CN101759275A - Method for removing organic pollutant in water - Google Patents
Method for removing organic pollutant in water Download PDFInfo
- Publication number
- CN101759275A CN101759275A CN201010039565A CN201010039565A CN101759275A CN 101759275 A CN101759275 A CN 101759275A CN 201010039565 A CN201010039565 A CN 201010039565A CN 201010039565 A CN201010039565 A CN 201010039565A CN 101759275 A CN101759275 A CN 101759275A
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- ferrate
- water
- ozone
- catalyzer
- organic pollutant
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Abstract
The invention discloses a method for removing an organic pollutant in water. The method comprises the following steps: weighing ferrate in a mass ratio of the ferrate to the pollutant of 0.1:1 to 10:1; weighing a catalyst in a mol ratio of the ferrate to the catalyst of 0.01:1 to 2:1; adding the ferrate and the catalyst into the water to be treated; stirring the solution at the water temperature of between10 and 50 DEG C and at a speed of between 150 and 200 r/min for 9 to 60 minutes; and filtering precipitate off, wherein the catalyst is hydrogen peroxide, ozone or a mixture containing any one of the hydrogen peroxide and the ozone; the mixture is the mixture of ferrous salt, ferric salt, aluminum salt, copper salt, a manganese containing compound, alkali, hypochlorite or an absorbent and the hydrogen peroxide or the ozone; and the mass of the hydrogen peroxide and the ozone accounts for over 50 percent of the gross mass of the catalyst. In the scheme of the invention, oxidizers Fe(IV), Fe(V) and hydroxyl free radicals with high activity can be produced to cooperate with one another to oxidize the organic pollutant, in particular a persistent organic pollutant, so that the aim of removing the organic pollutant in the water is fulfilled.
Description
Technical field
The invention belongs to environment protection and chemical technology field, relate to the method for the Persistent organic pollutants in a kind of water treatment method of removing organic pollutant in the water, particularly treating water.
Background technology
High valence iron generally be meant with+4 valencys ,+5 valencys ,+iron that 6 valencys exist, wherein modal existence form is ferrate (FeO
4 2-, Fe (VI)).Ferrate is a kind of inorganic strong oxidizer, and its Standard Electrode Potentials under acid and alkaline condition is respectively 2.2V (FeO
4 2-+ 8H
++ 3e → Fe
3++ 4H
2O) and 0.72V (FeO
4 2-+ 4H
2O+3e → Fe (OH)
3+ 5OH
-) (Lee et al., 2004).In water treatment procedure, ferrate is considered to green oxygenant, coagulating agent and sterilizing agent (Sharma, 2002; Jiang and Lloyd, 2002; Lee et al., 2004), the various organic pollutants (as alcohols, carboxylic-acid, amino acids, organic nitrogen compound, sulfocompound, thiocarbamide etc.) of can effectively degrading, removal inorganic pollutant (as prussiate, ammonia, hydrogen sulfide etc.), metal (Fe
2+, Fe
3+, Mn
2+, Cu
2+) and heavy metal (Pb
2+, Cd
2+, Cr
3+, Hg
2+), (Jiang and Lloyd, 2002) such as degraded algae and microorganisms.Ferrate not only has oxidation capacity than strong advantages such as hydrogen peroxide, potassium permanganate, ozone, the more important thing is that ferrate not only can not produce secondary pollution in the process that is reduced, can not cause any infringement to the mankind and environment, and the Fe of the nascent state of its reduction generation
3+Or Fe (OH)
3Has very strong flocculation activity.
In addition, the oxidation capacity of the intermediate state reduction product Fe (V) of Fe (VI) and Fe (IV) is than Fe (VI) difference strong 3-5 order of magnitude (Sharma, 2004) and 2-3 the order of magnitude (Sharma et al., 2001).
Summary of the invention
Because the intermediate state reduction product Fe (V) of Fe (VI) and the oxidation capacity of Fe (IV) are than Fe (VI) difference strong 3-5 order of magnitude and 2-3 the order of magnitude, therefore the purpose of this invention is to provide the highly active oxygenant Fe of a kind of generation (IV), Fe (V) and hydroxyl radical free radical, come organic pollutant, particularly Persistent organic pollutants in the synergistic oxidation water, thereby reach the method for removing organic pollutant in the water.A kind of method that improves organic pollutant in the ferrate oxidation water promptly is provided.
The method that the present invention removes organic pollutant in the water is following steps:
(1) detection of contamination content, take by weighing ferrate by ferrate and 0.1: 1～10: 1 mass ratio of pollutent, by the mol ratio of ferrate and catalyzer is to take by weighing catalyzer in 0.01: 1～2: 1, described catalyzer be hydrogen peroxide, ozone or contain the two one of mixture;
(2) 9～60min to wherein adding ferrate and catalyzer, 10～50 ℃ of water temperatures, is stirred under speed 150～200r/min condition in pH value to 6～8 of the pending water of adjusting;
(3) filter the removal precipitation.
Above step is described contain the two one of mixture be the mixture of hydrogen peroxide or ozone and one or more medicaments, described medicament is: divalent iron salt, trivalent iron salt, aluminium salt, mantoquita, contain manganic compound, alkali, hypochlorite or sorbent material; As: ferrous sulfate, iron protochloride, iron trichloride, ferric sulfate, polymerization iron, ferric-polysilicate, Tai-Ace S 150, aluminum chloride, polyaluminium sulfate, polymerize aluminum chloride, aluminium silicate polymer, poly aluminium iron silicate, copper sulfate, Manganse Dioxide, permanganate, sodium hydroxide, potassium hydroxide, Losantin, clorox, gac, zeolite, wilkinite, kaolin, diatomite; Hydrogen peroxide or ozone quality account for more than 50% of catalyzer total mass in the mixture.
Each component of catalyzer is that the combination of liquid liquid adds or liquid-solidly adds respectively in the step (2).
The described ferrate that uses can be potassium ferrate or Na2Fe04.Can be that solid form adds, also can be to be dissolved into liquid form to add.
Can contain hydrogen peroxide and ozone simultaneously in the catalyzer; The ozone that adds can be ozone solution or ozone gas.
Method of the present invention can be used to contain the pre-treatment of the water body of organic pollutant, also can be used for its advanced treatment.
The new catalyst that the present invention will contain hydrogen peroxide or ozone adds pending target compound solution, adds ferrate simultaneously, can produce highly active oxygenant Fe (IV), Fe (V) and the hydroxyl radical free radical target compound of degrading.
In the method for the invention, the existence that contains the catalyzer of hydrogen peroxide or ozone can promote the oxidative decomposition of ferrate and the generation of active middle valence state iron (Fe (IV) and Fe (V)), Fe (VI) is converted into middle valence state iron effectively, the oxygen that produces in remaining ferrate or the ferrate self-decomposition process can promote the generation of Fenton reaction, and then produce oxygenant hydroxyl radical free radical efficiently simultaneously, step is simple, and reaction can be carried out at normal temperatures.The present invention-ferrate catalyzed oxidation water technology can be used in feedwater and sewage disposal separately, also can unite use with other water technology.Because catalyzer participates in the removal of ferrate to organism and inorganics, this method can effectively be removed the organic pollutant in the water, as pollutents such as colourity, turbidity, bacterium, virus, algae.The present invention has very high depollution efficient, can improve more all sidedly and handle back water quality.Method of the present invention is easy to realize, can realize industrialized online application, has broad application prospects at water treatment field, and economic benefit is considerable, has the advantage that technology is simple, energy consumption is low, by product is few.The present invention is applicable to the processing of the former water of various water quality.
Embodiment
Embodiment 1: handle the water body contain organic pollutant, as: micro-polluted raw, waste water from dyestuff, contain organophosphorus pesticide sewage, contain endocrine disrupter sewage or sanitary sewage etc.
Detecting the content of water pollutant, take by weighing ferrate by ferrate and 0.1: 1～10: 1 mass ratio of pollutent, is to take by weighing hydrogen peroxide as catalyzer in 0.01: 1～2: 1 by the mol ratio of ferrate and catalyzer; Regulate pH value to 6～8 of pending water, in pending water, add ferrate earlier, add the catalyzer that contains hydrogen peroxide again; Pending water behind the adding water purification agent is stirred fast, and water temperature is 10～50 ℃, and stirring velocity is 150～200r/min; Be 10～60min the duration of contact of ferrate and water, and be 9～60min the duration of contact of catalyzer and ferrate, water; After the filtration, get final product water outlet.
Embodiment 2: the difference of present embodiment and embodiment 1 is: the catalyzer that uses is the mixture of hydrogen peroxide and following one or more medicaments: divalent iron salt, trivalent iron salt, aluminium salt, mantoquita, contain manganic compound, alkali, hypochlorite, sorbent material, ozone, wherein the hydrogen peroxide quality accounts for more than 50% of catalyzer total mass.Other step is identical with specific embodiment 1.
Be arbitrary proportion between other medicaments in the present embodiment except that hydrogen peroxide.
Embodiment 3: the difference of present embodiment and embodiment 2 is: the divalent iron salt that uses is in ferrous sulfate, the iron protochloride one or more.
Embodiment 4: the difference of present embodiment and embodiment 2 is: the trivalent iron salt that uses is in iron trichloride, ferric sulfate, polymerization iron, ferric-polysilicate, the poly aluminium iron silicate one or more.
Embodiment 5: the difference of present embodiment and embodiment 2 is: the aluminium salt that uses is in Tai-Ace S 150, aluminum chloride, polyaluminium sulfate, polymerize aluminum chloride, the aluminium silicate polymer one or more.
Embodiment 6: the difference of present embodiment and embodiment 2 is: the manganic compound that contains that uses is in Manganous chloride tetrahydrate, Manganse Dioxide, the permanganate one or more.
Embodiment 7: the difference of present embodiment and embodiment 2 is: the alkali that uses is in sodium hydroxide, the potassium hydroxide one or more.
Embodiment 8: the difference of present embodiment and embodiment 2 is: the hypochlorite that uses is in Losantin, the clorox one or more.
Embodiment 9: the difference of present embodiment and embodiment 2 is: the sorbent material that uses is in gac, zeolite, wilkinite, kaolin, the diatomite one or more.
Embodiment 10: change the superoxol in the catalyzer into ozone solution or ozone gas.Other are identical with specific embodiment 1 or 2.
Embodiment 11: the ferrate in the present embodiment is selected potassium ferrate or Na2Fe04 for use; Ferrate can for solid-state also can be for liquid state.Other are identical with specific embodiment 1 or 2.
Embodiment 12: the ferrate of present embodiment and the mol ratio of hydrogen peroxide are 0.01-0.1.Other are identical with specific embodiment 1.
Embodiment 13: ferrate and catalyzer in the present embodiment add simultaneously.Other are identical with specific embodiment 1 or 2.
Embodiment 14: each component of the catalyzer in the present embodiment can make up and add also and can add respectively; The composition of catalyzer can be for liquid state, also can contain solid-state composition.Other are identical with specific embodiment 1 or 2.
Embodiment 15: the difference of present embodiment and specific embodiment 1 or 2 is: stirring velocity is 150r/min, and churning time is 6～8min, 10～15 ℃ of water temperatures.Other step is identical with embodiment 1 or 2.
Embodiment 16: the difference of present embodiment and specific embodiment 1 or 2 is: stirring velocity is 170r/min, and churning time is 6～8min, 10～15 ℃ of water temperatures.Other step is identical with embodiment 1 or 2.
Embodiment 17: the difference of present embodiment and specific embodiment 1 or 2 is: stirring velocity is 200r/min, and churning time is 10min, 10～25 ℃ of water temperatures.Other step is identical with embodiment 1 or 2.
Embodiment 18: present embodiment carries out conventional pre-treatment with pending water earlier.Other step is identical with embodiment 1 or 2.
Embodiment 19: present embodiment carries out oxidation pre-treatment with pending water earlier.Other step is identical with embodiment 1 or 2.
Embodiment 20: it is 0.5～2 that present embodiment is selected the mass ratio of ferrate and pollutent, and other step is identical with embodiment 1 or 2.This implementation method is used for oxide treatment.
Embodiment 21: it is 0.1～0.5 that present embodiment is selected the mass ratio of ferrate and pollutent.Other step is identical with embodiment 1 or 2.This implementation method is used for pre-oxidation treatment.
After the above embodiment of process handled and contains the water body of organic pollutant, the organic removal rate that detects in the water outlet was 50-99%.
Method of the present invention is carried out statistical procedures through a large amount of enforcement to data, obtains to draw a conclusion:
Handle the data such as the following table of the pending water ratio that contains organic pollutant with independent use ferrate:
| Clearance (%) | Oil of mirbane | Malachite green | Dimethyl phthalate |
| Independent ferrate | ??40％ | ??50％ | ??20％ |
| Clearance (%) | Oil of mirbane | Malachite green | Dimethyl phthalate |
| Ferrate+catalyzer | Greater than 80% | Greater than 90% | Greater than 50% |
Claims (5)
1. method of removing organic pollutant in the water, it is characterized in that following steps: (1) detection of contamination content, take by weighing ferrate by ferrate and 0.1: 1～10: 1 mass ratio of pollutent, by the mol ratio of ferrate and catalyzer is to take by weighing catalyzer in 0.01: 1～2: 1, described catalyzer be hydrogen peroxide, ozone or contain the two one of mixture; (2) 9～60min to wherein adding ferrate and catalyzer, 10～50 ℃ of water temperatures, is stirred under speed 150～200 r/min conditions in pH value to 6～8 of the pending water of adjusting; (3) filter the removal precipitation.
2. according to the method for organic pollutant in the described removal water of claim 1, it is characterized in that: described contain the two one of mixture be the mixture of hydrogen peroxide or ozone and one or more medicaments; Described medicament is: divalent iron salt, trivalent iron salt, aluminium salt, mantoquita, contain manganic compound, alkali, hypochlorite or sorbent material; Hydrogen peroxide or ozone quality account for more than 50% of catalyzer total mass in the mixture.
3. according to the method for organic pollutant in the described removal water of claim 1, it is characterized in that in the step (2) that each component of catalyzer is that the combination of liquid liquid adds or liquid-solidly adds respectively.
4. according to the method for organic pollutant in the described removal water of claim 1, it is characterized in that: the ferrate that uses is potassium ferrate or Na2Fe04; Adding or be dissolved into liquid form with solid form adds.
5. according to the method for organic pollutant in the described removal water of claim 1, it is characterized in that: contain hydrogen peroxide and ozone in the catalyzer simultaneously; The ozone that adds is ozone solution or ozone gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010039565A CN101759275A (en) | 2010-01-07 | 2010-01-07 | Method for removing organic pollutant in water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010039565A CN101759275A (en) | 2010-01-07 | 2010-01-07 | Method for removing organic pollutant in water |
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| CN101759275A true CN101759275A (en) | 2010-06-30 |
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Cited By (26)
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|---|---|---|---|---|
| CN101857300A (en) * | 2010-07-16 | 2010-10-13 | 太原工业学院 | In-depth coking wastewater and biochemical tail water treatment agent |
| CN101985378A (en) * | 2010-11-19 | 2011-03-16 | 浙江工业大学 | Aluminum-iron combined high-grade oxidation treatment method for organic wastewater |
| CN102167460A (en) * | 2011-03-25 | 2011-08-31 | 中国科学院南京土壤研究所 | Organic phosphonic acid and inorganic phosphorus-containing wastewater treatment technology |
| CN102897893A (en) * | 2012-11-08 | 2013-01-30 | 哈尔滨工业大学 | Method for carrying out oxidation treatment on organic matter in water by using high-activity intermediate state iron |
| CN103693827A (en) * | 2013-12-10 | 2014-04-02 | 江苏绿威环保科技有限公司 | Pre-treatment method for dewatering sludge |
| CN103787482A (en) * | 2014-03-05 | 2014-05-14 | 南京农业大学 | Method for removing endocrine disrupters and phosphorus in water at the same time |
| CN105036293A (en) * | 2015-08-27 | 2015-11-11 | 哈尔滨工业大学 | Method for removing organic pollutants in water by ferrate reinforced ozone oxidation |
| CN105236694A (en) * | 2015-11-16 | 2016-01-13 | 南京大学盐城环保技术与工程研究院 | System and method for deeply treating chemical wastewater and biochemical tail water |
| CN105347587A (en) * | 2015-11-26 | 2016-02-24 | 北京金泽环境能源技术研究有限公司 | Microwave-induced catalytic oxidation method for treating coking biochemical effluent |
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| CN106001096A (en) * | 2016-07-26 | 2016-10-12 | 湖南恒凯环保科技投资有限公司 | Ferrate oxidation co-precipitation-based arsenic-contaminated soil remediation method |
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| CN106241986A (en) * | 2016-08-22 | 2016-12-21 | 陈永桥 | A kind of novel source water ammonia nitrogen removal agent |
| CN107445282A (en) * | 2017-08-30 | 2017-12-08 | 河海大学 | Ruthenium joint high price iron removes the method for treating water of depollution |
| CN108046404A (en) * | 2017-12-20 | 2018-05-18 | 浙江省环境保护科学设计研究院 | A kind of in situ chemical oxidation restorative procedure of organic pollution underground water |
| CN108128925A (en) * | 2017-12-27 | 2018-06-08 | 重庆耐德水处理科技有限公司 | Method for simultaneously removing COD (chemical oxygen demand) and total phosphorus |
| CN108383236A (en) * | 2018-03-30 | 2018-08-10 | 哈尔滨工业大学 | A method of microorganism flco is activated to improve cohesion and dephosphorization performance using ferrate |
| CN108483757A (en) * | 2018-03-19 | 2018-09-04 | 复旦大学 | A kind of method of efficient pre-oxidation enhanced-coagulation |
| CN109250840A (en) * | 2018-09-30 | 2019-01-22 | 江苏农林职业技术学院 | A method of black and odorous water is handled using potassium ferrate and activated carbon combined enhanced coagulation |
| CZ307737B6 (en) * | 2014-01-20 | 2019-04-10 | Univerzita Palackého v Olomouci | Method of treatment of polluted and waste water, in particular sewage and industrial effluents, by a combined use of Fe (0) and Fe (IV) and/or Fe (VI) particles to reduce and oxidize the pollutants under protective atmosphere and a facility to carry it out |
| CN110156144A (en) * | 2018-03-30 | 2019-08-23 | 铜仁学院 | A method of strengthening ozone oxidation using ferrate and removes organic pollutants |
| CN111661911A (en) * | 2020-06-01 | 2020-09-15 | 五邑大学 | Method for removing organic pollutants in 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 |
| CN114804456A (en) * | 2022-04-11 | 2022-07-29 | 天津大沽化工股份有限公司 | Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method |
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2010
- 2010-01-07 CN CN201010039565A patent/CN101759275A/en active Pending
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| CN101857300B (en) * | 2010-07-16 | 2012-01-25 | 太原工业学院 | In-depth coking wastewater and biochemical tail water treatment agent |
| CN101857300A (en) * | 2010-07-16 | 2010-10-13 | 太原工业学院 | In-depth coking wastewater and biochemical tail water treatment agent |
| CN101985378A (en) * | 2010-11-19 | 2011-03-16 | 浙江工业大学 | Aluminum-iron combined high-grade oxidation treatment method for organic wastewater |
| CN101985378B (en) * | 2010-11-19 | 2012-07-25 | 浙江工业大学 | Aluminum-iron combined high-grade oxidation treatment method for organic wastewater |
| CN102167460A (en) * | 2011-03-25 | 2011-08-31 | 中国科学院南京土壤研究所 | Organic phosphonic acid and inorganic phosphorus-containing wastewater treatment technology |
| CN102167460B (en) * | 2011-03-25 | 2012-07-25 | 中国科学院南京土壤研究所 | Organic phosphonic acid and inorganic phosphorus-containing wastewater treatment technology |
| CN102897893A (en) * | 2012-11-08 | 2013-01-30 | 哈尔滨工业大学 | Method for carrying out oxidation treatment on organic matter in water by using high-activity intermediate state iron |
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| CN103693827A (en) * | 2013-12-10 | 2014-04-02 | 江苏绿威环保科技有限公司 | Pre-treatment method for dewatering sludge |
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| CN108046404B (en) * | 2017-12-20 | 2020-04-10 | 浙江省环境保护科学设计研究院 | In-situ chemical oxidation remediation method for organic-polluted underground water |
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| CN108128925B (en) * | 2017-12-27 | 2021-03-02 | 重庆耐德水处理科技有限公司 | Method for simultaneously removing COD (chemical oxygen demand) and total phosphorus |
| CN108483757A (en) * | 2018-03-19 | 2018-09-04 | 复旦大学 | A kind of method of efficient pre-oxidation enhanced-coagulation |
| CN108383236A (en) * | 2018-03-30 | 2018-08-10 | 哈尔滨工业大学 | A method of microorganism flco is activated to improve cohesion and dephosphorization performance using ferrate |
| CN110156144A (en) * | 2018-03-30 | 2019-08-23 | 铜仁学院 | A method of strengthening ozone oxidation using ferrate and removes organic pollutants |
| CN109250840A (en) * | 2018-09-30 | 2019-01-22 | 江苏农林职业技术学院 | A method of black and odorous water is handled using potassium ferrate and activated carbon combined enhanced coagulation |
| CN111661911A (en) * | 2020-06-01 | 2020-09-15 | 五邑大学 | Method for removing organic pollutants in 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 |
| CN114804456A (en) * | 2022-04-11 | 2022-07-29 | 天津大沽化工股份有限公司 | Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method |
| CN115050947A (en) * | 2022-07-29 | 2022-09-13 | 湖北亿纬动力有限公司 | Modified ferrate cathode material, preparation method thereof and lithium ion battery |
| CN116375173A (en) * | 2023-05-24 | 2023-07-04 | 天津大学 | Method for degrading COD in wastewater by activating ferrate/hydrogen peroxide through iron mud catalyst |
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Application publication date: 20100630 |