CN1382649A - Process for treating used water difficult to degradate by catalytic internal electrolysis of iron - Google Patents
Process for treating used water difficult to degradate by catalytic internal electrolysis of iron Download PDFInfo
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- CN1382649A CN1382649A CN 02111901 CN02111901A CN1382649A CN 1382649 A CN1382649 A CN 1382649A CN 02111901 CN02111901 CN 02111901 CN 02111901 A CN02111901 A CN 02111901A CN 1382649 A CN1382649 A CN 1382649A
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Abstract
A process for removing heavy metals and the organic substance difficult to degradate from sewage includes proportioning Fe and Cu, adding cationic surfactant modified zeolite, stirring, loading the mixture in filter pool, regulating pH value to 4.5-11, reaction, and regulating pH value to 8-9 to generate Fe(OH)3 as flocculant, which can coagulate the suspended solid and colloid and absorb and soluble pollutants for depositing them. Its advanrtages are high power, effect and high speed.
Description
Technical field
The present invention relates to the technique for treating industrial wastewater of difficult degradation.Further relate to as biochemical pretreatment process, remove in advance in the trade effluent of difficult degradation to the poisonous and hazardous heavy metal of microorganism and organic hard-degraded substance, improve the value of BOD/COD, make waste water be more suitable for follow-up biochemical treatment.
Background technology
Often contain a large amount of Persistent organic pollutants and deleterious heavy metal in the waste water that discharges in the Industrial processes, this type of chemical substance has persistence, can remain in the environment midium or long term, and environment is caused serious harm.According to statistics, the disease in the whole world 80% is all relevant with the water pollution, and mankind itself's health in a large amount of pollutent serious threats in the water body.Usually, the BOD/COD of trade effluent ratio is far smaller than sanitary wastewater, therefore usually need carry out various physical chemistry pre-treatment earlier before traditional biological treatment.Such as filtration, use the advanced oxidation processes of ultraviolet, hydrogen peroxide, ozone, extraction process, methods such as coagulant sedimentation.But the ability of the removal pollutent that these methods have relatively a little less than, relatively poor to Persistent organic pollutants and deleterious heavy metal removal effect, though high processing costs costliness is invested in producing effect of having.The focus that this class is poisonous, the Research on New of the Industrial Wastewater Treatment of difficult for biological degradation is still current research work.
The effect of adopting the internal electrolysis of iron method of simple iron filings in wastewater treatment, to have its uniqueness.It is to utilize iron filings to form the filter tank as filtrate, and a series of electrochemistry takes place during by this filter tank waste water and physical chemistry (chemical reaction and coagulation) makes the difficult degradation thing obtain handling.The material therefor iron filings are wastes of mechanical workout, so processing costs is very low.Its principle of work is in containing the aqueous solution of acidic electrolyte bath, forms numerous small galvanic cell between the carbon that contains in iron and the iron filings (as impurity, form cementite-iron-carbon compound with iron, its electrochemical properties is similar to graphite).Be oxidized to Fe as anodic iron
2+, heavy metal and organic pollutant then can reduce on the carbon as negative electrode; The Fe of Chan Shenging on the other hand
2+Stronger reducing power is arranged, also can make pollutent be reduced into ortho states: part difficult degradation ring-type organism ring crack is separated, and generates the open loop organism of phase commute degraded, has improved the ratio of BOD/COD, thereby improves the biodegradability of waste water.The internal electrolysis of iron method developed into electrolysis in the iron charcoal afterwards, promptly in iron filings, add carbon granule (coke, granular active carbon etc.), this is actually the area that has increased greatly as the carbon of negative electrode, has just increased the quantity of galvanic cell, has significantly improved electrochemical reaction efficient.Gac has very strong adsorption, again as negative electrode, has play a part organism is enriched to negative electrode, has quickened the reduction of organic pollutant.The Fe that produces
2+Become Fe after oxidized
3+, after neutralization, obtain having the Fe (OH) of very strong throwing out
3Suspended solids, coacervation of colloid precipitation in the waste water can be adsorbed great amount of soluble organic pollutant coprecipitation simultaneously, waste water is further purified.
Though electrolysis has many advantages in iron, the iron charcoal, iron filings can be formed piece after the long-time running, and effect greatly descends, even can't move.This is the reason that this technology can not obtain fine application.
Summary of the invention
The objective of the invention is to disclose a kind of treatment process of efficient and economic indegradable industrial effluent.
In order to achieve the above object, the present invention adds the zeolite of copper and cats product modification as catalyzer in internal electrolysis of iron.Iron is as the anode of galvanic cell, and copper replaces carbon to become the negative electrode of galvanic cell.Difference in Electrode Potential between the iron copper is bigger than the difference in Electrode Potential between the iron charcoal, so just has a greater variety of heavy metals and organic pollutant can obtain removing on electrode and reduction.And the zeolite of cats product modification has quickened the mass transfer process of these pollutents to electrode surface to heavy metal and organic pollutant adsorption inrichment, has further improved treatment effect.The inventive method specifically is divided into three steps:
The first step: copper and iron are pressed W
Cu/ W
Fe=0.1～1.0 ratio weighings are good, and add the zeolite of cats product modification according to the different situations of waste water, its content is the 0%-10% of iron and copper gross weight, thorough mixing, iron, copper and the zeolite of cats product modification are fully contacted, put into the filter tank as filler.Above-mentioned metallic iron can be the leftover bits of iron plate, iron filings, iron powder, iron ball or iron; Metallic copper also can be the leftover bits of sheet, chip, powdery, copper or be processed into tubulose, netted and other shape with copper material, even the box or cage reactor that can directly make by copper material, the zeolite of iron and cats product modification is packed into wherein, form the filter tank.So in use can regularly hang out easily and clean and charging, overcome the weakness in the interior electrolysis of iron (iron charcoal) filter tank, solve the problem of iron filings long-time running meeting caking.
Second step: transfer pH to suitable value (being generally 4.5～11.0) waste water in the filter tank.Improve water temperature and help the carrying out that react, the general high more effect of temperature is good more, but the heating of a large amount of waste water increases processing cost widely, generally can under the natural temperature of waste water, allow waste water in the filter tank, circulate repeatedly, its reflux ratio depends on the type of waste water, be generally 2: 1～10: 1, and made waste water that the sufficient reaction times be arranged in the filter tank.Entire reaction course needs to carry out under the situation of aeration not.
The 3rd step: after reflux finishing, the pH of waste water is transferred to 8.0～9.0, makes the Fe that in second step, generates
3+Further generate flocculation agent Fe (OH)
3, with suspended solids, coacervation of colloid in the waste water, and the solubility pollutent coprecipitation in the absorption waste water, waste water is purified.
Advantage of the present invention is as follows:
1. because the present invention has used the metallic copper of a katalysis, widened the potential difference between the anode and cathode in the galvanic cell, made that more heavy metal and organic pollutant can directly react in the waste water on electrode.And entire reaction is to carry out under the anaerobic conditions of aeration not, do not have dissolved oxygen to participate in the electrode reaction of galvanic cell, more is that pollutent reacts on electrode.Therefore method of the present invention is than far better with electrolysis effectiveness in internal electrolysis of iron or the iron carbon, and the ability of handling the difficult degradation pollutent is stronger, and decolorizing effect is remarkable.
2. the adsorption and enrichment effect of the zeolite of cats product modification has improved treatment effect and speed especially.
3. electrolysis generally can only be carried out under acidic conditions in iron, the iron charcoal, and the pH scope that the present invention is suitable for is big, can not only carry out under acidic conditions, and can carry out under neutral and weak basic condition (handling the pH standard of back water outlet) usually.
4. because aeration not, the dissolved oxygen in the water seldom, metallic iron and Fe
2+Can be not in a large number and O
2The consumption of inaction is done in reaction, so the sludge quantity that the consumption of iron filings of the present invention and reaction produce is wanted much less than electrolysis in iron, the iron charcoal.
5. the entire treatment expense is cheap.Employed iron is the waste material of metal works processing often, and is very cheap; The present invention has just increased the zeolite as the metallic copper of catalyzer and cats product modification, copper also can be the waste material of metal works processing, and it can not consume basically as negative electrode in whole wastewater treatment, and the expense of copper is disposable investment.The price of the zeolite of cats product modification is also inexpensive, but also life-time service.
6. the present invention often does pre-treatment, can will remove the poisonous and hazardous hard-degraded substance of microorganism in advance, has improved BOD/COD, makes waste water be more suitable for follow-up biochemical treatment, makes water outlet up to standard fully.
Embodiment
Embodiment 1: the effect of handling waste water with method of the present invention and prior art compares.
The first step: weigh the iron filings of three parts of identical weight, first part does not add catalyzer copper and modified zeolite, is simple iron filings, is called filtrate A; Second part adds catalyzer copper, and iron filings and copper scale are pressed W
Cu/ W
Fe=0.6 ratio, thorough mixing is formed filtrate B; The 3rd part of zeolite that adds 3% cats product modification of iron filings and copper scale total amount on second part basis again, thorough mixing is formed filtrate C.A, B, three parts of filtrates of C are put into three filter tanks respectively.Following implementation step is identical.
Second step: waste water in the filter tank is transferred pH to 8.5, and aeration does not allow waste water at above-mentioned filter tank internal recycle with 5: 1 reflux ratio at normal temperatures, and hydraulic detention time is 1.5 hours, makes waste water fully reaction in the filter tank.
The 3rd step: quiescent setting 30 minutes, survey its supernatant liquor.
In the filter tank that above-mentioned A, B, three filtrates of C are formed, adopt two kinds of reactive brilliant red waste water from dyestuff 1 of identical art breading and 2.The COD of reactive brilliant red waste water from dyestuff 1 is 600mg/l before the pre-treatment, and BOD is 0.COD before 2 pre-treatment of reactive brilliant red waste water from dyestuff is 660mg/l, and BOD is 0.Detected result after the processing shows: two kinds of method effects of the present invention of B, C are better, as follows the table 1 of face.
Table 1: the inventive method and prior art iron pretreating effect are relatively
| Kind of waste water | Filtrate A handles back COD (mg/l) | Filtrate A handles back BOD (mg/l) | Filtrate B handles back COD (mg/l) | Filtrate B handles back BOD (mg/l) | Filtrate C handles back COD (mg/l) | Decolorizing effect after filtrate C handles |
| Reactive brilliant red waste water from dyestuff 1 | ????530 | ????15 | ???415 | ????55 | ????365 | Bright red → light dark red |
| Reactive brilliant red waste water from dyestuff 2 | ????590 | ????10 | ???488 | ????43 | ????430 | Bright red → light dark red |
Embodiment 2: with method of the present invention gasoline waste water is handled.
The first step: copper sheet and iron plate are pressed W
Cu/ W
Fe=0.5 ratio weighing is good, adds the zeolite of 3% cats product modification of copper sheet and iron plate gross weight, and thorough mixing is formed filtrate and put into the filter tank.
Second step: the pH that regulates waste water is 8.0, and aeration does not allow waste water at above-mentioned filter tank internal recycle with 6: 1 reflux ratio at normal temperatures, and hydraulic detention time is 1 hour, and waste water is reacted in the filter tank fully.
The 3rd step: quiescent setting 30 minutes, survey its supernatant liquor, the results are shown in Table 2.
The treatment effect of table 2. gasoline waste water
| Kind of waste water | COD (mg/l) before the pre-treatment | BOD (mg/l) before the pre-treatment | COD after the pre-treatment (mg/l) | BOD after the pre-treatment (mg/l) | Decolorizing effect |
| Gasoline waste water | ????590 | ????21 | ????100 | ????60 | Black muddiness → the water white transparency of band |
Embodiment 3: with the processing of method of the present invention to Craft in Chemical Industrial Area waste water
The first step: copper sheet and iron plate are pressed W
Cu/ W
Fe=0.4 ratio weighing is good, adds the zeolite of 3% cats product modification of copper sheet and iron plate gross weight, and thorough mixing is put into the filter tank.
Second step: waste water is transferred pH to 7.5, and aeration does not allow waste water at above-mentioned filter tank internal recycle with 6: 1 reflux ratio at normal temperatures, and hydraulic detention time is 2 hours, and waste water is reacted in the filter tank fully.
The 3rd step: reflux and finish, regulate pH to 8.5, quiescent setting 30 minutes is surveyed its supernatant liquor (seeing Table 3).
The treatment effect of table 3. wastewater from chemical industry
| Kind of waste water | COD (mg/l) before the pre-treatment | BOD (mg/l) before the pre-treatment | COD after the pre-treatment (mg/l) | BOD after the pre-treatment (mg/l) | Decolorizing effect |
| Wastewater from chemical industry | ????460 | ????175 | ????210 | ????120 | Purplish red → pale brown look |
Embodiment 4: the temperature of the inventive method is to the influence of coking water treatment effect
The first step: copper sheet and iron plate are pressed W
Cu/ W
Fe=0.5 ratio weighing is good, adds the zeolite of 4% cats product modification of copper sheet and iron plate gross weight, and thorough mixing is put into the filter tank.
Second step: the pH of waste water is 7.0 in the filter tank, and aeration not allows waste water at the filter tank internal recycle T=25 ℃ and 50 ℃ of reflux ratios with 5: 1 respectively, and hydraulic detention time is 1.5 hours, and waste water is reacted in the filter tank fully.
The 3rd step: regulate pH to 8.5, quiescent setting 30 minutes is surveyed its supernatant liquor (seeing Table 4).
Table 4. temperature is to the influence of coking water treatment effect
| Temperature (℃) | COD (mg/l) before the pre-treatment | BOD (mg/l) before the pre-treatment | COD after the pre-treatment (mg/l) | BOD after the pre-treatment (mg/l) | Decolorizing effect |
| ????25 | ????650 | ????153 | ????450 | ????95 | Dark-brown → bright yellow |
| ????50 | ????650 | ????153 | ????370 | ????80 | Dark-brown → bright yellow |
Example is only for the part example among the present invention, and is not as a limitation of the invention.
Claims (2)
1. the method for the treatment of used water difficult to degradate by catalytic internal electrolysis of iron is characterized in that:
The first step: copper and iron are pressed W
Cu/ W
Fe=0.1～1.0 ratio weighings are good, and add the zeolite of 0%～10% cats product modification of copper and iron gross weight according to the different situations of sewage, and thorough mixing as filtrate, is put into the filter tank;
Second step: the pH of pending waste water is transferred to 4.5～11.0, under the natural temperature of sewage, allow waste water in the filter tank, circulate repeatedly, its reflux ratio is 2: 1～10: 1, make waste water that the sufficient reaction times be arranged in the filter tank, entire reaction course needs to carry out under the situation of aeration not;
The 3rd step: after reflux finishing, the pH of the waste water in the filter tank is transferred to 8.0～9.0, makes the Fe that in second step, generates
3+Further generate flocculation agent Fe (OH)
3, with suspended solids, colloidalmaterial cohesion in the sewage, and the solubility pollutent coprecipitation in the absorption sewage, sewage is purified.
2. the method for the treatment of used water difficult to degradate by catalytic internal electrolysis of iron according to claim 1, it is characterized in that: described filtrate can also directly be made box by copper material or the cage reactor, the zeolite of iron and cats product modification is packed into wherein, as filtrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021119015A CN1167627C (en) | 2002-05-31 | 2002-05-31 | Process for treating used water difficult to degradate by catalytic internal electrolysis of iron |
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|---|---|---|---|
| CNB021119015A CN1167627C (en) | 2002-05-31 | 2002-05-31 | Process for treating used water difficult to degradate by catalytic internal electrolysis of iron |
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| CN1167627C CN1167627C (en) | 2004-09-22 |
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| CN1331782C (en) * | 2003-09-25 | 2007-08-15 | 同济大学 | Method for improving capability of linking up with biomembrane of suspension padding |
| CN100391871C (en) * | 2006-10-19 | 2008-06-04 | 上海交通大学 | Anoxybiotic/aerobic two-section internal electrolysis organic waste water treating method |
| CN100400433C (en) * | 2005-08-16 | 2008-07-09 | 同济大学 | Strengthened primary treatment method for internal electrolyzing sewage through aeration and catalyzing iron |
| CN100402441C (en) * | 2005-09-19 | 2008-07-16 | 上海城市污染控制工程研究中心 | Method for treating sewage by catalytic iron internal electrogravimetry and its filler |
| CN101955279A (en) * | 2010-07-13 | 2011-01-26 | 同济大学 | Advanced treatment method of industrial waste water by combining catalysis internal electrolysis, coupling, oxidization and flocculation |
| CN101691269B (en) * | 2009-10-22 | 2011-04-13 | 同济大学 | Method for pre-treating difficultly-degradable wastewater by catalyzed iron inner electrolysis fluidized bed |
| CN102101733A (en) * | 2011-01-12 | 2011-06-22 | 中国科学院生态环境研究中心 | Method for treating electroplating comprehensive wastewater by scrap iron electrolysis and electrochemical technology |
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| CN102336454A (en) * | 2010-08-26 | 2012-02-01 | 隆润新技术发展有限公司 | Application of catalyzed inner electrolysis method in organosilicone waste water treatment |
| CN101734826B (en) * | 2008-11-18 | 2013-01-02 | 南京理工大学 | Process method for treating coking wastewater |
| CN103787466A (en) * | 2014-01-24 | 2014-05-14 | 中南大学 | Pulse enrichment device and method for quick treatment of high-concentration heavy metal wastewater |
| CN104250045A (en) * | 2013-06-25 | 2014-12-31 | 株式会社韩美Entec | Water treatment system for treating ionic materials and hardly degradable substances by utilizing alloy catalytic reactor |
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| CN115259487A (en) * | 2022-07-27 | 2022-11-01 | 四川天宇油脂化学有限公司 | Industrial wastewater treatment method |
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2002
- 2002-05-31 CN CNB021119015A patent/CN1167627C/en not_active Expired - Fee Related
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| CN100400433C (en) * | 2005-08-16 | 2008-07-09 | 同济大学 | Strengthened primary treatment method for internal electrolyzing sewage through aeration and catalyzing iron |
| CN100402441C (en) * | 2005-09-19 | 2008-07-16 | 上海城市污染控制工程研究中心 | Method for treating sewage by catalytic iron internal electrogravimetry and its filler |
| CN100391871C (en) * | 2006-10-19 | 2008-06-04 | 上海交通大学 | Anoxybiotic/aerobic two-section internal electrolysis organic waste water treating method |
| CN101734826B (en) * | 2008-11-18 | 2013-01-02 | 南京理工大学 | Process method for treating coking wastewater |
| CN101643259B (en) * | 2009-08-25 | 2011-10-19 | 苏州大学 | Additive of dyeing process for reclaimed water reusing |
| CN101691269B (en) * | 2009-10-22 | 2011-04-13 | 同济大学 | Method for pre-treating difficultly-degradable wastewater by catalyzed iron inner electrolysis fluidized bed |
| CN101955279A (en) * | 2010-07-13 | 2011-01-26 | 同济大学 | Advanced treatment method of industrial waste water by combining catalysis internal electrolysis, coupling, oxidization and flocculation |
| CN102336454A (en) * | 2010-08-26 | 2012-02-01 | 隆润新技术发展有限公司 | Application of catalyzed inner electrolysis method in organosilicone waste water treatment |
| CN102101733A (en) * | 2011-01-12 | 2011-06-22 | 中国科学院生态环境研究中心 | Method for treating electroplating comprehensive wastewater by scrap iron electrolysis and electrochemical technology |
| CN102101733B (en) * | 2011-01-12 | 2013-06-12 | 中国科学院生态环境研究中心 | Method for treating electroplating comprehensive wastewater by scrap iron electrolysis and electrochemical technology |
| CN104250045A (en) * | 2013-06-25 | 2014-12-31 | 株式会社韩美Entec | Water treatment system for treating ionic materials and hardly degradable substances by utilizing alloy catalytic reactor |
| CN103787466A (en) * | 2014-01-24 | 2014-05-14 | 中南大学 | Pulse enrichment device and method for quick treatment of high-concentration heavy metal wastewater |
| CN103787466B (en) * | 2014-01-24 | 2016-05-18 | 中南大学 | A kind of device and method of high-concentration heavy metal waste water fast processing pulse enrichment |
| CN105696017A (en) * | 2016-04-19 | 2016-06-22 | 盐城工学院 | Novel technical method for reducing nitrobenzene by using iron |
| CN108218171A (en) * | 2018-02-06 | 2018-06-29 | 河海大学 | The in-situ remediation method of huge reservoir polluted bed mud under a kind of anaerobic in low temperature environment |
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| CN115259487B (en) * | 2022-07-27 | 2024-01-23 | 四川天宇油脂化学有限公司 | Industrial wastewater treatment method |
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