CN110015744A - Strengthen Fenton/class Fenton's reaction system removal water pollutant method using free chlorine - Google Patents

Strengthen Fenton/class Fenton's reaction system removal water pollutant method using free chlorine Download PDF

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Publication number
CN110015744A
CN110015744A CN201910350303.9A CN201910350303A CN110015744A CN 110015744 A CN110015744 A CN 110015744A CN 201910350303 A CN201910350303 A CN 201910350303A CN 110015744 A CN110015744 A CN 110015744A
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water
fenton
pollutant
added
reaction system
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马军
王鲁
刘玉蕾
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/763Devices for the addition of such compounds in gaseous form
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

Strengthen Fenton/class Fenton's reaction system removal water pollutant method using free chlorine, the present invention relates to a kind of method for treating water, and there are H in order to solve existing Fenton system for handling for it2O2Consumption is big, the problem that iron throwing amount is more and pollutant removal is poor.Method for treating water: one, the pH value of pending water is adjusted in 2.0~4.0 ranges;Two, ferrous salt is then added into pending water, stirs pending water, and hydrogenperoxide steam generator is added;Three, hypochlorite solutions are added or are passed through chlorine, makes 1~15mg/L of concentration of effective chlorine in system, carries out reinforcing reaction, to remove water pollutant.The present invention can be improved 30%~50% to the removal rate of pollutant using the method that free chlorine strengthens Fenton's reaction system removal water pollutant, so that the dosage of hydrogen peroxide or persulfate is reduced 20%~50%, the dosage of ferrous iron or other metal salts is made to reduce 30%~60%.

Description

Strengthen Fenton/class Fenton's reaction system removal water pollutant using free chlorine Method
Technical field
The present invention relates to a kind of method for treating water, and in particular to strengthens Fenton/class Fenton's reaction system using free chlorine and goes Except the method for water pollutant.
Background technique
Fenton's reaction is by ferrous ion (Fe2+) and hydrogen peroxide (H2O2) composition a kind of advanced chemical oxidation technology, The hydroxyl radical free radical (HO) of strong oxidizing property can be generated, oxidation reaction can occur with hardly degraded organic substance in aqueous solution to broken Its bad structure, therefore have a wide range of applications in multiple fields.Fenton reagent is to be sent out by French scientist Fenton in 1894 It is existing, have many advantages, such as applied widely, the small, strong antijamming capability of pollution and is swift in response.In Fenton's reaction, H2O2In Fe2 +The hydroxyl radical free radical (HO) with strong oxidizing property can be generated under catalysis, and generate Fe3+, Fe3+Can also and H2O2Reaction, it is raw At Fe2+.Entire reaction process realizes Fe2+And Fe3+Between circulation, and continuously generate living radical (HO, HOO·).HO electron affinity energy power is high, with non-selectivity can quickly aoxidize various organic compounds, be oxidized rapidly for CO2Or H2O is converted into other organic matters being readily biodegradable.Class Fenton's reaction system refers to using Fenton reagent, changes one A little conditions (such as ultraviolet lighting, electric Fenton) or the reaction for being doped with metal (copper, zinc, zirconium) other than iron etc..
Fenton's reaction, which has waste water difficult for biological degradation, toxic wastewater and Biostatic waste water, to be stablized, effectively removes Function can handle different types of waste water because it is swift in response, applied widely, degrade a variety of polysaccharide polymers the advantages that, More and more attention are at home and abroad obtained.
But there are H for individual Fenton system for handling2O2The disadvantages of consumption is big, and iron throwing amount is more, at high cost, pH narrow application range.
Summary of the invention
The purpose of the present invention is to solve existing Fenton system for handling, there are H2O2Consumption is big, and iron throwing amount is more and pollutes The poor problem of object removal effect, and provide and strengthen Fenton/class Fenton's reaction system removal water pollutant using free chlorine Method.
The present invention follows these steps to realize using the method that free chlorine strengthens Fenton's reaction system removal water pollutant:
One, the pH value of pending water is adjusted in 2.0~4.0 ranges;
Two, ferrous salt is then added into pending water, stirs pending water, and hydrogenperoxide steam generator is added;
Three, (quick) addition hypochlorite solutions or be passed through chlorine again, make the concentration 1 of effective chlorine in system~ 15mg/L carries out reinforcing reaction, to remove water pollutant.
The present invention follows these steps to realize using the method that free chlorine strengthens class Fenton's reaction system removal water pollutant:
One, the pH value of pending water is adjusted in 2.0~4.0 ranges;
Two, transition metal salt is then added into pending water, stirs pending water, and single persulfate is added or crosses two sulphur Hydrochlorate;
Three, (quick) addition hypochlorite solutions or be passed through chlorine again, make the concentration 1 of effective chlorine in system~ 15mg/L carries out reinforcing reaction, to remove water pollutant;
Wherein transition metal salt described in step 2 be one of ferrous salt, mantoquita, zinc salt, zirconates, cobalt salt, manganese salt or The a variety of mixtures of person.
Fenton or Fenton-like itself of the present invention can generate the strong free radical of oxidation, certainly such as hydroxyl By base, potentiometric titrations etc..But the stability of hydroxyl radical free radical, potentiometric titrations is poor, Css in the solution It is low.After free chlorine (hypochlorite or chlorine) is added in system, pass through free chlorine and chloride ion and hydroxyl radical free radical and sulfuric acid The reaction of root free radical generates a large amount of Cl, ClO, Cl2The high Kinds of Free Radicals of equal Css, thus improve Fenton Degradation effect of the system to pollutant.
The present invention using free chlorine strengthen Fenton's reaction system remove water pollutant method compared to individual Fenton/ Fenton-like can be improved 30%~50% to the removal rate of pollutant, subtract the dosage of hydrogen peroxide or persulfate Few 20%~50%, so that the dosage of ferrous iron or other metal salts is reduced 30%~60%, the reaction time is made to shorten 2~10 Times.
Specific implementation method
Specific embodiment 1: present embodiment strengthens the side of Fenton's reaction system removal water pollutant using free chlorine Method follows these steps to implement:
One, the pH value of pending water is adjusted in 2.0~4.0 ranges;
Two, ferrous salt is then added into pending water, stirs pending water, and hydrogenperoxide steam generator is added;
Three, (quick) addition hypochlorite solutions or be passed through chlorine again, make the concentration 1 of effective chlorine in system~ 15mg/L carries out reinforcing reaction, to remove water pollutant.
After present embodiment adds hydrogenperoxide steam generator, hypochlorite solutions are added in 1~30min or are passed through chlorine Gas.
Ferrous salt described in present embodiment is frerrous chloride, ferrous nitrate or ferrous sulfate.
Pending water can be trade effluent, the life of high COD, high phosphorus waste water, high ammonia nitrogen or high chroma in present embodiment Sewage or landfill leachate etc. living.Its pollutant kind include all kinds of antibiotic, synthetic musk, anodyne, depressor, Contraceptive, somnifacient, slimming drugs, hair jelly, hair dye and fungicide etc..
It can make to drink using the method that free chlorine strengthens Fenton's reaction system removal water pollutant using present embodiment The removal rate of trace contaminant reduces by 60%~90% up to COD content in 80% or more or sewage in the water of source.
Specific embodiment 2: the present embodiment is different from the first embodiment in that when pending water is to drink source Water, the throwing amount of hydrogen peroxide is 0.5~5mg/L in step 2.
Pollutant concentration in present embodiment drinking water is lower, and general COD concentration is in 0.001~10mg/L range It is interior.Hydrogen peroxide is to add in form of an aqueous solutions.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that working as the COD of pending water When concentration is greater than 10mg/L, step 2 controls the mass concentration ratio of additional amount (mg/L) and COD of hydrogen peroxide in pending water For 0.1~1:1.
High COD in present embodiment, high phosphorus waste water, can be the trade effluent of high ammonia nitrogen or high chroma, sanitary sewage or Person's landfill leachate etc..Its pollutant kind include all kinds of antibiotic, synthetic musk, anodyne, depressor, contraceptive, Somnifacient, slimming drugs, hair jelly, hair dye and fungicide etc..
Specific embodiment 4: ferrous in step 2 unlike one of present embodiment and specific embodiment one to three Salt and hydrogen peroxide (Fe:H2O2) molar ratio be 0.5~1:3.
Specific embodiment 5: being stirred in step 2 unlike one of present embodiment and specific embodiment one to four Speed be 100~1000r/min.
Specific embodiment 6: step 3 unlike one of present embodiment and specific embodiment one to five strengthen it is anti- The time answered is 5~60min.
Specific embodiment 7: present embodiment strengthens class Fenton's reaction system removal water pollutant using free chlorine Method follows these steps to implement:
One, the pH value of pending water is adjusted in 2.0~4.0 ranges;
Two, transition metal salt is then added into pending water, stirs pending water, and single persulfate is added or crosses two sulphur Hydrochlorate;
Three, (quick) addition hypochlorite solutions or be passed through chlorine again, make the concentration 1 of effective chlorine in system~ 15mg/L carries out reinforcing reaction, to remove water pollutant;
Wherein transition metal salt described in step 2 be one of ferrous salt, mantoquita, zinc salt, zirconates, cobalt salt, manganese salt or The a variety of mixtures of person.
Peroxydisulfate described in present embodiment is potassium persulfate, sodium persulfate or peroxy-disulfuric acid ammonia, single over cure Hydrochlorate is permonosulphuric acid potassium, permonosulphuric acid sodium or permonosulphuric acid ammonia, and mantoquita is stannous chloride, cuprous nitrate or cuprous sulfate.
Specific embodiment 8: present embodiment from unlike specific embodiment seven in step 2 when single over cure is added When hydrochlorate, make 20~50:1 of equivalent molar ratio of transition metal salt and single persulfate.
Specific embodiment 9: present embodiment from unlike specific embodiment seven in step 2 when two sulphur were added When hydrochlorate, make 5~50:1 of equivalent molar ratio of transition metal salt and peroxydisulfate.
Specific embodiment 10: present embodiment pending water unlike specific embodiment one or seven is to drink ground Table water, Drinking Water, sanitary sewage or industrial wastewater.
Embodiment one: the present embodiment strengthens the method for Fenton's reaction system removal water pollutant by following using free chlorine Step is implemented:
One, include the trace contaminants such as atrazine, nitrobenzene, Iopromide, pollutant in surface water to be processed after measured Concentration is 2.0mg/L;
Two, the dosage for determining hydrogen peroxide is 2.0mg/L;
Three, the dosage for determining ferrous sulfate is 0.6mg/L;
Four, the pH value for adjusting pending water is 2.5;
Five, ferrous sulfate is then added into pending water, pending water is stirred with the revolving speed of 500r/min, peroxide is added Change hydrogen solution;
Six, the hypochlorite stock solution that effective chlorine density is 10% is rapidly joined again, makes the concentration of effective chlorine in system For 2.5mg/L, carry out strengthening reaction 15min, to remove water pollutant.
The present embodiment can make the removal rate of trace contaminant in drinking water up to 85% or more.
Embodiment two: the present embodiment strengthens the method for Fenton's reaction system removal water pollutant by following using free chlorine Step is implemented:
One, the concentration of COD is 500mg/L in waste water from dyestuff to be processed;
Two, taking the ratio between hydrogen peroxide and the mass concentration of COD is 0.5:1, determines that the dosage of hydrogen peroxide is 250mg/ L;
Three, it is 0.5:3 according to the ratio between molar concentration of divalent iron salt and hydrogen peroxide, determines the dosage of divalent iron salt (70mg/L);
Four, the pH value for adjusting pending water is 3;
Five, divalent iron salt is then added into pending water, pending water is stirred with the revolving speed of 1000r/min, was added Hydrogen peroxide solution;
Six, hypochlorite solutions are rapidly joined again, are made the concentration 10mg/L of effective chlorine in system, are carried out reinforcing reaction 30min, to remove water pollutant.
The present embodiment, which can make to handle COD content in water, reduces by 80%.
Embodiment three: the present embodiment strengthens the method for Fenton's reaction system removal water pollutant by following using free chlorine Step is implemented:
One, the concentration through COD in sanitary sewage to be processed is 200mg/L;
Two, taking the ratio between hydrogen peroxide and the mass concentration of COD is 0.75:1, determines that the dosage of hydrogen peroxide is 150mg/ L;
Three, it is 0.75:3 according to the ratio between molar concentration of divalent iron salt and hydrogen peroxide, determines the dosage of divalent iron salt (62mg/L);
Four, the pH value for adjusting pending water is 3.5;
Five, divalent iron salt is then added into pending water, pending water is stirred with the revolving speed of 750r/min, peroxide is added Change hydrogen solution;
Six, it is quickly passed through chlorine again, makes the concentration 5mg/L of effective chlorine in system, carries out strengthening reaction 20min, thus Remove water pollutant.
The present embodiment can make COD content in sanitary sewage reduce by 90%.
Example IV: the present embodiment strengthens the method for Fenton's reaction system removal water pollutant by following using free chlorine Step is implemented:
One, it is 35mg/L that pending water, which is ammonia-nitrogen content, and COD content is the sewage of farm of 100mg/L;
Two, taking the ratio between hydrogen peroxide and the mass concentration of COD is 0.5:1, determines that the dosage of hydrogen peroxide is 50mg/L;
Three, it is 0.75:3 according to the ratio between molar concentration of ferrous iron and hydrogen peroxide, determines ferrous dosage;
Four, the pH value for adjusting pending water is 3.0;
Five, divalent iron salt is then added into pending water, pending water is stirred with the revolving speed of 500r/min, peroxide is added Change hydrogen solution;
Six, hypochlorite solutions are rapidly joined again, are made the concentration 7.5mg/L of effective chlorine in system, are carried out reinforcing reaction 30min, to remove water pollutant.
The present embodiment, which can make ammonia nitrogen in sewage content reduce by 80%, COD content, reduces by 75%.
Embodiment five: the present embodiment is pressed using the method that free chlorine strengthens class Fenton's reaction system removal water pollutant Column step is implemented:
One, pending water be drink surface water, it includes trace contaminant mainly have Iopromide, Diclofenac, card Horse Xiping etc., concentration are about 2.5mg/L;
Two, the dosage for determining single persulfate is 3mg/L;
Three, it is 1.5:3 according to the ratio between cobalt chloride and the molar concentration of single persulfate, determines the dosage of cobalt chloride;
Four, the pH value for adjusting pending water is 3.5;
Five, cobalt chloride then being added into pending water, pending water being stirred with the revolving speed of 1000r/min, single mistake is added Sulfate liquor;
Six, hypochlorite solutions are rapidly joined again, are made the concentration 2mg/L of effective chlorine in system, are carried out reinforcing reaction 15min, to remove water pollutant.
The present embodiment can make the removal rate of trace contaminant in drinking water up to 85% or more.
Embodiment six: the present embodiment is pressed using the method that free chlorine strengthens class Fenton's reaction system removal water pollutant Column step is implemented:
One, pending water be drink surface water, it includes trace contaminant mainly have Iopromide, Diclofenac, card Horse Xiping etc., concentration are about 2.5mg/L;
Two, the dosage for determining single persulfate is 3mg/L;
Three, the dosage for determining cuprous salt is 0.85mg/L;
Four, the pH value for adjusting pending water is 3.0;
Five, cuprous salt is then added into pending water, pending water is stirred with the revolving speed of 1000r/min, be added single Persulfate solution;
Six, hypochlorite solutions are rapidly joined again, are made the concentration 2mg/L of effective chlorine in system, are carried out reinforcing reaction 10min, to remove water pollutant.
The present embodiment can make the removal rate of trace contaminant in drinking water up to 90% or more.
Embodiment seven: the present embodiment is pressed using the method that free chlorine strengthens class Fenton's reaction system removal water pollutant Column step is implemented:
One, the concentration for measuring COD in landfill leachate to be processed is 1000mg/L;
Two, taking the ratio between peroxydisulfate and the mass concentration of COD is 0.5:1, i.e. the dosage of peroxydisulfate is 500mg/L;
It three, is 0.5:3 according to the ratio between molar concentration of divalent iron salt and peroxydisulfate;
Four, the pH value for adjusting pending water is 3.0;
Five, divalent iron salt is then added into pending water, pending water is stirred with the revolving speed of 1000r/min, was added Dithionate solution;
Six, hypochlorite solutions are rapidly joined again, are made the concentration 15mg/L of effective chlorine in system, are carried out reinforcing reaction 40min, to remove water pollutant.
The present embodiment, which can make to handle COD content in water, reduces by 85%.

Claims (10)

1. strengthening the method for Fenton's reaction system removal water pollutant using free chlorine, it is characterised in that this method presses following step It is rapid to realize:
One, the pH value of pending water is adjusted in 2.0~4.0 ranges;
Two, ferrous salt is then added into pending water, stirs pending water, and hydrogenperoxide steam generator is added;
Three, hypochlorite solutions are added or are passed through chlorine, make 1~15mg/L of concentration of effective chlorine in system, are carried out strong Change reaction, to remove water pollutant.
2. the method according to claim 1 for strengthening Fenton's reaction system removal water pollutant using free chlorine, special Sign is that when pending water be drinking water, and the throwing amount of hydrogen peroxide is 0.5~5mg/L in step 2.
3. the method according to claim 1 for strengthening Fenton's reaction system removal water pollutant using free chlorine, special Sign be when the COD concentration of pending water be greater than 10mg/L when, step 2 control pending water in hydrogen peroxide additional amount with The mass concentration ratio of COD is 0.1~1:1.
4. the method according to claim 1 for strengthening Fenton's reaction system removal water pollutant using free chlorine, special Sign is in step 2 that the molar ratio of ferrous salt and hydrogen peroxide is 0.5~1:3.
5. the method according to claim 1 for strengthening Fenton's reaction system removal water pollutant using free chlorine, special Sign is that the speed stirred in step 2 is 100~1000r/min.
6. the method according to claim 1 for strengthening Fenton's reaction system removal water pollutant using free chlorine, special The time that sign is that step 3 strengthens reaction is 5~60min.
7. strengthening the method for class Fenton's reaction system removal water pollutant using free chlorine, it is characterised in that this method is by following Step is realized:
One, the pH value of pending water is adjusted in 2.0~4.0 ranges;
Two, transition metal salt is then added into pending water, stirs pending water, and single persulfate or peroxy-disulfuric acid is added Salt;
Three, hypochlorite solutions are added or are passed through chlorine, make 1~15mg/L of concentration of effective chlorine in system, are carried out strong Change reaction, to remove water pollutant;
Wherein transition metal salt described in step 2 is one of ferrous salt, mantoquita, zinc salt, zirconates, cobalt salt, manganese salt or more Kind mixture.
8. the method according to claim 7 for strengthening class Fenton's reaction system removal water pollutant using free chlorine, Be characterized in that in step 2 making when single persulfate is added the equivalent molar ratio 20 of transition metal salt and single persulfate~ 50:1.
9. the method according to claim 7 for strengthening class Fenton's reaction system removal water pollutant using free chlorine, Be characterized in that in step 2 making when peroxydisulfate is added the equivalent molar ratio 5 of transition metal salt and peroxydisulfate~ 50:1.
10. the method for removal water pollutant according to claim 1 or claim 7, it is characterised in that pending water is to drink ground Table water, Drinking Water, sanitary sewage or industrial wastewater.
CN201910350303.9A 2019-04-28 2019-04-28 Strengthen Fenton/class Fenton's reaction system removal water pollutant method using free chlorine Pending CN110015744A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627176A (en) * 2019-09-19 2019-12-31 陕西驭腾实业有限公司 COD (chemical oxygen demand) degrading agent and method for degrading COD in wastewater
CN110723803A (en) * 2019-10-22 2020-01-24 哈尔滨工业大学 Method for removing pollutants in water by using high-valence ferric salt composite reagent
CN112777716A (en) * 2020-12-09 2021-05-11 北京理工大学 Method for photocatalytic degradation of trace organic macromolecules in surface water
CN114477418A (en) * 2022-01-29 2022-05-13 哈尔滨工业大学 Method for removing organic pollutants in water by zero-valent iron reinforced hypochlorite
CN115571967A (en) * 2022-09-09 2023-01-06 哈尔滨工业大学 Method for treating salt-containing organic wastewater by using inorganic anion reinforced copper-containing catalyst Fenton system

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