CN1228138C - Modified titanium dioxide immobilization method for degrading organic pollutant in water - Google Patents
Modified titanium dioxide immobilization method for degrading organic pollutant in water Download PDFInfo
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- CN1228138C CN1228138C CN 03132585 CN03132585A CN1228138C CN 1228138 C CN1228138 C CN 1228138C CN 03132585 CN03132585 CN 03132585 CN 03132585 A CN03132585 A CN 03132585A CN 1228138 C CN1228138 C CN 1228138C
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Abstract
The present invention relates to a modified titanium dioxide immobilization method for degrading organic pollutants in water, which relates to a method for growing titanium dioxide ceramic membranes in the original positions of the surface of pure titanium metal. The present invention has the specific steps: the surface of the pure titanium metal is deoiled, washed, pickled and washed again; an acidic system electrolyte with the sulfuric acid content of 20 to 80 grams / liter is used; titanium metal is used as an anode, a stainless steel tank filled with the electrolyte is used as a cathode, and the titanium metal is arranged in the electrolyte; a direct-current power supply is used for carrying out micro-plasma oxidation, namely the voltage is regulated to 140 to 200V in 10 minutes, the voltage is constant for 5 to 30 minutes, and the temperature of the electrolyte is controlled from 10 to 40 DEG C. The present invention uses the micro-plasma oxidation technology which is arisen in recent years to grow a layer of porous titanium dioxide ceramic membranes in the original position of the surface of the pure titanium metal. Because a ceramic layer generated by the micro-plasma oxidation technology grows on a basal body, the ceramic layer is tightly combined with the basal body and is hard to fall.
Description
Technical field: the present invention relates to a kind of method at pure titanium metal surface in situ growth porous titanium dioxide ceramic film.
Background technology: titanium dioxide semiconductor has suitable energy gap, and stability is preferably arranged in the photocatalysis system, is a kind of comparatively desirable semiconductor light-catalyst.Titanium dioxide starts from the seventies in 20th century as the research of organic pollution in the photocatalyst for degrading water, early stage research is based on the suspension system photocatalysis, the difficult separation and recycling but the titanium dioxide molecule easily runs off, people turn to the stationary state titanium deoxide catalyst with research emphasis.Immobilization can be divided into physics method and chemical method generally: the titanium dioxide powder for preparing is loaded into physical method on the carrier by binding agent, the problem that exists powder to be embedded in effective catalysis area is reduced or come off from carrier.Chemical method: as less employing such as chemical vapour deposition (CVD) cost height, experiment condition be wayward; Titanium dioxide and matrix bond that liquid phase deposition generates are not tight; Sol-gel process gained titanium dioxide granule is little, but is coated with the long realization suitability for industrialized production that is difficult to of the complicated manufacturing cycle of membrane process.The titanium dioxide immobilization faces two technological difficulties: the one, to guarantee in use not come off in conjunction with firmly between titanium dioxide and carrier; The 2nd, must have high catalytic activity simultaneously.These two targets are a pair of paradox under a lot of situations, specific area are reduced in conjunction with firmly the time, thereby photocatalytic activity decline.In use easily come off and reduce its service life again when catalytic activity is high from carrier.CN1386916A discloses " a kind of preparation method of optically catalytic TiO 2 film " its electrolyte and has adopted alkaline system, acquisition be non-porous film, its specific area is low.
Summary of the invention: can not make to combine between titanium dioxide and carrier and make the good problem of photocatalytic activity again firm the time for solving prior art, the invention provides a kind of modifying titanium dioxide process for fixation that is used for the degradation water organic pollution.Method of the present invention is with little plasma oxidation technology, and at pure titanium metal surface in situ growth layer of titanium dioxide ceramic membrane, concrete steps are: (1) carries out oil removing, washing, pickling and washing again with the pure titanium metal surface; (2) the employing sulfuric acid content is that the acid system aqueous solution of 20-80 grams per liter is electrolyte; (3) with the titanium be anode, be negative electrode with the stainless steel tank that electrolyte is housed, and titanium is placed electrolyte; (4) adopt dc source to carry out little plasma oxidation, promptly in 10 minutes, make voltage transfer to 140-200V, and constant voltage 5-30 minute, the temperature of electrolyte is controlled at 10-40 ℃.Electrolyte of the present invention can also be doping system, promptly adds the sulfate of iron in the electrolyte of described acid system, perhaps the nitrate of lanthanide rare or silicate.This method can be by changing technological parameter (electrolyte solution composition, current density and time etc.), on titanium, form the Detitanium-ore-type of different proportion and the ceramic membrane and the modified titanium dioxide doped as required ceramic membrane of rutile titanium dioxide mixing crystal formation, ceramic membrane surface is a microcellular structure, and roughness is 30～100nm; The thickness range of rete is 1～30 μ m; Crystallite dimension is 30～500nm.The present invention is based on titanium dioxide immobilization technology present situation, the modifying titanium dioxide particle that prepare a kind of existing high surface again can with the firm catalyst film of matrix bond, and on membrane process, to help suitability for industrialized production, and be easy to recycling utilization.The photocatalysis performance evaluation of the product that method of the present invention is produced: selecting this basic-dyeable fibre of rhodamine B for use is the target degradation product; The photocatalytic degradation device mainly is made up of cylindrical quartz reactor, ultraviolet source, air-blowing pump; By spectrophotometer, under the 552nm wavelength, survey the rhodamine B solution absorbency, and then try to achieve clearance.(1) titanium dioxide porous membrane that makes of acid system, the clearance of 50%, 90 minute rhodamine B of clearance of 30 minutes rhodamine Bs of degradation treatment is more than 98%; (2) mix iron modifying titanium dioxide perforated membrane, the clearance of 30 minutes rhodamine Bs of degradation treatment is more than 90%; (3) mix lanthanum modifying titanium dioxide perforated membrane, the clearance 90% of 30 minutes rhodamine Bs of degradation treatment; (4) mix europium modifying titanium dioxide perforated membrane, the clearance 99% of 90%, 30 minute rhodamine B of clearance of 15 minutes rhodamine Bs of degradation treatment; (5) iron silicon composite doping modification titanium dioxide porous membrane, the clearance 98% of 30 minutes rhodamine Bs of degradation treatment.The present invention utilizes the plasma oxidation method, directly forms the porous titanium oxide film on the Titanium surface, and following characteristics are arranged: 1. can and change bath composition by the control electrical quantity, reconcile thickness, composition etc.; 2. this method system film can be realized suitability for industrialized production; 3. rete become loose or obscission do not appear after reusing 20 times in the long service life of this porous catalyst film, and catalytic performance does not reduce.4. compare with outstanding slurry method, when handling with the volume rhodamine B, mix europium modifying titanium dioxide perforated membrane, the speed of degradation treatment rhodamine B is higher than the outstanding slurry system of 0.1% Detitanium-ore-type p-25, and has overcome the difficult shortcoming that reclaims of separating of powder.5. the clearance of 15 minutes rhodamine Bs of perforated membrane catalyst degradation processing of this method preparation just reaches 90%, and this efficient is expected to be used for the practical application of Treatment of Industrial Water.
The specific embodiment one: the step of present embodiment is: (1) carries out oil removing, washing, pickling and washing again with the pure titanium metal surface, and it is the hydrofluoric acid of 3%-6% that concentration is adopted in pickling; (2) electrolyte of Cai Yonging is the doping system electrolyte of ferric sulfate 0.2 grams per liter+sulfuric acid 49 grams per liters; (3) with the titanium be anode, be negative electrode with the stainless steel tank that electrolyte is housed, and titanium is placed electrolyte; (4) adopt dc source to carry out little plasma oxidation (power source voltage scope of compromise 0-700V, electric current scope of compromise 0.1-2A, this power supply has constant voltage, constant current function), in 4 minutes tank voltage is transferred to 160V, constant voltage is 6 minutes then, and makes the temperature of electrolyte be controlled at 10-40 ℃; Take out the product cleaning-drying at last.In this rete content of titanium dioxide account for 70%, surface roughness 69nm, average grain size 500nm, average pore size 250nm.The clearance of handling 30 minutes rhodamine Bs with this membrane degradation can reach 90%.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that used electrolyte is: the doping system electrolyte of lanthanum nitrate 0.05 grams per liter+sulfuric acid 49 grams per liters.In 1 minute tank voltage is transferred to 140V in little plasma oxidation process, with 3 minutes tank voltage is transferred to 160V again, constant voltage was taken out cleaning-drying in 6 minutes.The surface roughness of this film is 64nm.The clearance of handling 90 minutes rhodamine Bs with this membrane degradation can reach 90%.
The specific embodiment three: what present embodiment and the specific embodiment one were different is that used electrolyte is: the doping system electrolyte of ferric sulfate 0.2 grams per liter+sulfuric acid 49 grams per liters+sodium metasilicate 0.5 grams per liter.In 1 minute tank voltage is transferred to 140V in little plasma oxidation process, with 3 minutes tank voltage is transferred to 160V again, constant voltage was taken out cleaning-drying in 6 minutes.The surface roughness of this film is 112nm.The clearance of handling 15 minutes rhodamine Bs with this membrane degradation can reach 90%.
The specific embodiment four: what present embodiment and the specific embodiment one were different is that used electrolyte is: the doping system electrolyte of europium nitrate 0.05 grams per liter+sulfuric acid 49 grams per liters.In 1 minute tank voltage is transferred to 160V in little plasma oxidation process, constant voltage was taken out the sample cleaning-drying in 10 minutes.The clearance of handling 15 minutes rhodamine Bs with this membrane degradation can reach 90%.
The specific embodiment five: what present embodiment and the specific embodiment one were different is, electrolyte is acid system electrolyte, and wherein the concentration of sulfuric acid is 80 grams per liters, and other parameter is identical with the specific embodiment one.The clearance of handling 120 minutes rhodamine Bs with the membrane degradation that is obtained can reach 80%.
The specific embodiment six: what present embodiment and the specific embodiment one were different is, electrolyte is acid system electrolyte, wherein the concentration of sulfuric acid is 20 grams per liters, in 4 minutes tank voltage is transferred to 200V in little plasma oxidation process, and constant voltage was taken out the sample cleaning-drying in 30 minutes.Other parameter is identical with the specific embodiment one.The clearance of handling 180 minutes rhodamine Bs with the membrane degradation that is obtained can reach 90%.
Claims (1)
1, a kind of modifying titanium dioxide process for fixation that is used for the degradation water organic pollution is characterized in that concrete steps are: (1) carries out oil removing, washing, pickling and washing again with the pure titanium metal surface, and it is the hydrofluoric acid of 3%-6% that concentration is adopted in pickling; (2) the employing sulfuric acid content is that the acid system aqueous solution of 20-80 grams per liter is electrolyte, adds the sulfate of iron in the electrolyte of acid system, perhaps the nitrate of lanthanide rare or silicate; (3) with the titanium be anode, be negative electrode with the stainless steel tank that electrolyte is housed, and titanium is placed electrolyte; (4) adopt dc source to carry out little plasma oxidation, promptly in 10 minutes, make voltage transfer to 140-200V, and constant voltage 5-30 minute, the temperature of electrolyte is controlled at 10-40 ℃.
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| CN 03132585 CN1228138C (en) | 2003-08-29 | 2003-08-29 | Modified titanium dioxide immobilization method for degrading organic pollutant in water |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1312050C (en) * | 2004-10-28 | 2007-04-25 | 上海交通大学 | Method for light catalytic degrading carbamate pesticide in water |
| CN102614877B (en) * | 2012-02-29 | 2014-06-11 | 华南理工大学 | Preparation method of transition metallic element and non-metallic element doped nano titanium dioxide modified photocatalyst |
| CN104709970A (en) * | 2015-03-20 | 2015-06-17 | 大连海事大学 | Method for catalyzing water treatment by performing microplasma arc discharge with asymmetric electrodes |
| CN104709971A (en) * | 2015-03-20 | 2015-06-17 | 大连海事大学 | Micro-plasma arc discharge catalyzed water treatment method utilizing alternating-current power source |
| CN105126851B (en) * | 2015-08-28 | 2018-04-17 | 江苏大学 | One kind oxidation Fe2O3 doping two-phase titanium deoxid film visible light catalyst preparation method |
| CN105063723B (en) * | 2015-08-28 | 2018-08-21 | 江苏大学 | A kind of method that differential arc oxidation directly prepares iron-silicon-sulphur codope titanium dioxide thin film |
| CN105568343B (en) * | 2015-12-29 | 2017-11-03 | 哈尔滨工业大学 | The methods and applications of ferriferous oxide ceramic film class fenton catalyst are prepared in titanium alloy surface using plasma electrolytic oxidation method |
| CN111334838B (en) * | 2020-04-13 | 2021-01-05 | 中国计量大学 | Preparation method of titanium alloy composite oxide film and product thereof |
| CN112387264B (en) * | 2020-11-16 | 2022-02-08 | 西南石油大学 | TiO based on plasma treatment2Method of modifying TiO2Photocatalyst and application |
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