CN1118322C - Process for preparing modified titanium dioxide nano photocatalysis material - Google Patents

Process for preparing modified titanium dioxide nano photocatalysis material Download PDF

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CN1118322C
CN1118322C CN 01118119 CN01118119A CN1118322C CN 1118322 C CN1118322 C CN 1118322C CN 01118119 CN01118119 CN 01118119 CN 01118119 A CN01118119 A CN 01118119A CN 1118322 C CN1118322 C CN 1118322C
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concentration
solution
titanium dioxide
titanate
value
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CN1385237A (en
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张玲娟
胡晓明
江雷
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Abstract

The present invention belongs to the technical field of chemical industry and particularly relates to a preparation method for modified titanium dioxide nanometer photocatalysis material. Titanate, metatitanic acid, titanium tetrachloride or a mixture of the titanate, the metatitanic acid and the titanium tetrachloride is used as a precursor and prepared into a solution with the concentration of 10% to 40%; the pH value id regulated from 3.0 to 5.0; then, a JL-1 additive agent with the concentration of 0.01 to 0.50 g/ml is added and heated to 30 to 80 DEG C, and the temperature is kept to make the JL-1 additive agent thoroughly activated; acid liquor is added to regulate the pH value from 4.0 to 6.0; the temperature is continuously kept, and alkaline liquor is used for regulating the pH value from 6.5 to 8.5 to manufacture nanometer photocatalysis mother liquid; the nanometer photocatalysis mother liquid is sucked, filtered and dried to prepare the modified titanium dioxide nanometer photocatalysis material. Compared with a titanium dioxide nanometer catalyst which is not processed, the photocatalysis activity of the present invention is increased by 2 to 10 times.

Description

The preparation method of the titanium dioxide nano photocatalysis material of modification
Technical field
The invention belongs to chemical technology field, particularly the preparation method of the titanium dioxide nano photocatalysis material of modification.
Background technology
In the today that enters 21 century, the conductor photocatalysis technology will be to promise to be one of environmentally friendly catalysis new technology most.This technology has characteristics such as low energy consumption, easy to operate, non-secondary pollution, and can make full use of solar energy, is a kind of very promising environmental improvement technology.TiO 2Be a kind of important semi-conducting material, TiO 2Advantages such as it is inexpensive, nontoxic, stable and recyclable that semi-conducting material has are desirable photochemical catalysts.
In general, the nano-material surface atom accounts for significant proportion and is unordered class gaseous structure, and particle inside then is the order-disorder structure.Compare with conventional powder body material; the nano particle specific structure makes it have special natures such as small-size effect, skin effect, macro quanta tunnel effect; make it show many unusual physics and chemical property at aspects such as catalysis, photoelectricity, magnetic, mechanics; have many important use and be worth, can be widely used in fields such as aerospace, national defense industry, magnetic recording equipment, computer engineering, environmental protection, chemical industry, medicine, bioengineering and nuclear industry.
TiO 2Particle shape comprises particle diameter, crystal formation, surface nature etc., and it has considerable influence to photocatalytic activity, wherein nano-TiO 2The catalytic activity height is big rising photocatalysis new material.Nano-TiO 2The activity of catalysis material depends on the form (comprising particle diameter and distribution, crystal formation and content etc.) of product to a great extent, and particle shape and technology of preparing, method of modifying are closely related.
Application for a patent for invention number is 98115808 to disclose a kind of porous, Large ratio surface solid super strong acid photocatalyst, promptly with conductor oxidate TiO 2Or contain TiO 2Binary composite oxides (as: TiO 2-SiO 2, TiO 2-ZrO 2, TiO 2-Al 2O 3) make.This catalyst has very strong photochemical catalytic oxidation decomposability to organic matter, and has the strong disinfecting performance.
The main commodity TiO that adopts in most of photocatalysis technology researchs 2Or will use after its modification, be difficult to when Preparation of Catalyst, optimize and the closely-related morphological index of catalytic activity.Generally prepare TiO with liquid phase method 2Photochemical catalyst, but reaction process is long, quantity of three wastes is big, and calcining easily makes particle shape change.
Summary of the invention
The objective of the invention is to overcome that above-mentioned reaction process is long during titanium dioxide nano photocatalysis material, quantity of three wastes is big in preparation, and the defective that calcining easily makes particle shape change, a kind of preparation method of titanium dioxide nano photocatalysis material of modification is provided, can the controllable high-efficiency nano-TiO 2Form.
The present invention utilizes raw material of industry butyl titanate, tetraethyl titanate, isopropyl titanate, metatitanic acid or titanium tetrachloride to make presoma, what make modification by chemical reaction, separation, drying, making beating is the suspended substance of decentralized medium with water, and the particle of suspended substance is the TiO of modification 2Nano particle.Be mainly used in the photocatalysis material of titanium dioxide of support type.
The preparation method of the titanium dioxide nano photocatalysis material of modification of the present invention: make presoma with titanate esters, metatitanic acid, titanium tetrachloride or their mixture under the room temperature, be made into weight percent concentration and be 10%～40% solution, add alkali and/or acid-conditioning solution pH value is 3.0～5.0, adding concentration subsequently again is the JL-1 additive solution of 0.01～0.50g/ml, additive solution and precursor solution volume ratio are 1: 10～1: 40, be heated to 30～80 ℃, be incubated 10～80 minutes, it is fully activated; Adding weight percent concentration again is 15%～30% acid solution, regulating pH is 4.0～6.0, continued insulation reaction 10～80 minutes, be that 20%～60% alkali lye adjusting pH is 6.5～8.5 with weight percent concentration then, make the nano-photo catalytic mother liquor, pass through suction filtration, oven dry again, be prepared into the titanium dioxide nano photocatalysis material of modification.
The titanium dioxide nano photocatalysis material of modification of the present invention, the mother liquor that is made into suitable concn according to different purposes uses.
Described alkali is KOH or NaOH; Described acid is HCl, CH 3COOH, HNO 3, H 2SO 4Or H 2SO 3
Described titanate esters is butyl titanate, tetraethyl titanate or isopropyl titanate.
Described JL-1 additive is the product that Jia Ling auxiliary reagent factory, Shanghai produces.The solvent of described JL-1 additive solution is HNO 3, H 2SO 4, CH 3COOH, HCl or H 2SO 3
Method of the present invention can improve the photocatalytic activity of nano TiO 2 powder.To use up by the modifying titanium dioxide nano-photocatalyst that the inventive method is prepared and decompose effect detection instrument mensuration, and observe and find, its photocatalytic activity increases 2-10 doubly than untreated nano titania catalyst.Method of the present invention is simple to operate, and is pollution-free, and particularly the photocatalysis material of titanium dioxide as support type is with a wide range of applications.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.
Embodiment 1:
With concentration is 10% tetraethyl titanate 200ml, and adding concentration and be 20% KOH and concentration and be 15% HCl, to regulate the pH value be 5.0, and adding concentration subsequently again is the JL-1 additive solution 20ml of 0.01g/ml, is heated to 30 ℃, is incubated 10 minutes, and it is fully activated; Adding concentration again and be 15% HCl, to regulate pH value be 4.0, continued insulation reaction 80 minutes, is suction filtration behind 20% the NaOH adjusting pH=8.5, oven dry with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 2:
With concentration is that 10% butyl titanate and concentration be 15% tetraethyl titanate with volume ratio are to mix at 3: 2, cumulative volume is 250ml, adding concentration and be 30% KOH and concentration and be 20% HCL, to regulate pH value be 3.4, adding concentration subsequently again is the JL-1 additive solution 13ml of 0.09g/ml, be heated to 34 ℃, be incubated 15 minutes, it is fully activated: add concentration again and be 30% H 2SO 4Regulating pH value is 4.2, continues insulation reaction 70 minutes, is that 30% KOH and concentration are suction filtration behind 20% the HCL adjusting pH=7.5, oven dry with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 3:
With concentration is that 15% isopropyl titanate and concentration be 11% titanium tetrachloride with volume ratio are to mix at 4: 3, cumulative volume is 350ml, adding concentration and be 26% KOH and concentration and be 22% HCl solution, to regulate the pH value be 3.0, adding concentration subsequently again is the JL-1 additive solution 24ml of 0.12g/ml, be heated to 45 ℃, be incubated 33 minutes, it is fully activated; Add concentration again and be 22% HCl solution, regulating pH value is 5.1, continues insulation reaction 60 minutes, is suction filtration behind 40% the NaOH adjusting pH=8.0, oven dry with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 4:
With concentration 40% industrial metatitanic acid 400ml, adding concentration and be 60% NaOH and concentration and be 25% HCl solution, to regulate pH value be 4.5, and adding concentration subsequently again is the JL-1 additive solution 20ml of 0.10g/ml, is heated to 80 ℃, be incubated 60 minutes, it is fully activated; Add concentration again and be 30% CH 3COOH solution, regulating pH value is 4.5, continues insulation reaction 10 minutes, is that 60% NaOH adjusting pH is 6.5 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 5:
With concentration 20% titanium tetrachloride 250ml, adding concentration and be 35% NaOH and concentration and be 30% HCl solution, to regulate the pH value be 3.5, and adding concentration subsequently again is the JL-1 additive solution 6ml of 0.25g/ml, is heated to 50 ℃, be incubated 45 minutes, it is fully activated; Add concentration again and be 20% HCl solution, regulating pH value is 5.0, continues insulation reaction 50 minutes, is that 50% KOH adjusting pH is 7 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 6:
With concentration is that 25% industrial metatitanic acid and concentration be 30% butyl titanate with volume ratio are to mix at 2: 1, cumulative volume is 250ml, adding concentration and be 20% KOH and concentration and be 35% HCl solution, to regulate the pH value be 4.2, adding concentration subsequently again is the JL-1 additive solution 9ml of 0.28g/ml, be heated to 54 ℃, be incubated 40 minutes, it is fully activated; Add concentration again and be 25% HNO 3Solution, regulating pH value is 5.8, continues insulation reaction 52 minutes, is that 35% NaOH adjusting pH is 7.8 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 7:
With concentration is 30% butyl titanate 230ml, adds concentration and be 50% NaOH and concentration and be 25% HNO 3It is 3.5 that solution is regulated the pH value, and adding concentration subsequently again is the JL-1 additive solution 10ml of 0.50g/ml, is heated to 70 ℃, is incubated 25 minutes, and it is fully activated; Add concentration again and be 18% HCl solution, regulating pH value is 5.2, continues insulation reaction 35 minutes, is that 35% NaOH adjusting pH is 8 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 8:
With concentration is 35% industrial metatitanic acid 400ml, and adding concentration and be 45% KOH and concentration and be 25% HCL, to regulate the pH value be 3.8, and adding concentration subsequently again is the JL-1 additive solution 18ml of 0.30g/ml, is heated to 60 ℃, is incubated 35 minutes, and it is fully activated; Add concentration again and be 25% HNO 3Solution, regulating pH value is 5.8, continues insulation reaction 25 minutes, is that 45% KOH adjusting pH is 8.5 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 9:
With concentration is that 30% tetraethyl titanate and concentration be 10% titanium tetrachloride with volume ratio are to mix at 2: 5, and cumulative volume is 500ml, adds concentration and be 26% KOH and concentration and be 25% H 2SO 4Regulating the pH value is 4.3, and adding concentration again is the JL-1 additive solution 18ml of 0.30g/ml, is heated to 40 ℃, is incubated 30 minutes, and it is fully activated; Add concentration again and be 30% HCOOH solution, regulating pH value is 6.0, continues insulation reaction 45 minutes, is that 50% NaOH adjusting pH is 7.0 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 10:
With concentration is that 25% metatitanic acid orthocarbonate and concentration be 12% metatitanic acid with volume ratio are to mix at 3: 4, cumulative volume is 210ml, adding concentration and be 45% KOH and concentration and be 30% HCL, to regulate the pH value be 3.5, adding concentration again is the JL-1 additive solution 18ml of 0.25g/ml, be heated to 45 ℃, be incubated 45 minutes, it is fully activated; Add concentration again and be 30% HCL solution, regulating pH value is 5.8, continues insulation reaction 50 minutes, is that 60% NaOH adjusting pH is 7.5 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.Be made into 40% mother liquor during use with deionized water.
Embodiment 11:
With concentration is 26% isopropyl titanate 250ml, adds concentration and be 34% NaOH and concentration and be 35% HNO 3Regulating the pH value is 4.2, and adding concentration subsequently again is the JL-1 additive solution 12ml of 0.45g/ml, is heated to 55 ℃, is incubated 30 minutes, and it is fully activated; Add concentration again and be 15% H 2SO 4Solution, regulating pH value is 6.0, continues insulation reaction 30 minutes, is that 40% KOH adjusting pH is 7.3 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 12:
With concentration is 35% butyl titanate 350ml, and adding concentration and be 30% KOH and concentration is 25%H 2SO 4Adjusting pH value be 3.4, adding concentration subsequently again is the JL-1 additive solution 16ml of 0.40g/ml, is heated to 75 ℃, is incubated 48 minutes, and it is fully activated; Add concentration again and be 22% CH 3COOH solution, regulating pH value is 4.4, continues insulation reaction 22 minutes, is that 36% NaOH adjusting pH is 8.2 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.
Embodiment 13:
With concentration 25% titanium tetrachloride 230ml, adding concentration and be 50% NaOH and concentration and be 30% HCL, to regulate the pH value be 3.8, and adding concentration subsequently again is the JL-1 additive solution 10ml of 0.32g/ml, is heated to 70 ℃, be incubated 25 minutes, add concentration again and be 17% H 2SO 4Solution, regulating pH value is 4.8, continues insulation reaction 25 minutes, is that 50% KOH adjusting pH is 8.0 suction filtrations, oven dry afterwards with concentration then, is prepared into the titanium dioxide nano photocatalysis material of modification.

Claims (7)

1. the preparation method of the titanium dioxide nano photocatalysis material of a modification, it is characterized in that: make presoma with titanate esters, metatitanic acid, titanium tetrachloride or their mixture under the room temperature, be made into weight percent concentration and be 10%～40% solution, add alkali and/or acid-conditioning solution pH value is 3.0～5.0, adding concentration subsequently again is the JL-1 additive solution of 0.01～0.50g/ml, additive solution and precursor solution volume ratio are 1: 10～1: 40, be heated to 30～80 ℃, insulation fully activates it; Add acid solution again, regulating pH is 4.0～6.0, continues insulation reaction, and regulating pH with alkali lye then is 6.5～8.5, makes the nano-photo catalytic mother liquor, passes through suction filtration, oven dry again, is prepared into the titanium dioxide nano photocatalysis material of modification;
Described temperature retention time is 10～80 minutes.
2. the method for claim 1, it is characterized in that: described acid is HCl, CH 3COOH, HNO 3, H 2SO 4Or H 2SO 3
3. the method for claim 1, it is characterized in that: described alkali is KOH or NaOH.
4. method as claimed in claim 1 or 2 is characterized in that: the concentration of described acid solution is 15%～30%.
5. as claim 1 or 3 described methods, it is characterized in that: the concentration of described alkali lye is 20%～60%.
6. the method for claim 1, it is characterized in that: described titanate esters is butyl titanate, tetraethyl titanate or isopropyl titanate.
7. the method for claim 1, it is characterized in that: the solvent of described JL-1 additive solution is HNO 3, H 2SO 4, CH 3COOH, HCl or H 2SO 3
CN 01118119 2001-05-16 2001-05-16 Process for preparing modified titanium dioxide nano photocatalysis material Expired - Fee Related CN1118322C (en)

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Publication number Priority date Publication date Assignee Title
CN100384745C (en) * 2003-01-29 2008-04-30 河南大学 Process for preparing nm-TiO*
CN1314485C (en) * 2004-04-08 2007-05-09 中国科学院过程工程研究所 Surface modification of titanium oxide base light catalyzed material
CN100460332C (en) * 2006-03-31 2009-02-11 北京化工大学 Method for modifying titanium dioxide film by heterocyclic compound
CN100395018C (en) * 2006-08-25 2008-06-18 清华大学 Method for preparing visible light excited TiO2 photocatalyst utilizing industrial metatitanic acid
CN102011751A (en) * 2010-09-27 2011-04-13 东莞市格瑞卫康环保科技有限公司 Low-noise centrifugal wind wheel with purification function
CN111632585A (en) * 2019-03-01 2020-09-08 龙蟒佰利联集团股份有限公司 Denitration TiO2-ZrO2Composite carrier and preparation method thereof

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