CN101406831A - Method for producing MnO2 supported catalyst as well as method of using the same and apparatus for treating waste water - Google Patents
Method for producing MnO2 supported catalyst as well as method of using the same and apparatus for treating waste water Download PDFInfo
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- CN101406831A CN101406831A CNA2008101991237A CN200810199123A CN101406831A CN 101406831 A CN101406831 A CN 101406831A CN A2008101991237 A CNA2008101991237 A CN A2008101991237A CN 200810199123 A CN200810199123 A CN 200810199123A CN 101406831 A CN101406831 A CN 101406831A
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Abstract
The invention discloses a method for preparing MnO2 supported catalysts, an application method thereof and a wastewater treatment device. The preparation method comprises the following steps: manganese acetate is prepared into a solution; one of activated carbon, active aluminium sesquioxide, white silica gel, a molecular sieve, zeolite or diatomite is taken as a carrier and dipped in the solution; and supported solid catalysts are prepared through dipping, evaporation, concentration, drying and roasting. A reactor of the wastewater treatment device is divided into a plurality of reaction spaces by baffles, and the catalysts exist as fluidized beds on every baffle. When the MnO2 supported catalysts prepared by the method are used in the reaction of degrading refractory organic matter through ozone catalytic oxidation, the contact time among the MnO2 supported catalysts, wastewater and ozone is between10 and 120 minutes, and the mass ratio of the adding amount of the catalysts to the wastewater in the reaction is between 1 to 200 and 1 to 20. The MnO2 supported catalysts prepared by the method have the characteristics of easy recovery, high repeat utilization property and high efficiency of catalyzing and degrading refractory organic matters.
Description
Technical field
The present invention relates to MnO
2The preparation method of loaded catalyst and using method, and use MnO
2Loaded catalyst is handled the reaction unit of organic wastewater, decomposes in the reactor of reaction unit and removes the difficult degradation toxic organics.
Background technology
Ozone is just progressively paid attention to by people with its distinctive advantage as a kind of strong oxidizer, is widely used in sterilization, and the deodorizing of the environment field such as eliminate the unusual smell of sterilization, the body surface of sterilization, the air of water.Since ozone was used in water treatment, because the equipment and the operating cost of ozone treatment are higher, though carried out extensive studies afterwards, except being used for drinking water disinfection, other practical application also seldom.In recent years, because the difficulty of in the water treatment practice, running into, shortage effective methods such as improvement as chlorine disinfection by-product, difficult for biological degradation or poisonous and harmful organic wastewater, raising along with the ozone generating apparatus performance, ozone technology has obtained attention again, and improves and developed the Ozone Water treatment technology.
Ozone is oxidant selectively, and can not oxidation all pollutants have significant limitation to reach the purpose of thorough destroy contaminants so simple ozone oxidation organic matter is used, and advanced oxidation processes in order to improve the treatment effect of technology, to develop.Metal oxide oxidation catalyst ozone degradation organic matter is the new technique that just grew up in recent years, development from ozone technology, base catalysis from the beginning is to photocatalysis, metal oxide oxidation catalyst, purpose promotes ozone to decompose exactly, strengthens the oxidability of ozone to produce free radical isoreactivity intermediate.But first problem that nearly all catalysis technique need solve is exactly the development of effective catalyst, and the metal oxide oxidation catalyst oxidation is no exception.
Problems such as catalyst is difficult to reclaim because homogeneous catalyst exists in use, medicament expense height, introducing impurity are so the use of heterogeneous catalysis receives much concern.Generally speaking, heterogeneous metal catalytic ozone is with Al
2O
3Perhaps active carbon is a carrier, and carried metal or metal oxide prepare heterogeneous catalysis thereon.
Summary of the invention
The objective of the invention is for solving in the homogeneous phase catalytic ozonation, catalyst is difficult to recycling, in the heterogeneous catalytic ozonation, to the not high problem of difficult organic matter degradation efficient, provides a kind of MnO
2The preparation method of loaded catalyst and catalytic ozonization water treatment method also provide a kind of wastewater treatment equipment.
MnO of the present invention
2The preparation method of loaded catalyst is as follows: with active carbon, active alundum (Al, white silica gel, molecular sieve, zeolite or diatomite is carrier, and catalyst is MnO
2Being mixed with mass percentage concentration with manganese acetate is 2%～20% solution, with a kind of impregnated in this solution in active carbon, active alundum (Al, white silica gel, molecular sieve, diatomite or the zeolite, at room temperature flooded 2～48 hours, following dry 1～10 hour after the evaporation and concentration at 105 ℃, place Muffle furnace 200 ℃～800 ℃ roasting temperature 1～10 hour, make MnO
2Loaded catalyst.
The preferred mass percentage concentration of above-mentioned manganese acetate solution is 5%.
Above-mentioned dip time is preferably 24 hours.
Following dry preferred 2 hours after the described evaporation and concentration at 105 ℃.
Describedly place Muffle furnace preferred 4 hours with 700 ℃ roasting temperature.
The present invention uses MnO
2Loaded catalyst is handled the reaction unit of organic wastewater, the reactor of this reaction unit is divided into 1～10 reaction compartment by dividing plate, the micro-pore aeration hole is arranged above each layer dividing plate, catalyst branch multilayer is arranged on the dividing plate in the reaction unit, there is the gas outlet upper end of reaction unit reactor, the air inlet of reaction unit reactor lower end is connected with ozone generator, and reaction unit reactor outer wall has the catalyst charge door.
Described reactor is made with stainless steel or polyvinyl chloride is made or lucite is made or made and liner resistance to oxidation corrosion-inhibiting coating with other materials.
Use MnO of the present invention
2The method of loaded catalyst ozone oxidation organic wastewater is MnO
2Be 10～120 minutes the time of contact of loaded catalyst and waste water and ozone, the mass ratio of waste water is 1: 200～1: 20 in the dosage of catalyst and the reaction, during reaction, ozone gas enters reactor by the micro-pore aeration of reactor bottom dividing plate, and the micro-pore aeration by dividing plate enters the upper strata reaction compartment step by step, and catalyst exists on each layer dividing plate with the form of fluid bed.
The present invention is the manganese source with the manganese acetate, and active carbon, alundum (Al, white silica gel, molecular sieve, zeolite or diatomite are carrier, have prepared MnO
2Loaded catalyst has enriched ozonation technology, has graininess better, easily reclaims, and is easy to subsequent treatment, and the advantage that reuse is high makes MnO
2Loaded catalyst is handled the difficult degradation pollutant at method for treating water bigger advantage.The present invention has designed with dividing plate a plurality of spaces of reaction unit layering, has prolonged the time of staying of ozone in system effectively, has increased the effective area of reaction, has improved reaction efficiency.The MnO of the present invention's preparation
2Loaded catalyst has the recovery of being easy to, and the reuse height is to unmanageable catalytic organism better degradation characteristics.
Description of drawings
Fig. 1 is that catalytic ozonation of the present invention is handled the organic wastewater reaction unit.
Wherein: 1 air inlet, 2 catalyst, 3 micro-pore aerations, 4 dividing plates, 5 gas outlets, 6 catalyst charge doors, 7 ozone generators.
The specific embodiment
Embodiment one
The MnO of present embodiment
2The preparation method of loaded catalyst is as follows: be carrier with the active carbon, active part is MnO
2It is 5% solution that manganese acetate is mixed with mass percentage concentration, active carbon be impregnated in this solution, at room temperature flooded 24 hours, following dry 2 hours after the evaporation and concentration at 105 ℃, place Muffle furnace 700 ℃ roasting temperature 4 hours, make solid catalyst, use before the catalyst washing 3 times.
Embodiment two
The MnO of present embodiment
2The preparation method of loaded catalyst is as follows in addition: with active alundum (Al, white silica gel, molecular sieve, zeolite or diatomite are carrier, and active part is MnO
2It is 5% solution that manganese acetate is mixed with mass percentage concentration, with active alundum (Al, white silica gel, molecular sieve, zeolite or diatomite are wherein a kind of to be impregnated in this solution, at room temperature floods 24 hours, following dry 2 hours after the evaporation and concentration at 105 ℃, place Muffle furnace 700 ℃ roasting temperature 4 hours, make solid catalyst, use before the catalyst washing 3 times.
Embodiment three
As shown in Figure 1, catalytic ozonation processing organic wastewater reaction unit of the present invention is made up of air inlet 1, catalyst 2, micro-pore aeration 3, dividing plate 4, gas outlet 5, catalyst charge door 6, ozone generator 7 etc.Reactor should be made with processing and fabricating such as stainless steel, polyvinyl chloride, lucite or with the material that other liners scribble the resistance to oxidation corrosion-inhibiting coating.During reaction, gas enters reactor by bottom aerator 1, enters the upper strata reaction compartment by the microporous aeration device on the dividing plate 43 step by step, and catalyst 2 exists on each layer dividing plate with the fluid bed form, tail gas is got rid of by gas outlet 5, handles through device for absorbing tail gas.
Embodiment four
The MnO of this enforcement
2The method of loaded catalyst ozonization water treatment, MnO
2Loaded catalyst and waste water, be 60 minutes the time of contact of ozone and solution, the mass ratio of waste water is 1: 100 in the dosage of catalyst and the reaction.Reactor is divided into 5 little reaction compartments by dividing plate, uses micro-pore aeration above each layer dividing plate.Catalyst divides 5 layers to be arranged on the dividing plate in the reaction unit.
Claims (8)
1. MnO
2The preparation method of loaded catalyst is characterized in that: with active carbon, active alundum (Al, white silica gel, molecular sieve, diatomite or zeolite is carrier, and catalyst is MnO
2Being mixed with mass percentage concentration with manganese acetate is 2%～20% solution, with a kind of impregnated in this solution in active carbon, active alundum (Al, white silica gel, molecular sieve, zeolite or the diatomite, at room temperature flooded 2～48 hours, following dry 1～10 hour after the evaporation and concentration at 105 ℃, place Muffle furnace 200 ℃～800 ℃ roasting temperature 1～10 hour, make MnO
2Loaded catalyst.
2. MnO according to claim 1
2The preparation method of loaded catalyst is characterized in that: the mass percentage concentration of described manganese acetate solution is 5%.
3. MnO according to claim 1
2The preparation method of loaded catalyst is characterized in that: described dip time is 24 hours.
4. MnO according to claim 1
2The preparation method of loaded catalyst is characterized in that: following dry 2 hours at 105 ℃ after the described evaporation and concentration.
5. MnO according to claim 1
2The preparation method of loaded catalyst is characterized in that: the described Muffle furnace that places was with 700 ℃ roasting temperature 4 hours.
6. one kind is used MnO
2Loaded catalyst is handled the reaction unit of organic wastewater, it is characterized in that: the reactor of this reaction unit is divided into 1～10 reaction compartment by dividing plate, above each layer dividing plate micro-pore aeration is arranged, catalyst branch multilayer is arranged on the dividing plate in the reaction unit, there is the gas outlet upper end of reaction unit reactor, the air inlet of reaction unit reactor lower end is connected with ozone generator, on the reactor outer wall of reaction unit the catalyst charge door is arranged.
7. reaction unit according to claim 6 is characterized in that: described reactor is made with stainless steel or polyvinyl chloride is made or lucite is made or made and liner resistance to oxidation corrosion-inhibiting coating with other materials.
8. one kind is used MnO
2The method of loaded catalyst O3 catalytic oxidation organic wastewater is characterized in that: described MnO
2Be 10～120 minutes the time of contact of loaded catalyst and waste water and ozone, the mass ratio of waste water is 1: 200～1: 20 in the dosage of catalyst and the reaction, during reaction, ozone gas enters reactor by the micro-pore aeration of reactor bottom dividing plate, and the micro-pore aeration by dividing plate enters the upper strata reaction compartment step by step, and catalyst exists on each layer dividing plate with the fluid bed form.
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|---|---|---|---|
| CNA2008101991237A CN101406831A (en) | 2008-10-14 | 2008-10-14 | Method for producing MnO2 supported catalyst as well as method of using the same and apparatus for treating waste water |
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| CNA2008101991237A CN101406831A (en) | 2008-10-14 | 2008-10-14 | Method for producing MnO2 supported catalyst as well as method of using the same and apparatus for treating waste water |
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| CN102001767A (en) * | 2010-10-26 | 2011-04-06 | 中国矿业大学(北京) | Advanced treatment system of coking wastewater |
| CN102114424A (en) * | 2010-12-29 | 2011-07-06 | 国电科学技术研究院 | Low-temperature smoke denitration SCR (silicon controlled rectifier) catalyst and preparation method |
| CN102502942A (en) * | 2011-11-02 | 2012-06-20 | 武汉森泰环保工程有限公司 | Multi-segment multielement catalytic oxidation treatment device |
| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
| CN102049253B (en) * | 2009-10-28 | 2013-03-06 | 中国石油化工集团公司 | Preparation method of special catalyst for waste water treatment by ozone oxidation |
| CN103100383A (en) * | 2013-01-30 | 2013-05-15 | 刘立文 | Catalyst for decomposing calcium sulfate to produce sulfuric acid and preparation method thereof |
| CN104437593A (en) * | 2014-11-24 | 2015-03-25 | 北京明信德诚环境设备有限公司 | Method for preparing manganese catalyst filter material |
| CN104874393A (en) * | 2015-04-30 | 2015-09-02 | 苏州清然环保科技有限公司 | Preparation method of ozone catalyst |
| CN104876403A (en) * | 2015-06-11 | 2015-09-02 | 武汉钢铁(集团)公司 | Process and device for advanced treatment and reuse of coking wastewater |
| CN105080523A (en) * | 2015-07-23 | 2015-11-25 | 武汉钢铁(集团)公司 | Preparation method for catalyst in catalytic ozonation for treating organic matter-containing wastewater |
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