CN108083366A - A kind of method using low grade heat energy oxidative degradation organic wastewater - Google Patents

A kind of method using low grade heat energy oxidative degradation organic wastewater Download PDF

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CN108083366A
CN108083366A CN201711384061.2A CN201711384061A CN108083366A CN 108083366 A CN108083366 A CN 108083366A CN 201711384061 A CN201711384061 A CN 201711384061A CN 108083366 A CN108083366 A CN 108083366A
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organic wastewater
low grade
heat energy
oxidative degradation
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徐士鸣
吴曦
冷强
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Dalian University of Technology
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/10—Energy recovery
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

A kind of method using low grade heat energy oxidative degradation organic wastewater belongs to organic waste water advanced oxidation degradation field, including two processes：Low grade heat energy is converted to the chemical potential energy of working solution by separator；Recycle the oxidation reaction at reverse electrodialysis RED battery pile inner anodes and the reduction reaction at cathode that the chemical potential energy of solution is converted to organic wastewater oxidative degradation and can and export electric energy；After solution chemistry potential energy is converted to organic wastewater oxidative degradation energy and electric energy, strong solution concentration declines, weak solution concentration raises, intermediate concentration solution is mixed into after the two outflow RED piles, intermediate concentration solution is heated separation by low grade heat energy again after solution preheats and hands over heat temperature raising into separator, completes a Xun Huan.The present invention advantage be：Low grade heat energy can obtain abundant, continuous, cascade utilization；It is simple system, reliable, capacity configuration flexibly, operational safety；It can effectively degrade and be difficult to the various high concentrated organic wastewaters of biochemical degradation.

Description

A kind of method using low grade heat energy oxidative degradation organic wastewater
Technical field
The invention belongs to organic waste water advanced oxidation degradation fields, are related to a kind of new having by low grade heat energy driving Machine wastewater oxidation biodegrading process.
Background technology
Existing method for processing organic wastewater includes two major class of biochemical degradation method and advanced oxidation degradation method.Including anaerobic process and Biochemical degradation method including aerobic method is by the coordination of multiple-microorganism and own metabolism process, in anaerobic or aerobic In the environment of organic matter is decomposed into the substance of environmental sound.This method has been widely used for handling low concentration organic waste Water simultaneously achieves good effect.However, discharged for including the production processes such as medicine, pesticide, printing and dyeing, refinery, coking Organic wastewater, it is difficult to be effectively treated by using biochemical degradation method to it.Propose therefore including：Supercritical water oxidation Method, plasma advanced oxidation processes, Fenton reagent or electric Fenton oxidation method, Ozonation, photocatalytic oxidation, ultrasonic wave added The organic waste water advanced oxidations facture such as oxidizing process.But these method for processing organic wastewater need to consume a large amount of electric energy or chemistry examination Agent causes treatment of Organic Wastewater costly.Actually in industrial processes, while substantial amounts of organic wastewater is generated Often need to arrange to environment with substantial amounts of tow taste heat.If made using all kinds of discarded or low value low grade heat energy For the drive energy for the treatment of of Organic Wastewater, then treatment of Organic Wastewater cost can be substantially reduced.
The content of the invention
For existing biochemical and advanced oxidation degradation Technologies for Organic Wastewater Treatment deficiency, the present invention proposes a kind of utilization Low grade heat energy oxidative degradation organic wastewater method；First by the distillation of distiller, low grade heat energy is converted into work Make the chemical potential energy of solution, generated redox in yin, yang electrode chamber is recycled in reverse electrodialysis (RED) pile to make With, the chemical potential energy of working solution is converted into organic wastewater oxidative degradation and can and generate a certain amount of electric energy or externally output, Or the devices such as driving Electro-catalytic Oxidation Process reactor, for the oxidative degradation of organic wastewater.
In order to achieve the above object, technical solution of the invention is：
A kind of new low grade heat energy oxidative degradation organic wastewater method, including following two processes：
The first step：Low grade heat energy is converted into the process of working solution chemical potential energy.
First with the working solution in (45 DEG C or more) heating distillers of low grade heat energy, the part in working solution is low Boiling point component is evaporated from working solution and is separated, and is condensed into liquid into the condenser medium that is cooled；It isolates Low boiling component steam in allow to carry secretly a small amount of working solution drop to increase the liquid formed after low boiling component condensation The electrical conductivity of body (weak solution)；Working solution because isolate part low boiling component make its concentration raise due to become concentrated solution；It is dense Concentration difference is generated between solution and weak solution and to make it have chemical potential energy poor.
Second step：Using RED battery piles, chemical potential energy dilute, between concentrated solution is converted into organic wastewater oxidative degradation energy With the process of electric energy.
Concentrated solution flows out distiller and each concentrated solution room in RED battery piles is pumped by concentrated solution pump pressurization；In condenser It condenses the weak solution outflow condenser formed and each weak solution room in RED battery piles is pumped by weak solution pump pressurization；RED batteries Dilute, concentrated solution room in heap are alternately arranged, and the solute anions and canons in concentrated solution room are moved respectively by anions and canons exchange membrane It moves in adjacent weak solution room；Because the migration of anions and canons is formed between anions and canons exchange membrane in RED battery piles Ion stream is oriented, and potential is generated at two electrode of yin, yang of RED battery piles.
Organic wastewater after pH value and electrical conductivity are adjusted flows through positive electricity pole room after pressurizeing by organic wastewater circulating pump, Under the effect of working solution difference in chemical potential, the Cl of the anion-exchange membrane migration by forming positive electricity pole room-Ion is at anode Generation oxidation reaction, ejected electron generation Cl2Gas；Cl2Gas with flowing through the organic wastewater of positive electricity pole room with acting on generation with strong oxygen The hypochlorous acid (HOCl) for the property changed, the organic substance in HOCl oxidative degradation waste water generate CO2, water and oxidation operation degradation after Intermediate product and flow out positive electrode room, electronics is then transferred to cathode by external circuit from anode；Flow out the organic of positive electricity pole room Waste water after air pump adds in air or oxygen, is therewith flowing into negative electricity pole room into before negative electricity pole room；In acid atmosphere Enclose the H in lower organic wastewater+Ion obtains electronics and the O with being dissolved in organic wastewater at cathode2Generation reduction reaction, it is raw Into hydrogen peroxide (H2O2)；H2O2With catalyst Fe2+Ion reacts, generate with strong oxidizing property hydroxyl radical free radical ( OH), hydroxyl (OH-1) and Fe3+Ion；Organic matter effect in OH oxidized waste waters, generates CO2, water and oxidation operation drop Intermediate product after solution, the Fe generated after reaction3+An electronics is obtained at cathode and is reduced into Fe again2+；Reach oxidation drop Part organic wastewater after solution requirement leaves system by regulating valve and is post-processed, and part organic wastewater flows back to organic waste water pot It mixes with pending organic waste water stream, then is followed through the pressurization of organic wastewater circulating pump in the positive and negative electrode chamber of RED battery piles Circulation moves, and the organic matter in waste water is by oxidative degradation.In oxidative degradation organic wastewater, generated in external circuit due to electron transfer It is loaded outside electric current output electrical energy drive.
Working solution chemical potential energy, which is converted to organic wastewater oxidative degradation, to flow through the dense molten of concentrated solution runner with after electric energy Liquid concentration declines, and flows through the weak solution concentration rise of weak solution runner, the two outflow RED battery piles and to be mixed into intermediate concentration molten Liquid, intermediate concentration solution heat separation again into distiller after solution preheater heat temperature raising by low grade heat energy stream stock, An organic wastewater degraded and power generation cycle are completed, releases the low grade heat energy stream stock outflow system after heat.
The organic wastewater for needing oxidative degradation, at normal temperatures after pH value and electrical conductivity are adjusted, pH value is less than 6, conductance Rate is more than 5mScm-1；Yin, yang electrode chamber mean flow rate is flowed through more than 0.5cms-1, RED output voltages are more than 1.0V, cycle The organic wastewater oxidative degradation processing mean time length of flowing is more than 5mim, and organic wastewater percent of decolourization is more than 50% after oxidative degradation, COD removal rates are more than 30%, and extend with the rise of RED output voltages and handling duration, and percent of decolourization and COD removal rates accordingly increase Add.
The outer load can be various electrocatalytic oxidation organic wastewater degraded reactors, and system capacity is used to have entirely at this time Machine wastewater oxidation is degraded, and does not export electric energy externally.
The catalyst Fe+2Cationic cure is in cathode or addition is in processed organic wastewater.The anode uses Investigation of titanium anode coated with metal oxide, cathode use carbon based gas diffusion electrode.
Single-action can be used according to low grade heat energy temperature grade for the distiller or multiple-effect separates.
The working solution is easily by the electrolyte solution of thermal release, the heated low boiling component isolated contains a small amount of electricity Xie Zhi.
The distiller and condenser is identical with the single-action commonly used in sea water desalination or multiple effect distillator, and effect is Solution is separated into dilute, dense two strands of solution using low grade heat energy.
The organic wastewater degraded is essentially identical with RED electric pile structures and the RED battery pile structures of salt error power generation, no It is with part：Anode uses investigation of titanium anode coated with metal oxide, and cathode uses carbon based gas diffusion electrode, organic wastewater drop Solution (salt error power generation RED piles cation-exchange membrane ratio one more than cation-exchange membrane with anion-exchange membrane in RED piles Anion-exchange membrane is one more), be specially：It is anion-exchange membrane that organic wastewater degraded is outermost with both ends in RED piles, And the RED battery piles both ends of salt error power generation are outermost for cation-exchange membrane.By interlaced arrangement in the RED battery piles Anions and canons exchange membrane module and are separated out dilute, concentrated solution runner, and the dilute of flowing, concentrated solution are in concentration difference (difference in chemical potential) in runner Under driving, the solute in concentrated solution runner is moved into dilute molten by anions and canons exchange membrane module respectively in the form of anions and canons Liquid stream road；Concentrated solution in the concentrated solution runner concentration when solute ions are moved out declines, and the weak solution in weak solution runner is because molten Moving into for matter ion and concentration raise, and the solution that intermediate concentration is mixed into after the two outflow RED battery piles enters in distiller It is heated, separates, so as to complete a complete working cycles again by low grade heat energy.
In the above-mentioned method using new low grade heat energy oxidative degradation organic wastewater, supplied for unstable or intermittence Low grade heat energy, dilute, concentrated solution storage tank, intermediate concentration solution reservoir and intermediate concentration solution pump can be added, it is dilute, dense and intermediate Strength solution storage tank plays the role of storing or releasing energy, and RED battery piles in workflow is made to have handled in a stable manner Machine waste water changes without the variation with low grade heat energy parameter (temperature and heat).
The beneficial effects of the invention are as follows：1) low grade heat energy can obtain abundant, continuous, cascade utilization, and effectively reducing has Machine cost for wastewater treatment；2) organic wastewater treating system is simple, reliably, almost without secondary pollution generates；3) system can fit All kinds of low temperature heat energies are answered, and can fully recycle its hot grade, exportable a certain amount of electric energy while degradation of organic substances； 4) organic wastewater treating system composition is flexible, and manufacture is easy, and moving component is few, long working life, and operation is quiet, floor space It is small；5) organic wastewater being difficult to using biochemical process degradation can be handled.
Description of the drawings
Fig. 1 is the low grade heat energy oxidative degradation organic wastewater side that a kind of series connection of organic wastewater flows through RED yin, yang electrode chambers Method working cycles flow chart.
Fig. 2 is organic wastewater oxidative degradation internal system RED battery pile structure schematic diagrames.
Fig. 3 is the low grade heat energy oxidative degradation organic wastewater method work that a kind of organic wastewater parallel connection flows through RED cathode and anodes Make circulation process figure.
Fig. 4 is a kind of working cycles flow for possessing energy-storage function low grade heat energy oxidative degradation organic wastewater method.
In figure：1 condenser, 1a coolings stream stock go out into, 1b cooling stream stock, 2 distillers, and 2a low grade heat energy stream stocks are into 2b Low grade heat energy stream stock goes out, 3 weak solutions pump, 4 concentrated solutions pump, 5 RED battery piles, 6 anodes (cathode), 6a positive electricity pole rooms, 7 it is cloudy from Proton exchange, 7a concentrated solution runners, 8 cation-exchange membranes, 8a weak solution runners, 9 air pumps, 9a air is into 10 cathodes are (just Pole), 10a negative electricity pole rooms, 11 regulating valves, organic wastewater goes out after 11a processing, 12 solution preheaters, 13 organic wastewater circulating pumps, and 14 Organic waste water pot, the pending organic waste water streams of 14a into, 14b gases go out, load (electric energy output) outside 15,16 RED end plates, 17 Weak solution storage tank, 18 concentrated solution storage tanks, 19 intermediate concentration solution pumps, 20 intermediate concentration solution reservoirs.
Arrow direction is stream stock flow direction in attached drawing, and solid line is concentrated solution stream stock, and dotted line is weak solution stream stock, point Setting-out is intermediate concentration solution stream stock, and two-dot chain line is organic waste water stream, and three dotted lines are external circuit.
Specific embodiment
With reference to the specific implementation process of technical solution and attached drawing, in detail the narration present invention.
A kind of method of new low grade heat energy oxidative degradation organic wastewater, including following two processes：
The first step：Low grade heat energy is converted into the process of working solution chemical potential energy.
First with the working solution in low grade heat energy heating distiller, part low boiling component in working solution from It is evaporated in solution and is separated and enters the condenser medium that is cooled and be condensed into liquid；Working solution is low because isolating part Boiling point component raises its concentration and becomes concentrated solution；Concentration difference is generated between concentrated solution and weak solution and there is chemical potential energy Difference.Working solution is sodium chloride, potassium chloride or lithium chloride solution in the embodiment.
Second step：Using RED battery piles, chemical potential energy dilute, between concentrated solution is converted into organic wastewater oxidative degradation energy With the process of electric energy.
The technical parameter of oxidative degradation organic wastewater is in the embodiment：Organic wastewater pH value adjustment when normal temperature oxidation is degraded It is more than 5mScm to less than 6, electrical conductivity adjusts to arrive-1, organic wastewater flows through yin, yang electrode chamber mean flow rate more than 0.5cms-1, RED output voltages are more than 1.0V, and organic wastewater percent of decolourization is more than 50%, COD removal rates and is more than 30% after oxidative degradation, oxidation Degradation treatment mean time length is more than 5mim, and extends with the rise of RED output voltages and processing time, percent of decolourization and COD removal rates It is corresponding to improve.
The principle of oxidative degradation organic wastewater is as follows：
When RED battery piles both ends form closed circuit by electrode and external loading, under the effect of solution chemistry potential difference, In concentrated solution anion (such as：Chlorion) enter through anion-exchange membrane by outermost anion-exchange membrane, anode plate The positive electricity pole room formed with RED battery pile end plates, two electronics of releasing are oxidized to active chlorine at anode；In acid atmosphere Enclosing lower active chlorine and water reaction generation, there is the hypochlorous acid deoxidation of strong oxidizing property to flow through the organic matter in positive electricity pole room waste water, Product after generation oxidation.The main reaction equation of oxidation degradation of organic substances process is in positive electrode room：
2Cl-→Cl2+2e-；
Cl2+H2O→HOCl+H++Cl-；
HOCl+Organics→Oxidation prodcuts+inorganic salts。
Electronics reaches cathode by external circuit, and oxygen or air are constantly passed through in negative electrode room and keeps acid atmosphere Under, hydrogen ion obtains two electronics at cathode and reduction reaction occurs with needing to be oxidized the organic waste oxygen in water of degradation, raw Into hydrogen peroxide (H2O2)；H2O2With adding the catalyst Fe in organic wastewater2+Reaction generates the hydroxyl with strong oxidizing property Organic matter in free radical (OH) oxidized waste water, and generate product after oxidation, the Fe generated after reaction3+It can be obtained again at cathode It obtains an electronics and is reduced into Fe again2+.The main reaction equation of oxidation degradation of organic substances process is in negative electrode room：
O2+2H++2e-→H2O2；
H2O2+Fe2+→Fe3++·OH+OH-；
Fe3++e-→Fe2+；
·OH+Organics→Oxidation products+inorganic salts。
It needs, by after the adjusted PH of the organic wastewater of oxidative degradation and conductivity value processing, the side of parallel fluid flow can be passed through Formula each flows through yin, yang electrode chamber and carries out oxidative degradation processing respectively, and yin, yang electricity can also be flowed through by way of series flow Pole room carries out oxidative degradation processing.While the organic wastewater oxidative degradation to flowing through two electrode chambers is handled, RED battery piles are also Outwards output electric energy is for driving in organic wastewater treating system all kinds of current consuming apparatus or for driving external organic waste water power Catalyst oxidation reactor, oxidative degradation organic wastewater.
Attached drawing 1 is the low grade heat energy oxidative degradation organic wastewater that a kind of organic wastewater series connection flows through RED yin, yang electrode chambers The working cycles flow of method, wherein attached drawing 2 are the knots of the RED battery piles 5 for organic wastewater oxidative degradation in working cycles Structure schematic diagram；Its course of work is：The low grade heat energies stream stock 2a such as low-temperature water heating, low pressure water vapor or low temperature hot gas, flows through Distiller 2；Heating work solution is (such as in distiller 2：The electrolyte solutions such as NaCl, KCl, LiCl), according to low grade heat energy Temperature, distiller 2 can be single-action or multiple-effect；Low grade heat energy stream stock 2a is flowed through after distiller 2 releases heat and is passed through preheating Device 12 continues to release heat, finally flows out preheater 2b；After working solution obtains heat in distiller 2, low boiling component is (molten Agent) under low pressure by partial gasification, it is separated in the form of steam from working solution；Gas-liquid separation dress is not set in distiller It puts, allows to carry a small amount of working solution drop in the solvent vapour isolated secretly；Go out the solvent vapour of distiller most end effect into cold Be cooled medium 1a, 1b condensation in condenser 1, contains a small amount of electrolyte components in condensation water to increase the electricity of condensation water (weak solution) Conductance；The working solution after partial solvent is isolated as concentrated solution, it forms concentration difference between weak solution and makes it have Difference in chemical potential；Outflow condenser 1 and the dilute of distiller 2, concentrated solution through dilute, 3,4 pressurization of concentrated solution pump and are introduced into RED respectively Dilute, concentrated solution runner 8a, 7a that battery pile 5 is separated out by the anions and canons exchange membrane 7,8 being alternately arranged；It is dilute, concentrated solution is dense Spend (chemical potential) difference driving under, in concentrated solution runner 8a in concentrated solution solute in the form of anions and canons respectively by yin, yang from Proton exchange 7,8 migrates into weak solution runner 8a, so as to form orientation ion stream inside RED battery piles 5 and generate potential； In the electrode chamber (6a, 10a) being separated out at 5 both ends of RED battery piles by anion-exchange membrane 7 and end plate 16, titanium-based is respectively equipped with Metal oxides coating of anode 6 (being cathode for battery) and carbon based gas dispenser cathode 10 (are just for battery Pole)；In positive electricity pole room 6a, the Cl that is migrated from adjacent concentrated solution runner 7a through anion-exchange membrane 7-Ion, in RED It under the action of 5 potential of battery pile, loses electronics at anode 6 and oxidation reaction occurs, generate active chlorine；Generation Chlorine reacts with flowing through the organic wastewater of positive electricity pole room 6a, hypochlorous acid (HOCl) of the generation with strong oxidizing property；Hypochlorous acid Generating oxidation reaction with the organic matter in waste water makes organic matter degrade, and generates CO2The oxidation production of gas, water and organic matter Object etc.；Go out the organic wastewater of positive electricity pole room 6a after air 9a is added in by air pump 9 into before negative electricity pole room 10a, with air 9a enters negative electricity pole room 10a together；Under the action of 5 potential of RED battery piles, the H in negative electricity pole room 10a organic wastewaters is flowed into+ Ion obtained at cathode 10 by external circuit transfer come electronics and the oxygen with being dissolved in organic wastewater transmission change reaction, Generate hydrogen peroxide (H2O2)；In addition in organic wastewater or the catalyst Fe being solidificated in carbon based gas diffusion electrode (cathode)2 +Under effect, H2O2Decomposing generation has the free hydroxyl (OH) of strong oxidizing property and hydroxyl (OH-1), in free hydroxyl and waste water Organic matter occur oxidation reaction organic matter is made to degrade, generation CO2Oxidation product of gas, water and organic matter etc.；Fe3+ Electronics is obtained at cathode and is reduced into Fe2+；Flow through positive electricity pole room and negative electricity pole room and by the part organic wastewater after oxidative degradation Adjusted 11 outflow system of valve carries out subsequent processing, and rest part flows into organic waste water pot 14, with organic waste after pretreatment Water raw water 14a mix, by organic wastewater circulating pump 13 between positive and negative electrode chamber 6a, 10a and organic waste water pot recycle stream It is dynamic, the gas that oxidation operation degradation generates and the air outflow organic wastewater tank 14b for having neither part nor lot in cathodic reduction reaction；In RED During yin, yang electrode chamber 6a, 10a oxidative degradation organic wastewater, electronics migrates to generate electric current and outwards output electricity by external circuit Energy；Flow through that RED battery piles 5 are dilute, dilute, concentrated solution after concentrated solution runner 8a, 7a merge into centre in 5 exit of RED battery piles The working solution of concentration is separated after the preheating of solution preheater 12 into distiller 2 by low grade heat energy, again so as to complete one A complete working cycles.
Attached drawing 3 is that the low grade heat energy oxidative degradation that a kind of organic wastewater parallel connection flows through RED battery pile yin, yang electrode chambers has The working cycles flow of machine method for waste water, basic procedure explanation is identical with attached drawing 1, the difference is that organic matter in this flow Waste water carries out independent degradation in yin, yang electrode chamber 6a, 10a respectively；I.e., it would be desirable to the organic wastewater raw water 14a difference of processing Two organic wastes water pot 14A and 14B are introduced, and two organic wastewater circulating pumps 13A and 13B are set respectively；Organic waste water pot 14A Organic wastewater oxidative degradation circuit one is formed together with positive electricity pole room 6a with organic wastewater circulating pump 13A；Organic waste water pot 14B, Organic wastewater circulating pump 13B, air pump 9 form organic wastewater oxidative degradation circuit two together with negative electricity pole room 10a, at the two Oxidative degradation is carried out to organic wastewater respectively in circuit；Organic wastewater after degradation passes through regulating valve 11A and 11B outflow system (stream stock 11a) carries out subsequent processing.
Attached drawing 4 is a kind of working cycles flow for possessing energy-storage function low grade heat energy oxidative degradation organic wastewater method, Its basic procedure explanation is identical with attached drawing 1, and difference is being additionally arranged dilute, concentrated solution storage tank 17,18, intermediate concentration solution in flow Storage tank 20 and intermediate concentration solution pump 19, the workflow are suitable for the low grade heat energy supplied using unstable or intermittence； When using unstable or intermittence low grade heat energy, dilute, dense and intermediate concentration solution reservoir 17,18,20 plays storage or releases The effect of exoergic amount, and RED battery piles 5 in workflow is made to handle organic wastewater in a stable manner and export electric energy.Its work It is as principle：When the rise of low grade heat energy temperature or load increase, the flow increase of intermediate concentrated solution pump 19,2 He of distiller Dilute, the concentrated solution flow isolated in condenser 1 can accordingly increase, and it is steady to flow through the dilute of RED battery piles 5, concentrated solution flow It is fixed, it is extra go out dilute, concentrated solution be stored in dilute, concentrated solution storage tank 17,18, the chemical potential energy of solution is stored, at the same in Between in strength solution tank 20 amount of solution can gradually decrease；When low grade heat energy temperature reduces or load reduces, intermediate concentration is molten 19 flow of liquid pump reduces, and dilute, the concentrated solution flow isolated in distiller 2 and condenser 1 also accordingly reduce, and flows through RED electricity The dilute of pond heap 5, concentrated solution flow are constant, can be gradually reduced amount of solution dilute, in concentrated solution storage tank 17,18, the solution of storage Chemical potential energy is released, while amount of solution gradually increases in intermediate concentration solution reservoir 20.

Claims (8)

  1. A kind of 1. new low grade heat energy oxidative degradation organic wastewater method, it is characterised in that comprise the following steps：
    The first step, low grade heat energy are converted into solution chemistry potential energy；
    Low grade heat energy heats the working solution in distiller (2), and part low boiling component is by thermal evaporation outflow in working solution Distiller (2) is interior into condenser (1), and cooled medium is condensed into the weak solution with electrical conductivity；Isolate part low boiling point Working solution after component is concentrated solution；It is poor with chemical potential energy between concentrated solution and weak solution；
    Chemical potential energy is converted into organic wastewater oxidative degradation energy and electric energy by second step, reverse electrodialysis RED battery piles (5)；
    Concentrated solution outflow distiller (2) is introduced into each concentrated solution runner in RED battery piles (5) after concentrated solution pumps (4) pressurization (7a)；The weak solution that condensation forms in condenser (1) is introduced into each weak solution in RED battery piles (5) after weak solution pumps (3) pressurization Runner (8a)；The anion-exchange membrane (7) and sun that anion and cation pass through RED piles (5) interior interlaced arrangement in concentrated solution Amberplex (8) is migrated to weak solution runner (8a), forms electric current in orientation ion stream and generation；
    Organic wastewater flows through positive electricity pole room (6a) after pressurizeing by organic wastewater circulating pump (13), is acted in solution chemistry potential difference Under, the Cl of anion-exchange membrane (7) migration by forming positive electricity pole room (6a)-It is anti-that oxidation occurs at anode (6) for ion Ejected electron is answered to generate Cl2Gas；Cl2Gas and the organic substance in water effect generation hypochlorous acid HOCl oxidative degradation waste water, generation CO2, water and intermediate product and flow out positive electrode room (6a), electronics is transferred to cathode (10) by external circuit from anode (6)；Air Pump (9) is pumped air into organic wastewater and flowed through at negative electricity pole room (10a), the H under acid atmosphere in waste water+Ion exists Electronics and and O are obtained at cathode (10)2Generation reduction reaction, generation hydrogen peroxide H2O2；H2O2With catalyst Fe2+Ion occurs Reaction generates OH hydroxyl radical free radicals and Fe3+Ion, the organic matter effect in OH oxidized waste waters, generates CO2, water and centre Product, the Fe generated after reaction3+An electronics is obtained at cathode (10) and is reduced into Fe again2+；Reach oxidative degradation requirement Part organic wastewater afterwards is post-processed by regulating valve (11) system of leaving, and part organic wastewater flows back to organic waste water pot (14) mix with pending organic waste water stream (14a), then pressurize through organic wastewater circulating pump (13) in RED battery piles (5) It is circulated in positive and negative electrode chamber (6,10), the organic matter in waste water is by oxidative degradation；It is produced in external circuit due to electron transfer (15) are loaded outside raw electric current output electrical energy drive；
    Solution chemistry potential energy is converted to organic wastewater oxidative degradation can be with after electric energy, and the concentrated solution for flowing through concentrated solution runner (7a) is dense Degree declines, and flows through the weak solution concentration rise of weak solution runner (8a), and the two outflow RED battery piles (5) are simultaneously mixed into intermediate dense Solution is spent, intermediate concentration solution is after solution preheater (12) heat temperature raising into distiller (2) by low grade heat energy stream stock (2a) heating separation again, completes an organic wastewater degraded and power generation cycle, releases the low grade heat energy stream stock after heat (2b) outflow system；
    The pH value of the organic wastewater is less than 6, and electrical conductivity is more than 5mScm-1；Yin, yang electrode chamber mean flow rate is flowed through to be more than 0.5cm·s-1, more than 1.0V, the mean time length of the organic wastewater oxidative degradation processing circulated is more than RED output voltages 5mim；
    The anode (6) uses investigation of titanium anode coated with metal oxide；Cathode (10) uses carbon based gas diffusion electrode；It is described to urge Agent Fe+2Cationic cure is in cathode (10) or addition is in processed organic wastewater.
  2. 2. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 1, it is characterised in that：Institute Anion-exchange membrane (7) is stated in the reverse electrodialysis RED battery piles (5) for degradation of organic waste water one more than cation-exchange membrane Part.
  3. 3. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 1 or 2, feature exist In：The outer load (15) can be various electrocatalytic oxidation organic wastewater degraded reactors, and system capacity is used to have entirely at this time Machine wastewater oxidation is degraded, and does not export electric energy externally.
  4. 4. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 1 or 2, feature exist In：According to low grade heat energy temperature grade, single-action or multiple-effect separation can be used in the distiller (2).
  5. 5. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 3, it is characterised in that：Root According to low grade heat energy temperature grade, single-action or multiple-effect separation can be used in the distiller (2).
  6. 6. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 1 or 2 or 5, feature It is：The working solution is easily by the electrolyte solution of thermal release, the heated low boiling component isolated contains a small amount of electrolysis Matter.
  7. 7. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 3, it is characterised in that：Institute Working solution is stated as easily by the electrolyte solution of thermal release, the heated low boiling component isolated contains a small amount of electrolyte.
  8. 8. a kind of new low grade heat energy oxidative degradation organic wastewater method according to claim 4, it is characterised in that：Institute Working solution is stated as easily by the electrolyte solution of thermal release, the heated low boiling component isolated contains a small amount of electrolyte.
CN201711384061.2A 2017-12-20 2017-12-20 A kind of method using low grade heat energy oxidative degradation organic wastewater Pending CN108083366A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111342703A (en) * 2020-04-10 2020-06-26 大连海事大学 Solution concentration 'heat-electricity' conversion circulation system based on steam ejector
CN112624234A (en) * 2020-11-26 2021-04-09 大连理工大学 System and method for treating organic wastewater by using low-grade heat energy
US11339483B1 (en) 2021-04-05 2022-05-24 Alchemr, Inc. Water electrolyzers employing anion exchange membranes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105261808A (en) * 2015-10-21 2016-01-20 大连理工大学 Novel low-grade heat energy power generation method and device
KR20170044579A (en) * 2015-10-15 2017-04-25 한양대학교 산학협력단 Microbial reverse electrodialysis electrolysis device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170044579A (en) * 2015-10-15 2017-04-25 한양대학교 산학협력단 Microbial reverse electrodialysis electrolysis device
CN105261808A (en) * 2015-10-21 2016-01-20 大连理工大学 Novel low-grade heat energy power generation method and device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
O. SCIALDONE ET AL.: "Energy generation and abatement of Acid Orange 7 in reverse electrodialysis cells using salinity gradients", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111342703A (en) * 2020-04-10 2020-06-26 大连海事大学 Solution concentration 'heat-electricity' conversion circulation system based on steam ejector
CN111342703B (en) * 2020-04-10 2024-04-05 大连海事大学 Solution concentration difference 'heat-electricity' conversion circulation system based on steam injector
CN112624234A (en) * 2020-11-26 2021-04-09 大连理工大学 System and method for treating organic wastewater by using low-grade heat energy
CN112624234B (en) * 2020-11-26 2021-12-14 大连理工大学 System and method for treating organic wastewater by using low-grade heat energy
US11339483B1 (en) 2021-04-05 2022-05-24 Alchemr, Inc. Water electrolyzers employing anion exchange membranes

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