CN100335416C - Method for preparing rutile type nanometer Ti02 in low temperature using carboxylic acid as finishing agent - Google Patents
Method for preparing rutile type nanometer Ti02 in low temperature using carboxylic acid as finishing agent Download PDFInfo
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- CN100335416C CN100335416C CNB200510038935XA CN200510038935A CN100335416C CN 100335416 C CN100335416 C CN 100335416C CN B200510038935X A CNB200510038935X A CN B200510038935XA CN 200510038935 A CN200510038935 A CN 200510038935A CN 100335416 C CN100335416 C CN 100335416C
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Abstract
The present invention relates to a method for preparing nano rutile type TiO2, particularly to a method for preparing nano rutile type TiO2 by a hydrothermal synthesis method adopting titanium tetrachloride as raw materials and adding carboxylic acid. The present invention is characterized in that a titanium tetrachloride solution is added to dilute hydrochloric acid to be diluted, and an alkaline aqueous solution is added to the dilute solution by dripping until the pH value reaches more than 7; an organic modifier containing hydroxy groups and carboxyl groups are added to the dilute solution and simultaneously stirred after the addition of the alkaline aqueous solution; the organic modifier is one of glycerol, succinic acid, formic acid, tartaric acid, gallic acid monohydrate, lauric acid and benzoic acid; the mixed solution is aged at a temperature of 40 to 80 DEG C for 0.5 to 3 hours; precipitates are washed with distilled water until the electric conductivity of the filtered solution is smaller than 20 ms/m; nitric acid or hydrochloric acid and distilled water are added to the filtered solution to enable the pH value of the filtered solution to reach below 0.7; the filtered solution is aged at room temperature for 1 to 3 hours; a suspension after ageing is put in a polytetrafluoroethylene-lined stainless hydrolyzation vessel to react at a temperature of 120 to 220 DEG C for 10 to 18 hours to obtain nano rutile type titanium dioxide. The nano rutile type titanium dioxide prepared by the method has small particle diameter of 15 nm to 70 nm. The method has the advantages of mild reaction condition, easy reaction control, low cost and convenient process and process flow.
Description
Technical field
The present invention relates to a kind of method for preparing rutile type nano titanic oxide, refer in particular to the carboxylic acid and prepare rutile type nano TiO for modifier low temperature
2Method
Background technology
Nano titanium oxide is widely used in various fields, for example environmental purification, opto-electronic conversion, anti-atomizing, clean surfaces, pigment, makeup and photochemical catalysis etc.The method that many synthesis of nano titanium dioxide are arranged, for example titanium tetrachloride flame oxidation method, anti-glue crystallization process, supercritical CO
2Crystallization process, light assisting sol-gel method, polymer template method, hydrothermal synthesis method.These methods use pure titanium salt, titanium tetrachloride and titanium sulfate etc. as initial reactant usually.The physicochemical property of the nano titanium oxide that different building-up processes is prepared are also different.The shortcoming of these methods is need calcine down at high temperature (1173K-1273K) to obtain nano titanium oxide, consumes a large amount of energy, the aggravation environmental pollution, and the titanium dioxide granule that makes is thick, and size distribution is inhomogeneous.
Summary of the invention
The objective of the invention is to propose a kind of be raw material with the titanium tetrachloride, be the method that modifier, hydrothermal synthesis method prepare rutile type nano titanic oxide by adding the carboxylic acid organism, to overcome above-mentioned drawback.
Its preparation method is as follows:
Titanium tetrachloride solution joined in the dilute hydrochloric acid dilute, dropwise add alkaline aqueous solution then, up to the pH value more than 7, add after the alkali lye, stir on one side, the organism modifier that adds on one side hydroxyl, carboxyl, modifier are a kind of in glycerine, Succinic Acid, formic acid, tartrate, gallic acid, lauric acid, the phenylformic acid, at 40-80 ℃ of aging 0.5-3h; Be precipitated to the specific conductivity of filtrate less than 20mS/m with distilled water wash; Filter cake after handling as stated above is divided into three parts, gets a copy of it and add nitric acid or hydrochloric acid and distilled water, make that pH is below 0.7; At room temperature aging 1-3 hour then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 120-220 ℃ of reaction 10-18h, obtain rutile type nano titanic oxide.
With the rutile type nano titanic oxide of this method preparation, grain diameter is little, and the grain diameter size is between 15nm～70nm.Present method has that reaction conditions gentleness, reaction are easy to control, cost is low, the advantage of technology and simple flow.
Description of drawings
Fig. 1: glycerine is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Fig. 2: Succinic Acid is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Fig. 3: formic acid is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Fig. 4: tartrate is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Fig. 5: gallic acid is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Fig. 6: lauric acid is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Fig. 7: phenylformic acid is the atomic force micrograph of the rutile type nano titanic oxide product of coating materials
Embodiment
The present invention will be further described below in conjunction with concrete embodiment.
Example 1
As scheme A1, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/L and dilute, dropwise add the Na of 2.1M/L then
2CO
3The aqueous solution equals 7 up to pH.Add after the alkali lye, stir on one side, add 2.3g glycerine on one side.At 40 ℃ of aging 0.5h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 18mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds nitric acid (60%) and distilled water up to cumulative volume 200ml, and pH is 0.7.At room temperature aging 1 hour then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 120 ℃ of reaction 10h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 20-55 nanometer, median size 36 nanometers.
Example 2
As scheme A2, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/l and dilute, dropwise add the NaOH aqueous solution of 1.5M/L then, equal 9 up to pH.Add after the alkali lye, stir on one side, add the 4.425g Succinic Acid on one side.At 60 ℃ of aging 1.5h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 17mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds hydrochloric acid (36%) and distilled water up to cumulative volume 200ml, and pH is 0.5.At room temperature aging 3 hours then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 200 ℃ of reaction 12h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 35-65 nanometer, median size 49 nanometers.
Example 3
As scheme A3, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/l and dilute, dropwise add the NH of 2.0M/L then
3The OH aqueous solution equals 10 up to pH.Add after the alkali lye, stir on one side, add 3.45g formic acid on one side.At 60 ℃ of aging 2h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 15mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds nitric acid (60%) and distilled water up to cumulative volume 200ml, and pH is 0.4.At room temperature aging 2 hours then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 210 ℃ of reaction 13h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 25-55 nanometer, median size 35 nanometers.
Example 4
As scheme A4, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/l and dilute, dropwise add the Na of 2.1M/L then
2CO
3The aqueous solution equals 12 up to pH.Add after the alkali lye, stir on one side, add 2.81g tartrate on one side.At 80 ℃ of aging 2h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 19mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds nitric acid (60%) and distilled water up to cumulative volume 200ml, and pH is 0.2.At room temperature aging 1 hour then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 150 ℃ of reaction 15h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 35-60 nanometer, median size 46 nanometers.
Example 5
As scheme A5, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/l and dilute, dropwise add the Na of 2.1M/L then
2CO
3The aqueous solution equals 13 up to pH.Add after the alkali lye, stir on one side, add the 3.19g gallic acid on one side.At 60 ℃ of aging 2.5h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 16mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds nitric acid (60%) and distilled water up to cumulative volume 200ml, and pH is 0.1.At room temperature aging 3 hours then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 220 ℃ of reaction 16h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 10-40 nanometer, median size 20 nanometers.
Example 6
As scheme A6, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/l and dilute, dropwise add the Na of 2.1M/L then
2CO
3The aqueous solution equals 10 up to pH.Add after the alkali lye, stir on one side, add the 15g lauric acid on one side.At 60 ℃ of aging 3h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 18mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds hydrochloric acid (36%) and distilled water up to cumulative volume 200ml, and pH is 0.6.At room temperature aging 3 hours then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 130 ℃ of reaction 17h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 20-45 nanometer, median size 31 nanometers.
Example 7
As scheme A7, and measure the 68ml titanium tetrachloride solution, join in the dilute hydrochloric acid that 204ml concentration is 0.5mol/l and dilute, dropwise add the Na of 2.1M/L then
2CO
3The aqueous solution equals 10 up to pH.Add after the alkali lye, stir on one side, add the 9.15g phenylformic acid on one side.At 80 ℃ of aging 1h.The specific conductivity that is precipitated to filtrate with distilled water wash is that the filter cake after 17mS/m. will handle as stated above is divided into three parts, gets a copy of it and adds nitric acid (60%) and distilled water up to cumulative volume 200ml, and pH is 0.1.At room temperature aging 3 hours then.Suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 160 ℃ of reaction 18h., obtain rutile type nano titanic oxide.Product is through the atomic force microscope analysis, and particle diameter is in the 15-40 nanometer, median size 26 nanometers.
Claims (1)
1. one kind prepares rutile type nano TiO with the carboxylic acid for modifier low temperature
2Method, it is characterized in that: titanium tetrachloride solution is joined in the dilute hydrochloric acid dilute, dropwise add alkaline aqueous solution then, up to the pH value more than 7, add after the alkali lye, stir on one side, add modifier on one side, described modifier is a kind of in Succinic Acid, formic acid, tartrate, gallic acid, lauric acid, the phenylformic acid, at 40-80 ℃ of aging 0.5-3h; Be precipitated to the specific conductivity of filtrate less than 20mS/m with distilled water wash; Add nitric acid or hydrochloric acid and distilled water, make pH value of solution below 0.7, at room temperature aging 1-3 hour then, the suspension after aging is put into the stainless steel hydrolysis still of teflon lined, behind 120-220 ℃ of reaction 10-18h, obtain rutile type nano titanic oxide.
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| CN100537433C (en) * | 2006-04-30 | 2009-09-09 | 中国科学院合肥物质科学研究院 | Preparation method of red schorl type titanium oxide nano powder |
| CN101148538B (en) * | 2006-09-23 | 2010-08-11 | 宁波荣山新型材料有限公司 | Method for preparing nano titanium dioxide modified polyurethane material and products thereof |
| CN101456583B (en) * | 2007-12-12 | 2011-05-25 | 中国科学院理化技术研究所 | Synthetic method for preparing rutile type nano titanic oxide sol or powder at low temperature |
| CN101823766B (en) * | 2010-05-17 | 2012-01-18 | 山东理工大学 | Preparation method of hafnium oxide powder with nano-porous structure |
| JP5170342B2 (en) * | 2010-08-17 | 2013-03-27 | 堺化学工業株式会社 | Method for producing dispersion of rutile titanium oxide particles |
| CN102383180B (en) * | 2011-10-24 | 2013-11-27 | 中山大学 | Synthesizing method for titanium dioxide single-crystal rutile nanowire array film |
| CN106315670A (en) * | 2015-11-10 | 2017-01-11 | 河南大学 | Dispersible wedge nano titanium dioxide, and preparation method and application thereof |
| CN106345396A (en) * | 2016-11-07 | 2017-01-25 | 苏州寰泰环境工程技术有限公司 | Preparation method of nano TiO2 adsorbent for purifying oily substance in water |
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| WO1999036362A1 (en) * | 1998-01-13 | 1999-07-22 | Metallgesellschaft Aktiengesellschaft | METHOD FOR PRODUCING TiO2 ACCORDING TO THE SULFATE METHOD |
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| WO1999036362A1 (en) * | 1998-01-13 | 1999-07-22 | Metallgesellschaft Aktiengesellschaft | METHOD FOR PRODUCING TiO2 ACCORDING TO THE SULFATE METHOD |
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