CN1180987C - Method of treating industrial waste water by actived sludge-micro-electrolytic process - Google Patents

Method of treating industrial waste water by actived sludge-micro-electrolytic process Download PDF

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Publication number
CN1180987C
CN1180987C CNB011428589A CN01142858A CN1180987C CN 1180987 C CN1180987 C CN 1180987C CN B011428589 A CNB011428589 A CN B011428589A CN 01142858 A CN01142858 A CN 01142858A CN 1180987 C CN1180987 C CN 1180987C
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waste water
wastewater
sludge
iron
carbon steel
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CN1429779A (en
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斌 黄
黄斌
邓建利
张方银
杨晓奕
路明义
潘咸峰
吕军
张淑红
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Sinopec Qilu Co
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Sinopec Qilu Co
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Abstract

The present invention provides an efficient method for treating industrial wastewater containing substances difficult to biologically degrade. The method comprises: the treatment of orlon wastewater, dyeing wastewater, textile wastewater and petrochemical wastewater, particularly the dry treatment of orlon wastewater. The method has the advantages of low slag producing quantity, high COD removal rate, simple process and easy implement. The process comprises: industrial wastewater is treated by using activated sludge and a micro electrolysis method, and specifically carbon steel is arranged in a common activated sludge system; industrial wastewater is treated by using the micro electrolysis principle; and the pH value regulating range is from 3.5 to 9.

Description

Method for the treatment of industrial waste water by actived sludge-micro-electrolytic process
1. technical field
The present invention relates to a kind of processing method of industrial waste water.
2. background technology
At present, the method that the processing trade effluent the most generally adopts is an activated sludge process, this method has characteristics such as economy, effective and easy industrial implementation, but contain the trade effluent of recalcitrant substance for those, as Nitrilon waste water, dyeing waste water etc., adopt the processing of activated sludge process often not reach expected effect, so people usually increase the pre-treatment measure before activated sludge process.Iron dust filtration also claims microbattery method or corrosion cell method, promptly is a kind of important pretreatment process.That this method has is applied widely, treatment effect good, the characteristics of with low cost and convenient operating maintenance, and mostly the iron filings that use be also not need to consume limited electric power resource from the rubbish of cutting industry, has the meaning of " treatment of wastes with processes of wastes against one another ".The shortcoming that the investment that this method has changed conventional waste water disposal system to a certain extent is big, working cost is high.
Iron dust filtration method processing trade effluent is based on the cell reaction in the electrochemistry, we know with metal anode directly and cathode material contact, be immersed in and then cell reaction take place in the electrolyte solution and form corrosion cell, so-called corrosion reaction just takes place, and metal anode is corroded and consumes.Corrosion cell can be divided into microcosmic corrosion cell and macro etch battery again, and the former is meant that in the metallic surface owing to the battery that exists many atomic little electrodes to form, the latter is meant " macrocell " that electrode constituted that can be seen by naked eyes.Iron filings are alloys of iron and carbon, promptly are made up of pure iron and iron carbide and some impurity.Iron carbide and other impurity particle are dispersed in the iron filings with minimum particulate form, because their electrode potential is lower than iron, just formed numerous corrosion microbattery in the time of in being in electrolyte solution, just there is electric current in thousands of tiny batteries, to flow on its surface, iron is as the anode consumption that is corroded, when macroscopical cathode materials such as gac is arranged in the system exist, can form the macro etch battery again.The nascent state Fe that electrode reaction generates 2+And the Fe of further oxidation generation 3+The hydrate that reaches them has stronger absorption-flocculation activity, and particularly original position generates Fe (OH) after adding the adjusting PH with base value 2And Fe (OH) 3Colloid flocculation agent, its adsorptive power are higher than the Fe (OH) that general medicament hydrolysis obtains 3, can adsorb dispersive molecule, metal ion and organic macromolecule in the waste water in a large number, and flocculation sediment gets off.In the environment of neutrality or slant acidity, iron filings electrode itself and the nascent state H, the Fe that are produced 2+Deng can with many component generation redox reactions in the waste water.Such as chromophoric group that can destroy the coloring matter in the colorful wastewater or auxochrome group, even chain rupture, can decolour, reduce COD and improve biodegradability, all right reducing heavy metal ion, reduce its toxicity etc., the organism in the used water difficult to degradate is had removal effect preferably.
Handle waste water since its birth beginning with the corrosion cell method, just cause extensive attention, and carried out big quantity research." environmental engineering " 1999,17 the 4th phases of volume " little electrolysis-acidication/contact oxidation technology is handled dying Study on wastewater " adopt little electrolysis-H/O technology that dying waste water has been carried out handling research, its shortcoming is, during little electrolysis treatment for reaching treatment effect preferably, need to consume a large amount of acid and adjust water inlet pH value in the strongly-acid scope, best less than 1.8.This is because the pH value is low more, H +The concentration height, the Fe that reaction generates 2+Also many more, help reducing chromophoric group and Fe (OH) 2Generate also morely, help flocculation reaction, also will adjust the pH value so that carry out subsequent disposal with alkali afterwards, make operation become loaded down with trivial details, acid and alkali consumption has increased running cost again.In addition, this micro-electrolysis method is lower for the COD clearance of trade effluent that those contain recalcitrant substance.
" Xi'an University of Architecture and Technology's journal " 1997, in 29 the 3rd phases of volume " effect of little aeration in the iron filings method treatment of dyeing and printing inquired into " literary composition, by the dissolved oxygen in the aeration increase waste water, strengthen the eliminating that little electrolytic action promotes the iron filings surface mass again, improved the processing efficiency of iron filings methods to a certain extent.Still there is following shortcoming in this technology: need when iron chip corrosion battery method is handled trade effluent iron filings are mixed the composition battery system with gac or carbonaceous material, increased processing cost or produced the quantity of slag, cause bigger difficulty for the processing of follow-up slag.
3. summary of the invention
The invention reside in provides a kind of high efficiency pre-treatment to contain the method for the trade effluent of recalcitrant substance, comprises Nitrilon waste water, dyeing waste water, textile waste and petrochemical wastewater, and this method product quantity of slag is low, COD decreasing ratio height, technology is simple, and cost for wastewater treatment is low, and is easy to implement.
According to the present invention, the method for a kind of active sludge-little processing of industrial waste water by electrolysis is provided, be included in and arrange carbon steel 2 (see figure 1)s in the common active sludge system, pH value in conditioned reaction district is 3.5~9.The carbon steel of being arranged 2 can be an angle bar, also can be cast iron, and this material is so long as the alloy of iron that is easy to get rusty and carbon all belongs to this patent scope of invention.
In above-mentioned system, iron is reducing substances, and when oxidized, its two electronics that provide have the organic structure function of destruction, even can chain rupture by electrode reaction.The product Fe of electrode reaction 2+Also have more intense reductibility, help Fe 3+Generation, produce the very strong Fe (OH) of cohesive force 3Colloid, the organism in the absorption sewage.When this system and the coexistence of active sludge system,, can play on the one hand and stir and the effect of minimizing concentration polarization by aeration, the carrying out of accelerating electrode reaction, simultaneously provide oxygen, make that microorganism is easier in the active sludge decomposes the organism in the system, reduce waste water COD to active sludge.
The control of reaction zone pH value is very important, in above-mentioned scope, has both helped the carrying out of micro-electrolysis reaction, also is in the scope that microorganism can survive in the active sludge, and active sludge is by domestication, and its pH value of standing can reduce.PH value scope is 4.5~6.5 preferably, and this pH value helps quickening the corrosion of iron down, thereby quickens Sludge System to organic removal ability.
Mud should be kept certain concentration in the reaction zone, and sludge concentration is too high, and mud-water separation is difficulty comparatively, and air consumption is big, and low then not the reaching of concentration removed organic purpose effectively, and the sludge concentration scope is 2~4g/L preferably.Sludge retention time should maintain 8~12 days.Reaction zone dissolved oxygen scope preferably is greater than 0.5mg/L.Hydraulic detention time should be greater than 2 hours, and hydraulic detention time prolongs the treatment effect that can improve waste water.Temperature of reaction is a normal temperature.In system of the present invention, carry out pure oxygen aeration or add measures such as Powdered Activated Carbon all can improving the inventive method to removal effect of organic matter.
In stage on-test, active sludge need be tamed, and the dry acrylic fiber processing wastewater be the results are shown in Figure 2 at 20# carbon steel and two kinds of unlike materials of angle bar as the domestication that corrosive medium carries out.Among the figure, active sludge-little electrolytic trial is through the time about an about week, the waste water COD decreasing ratio begins to rise gradually, the COD decreasing ratio can reach more than 40% after two weeks, the sludge acclimatization time that employing active sludge-micro-electrolysis treatment acrylic fibers waste water by dry process is described is shorter, and the industrial application ratio is easier to realize.
This method is compared with conventional iron chip corrosion battery method, produces the quantity of slag and reduces significantly.When handling trade effluent, iron chip corrosion battery method needs iron filings are mixed the composition battery system with gac or carbonaceous material, so after reaction finished, a large amount of gacs or carbonaceous material were discharged with the form of waste residue.And adopt the carbon steel piece in the inventive method, the Fe (OH) that only responds and produce 3Colloid is discharged with the discharge of excess sludge, and producing the quantity of slag only is to have increased the Fe (OH) that discharges 3Colloid obviously reduces than the product quantity of slag of iron chip corrosion battery method.
In addition, this law is for the COD decreasing ratio height of the trade effluent that contains difficult for biological degradation, and for acrylic fibers waste water by dry process, the COD decreasing ratio can reach 51.3%.COD and colourity for waste water from dyestuff all have removal effect preferably.
And this law has been saved and has been adopted soda acid to regulate the step of pH value repeatedly, saves the soda acid expense and makes technology become simple.The iron loss vector is little in this law, and the etching extent of 20# carbon steel and angle bar is respectively 31.25mg/L waste water and 43.33mg/L waste water, from considering this method economical and effective economically.
4. description of drawings
Fig. 1 is active sludge-micro-electrolysis treatment trade effluent equipment therefor and schematic flow sheet.In integral bio reaction tank 1, arrange carbon steel 2, in the integral bio reaction tank 1 active sludge is housed, feed pressurized air from bottom, pond gas pipe 3, the bottom water inlet, water inlet mixes the back in the bottom with active sludge and fully contacts with carbon steel 2 at reaction zone, enters the negative area after the reaction and carries out mud-water separation, and active sludge returns reaction zone along the hypotenuse sedimentation after the sedimentation of negative area, discharge excess sludge from the hypotenuse bottom, the waste water after the processing is discharged in the top overflow.The present invention not only is confined to integral bio reaction tank 1 shown in Figure 1, and reaction zone and negative area can separate.When separating, reaction zone and negative area need have the mud return-flow system.
Fig. 2 is a COD change curve during the method for the treatment of industrial waste water by actived sludge-micro-electrolytic process activated sludge acclimatization.Curve 4 is activated sludge acclimatization results that the dry acrylic fiber processing wastewater is carried out as corrosive medium at the 20# carbon steel; Curve 5 is activated sludge acclimatization results that the dry acrylic fiber processing wastewater is carried out as corrosive medium at angle bar.
Fig. 3 is that the iron dust filtration method is handled trade effluent device schema.The 6th, iron charcoal fixed bed, the high 70cm of post, diameter 8.2cm, filler 7 wherein are that volume ratio is 1: 1 iron filings and gac, loading height 42cm.At first wash filler with tap water after 12 hours, then treatment sewage is fed in the iron charcoal fixed bed 6 from the bottom, handle the back from the top water outlet through the iron dust filtration method with 1% salt acid soak.
5. embodiment
Embodiment 1
Test used active sludge and take from sewage-farm one, the Qilu Petrochemical company triumph refinery south pond active sludge that exposes to the sun, after tap water washing for several times, pour in the pond.25 * 25 waste and old angle bar that 25cm is long hang on Chi Shuizhong.Handling waste water is the dry acrylic fiber process spent water, and COD is 1315.4mg/L behind coagulation-sedimentation removal non-solubility COD.
The control reaction zone temperature is a normal temperature, the pH value is between 4.5~6.5, the control dissolved oxygen is greater than 0.5mg.L, sludge concentration 2~4g/L, the domestication of active sludge is to begin to carry out in 24 hours by hydraulic detention time, gradually reduces hydraulic detention time later on, is controlled in 10 hours up to hydraulic detention time, the COD clearance is 45%, and this moment, activated sludge acclimatization finished.
Control the pH value 6.0~6.5, hydraulic detention time 10 hours, dissolved oxygen 2mg/L, sludge concentration 3/L, sludge retention time 10 days, waste water COD decreasing ratio are 51.2%.
Embodiment 2
Press embodiment 1 Step By Condition, but control reaction zone pH value 3.5~4.0, hydraulic detention time 10 hours, waste water COD decreasing ratio are 48.5%.
Embodiment 3
Press embodiment 1 Step By Condition, but use the 20# carbon steel to replace angle steel that active sludge is tamed.After domestication finished, control pH value was 6.0~6.5, and hydraulic detention time 10 hours, waste water COD decreasing ratio are 51.3%.
Comparative Examples 1
Dry acrylic fiber process spent water among the embodiment 1 is carried out the iron dust filtration method handle, water inlet COD is 1315.4mg/L.Equipment therefor is seen Fig. 3, and water inlet pH value is adjusted to 3.Water flowing after 10 hours COD begin to descend, the minimum 995.3mg/L that reduces to, COD decreasing ratio are 24.3%, well below the decreasing ratio of the inventive method COD.And the product quantity of slag is bigger.

Claims (9)

1, the method for a kind of active sludge-little processing of industrial waste water by electrolysis is included in the common active sludge system and arranges carbon steel, and regulating pH value is 4.5~6.5.
2, method according to claim 1 is characterized in that described carbon steel is an angle bar.
3, method according to claim 1 is characterized in that described carbon steel is a cast iron.
4, method according to claim 1 is characterized in that hydraulic detention time was greater than 2 hours.
5, method according to claim 1 is characterized in that sludge retention time maintains 8~12 days.
6, method according to claim 1 is characterized in that the reaction zone dissolved oxygen is greater than 0.5mg/L.
7, method according to claim 6 is characterized in that logical pure oxygen aeration in system.
8, method according to claim 1 is characterized in that the sludge concentration scope is 2~4g/L.
9, method according to claim 1 is characterized in that adding Powdered Activated Carbon in system.
CNB011428589A 2001-12-30 2001-12-30 Method of treating industrial waste water by actived sludge-micro-electrolytic process Active CN1180987C (en)

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CN108358261A (en) * 2018-03-23 2018-08-03 成都工业学院 A kind of method of wastewater treatment
CN110563122A (en) * 2019-10-17 2019-12-13 中国科学院城市环境研究所 Method for pretreating phenolic wastewater by microorganism-assisted iron-carbon micro-electrolysis

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