CN106475098B - A method of magnetic photocatalyst is prepared by acid regeneration desiliconization mud cake - Google Patents
A method of magnetic photocatalyst is prepared by acid regeneration desiliconization mud cake Download PDFInfo
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- CN106475098B CN106475098B CN201510546834.7A CN201510546834A CN106475098B CN 106475098 B CN106475098 B CN 106475098B CN 201510546834 A CN201510546834 A CN 201510546834A CN 106475098 B CN106475098 B CN 106475098B
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- magnetic photocatalyst
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Abstract
The invention discloses a kind of methods for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake comprising following steps: dispersing desiliconization mud cake in ethyl alcohol, add polyethylene glycol, obtains desiliconization mud；Titanium source is added in the desiliconization mud, obtains the mixture of titanium source Yu desiliconization mud；After being 2~4 with the pH value that the mixed acid of hydrofluoric acid and nitric acid adjusts the mixture of the titanium source and desiliconization mud, is reacted at 70~90 DEG C, obtain no silicon magnetic photocatalyst presoma；The no silicon magnetic photocatalyst presoma is calcined under 450~700 DEG C of vacuum condition, is obtained containing TiO2Magnetic photocatalyst.The present invention provides a kind of methods that acid regeneration desiliconization mud cake prepares magnetic photocatalyst, and preparation process environmental pollution is small, are a kind of environmental-friendly friendly process processes.
Description
Technical field
The present invention relates to trade waste preparations to have magnetic TiO2The method of photochemical catalyst particularly belongs to waste and returns
Receive recycling, environmental protection scope.
Background technique
Currently, in the cold-rolling process of silicon steel, due to having the characteristics that pickling speed is fast, high-quality, acid regeneration is easy, salt
Pickling has become the mainstream technology in strip pickling, and the Si concentration in pickling silicon steel spent acid must will increase dramatically at that time.Acid
Washing waste liquid and entering regeneration technology need to add except silicon device.The process route that usual heavy steel rolling mill uses is by pickle liquor through molten
After iron flask reaction, 20% ammonium hydroxide adjustment pH value is added, then is passed through compressed air and generates ferric iron for the SiO in solution2Cladding,
Then flocculant is added, by the Fe (OH) of generation3Together with SiO2It settles together, to remove the SiO in pickling solution2.This process will
Produce a large amount of desiliconization mud cake.
The yield of this desiliconization mud cake is very big, and a medium scale pickling unit, yield can achieve
2000 tons/year or more, be 800 yuan of calculating according to per car waste disposal fee, the negative value investment applied to desiliconization mud cake more than 300,000/
Year；Simultaneously because the mud cake of this dark brown carries out burial processing, environmental pollution is caused, becomes many iron and steel enterprise's integrated treatments
An important topic.
Summary of the invention
The present invention provides a kind of method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake, using simply beating
Slurry, mixing, remove silicon, the processes such as sol-gel, vacuum calcining prepare have can magnetic recovery, the lesser magnetism of band gap
TiO2Optic catalytic composite material.
To achieve the goals above, technical scheme is as follows:
A method of magnetic photocatalyst being prepared by acid regeneration desiliconization mud cake comprising following steps:
It disperses desiliconization mud cake in ethyl alcohol, adds polyethylene glycol, obtain desiliconization mud；
Titanium source is added in the desiliconization mud, obtains the mixture of titanium source Yu desiliconization mud；
After being 2~4 with the pH value that the mixed acid of hydrofluoric acid and nitric acid adjusts the mixture of the titanium source and desiliconization mud,
It is reacted at 70~90 DEG C, obtains no silicon magnetic photocatalyst presoma；
The no silicon magnetic photocatalyst presoma is calcined under 450~700 DEG C of vacuum condition, is contained
TiO2Magnetic photocatalyst.
Preferably, the mass ratio of the desiliconization mud cake and ethyl alcohol is (10~15): 1.
Preferably, the additive amount of the polyethylene glycol is the 2~5% of desiliconization mud cake weight.
Preferably, the desiliconization mud and the mass ratio of titanium source are 1: (5~10).
Preferably, the titanium source is selected from tetrabutyl titanate, titanium tetrachloride, titanyl sulfate etc..
Preferably, in the mixed acid of the hydrofluoric acid and nitric acid, the volume ratio of hydrofluoric acid and nitric acid is 3: 1.
Preferably, the concentration of the hydrofluoric acid is 40%, and the concentration of the nitric acid is 0.01mol/L.
HF can be with SiO2Reaction, plays the purpose except silicon, HNO3Be added to provide H+, improve the speed of this reaction
Rate.
In invention, the higher desiliconization mud cake of iron-content by being simply beaten, mixing, removes silicon, colloidal sol-as template
The processes such as gel, vacuum calcining prepare have can magnetic recovery, the lesser magnetism TiO of band gap2Optic catalytic composite material,
In the composite material, TiO is removed2It outside, also include ferroso-ferric oxide or gamma-iron oxide.
The present invention provides a kind of method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake, preparation process
Environmental pollution is small, is a kind of environmental-friendly friendly process process.Present invention process is simple, easily operated, and continuity is strong, vacuum
Calcining obtains magnetic TiO higher, photocatalysis performance is good2Catalyst preferably realizes the problem of resource reclaim recycles.
The magnetic photocatalyst that the present invention obtains irradiates 20min under 500 DEG C of ultraviolet lights can make the acid fuchsin of 200mg/L
100% degradation and decolorization of solution, 210min photocatalytic activity is up to 80% under visible light.The TiO prepared with the method2Photocatalysis
Degradation adds 3gTiO in every liter of waste water containing the COD and ammonia nitrogen in sour industrial wastewater2, illumination 3 hours, when pH=5, degradation
Rate is respectively 94.1% and 84.5%, shows higher photocatalysis performance.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A method of magnetic photocatalyst being prepared by acid regeneration desiliconization mud cake comprising following steps:
It disperses desiliconization mud cake in ethyl alcohol, adds polyethylene glycol, obtain desiliconization mud；
Titanium source is added in the desiliconization mud, obtains the mixture of titanium source Yu desiliconization mud；
After being 2~4 with the pH value that the mixed acid of hydrofluoric acid and nitric acid adjusts the mixture of the titanium source and desiliconization mud,
It is reacted at 70~90 DEG C, obtains no silicon magnetic photocatalyst presoma；
The no silicon magnetic photocatalyst presoma is calcined under 450~700 DEG C of vacuum condition, is contained
TiO2Magnetic photocatalyst.
Preferably, the mass ratio of the desiliconization mud cake and ethyl alcohol is (10~15): 1.
Preferably, the additive amount of the polyethylene glycol is the 2~5% of desiliconization mud cake weight.
Preferably, the desiliconization mud and the mass ratio of titanium source are 1: (5~10).
Preferably, the titanium source is selected from tetrabutyl titanate, titanium tetrachloride, titanyl sulfate etc..
Preferably, in the mixed acid of the hydrofluoric acid and nitric acid, the volume ratio of hydrofluoric acid and nitric acid is 3: 1.
Preferably, the concentration of the hydrofluoric acid is 40%, and the concentration of the nitric acid is 0.01mol/L.
Embodiment 1
(a) desiliconization mud cake is distributed to heat in ethyl alcohol and is beaten, the adding proportion of mud cake and ethyl alcohol is 10: 1, is added 2%
The PEG of wt forms the preferable desiliconization mud of dispersibility；
It (b) is to continue to be beaten in 1: 10 addition tetrabutyl titanate according to mass ratio by (a) resulting desiliconization mud and titanium source
Stirring, obtains the mixture of titanium source Yu desiliconization mud；
(c) HF: HNO is utilized3=3: 1 nitration mixture, regulates and controls the pH=3 of mixture in (b), and reacts 4h at 80 DEG C, obtains
To no silicon magnetic photocatalyst presoma；
(d) presoma in (c) is calcined into 5h under 450 DEG C of vacuum conditions, obtains having magnetic anatase TiO2Light
Catalyst.
Embodiment 2
(a) desiliconization mud cake is distributed to heat in ethyl alcohol and is beaten, the adding proportion of mud cake and ethyl alcohol is 12: 1, is added 5%
The PEG of wt forms the preferable desiliconization mud of dispersibility；
It (b) is to continue to be beaten in 1: 7.5 addition titanium tetrachloride according to mass ratio by (a) resulting desiliconization mud and titanium source
Stirring, obtains the mixture of titanium source Yu desiliconization mud；
(c) HF: HNO is utilized3=3: 1 nitration mixture, regulates and controls the pH=2 of mixture in (b), and reacts 4h at 80 DEG C, obtains
To no silicon magnetic photocatalyst presoma；
(d) presoma in (c) is calcined into 4h under 500 DEG C of vacuum conditions, obtains having magnetic anatase tio2 light
Catalyst.
Embodiment 3
(a) desiliconization mud cake is distributed to heat in ethyl alcohol and is beaten, the adding proportion of mud cake and ethyl alcohol is 15: 1, is added
The PEG of 2.5%wt forms the preferable desiliconization mud of dispersibility；
It (b) is to continue mashing in 1: 8 addition titanyl sulfate and stir according to mass ratio by (a) resulting desiliconization mud and titanium source
It mixes, obtains the mixture of titanium source Yu desiliconization mud；
(c) HF: HNO is utilized3=3: 1 nitration mixture, regulates and controls the pH=4 of mixture in (b), and reacts 4h at 80 DEG C, obtains
To no silicon magnetic photocatalyst presoma；
(d) presoma in (c) is calcined into 4h under 600 DEG C of vacuum conditions, obtains that there is magnetic anatase TiO2Light is urged
Agent.
Embodiment 4
(a) desiliconization mud cake is distributed to heat in ethyl alcohol and is beaten, the adding proportion of mud cake and ethyl alcohol is 15: 1, is added 2%
The PEG of wt forms the preferable desiliconization mud of dispersibility；
It (b) is to continue to be beaten in 1: 10 addition tetrabutyl titanate according to mass ratio by (a) resulting desiliconization mud and titanium source
Stirring, obtains the mixture of titanium source Yu desiliconization mud；
(c) HF: HNO is utilized3=3: 1 nitration mixture, regulates and controls the pH=2 of mixture in (b), and reacts 4h at 80 DEG C, obtains
To no silicon magnetic photocatalyst presoma；
(d) presoma in (c) is calcined into 5h under 700 DEG C of vacuum conditions, obtains having magnetic anatase-rutile
Mix TiO2Photochemical catalyst.
In conclusion only presently preferred embodiments of the present invention, is not used to limit the scope of implementation of the present invention, it is all according to
Equivalent changes and modifications carried out by shape described in scope of the invention as claimed, construction, feature and spirit should be included in this
In the scope of the claims of invention.
Claims (7)
1. a kind of method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake, which comprises the steps of:
It disperses desiliconization mud cake in ethyl alcohol, adds polyethylene glycol, obtain desiliconization mud；
Titanium source is added in the desiliconization mud, obtains the mixture of titanium source Yu desiliconization mud；
After being 2~4 with the pH value that the mixed acid of hydrofluoric acid and nitric acid adjusts the mixture of the titanium source and desiliconization mud, 70~
It is reacted at 90 DEG C, obtains no silicon magnetic photocatalyst presoma；
The no silicon magnetic photocatalyst presoma is subjected to calcining 5h, in 500 DEG C of vacuum conditions under 450 DEG C of vacuum condition
Lower calcining 4h, 4h is calcined under 600 DEG C of vacuum conditions or carries out calcining 5h under 700 DEG C of vacuum condition, obtain containing TiO2
Magnetic photocatalyst.
2. the method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake as described in claim 1, which is characterized in that institute
The mass ratio for stating desiliconization mud cake and ethyl alcohol is (10~15): 1.
3. the method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake as described in claim 1, which is characterized in that institute
The additive amount for stating polyethylene glycol is the 2~5% of desiliconization mud cake weight.
4. the method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake as described in claim 1, which is characterized in that institute
The mass ratio for stating desiliconization mud and titanium source is 1: (5~10).
5. the method as described in claim 1 or 4 for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake, feature exist
In the titanium source is selected from least one of tetrabutyl titanate, titanium tetrachloride, titanyl sulfate.
6. the method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake as described in claim 1, which is characterized in that institute
In the mixed acid for stating hydrofluoric acid and nitric acid, the volume ratio of hydrofluoric acid and nitric acid is 3: 1.
7. the method for preparing magnetic photocatalyst by acid regeneration desiliconization mud cake as claimed in claim 6, which is characterized in that institute
The concentration for stating hydrofluoric acid is 40%, and the concentration of the nitric acid is 0.01mol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807263A (en) * | 2006-02-21 | 2006-07-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black using desilicified mud cake |
| CN102863029A (en) * | 2012-09-25 | 2013-01-09 | 上海应用技术学院 | Method of using acid regeneration desiliconized mud cakes to prepare superfine iron oxide red |
| CN102863030A (en) * | 2012-09-25 | 2013-01-09 | 上海应用技术学院 | Method for preparing nanometer ferroferric oxide through acid-regenerating desilicated mud cake |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100491091B1 (en) * | 2002-09-30 | 2005-05-24 | 코스모정밀화학 주식회사 | A Preparation Method Of Zeolite |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807263A (en) * | 2006-02-21 | 2006-07-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black using desilicified mud cake |
| CN102863029A (en) * | 2012-09-25 | 2013-01-09 | 上海应用技术学院 | Method of using acid regeneration desiliconized mud cakes to prepare superfine iron oxide red |
| CN102863030A (en) * | 2012-09-25 | 2013-01-09 | 上海应用技术学院 | Method for preparing nanometer ferroferric oxide through acid-regenerating desilicated mud cake |
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