CN104014298A - Preparation method of solid titanium peroxide material for adsorption of cationic dye wastewater - Google Patents
Preparation method of solid titanium peroxide material for adsorption of cationic dye wastewater Download PDFInfo
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- CN104014298A CN104014298A CN201410299619.7A CN201410299619A CN104014298A CN 104014298 A CN104014298 A CN 104014298A CN 201410299619 A CN201410299619 A CN 201410299619A CN 104014298 A CN104014298 A CN 104014298A
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Abstract
The invention discloses a preparation method of a solid titanium peroxide material for adsorption of cationic dye wastewater, relating to the technical field of new material preparation. According to the preparation method of the solid titanium peroxide material, titanous sulfate, sulphuric acid, hydrogen peroxide, ammonium hydroxide and distilled water are used as main raw materials; main devices comprise a thermometer, a magnetic stirring apparatus and a thermostat water bath; the preparation method comprises the steps of using dilute sulphuric acid to prepare titanous sulfate solution with certain mass fraction, reacting with the hydrogen peroxide to generate a reddish brown solution, regulating the pH value of the reddish brown solution to be neutral to generate yellow solids, washing, standing and drying by distillation to obtain the solid titanium peroxide. The method has the characteristics that the raw materials are easily accessible, the method is simple and easy to operate, and the reaction conditions are mild; the prepared titanium peroxide powder is a mesoporous material and has strong adsorption property to cationic dyes.
Description
Technical field
The present invention relates to the technical field of the preparation of new material, relate in particular to the preparation method of the solid peroxygen titanium sorbing material of simple possible under a kind of temperate condition.
Background technology
Titanium-based nano material has good catalysis, electricity, magnetic and optical property, is the brand-new material that a class has applications well prospect.Due to the unstability of peroxide bridge, people are fewer to the research of the peroxide of titanium.At present, about the research of the peroxide systems of titanium, focus mostly in titanium peroxide complex (Peroxo Titanium Complex, PTC) as the application of reaction intermediate, utilize the stability of water-based titanium peroxide complex, with it as synthetic TiO
2the presoma of nano particle, to prepare the TiO 2 particles of different-shape, and explores the effect in synthetic titanium base functionalized nano material under cryogenic conditions of titanium peroxide complex.And these researchs all fail to propose a kind of effective ways of preparing solid peroxygen titanium.
Summary of the invention
The technical problem to be solved in the present invention is, successfully preparing under normal temperature can be compared with the solid peroxygen titanium of stable existence, and titanium peroxide powder has strong characterization of adsorption to the dye of positive ion.
Have been found that solid peroxygen titanium can be prepared as follows: use certain density dilute sulfuric acid and titanium sulfate to be mixed with the titanium sulfate (Ti (SO of certain mass mark
4)
2) solution, in this solution of 150mL, slowly drip about 30mL30% hydrogen peroxide (H
2o
2) solution, continue stir about 1 hour, obtain a kind of rufous strongly acidic solution (pH < 1), then use ammoniacal liquor (NH
4oH) solution regulates pH to neutral, and red tan solution transfers yellow gradually to, and occurs yellow solid matter.In this process, constantly stir and control rate of addition and be no more than 50 ℃ to guarantee reaction solution temperature.Finally, use distilled water by gained precipitation repeatedly quiet heavy, washing 3 to 5 times to remove ammonium radical ion, sulfate ion etc., obtain light yellow solid material and be placed in thermostat water bath, keep grinding after 40 ℃ of evaporates to dryness.
Certain density dilute sulfuric acid of the present invention can be 5wt%～30wt%, its objective is and suppresses the fast hydrolyzing of titanium sulfate in process for preparation; The titanium sulfate solution of described certain mass mark can be 10wt%～20wt%; Ammonia spirit can according to different embodiments carry out corresponding concentration adjustment with reach regulate pH with the object of controlling reaction temperature; Described adjusting pH is to neutral, and its scope can be for 5.5 to 8.5, as 6.5～7.5.
Concrete technical scheme is summarized as follows.
A preparation method for the solid peroxygen titanium material adsorbing for dye of positive ion waste water, the dilute sulfuric acid that service property (quality) concentration is 5%～30% and titanium sulfate are mixed with titanium sulfate (Ti (SO
4)
2) solution, making the mass concentration of titanium sulfate in dilute sulfuric acid is 10%～20%; Under continuing to stir, in titanium sulfate solution, drip mass concentration 30% hydrogen peroxide (H
2o
2) solution, to the red tan solution that obtains pH < 1; Stir and reaction solution temperature at 10～50 ℃, use ammoniacal liquor (NH
4oH) regulating pH value is 5.5～8.5, to obtaining yellow solid matter precipitation; Quiet heavy 3～5 times of gained precipitation washing, evaporate to dryness obtains light yellow solid material.
Described reaction solution temperature, can be at 25～50 ℃, can by control drip ammoniacal liquor speed, stirring or/and the measures such as additional ice-water bath cooling realize.
Described ammoniacal liquor can be that volume fraction is 5%～28% ammoniacal liquor.
Described use ammoniacal liquor (NH
4oH) solution regulates pH value, is preferably in 6.5～7.5 scopes.
Described evaporate to dryness can be at low temperature (30～50 ℃) evaporate to dryness in thermostat water bath.
Method of the present invention has that raw material is simple and easy to get, the feature of method simple and feasible, reaction condition gentleness, and prepared titanium peroxide powder is mesoporous material, under normal temperature, can, compared with stable existence, to the dye of positive ion, have strong characterization of adsorption.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of titanium peroxide material of the present invention.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the sample that makes of embodiment 1.
Fig. 3 is X-ray diffraction (XRD) spectrogram of the sample that makes of embodiment 1 after 550 ℃ of calcination 30min.
Fig. 4 is transmission electron microscope scanning (TEM) photo of the sample that makes of embodiment 1.
Transmission electron microscope scanning (TEM) photo that Fig. 5 is the sample that makes of embodiment 1 under high-amplification-factor more.
Fig. 6 is the XPS spectrum figure of Ti2p in the sample that makes of embodiment 1.
Fig. 7 is the XPS spectrum figure of O1s in the sample that makes of embodiment 1.
Fig. 8 is Fourier infrared spectrum analysis (FT-IR) spectrogram of the sample that makes of embodiment 1.
Fig. 9 is before titanium peroxide material absorption methylene blue of the present invention, in process and adsorbs the variation photo after methylene blue.
Figure 10 is the relation curve of titanium peroxide material of the present invention to methylene blue dye eliminating rate of absorption and time.
Figure 11 is the relation curve of titanium peroxide material of the present invention to malachite green Dye Adsorption clearance and time.
Figure 12 is titanium peroxide material centering red eliminating rate of absorption of the present invention and the relation curve of time.
The specific embodiment
Embodiment of the present invention will, according to following non-limiting example, be further described explanation.
Embodiment 1 prepares the example 1 of titanium peroxide material
The present embodiment is preferred embodiment.
Use dilute sulfuric acid and the titanium sulfate solid of 10wt% to be mixed with 15wt% titanium sulfate (Ti (SO
4)
2) solution, in this solution of 150mL, slowly drip about 30mL30% hydrogen peroxide (H
2o
2) solution, on magnetic stirring apparatus, continue stir about 1 hour, obtain a kind of rufous strongly acidic solution (pH < 1), then use ammoniacal liquor (NH
4oH) solution regulates pH to 6.5～7.5, and red tan solution transfers gradually yellow in this process, and occurs yellow solid matter.In this process, constantly stir and control rate of addition and be no more than 50 ℃ to guarantee reaction solution temperature.Finally, use deionized water by gained precipitation repeatedly quiet heavy, washing 3 to 5 times to remove ammonium radical ion, sulfate ion etc., obtain light yellow solid material and be placed in thermostat water bath, keep after 40 ℃ of evaporates to dryness grinding, obtain pale yellow powder shape titanium peroxide.
Comparison diagram 2 and Fig. 3, illustrate that prepared sample is the material that a kind of amorphous state exists, and changes the TiO of anatase into after calcination
2.Fig. 4 and Fig. 5 are sample transmission electron microscope scanning (TEM) photos under different amplification, the phenomenon that sample is reunited seldom, and do not observe lattice fringe and duct feature, this conforms to the result in XRD, has further proved that sample exists naturally with amorphous state.Fig. 6 and Fig. 7 are the XPS spectrum figure of Ti2p and O1s in sample, have proved Ti
4+, Ti-O and hydroxyl existence.Fig. 8 is Fourier infrared spectrum analysis (FT-IR) spectrogram of sample, appears at 898cm
-1the peak of position has proved the existence of peroxy-radical (O-O-).
Embodiment 2 prepares the example 2 of titanium peroxide material
Use dilute sulfuric acid and the titanium sulfate solid of 5wt% to be mixed with 15wt% titanium sulfate (Ti (SO
4)
2) solution, in this solution of 300mL, slowly drip about 60mL30% hydrogen peroxide (H
2o
2) solution, on magnetic stirring apparatus, continue stir about 1 hour, obtain a kind of rufous strongly acidic solution (pH < 1), then use ammoniacal liquor (NH
4oH) solution regulates pH to 8.5, and red tan solution transfers gradually yellow in this process, and occurs yellow solid matter.In this process, constantly stir and control rate of addition and be no more than 50 ℃ to guarantee reaction solution temperature.Finally, use deionized water by gained precipitation repeatedly quiet heavy, washing 5 times to remove ammonium radical ion, sulfate ion etc., obtain light yellow solid material and be placed in thermostat water bath, keep after 50 ℃ of evaporates to dryness grinding, obtain pale yellow powder shape titanium peroxide.
Embodiment 3 prepares the example 3 of titanium peroxide material
Use dilute sulfuric acid and the titanium sulfate solid of 30wt% to be mixed with 15wt% titanium sulfate (Ti (SO
4)
2) solution, in this solution of 150mL, slowly drip about 30mL30% hydrogen peroxide (H
2o
2) solution, on magnetic stirring apparatus, continue stir about 1 hour, obtain a kind of rufous strongly acidic solution (pH < 1), then use ammoniacal liquor (NH
4oH) solution regulates pH to 5.5, and red tan solution transfers gradually yellow in this process, and occurs yellow solid matter.In this process, constantly stir and control rate of addition to guarantee that reaction solution temperature is at 25～30 ℃.Finally, use deionized water by gained precipitation repeatedly quiet heavy, washing 3 times to remove ammonium radical ion, sulfate ion etc., obtain light yellow solid material and be placed in thermostat water bath, keep after 30 ℃ of evaporates to dryness grinding, obtain pale yellow powder shape titanium peroxide.
The application of embodiment 4 titanium peroxide Liquidity limit dyestuff simulated wastewaters
Choose three kinds of dyes of positive ion such as methylene blue, malachite green, dimethyl diaminophenazine chloride, be mixed with separately variable concentrations (50mgL
-1, 100mgL
-1, 200mgL
-1, 400mgL
-1) simulated wastewater, get 400mL simulated wastewater and put into glass, add prepared titanium peroxide to adsorb, dosage is 1.0gL
-1, reaction temperature is 25 ℃, pH is about 7, in the overall process of reaction, continues to carry out magnetic agitation, guarantees fully reaction.
Fig. 9 provides titanium peroxide material absorption methylene blue (solution concentration 100mgL of the present invention
-1) in front, process and the variation photo after absorption methylene blue.The difference that has shown intuitively the forward and backward color of titanium peroxide material absorption methylene blue, also shows methylene blue solution and adsorbs forward and backward change.
By experiment, titanium peroxide material absorption methylene blue, malachite green, the eliminating rate of absorption of dimethyl diaminophenazine chloride and the relation of adsorption time have been obtained, result as shown in Figure 10,11,12, has proved the application of prepared titanium peroxide on Liquidity limit waste water from dyestuff respectively.
Claims (5)
1. a preparation method for the solid peroxygen titanium material adsorbing for dye of positive ion waste water, dilute sulfuric acid and titanium sulfate that service property (quality) concentration is 5%～30% are mixed with titanium sulfate solution, and making the mass concentration of titanium sulfate in dilute sulfuric acid is 10%～20%; Under continuing to stir, in titanium sulfate solution, drip mass concentration 30% hydrogenperoxide steam generator, to the red tan solution that obtains pH < 1; Stir and reaction solution temperature at 10～50 ℃, using ammoniacal liquor to regulate pH value is 5.5～8.5, to obtaining yellow solid matter, precipitates; Quiet heavy 3～5 times of gained precipitation washing, evaporate to dryness obtains light yellow solid material.
2. according to the preparation method of the solid peroxygen titanium material for the absorption of dye of positive ion waste water claimed in claim 1, it is characterized in that, described reaction solution temperature, at 25～50 ℃, by control drip ammoniacal liquor speed, stirring or/and the measure of additional ice-water bath cooling realize.
3. according to the preparation method of the solid peroxygen titanium material for the absorption of dye of positive ion waste water claimed in claim 1, it is characterized in that, described ammoniacal liquor, volume fraction is 5%～28%.
4. according to the preparation method of the solid peroxygen titanium material for the absorption of dye of positive ion waste water claimed in claim 1, it is characterized in that, use ammoniacal liquor to regulate pH value in 6.5～7.5 scopes.
5. according to the preparation method of the solid peroxygen titanium material for dye of positive ion waste water absorption claimed in claim 1, it is characterized in that described evaporate to dryness is evaporate to dryness at 30～50 ℃ in thermostat water bath.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120125844A1 (en) * | 2009-07-31 | 2012-05-24 | Council Of Scientific & Industrial Research | Removal of organic dyes and organic pollutants by titanium peroxide gel |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120125844A1 (en) * | 2009-07-31 | 2012-05-24 | Council Of Scientific & Industrial Research | Removal of organic dyes and organic pollutants by titanium peroxide gel |
Non-Patent Citations (1)
| Title |
|---|
| XIAO-GUANG ZHAO等: "Preparation of titanium peroxide and its selective adsorption property on cationic dyes", 《APPLIED SURFACE SCIENCE》, vol. 292, 12 December 2013 (2013-12-12), pages 2 - 2 * |
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