CN109095591A - Activate persulfate, the method for removing pollutant, application - Google Patents

Activate persulfate, the method for removing pollutant, application Download PDF

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Publication number
CN109095591A
CN109095591A CN201811050209.3A CN201811050209A CN109095591A CN 109095591 A CN109095591 A CN 109095591A CN 201811050209 A CN201811050209 A CN 201811050209A CN 109095591 A CN109095591 A CN 109095591A
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China
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persulfate
degradation
pentanedione
acetylacetone
pollutant
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CN201811050209.3A
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CN109095591B (en
Inventor
靳永胜
李晓薇
郑燕英
陆艺飞
付雪晴
韩飞
刘欣玮
吴峥
罗健
郑鑫阳
程培焱
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Beijing Compaq Tongchuang Biotechnology Co Ltd
Beijing University of Agriculture
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Beijing Compaq Tongchuang Biotechnology Co Ltd
Beijing University of Agriculture
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The present invention provides a kind of acetylacetone,2,4-pentanedione joint ferrous ion activation persulfate system and its method of pollutant, application are removed, ferrous iron coordination activation persulfate system will be by acetylacetone,2,4-pentanedione, Fe2+And persulfate composition, the method for persulfate removal pollutant include: that ferrous iron is coordinated activation persulfate system to be added in the waste water to be processed containing organic pollutant and nitrogen-containing pollutant, the pH value of reaction system controls between 2-12；15-50 DEG C of degradation treatment 5-60min.The compound activation persulfate system of ferrous coordination activation persulfate System forming of the invention, can effective Fe2+Protection mechanism not will cause the meaningless consumption of persulfate to achieve the purpose that activate persulfate.

Description

Activate persulfate, the method for removing pollutant, application
Technical field
The present invention relates to pollutant process fields, activate in particular to a kind of acetylacetone,2,4-pentanedione joint ferrous ion Sulfate advanced oxidation system and its method of depth degradation pollutant, application.
Background technique
Increase with the rapid development of our country's economy with the intensification of urbanization degree, industrial wastewater and domestic waste object amount More, environmental pollution has become increasingly serious.In recent years, environmental improvement receives much attention, and wherein water pollution problem is the most urgent.In water body COD content and nitrogen it is excessively high be current environmental improvement a great problem.COD in water body value is higher, and to represent organic pollution tighter Weight.The severe overweight of nitrogen can make water eutrophication, lead to algal bloom, reduce content of oxygen dissolved in water, draw Play the mortality of aquatic animal.In addition, nitrate nitrogen also has potential influence on people, nitrate can be reduced into Asia in human body Nitrate reacts with amine substance, generates strong carcinogen N-nitrosamine.Nitrate can also destroy hemoglobin, raw At ferrihemoglobin, hemoglobin is made to carry the Disability of oxygen, endangers human life's safety.
Nitrogenous compound in sewage is mainly from nitrogenous industrial wastewater, city domestic sewage and the nitrogen in agricultural irrigation The leaching loss of fertilizer, nitrogen mostly exists with nitrate nitrogen, ammonium nitrogen and a small amount of nitrite nitrogen, organic nitrogen form in water, but organic nitrogen Water solubility is relatively poor and is easily biodegradable.Therefore, focusing on to nitrate nitrogen and ammoniacal nitrogen for water body nitrogen content is reduced Degradation.
The main method of degradation of nitrogen-containing compound has at present: biological denitrificaion method, will under aerobic conditions using nitrobacteria Ammoniacal nitrogen is converted into nitrate nitrogen, recycles denitrifying bacteria that nitrate nitrogen, cultured water are reduced to N in anaerobic condition2.Biology is de- Nitrogen method process green, degradation effect is preferable, but condition requires strictly, and processing cost is higher, low to high electrolyte content or BOD value System poor effect；Catalytic reduction denitrogenation method mainly has: photocatalytic method, using titanium dioxide as carrier, in ultraviolet lighting Under nitrate nitrogen is removed；Electrocatalytic method removes the nitrate nitrogen in water by extra electric field, although catalytic reduction method Denitrification effect is good, but cannot achieve reaction condition required by electro-catalysis reduction method in actual sewage processing, it is difficult to reach reason The degradation effect thought；The simplest is chemical reduction method, is reducing agent frequently with active metal such as Fe, Mg etc..Iron is because have Ferric iron that is from a wealth of sources, cheap, generating after reaction does not have toxic action to environment and is easy to be reduced agent again also Original utilize the advantages that and by favor.But it is influenced very greatly with the system of iron reduction nitrate nitrogen by pH value, it is reported that, in pH value > 4, Fe are reacted with nitrate anion stopping, and are readily generated ammonium ion, can not achieve the removal of nitrate nitrogen truly. There is presently no the ideal methods of the COD and TN that can synchronize in removal sewage.
In view of this, the present invention is specifically proposed.
Summary of the invention
It is (nitrogenous including the organic pollutant in waste water for depth degradation pollutant that it is an object of that present invention to provide one kind Pollutant) acetylacetone,2,4-pentanedione collaboration ferrous ion activation persulfate advanced oxidation reaction system, the system is mainly by acetyl Acetone, Fe2+And persulfate composition, to form compound activation persulfate system.The system can be effectively protected, is multiple Fe in reaction system living2+, while acetylacetone,2,4-pentanedione can also helper activity persulfate, thus can reach lasting, stable, efficiently living Change persulfate and reduce or deduction and exemption persulfate unnecessary consumption purpose, thus promoted COD and TN degradation efficiency and Removal effect.
The second object of the present invention is to provide a kind of above-mentioned acetylacetone,2,4-pentanedione collaboration ferrous ion activation persulfate system The method of (reproducibility complexant cooperates with ferrous ion to activate persulfate) removal pollutant, the theoretical foundation of this method such as formula (1) shown in:
Wherein L is other reproducibility complexants, and N is and Fe2+The miscellaneous metal ion coexisted.In no L and N, in system Fe2+Effective concentration mainly by Fe2+, AA dosage, Fe2+: AA ratio and pH control.
It, can be in conjunction with the ferrous ion drifted in solution, thus suitable by introducing reproducibility complexant in this method When the concentration for reducing iron ion in reaction, and pass through pH, complexant dosage and complexant: Fe2+'sProportion is to regulate and control free Fe2+ Concentration makes to react towards the progress of the direction of attack pollutant, send out to greatest extent to control the generating rate of potentiometric titrations The efficiency of medicament is waved, the removal efficiency of object pollutant is improved.
Furthermore for the complexant in this method other than having the function of conventional complexant, itself also has excellent resurrection Fe2+Ability, and with direct activation over cure acid group generate potentiometric titrations ability therefore with optimal conditions can Realization can be realized Fe2+Long-effect active, and keep Fe2+Constant concentration, to ensure that the lasting, steady of potentiometric titrations It is shaped as, provides condition for the efficient depth degradation of organic pollutant and nitrogen-containing pollutant, therefore this method is with good Application prospect.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
The present invention provides a kind of acetylacetone,2,4-pentanedione joint ferrous ion activation persulfate advanced oxidation system, mainly by Acetylacetone,2,4-pentanedione, Fe2+And persulfate composition, acetylacetone,2,4-pentanedione can form good as reproducibility complexant with ferrous ion Complexing ligands system.Acetylacetone,2,4-pentanedione: Fe2+: the molar ratio between persulfate is controlled at (1-5): (1-20): between (1-8).
In general, in traditional single oxidation process denitrification system of Fe (0), Fe (0) is easily oxidized to Fe3+, and in solution just Beginning ferrous ion concentration is excessively high, be easy to generate when handling the total nitrogen in pollutant ammonium nitrogen and water body pollutant it One, it is unfavorable for the nontoxic degradation of nitrogenous compound.In the present solution, using AA-Fe2+Advanced oxidation system, utilizes Fe2+, draw Enter reproducibility complexant acetylacetone,2,4-pentanedione (AA), effectively combine the ferrous ion drifted in solution, reduces to a certain extent anti- The effective concentration for answering middle ferrous ion, makes Fe2+With reducing power appropriate, control do not generated in denitrification process ammonium root from Son directly generates N2.Meanwhile regulating and controlling the coordination ability of complexant by pH, free Fe is regulated and controled by complexant dosage2+Concentration, To control the generation of potentiometric titrations, makes to react towards the progress of the direction of attack nitrogenous compound, avoid excessive sulphur Acid group free radical and Fe2+Side reaction, which is buried in oblivion and mutually collided, to be quenched, and over cure acid group and Fe are reduced2+Side reaction, cause persulfuric acid The unnecessary consumption of root, thus the efficiency of medicament can be played to greatest extent.With the progress of reaction, Fe in solution2+Concentration subtracts Few, coordination balance is mobile towards dissociation direction, thus freeing that Fe out2+；Conversely, working as Fe3+It is reduced and generates Fe2+, coordination balance to Generate complex direction it is mobile, Fe2+Amount reduces.As a result, being coordinated Balancing relization system Fe2+One dynamic of concentration Balance.Thus, in the presence of having over cure acid group in system, it may be implemented to continue, steadily excite, certainly for system sulfate radical Premise is provided by lasting, the steady generation of base and the continued oxidation degradation of organic pollutant.
AA additional amount changes to metal cations Fe2+Concentration plays effective adjustment effect, in acetylacetone,2,4-pentanedione-Fe2+System is deposited In optimal ratio.Excessively high coordination dosage or excessively high Fe2+Concentration all can in influence system total nitrogen degradation.Therefore inventor Adjustment is optimized for AA additional amount.
Preferably, acetylacetone,2,4-pentanedione: Fe2+: the molar ratio between persulfate is preferably controlled in (2-4): (4-15): (2-7) Between, it is optimally controlled between 3:10:4, controls under the conditions of optimal ratio, degradation effect can achieve most preferably.
Under the control condition of above-mentioned molar ratio, either to the COD in sewage, or total nitrogen pollutant have it is very good Good degradation effect, the type of the pollutant according to contained in handled sewage is different certainly, can carry out to above-mentioned molar ratio Certain adjustment, the special type in actual application especially to landfill leachate, nanofiltration concentrate etc. containing hard-degraded substance are useless There is very extensive application prospect in terms of water process.
The present invention is specifically included in addition to providing the method for carrying out depth degradation pollutant using above-mentioned persulfate system Following steps:
(A) acetylacetone,2,4-pentanedione joint ferrous ion activation persulfate is added to be processed containing organic pollutant and nitrogenous In the waste water of pollutant, the pH value of reaction system is controlled between 2-12；
(B) 15-50 DEG C of degradation treatment 5-60min.
In the method, the meaning of pH regulation mainly includes two aspects: 1) influencing stimulator Fe2+Effective concentration, In the case that pH is higher, Fe2+It will be with Fe (OH)2Form exists, and comparatively fast will be oxidized to Fe (OH)3And it inactivates；2) it influences to match Position agent and metal ion share electronic capability, in the lesser situation of pH, the H of higher concentration+Will in complexant outside O element core Lone pair electrons combine, and lose it and share electronic capability with metal ion, thus lose coordination ability.3) total nitrogen compound is influenced Body distribution and reaction complexity, by NH4 +Body distribution map is as shown in Figure 6, when pH is 9.26, in solution ammonium nitrogen with Ammonium ion and ammonium hydroxide form coexist, and are easy to volatilize in the form of ammonia in processing, cause secondary pollution to environment；Foundation simultaneously Nitrate anion half-reaction equation is reduced it is found that reducing pH value conducive to nitrate anion.
12H++2NO3 -=N2+6N2O
Nitrate anion half-reaction equation
Therefore, the present invention is by having obtained its optimal pH value when complexant is acetylacetone,2,4-pentanedione after experiment.Pass through regulation PH can significantly improve degradation rate, enable pollutant that the drop of total nitrogen in depth degradation, especially pollutant is done step-by-step Solution.
Preferably, pH value control is between 6-9, and more preferably pH is 8, according to the type of handled pollutant, to specific PH value is adjusted, if more excellent pH value range is 8-12, if in order to reduce dirt just for organic pollutant Total nitrogen in dye object should suitably reduce pH value according to the principle analysis of Fig. 6, for example can control between pH 2-5.
Although degrade total nitrogen when, pH value is not suitable for excessively high, and the low nitrate anion that is conducive to of pH value is reduced, if PH value is too low then because of the influence to the reducing powers such as AA and coordination ability, may will affect the effect of degradation again, therefore best It controls in suitable pH value range.
Persulfate of the invention can be sodium peroxydisulfate, potassium peroxydisulfate, one of ammonium persulfate or a variety of mixing, it is excellent Be selected as the mixing of sodium peroxydisulfate or potassium peroxydisulfate or both, the ferrous source of iron of ferrous ion can for green vitriol, Any of which in ferrous acetate, Iron dichloride tetrahydrate, it is therefore preferable to which green vitriol or four chloride hydrates are sub- Iron.
Furthermore, it is necessary to it is to be noted that the control of each operating parameter during degradation reaction in step (B) of the invention System, the time of degradation reaction of the present invention, which is about 5-60min, can be completed degradation, degradation efficiency be improved, when saving operation Between, other biodegrading process may need 2-3h or even 7-8h that could complete to degrade in the prior art, in comparison of the invention Not only the degradation reaction used time is short for biodegrading process, and degradation effect is also more excellent, and COD and total nitrogen also may be implemented under optimal conditions Synchronous degradation.
More preferably, the processing time of degradation controls between 10-30min.
Preferably, the temperature of degradation treatment controls between 20-35 DEG C, and more excellent is 30 DEG C.
Preferably, the mode of degradation treatment includes one of or several knot stood, in stirring, concussion and ultrasound It closes.Optimal processing mode is successively to carry out degradation treatment by standing, stirring, concussion and ultrasound.
Preferably, the rate control of concussion is more preferably 210rpm between 200-250rpm.
Preferably, ultrasonic power is in 40W.
By using the method for stirring degradation of the invention, the degradation rate of total nitrogen measures parachlorophenol up to 85% or more Degradation rate is up to 95% or more.
Compared with prior art, the invention has the benefit that
(1) acetyl of the invention in depth degradation pollutant (including the organic pollutant in waste water, nitrogen-containing pollutant) Acetone cooperates with the advanced oxidation reaction system of ferrous ion activation persulfate, and the system is mainly by acetylacetone,2,4-pentanedione, Fe2+And mistake Sulfate composition, to form compound activation persulfate system.The system can be effectively protected, bring back to life in reaction system Fe2+, while acetylacetone,2,4-pentanedione can also helper activity persulfate, thus can reach lasting, stable, efficiently activation and is dropped at persulfate The purpose of low or deduction and exemption persulfate unnecessary consumption, to promote the degradation efficiency and removal effect of COD and TN.
(2) method degraded by using the present invention, the final degradation rate for measuring total nitrogen are measured up to 85% or more to chlorobenzene The degradation rate of phenol is up to 95% or more, particularly with the organic pollutant, inorganic in the more serious various pollution sources of municipal pollution Pollutant is able to achieve depth degradation, and degradation rate is very high, has wide application prospects.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that the acetylacetone,2,4-pentanedione of the embodiment of the present invention 4 cooperates with the drop of ferrous ion activation persulfate degradation parachlorophenol Solution rate figure；
Fig. 2 is that the acetylacetone,2,4-pentanedione of the embodiment of the present invention 5 cooperates with the degradation rate of ferrous ion activation persulfate degradation total nitrogen Figure；
Fig. 3 is the independent Fe of experimental example 2 of the present invention2+Activate the experimental result picture of persulfate degradation total nitrogen；
Fig. 4 is the experimental result picture of the independent AA activation persulfate degradation total nitrogen in experimental example 2 of the present invention；
Fig. 5 is the activating mechanism of the reproducibility complexant collaboration ferrous ion activation persulfate in experimental example 2 of the present invention Figure；
Fig. 6 is NH4 after the degradation treatment of the invention for carrying out nitrogenous compound at various ph values+The figure of changing of-N.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
Embodiment 1
1) selection of iron ion source:
The ferrous source of iron that the present embodiment selects is green vitriol.
2) selection of persulfate:
The persulfate that the present embodiment selects is sodium peroxydisulfate.
3) selection of complexant: acetylacetone,2,4-pentanedione
4) specific degradation process is implemented in accordance with the following steps:
The parachlorphenol aqueous solution (concentration 20mg/L) adjusted within the scope of pH value 10-12 is taken, acetylacetone,2,4-pentanedione: Fe is added2+: mistake Sodium sulphate molar ratio is 1:20:8, total volume 50ml, and at 30 DEG C, the shaking table oscillation 25min of 200rpm carries out reaction degradation；
Solution after taking 3ml reaction degradation is extracted with isometric ethyl acetate in 10ml centrifuge tube, crosses 0.22um water system Filter membrane is 95% with efficient liquid phase characterization 20min detection parachlorphenol (4-CP) degradation rate.Garbage filter is handled with the reaction system Concentrated liquor, landfill leachate nanofiltration concentrate COD removal rate are 93%, nitrogen removal rate 85%.
Embodiment 2
1) selection of iron ion source:
The ferrous source of iron that the present embodiment selects is ferrous acetate and green vitriol.
2) selection of persulfate:
The persulfate that the present embodiment selects is sodium peroxydisulfate.
3) selection of complexant: acetylacetone,2,4-pentanedione
4) specific degradation process is implemented in accordance with the following steps:
The parachlorphenol aqueous solution (concentration 20mg/L) adjusted within the scope of pH value 8-9 is taken, acetylacetone,2,4-pentanedione: Fe is added2+: over cure Sour sodium molar ratio is 5:1:1, total volume 50ml, and at 35 DEG C, the shaking table oscillation 30min of 210rpm carries out reaction degradation；
Solution after taking 3ml reaction degradation is extracted with isometric ethyl acetate in 10ml centrifuge tube, crosses 0.22um water system Filter membrane is 96% with efficient liquid phase characterization 20min detection parachlorphenol (4-CP) degradation rate.Garbage filter is handled with the reaction system Concentrated liquor, landfill leachate nanofiltration concentrate COD removal rate are 94%, nitrogen removal rate 84%.
Embodiment 3
1) selection of iron ion source:
The ferrous source of iron that the present embodiment selects is Iron dichloride tetrahydrate.
2) selection of persulfate:
The persulfate that the present embodiment selects is potassium peroxydisulfate and sodium peroxydisulfate.
3) selection of complexant: acetylacetone,2,4-pentanedione
4) specific degradation process is implemented in accordance with the following steps:
The parachlorphenol aqueous solution (concentration 20mg/L) adjusted within the scope of pH value 8-9 is taken, acetylacetone,2,4-pentanedione: Fe is added2+: over cure Sour sodium molar ratio is 2:15:7, total volume 50ml, and at 20 DEG C, the shaking table oscillation 60min of 250rpm carries out reaction degradation；
Solution after taking 3ml reaction degradation is extracted with isometric ethyl acetate in 10ml centrifuge tube, crosses 0.22um water system Filter membrane is 98% with efficient liquid phase characterization 20min detection parachlorphenol (4-CP) degradation rate.Garbage filter is handled with the reaction system Concentrated liquor, landfill leachate nanofiltration concentrate COD removal rate are 95%, nitrogen removal rate 86%.
Embodiment 4
The ferrous source of iron that the present embodiment selects is green vitriol.
2) selection of persulfate:
The persulfate that the present embodiment selects is ammonium persulfate.
3) selection of complexant: acetylacetone,2,4-pentanedione
4) specific degradation process is implemented in accordance with the following steps:
The parachlorphenol aqueous solution (concentration 20mg/L) adjusted within the scope of pH value 8-9 is taken, acetylacetone,2,4-pentanedione: Fe is added2+: over cure Sour sodium molar ratio is 2:2:1, total volume 50ml, and at 26 DEG C, the shaking table oscillation 60min of 250rpm carries out reaction degradation；
Solution after taking 3ml reaction degradation is extracted with isometric ethyl acetate in 10ml centrifuge tube, crosses 0.22um water system Filter membrane is 100% with efficient liquid phase characterization 20min detection parachlorphenol (4-CP) degradation rate.It is seeped with reaction system processing rubbish Filtrate concentrate, landfill leachate nanofiltration concentrate COD removal rate are 97%, nitrogen removal rate 86%, the specific degradation of 4-CP Figure line is shown in attached drawing 1.
Embodiment 5
The ferrous source of iron that the present embodiment selects is green vitriol.
2) selection of persulfate:
The persulfate that the present embodiment selects is sodium peroxydisulfate.
3) selection of complexant: acetylacetone,2,4-pentanedione
4) specific degradation process is implemented in accordance with the following steps:
It takes and adjusts pH value 4-5, nitre state potassium concn is 8g/L, and ammonium sulfate concentrations are the nitrogenous aqueous solution 50ml of 10g/L, is added Acetylacetone,2,4-pentanedione: Fe2+: sodium peroxydisulfate molar ratio 3:10:4 shakes 210rpm 10min, 40w ultrasound 10min, stands at 30 DEG C 20min carries out reaction degradation；1ml sample liquid total nitrogen kit measurement is taken, nitrogen removal rate is 85% or more, specific total nitrogen degradation Curve is shown in attached drawing 2.
Embodiment 6
The ferrous source of iron that the present embodiment selects is green vitriol.
2) selection of persulfate:
The persulfate that the present embodiment selects is sodium peroxydisulfate.
3) selection of complexant: acetylacetone,2,4-pentanedione
4) specific degradation process is implemented in accordance with the following steps:
It takes and adjusts pH value 2-4, nitre state potassium concn is 16g/L, and ammonium sulfate concentrations are the nitrogenous aqueous solution 50ml of 4g/L, is added Acetylacetone,2,4-pentanedione: Fe2+: sodium peroxydisulfate molar ratio 3:12:5 stirs 5min at 40 DEG C, shakes 220rpm 10min, 40w ultrasound 10min, 10min is stood, carries out reaction degradation；1ml sample liquid total nitrogen kit measurement is taken, nitrogen removal rate is 92% or more.
Comparative example 1
Concrete operation step and embodiment 5 are consistent, only acetylacetone,2,4-pentanedione: Fe2+: sodium peroxydisulfate molar ratio 20:7:4, system PH be 1, degradation time 3h, by total nitrogen kit measurement, nitrogen removal rate 70%.
Comparative example 2
Concrete operation step and embodiment 5 are consistent, only acetylacetone,2,4-pentanedione: Fe2+: sodium peroxydisulfate molar ratio 1:70:1, system PH be 11, degradation time 5h, by total nitrogen kit measurement, nitrogen removal rate 75%.
Comparative example 3
Concrete operation step and embodiment 5 are consistent, only acetylacetone,2,4-pentanedione: Fe2+: sodium peroxydisulfate molar ratio 4:3:0.7, system PH be 1, degradation time 3h, by total nitrogen kit measurement, nitrogen removal rate 75%.
As can be seen that only parameters control within the scope of the solution of the present invention from attached drawing 1-2, reason can be only achieved The degradation effect thought, not only excellent to the degradation effect of organic pollutant, the degradation effect of total nitrogen is also very excellent, it is seen that if Some parameter does not control the present invention claims ideal degradation effect in range, is not achieved extending the time of degradation reaction Fruit, especially pH value, there are also the parameters such as the dosage of substance each in system to need to cooperate allotment in more excellent model In enclosing, if pH value control is within the scope of the invention, under conditions of dosage uses any proportion, although there is degradation effect, It is that degradation rate is not high.
Experimental example 1
By the ferrous coordination system of the embodiment of the present invention 5 activation persulfate processing actual sewage and it is in the prior art its He carries out degradation experiment comparison by process system, and specific experiment result is as shown in table 1 below:
1 experimental result of table
The method cost of degradable organic pollutant of the invention compares lower, and operating process is also simple, is easy to carry out big Scale is implemented, and realizes industrialized production, COD not only can be effectively reduced, for the depth degradation such as total nitrogen of nitrogen-containing pollutant Degradation also have extraordinary effect, other embodiments find that same effect can be obtained after above-mentioned test.
Experimental example 2
The function that resurrection and auxiliary to AA intensify over cure acid group is tested, and specific experiment process is as follows:
In advanced oxidation processes, activator Fe2+It is easily oxidized and generates Fe3+Inactivation, causes oxidative degradation to terminate. But in the presence of having acetylacetone,2,4-pentanedione (AA) in system, AA can be by Fe3+It is reduced to Fe2+, to realize Fe2+Resurrection.
From the Fe in Fig. 32+The degradation figure line of independent degradation system and the independent acetylacetone,2,4-pentanedione system of Fig. 4 can be seen that The reproducibility of AA is slightly above ferrous iron, if subsequent as reaction carries out, AA is can be by Fe3+It is reduced to Fe2+, to realize Fe2+Resurrection, in practice it has proved that, acetylacetone,2,4-pentanedione not only can be with Fe2+Coordination, can also restore Fe3+。
The reduction of AA the result shows that, AA has reduction Fe2+Reactivation, thus be conducive to the activation of advanced oxidation system Agent Fe2+Active holding is conducive to more continue the oxidative degradation for efficiently carrying out pollutant.
Independent Fe2+It is all undesirable with degradation effect of the independent acetylacetone,2,4-pentanedione to nitrogen in water phase, but when the two exists simultaneously, As reaction carries out, Fe in solution2+Concentration is reduced, and coordination balance is mobile towards dissociation direction, thus freeing that Fe out2+, otherwise work as Fe3+It is reduced and generates Fe2+, coordination balance is mobile towards the direction for generating complex, Fe2+Amount reduces.As a result, coordination balance Realize system Fe2+One dynamic equilibrium of concentration.Thus, it may be implemented to continue in system, steadily excite, held for system Continuous, steady degradation nitrate nitrogen and ammonium nitrogen provide premise.
In addition, the activating mechanism of acetylacetone,2,4-pentanedione collaboration ferrous ion activation persulfate of the invention is illustrated in fig. 5 shown below.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (10)

1. a kind of acetylacetone,2,4-pentanedione joint ferrous ion activates persulfate system, which is characterized in that mainly by acetylacetone,2,4-pentanedione, Fe2+ And persulfate composition；
Acetylacetone,2,4-pentanedione: Fe2+: the molar ratio between persulfate is controlled at (1-5): (1-20): between (1-8).
2. activation persulfate system according to claim 1, which is characterized in that acetylacetone,2,4-pentanedione: Fe2+: persulfate it Between molar ratio control at (2-4): (4-15): between (2-7)；
It is highly preferred that acetylacetone,2,4-pentanedione: Fe2+: the molar ratio between persulfate controls between 3:10:4.
3. the acetylacetone,2,4-pentanedione in the described in any item activation persulfate systems of claim 1-2 has and Fe2+Coordination is brought back to life Fe2+And the function of Assisted Activation over cure acid group.
4. the method for the activation persulfate system removal pollutant of any one of claim 1-2, which is characterized in that including as follows Step:
(A) ferrous iron is coordinated activation persulfate system and is added to the waste water to be processed containing organic pollutant and nitrogen-containing pollutant In, the pH value of reaction system controls between 2-12；
(B) 15-50 DEG C of degradation treatment 5-60min.
5. according to the method described in claim 4, it is characterized in that, in the step (A), the pH value control of system 6-9 it Between, more preferably pH is 8.
6. according to the method described in claim 4, it is characterized in that, the persulfate is persulfuric acid in the step (A) Any one in sodium, potassium peroxydisulfate, the one of which in ammonium persulfate, preferably sodium peroxydisulfate, potassium peroxydisulfate or two kinds.
7. according to the method described in claim 4, it is characterized in that, in the step (A), the Fe2+Ferrous source of iron be seven Ferrous sulfate hydrate, ferrous acetate, the one of which in Iron dichloride tetrahydrate, it is therefore preferable to green vitriol or four water Close frerrous chloride.
8. according to the described in any item methods of claim 4-7, which is characterized in that in the step (B), the temperature of degradation treatment Between 20-35 DEG C, more excellent is 30 DEG C for control.
9. according to the described in any item methods of claim 4-7, which is characterized in that in the step (B), the time of degradation treatment Control is between 10-30min.
10. according to the described in any item methods of claim 4-7, which is characterized in that in the step (B), degradation treatment mode Including one of or several combination in standing, stirring, concussion and ultrasound；
Preferably, concussion rate is more preferably 210rpm between 200-250rpm；
Preferably, ultrasonic power 40W；
Preferably, in the step (B), after stirring degradation, the degradation rate of total nitrogen is measured up to 85% or more, measures parachlorophenol Degradation rate is up to 95% or more.
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