CN102674505A - Special equipment for treating organic sewage by utilizing electro-Fenton reaction - Google Patents
Special equipment for treating organic sewage by utilizing electro-Fenton reaction Download PDFInfo
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- CN102674505A CN102674505A CN2011100612574A CN201110061257A CN102674505A CN 102674505 A CN102674505 A CN 102674505A CN 2011100612574 A CN2011100612574 A CN 2011100612574A CN 201110061257 A CN201110061257 A CN 201110061257A CN 102674505 A CN102674505 A CN 102674505A
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- 239000010865 sewage Substances 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
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- 230000007547 defect Effects 0.000 abstract 1
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- 239000002351 wastewater Substances 0.000 description 17
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 14
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- -1 hydroxyl radical free radical Chemical class 0.000 description 3
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- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses special equipment for treating organic sewage by utilizing electro-Fenton reaction. The special equipment is realized through a tower type reactor with a double-layer tower body consisting of an inner tower wall and an outer tower wall, a scrap iron cathode in the inner tower wall, a graphite rod anode between the inner tower wall and the outer tower wall and an aeration head and a water distribution pipe at the bottom of an inner tower. Since the treated scrap iron is used as the cathode, the defects of complex preparation process of an electrode material, high price, high equipment investment and high operation cost are overcome, meanwhile, the cathode has larger specific surface area, higher reaction rate and higher sewage quality transfer efficiency, the treatment effect and efficiency of organic pollutants in sewage are effectively improved, an oxidant and a catalyst are not required to be added, and further energy is saved and consumption is reduced. Compared with the prior art, the special equipment has prominent substantive characteristics and obvious improvement. The special equipment also has the advantages of novel and unique conception, compact and rational structural design, stable and reliable working performance, easiness, convenience and practicability in operation and control, remarkable economic and practical effects, quite broad application prospect, suitability for promotion of the industry and the like.
Description
Technical field
The invention belongs to electrochemical reaction and handle organic contamination Technology of Sewage field, relate to a kind of equipment that utilizes Fenton process to handle organic sewage specifically.
Background technology
Along with the development of society, the effective processing and the utilization of organic sewage become people's question of common concern.In recent years, country pays much attention to environmental improvement, and this makes a lot of enterprises also quite pay attention to the processing of self water, and pressing for provides corresponding sewage disposal technology and equipment, satisfies energy-saving and emission-reduction, the demand of waste water control.
For a long time, the processing of bio-refractory organic waste water is the difficult point in the environmental improvement always.Traditional biological process seems powerless when handling this type organic.Widely used now method has coagulating sedimentation, absorption, chemical oxidation, IX etc., but all need consume more pharmaceutical chemicals and starting material, and expense is higher, complicated operation, and have the secondary pollution problem.
Advanced oxidation processes (Advanced Oxidation Process; Be called for short AOPs) claim that again deep oxidation is technological; Cause the attention of countries in the world gradually because of it has advantages such as speed of response is fast, processing is complete, nuisanceless, applied widely, and carried out the research and development work of this direction in succession.Generally believe that at present this technology is characteristics with the hydroxyl radical free radical that generation has strong oxidation capacity; Under reaction conditionss such as high temperature, high pressure, electricity, ultrasonic, photoirradiation, catalyzer, make the oxidative degradation of macromole hardly degraded organic substance become low toxicity or nontoxic small-molecule substance even permineralization to become carbonic acid gas and water.In numerous advanced oxidation processes the Fenton advanced oxidation processes ripe relatively because of its technology, simply, do not need special device to realize, and iron has economic advantages as the reactant and the catalyzer of oxidizing reaction, so caused attention both domestic and external gradually.But; Simple Fenton high-level oxidation technology treatment of high concentration organic waste water has its unsatisfactory part equally; For example: the hydrogen peroxide of needs use higher concentration and catalyzer and consumption are big; Make processing cost higher, can produce more iron containing sludge simultaneously has pendingly, still makes to apply to be restricted.And cathodic electricity Fenton technology generates hydrogen peroxide through the negative electrode aeration, the Fe of cathode surface reduction simultaneously
3+Be Fe
2+Make and form the Fenton's reaction district in the electrolyzer near the negative electrode; Anode also can pass through the Electrooxidation degradation partial organic substances simultaneously; Therefore electric Fenton technology has overcome the drawback of traditional Fenton treatment technology, can realize the innoxious conversion to most of hardly degraded organic substance through suitable process adjustments simultaneously.Electricity Fenton technology can be used as industrial organic waste water main processing technology, waste water pre-treatment or advanced treatment technology and be applied to produce actual, have broad application prospects.
At present, can form by devices such as reaction tank, negative electrode, anode, aerators according to the cathodic electricity Fenton water treating equipment of document announcement.Handle though it can pollute sewage to the machine thing, but still exist floor space big, energy consumption is high, and electrode materials complicated process of preparation and costing an arm and a leg causes the high problem of investment of devices and working cost.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide that a kind of floor space is little, electrode materials is cheap, a kind of specific equipment that utilizes electro-Fenton reaction to handle organic sewage that investment is lower with working cost.
The object of the invention will be achieved through following technical proposals: it comprises dc power supply, water inlet pipe, rising pipe, vent valve; Also comprise tower reactor with inner tower wall and the double-deck tower body of outer tower wall; Iron filings negative electrode in the inner tower wall; Graphite-rod anode between inner tower wall and the outer tower wall, and set aeration head of interior tower bottom and water distributor.
The negative electrode that the present invention utilizes the waste iron filing after the processing to constitute; Be filled in the inner tower wall, with graphite rod as anode, through internal tower aeration; Sewage in tower reactor Nei Ta and outside form internal recycle between the tower and flow; Make oxygen molecule generate hydrogen peroxide in cathode surface reduction effectively, a certain amount of ferrous ion or iron ion generation Fenton's reaction in hydrogen peroxide and the sewage reach the purpose of organic pollutant in the degradation of sewage.The present invention compared with prior art has the following advantages and beneficial effect:
1, because the present invention utilizes waste iron filing after the processing as negative electrode; Refuse is fully used; Reduce cost, overcome electrode materials complicated process of preparation in the prior art, cost an arm and a leg, caused the high disadvantage of facility investment and working cost; And the iron filings negative electrode compares with traditional electrode and has higher specific surface area, can effectively improve speed of reaction, the treatment effect of organic pollutant in the sewage and raises the efficiency.Compared with prior art, have outstanding substantive distinguishing features and obvious improvement.
2, because the present invention utilizes waste iron filing after the processing as negative electrode; In the cathodic electricity Fenton's reaction of WWT, it need not add oxygenant and catalyzer separately with the reactant and the catalyzer of the iron filings after handling as oxidation; Can further save energy consumption, reduce cost.And make the hydrogen peroxide and the catalyst consumption amount that exist in the prior art big, processing cost is high, and it is pending to produce iron containing sludge, applies restricted problem and is solved.Still have outstanding substantive distinguishing features and obvious improvement.
3, because the present invention has taked to have the tower reactor structure of inner tower wall and the double-deck tower body of outer tower wall; Can make sewage the Nei Ta of tower reactor and outside form internal recycle between the tower and flow; Thereby effectively improve the mass transfer efficiency of sewage; Organism in the sewage can fully be contacted with the hydroxyl radical free radical of cathodic electricity Fenton's reaction generation and react, obviously improve wastewater purifying efficiency.
4,, compare with the common response pond that not only floor space is little, and it is fast to have speed of response, high efficiency, the outstanding advantage that treatment effect is good because the present invention has taked to have the tower reactor structure of inner tower wall and outer tower wall bilayer tower body.
5,, the internal recycle mobilization of tower reactor is strengthened, thereby accelerated reaction effectively improve processing efficiency because the present invention has taked on inner tower wall, to be provided with the structure of pod apertures.
6, the present invention is except that said characteristics, advantages such as also having inventive concept novel uniqueness, structure design compact and reasonable, stable and reliable working performance, control simple and easy to do, economical and practical remarkable benefit, quite wide, the suitable industry of application prospect is promoted.
Description of drawings
Fig. 1 is a structural representation of the present invention;
Fig. 2 is a plan structure synoptic diagram of the present invention.
Embodiment
A kind of specific equipment that utilizes electro-Fenton reaction to handle organic sewage of the present invention; It is a tower reactor with double-deck tower body formation of inner tower wall 4, outer tower wall 1; The external stability of this tower reactor has water inlet pipe 11, rising pipe 6, top vent valve 9 and bottom gas-feeding pipe 7.The iron filings negative electrode 3 that constitutes for the iron filings after handling in the tower in inner tower wall 4 being is provided with the anode 5 that graphite rod constitutes between inner tower wall 4 and outer tower wall 1, said anode 5 is connected with negative pole with the positive pole of outside dc power supply 10 respectively with negative electrode 3.Also be provided with the aeration head 8 and water distributor 12 that is connected with air-supply duct 7 and water inlet pipe 11 respectively in the bottom of interior tower.
Said iron filings negative electrode 3 is that the waste iron filing that produces with metal processing is a material; Adopt 10% mass concentration Hydrogen chloride to clean and removed surface and oil contaminant in 20 minutes; Use flushing with clean water to be 6-8 again, then at its surface chemistry metal refining Ag or Ti, to form electric Fenton bimetal negative electrode to washing back water pH value.Among the tower, bulk density was 2.0T/ m in it was filled in
3～2.5T/ m
3And iron filings negative electrode 3 is linked to each other with dc power supply 10 negative poles with lead.Place the anode 5 between inner tower wall 4 and the outer tower wall 1 to be graphite rod, the graphite rod diameter is 1cm～5cm, and number can be 3～8, with 10 anodal linking to each other of dc power supply.The interior tower outer wall 1cm～10cm of graphite rod distance, distance is crossed conference and is caused current efficiency to reduce.In order to increase the current efficiency between negative electrode 3 and the anode 5, on inner tower wall 4, be provided with equally distributed pod apertures 2, pod apertures 2 diameters are 1cm～5cm, total percentage of open area is 10%～20% on the inner tower wall 4.
Use the present invention; The pH value that should make sewage is 2～4; And has certain supporting electrolyte concentration to reach the effect that improves electric current; Select suitable ferrous ion concentration according to different sewage qualities, therefore before sewage gets into this tower reactor, should regulate, make it to reach the reaction conditions of regulation sewage.The organic contamination sewage of sewage biochemical oxygen demand between 200mg/L to 300mg/L for example, its best pretreatment condition should reach: the pH value is 2～4, and total dissolved solid can be 400mg/L～600mg/L, ferrous ion concentration is 0.2mmol/L～0.4mmol/L.
When the present invention worked, pending sewage got into tower base fabric water pipe 12 through water inlet pipe 11, tower in getting into through water distributor 12.Pressurized air arrives 8 pairs of sewage of aeration head through air-supply duct 7 and carries out aeration.Sewage is upwards flowed by interior tower under the drive of aeration air, between outer tower wall 1 and inner tower wall 4, flows downward again behind the top of tower in arriving and returns tower bottom, forms internal recycle and flows.And it is mobile under pod apertures 2 effects, further to have strengthened internal recycle.In this process, negative electrode 3 generates hydrogen peroxide through aeration, simultaneously negative electrode 3 surface reduction Fe
3+Be Fe
2+, near negative electrode 3, form the electro-Fenton reaction district, make organism generation chain rupture or open loop in the sewage, and by rapid oxygenolysis.Meanwhile, anode 5 also can pass through the Electrooxidation degradation partial organic substances, thereby realizes the processing of the present invention to bio-refractory organic waste water.Sewage after the processing is discharged the final purification that gets into follow-up filtration or precipitation process unit realization sewage by rising pipe 6.The gas that said reaction process produces is discharged outside the tower through cat head vent valve 9.
In order to show that the present invention is the effect of negative electrode to WWT with the iron filings after handling, we are anode with the graphite rod, and respectively with graphite, iron plate, waste iron filing are negative electrode, investigate the influence of different negative electrodes to the degraded of methyl orange solution electro-fenton process.Test as follows:
Reaction target solution volume: 750mL
The reaction target solution: tropeolin-D concentration is 0.05mmolL
-1
The pH value is 3
Na
2SO
4Concentration is 14.08mmolL
-1
FeSO
4Concentration is 0.27mmolL
-1
Air velocity: 0.1m
3/ h
Groove is pressed and is 5V
Cathode electrode is filled diameter: 60mm
Cathode electrode packing height: 300mm
Under identical condition, it is as shown in table 1 to take electro-Fenton reaction to handle back methyl orange solution percent of decolourization respectively:
The percent of decolourization of the different cathode material degraded of table 1 methyl orange solution
| Time (min) | 5 | 10 | 20 | 30 |
| Graphite cathode | 26.5% | 42.5% | 62.2% | 76.6% |
| The iron plate negative electrode | 37.8% | 45.3% | 68.7% | 82.7% |
| The iron filings negative electrode | 55.5% | 76.2% | 92.4% | 96.8% |
Can find out that from experimental result as negative electrode, its electric Fenton method degradation and decolorization azoic dyestuff has better reaction effect than graphite and iron plate as negative electrode with iron filings.
On this basis, we also use the differential responses device that the degradation and decolorization methyl orange solution has been done the contrast experiment:
Reaction target solution volume is: 750mL
The reaction target solution: tropeolin-D concentration is 0.05mmolL
-1
The pH value is 3
Na
2SO
4Concentration is 14.08mmolL
-1
FeSO
4Concentration is 0.27mmolL
-1
Air velocity: 0.1m
3/ h
Groove is pressed and is 5V
Cathode electrode of the present invention is filled diameter: 60mm, cathode electrode packing height: 300mm
Square reaction tank cathode plate area: 70cm
2, polar plate spacing 4cm
Adopt two kinds of different electric Fenton reactor forms to carry out the processing of same simulated wastewater, it is as shown in table 2 to handle back methyl orange solution percent of decolourization.
The contrast of the multi-form electro-Fenton reactor degraded of table 2 methyl orange solution percent of decolourization
| Reactor types | Tower reactor of the present invention | Square electrolyzer |
| Solution percent of decolourization behind the reaction 15min | 96.7% | 61.2% |
Can find out that through above-mentioned experiment electric Fenton tower reactor of the present invention is higher with respect to the efficient of square electrolyzer degradation and decolorization azoic dyestuff methyl orange solution, the reaction times is shorter.
Meanwhile, we have also done the experiment that the present invention handles furfural production waste water:
Reaction target solution volume is: 750mL
The reaction target solution: through the industrial wastewater from furfural production after the qualitative filter paper filtration,
Chemical oxygen demand COD is 8910～12610mgL
-1
The pH value is 2.45 ~ 3.25
Add Na
2SO
4Concentration is 80mgL
-1
Air velocity: 0.1m
3/ h
Groove is pressed and is 8V
Cathode electrode is filled diameter: 60mm, cathode electrode packing height: 300mm
Adopt reactor drum of the present invention to carry out the processing of furfural production waste water; Reaction time is 5 hours; Adding mass concentration after the processing and be 5% NaOH solution regulator solution pH value is 9, adopts qualitative filter paper to filter then, filter back solution C OD with handle before furfural waste-water COD as shown in table 3.
Table 3 utilizes the present invention to handle furfural production waste water and handles the front and back contrast
| Furfural waste-water COD | Through waste water COD after the filter after the present invention's processing |
| 8910~12610 mg·L -1 | 98 ~83mg·L -1 |
Can be found out obviously that by this experiment utilize the present invention to handle back furfural production waste water COD and have and decline to a great extent, clearance reaches 99%, water outlet meets the primary standard among the national sewage comprehensive emission standard GB8978-1996.
In order to show that further the present invention handles organic effect that sewage is arranged, we have made treatment of dyeing and printing again
Experiment:
Reaction target solution volume is: 750mL
The reaction target solution: certain after the process qualitative filter paper filters is knitted Socks Factory's dyeing waste water,
Chemical oxygen demand COD is 1260～2140mgL
-1
Colourity is 650～1900 times
The pH value is 10.5 ~ 13.5
Add mass concentration and be 5% H
2SO
4It is 3 that solution is regulated the pH value
Add Na
2SO
4Concentration is 100mgL
-1
Air velocity: 0.1m
3/ h
Groove is pressed and is 7V
The internal recycle cathode electrode is filled diameter: 60mm, cathode electrode packing height: 300mm
Adopt the present invention to carry out the processing of dyeing waste water; Reaction time is 3 hours; Adding mass concentration after the processing and be 5% NaOH solution regulator solution pH value is 9, adopts qualitative filter paper to filter then, filter back solution C OD with handle before dyeing waste water COD and percent of decolourization thereof see table 4 for details.
Table 4 utilizes treatment of dyeing and printing situation of the present invention
| Dyeing waste water COD | Waste water COD after the filter after the present invention handles | Percent of decolourization |
| 1260～2140mg·L -1 | 86 ~72mg·L -1 | 95~98% |
Dyeing waste water COD declines to a great extent after experiment can be found out, utilize device processes of the present invention, and percent of decolourization reaches 95% ~ 98%, and water outlet meets the primary standard in the national textile dyeing and finishing industrial water pollution thing emission standard (GB 4287-92).
In sum, it is little that the present invention has floor space, and speed of response is fast; Treatment effect is good; Advantages such as high efficiency, running cost are low, less investment instant effect compared with prior art have outstanding substantive distinguishing features and obvious improvement, are ideal organic sewage treatment facilities at present.Be fit to multiple sector applications such as chemical industry, have bright development prospect and promotional value.
Claims (4)
1. specific equipment that utilizes electro-Fenton reaction to handle organic sewage; Comprise dc power supply (10), water inlet pipe (11), rising pipe (6), vent valve (9); It is characterized in that: this equipment also comprises the tower reactor with inner tower wall (4) and the double-deck tower body of outer tower wall (1); Iron filings negative electrode (3) in the inner tower wall (4), the graphite-rod anode (5) between inner tower wall (4) and the outer tower wall (1), and set aeration head of interior tower bottom (8) and water distributor (12).
2. according to the described specific equipment that utilizes electro-Fenton reaction to handle organic sewage of claim 1; It is characterized in that: said negative electrode (3) is that the waste iron filing that produces with metal processing is a material, adopts 10% mass concentration Hydrogen chloride to clean and removes surface and oil contaminant in 20 minutes, uses flushing with clean water to be 6-8 to washing back water pH value again; Then at its surface chemistry metal refining Ag or Ti; Forming electric Fenton bimetal negative electrode, among the tower, bulk density was 2.0T/ m in said negative electrode (3) was filled in
3～2.5T/ m
3
3. according to the described specific equipment that utilizes electro-Fenton reaction to handle organic sewage of claim 1, it is characterized in that: said graphite rod diameter as anode (5) is 1cm～5cm, and number can be 3～8, the interior tower outer wall 1cm～10cm of distance.
4. according to the described specific equipment that utilizes electro-Fenton reaction to handle organic sewage of claim 1; It is characterized in that: said inner tower wall (4) is provided with equally distributed pod apertures (2); Pod apertures (2) diameter is 1cm～5cm, and total percentage of open area is 10%～20%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110061257 CN102674505B (en) | 2011-03-15 | 2011-03-15 | Special equipment for treating organic sewage by utilizing electro-Fenton reaction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110061257 CN102674505B (en) | 2011-03-15 | 2011-03-15 | Special equipment for treating organic sewage by utilizing electro-Fenton reaction |
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| Publication Number | Publication Date |
|---|---|
| CN102674505A true CN102674505A (en) | 2012-09-19 |
| CN102674505B CN102674505B (en) | 2013-09-11 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496003A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院天津工业生物技术研究所 | Hydroxy free radical high-efficiency generation application device and application method thereof |
| CN104828909A (en) * | 2015-05-16 | 2015-08-12 | 赵东旭 | Wastewater treatment device |
| CN107129012A (en) * | 2017-05-12 | 2017-09-05 | 广州半导体材料研究所 | Reactor |
| CN108840403A (en) * | 2018-05-31 | 2018-11-20 | 长江大学 | A kind of graphite felt cathode material preparation method and modified graphite felt cathode Fenton reactor |
| CN110282705A (en) * | 2019-06-26 | 2019-09-27 | 南京润科环境有限公司 | A kind of novel pipe electricity Fenton oxidation reaction unit |
| CN118084147A (en) * | 2024-04-23 | 2024-05-28 | 交通运输部天津水运工程科学研究所 | Device for realizing pretreatment of port oily sewage based on iron ore powder recovery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496003A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院天津工业生物技术研究所 | Hydroxy free radical high-efficiency generation application device and application method thereof |
| CN104828909A (en) * | 2015-05-16 | 2015-08-12 | 赵东旭 | Wastewater treatment device |
| CN104828909B (en) * | 2015-05-16 | 2016-10-05 | 山东毅康科技股份有限公司 | Wastewater treatment system |
| CN106006855A (en) * | 2015-05-16 | 2016-10-12 | 赵东旭 | Water treatment system |
| CN106006855B (en) * | 2015-05-16 | 2019-02-22 | 南京中洲环保科技有限公司 | A kind of water treatment system |
| CN107129012A (en) * | 2017-05-12 | 2017-09-05 | 广州半导体材料研究所 | Reactor |
| CN108840403A (en) * | 2018-05-31 | 2018-11-20 | 长江大学 | A kind of graphite felt cathode material preparation method and modified graphite felt cathode Fenton reactor |
| CN110282705A (en) * | 2019-06-26 | 2019-09-27 | 南京润科环境有限公司 | A kind of novel pipe electricity Fenton oxidation reaction unit |
| CN118084147A (en) * | 2024-04-23 | 2024-05-28 | 交通运输部天津水运工程科学研究所 | Device for realizing pretreatment of port oily sewage based on iron ore powder recovery |
| CN118084147B (en) * | 2024-04-23 | 2024-06-25 | 交通运输部天津水运工程科学研究所 | Device for realizing pretreatment of port oily sewage based on iron ore powder recovery |
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