CN1445181A - Water handles technique by using electrolysis bioactivity carbon - Google Patents
Water handles technique by using electrolysis bioactivity carbon Download PDFInfo
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- CN1445181A CN1445181A CN 02104958 CN02104958A CN1445181A CN 1445181 A CN1445181 A CN 1445181A CN 02104958 CN02104958 CN 02104958 CN 02104958 A CN02104958 A CN 02104958A CN 1445181 A CN1445181 A CN 1445181A
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Abstract
An electrolysis-bioactive carbon process for treating water including organic sewage is composed of electrolysis unit for oxidizing the water by the hydroxy free radicals generated by anode and catalytic addition reaction by the hydrogen's free radicals generated by cathode to degradate and detoxicate the organic substance, and the bioactive carbon unit receiving the molecular oxygen generated by anode for further removing organic pollutant.
Description
The invention belongs to the efficient treatment process that utilizes organic micro-pollutants in the electrolytic-biological activated carbon process processing drinking water or other organic wastewater with difficult degradation thereby.
Electrochemical process is common process in the water treatment.It utilizes the chemical reaction process of electrode surface can the oxidation or all kinds of pollution substances that reduce, it can be under electric field action direct some compound of cracking, also can make some compound polymerization become macromolecular cpd under the electric field action, can also make the gaseous oxidizer and the reductive agent of generation carry out redox reaction, can also utilize the gas of generation to make separated from contaminants simultaneously as the air supporting carrier gas in liquid phase.Therefore, sewage treatment process such as electrolysis, electric flotation arise at the historic moment, and have played vital role in water treatment.
In the materialization treating processes of water, charcoal absorption plays an important role, and gac can adapt to all kinds of different pollutents of absorption, purifying water body.But adsorption process is a materializing procedure, after pollutent is transferred to solid phase (gac) from water, needs a regenerative process-desorb, the material after the absorption is got rid of, further processing and utilizing.So the efficient of absorption is not only relevant with adsorption process, also relevant with regenerative process, regenerative process directly has influence on the ability of absorption again.Methods such as the regeneration of gac can be regenerated with chemical reagent usually, water vapour is regenerated, the regeneration of pyrolytic decomposition heat; its energy consumption and reagent consumption are all high; these methods also improve the rate of loss of gac simultaneously; more increased the adsorption treatment cost, caused in water treatment and can not utilize gac cost-effectively with good absorption property.
Electrolysis free-radical oxidn process is made basic ideas of the present invention with combining of biological activated carbon absorption degradation process, its target is by selecting the suitable oxygen electrode of analysing for use, make that the overpotential of oxygen reduces greatly in the electrolytic process, reduce the energy loss of electrolytic process, thereby emit a large amount of hydroxyl radical free radicals effectively.Utilize micro quantity organic pollutant or other hardly degraded organic substance in the strong oxidisability oxidative degradation water body of hydroxyl radical free radical; Select suitable negative electrode simultaneously for use, make in the electrolytic process and can either emit hydroperoxyl radical effectively, and overpotential is low, can make the polycyclic aromatic hydrocarbons addition be converted into polycyoalkane as the catalyzer of polycyclic aromatic hydrocarbons addition again, reduce its toxic.In addition, in electrolytic process, part has neither part nor lot in the hydroxyl radical free radical of oxidation can be in conjunction with the generation molecular oxygen, at the end of electrolysis section one biological activated carbon treatment system is set, the microorganism that the molecular oxygen that electrolysis generates can be supplied with on the biological activated carbon utilizes, and improves the efficient of microbiological deterioration.
The objective of the invention is to provide a kind of combination process that can be used for processes such as drink water purifying, organic wastewater with difficult degradation thereby processing based on continuous electrolysis-biological activated carbon absorption degradation principle, achieve micro quantity organic pollutant and hardly degraded organic substance in the continuous high-efficient ground removal water body, reach the purpose of water body purification.
Compared with prior art, the advantage and the beneficial effect that have of technology of the present invention is as follows:
1. in process of the present invention, at first electrolysis and biological activated carbon technology are organically combined, the hydroxyl radical free radical that generates in the electrolytic process organism in the water body of not only can degrading, and the microorganism that the molecular oxygen that generates can be supplied with on the biological activated carbon utilizes, improve the Degradation of microorganism, the two complements each other, and improves organic removal efficient in the water body.
2. selected special negative electrode in electrolytic process for use, negative electrode not only plays the effect of current delivery in the electrolytic process, and can be used as the hydroperoxyl radical of emitting in the electrolytic process and the catalyzer of polycyclic aromatic hydrocarbons addition, reduces and poisons organic toxic action.
3. in the present invention, selected for use very ideal to analyse oxygen anodes, make that the overpotential of oxygen reduces effectively in the electrolytic process, and the precipitation efficiency of hydroxyl radical free radical has improved in the electrolytic process, has improved organic oxidation efficiency.
4. in the present invention, anode region and cathode zone utilize a kind of ion-exchange membrane to separate, so both can stop the hydroperoxyl radical generation redox processes that produces on hydroxyl radical free radical that electrolysis produces on the anode and the negative electrode easily, improve the utilization ratio of hydroxyl radical free radical and hydrogen base free radical; And can make anode and negative electrode keep very little distance, reduce the voltage of electrolytic process.
Of the present invention being constructed as follows:
The present invention can select different structure formation for use according to handling the different of the water yield and water quality type, now the most basic a kind of structure formation is described below:
Fig. 1 is the cylindricality electrolysis bioactivity carbon Processing Structure unit that intakes
The electrolysis free-radical oxidation biological activated carbon degraded organic micro-pollution equipment of the type basic composition is: (1) processing unit post Body, (2) liberation of hydrogen catalytic cathode, (3) cathode terminal, (4) anode terminal, (5) analyse oxygen anodes, (6) fixed screw, (7) method hurdle, (8) water inlet, (9) rubber cushion, (10) water-locator, (11) support, (12) cation-exchange membrane, (13) Dividing plate, (14) outer tube, (15) inner sleeve, (16) cover plate, (17) biological activated carbon dividing plate, (18) biological activated carbon, (19) delivery port.
In structure of the present invention, cylinder (1) is cylindrical, generally can be with tools such as lucite tube or PVC The material that certain corrosion resistance and withstand voltage properties are arranged, the size of cylinder is decided according to size and the hydraulic detention time of processing the water yield, Hydraulic detention time generally changed in 0.2～3 hour, depended primarily on to process former water pollutant concentration, and waterpower is stopped during high concentration Stay the time long, hydraulic detention time is short during low concentration, and is simultaneously also relevant with desired processing horizontal, and the processing horizontal of requirement more Height, then the time of staying is more long.
Theoretically, the electrode of any generation hydrogen all can be used as negative electrode (2), and this class electrode comprises nickel and take it as main alloy, Such as the alloy take nickel and chromium as matrix; Stainless steel, their model have 304,310,316 etc.; Graphite, graphite tape, multilayer Graphite cloth; Titanium or other valve metal and the metal that is coated with the overpotential that can reduce hydrogen at valve metal. But, examine Worry is to utilize the hydroperoxyl radical that produces in the electrolytic process that the polycyclic aromatic hydrocarbon in the water body is added to one of them Main Function of the present invention Become, negative electrode doubles as the effect of catalyst simultaneously. Therefore, the negative electrode that meets this requirement mainly comprises nickel electrode, perhaps take nickel as Other main alloy electrode.
The special anode of anode of the present invention (5) normal operation, these anodes comprise the sun of some common on market stable configurations The utmost point. And these anodes must be a kind of oxygen electrodes of analysing, and these electrodes are generally preferably selected netted or other has high specific surface Electrode. Electrode material comprises platinum, gold, palladium or their alloy and their mixture, or various inertial bases (as The valve metal titanium) plates a kind of monomer of these metals or the mixture of various ingredients on. In addition, the oxygen of iridium, ruthenium, rubidium The alloy of compound or they and platinum group metal or other rare metal also can be used as this class anode and uses. At present existing on the market This class anode has in the acid medium that Metal Corrosion and Protection Inst., Chinese Academy of Sciences produces serial oxide analyse oxygen anodes, perhaps Guangdong Province non-ferrous metal research institute development analyse oxygen anodes. Other electrode material comprises graphite rod, graphite network etc., but they It is generally lower to analyse oxygen efficiency.
In the present invention, should be class inert coating, i.e. a water body for the cation-exchange membrane (12) of separating anode region and cathodic region In material and the free radical that produces of the free radical that produces of anode electrolysis or catholyte can not with film reaction. And it does not have and penetrates The property, the gas that namely electrolysis produces in the electrolyte in antianode zone and the cathode zone and each zone all can not pass this exchange Film. As everyone knows, include fixing anionic group at cation-exchange membrane, and the cation on it is dissociable Part, can exchange with external cation, but it repels external anion. Usually the matrix of resin type exchange membrane is One class cross-linked copolymer has charged group such as-SO at the matrix of this analog copolymer3 -Or it and-mixture of COOH. The resin that can be used for making exchange membrane comprises fluorocarbon, vinyl compound, TPO material, hydrocarbon and some other altogether Polymers. Resin that be used for to make cation-exchange membrane is poly-by with polar group sulfonic group and carboxylic acid group's fluorocarbon mainly The materials such as the compound of compound or vinyl such as vinyl benzene consist of. Here " sulfonic group " and " carboxylic acid group " comprise hydrolyzable The salts substances of ionization.
Suitable cation-exchange membrane is at home just available, such as the 3361-BW polyethylene out-phase cation of chemical plant, Shanghai production The polyethylene out-phase cation-exchange membrane that exchange membrane and Linan, Zhejiang Organic Chemical Plant produce, and Shunyi, Beijing water treatment facilities factory The Kynoar homogeneous phase cation exchange film that the YU-2 homogeneous phase cation exchange film of producing and Shanghai nuclear research are produced. Have abroad the type of anti-teflon cation-exchange membrane of E.I.Du Pont Company's production of non-oxidizability and high temperature resistant type on the market, its performance more For superior.
Method hurdle (7) is mainly used in fixedly lower bottom base and cylinder, generally makes with the identical material of cylinder, can effectively prevent like this Only material causes the cracking between lower bottom base and cylinder because expanding with heat and contract with cold. Between base and cylinder, place rubber cushion (9), in case connect Seepage between the seam. Dividing plate (13) must have certain intensity, and on dividing plate top a lot of uniformly eyelets, make the anode region Ion between territory and the cathode zone by eyelet and then by amberplex, exchanges earlier, reaches the order of conductive electric current . Cation-exchange membrane (12) and dividing plate (13) are equipped with in the bottom of outer tube (14), and are used in the identical material of cylinder and fix On the inwall of post, simultaneously outer tube (14) will maintain a certain distance with cylinder (1), makes to process that water can be along return duct Outer wall enters in the inner sleeve (15). Inner sleeve (15) is fixed on the cylinder (1) by cover plate (16), in cover plate (16) makes The sealing of sleeve pipe (15) and cylinder (1), thus the processing water that enters in the post flowed along as shown in the figure circuit, reach advanced treating Purpose.
In the part that biological activated carbon is processed, biological activated carbon (18) is placed on the active carbon supporting clapboard (17), at active carbon Supporting clapboard leaves eyelet on (17) equally equably, can make to process water and flow through smoothly active carbon layer, simultaneously active carbon layer every Plate also has the effect of water-locator concurrently. On dividing plate (17), at first place the sand grains that is fit to particle diameter, place in the above then biological Active carbon (18) can prevent effectively that like this active carbon from entering the part of electrolytic treatments. Simultaneously, be loaded at biological activated carbon When processing post, the microorganism on the active carbon at first will be through domestication, in acclimated microorganism, and should be according to processing water water quality Difference is selected different nutrition bases. Be the main unit of processing object, acclimated microorganism for organic micro-pollutants in drinking water The nutrition base preferably do not add nitrogenous source and phosphorus source, cultivate aerobic microbiological at active carbon. For take organic wastewater with difficult degradation thereby as main Process the treatment system of object, with processing former water, same acclimated microorganism is with good as much as possible for the nutrient solution of acclimated microorganism Oxygen animalcule is main.
In the present invention, the biological activated carbon processing layer should maintain a certain distance with electrolysis section, and distance is excessive, make the processing unit volume excessive, distance is too small, and the hydroxyl radical free radical that electrolytic process generates can play certain killing action to the microorganism on the gac, reduces the effect of biological activated carbon.In structure of the invention process, the distance of active carbon layer and electrolysis section remains on about 600mm.
In the present invention, treating water is from water-in (8) access arrangement, behind even water distributor (10), after the hydroxyl radical free radical oxidation of electrolytic anode zone, enter cathode zone through the recirculating zone, after the addition of cathode zone hydroperoxyl radical, enter the biological activated carbon treating part then, remaining organic pollutant flows out treatment system by water outlet (19) in the water body after biological activated carbon (18) is gone up further degraded.
The actuating current density of process of the present invention is at 0.01KA/m
2-10KA/m
2Between, scope commonly used usually is 0.05KA/m
2-3KA/m
2Between, optimum current density is at 0.1KA/m
2-1KA/m
2Between.Distance between anode and the negative electrode can change electrolysis section electrolysis voltage and current efficiency.Pole span is littler, and intermembranous resistance is just little, and then electrolysis voltage is just little, and current efficiency is higher.This spacing is selected between 0.1-10cm, and common scope is 0.3-2cm.
Equipment of the present invention, its power configuration can be used constant voltage dc source, Voltage pulsating direct-current supply or dither direct supply, it is different with water quality to look process object.Voltage of supply should adopt 36 volts of following safety voltages.
The effect that the present invention can reach is:
1. applied widely, this treatment process not only goes for the removal of organic micro-pollutants in the tap water, but also applicable to organic removal in all kinds of organic waste waters.Comprise city domestic sewage, hotels' life and bath wastewater, refining of petroleum waste water, petrochemical wastewater, dyeing waste water, synthetic substantially organic waste water and agricultural byproducts comprehensive utilization processing waste water etc.
2. processing cost is low, the processing cost of this technology depends primarily on the concentration of pollutent, and for the removal of organic micro-pollutants in the tap water, power consumption generally maintains about the 0.1KWH/ ton, and for handling the waste water of COD concentration below 1000mg/L, power consumption is generally 0.2～0.8KWH/ ton.
3. treating processes is simple, in the biological activated carbon treating processes, does not need to add aerating apparatus, and can realize operate continuously, control automatically, does not need manual operation and maintenance substantially.
Embodiment:
1. electrolysis bioactivity carbon processing unit as shown in the figure is used for the organic micro-pollutants in processing drinking water source.In water inlet, the concentration total content of 11 kinds of volatility organic micro-pollutantses is 46mg/L, hydraulic detention time in processing unit is 15 minutes, after this processing unit free-radical oxidn reduction and biological activated carbon processing, contain 7 kinds of volatile matter in the treat effluent, total concn is 5.1mg/L, and the basic thoroughly removal of larger molecular organics.Power consumption is the 0.08KWH/ ton.
2. the purpose of water reuse during treatment of domestic sewage advanced reaches.The COD of comprehensive sanitary sewage is 340mg/L, and after sedimentation, biochemical treatment, COD is 108mg/L, and after employing electrolysis bioactivity carbon processing unit was as shown in the figure further handled, water outlet COD only was 28mg/L, reaches the standard of water reuse in the country fully.In treating processes, hydraulic detention time is 60 minutes, and power consumption is the 0.52KWH/ ton.
Claims (1)
- A kind of electrolysis free-radical oxidn biological activated carbon water technology, mainly comprise: the cylinder of a splendid attire processing unit (1) and be contained in the combination of post intravital electrolysis treatment unit and biological activated carbon processing unit, it is characterized in that: reactor cylinder (1) is vertical to be placed, even water distributor (10) is placed in bottom at cylinder, the special oxygen anodes (5) of analysing, catalytic hydrogen evolution electrode (2) is made negative electrode, anode electrolysis district and catholyte district utilize dividing plate (13) and cationic exchange membrane (12) to separate, treating water is entered by water inlet pipe (11), behind the free-radical oxidn of positive column, enter outer layer sleeve (14), enter inner layer sleeve (15) then and arrive the cathodic area, handle the back by biological activated carbon (18) at last and discharge treatment system by water outlet (19).
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02104958 CN1445181A (en) | 2002-03-19 | 2002-03-19 | Water handles technique by using electrolysis bioactivity carbon |
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| CN 02104958 CN1445181A (en) | 2002-03-19 | 2002-03-19 | Water handles technique by using electrolysis bioactivity carbon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921980A (en) * | 2019-11-13 | 2020-03-27 | 河海大学 | Electrochemical enhanced ozone-biological activated carbon water treatment equipment and method for treating water by using same |
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921980A (en) * | 2019-11-13 | 2020-03-27 | 河海大学 | Electrochemical enhanced ozone-biological activated carbon water treatment equipment and method for treating water by using same |
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