CN103894236A - Ceramsite carrier applicable to fenton fluidized bed and having catalytic action, preparation method and application of carrier - Google Patents
Ceramsite carrier applicable to fenton fluidized bed and having catalytic action, preparation method and application of carrier Download PDFInfo
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- CN103894236A CN103894236A CN201410095647.7A CN201410095647A CN103894236A CN 103894236 A CN103894236 A CN 103894236A CN 201410095647 A CN201410095647 A CN 201410095647A CN 103894236 A CN103894236 A CN 103894236A
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- fenton
- ceramsite
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- ceramsite carrier
- haydite
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Abstract
The invention discloses a ceramsite carrier applicable to a fenton fluidized bed and having a catalytic action, a preparation method and application of the carrier. The method comprises the following steps: dissolving metal salt with a fenton reaction catalytic activity in water, mixing a metal salt aqueous solution with a ceramsite raw material, preparing a ceramsite blank body by using a granulator, and sintering the ceramsite blank body at high temperatures to obtain a particulate ceramsite carrier containing metal oxide. The particulate ceramsite carrier containing metal oxide can be used for independently processing water and also can be used together with other methods. After adding the ceramsite carrier, the fenton fluidized bed is capable of removing organic pollutants in the water more efficiently, thus the oxidizing capacity of the fenton fluidized bed is obviously improved; under the condition of same processing effect, by adding the particulate ceramsite carrier containing metal oxide, the utilization rate and the oxidizing efficiency of a fenton reaction medicament can be greatly improved under the conditions with the same processing effect, thus the dosage of hydrogen peroxide is reduced by about 50%, and the operation cost is saved; the ceramsite carrier containing catalytic components can be repeatedly used and is free of secondary pollution.
Description
Technical field
The invention belongs to catalytic action ceramsite carrier preparing technical field, particularly a kind of Fenton fluid bed that is applied to has ceramsite carrier of catalytic action and preparation method thereof and application.
Background technology
Fenton (Fenton) oxidation technology is current domestic and international application a kind of wastewater treatment high-level oxidation technology comparatively widely, is characterized in hydrogen peroxide (H
2o
2) at Fe
2+catalytic action under can produce the hydroxyl radical free radical (OH) in a large number with extremely strong oxidisability.The oxidizing potential of hydroxyl radical free radical, up to+2.80V, is only second to fluorine, the therefore organic matter of difficult for biological degradation in oxidable Decomposition Wastewater, thus reach the object of removing difficult for biological degradation organic pollution in waste water.Fenton oxidation method is specially adapted to the wastewater treatment that contains refractory organic, and is applied to gradually percolate, in the processing engineering of the waste water such as dyestuff, paper pulp papermaking, daily use chemicals, agricultural chemicals, has good application prospect.
Fenton oxidation technology has that oxidability is strong, easy to use, simple to operate, reaction fast, can produce the advantages such as flocculation.The occupation mode of this technology can be divided into independent use or with other processing method couplings.Use is mainly applicable to the follow-up advanced treating of low-concentration organic waste water, percolate, the processing of difficult degradation persistent pollutant separately; Coupling mode mainly plays the toxicity that reduces waste water, improves the effect such as the biodegradability of waste water or the operating load of minimizing subsequent treatment process.
In practical engineering application, Fenton fluidization is a technology that improves Fenton efficiency.Fenton's reaction is applied to the system in fluidized-bed reactor by it.Hydrogen peroxide joins in high-speed circulating system on the one hand, reduce hydrogen peroxide concentration, reduce the invalid degraded of hydrogen peroxide, the catalyst that is carried in addition fluid bed surface can participate in catalytic decomposition hydrogen peroxide, reduce adding of iron ion, reduce the processing cost of iron containing sludge, and adopt the reaction system of fluid bed, the contact problems that solved catalyst and catalysant and be decomposed between thing can improve catalytic oxidation efficiency under the prerequisite of not adding more multiple medicines agent.
Therefore, exploitation one is applicable to Fenton fluid bed, and excellent catalytic effect, can reuse, non-secondary pollution, and the carrier that can reduce processing cost just can address the above problem.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of Fenton fluid bed that is applied to have ceramsite carrier of catalytic action and preparation method thereof and application.This preparation method by adding the component with catalytic activity as its raw materials for production in haydite production process, prepare the ceramsite carrier of Fenton's reaction catalytic action, improve Fenton treatment effeciency, there is not secondary pollution, reduce Fenton treatment agent dosage, thereby reduce the operating cost of Fenton fluidized bed processing waste water.
The containing metal oxide particulate ceramsite carrier that provides said method to prepare is provided the object of the invention.
Object of the present invention realizes by following proposal:
A preparation method for containing metal oxide particulate ceramsite carrier, comprises following concrete steps:
Soluble in water the slaine with Fenton's reaction catalytic activity, obtain aqueous metal salt, aqueous metal salt is mixed with haydite materials, utilize comminutor to prepare haydite idiosome, high temperature sintering, obtains containing metal oxide particulate ceramsite carrier.
In said method, the slaine with Fenton's reaction catalytic activity is soluble in water, obtains aqueous metal salt, is used for replacing the water of manufacturing haydite blank, and makes haydite blank, through high temperature sintering, obtains the catalytic ceramsite carrier of containing metal oxide particulate.
In said method, described in there is Fenton's reaction catalytic activity slaine refer at least one in metal sulfate and metal nitrate; Described haydite materials comprises more than one in flyash, kaolin and swelling agent.
In said method, described in there is Fenton's reaction catalytic activity slaine comprise more than one in manganese sulfate, cobaltous sulfate, copper sulphate, manganese nitrate, cobalt nitrate and copper nitrate.
In said method, the concentration of described aqueous metal salt is 1 wt% ~ 40 wt%; Described have the slaine of Fenton's reaction catalytic activity and the mass ratio of haydite materials for (0.004 ~ 0.1): 1.
In said method, in described high temperature sintering, temperature is 1100 ~ 1250 ℃; The particle diameter of described haydite idiosome is 0.1 ~ 3.0 mm; The described haydite idiosome for preparing refers to prepare haydite idiosome by comminutor.
The containing metal oxide particulate ceramsite carrier that said method prepares.
The active component of described containing metal oxide particulate ceramsite carrier is MnO
2, CuO, CoO and Co
3o
4in at least one, carrier is haydite.In the time carrying out Fenton's reaction, this composition had both played the catalytic action that improves Fenton oxidation efficiency, again because it is solid particle, thereby can reuse, and minimizing secondary pollution is difficult for again running off and causes secondary pollution to waste water.
The application of above-mentioned containing metal oxide particulate haydite in water treatment.
This containing metal oxide particulate haydite both can be processed water separately, also can with additive method coupling.Add after this haydite, Fenton fluid bed can more effectively be removed organic pollutants, its oxidability is significantly improved, under the condition of same treatment effect, can greatly improve utilization rate and the oxidation efficiency of Fenton's reaction medicament, the dosage that has reduced hydrogen peroxide nearly 50%, has saved operating cost; Ceramsite carrier containing catalytic active component used, can reuse, and does not have secondary pollution.
Mechanism of the present invention is:
The raw material that haydite is produced is all dusty raw materials, in production process, must, by mixing with water, form haydite blank, forms haydite through sintering.The present invention is by soluble in water the slaine with Fenton's reaction catalytic activity, obtain the aqueous solution of slaine, be used for replacing the water of manufacturing haydite blank, and make haydite blank, through high temperature sintering, obtain the catalytic ceramsite carrier of containing metal oxide particulate, the present invention is directed to product and be applied to Fenton fluid bed, make specific area moderate, catalysis load area is large and be conducive to form the ceramsite carrier of fluidisation state, and the particle diameter of this ceramsite carrier is 0.1 ~ 3.0mm.
Slaine in metal salt solution during higher than 800 ℃, is decomposed into the gases such as metal oxide and sulfur dioxide, nitrogen dioxide in temperature, and gas discharges after treatment with the tail gas of heating furnace.And the metal oxide being decomposed to form, particle is tiny, is uniformly distributed in haydite, has improved the activity of metal oxide active component.
The present invention, by slaine is soluble in water, is mixed to form haydite stock with haydite materials; Slaine is at high temperature decomposed into the gases such as metal oxide, sulfur dioxide or nitrogen dioxide, gas discharges after treatment with the tail gas of heating furnace, and the metal oxide particle being decomposed to form is tiny, be uniformly distributed in haydite, improve the activity of metal oxide active component.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) slaine that the present invention has Fenton's reaction catalytic activity by handle is water-soluble, prepares haydite stock together with haydite materials; In high-temperature sintering process, it is tiny that slaine decomposes the metal oxide particle obtaining, and is uniformly distributed in haydite, improved the utilization rate of metal oxide active component, reduced production cost.
(2) ceramsite catalyst that prepared by the present invention can be reused, thereby reduces secondary pollution, reduces Fenton fluid bed operating cost, more easily realizes large-scale industrial production.
(3) containing metal oxide particulate ceramsite carrier of the present invention both can be processed water separately, also can with additive method coupling.Add after this ceramsite carrier, Fenton fluid bed can more effectively be removed organic pollutants, and its oxidability is significantly improved.Under the condition of same treatment effect, by adding containing metal oxide particulate ceramsite carrier of the present invention, can greatly improve utilization rate and the oxidation efficiency of Fenton's reaction medicament, the dosage that has reduced hydrogen peroxide nearly 50%, has saved operating cost; Ceramsite carrier containing catalytic active component used, also can reuse, and does not have secondary pollution.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Select flyash, kaolin, swelling agent as haydite materials (above raw material is the dusty material that general haydite is produced).
Soluble in water to manganese sulfate and cobaltous sulfate; prepare solution; wherein; manganese sulfate, cobalt sulfate concentration are respectively 1 wt%, 1 wt%; metal salt solution is mixed with haydite materials; recycling comminutor prepares the haydite that particle diameter is 0.3 ~ 0.5mm, and sintering at 1150 ℃, prepares containing metal oxide particulate ceramsite carrier.
The quality of manganese sulfate used and cobaltous sulfate and with the mass ratio of haydite materials be 0.004:1.
Utilize the waste water after biochemical treatment of Fenton fluidized bed processing refuse landfill.Use general carrier, under Fenton's reaction optimum condition (hydrogen peroxide dosage is 0.048mol/L, and hydrogen peroxide dosage and ferrous dosage mol ratio are 1.67:1), waste water COD
crbe down to 393mg/L from 1240mg/L, clearance is about 68.3%; Use after containing metal oxide particulate ceramsite carrier, under identical ferrous dosage condition, hydrogen peroxide dosage can be down to 0.024mol/L, waste water COD
crbe down to 397mg/L from 1240mg/L, clearance is about 68.0%, can save 50% hydrogen peroxide consumption under identical treatment effect.
Embodiment 2
Select flyash, kaolin, swelling agent as haydite materials (above raw material is the dusty material that general haydite is produced).
Soluble in water to manganese sulfate or manganese nitrate; prepare solution; wherein manganese nitrate, concentration of copper sulfate are respectively 15 wt%, 10 wt%; metal salt solution is mixed with haydite materials; recycling comminutor prepares the haydite that particle diameter is 2.0 ~ 3.0 mm; sintering at 1200 ℃, prepares containing metal oxide particulate ceramsite carrier.
The gross mass of manganese nitrate used and copper sulphate and the mass ratio of haydite materials are 0.07:1.
Utilize Fenton fluidized bed processing printworks dyeing waste water, under Fenton's reaction optimum condition (hydrogen peroxide dosage is 0.036mol/L, and hydrogen peroxide dosage and ferrous dosage mol ratio are 1.25:1), waste water COD
crbe down to 201mg/L from 740mg/L, clearance is about 72.8%; Use after containing metal oxide particulate ceramsite carrier, under identical ferrous dosage condition, hydrogen peroxide dosage can be down to 0.024mol/L, waste water COD
crbe down to 212mg/L from 740mg/L, clearance is about 71.4%, can save 33% hydrogen peroxide consumption under identical treatment effect.
Embodiment 3
Select flyash, kaolin, swelling agent as haydite materials (above raw material is the dusty material that general haydite is produced).
Soluble in water to manganese sulfate, manganese nitrate; prepare solution; wherein manganese sulfate, manganese nitrate concentration are respectively 10 wt%, 10 wt%; metal salt solution is mixed with haydite materials; recycling comminutor prepares the haydite that particle diameter is 0.5 ~ 2.0 mm; sintering at 1200 ℃, prepares containing metal oxide particulate ceramsite carrier.
The gross mass of manganese sulfate used and manganese nitrate and the mass ratio of haydite materials are 0.1:1.
Utilize Fenton fluidized bed processing pharmaceutical factory pharmacy waste water, under Fenton's reaction optimum condition (hydrogen peroxide dosage is 0.040mol/L, and hydrogen peroxide dosage and ferrous dosage mol ratio are 1:1), waste water COD
crbe down to 136mg/L from 326mg/L, clearance is about 58.3%; Use after containing metal oxide particulate ceramsite carrier, under identical ferrous dosage condition, hydrogen peroxide dosage can be down to 0.030mol/L, waste water COD
crbe down to 139mg/L from 326mg/L, clearance is about 57.3%, can save 25% hydrogen peroxide consumption under identical treatment effect.
Embodiment 4
Select flyash, kaolin, swelling agent as haydite materials (above raw material is the dusty material that general haydite is produced).
Soluble in water to manganese sulfate and cobaltous sulfate; prepare solution; wherein; manganese sulfate, cobalt sulfate concentration are respectively 1 wt%, 1 wt%; metal salt solution is mixed with haydite materials; recycling comminutor prepares the haydite that particle diameter is 0.3 ~ 0.5mm, and sintering at 1150 ℃, prepares containing metal oxide particulate ceramsite carrier.
The quality of manganese sulfate used and cobaltous sulfate and with the mass ratio of haydite materials be 0.004:1.
Utilize the simulated wastewater (Potassium Hydrogen Phthalate solution) of Fenton fluidized bed processing laboratory configuration to carry out carrier recycling test.The initial COD of waste water
cr=480mg/L, through after Fenton fluidized bed processing for the first time, water outlet COD
cr=154mg/L, clearance is about 67.9%; By after twice of carrier flushing, continue treatment of simulated waste water, the water outlet COD after Fenton fluidized bed processing for the second time with clear water
cr=162mg/L, clearance is about 66.3%; With clear water, carrier is rinsed after twice again, continue treatment of simulated waste water, the water outlet COD after Fenton fluidized bed processing for the third time
cr=167mg/L, clearance is about 65.2%.
Claims (8)
1. one kind has the preparation method of the Fenton fluid bed ceramsite carrier of catalytic action; it is characterized in that; comprise following concrete steps: soluble in water the slaine with Fenton's reaction catalytic activity; obtain aqueous metal salt; aqueous metal salt is mixed with haydite materials; utilize comminutor to prepare haydite idiosome, high temperature sintering, obtains containing metal oxide particulate ceramsite carrier.
2. the preparation method of a kind of Fenton fluid bed ceramsite carrier with catalytic action according to claim 1, is characterized in that: described in there is Fenton's reaction catalytic activity slaine refer at least one in metal sulfate and metal nitrate; Described haydite materials comprises more than one in flyash, kaolin and swelling agent.
3. the preparation method of a kind of Fenton fluid bed ceramsite carrier with catalytic action according to claim 1, is characterized in that: described in there is Fenton's reaction catalytic activity slaine comprise more than one in manganese sulfate, cobaltous sulfate, copper sulphate, manganese nitrate, cobalt nitrate and copper nitrate.
4. the preparation method of a kind of Fenton fluid bed ceramsite carrier with catalytic action according to claim 1, is characterized in that: the concentration of described aqueous metal salt is 1 wt% ~ 40 wt%; Described have the slaine of Fenton's reaction catalytic activity and the mass ratio of haydite materials for (0.004 ~ 0.1): 1.
5. the preparation method of a kind of Fenton fluid bed ceramsite carrier with catalytic action according to claim 1, is characterized in that: in described high temperature sintering, temperature is 1100 ~ 1250 ℃; The particle diameter of described haydite idiosome is 0.1 ~ 3.0 mm.
6. prepare a kind of ceramsite carrier that is applied to Fenton fluid bed and has catalytic action by the arbitrary described preparation method of claim 1-5.
7. a kind of ceramsite carrier that is applied to Fenton fluid bed and has catalytic action according to claim 6, is characterized in that: in described containing metal oxide particulate ceramsite carrier, catalytic active component comprises MnO
2, CuO, CoO and Co
3o
4in more than one.
8. the ceramsite carrier described in claim 6 or 7 is applied to the wastewater treatment of Fenton fluid bed.
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| CN104815696A (en) * | 2015-04-15 | 2015-08-05 | 华南理工大学 | Metal oxalate nanofiber and preparation method as well as application thereof |
| CN105461103A (en) * | 2015-06-30 | 2016-04-06 | 广州市华绿环保科技有限公司 | Fenton fluidized bed wastewater treatment method using iron oxide red as carrier |
| CN105688930A (en) * | 2016-02-26 | 2016-06-22 | 煤炭科学技术研究院有限公司 | Coal-ash-based ozone oxidation catalyst and preparation method and application thereof |
| CN106914269A (en) * | 2015-12-28 | 2017-07-04 | 南京源泉环保科技股份有限公司 | A kind of efficient Fenton's reaction catalyst and preparation method and application |
| CN109772285A (en) * | 2019-03-01 | 2019-05-21 | 北京航空航天大学 | A kind of preparation method and application of heterogeneous light Fenton catalyst |
| CN109898321A (en) * | 2019-02-27 | 2019-06-18 | 天津科技大学 | It is a kind of to load Fe using carboxymethyl cellulose2+To the method for pulp fiber surface oxidation |
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| CN109898321A (en) * | 2019-02-27 | 2019-06-18 | 天津科技大学 | It is a kind of to load Fe using carboxymethyl cellulose2+To the method for pulp fiber surface oxidation |
| CN109772285A (en) * | 2019-03-01 | 2019-05-21 | 北京航空航天大学 | A kind of preparation method and application of heterogeneous light Fenton catalyst |
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Application publication date: 20140702 |