CN109734172A - A kind of method of iron complexing class Fenton's reaction processing organic wastewater - Google Patents
A kind of method of iron complexing class Fenton's reaction processing organic wastewater Download PDFInfo
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- CN109734172A CN109734172A CN201910192552.XA CN201910192552A CN109734172A CN 109734172 A CN109734172 A CN 109734172A CN 201910192552 A CN201910192552 A CN 201910192552A CN 109734172 A CN109734172 A CN 109734172A
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Abstract
The present invention provides a kind of methods of iron complexing class Fenton's reaction processing organic wastewater, belong to environmental wastewater and administer field.The following steps are included: by oxalic acid, FeSO4·7H2O and calper calcium peroxide are added sequentially in organic wastewater, carry out degradation reaction.Mesoxalic acid and FeSO of the present invention4·7H2O can generate ferric oxalate complexes, and calper calcium peroxide is the solids source of hydrogen peroxide, be readily transported storage, ferric oxalate complexes and CaO2Reaction obtains Fenton-like system, and stablizing for OH can be promoted to generate, avoid H2O2Disproportionation decompose, improve H2O2Utilization rate, while the addition of oxalic acid can extend free state Fe2+/Fe3+There are the time, and then the precipitating of iron cement is reduced, to improve Fenton-like system to the removal efficiency of useless Organic substance in water.Compared with traditional Fenton method, it can apply in the organic wastewater that pH value is 3~11.
Description
Technical field
The present invention relates to environmental wastewater Treatment process fields more particularly to a kind of iron complexing class Fenton's reaction to handle organic waste
The method of water.
Background technique
All the time, industrial organic waste water is one of the important sources of China's water environment pollution, and such organic wastewater is usual
Concentration height, complicated component, containing a large amount of difficult organic matters difficult to degrade, coloration height has peculiar smell, is easy to that water quality is caused to dislike
Change, and the organic matter in organic wastewater is easily accumulated in water body, is migrated, and type is more with quantity, pollution range extensively, harmfulness
Greatly.Therefore, the degradation of organic wastewater has become urgent problem to be solved.
Traditional physical method, bioanalysis and chemical method has been unable to meet to the requirement of the efficient process of organic wastewater, meet the tendency of and
Raw high-level oxidation technology (AOPs) has obviously advantage in processing organic wastewater with difficult degradation thereby field.It is wherein most widely used
General is Fenton oxidation method and embryonic stem-like cells oxidizing process.Fenton oxidation method is in acid such as CN 200910024817
By ferrous ion (Fe under the conditions of property2+) and H2O2Fenton reaction, i.e. Fe occurs2+Catalyzing hydrogen peroxide, which decomposes, generates hydroxyl free
Base (OH), OH have high oxidisability, non-selective can be difficult to degrade by conventional physical, biological and chemical method
Oxidation operation degradation, to improve the treatment effeciency of organic wastewater, still, the use scope of Fenton process is partially narrow, mainly
It carries out under acidic conditions, H2O2Disproportionation decomposition can occur in the reaction causes utilization rate to decline, and stores transport not
Just；In addition, source of iron recycling is difficult, it is easily converted to iron precipitating, influences effluent quality.Embryonic stem-like cells as an improvement
Fenton system is gradually risen in recent years, for example, CN 201410561933 proposes a kind of persulfate-calper calcium peroxide pair
The method that oxidant removes multiring aromatic hydrocarbon substance methyl naphthalene puts into dual oxidants into water, realizes the drop to organic substance
Solve effect.But there are the yield of living radical is lower, the not high problem of the degradation efficiency of organic wastewater.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of methods of iron complexing class Fenton's reaction processing organic wastewater.
Method provided by the invention is high to the degradation efficiency of useless Organic substance in water.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of methods of iron complexing class Fenton's reaction processing organic wastewater, comprising the following steps:
By oxalic acid, FeSO4·7H2O and calper calcium peroxide are added sequentially in organic wastewater, carry out degradation reaction.
Preferably, the oxalic acid and FeSO4·7H2The molar ratio of O is 1:1~1:9.
Preferably, the oxalic acid, FeSO4·7H2The molar ratio of O and calper calcium peroxide is 1:2:0.5~1:2:4.
Preferably, the temperature of the degradation reaction is room temperature.
Preferably, the organic wastewater includes industrial organic waste water and life organic wastewater.
Preferably, the pH value of the organic wastewater is 3~11.
Preferably, methyl orange is contained in the organic wastewater, the concentration of the methyl orange is 0.15~0.5mM.
The present invention provides a kind of methods of iron complexing class Fenton's reaction processing organic wastewater, comprising the following steps: will be careless
Acid, FeSO4·7H2O and calper calcium peroxide are added sequentially in organic wastewater, carry out degradation reaction.Mesoxalic acid of the present invention and
FeSO4·7H2O can generate ferric oxalate complexes, and calper calcium peroxide is the solids source of hydrogen peroxide, be readily transported storage, ferric oxalate
Complex compound and CaO2Reaction obtains Fenton-like system, and stablizing for OH can be promoted to generate, avoid H2O2Disproportionation decompose, mention
High H2O2Utilization rate, while the addition of oxalic acid can extend free state Fe2+/Fe3+There are the time, and then reduce the heavy of iron cement
It forms sediment, to improve Fenton-like system to the removal efficiency of useless Organic substance in water.Compared with traditional Fenton method, pH can apply to
Value is in 3~11 organic wastewater.Embodiment statistics indicate that, the present invention is up to 99.1% to the degradation rate of organic wastewater.
Detailed description of the invention
Fig. 1 is the schematic diagram that iron of the present invention is complexed that class Fenton's reaction handles organic wastewater；
Fig. 2 is each system in embodiment 1 to the degradation rate curve of methyl orange；
Fig. 3 is each system in embodiment 2 to the degradation rate curve of methyl orange；
Fig. 4 is each system in embodiment 3 to the degradation rate curve of methyl orange；
Fig. 5 is each system in embodiment 4 to the degradation rate curve of methyl orange.
Specific embodiment
The present invention provides a kind of methods of iron complexing class Fenton's reaction processing organic wastewater, comprising the following steps:
By oxalic acid, FeSO4·7H2O and calper calcium peroxide are added sequentially in organic wastewater, carry out degradation reaction.
In the present invention, the oxalic acid and FeSO4·7H2The molar ratio of O is preferably 1:1~1:9.
In the present invention, the oxalic acid, FeSO4·7H2The molar ratio of O and calper calcium peroxide is preferably 1:2:0.5~1:
2:4。
In the present invention, the temperature of the degradation reaction is preferably room temperature.
In the present invention, the organic wastewater preferably includes industrial organic waste water and life organic wastewater.
In the present invention, the pH value of the organic wastewater is preferably 3~11.
In the present invention, methyl orange is preferably comprised in the organic wastewater, the concentration of the methyl orange is preferably 0.15~
0.5mM。
Fig. 1 is the schematic diagram that iron of the present invention is complexed that class Fenton's reaction handles organic wastewater.Mesoxalic acid and FeSO of the present invention4·
7H2O can generate ferric oxalate complexes, including Fe2+/ oxalic acid and Fe3+/ oxalic acid, calper calcium peroxide are reacted with water, generate H2O2And O2,
H2O2It generates OH to degrade to the organic pollutant in organic wastewater, obtains CO2And H2O, O2Generate O2 -., to organic wastewater
In organic pollutant react, obtain by-product, the removal of useless Organic substance in water imitated to improve Fenton-like system
Rate.
In order to further illustrate the present invention, have below with reference to example to iron provided by the invention complexing class Fenton's reaction processing
The method of machine waste water is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Under normal temperature condition, by FeSO4·7H2O, oxalic acid and three kinds of reagent unitary systems of calper calcium peroxide, two-by-two system and three
The system of person is added to that concentration is 50mg/L and volume is to react in 100mL methyl orange solution respectively, in gained reaction solution
FeSO4·7H2O, the molar concentration of oxalic acid and calper calcium peroxide is respectively 1.5mM, 3mM and 3mM.As a result see Fig. 2.
Interpretation of result: after reaction 15min, in " oxalic acid ", " FeSO4·7H2O " " calper calcium peroxide ", " oxalic acid+FeSO4·
7H2Under O ", " oxalic acid+calper calcium peroxide " effect, almost without methyl orange degradation；Secondly, in " FeSO4·7H2O+ calper calcium peroxide " is made
Under, methyl orange degradation rate is only 34%；And in " FeSO4·7H2O+ oxalic acid+calper calcium peroxide " (i.e. iron complexing Fenton-like),
Methyl orange degradation rate reaches 99.1%." calper calcium peroxide ", " oxalic acid+calper calcium peroxide ", " FeSO in Fig. 24·7H2O ", " oxalic acid+
FeSO4·7H2O " and " oxalic acid " system are corresponding in turn to curve 1,2,3,4,5；"FeSO4·7H2O+ calper calcium peroxide " and " FeSO4·
7H2O+ oxalic acid+calper calcium peroxide " is corresponding in turn to curve 6,7, it can be seen that in iron complexing Fenton-like, FeSO4·7H2O、
There is significant coupling between three kinds of reaction determinants of oxalic acid and calper calcium peroxide.
Embodiment 2
Under normal temperature condition, FeSO is being added4·7H2In the case where O and oxalic acid, then the calper calcium peroxide of different volumes added
To concentration be 50mg/L and volume is to be reacted in the methyl orange solution of 100mL, obtains FeSO in reaction solution4·7H2O, oxalic acid
Molar concentration is respectively 1.5mM, 3mM, and the concentration of calper calcium peroxide is respectively 0.75mM, 1.5mM, 3mM, 4.5mM, 6mM.As a result see
Fig. 3.
Interpretation of result: successively right when calper calcium peroxide molar concentration adds as 0.75mM, 1.5mM, 3mM, 4.5mM, 6mM
Answer curve 8,9,10,11 and 12, the degradation rate for reacting methyl orange after 15min is respectively 69.4%, 94%, 99.1%, 96.8%,
96.8%.
Embodiment 3
Under normal temperature condition, in FeSO4·7H2The molar ratio of O and oxalic acid be 1:2 under the premise of, by 0.75mM, 0.3mM,
1.5mM、3mM FeSO4·7H2O and oxalic acid in proportion and calper calcium peroxide are added to that concentration is 50mg/L and volume is 100mL
Methyl orange solution in reacted, in gained reaction solution the molar concentration of calper calcium peroxide be 3mM.As a result see Fig. 4.
FeSO is worked as in interpretation of result4·7H2When O dosage is respectively 0.3mM, 0.75mM, 1.5mM and 3mM, it is corresponding in turn to song
Line 13,14,15 and 16.The degradation rate of methyl orange is respectively 31.7%, 85.5%, 99.1%, 97.4% after reaction 15min.
Embodiment 4
Under normal temperature condition, by FeSO4·7H2O, three kinds of oxalic acid, calper calcium peroxide reagents are successively added to molar concentration and are
It is reacted in the methyl orange solution that the different gradients and volume of 0.15mM to 0.5mM are 100mL, in gained reaction solution
FeSO4·7H2O, the molar concentration of oxalic acid and calper calcium peroxide is respectively 1.5mM, 3mM and 3mM.As a result see Fig. 5.
Interpretation of result: the methyl orange degradation curve of 0.15mM, 0.25mM, 0.35mM and 0.5mM are corresponding in turn to curve 17,
18,19 and 20.The degradation rate of methyl orange solution is gradually decreased with the increase of its initial concentration.Main cause is: FeSO4·
7H2O, oxalic acid and calper calcium peroxide keep a timing, and Fenton-like, the various active oxygen radicals that can be generated are complexed in entire iron
Quantity be certain, thus the unit time by curve 10 increases to 13 with methyl orange concentration, and degradation rate gradually decreases.Instead
After answering 15min, the degradation rate of curve 17 is 99.1%.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (7)
1. a kind of method of iron complexing class Fenton's reaction processing organic wastewater, which comprises the following steps:
By oxalic acid, FeSO4·7H2O and calper calcium peroxide are added sequentially in organic wastewater, carry out degradation reaction.
2. the method according to claim 1, wherein the oxalic acid and FeSO4·7H2The molar ratio of O be 1:1~
1:9。
3. method of any of claims 1 or 2, which is characterized in that the oxalic acid, FeSO4·7H2O and calper calcium peroxide rub
You are than being 1:2:0.5~1:2:4.
4. the method according to claim 1, wherein the temperature of the degradation reaction is room temperature.
5. the method according to claim 1, wherein the organic wastewater includes that industrial organic waste water and life have
Machine waste water.
6. method according to claim 1 or 5, which is characterized in that the pH value of the organic wastewater is 3~11.
7. method according to claim 1 or 5, which is characterized in that contain methyl orange, the methyl in the organic wastewater
The concentration of orange is 0.15~0.5mM.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217877A (en) * | 2019-06-03 | 2019-09-10 | 燕山大学 | The method for handling organic wastewater as the class Fenton's reaction of oxidant using perborate |
| CN110577273A (en) * | 2019-10-09 | 2019-12-17 | 彭阳立达尔农业发展有限公司 | Decolorization and deodorization of marigold silage fermentation liquor and utilization thereof |
| CN112110625A (en) * | 2020-08-28 | 2020-12-22 | 哈尔滨工业大学（深圳） | Method for removing refractory organic matters in polluted bottom mud based on calcium peroxide Fenton strengthening technology and application |
| CN113135631A (en) * | 2021-05-28 | 2021-07-20 | 杭州绿夏环境科技有限公司 | Wastewater treatment method with low sludge yield based on multidimensional catalytic oxidation process |
| CN115520952A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Fenton oxidation treatment method for organic wastewater |
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| CN103482751A (en) * | 2013-10-14 | 2014-01-01 | 河海大学 | Application of biodegradable chelating agent EDDS (Ethylenediaminedisuccinic Acid) to treatment on non-degradable organic wastewater |
| CN108059228A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of sulfamido antiseptic in removal livestock breeding wastewater |
| KR101866425B1 (en) * | 2017-02-06 | 2018-06-12 | 한국과학기술연구원 | Apparatus for treatment of high concentration organic wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103482751A (en) * | 2013-10-14 | 2014-01-01 | 河海大学 | Application of biodegradable chelating agent EDDS (Ethylenediaminedisuccinic Acid) to treatment on non-degradable organic wastewater |
| KR101866425B1 (en) * | 2017-02-06 | 2018-06-12 | 한국과학기술연구원 | Apparatus for treatment of high concentration organic wastewater |
| CN108059228A (en) * | 2017-12-20 | 2018-05-22 | 苏州科技大学 | A kind of method of sulfamido antiseptic in removal livestock breeding wastewater |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110217877A (en) * | 2019-06-03 | 2019-09-10 | 燕山大学 | The method for handling organic wastewater as the class Fenton's reaction of oxidant using perborate |
| CN110577273A (en) * | 2019-10-09 | 2019-12-17 | 彭阳立达尔农业发展有限公司 | Decolorization and deodorization of marigold silage fermentation liquor and utilization thereof |
| CN112110625A (en) * | 2020-08-28 | 2020-12-22 | 哈尔滨工业大学（深圳） | Method for removing refractory organic matters in polluted bottom mud based on calcium peroxide Fenton strengthening technology and application |
| CN113135631A (en) * | 2021-05-28 | 2021-07-20 | 杭州绿夏环境科技有限公司 | Wastewater treatment method with low sludge yield based on multidimensional catalytic oxidation process |
| CN115520952A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Fenton oxidation treatment method for organic wastewater |
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