CN103130270A

CN103130270A - Preparation method of titanium dioxide nanometer powder

Info

Publication number: CN103130270A
Application number: CN2011103942330A
Authority: CN
Inventors: 吕英英; 余乐书
Original assignee: Shangrao Normal University
Current assignee: Shangrao Normal University
Priority date: 2011-11-22
Filing date: 2011-11-22
Publication date: 2013-06-05

Abstract

The invention relates to a method of using titanium powder as precursor to prepare titanium dioxide nanometer powder in a scale mode. The method comprises the steps of feeding a certain ration of metal titanium powder and a certain volume (5-10mol/L ) concentrated alkaline into a high pressure kettle provided with a Teflon liner; the metal titanium powder and the concentrated alkaline reacting for 10-20 hours in a backing oven at 190-220 DEG C; recycling alkaline liquid remaining in the high pressure kettle after natural cooling; washing a product with distilled water until the product is neutral; soaking filtered matters in 0.1-0.5 mol/L diluted hydrochloric acid for 10-20 hours; filtering and obtaining titanium acid sediments; and obtaining titanium dioxide power materials after calcining at 400-500 DEG C. No extra impurity can be introduced into the whole preparation process so that pure titanium dioxide (TiO2) nanometer powder materials can be prepared through the method. The method has the advantages of being simple, convenient, economic, environment-friendly, capable of preparing in a large scale, and the like.

Description

A kind of preparation method of nano TiO 2 powder

Technical field

The present invention relates to a kind of preparation method of nano TiO 2 powder, but especially a kind of method of pure titinium dioxide nano-powder for preparing take titanium valve as the precursor mass-producing.

Background technology

Since reported first titanium dioxide electrodes in 1972 at (Nature 1972,238,37.) since water of decomposition effectively under ultraviolet radiation, nano level TiO ₂, high light catalytic activity nontoxic with it and good chemical stability form the object into the broad research of people.Correspondingly, people have also attempted the whole bag of tricks and have prepared TiO ₂Nano material is in order to explore its potential application (Chem.Rev.2007,107,2891.) aspect photocatalysis field.Yet, at the preparation TiO that reports at present ₂In the method for nano material, all obviously there are a lot of weak points, comprise that the product preparation cost is high, serious and industrial scale is little to equipment corrosion and be difficult to industrialization etc.For example, some organometallicss that contain titanium elements are selected as precursor and synthesize TiO ₂Nano material, but these precursors obviously will be held high more expensive than titanium valve on price, and be difficult for the transportation storage.These unfavorable factors can cause sharp increase (J.Alloys Compd.2009,488,314 of synthetic product cost undoubtedly; Mater.Lett.2010,64,2036; Angew Chem.Int.Ed.2008,47,4516.).In addition, titanium base muriate also usually is used as the titanium source and makes titanium dioxide nano material (Appl.Sur.Sci.2009,255,9548 by hydrolysis; CrystEngComm 2010,12, and 1759; Nature, 2008,453,638; Mater.Lett.2009,63,1797.).Unique commercial Degussa P25 (a kind of titanium oxide that mixes crystal formation) passes through at O at present ₂/ H ₂Burning titanium base muriate in gas mixture makes.But the muriatic use of these titanium bases inevitably produces acid mist, and this will not only pollute surrounding environment, and the meeting etching apparatus, finally can cause the increase of product cost.Therefore to prepare titanium dioxide nano material for low-cost, large-scale and environmental protection ground be not titanium source in ideal to above titanium base precursor.

Metallic titanium powder is a kind of cheapness, safety, unique raw material that contains titanium elements, take the price of the nano TiO 2 powder for preparing as the titanium source will greatly reduce but purity can improve greatly.Yet in oxygenated environment, the refractory metal titanium is the passivation very torpescence that becomes very easily, makes (Adv.Funct.Mater.2006,16,1355 oxide in trace quantities since titanium nano wire, nano-tube array except having at the titanium elements by oxidized surface on the titanium sheet at present; ACS Nano, 2008,2,1113.), so that rarely have about prepare the report of nano titanium oxide powder with metallic titanium powder.In the recent period the people such as Kwon dense subtract solution in H ₂O ₂Titanium oxide powder has prepared the titanium dioxide nanowire array powder, but the introducing of hydrogen peroxide also will increase the cost (Bull.Korean Chem.Soc.2004,25,1341.) of preparation product.The people such as nearest Chen use titanium valve and ammonium chloride to prepare nano TiO 2 powder (Mater.Lett.2009,63,1797.) in unlimited system heating.Yet the hydrochloric acid that decomposition produces and ammonia be etching apparatus not only, and has polluted environment.Here, we are take titanium valve as the titanium source, and water is oxygenant, react in 190-220 ℃ dense subtracts solution, then pass through ion-exchange and calcining, have finally obtained a large amount of nano TiO 2 powder materials, and the utilization ratio of titanium elements is more than 95%.Due in this experimentation be take titanium valve as the titanium source, water is as oxygenant, productive rate is high especially, operation steps is simple, so the cost of preparation nano titanium oxide powder greatly reduce, and suitable large-scale production nano titanium oxide powder.

Summary of the invention

The object of the invention: a kind of extensive method for preparing the pure titinium dioxide nano-powder that easy economy is provided.

Technical scheme of the present invention is: the concentrated base of a certain amount of metallic titanium powder and a certain amount of volume (5-10mol/L) is added in the teflon-lined autoclave, reaction is 10-20 hour in the baking oven of 190-220 ℃, after naturally cooling, with remaining recycle of alkali liquor utilization in autoclave, extremely neutral with the distilled water wash products, then filtrate was immersed in dilute hydrochloric acid (0.1-0.5mol/L) middle 10-20 hour, filtration obtains the metatitanic acid settling, the titanium oxide powder material that makes at 400-500 ℃ of temperature lower calcination.

Description of drawings

Fig. 1 is the X-ray diffraction picture of each product of obtaining in preparation process of the present invention.Test operation is as follows: 2.000 gram titanium valves and 70.0 milliliters of NaOH solution (10mol/L) add in the polytetrafluoroethylliner liner of 100.0 milliliters, the outer casing stainless steel autoclave.Whole reaction system constant temperature 10 hours in the baking oven of 220 ℃, naturally cooling takes out inner bag, and washed product obtains the sodium titanate that 4.130 grams contain crystal water; Sodium titanate is immersed in dilute hydrochloric acid solution (1mol/L) makes 3.437 gram metatitanic acids through ion-exchange, calcining 3 hours in retort furnace under 400-500 ℃ at last can get titanium oxide product 3.160 grams, productive rate 95%.As shown in Figure 1, what product obtained 400 ℃ of calcinings is anatase octahedrite, and 450 ℃ of lower calcinates are anatase octahedrite and rutile being close to the mixed phase of 1: 1 ratio, and are pure rutile at the product of 500 ℃ of calcinings.This invert point with the pure zirconia titanium of expection matches, and illustrates that also the product that present method prepares is the pure zirconia titanium.

Fig. 2 is the thermogram of metatitanic acid, shows that metatitanic acid is decomposed into titanium oxide at 300-400 ℃, is constantly transformed to rutile by anatase octahedrite at 400-500 ℃ of titanium oxide.

Fig. 3 is field emission scanning electron microscope (SEM) and the ultimate analysis of calcinate under differing temps, show that the product pattern is nano wire bundle, nanometer sheet bundle, the length of wire harness and sheet bundle is at several to dozens of microns, and thickness only has about ten nanometers, and product only contains Ti, O element.

Fig. 4 is the x-ray photoelectron power spectrum of product, shows that product only contains Ti, O element, and Ti: O was near 1: 2.

Embodiment

Embodiment 1

Take 2.000 gram titanium valves and 70.0 milliliters of NaOH solution (10mol/L), add in the polytetrafluoroethylliner liner of 100.0 milliliters the outer casing stainless steel autoclave.Whole reaction system in the baking oven of 190-220 ℃ constant temperature 10-20 hour, naturally cooling takes out inner bag, and washed product obtains the sodium titanate that 4.130 grams contain crystal water; Sodium titanate is immersed in dilute hydrochloric acid solution (1mol/L) makes 3.437 gram metatitanic acids through ion-exchange, calcining 3 hours in retort furnace under 400 ℃ at last can get anatase titanium oxide product 3.160 grams, productive rate 95%.

Embodiment 2

Step is substantially with embodiment 1, but the calcining temperature of last metatitanic acid is 450 ℃, and can get product is the mixed phase titanium oxide of anatase octahedrite and rutile.

Embodiment 3

Step is substantially with embodiment 1, but the calcining temperature of last metatitanic acid is 500 ℃, can get the titanium oxide that product is pure rutile.

Claims

1. the preparation method of a nano TiO 2 powder, it is characterized in that the concentrated base of a certain amount of metallic titanium powder and a certain amount of volume (5-10mol/L) is added in the teflon-lined autoclave, reaction is 10-20 hour in the baking oven of 190-220 ℃, after naturally cooling, with remaining recycle of alkali liquor utilization in autoclave, extremely neutral with the distilled water wash products, then filtrate was immersed in dilute hydrochloric acid (0.1-0.5mol/L) middle 10-20 hour, filtration obtains the metatitanic acid settling, makes TiO at 400-500 ℃ of temperature lower calcination ₂Nano-powder material.