CN101147856A - Method for preparing immobilized titanium dioxide suspending carrier - Google Patents
Method for preparing immobilized titanium dioxide suspending carrier Download PDFInfo
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- CN101147856A CN101147856A CNA2007100452009A CN200710045200A CN101147856A CN 101147856 A CN101147856 A CN 101147856A CN A2007100452009 A CNA2007100452009 A CN A2007100452009A CN 200710045200 A CN200710045200 A CN 200710045200A CN 101147856 A CN101147856 A CN 101147856A
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- titanium dioxide
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Abstract
The present invention belongs to the field of environment-protecting water treatment filler preparation technology, in the concrete, it relates to a preparation method of immobilized nano titanium dioxide suspension filler. Said method includes the following steps: preparing mixed aqueous solution whose mole concentration ratio is 1:2-1:5, adding a certain quantity of nano crystallization inducing agent, stirring and filtering to obtain reaction solution for deposition, soaking polyurethane foam carrier in said reaction solution, under the microwave radiation with a certain power making deposition for a certain time, taking out said carrier, washing said carrier by using distilled water, drying so as to obtain the invented immobilized suspension carrier.
Description
Technical field
The invention belongs to environmental protection water treatment filler manufacturing process technology field, be specifically related to a kind of preparation method of immobilization nano titanium oxide floating stuffing.
Background technology
Light-catalyzed reaction is with TiO
2Deng conductor oxidate is photochemical catalyst, under the optical energy irradiation greater than its forbidden band energy, excites to form light induced electron and photoproduction hole.Polluter produces a series of redox reaction on the photocatalyst granular surface, is broken down into small-molecule substance, and is innocuous substances such as water and carbon dioxide by permineralization further.Finally make it.
Current nano titanium oxide is in research and use, mainly with two kinds of forms: a kind of is that powder nanometer titanium dioxide is directly added among the solution, by certain approach powder is fully mixed with liquid and contact, decomposition goal material under ultraviolet light or visible light photograph.Under this state, powder suspends in solution, is suspension system.Another kind is that nano titanium oxide is fixed on certain specific support by certain process for fixation, and this carrier can suspend, and also can fix.These two kinds of forms, because the titanium dioxide of powder type contacts with target substance evenly fully, specific area is bigger, so its disposal efficiency is higher.Yet it is tiny that powder titanium dioxide suspending system exists powder particle, therefore exists the drawback that reclaims difficulty, is unfavorable for reusing, how used in research experiment.And immobilized titanium dioxide carrier thereon is one of main direction of present stage research, immobilization TiO
2Carrier has the separation of being easy to, and is convenient to reusable advantage, has good future in engineering applications.
Floated carrier is meant that the full response device can reach the carrier of fluidized state when aeration, and can not be suspended on the water surface in the aeration.The nano-TiO that will have photocatalytic activity
2Be fixed on the floated carrier and have remarkable advantages, this is that light-catalysed degradation step determines: under the irradiation situation, and nano-TiO
2The hydroxyl radical free radical with strong oxidizing property that is produced that is stimulated only is present in nano-TiO
2Near the particle surface, just near the carrier surface.And polluter arrives nano-TiO also by diffusion
2Photocatalytic degradation has taken place near surface.Chemical reaction process is little if diffusion velocity is wanted specific surface, then becomes rate controlling step.And under fluidized state, make to be fixed with TiO
2Carrier fluidisation in reaction system, eliminated diffusion influence.So can improve degradation efficiency.
In recent years, all there is the related invention of fixed titanium deoxide catalyst to occur both at home and abroad.People such as the Floating Xu Gaotian of having are fixed in the commodity nano titanium oxide on the poly-propyl ester many-sided ball (CN200510025858.4) with binder method.More be fixed carrier, generate titanium dioxide nanoparticle (CN200510026139.4) with sol-gel process at the glass fibre net surface as Li Tian etc.In air purification field, fixed carrier has widely to be used.As inventions such as Choi Sungwook fixed titania support is used to remove peculiar smell and volatile organic matter (KR100413543B), Rengakuji Seiichi etc. by TiO 2 sol coating, high-temperature roasting etc. with TiO
2Be fixed in (US2002025428) on the carrier application representative for air purification field.From the bearer type and the application of related invention, floated carrier adopts less, uses less in the water treatment field.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of immobilized titanium dioxide suspending carrier.
The preparation method of the immobilized titanium dioxide suspending carrier that the present invention proposes, its concrete steps are as follows:
(1) mixed aqueous solution of preparation ammonium titanium fluoride and boric acid adds the crystallization derivant then in mixed aqueous solution, stirred 10～30 minutes, filters, and obtains transparent deposition reaction liquid; Wherein, the molar concentration rate of ammonium titanium fluoride and boric acid is 1: 2～1: 5, and the crystallization derivant adopts nano-TiO
2Powder, in the mixed aqueous solution that every liter of ammonium titanium fluoride and boric acid are formed, nano-TiO
2The powder addition is 0.5g/L～2g/L;
(2 are immersed in polyurethane foamed blocks in step (1) the gained deposition reaction liquid, then reactant liquor are placed under the microwave irradiation environment, and under the power of 500-1000W, under 90 ℃～100 ℃ temperature, the irradiation sedimentation time is 15 minutes～40 minutes;
(3) after deposition finishes, polyurethane foamed blocks is taken out, washing washes away foam surface and deposits unstable particle, until no obvious TiO
2Till coming off, drying promptly gets required product.
Among the present invention, nano-TiO described in the step (1)
2The particle diameter of powder is between 10nm～20nm.
Among the present invention, employed polyurethane foamed blocks will be in advance through rare nitric acid, absolute ethyl alcohol, distilled water supersound washing in the step (2).
Among the present invention, distilled water washing 4-6 time is adopted in washing described in the step (3).
Among the present invention, drying described in the step (3) is to descend a kind of of oven dry or natural air drying at 60 ℃～100 ℃.
The present invention adopts microwave to assist liquid phase deposition, and titanium dichloride load to the polyurethane foam surface, is made into floated carrier of photocatalyst, is applicable in the water treatment facilities of the photochemical catalytic oxidation of fluid bed form and biological oxidation.
The present invention considers that in conjunction with the domestic and international research present situation there is drawbacks such as reclaiming difficulty in powder titanium dioxide suspending system, and nano titanium oxide is loaded to the polyurethane foam surface, makes the suspending carrier of loaded titanium dioxide photocatalyst.Because polyurethane foam has very big voidage (97%), therefore can improve the load capacity of titanium dioxide and the avtive spot of absorption target substance effectively, and then improve the efficient of photocatalytic degradation.This kind filler can be used for the photocatalytic water treatment reactor of fluid bed form, under fluidized state, catalyst carrier and target substance full contact are even, has higher activity, particularly organic matter had good removal effect, and can use continuously, need not extra separating measure.Operating cost is low, can not produce secondary pollution.
Description of drawings
Fig. 1 is for characterizing the service life of titania support by the variation of each time percent of decolourization among the embodiment 1.
The product that Fig. 2 makes for the embodiment 1 bisphenol-A waste strength change curve that is used to degrade.
The specific embodiment
Further specify the present invention below by embodiment.
Embodiment 1:
(1) preparation ammonium titanium fluoride and boric acid concentration are respectively the mixed aqueous solution 500ml of 0.1mol/L and 0.3mol/L, add the nano-TiO of 1g/L
2Powder is as the crystallization derivant.Adopt common magnetic stirrer to filter after 10 minutes and obtain transparent deposition reactant liquor.
(2) general is submerged in the deposition reaction liquid through the polyurethane foamed blocks of rare nitric acid, absolute ethyl alcohol, distilled water supersound washing in advance.Reactant liquor is placed in the micro-wave oven, under 700W power, irradiation deposition 30 minutes.
(3) after deposition finishes, polyurethane foamed blocks is taken out,, wash away the unstable particle of deposition, until no obvious TiO with distilled water drip washing 5 times
2Till coming off.Oven dry down promptly gets required product in 60 ℃ of baking ovens.
Above-mentioned products obtained therefrom is used for photocatalysis performance detects, its concrete steps are as follows:
Getting 100ml concentration is rhodamine B.Characterize immobilization TiO by measuring rhodamine B in difference absorbance constantly
2Photocatalytic activity.
The rhodamine B solution of getting 100ml concentration and be 10mg/L places beaker, adds a certain amount of polyurethane foam carrier simultaneously.The beaker bottom magnetic stirrer makes carrier of photocatalyst fully contact with solution.Place the Philips low pressure mercury lamp of 25w above beaker apart from liquid level 4cm place, characteristic wavelength is 254nm.Under stable light source irradiation, through the degraded of certain hour, measure the absorbance of solution and change at the maximum absorption wavelength 554nm place of rhodamine B, calculate the percent of decolourization of rhodamine B then.
Simultaneously carrier is carried out repeated experiments, the variation by each time percent of decolourization characterizes TiO
2The service life of carrier.The result as shown in Figure 1.Remove use first after, catalyst slightly comes off, it is secondary 89.23% to make that percent of decolourization has dropped to from 95.03%, 5 percent of decolourizations all maintain about 85% afterwards.Show that the fixing photochemical catalyst adhesion property of this method is good, the life-span is longer; And coloured dyestuff had decolorizing effect preferably.
The product that makes with the inventive method is degraded and is contained bisphenol-A waste water, and wherein the concentration of bisphenol-A is 10mg/L.The treatment effect of more direct simultaneously photodissociation and catalytic degradation.Its concentration curve as shown in Figure 2.As can be seen from Fig. 2, within 120 minutes, under the simple UV-irradiation, Zu bisphenol-A has only small amount of degradation in contrast, degradation rate is no more than 5%, and in the identical time, as the bisphenol-A of experimental group after adding this catalyst carrier, final degradation efficiency reaches more than 95%, shows that this catalyst has good catalytic degradation effect to the recalcitrant substance of bisphenol-A etc.
Embodiment 2:
(1) preparation ammonium titanium fluoride and boric acid concentration are respectively the mixed aqueous solution 500ml of 0.1mol/L and 0.5mol/L, add the nano-TiO of 0.7g/L
2Powder is as the crystallization derivant.Adopt common magnetic stirrer to filter after 10 minutes and obtain transparent deposition reactant liquor.
(2) general is submerged in the deposition reaction liquid through the polyurethane foamed blocks of rare nitric acid, absolute ethyl alcohol, distilled water supersound washing in advance.Reactant liquor is placed in the micro-wave oven, under 1000W power, irradiation deposition 20 minutes.
(3) after deposition finishes, polyurethane foamed blocks is taken out,, wash away the unstable particle of deposition, until no obvious TiO with distilled water drip washing 5 times
2Till coming off.90 ℃ of drying in oven, promptly get required product.
Embodiment 3:
(1) preparation ammonium titanium fluoride and boric acid concentration are respectively the mixed aqueous solution 500ml of 0.1mol/L and 0.2mol/L, add the nano-TiO of 1.3g/L
2Powder is as the crystallization derivant.Adopt common magnetic stirrer to filter after 20 minutes and obtain transparent deposition reactant liquor.
(2) general is submerged in the deposition reaction liquid through the polyurethane foamed blocks of rare nitric acid, absolute ethyl alcohol, distilled water supersound washing in advance.Reactant liquor is placed in the micro-wave oven, under 900W power, irradiation deposition 40 minutes.
(3) after deposition finishes, polyurethane foamed blocks is taken out,, wash away the unstable particle of deposition, until no obvious TiO with distilled water drip washing 5 times
2Till coming off.Natural air drying promptly gets required product.
Claims (6)
1. the preparation method of an immobilized titanium dioxide suspending carrier is characterized in that concrete steps are as follows:
(1) mixed aqueous solution of preparation ammonium titanium fluoride and boric acid adds the crystallization derivant then in mixed aqueous solution, stirred 10 minutes～30 minutes, filters, and obtains transparent deposition reaction liquid; Wherein, the molar concentration rate of ammonium titanium fluoride and boric acid is 1: 2～1: 5, and the crystallization derivant adopts nano-TiO
2Powder, in the mixed aqueous solution that every liter of ammonium titanium fluoride and boric acid are formed, nano-TiO
2The powder addition is 0.5g/L～2g/L;
(2) polyurethane foamed blocks is immersed in step (1) the gained deposition reaction liquid, then reactant liquor is placed under the microwave irradiation environment, under the power of 500-1000W, under 90 ℃～100 ℃ temperature, the irradiation sedimentation time is 15 minutes～40 minutes;
(3) after deposition finishes, polyurethane foamed blocks is taken out, washing washes away foam surface and deposits unstable particle, until no obvious TiO
2Till coming off, drying promptly gets required product.
2. the preparation method of immobilized titanium dioxide suspending carrier according to claim 1 is characterized in that the described nano-TiO of step (1)
2The particle diameter of powder is 5nm～20nm.
3. the preparation method of immobilized titanium dioxide suspending carrier according to claim 1 is characterized in that the employed polyurethane foamed blocks of step (2) will be in advance through rare nitric acid, absolute ethyl alcohol, distilled water supersound washing.
4. the preparation method of immobilized titanium dioxide suspending carrier according to claim 1 is characterized in that the employing of washing described in the step (3) distilled water washing 4-6 time.
5. the preparation method of immobilized titanium dioxide suspending carrier according to claim 1 is characterized in that described in the step (3) dry for descending a kind of of oven dry or natural air drying at 60 ℃～100 ℃.
6. the application of the titanium dioxide suspending carrier that obtains of a preparation method as claimed in claim 1 in the water treatment facilities of the photochemical catalytic oxidation of fluid bed form and biological oxidation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100452009A CN101147856A (en) | 2007-08-23 | 2007-08-23 | Method for preparing immobilized titanium dioxide suspending carrier |
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|---|---|---|---|
| CNA2007100452009A CN101147856A (en) | 2007-08-23 | 2007-08-23 | Method for preparing immobilized titanium dioxide suspending carrier |
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| CN101147856A true CN101147856A (en) | 2008-03-26 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966469A (en) * | 2010-08-27 | 2011-02-09 | 河南师范大学 | Load type photocatalytic material and preparation method thereof |
| CN102008904A (en) * | 2010-10-27 | 2011-04-13 | 长安大学 | Method for preparing membrane material for multifunctional catalytic composite membrane bioreactor |
| CN103214083A (en) * | 2013-04-24 | 2013-07-24 | 河海大学 | TiO2-loaded packing and preparation method thereof |
| CN105293709A (en) * | 2015-11-18 | 2016-02-03 | 河海大学 | Ecological floating bed for oil-polluted water remediation |
| CN105749980A (en) * | 2016-02-04 | 2016-07-13 | 中国地质大学（北京） | Bismuth oxyhalogen photocatalytic foam and preparation method thereof |
| CN107570156A (en) * | 2017-09-05 | 2018-01-12 | 苏州科尔玛电子科技有限公司 | A kind of catalyzing hydrogen peroxide prepares catalyst of oxygen and preparation method thereof |
| CN107739730A (en) * | 2017-09-18 | 2018-02-27 | 西南交通大学 | Titanium dioxide nanoparticle surface deposition improves material anticoagulant property and the method for preparing biological micrographics |
| CN107803224A (en) * | 2016-09-09 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of low-gravity catalytic ozone oxidation catalyst and preparation method thereof |
| CN108031488A (en) * | 2017-11-28 | 2018-05-15 | 苏州艾缇克药物化学有限公司 | A kind of production method of graphene-based composite catalyst of carried heteropoly acid ionic liquid and the application in limonene derivatives |
| CN110394196A (en) * | 2019-07-05 | 2019-11-01 | 广西大学 | A kind of preparation method of nano-titanium dioxide-polyurethane sponge composite material |
| CN112723530A (en) * | 2020-12-11 | 2021-04-30 | 温州大学 | Preparation method of immobilized composite filler |
| CN113104995A (en) * | 2021-06-16 | 2021-07-13 | 天津市环境保护技术开发中心设计所 | Magnetic polyurethane photoproduction coupling filler and preparation method thereof |
-
2007
- 2007-08-23 CN CNA2007100452009A patent/CN101147856A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966469B (en) * | 2010-08-27 | 2012-08-08 | 河南师范大学 | Load type photocatalytic material and preparation method thereof |
| CN101966469A (en) * | 2010-08-27 | 2011-02-09 | 河南师范大学 | Load type photocatalytic material and preparation method thereof |
| CN102008904A (en) * | 2010-10-27 | 2011-04-13 | 长安大学 | Method for preparing membrane material for multifunctional catalytic composite membrane bioreactor |
| CN103214083A (en) * | 2013-04-24 | 2013-07-24 | 河海大学 | TiO2-loaded packing and preparation method thereof |
| CN103214083B (en) * | 2013-04-24 | 2014-12-31 | 河海大学 | Preparation method of TiO2-loaded packing |
| CN105293709B (en) * | 2015-11-18 | 2017-06-16 | 河海大学 | For the biological floating bed of oil polluted water reparation |
| CN105293709A (en) * | 2015-11-18 | 2016-02-03 | 河海大学 | Ecological floating bed for oil-polluted water remediation |
| CN105749980B (en) * | 2016-02-04 | 2018-06-19 | 中国地质大学（北京） | A kind of oxyhalogen bismuth photocatalysis foam and preparation method thereof |
| CN105749980A (en) * | 2016-02-04 | 2016-07-13 | 中国地质大学（北京） | Bismuth oxyhalogen photocatalytic foam and preparation method thereof |
| CN107803224A (en) * | 2016-09-09 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of low-gravity catalytic ozone oxidation catalyst and preparation method thereof |
| CN107570156A (en) * | 2017-09-05 | 2018-01-12 | 苏州科尔玛电子科技有限公司 | A kind of catalyzing hydrogen peroxide prepares catalyst of oxygen and preparation method thereof |
| CN107739730A (en) * | 2017-09-18 | 2018-02-27 | 西南交通大学 | Titanium dioxide nanoparticle surface deposition improves material anticoagulant property and the method for preparing biological micrographics |
| CN108031488A (en) * | 2017-11-28 | 2018-05-15 | 苏州艾缇克药物化学有限公司 | A kind of production method of graphene-based composite catalyst of carried heteropoly acid ionic liquid and the application in limonene derivatives |
| CN110394196A (en) * | 2019-07-05 | 2019-11-01 | 广西大学 | A kind of preparation method of nano-titanium dioxide-polyurethane sponge composite material |
| CN112723530A (en) * | 2020-12-11 | 2021-04-30 | 温州大学 | Preparation method of immobilized composite filler |
| CN113104995A (en) * | 2021-06-16 | 2021-07-13 | 天津市环境保护技术开发中心设计所 | Magnetic polyurethane photoproduction coupling filler and preparation method thereof |
| CN113104995B (en) * | 2021-06-16 | 2021-09-24 | 天津市环境保护技术开发中心设计所有限责任公司 | Magnetic polyurethane photoproduction coupling filler and preparation method thereof |
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