CN108726740A - A kind of high sodium chloride waste water Zero discharge treatment method - Google Patents
A kind of high sodium chloride waste water Zero discharge treatment method Download PDFInfo
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C02F1/46—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
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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
- C02F1/46—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
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
Abstract
A kind of high sodium chloride waste water Zero discharge treatment method, includes the following steps：Fenton oxidation：Once oxidation processing is carried out for organic matter in the high sodium chloride waste water of 2.5-3.5 to pH value using hydrogen peroxide and ferrous iron；Mud-water separation processing is carried out to the water outlet of Fenton oxidation；Catalytic and oxidative electrolysis technology is carried out to the supernatant after mud-water separation, completes secondary oxidative treatments；Carry out resin adsorption processing to being discharged after catalytic and oxidative electrolysis technology；Film electrolysis processing is carried out to water outlet after resin adsorption, water outlet can direct emission or reuse.Using method disclosed by the invention to after the processing of high sodium chloride waste water, it can be achieved that the fully recovering of sodium chloride waste water, abraum salt content is almost nil in waste water, by-product chlorine, hydrogen and sodium hydroxide solution, can reduce processing cost, saves processing cost.
Description
Technical field
The present invention relates to a kind of wastewater purification technical fields, are urged using Fenton oxidation+electrolysis more particularly, to a kind of
Change the method that oxidation+absorption+film electrolysis combined technology handles high sodium chloride waste water
Background technology
The waste water generated in chemical process mostly has higher salinity, such as sulfate, villaumite and nitrate.Wherein
Sodium chloride-containing waste water in the majority with sodium chloride waste water in villaumite waste water, being generated such as some pharmacy, Pigment Intermediates, salt chemical engineering industry
The content of middle sodium chloride is up to 20%, in such waste water the source of sodium chloride mainly in process of production using hydrochloric acid as material,
The acid waste water of generation carries out neutralization formation, while such waste water also organic matter containing higher concentration using sodium hydroxide.This
A little high sodium chloride waste waters can not be handled directly using bioanalysis, if handled using technique biochemical after first evaporating,
What is not only evaporated is costly, and the sodium chloride steamed belongs to dangerous solid waste because containing organic matter, needs to entrust related single
Position carries out after-treatment, also needs higher processing cost.
Invention content
The present invention provides a kind of method of high sodium chloride waste water processing, and this method is urged using Fenton oxidation+precipitation+electrolysis
Change oxidation+absorption+film electrolysis combined technology to handle high sodium chloride waste water, not only solves enterprise wastewater high disposal expense
Problem, and the treatment of wastes with processes of wastes against one another can utilize waste water pair to give birth to raw materials for production, have higher economic benefit, the technical solution of use
It is：A kind of high sodium chloride waste water Zero discharge treatment method, includes the following steps：
1) Fenton oxidation：PH value is carried out for organic matter in the high sodium chloride waste water of 2.5-3.5 using hydrogen peroxide and ferrous iron
Once oxidation processing；
2) mud-water separation processing is carried out to the water outlet of Fenton oxidation；
3) catalytic and oxidative electrolysis technology is carried out to the supernatant after mud-water separation, completes secondary oxidative treatments；
4) the carry out resin adsorption processing to being discharged after catalytic and oxidative electrolysis technology；
5) film electrolysis processing is carried out to water outlet after resin adsorption, water outlet can direct emission or reuse.
Preferably：Hydrogen peroxide and ferrous molar ratio are 5 in the step 1):1-10:1.
Preferably：The Fenton oxidation time is 2-4 hours in the step 1).
Preferably：Current density is 5.0-20mA/cm between catalytic and oxidative electrolysis technology device pole plate in the step 3), between pole plate
Away from for 1-5cm.
Preferably：Resin used is macroreticular resin in the step 4).
Preferably：At least one set of anode, cathode parallel arranged in film electrolysis reactor in the step 5)；Anode is titanium-based
Coated electrode, coating material IrO2, RuO2 molar ratio 1:1 mixture, cathode are nickel electrode；Anode tap sets chlorine collection
Pipe, cathode terminal set Hydrogen collection pipe；There is cation-exchange membrane close to anode-side, has anion-exchange membrane close to cathode.
Preferably：The cathode upper end of the film electrolysis reactor sets water inlet, and bottom end sets alkali outlet；Anode upper end sets charging
Mouthful, lower end sets out material mouth, is to be concentrated by evaporation section between inlet port and outlet port.
The beneficial effects of the present invention are：The present invention first uses Fenton oxidation to carry out at once oxidation useless Organic substance in water
Reason, once oxidation water outlet enter sedimentation basin and carry out mud-water separation, and supernatant enters catalytic and oxidative electrolysis technology and carries out secondary oxidative treatments,
Secondary oxidation water outlet further decreases the content of organics in waste water into macroporous resin adsorption technique, and work is electrolysed subsequently into film
Skill is handled, production water can direct reuse in production, while by-product chlorine, hydrogen and sodium hydroxide solution；Using of the invention public
The method opened to after the processing of high sodium chloride waste water, it can be achieved that the fully recovering of sodium chloride waste water, abraum salt content is almost in waste water
Zero, by-product chlorine, hydrogen and sodium hydroxide solution can reduce processing cost, save processing cost.
Description of the drawings
Attached drawing 1 is processing flow schematic diagram of the present invention, and attached drawing 2 is film forgoing electrolyzer constructions schematic diagram, wherein 1- Fenton oxidations
System, 2- sedimentation basins, 3- catalytic and oxidative electrolysis technology systems, 4- resin adsorption systems, 5- film electrolysis systems, 6- resin regeneration systems,
7- evaporation concentration systems, 8- discharge outlet, 9- chlorine gas outlets, 10- hydrogen outlets, the outlet of 11- liquid caustic soda.
Specific implementation mode
Below in conjunction with the accompanying drawings, description of specific embodiments of the present invention.
A kind of high sodium chloride waste water Zero discharge treatment method, includes the following steps：
1, Fenton oxidation：PH value is carried out for organic matter in the high sodium chloride waste water of 2.5-3.5 using hydrogen peroxide and ferrous iron
Once oxidation processing.
In acid condition, ferrous ion catalysis hydrogen peroxide generates hydroxyl radical free radical, hydroxyl free
Base aoxidizes organic matter, generates carbon dioxide and water.
1) water inlet PH controls are in 2.5-3.5；
2) hydrogen peroxide：Ferrous molar ratio 5:1-10:1；
3) Fenton oxidation time 2-4 hours.
2, mud-water separation processing is carried out to the water outlet of Fenton oxidation.
Iron ion after Fenton water outlet plus alkali in water produces iron hydroxide flco, iron hydroxide flco
It is deposited to bottom under the effect of gravity, supernatant flows automatically to next technique.
1) sedimentation basin surface loading 0.4-0.8m/s；
2) sedimentation basin form is radial-flow or flat flow.
3, catalytic and oxidative electrolysis technology is carried out to the supernatant after mud-water separation, completes secondary oxidative treatments.
Under the action of applying direct current electric field, Organic substance in water is adsorbed to anode surface, in the catalytic action of catalyst
Under aoxidized, in addition chlorion is oxidized to chlorine in anode in water, and chlorine is hydrolyzed to hypochlorous acid, and hypochlorous acid is equally to organic
Object is by oxidation, and the ammonium oxidation in water can be nitrogen by hypochlorous acid, so catalytic and oxidative electrolysis technology can remove simultaneously
Organic matter in water and ammonia nitrogen.
1) catalytic and oxidative electrolysis technology reactor is square structure, parallel arranged at least one set positive and negative pole in reactor, positive and negative
Pole is alternately arranged.Anode is ti-based coating electrode, coating material PbO2, IrO2, one or more of TaO2；Negative electrode
For titanium-matrix electrode；
2) current density is 5.0-20mA/cm between pole plate, and pole plate spacing is 1-5cm；
3) oxidization time is 30-120 minutes.
4, the carry out resin adsorption processing to being discharged after catalytic and oxidative electrolysis technology.
Macroporous absorbent resin is a kind of preparation for being free of cation exchange groups and having macroporous structure, is had good
Macroreticular structure and larger specific surface area are the novel organic polymer adsorbents to grow up the 1960s.Greatly
Resin adsorption effect in hole is huge to compare table by it by the Van der Waals force between it and the molecule (adsorbate) that is adsorbed
Face carries out physical absorption and works, and allows organic compound according to having adsorption capacity and its molecular size range to be eluted through certain solvent
Separate and the different purposes such as reach separation, purifying, removal of impurities, concentration.
1) resin used by is macroporous absorbent resin；
2) 0.5-4.0 times of resin volume of adsorption section waste water flow velocity；
3) resin regeneration system uses alkali liquid regeneration or solvent reclamation mode.
5, film electrolysis processing is carried out to water outlet after resin adsorption, water outlet can direct emission or reuse.
Film electrolysis is handled, also known as film electricity slot electrolysis, is that unit electrolytic bath is divided into anode using cation-exchange membrane
Room and cathode chamber, the method for making electrolytic production separate.Membrane electrolysis is on the basis of ion exchange resin (see ion-exchanger)
On a new technology growing up.Have the characteristic that selection penetrates, allowed band a kind of zwitterion using amberplex
The ion of charge by by limit the ion of opposite charges and pass through, synthesized with reaching concentration, desalination, purification, purification and electrification
Purpose.
Sodium chloride solution enters near the anode of film electrolysis reactor, and chlorion is anodized as chlorine from anode top
It overflows, the sodium ion in water is entered by the amberplex among anode and cathode near cathode, and water electrolysis is by cathode
OH-And H2, OH-And Na+Sodium hydroxide solution discharge is generated, hydrogen is discharged from cathode upper end.
1) film electrolysis reactor is square structure, parallel arranged at least one set positive and negative pole in reactor, positive and negative pole alternating
Arrangement.Anode is ti-based coating electrode, coating material IrO2, RuO2 molar ratio 1:1 mixture；Cathode extremely nickel electrode；
2) anode top sets chlorine collecting pipe, and cathode tip sets Hydrogen collection pipe；
3) have cation-exchange membrane close to anode-side, nearby have an anion-exchange membrane close to cathode, anion-exchange membrane and
Spacing is 0.5-2 centimetres between cation-exchange membrane；
4) cathode upper end sets water inlet, and bottom end is equipped with alkali outlet；Anode upper end sets feed inlet, and lower end sets out material mouth, charging
Evaporating and concentrating process is equipped between mouth and discharge port, to be concentrated to material；
5) evaporating and concentrating process is by discharge port dilute sodium chloride Waste water concentrating to 10% or more sodium chloride content.
Process flow chart is as shown in Fig. 1, and the method realizes zero-emission by the following means：
Pending waste water, which is added after hydrochloric acid adjusts PH to certain value, enters Fenton oxidation system 1, and quantitative chlorination is then added
Ferrous and hydrogen peroxide, stirring is anti-, and the addition liquid caustic soda solution of sedimentation basin 2 is entered after certain hour and carries out mud-water separation, is sunk
Shallow lake bottom of pond portion Fe (OH)3Precipitation is discharged from mud discharging mouth 12, and supernatant enters catalytic and oxidative electrolysis technology system 3, is acted in DC electric field
Lower organic matter and ammonia nitrogen carry out catalysis oxidation decomposition, and oxidation is adsorbed into resin adsorption system 4 after a certain period of time, into one
Walking reduces content of organics, and regeneration treatment is carried out to it by resin regeneration system 6 after resin saturation, and resin adsorption system 4 is discharged
Into film electrolysis system 5, chlorion, which is discharged after anode is oxidized to chlorine from chlorine gas outlet 9, under DC electric field effect receives
Collection, the hydrogen that cathode nearby generates are discharged from hydrogen outlet 10 and collect, the hydroxyl that cathode generates through anion-exchange membrane and
Sodium hydroxide is formed from 11 discharge of liquid caustic soda outlet through the sodium ion of cation-exchange membrane；5 treated dilute sodium chloride of film electrolysis
Waste water enters evaporation concentration system 7 and is concentrated, and reuse, the chlorination after concentration is discharged from discharge outlet 8 in the condensed water for concentrating generation
Sodium dope is back to film electrolysis system 5 and carries out circular treatment.
Embodiment 1
Certain chemical enterprises produces waste water：COD is 3100mg/L, ammonia nitrogen 400mg/L, sodium chloride content 100g/L.
It is handled using the processing method provided by the present invention：Pending waste water is added hydrochloric acid and adjusts PH to 3.0 into sweet smell
Then oxidative system 1 is added the hydrogen peroxide of the frerrous chloride and 1500mg/L of 4500mg/L, enters after being stirred to react 4 hours
Sedimentation basin 2 is added sodium hydroxide solution and PH is adjusted to 8.5 or so progress mud-water separations, sedimentation basin bottom Fe (OH)3Precipitation is certainly
Mud discharging mouth 12 is discharged, and supernatant enters catalytic and oxidative electrolysis technology system 3, and organic matter and ammonia nitrogen are catalyzed under DC electric field effect
Oxygenolysis, in current density 20mA/cm2Under the conditions of aoxidize 4 hour time after adsorbed into resin adsorption system 4, into
One step reduces content of organics to 10mg/L hereinafter, being saturated after continuous 72 hours with 1 times of resin volume flow velocity, after resin saturation by
Resin regeneration system 6 carries out it regeneration treatment, and regenerative agent uses 10% lye；The water outlet of resin adsorption system 4 enters film electricity
Solution system 5, in current density 300mA/cm2Lower chlorion is discharged from chlorine gas outlet 9 after anode is oxidized to chlorine and collects, cloudy
The hydrogen extremely nearby generated is discharged from hydrogen outlet 10 and collects, and the hydroxyl that cathode generates is through anion-exchange membrane and through sun
The sodium ion of amberplex forms sodium hydroxide from 11 discharge of liquid caustic soda outlet；5 treated dilute sodium chloride (5%) of film electrolysis is useless
Water enters evaporation concentration system 7 and is concentrated, and reuse, the sodium chloride after concentration is discharged from discharge outlet 8 in the condensed water for concentrating generation
Dope (15%) is back to film electrolysis system 5 and carries out circular treatment.
For the waste water after method provided by the invention processing, waste water per ton can generate chlorine 71kg, generate 30% hydrogen-oxygen
Change sodium solution 140kg, hydrogen 2kg, recycle-water 900kg, 40 yuan of wastewater treatment expense per ton.
Embodiment 2
High-chloride wastewater after certain chemical enterprise film：COD is 480mg/L, ammonia nitrogen 32mg/L, sodium chloride content 220g/L.
It is handled using the processing method provided by the present invention：Pending waste water is added hydrochloric acid and adjusts PH to 3.5 into sweet smell
Then the hydrogen peroxide of the frerrous chloride and 150mg/L of 450mg/L is added in oxidative system 1, it is heavy to enter after being stirred to react 2 hours
Shallow lake pond 2 is added sodium hydroxide solution and PH is adjusted to 8.5 or so progress mud-water separations, sedimentation basin bottom Fe (OH)3Precipitation is arranged certainly
Mud mouth 12 is discharged, and supernatant enters catalytic and oxidative electrolysis technology system 3, and organic matter and ammonia nitrogen carry out catalysis oxygen under DC electric field effect
Change and decompose, in current density 10mA/cm2Under the conditions of aoxidize 4 hour time after adsorbed into resin adsorption system 4, into one
Step reduces content of organics to 5mg/L hereinafter, being saturated after continuous 144 hours with 1 times of resin volume flow velocity, by setting after resin saturation
Fat regenerative system 6 carries out it regeneration treatment, and regenerative agent uses 10% lye；The water outlet of resin adsorption system 4 enters film and is electrolysed
System 5, in current density 200mA/cm2Lower chlorion is discharged from chlorine gas outlet 9 after anode is oxidized to chlorine and collects, cathode
The hydrogen nearby generated from hydrogen outlet 10 be discharged collect, cathode generate hydroxyl through anion-exchange membrane and through sun from
The sodium ion of proton exchange forms sodium hydroxide from 11 discharge of liquid caustic soda outlet；5 treated dilute sodium chloride (10%) of film electrolysis is useless
Water enters evaporation concentration system 7 and is concentrated, and reuse, the sodium chloride after concentration is discharged from discharge outlet 8 in the condensed water for concentrating generation
Dope (25%) is back to film electrolysis system 5 and carries out circular treatment.
For the waste water after method provided by the invention processing, waste water per ton can generate chlorine 150kg, generate 30% hydrogen
Sodium hydroxide solution 300kg, hydrogen 4.5kg, recycle-water 790kg, waste water per ton deduct the benefit generated and post-process about 15 yuan of expense.
Embodiment 3
Certain pesticide wastewater：COD is 750mg/L, sodium sulphate content 150g/L.
It is handled using the processing method provided by the present invention：It is handled using the processing method provided by the present invention：It waits for
Handle waste water and hydrochloric acid is added adjusts PH to 3.0 and enter Fenton oxidation system 1, be then added 2250mg/L frerrous chloride and
The hydrogen peroxide of 750mg/L enters sedimentation basin 2 after being stirred to react 3 hours, sodium hydroxide solution is added, PH is adjusted to 8.5 or so
Carry out mud-water separation, sedimentation basin bottom Fe (OH)3Precipitation is discharged from mud discharging mouth 12, and supernatant enters catalytic and oxidative electrolysis technology system 3,
Organic matter and ammonia nitrogen carry out catalysis oxidation decomposition under DC electric field effect, in current density 15mA/cm2Under the conditions of oxidation it is 3 small
When the time after adsorbed into resin adsorption system 4, further decrease content of organics to 5mg/L hereinafter, with 1 times of resin
Volume flow rate is saturated after continuous 96 hours, and regeneration treatment is carried out to it by resin regeneration system 6 after resin saturation, and regenerative agent uses
10% lye；The water outlet of resin adsorption system 4 enters film electrolysis system 5, and chlorion is in anode at current density 300mA/cm2
It is oxidized to that collection is discharged from chlorine gas outlet 9 after chlorine, the hydrogen that cathode nearby generates is discharged from hydrogen outlet 10 and collects, cathode
Sodium ion of the hydroxyl of generation through anion-exchange membrane and through cation-exchange membrane forms sodium hydroxide and is exported from liquid caustic soda
11 discharges；Treated dilute sodium chloride (10%) that waste water enters evaporation concentration system 7 is concentrated for film electrolysis 5, concentrates generation
Reuse is discharged from discharge outlet 8 in condensed water, and the sodium chloride concentrated liquid (25%) after concentration is back to film electrolysis system 5 and carries out at cycle
Reason.
For the waste water after method provided by the invention processing, waste water per ton can generate chlorine 100kg, generate 30% hydrogen
Sodium hydroxide solution 200kg, hydrogen 3kg, recycle-water 860kg, 23 yuan of wastewater treatment expense per ton.
Claims (7)
1. a kind of high sodium chloride waste water Zero discharge treatment method, includes the following steps：
1) Fenton oxidation：PH value is carried out for organic matter in the high sodium chloride waste water of 2.5-3.5 using hydrogen peroxide and ferrous iron primary
Oxidation processes；
2) mud-water separation processing is carried out to the water outlet of Fenton oxidation；
3) catalytic and oxidative electrolysis technology is carried out to the supernatant after mud-water separation, completes secondary oxidative treatments；
4) the carry out resin adsorption processing to being discharged after catalytic and oxidative electrolysis technology；
5) film electrolysis processing is carried out to water outlet after resin adsorption, water outlet can direct emission or reuse.
2. processing method described in accordance with the claim 1, it is characterised in that：Hydrogen peroxide and ferrous molar ratio in the step 1)
It is 5:1-10:1.
3. processing method described in accordance with the claim 1, it is characterised in that：The Fenton oxidation time is that 2-4 is small in the step 1)
When.
4. processing method described in accordance with the claim 1, it is characterised in that：In the step 3) between catalytic and oxidative electrolysis technology device pole plate
Current density is 5.0-20mA/cm, and pole plate spacing is 1-5cm.
5. processing method described in accordance with the claim 1, it is characterised in that：Resin used is macroreticular resin in the step 4).
6. processing method described in accordance with the claim 1, it is characterised in that：In the step 5) at least one in film electrolysis reactor
Group anode, cathode parallel arranged；Anode is ti-based coating electrode, coating material IrO2, RuO2 molar ratio 1:1 mixture,
Cathode is nickel electrode；Anode tap sets chlorine collecting pipe, and cathode terminal sets Hydrogen collection pipe；There is cation-exchange membrane close to anode-side,
There is anion-exchange membrane close to cathode.
7. processing method according to claim 6, it is characterised in that：The cathode upper end of the film electrolysis reactor sets water inlet
Mouthful, bottom end sets alkali outlet；Anode upper end sets feed inlet, and lower end sets out material mouth, is to be concentrated by evaporation section between inlet port and outlet port.
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| US20220034860A1 (en) * | 2020-07-29 | 2022-02-03 | Saudi Arabian Oil Company | Ion conductivity filter and measurement system |
| CN115254870A (en) * | 2022-06-16 | 2022-11-01 | 深圳市欧格尼绿氢科技有限公司 | Method and system for treating garbage and/or leachate thereof through electrochemical degradation by two-step oxidation method to produce hydrogen jointly |
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