CN103691445A - Magnetic metal composite oxide catalyst for dye wastewater degradation - Google Patents
Magnetic metal composite oxide catalyst for dye wastewater degradation Download PDFInfo
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- CN103691445A CN103691445A CN201310726027.4A CN201310726027A CN103691445A CN 103691445 A CN103691445 A CN 103691445A CN 201310726027 A CN201310726027 A CN 201310726027A CN 103691445 A CN103691445 A CN 103691445A
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Abstract
The invention relates to a preparation method and an application of a catalyst for dye wastewater degradation. At present, most reported dye wastewater catalysts cannot meet actual requirements of industrial production; some catalysts are low in catalytic efficiency, and take a long time to degrade the wastewater; some catalysts need assistance of light when performing the catalysis functions; some catalysts performs catalytic degradation at a higher temperature; some catalysts are difficult to be separated from the wastewater after using, and difficult to be recycled. The magnetic metal composite oxide catalyst is synthesized by taking a ferric salt and a cerate as the main raw materials, doping a catalyst carrier in the materials, and adopting a sol-gel method. The synthesized catalyst is good in magnetism and stability, high in catalytic efficiency and easy to recycle, and can be used for quick degradation of multiple dye wastewater.
Description
Technical field
This patent relates to inorganic chemistry and field of waste water treatment.
Background technology
The whole world approximately will produce the dyestuff of 700,000 tons every year, estimates at 10%～15% dyestuff and is in use released in environment, causes serious pollution, and wherein 80% is azo dyes.Because the active quantities in waste water from dyestuff is very high and very difficult biodegradation, as not treated just discharge, not only directly harm humans is healthy, and heavy damage water body, soil and the ecosystem, very large to ambient influnence.Therefore studying effective processing method has extremely important realistic meaning.
Processing method to waste water from dyestuff is a lot, is summed up the combination that mainly contains Physical, chemical method, bioanalysis or these methods.In numerous processing methods, Fenton method, because its reaction condition is gentle, degradation efficiency is high, easy to operate, with low cost, becomes a kind of Main Means of dye wastewater treatment.But traditional Fenton method also comes with some shortcomings: reaction will be carried out under the environment of pH ≈ 3 left and right, needs to regulate the pH value of waste water before and after reaction, expends a large amount of bronsted lowry acids and bases bronsted lowries; The utilization rate of hydrogen peroxide has much room for improvement; Water outlet is because containing a large amount of iron ion Show Colors, and iron ion is difficult to reclaim and easily produce secondary pollution etc.Therefore the immobilization of iron ion becomes the research direction of Fenton technology.
With iron, be that solid catalyst replaces the ferrous ion in solution, form heterogeneous Fenton reaction system with hydrogen peroxide, both degradation of dye effectively, can overcome again the shortcomings of traditional homogeneous phase Fenton system, is a kind of dye wastewater treatment technology that has application prospect.Thereby the exploitation of heterogeneous Fenton catalyst is current study hotspot.And current reported most of catalyst all can not meet industrial actual demand: some catalyst efficiency is low, need could realize degraded for a long time; Some catalyst
The performance of performance needs the auxiliary of light; Some catalyst needs higher temperature just can play catalytic degradation effect; Some catalyst is difficult to separated with waste water after using, reclaim difficulty.Therefore develop a kind of can be at normal temperatures can fast degradation dyestuff, the catalyst that is easy to reclaim, can reuse has practical significance.
Summary of the invention
In order to solve above-mentioned drawback, the object of this invention is to provide a kind of magnetic metal composite oxide catalysts, have degradation of dye speed fast, reclaim convenient, repeatability high.
Another object of the present invention is to provide a kind of preparation method of above-mentioned catalyst.
In order to achieve the above object, the technical solution used in the present invention is, a kind of magnetic metal composite oxide catalysts, and its following material of filling a prescription forms:
1) ammonium ceric nitrate
2) ferric sulfate
3) ethanol
4) polyethylene glycol
5) other metallic carriers
In above-mentioned formula, take containing molysite and containing cerium salt be primary raw material, other carrier (Al adulterates
2o
3), adopt sol-gal process synthesizing magnetic metal composite oxide catalyst.Synthetic obtain thering is magnetic, good stability, catalytic efficiency are high, be easy to the solid catalyst that reclaims, for the fast degradation of multiple waste water from dyestuff.
The present invention's industrial actual demand of combining closely, adopts simple sol-gal process synthesizing new magnetic solid catalyst, replaces traditional homogeneous phase Fenton reagent, the efficient degradation for waste water from dyestuff at normal temperatures and under neutral environment.The catalyst of preparation has magnetic, utilizes the magnetic of catalyst to realize the separated of catalyst and waste liquid, is convenient to recovery and the recycling of catalyst, thereby reduces the degraded cost of waste water from dyestuff.
In described formula, the weight of each material is respectively:
1) ammonium ceric nitrate 3g
2) ferric sulfate 5g
3) ethanol 35mL
4) polyethylene glycol 7mL
5) other metallic carriers 2g
Described other metallic carriers are a kind of of alundum (Al2O3) or titanium dioxide.
The method of preparing magnetic metal composite oxide catalysts of the present invention is comprised of following steps:
1) in beaker, by above-mentioned weight, weigh successively ammonium ceric nitrate, ferric sulfate, ethanol, polyethylene glycol and other metallic carriers;
2) by said mixture magnetic agitation 10 minutes at room temperature, then flood 1 hour;
3) with ammoniacal liquor, the above-mentioned mixture through dipping is regulated to pH to 7～8;
4) said mixture of adjusted pH is put into baking oven, regulate 80 ℃ of oven temperatures, ageing 12 hours;
5) with glass bar, the pastel after ageing is stirred evenly and put into Muffle furnace, roasting is 2 hours at 450 ℃;
6) take out cool drying, obtain finished product.
The characteristic of this patent is:
(1) take containing molysite, containing cerium salt is primary raw material, then other carrier that adulterates, and prepares composite metal composite catalyst.
(2) improve traditional sol-gel process, simplify synthetic route.
(3) utilize the catalyst of preparation to realize the normal temperature of waste water, the fast degradation under nearly neutrallty condition.
(4) catalyst of preparing has magnetic, utilizes the magnetic of catalyst to realize Separation of Solid and Liquid, is convenient to the recovery of catalyst.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is made and being further illustrated.
Embodiment 1: in beaker, by above-mentioned weight, weigh successively ammonium ceric nitrate 3g, ferric sulfate 5g, ethanol 35mL, polyethylene glycol 7mL, and alundum (Al2O3) 2g, at room temperature magnetic agitation is 10 minutes, then flood 1 hour, with ammoniacal liquor, the above-mentioned mixture through dipping is regulated to pH to 7～8, the said mixture of adjusted pH is put into baking oven, regulate 80 ℃ of oven temperatures, ageing 12 hours, with glass bar, the pastel after ageing is stirred evenly and put into Muffle furnace, roasting is 2 hours at 450 ℃, takes out dry cooling standby.50mL methyl orange is added in 100mL beaker, add above-mentioned catalyst 0.2g, room temperature lower magnetic force stirs.After 10min, the centrifugation that takes a morsel, gets supernatant liquor and under 466nm, tests absorbance and calculate the rate of fading, and the rate of fading is greater than 99%.
Embodiment 2: in beaker, by above-mentioned weight, weigh successively ammonium ceric nitrate 3g, ferric sulfate 5g, ethanol 35mL, polyethylene glycol 7mL, and titanium dioxide 2g, at room temperature magnetic agitation is 10 minutes, then flood 1 hour, with ammoniacal liquor, the above-mentioned mixture through dipping is regulated to pH to 7～8, the said mixture of adjusted pH is put into baking oven, regulate 80 ℃ of oven temperatures, ageing 12 hours, with glass bar, the pastel after ageing is stirred evenly and put into Muffle furnace, roasting is 2 hours at 450 ℃, takes out dry cooling standby.50mL methyl orange is added in 100mL beaker, add above-mentioned catalyst 0.2g, room temperature lower magnetic force stirs.After 10min, the centrifugation that takes a morsel, gets supernatant liquor and under 466nm, tests absorbance and calculate the rate of fading, and the rate of fading is greater than 99%%.
Claims (5)
1. a magnetic metal composite oxide catalysts, is characterized in that synthesizing simply, and catalyst has magnetic, and fast degradation dyestuff, is easy to reclaim at normal temperatures.
2. according to the catalyst described in right 1, it is characterized in that the formula of catalyst is consisted of ammonium ceric nitrate, ferric sulfate, ethanol, polyethylene glycol and catalyst carrier.
3. according to the catalyst formulation described in right 2, by 3g ammonium ceric nitrate, 5g ferric sulfate, 35mL ethanol, 7mL polyethylene glycol and 2g catalyst carrier, formed.
4. catalyst carrier according to claim 3 is alundum (Al2O3) or titanium dioxide.
5. the synthetic method of catalyst according to claim 1 is sol-gal process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726027.4A CN103691445A (en) | 2013-12-25 | 2013-12-25 | Magnetic metal composite oxide catalyst for dye wastewater degradation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726027.4A CN103691445A (en) | 2013-12-25 | 2013-12-25 | Magnetic metal composite oxide catalyst for dye wastewater degradation |
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| CN201310726027.4A Pending CN103691445A (en) | 2013-12-25 | 2013-12-25 | Magnetic metal composite oxide catalyst for dye wastewater degradation |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007035241A2 (en) * | 2005-09-15 | 2007-03-29 | Honda Motor Co., Ltd. | Methods for synthesis of high quality carbon single-walled nanotubes |
| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
| CN103357412A (en) * | 2012-03-26 | 2013-10-23 | 江南大学 | Preparation method and application of magnetic ferrum-cerium-metal-oxide solid acid catalyst |
-
2013
- 2013-12-25 CN CN201310726027.4A patent/CN103691445A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007035241A2 (en) * | 2005-09-15 | 2007-03-29 | Honda Motor Co., Ltd. | Methods for synthesis of high quality carbon single-walled nanotubes |
| CN102327773A (en) * | 2011-06-13 | 2012-01-25 | 清华大学 | Preparation method of nano Fe3O4/CeO2 composite material and application thereof |
| CN103357412A (en) * | 2012-03-26 | 2013-10-23 | 江南大学 | Preparation method and application of magnetic ferrum-cerium-metal-oxide solid acid catalyst |
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Application publication date: 20140402 |