CN1416948A - Prepn of new-type composite photocatalyst - Google Patents
Prepn of new-type composite photocatalyst Download PDFInfo
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- CN1416948A CN1416948A CN 02150913 CN02150913A CN1416948A CN 1416948 A CN1416948 A CN 1416948A CN 02150913 CN02150913 CN 02150913 CN 02150913 A CN02150913 A CN 02150913A CN 1416948 A CN1416948 A CN 1416948A
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- China
- Prior art keywords
- composite photocatalyst
- photocatalyst
- solution
- acid
- titanium dioxide
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The present invention relates to a preparing process of chemical preparation. The present invention is characterized by that the composite nanometer level photocatalyst including titania and alumina is prepared using metatitanic acid intermediate from sulfuric acid process of producing titanium white as feedstock and through acid dissolution and blending. The photocatalyst has an average crystal grain size of 10-20 nm. The prepared composite nanometer level photocatalyst has powerful photocatalytic activity and high photocatalytic efficiency.
Description
Technical Field
The invention relates to a preparation method of a novel composite photocatalyst, belonging to the technical field of preparation of chemical preparations.
Background
Because the environmental pollution is increasingly serious due to industrial wastewater, waste gas, domestic sewage and the like generated by the rapid development of economy, and the atmospheric pollution is also caused by automobile wastewater, industrial smoke dust, foul gas in the living environment and the like, the environmental protection and treatment are important social problems and need to be solved urgently.
Photocatalytic oxidation is a potential and ideal environmental management technology, and has been widely studied at home and abroad in recent years. Most of the current research is limited to the use of conventional titanium dioxide photocatalysts which can only be excited by ultraviolet light with a wavelength of less than 387nm, and the excited electron-hole pairs are easily recombined when migrating to the surface, and if no proper electron-hole pair trapping agent is available, the stored energy is consumed by recombination within a few nanoseconds. If appropriate capture agents or surface vacancies are selected to capture electrons and holes, recombination is inhibited and subsequent redox reactions occur. Therefore, the modification to reduce the recombination probability of photo-generated electron-hole pairs is one of the important means for preparing high-activity photocatalysts.
Chinese patent CN1220185A discloses a three-component system of titanium alkoxide-alcohol-water, which directly prepares a titanium dioxide photocatalyst by a sol-gel method; the photocatalyst has the characteristics of gaps, easiness in ventilation, water permeability, good light transmittance, large reaction specific surface area, easiness in cleaning and recycling, no secondary pollution, high catalytic efficiency and the like. Chinese patent CN1350884A discloses a ternary composite photocatalyst prepared by mutually containing and depositing silica sol and molybdenum titanium solution; the photocatalyst can be used for preparing antibacterial clean-keeping ceramics, and can also be used for paint with air purifying function and cosmetics. JP53095893 discloses a photocatalyst prepared by hydrolyzing a chloride of titanium such as titanium chloride or the like, which photocatalyst is low in activity. US4196101 discloses a photocatalyst containing spherical alumina prepared from titanium tetrachloride or an organic titanium compound (e.g., titanium alkoxide) as a main raw material, wherein the alumina content of the photocatalyst is 1 to 40%. However, most of these methods use organic materials as raw materials, and are expensive, long in reaction time and difficult to industrialize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel process with wide raw material sources, simple process and low cost to produce a novel nano composite photocatalyst.
The object of the invention can be achieved by the following measures:
the invention takes metatitanic acid as a raw material, which is an intermediate in the production of titanium white by a sulfuric acid method, and prepares the nano-scale composite photocatalyst by acid dissolution and blending processes. The preparation method comprises the following steps: preparing metatitanic acid into TiO at normal temperature220-40% of suspension, uniformly stirring, adding a hydrochloric acid solution, heating to boiling, stirring for 0.5-1.0 h, adding a sodium hydroxide solution, adjusting the pH value of the suspension to 7.0-8.0, adding an aluminum sulfate solution, heating to 70 ℃, then dropwise adding a sodium acetate solution at a speed of 3.0ml/min, controlling the stoichiometric amount of the generated alumina to be 5-10% in the composite particles, namely Al2O3/TiO25-10 wt%, keeping the temperature for 1 hr after the reaction, heating to 90 deg.C, keeping the temperature for 1 hr, and washing with 0.1mol/l AgNO3Solution detection of Cl-free-Until now. The obtained filter cake was dried at 100 ℃ andthen calcined at 300 ℃ for 2.0 hours. The nanometer level novel efficient composite photocatalyst can be obtained, and the catalyst has strong photocatalytic activity.
In the preparation process, the titanium dioxide is derived from metatitanic acid, and the metatitanic acid is dehydrated into anatase titanium dioxide after being calcined, and the reaction formula can be represented as follows:
the ionic reaction generated by the reaction of aluminum sulfate and sodium acetate can be expressed as:
the invention has wide source of raw materials and low cost; the average grain size of the prepared composite photocatalyst is 10-20nm, and the composite photocatalyst has strong photocatalytic activity. The nano-scale composite photocatalyst prepared by the invention is TiO2The alumina powder is of an anatase structure, the particle size is 10-20nm, and the content of alumina is 5-10%. The photocatalytic activity is higher than that of the P-25 titanium dioxide photocatalyst product of Degussa company in Germany.
The photocatalytic activity was evaluated by the following method: weighing a certain amount of acid red dye, preparing a solution with the concentration of 20mg/l, adjusting the pH value to be 2.5, and measuring the initial absorbance A0(ii) a Adding 0.01g of photocatalyst sample into the solution, and performing ultrasonic treatmentDispersing for 10 min to disperse the catalyst, stirring in a magnetic stirrer while irradiating with ultraviolet light or sunlight, and reacting at 0.08m from the bottom of the reactor3When the concentration of acid red is less than 70mg/l, the relationship between the absorbance A at the maximum absorption wavelength of 516nm and the concentration C follows the Langbei law, i.e. A ═ ε bC, then the decolorization rate of acid red η ═ A ═ ε bC0-A1)/A0。A1In order to extract about 30ml of the reaction solution at regular intervals, the reaction solution was filtered through a microporous membrane, and then the absorbance of the filtrate was measured with a 7230 spectrophotometer.
The invention uses different oxides to be compounded to serve as a trapping agent of electron-hole pairs, can reduce the recombination probability of photo-generated electron-hole pairs and improve the service life of the electron-hole pairs, and compared with the conventional titanium dioxide catalyst, the novel efficient composite photocatalyst has the advantages of high photocatalytic efficiency, strong deep oxidation capability, stable reaction activity and the like.
The specific implementation mode is as follows:
the first embodiment is as follows: preparing metatitanic acid into TiO at normal temperature when titanium white is produced by sulfuric acid method220 percent of suspension liquid is evenly stirred, a certain amount of hydrochloric acid solution with the concentration of 30 percent is added, the mixture is heated to boil and stirred for 1.0 hour, 30 percent of sodium hydroxide solution is added, the pH value of the suspension liquid is adjusted to be 7.0-8.0, aluminum sulfate solution is added, sodium acetate solution is dropwise added at the speed of 3.0ml/min after the mixture is heated to 70 ℃, the stoichiometry of the aluminum oxide generated by the reaction is controlled to be Al2O3The content is 5%, i.e. Al2O3/TiO25-10 wt%, keeping the temperature constant for 1.0h after the reaction is finished, heating to 90 deg.C, keeping the temperature constant for 1.0h, and filtering and washing with 0.1mol/l AgNO3Solution detection of Cl-free-And drying the obtained filter cake at 100 ℃, and calcining the filter cake at 300 ℃ for 2.0 hours to obtain the novel composite photocatalyst. Passing the product through a preceding processThe decolorization rate of the photocatalyst on acid red is 93 percent through the method, and the nano composite photocatalyst has strong photocatalytic activity.
Example two: the same procedure was followed as in the first preparation except that metatitanic acid was used to prepare TiO2A suspension with a content of 40%; in addition, the stoichiometry of the alumina is controlled to Al2O3The content is 10%, i.e. Al2O3/TiO2The final nano composite photocatalyst is tested by the method, and the decolorization rate is 67 percent.
Claims (2)
1. A preparation method of a novel composite photocatalyst is characterized in that the photocatalyst is compounded by titanium dioxide and other oxides; preparing a nano-scale composite photocatalyst by using metatitanic acid as an intermediate in titanium dioxide production by a sulfuric acid method as a raw material and performing acid dissolution and blending processes; the preparation process comprises the following steps: at normal temperature, the intermediate product metatitanic acid in the titanium dioxide production by the sulfuric acid method is made into TiO220-40% suspension, stirring, adding 30% hydrochloric acid solution, heating to boil, stirring for 1.0 hr, adding 30% sodium hydroxide solution, adjusting pH to 7.0-8.0, adding aluminum sulfate solution, heating to 700 deg.C, adding 3.0ml/min sodium acetate solution, and controlling the stoichiometryof aluminum oxide generated by reaction at Al2O3The content is 5-10%, that is, Al2O3/TiO25-10 wt%, keeping the temperature for 1 hr after the reaction, heating to 90 deg.C, keeping the temperature for 1 hr, and washing with 0.1mol/l AgNO3Solution detection of Cl-free-And drying the obtained filter cake at 100 ℃, and calcining the filter cake at 300 ℃ for 2 hours to obtain the novel composite photocatalyst.
2. The method for preparing a novel composite photocatalyst, as claimed in claim 1, wherein the average crystal size of said composite photocatalyst is 10-20 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021509131A CN1150981C (en) | 2002-12-03 | 2002-12-03 | Prepn of new-type composite photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021509131A CN1150981C (en) | 2002-12-03 | 2002-12-03 | Prepn of new-type composite photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1416948A true CN1416948A (en) | 2003-05-14 |
| CN1150981C CN1150981C (en) | 2004-05-26 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021509131A Expired - Lifetime CN1150981C (en) | 2002-12-03 | 2002-12-03 | Prepn of new-type composite photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1150981C (en) |
-
2002
- 2002-12-03 CN CNB021509131A patent/CN1150981C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1150981C (en) | 2004-05-26 |
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Free format text: FORMER OWNER: SHANGHAI SHANGHUI NANO TECHNOLOGY CO., LTD. Effective date: 20140611 Owner name: SHANGHAI SHANGHUI NANO TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: SHANGHAI UNIVERSITY Effective date: 20140611 |
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Free format text: CORRECT: ADDRESS; FROM: 200072 ZHABEI, SHANGHAI TO: 200436 BAOSHAN, SHANGHAI |
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Effective date of registration: 20140611 Address after: 200436 Shanghai, Shanghai, Shanghai Branch Road, Lane No. 1090, No. 3, building 100 Patentee after: SHANGHAI SHANGHUI NANO TECHNOLOGY Co.,Ltd. Address before: 200072 Zhabei District Yanchang Road, Shanghai, No. 149 Patentee before: Shanghai University Patentee before: SHANGHAI SHANGHUI NANO TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20180629 Address after: 266000 spring tide Road, New River eco chemical technology industrial base, Pingdu, Qingdao, Shandong 1 Patentee after: Qingdao Huixin new Mstar Technology Ltd. Address before: 200436 3, 100 Lane 1090 lane, Hu Tai Road, Baoshan District, Shanghai. Patentee before: SHANGHAI SHANGHUI NANO TECHNOLOGY Co.,Ltd. |
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Granted publication date: 20040526 |
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