CN102674505B - 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 PDF

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Publication number
CN102674505B
CN102674505B CN 201110061257 CN201110061257A CN102674505B CN 102674505 B CN102674505 B CN 102674505B CN 201110061257 CN201110061257 CN 201110061257 CN 201110061257 A CN201110061257 A CN 201110061257A CN 102674505 B CN102674505 B CN 102674505B
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tower
tower wall
sewage
negative electrode
wall
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CN102674505A (en
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杨春维
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Dalian haiyifengyue Technology Co.,Ltd.
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Jilin Normal University
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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

A kind of specific equipment that utilizes electro-Fenton reaction to handle organic sewage
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, 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 helpless when handling this type organic.Widely used method has coagulating sedimentation, absorption, chemical oxidation, ion-exchange etc. now, but all needs to 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, abbreviation AOPs) claims the deep oxidation technology again, cause the attention of countries in the world gradually because 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 reactant and the catalyzer of oxidizing reaction, so caused attention both domestic and external gradually.But, simple Fenton high-level oxidation technology is handled high concentrated organic wastewater 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 by 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 innoxious conversion to most of hardly degraded organic substance by suitable process adjustments simultaneously.Electricity Fenton technology can be used as the pre-treatment of main treatment technology, waste water of industrial organic waste water or advanced treatment technology and is applied to produce actual, has broad application prospects.
At present, can be formed 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, the energy consumption height, electrode materials complicated process of preparation and expensive causes investment and the high problem of working cost of equipment.
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.
Purpose of the present invention will be achieved by following technical proposals: it comprises dc power supply, water inlet pipe, rising pipe, vent valve, also comprise the 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 the 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, by 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, reduced cost, overcome electrode materials complicated process of preparation, expensive in the prior art, cause 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 sewage disposal, it need not add oxygenant and catalyzer separately with 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, the processing cost height, 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, because the present invention has taked to have the tower reactor structure of inner tower wall and outer tower wall bilayer tower body, 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.
5, because the present invention has taked to arrange at inner tower wall the structure of pod apertures, the internal recycle mobilization of tower reactor is strengthened, thereby accelerated reaction effectively improve processing efficiency.
6, the present invention is except described characteristics, also has novel uniqueness of inventive concept, structure design compact and reasonable, stable and reliable working performance, simple and easy to do, the economical and practical remarkable benefit of operation control, quite wide, the suitable industry of application prospect and advantage such as promotes.
Description of drawings
Fig. 1 is structural representation of the present invention;
Fig. 2 is 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, described 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 aeration head 8 and the water distributor 12 that is connected with air-supply duct 7 and water inlet pipe 11 respectively in the bottom of interior tower.
Described iron filings negative electrode 3 is that the waste iron filing that produces with metal processing is material, adopt 10% mass concentration dilute hydrochloric acid to clean and removed surface and oil contaminant in 20 minutes, be 6-8 with flushing with clean water to washing back water pH value again, then at its surface chemistry metal refining Ag or Ti, to form electric Fenton bimetal negative electrode.Among the tower, bulk density was 2.0T/ m in it was filled in 3~2.5T/ m 3And with lead iron filings negative electrode 3 is linked to each other with dc power supply 10 negative poles.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, be provided with equally distributed pod apertures 2 at inner tower wall 4, pod apertures 2 diameters are 1cm~5cm, total percentage of open area is 10%~20% on the inner tower wall 4.
Dc power supply 10 output voltages are between 3V~36V, and power requirement matches with the sewage disposal scale, are example per hour to handle 1 cubic metre of sewage, and peak power requires between 800W~1000W.Aeration head 8 sizes should be complementary with interior body of the tower diameter, and the body of the tower internal diameter gets final product in being slightly less than.Airing system pressure should be complementary with tower height, and minimum pressure should be greater than hydraulic pressure at the bottom of the tower and supply air line pressure-losses sum.Air demand is 0.1~0.3 m 3/ h.
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 enters this tower reactor, should regulate sewage, make it to reach the reaction conditions of regulation.The organic contamination sewage of sewage biochemical oxygen demand (BOD) 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 entered tower base fabric water pipe 12 by water inlet pipe 11, enters Nei Ta by water distributor 12.Pressurized air arrives 8 pairs of sewage of aeration head by air-supply duct 7 and carries out aeration.Sewage is upwards flowed by interior tower under the drive of aeration air, flows downward between outer tower wall 1 and inner tower wall 4 again behind the top of tower in arriving and returns tower bottom, forms internal recycle and flows.And it is mobile further to have strengthened internal recycle under pod apertures 2 effects.In this process, negative electrode 3 generates hydrogen peroxide by 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 that the present invention is to the processing of bio-refractory organic waste water.Sewage after the processing is discharged the final purification that enters follow-up filtration or precipitation process unit realization sewage by rising pipe 6.The gas that described reaction process produces is discharged outside the tower by cat head vent valve 9.
For show the present invention with the iron filings after handling be negative electrode to the effect of sewage disposal, we are anode with the graphite rod, respectively with graphite, iron plate, waste iron filing are negative electrode, investigate different negative electrodes to the influence of methyl orange solution electro-fenton process degraded.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%
From experimental result as can be seen, 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 different reactor 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 electro-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 by 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 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 (3)

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), graphite-rod anode (5) between inner tower wall (4) and the outer tower wall (1), and the set aeration head of interior tower bottom (8) and water distributor (12), wherein said iron filings negative electrode (3) is that the waste iron filing that produces with metal processing is material, adopt 10% mass concentration dilute hydrochloric acid to clean and removed surface and oil contaminant in 20 minutes, be 6-8 with flushing with clean water to washing back water pH value again, then at its surface chemistry metal refining Ag or Ti, to form electric Fenton bimetal negative electrode, among the tower, bulk density was 2.0T/m in described negative electrode (3) was filled in 3~2.5T/m 3
2. the specific equipment that utilizes electro-Fenton reaction to handle organic sewage according to claim 1, it is characterized in that: described graphite rod diameter as anode (5) is 1cm~5cm, and number is 3~8, the interior tower outer wall 1cm~10cm of distance.
3. the specific equipment that utilizes electro-Fenton reaction to handle organic sewage according to claim 1, it is characterized in that: described inner tower wall (4) is provided with equally distributed pod apertures (2), and pod apertures (2) diameter is 1cm~5cm, and total percentage of open area is 10%~20%.
CN 201110061257 2011-03-15 2011-03-15 Special equipment for treating organic sewage by utilizing electro-Fenton reaction Active CN102674505B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104496003B (en) * 2014-12-12 2017-01-25 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
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987005004A1 (en) * 1986-02-19 1987-08-27 Shlomo Tamir Process and device for preparing and disinfecting swimming and bathing pool water by using chlorine and ozone
CN101486518A (en) * 2009-02-27 2009-07-22 哈尔滨工业大学 Fenton-like-fluidized bed sewage processor and sewerage treating method therefor
CN102070230A (en) * 2010-12-10 2011-05-25 华中师范大学 Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987005004A1 (en) * 1986-02-19 1987-08-27 Shlomo Tamir Process and device for preparing and disinfecting swimming and bathing pool water by using chlorine and ozone
CN101486518A (en) * 2009-02-27 2009-07-22 哈尔滨工业大学 Fenton-like-fluidized bed sewage processor and sewerage treating method therefor
CN102070230A (en) * 2010-12-10 2011-05-25 华中师范大学 Method for removing organic matters in water by utilizing three-dimensional electrode electro-fenton and device thereof

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