparation titanium glue.
Under strong agitation, by load TiO 2The ratio of 10wt% splashes into an amount of titanium glue in the slurries of boehmite and absolute ethyl alcohol making beating.Be positioned in the air air dry 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 2Average grain diameter 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 2Load capacity be the ratio of 20wt% prepare titanium glue and splash into boehmite and the slurries of absolute ethyl alcohol making beating in, be positioned in the air air dry 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, average grain diameter 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 2Load capacity be the ratio of 30wt% prepare titanium glue and splash into boehmite and the slurries of absolute ethyl alcohol making beating in, be positioned in the air air dry 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, average grain diameter 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 2Load capacity be the ratio of 40wt% prepare titanium glue and splash into boehmite and the slurries of absolute ethyl alcohol making beating in, be positioned in the air air dry 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, average grain diameter is 17.4nm.By tem observation, TiO 2Particle diameter is between 15～20nm.
The prepared complex carrier of embodiment 7 usefulness embodiment 2 flooded cobalt nitrate 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 3Catalyst (8wt%).Institute's controlling catalyst and industrial Hydrobon catalyst T205 (1.52wt%CoO, 8.83wt%MoO 3) the hydrodesulfurization 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
Reaction temperature (K) 473 498 523 543 563 583
Thiophene conversion ratio 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) boehmite is mixed making beating with water or absolute ethyl alcohol;
(2) butyl titanate and ethanol, water and nitric acid are mixed with out colloidal sol, mol ratio is a butyl 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 boehmite to titanium colloidal sol
In the slurries;
(4) be positioned in the air air dry 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 (1)

* Cited by examiner, † Cited by third party
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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

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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
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
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
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

Cited By (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

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