CN105884108A - Treatment process for wastewater ammonolysis - Google Patents
Treatment process for wastewater ammonolysis Download PDFInfo
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- CN105884108A CN105884108A CN201610407029.0A CN201610407029A CN105884108A CN 105884108 A CN105884108 A CN 105884108A CN 201610407029 A CN201610407029 A CN 201610407029A CN 105884108 A CN105884108 A CN 105884108A
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- 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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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/08—Preparation of ammonia from nitrogenous organic substances
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- 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
- C02F1/46104—Devices therefor; Their operating or servicing
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- 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
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Abstract
The invention discloses a treatment process for wastewater ammonolysis. The treatment process includes the steps that organic matter is subjected to microelectrolysis and/or photocatalysis decomposition, amino groups on organic matter molecules fall off to form free ammonia which is dissolved in water in the form of inorganic ammonium salt, and then the free ammonia is collected or absorbed through membrane distillation to obtain ammonia water or ammonium salt. Membrane distillation is used for recovering ammonia, and equipment is simple and easy to operate.
Description
Technical field
The present invention relates to a kind of field of waste water treatment, be specifically related to the process technique of a kind of ammonolysis waste water.
Background technology
Ammonolysis waste water refers to the waste water produced during Organic substance generation ammonolysis reaction, containing mainly containing nothing in ammonolysis waste water
Machine free ammonia, a small amount of reaction raw materials or product (including organic amine compound).Such as: paranitrochlorobenzene ammonolysis
Waste water, DNFB ammonolysis waste water.Waste water similar to its nature also include T acid neutralize waste water,
In tobias acid and a class such as waste water, diallyl ammonolysis waste water in and waste water.
Prior art usually neutralizes or blows ammonia, condensing crystallizing or burning, said method cost to the process of ammonolysis waste water
Height, process are thorough, waste resource.
Summary of the invention
The present invention provides the process technique of a kind of ammonolysis waste water, by light electrolysis and photocatalysis Decomposition Organic substance, shape
Become free ammonia.Then by Membrane Materials, free ammonia is collected or absorption, obtain ammonia or ammonium salt.
The technical solution used in the present invention is:
The process technique of a kind of ammonolysis waste water, said method comprising the steps of:
(1) pretreatment: ammonolysis waste water is carried out pretreatment, described pretreatment is the process of decomposing organic matter,
The process step of described decomposing organic matter includes one or both in Fe-C light electrolysis, photocatalysis;As excellent
Choosing, carries out Fe-C light electrolysis, photochemical catalytic oxidation successively by ammonolysis waste water;Obtain pretreated waste water;
The operating procedure of described Fe-C light electrolysis is:
The pH value regulation of pending waste water is respectively wastewater quality to 2-3.5, Fe powder and activated carbon dosage
0.5-3.0% and 0.1-0.3%, stirring at normal temperature reaction 1-5h, then adjust pH value flocculate to 8-10, mistake
The waste water after Fe-C microelectrolysis processing is obtained after filter;
The operating procedure of described photochemical catalytic oxidation is:
By pending waste water regulation pH value to 3-6, be added thereto to hydrogen peroxide, hydrogen peroxide add quality with
The mass ratio of waste water is (0.2-1%) × (the COD numerical value ÷ 1000 in waste water), at mercury lamp prolonged exposure
Under, keep temperature 20-50 DEG C, aerated reaction 2-5 hour, obtain the waste water after Treatment by Photocatalysis Oxidation;Useless
The unit of the COD numerical value in water is mg/L.The mass percentage concentration of hydrogen peroxide is generally 30~35%.
(2) Membrane Materials
The pretreated waste water regulation that step (1) obtains, to alkalescence (preferably adjusting pH 9-12), rises after filtration
Temperature, to 15-60 DEG C (preferably 40~60 DEG C), is processed by Membrane Materials and removes free ammonia, during Membrane Materials processes, excellent
The flow velocity selecting waste water is 0.01-0.5m/s, and absorbent is water or the sulphuric acid of 5%-10% or hydrochloric acid, the stream of absorbent
Speed 0.01-0.5m/s, during Membrane Materials, free ammonia, by distillation film, arrives and absorbs side;Membrane Materials is used
It is water or the sulphuric acid of mass fraction 5%-10% or hydrochloric acid in the absorbent absorbing free ammonia;Further, described suction
When receipts agent is water, the absorbing liquid obtained is ammonia, when absorbent is sulphuric acid or the hydrochloric acid of 5%-10%, obtains
Absorbing liquid is ammonium sulfate or ammonium chloride solution.
During preferably absorbent is the sulphuric acid of mass fraction 5%-10% or hydrochloric acid, and Membrane Materials, keep absorbing
The mass percentage concentration of agent is more than 5%.
After Membrane Materials processes, the NH of Membrane Materials water outlet3-N concentration can be down to below 50mg/L;
Ammonolysis waste water of the present invention refers to the waste water produced during Organic substance generation ammonolysis reaction, main in ammonolysis waste water
To contain inorganic free ammonia, a small amount of reaction raw materials and/or the product containing organic amine compound.Of the present invention
Ammonolysis waste water include paranitrochlorobenzene ammonolysis waste water, DNFB ammonolysis waste water.With its character phase
As waste water also include T acid neutralize in waste water, tobias acid and waste water, diallyl ammonolysis waste water etc. one class neutralize
Waste water.
Further preferably, the present invention is to containing aniline, chloronitrobenzene, nitroaniline, chloronitrobenzene amine etc.
Waste water also has preferable treatment effect.
In above-mentioned process step, by micro-electrolysis reaction, Organic substance chain rupture is decomposed, and amino falls from Organic substance chain
Fall, form free ammonia;Organic substance can be decomposed by photocatalysis, and amino falls down from Organic substance chain, is formed
Free ammonia.Organic thing it is substantially free of, by treatment fluid regulation to alkalescence, trip in the treatment fluid that pretreatment obtains
Overflow from water from ammonia, by distillation film, arrive the opposite side of film, be collected or absorb, obtaining ammonia or ammonium
Salt.
For the Organic substance containing nitro, by micro-electrolysis reaction, the nitro in Organic substance can be reduced to amino,
Reduce the difficulty of subsequent treatment, improve the ammonia nitrogen response rate;In photocatalysis, the little molecule that light electrolysis generates is entered one
Step is decomposed, and makes amino split away off from Organic substance, becomes free ammonia;Waste water after photocatalysis is substantially free of
Organic substance, by distillation film, can be recycled to ammonia or ammonium salt.
For the waste water that organic components is more complicated, can aoxidize by humidification-type in pretreatment, improve organic point
Solve efficiency, obtain cleaner containing ammonia treatment liquid.
For improving the clearance of metal ion, membrane filtration, generally ultrafiltration-nanofiltration two can be added before Membrane Materials
Step filters.
So, as preferably, processing method of the present invention is implemented also by following steps:
(1) pretreatment described in pretreatment is the process of decomposing organic matter, and the process of described decomposing organic matter includes
One in Fe-C light electrolysis, photochemical catalytic oxidation or successively ammonolysis waste water is carried out Fe-C light electrolysis, photocatalysis
Aoxidize or carried out by ammonolysis waste water successively Fe-C light electrolysis, wet oxidation process, photochemical catalytic oxidation or successively will
Ammonolysis waste water carries out wet oxidation process, photochemical catalytic oxidation;Pretreatment stage needs the COD process of waste water
To below 500mg/L;
Further, described pretreatment for successively ammonolysis waste water being carried out Fe-C light electrolysis, wet oxidation processes,
During photochemical catalytic oxidation, described pre-treatment step includes following three steps:
(1-a) Fe-C light electrolysis
By the pH regulator of waste water to about 3, course of reaction adds acid, keeps pH constant, Fe powder and activity
Charcoal dosage is respectively 0.5-3.0% and 0.1-0.3% of wastewater quality, reacts 3-5h, then adjusts pH to 9-10
After flocculation, filtering, filtrate adds 0.02-0.2% activated carbon adsorption, filters, obtains treatment fluid 1;
(1-b) wet oxidation
Treatment fluid 1 carries out wet oxidation, oxidation Decomposition Organic substance, organic amine step (1) reduction obtained
Decompose, obtain ammonium salt, and larger molecular organics is resolved into little molecule;Wet oxidation conditions: temperature is
200-300 DEG C, pressure is 1-10MPa, is oxidant with air or oxygen;
(1-c) photochemical catalytic oxidation
Wet oxidation treatment fluid regulation pH to 3-6, be added thereto to hydrogen peroxide, hydrogen peroxide add quality with
The mass ratio of waste water is (0.2-1%) × (the COD numerical value ÷ 1000 in waste water), at mercury lamp prolonged exposure
Under, keep temperature 20-50 DEG C, aerated reaction 2-5 hour, obtain treatment fluid 2;
(2) membrane filtration
Treatment fluid 2 regulation, to alkalescence, is filtered by ultrafiltration-nanofiltration two step, is obtained clean treatment fluid;
(3) Membrane Materials
The treatment fluid that step (2) obtains carries out Membrane Materials, reclaims free ammonia, and the temperature arranging treatment fluid is
15-60 DEG C, flow velocity 0.01-0.5m/s, pH is 9-12, cools down the ammonia by film and/or steam with air,
Obtaining ammonia, the water outlet of Membrane Materials is treatment fluid 3.
As preferably, the photochemical catalytic oxidation of the present invention can be light Fenton, and available Fe-C light electrolysis produces
Ferrous ion is as catalyst, it is possible to add ferrous ion, under the irradiation of uviol lamp, the most appropriate
Add hydrogen peroxide, it is also possible to add the photocatalyst such as TiO of synthesis2Deng.
As preferably, when photocatalytic-oxidation turns to light Fenton, when being used in conjunction with light electrolysis, the following side of operation can be used
Formula carries out pretreatment:
(1-A) light electrolysis: by the pH regulator of pending waste water to 2~3.5, Fe powder and activated carbon dosage
Being respectively 0.5-3.0% and 0.1-0.3% of wastewater quality, stirring at normal temperature reaction 1-5h, in the filtrate being filtrated to get
Add adsorbent (typically adding 0.01-0.2% activated carbon adsorption), after filtration, obtain Fe-C microelectrolysis processing
After waste water;
(1-B) light Fenton: the waste water after Fe-C microelectrolysis processing is regulated pH to 3-6, is added thereto to
Hydrogen peroxide, the mass ratio adding quality and waste water of hydrogen peroxide is 0.2-1% × (COD numerical value in waste water
Divided by 1000), under mercury lamp prolonged exposure, holding temperature 20-50 DEG C, aerated reaction 2-5 hour, then
Adjusting pH value to flocculate to 8-10, filter, filtrate adds the 0.01-0.2% activated carbon of filtrate quality and adsorbs,
The waste water after Treatment by Photocatalysis Oxidation is obtained after filtration;
As preferably, wet oxidation can add catalyst, carries out CWO;Room temperature can also be used
The catalytic wet oxidation of normal pressure, with hydrogen peroxide as oxidant, adds heavy metal catalyst.
As preferably, in the present invention, before ultrafiltration-nanofiltration, conventional filtration can be done, it is to avoid during regulation pH
The precipitated metal thing blocking fenestra produced.
As preferably, Membrane Materials of the present invention can use deamination film, by the ammonia of air purging abjection, and will
It leads in absorbent and absorbs, and when absorbent is water, available ammonia, when absorbent is acid solution, absorbing liquid can
Obtain ammonium salt.
As preferably, the water outlet of Membrane Materials can mix with raw wastewater further, is circulated back to step (1) and carries out
Process.In Membrane Materials water outlet during saliferous, can concentration and recovery salt or reclaim bronsted lowry acids and bases bronsted lowry by bipolar membrane electrodialysis.
The beneficial effects of the present invention is:
1, reclaim the ammonia in ammonolysis waste water, reduce the cost that waste water processes;
2, method is simple to operation, and the clearance of Organic substance and ammonia nitrogen is all up more than 90%.
3, the method for concentration temperature that distillation film is more conventional is low, is difficult to bring the low-boiling-point organic compound of residual into absorption
In liquid, the ammonia obtained or the quality of ammonium salt are high.
Four, detailed description of the invention
Embodiment one
The paranitroanilinum waste water that paranitrochlorobenzene ammonolysis obtains, COD=29000mg/L, reddish brown, no
Transparent, there is strong impulse abnormal smells from the patient, pH=8.6, ammonia nitrogen is 647mg/L, and total nitrogen is 3351mg/L.
(1) Fe-C light electrolysis: take paranitroanilinum waste water, 10% sulfur in processing with step (3) deamination film
The acid absorbing liquid produced after acid solution absorbing ammonia is by the pH regulator of waste water to 3, Fe powder and activated carbon dosage
Be respectively wastewater quality 3.0% and 0.3%, react 3h, add in filtrate after filtration 0.1% activated carbon (with
On the basis of filtrate quality), to filter after stirring reaction 0.5h, the filtrate obtained is treatment fluid 1, records its water quality:
COD=3700mg/L, NH3-N=1900mg/L, pH=6.81.
(2) photocatalysis: the treatment fluid 1 that step (1) obtains regulates pH to 5, at the uniform velocity adds the matter of waste water
The hydrogen peroxide (mass concentration of hydrogen peroxide is 30%) of the 4.0% of amount, rate of addition is 0.01%/min, at hydrargyrum
Under lamp prolonged exposure, keeping reaction temperature is 25 DEG C, and aerated reaction 3 hours, (mass concentration is to add liquid caustic soda
The sodium hydroxide solution of 30%) adjust pH be 10, flocculate 0.5h sucking filtration, add the 0.02% of filtrate quality to filtrate
Activated carbon adsorption 0.5h, is filtrated to get photocatalysis water outlet.Photocatalysis effluent quality: COD=250mg/L, NH3-N=
2800mg/L, pH=6.81.
(3) deamination film: adding liquid caustic soda regulation pH to 11.3 in photocatalysis water outlet, waste water flow velocity is 0.21m/s,
Configure 10% sulfuric acid solution ammonia is absorbed, absorbing liquid flow velocity 0.07m/s.Treatment fluid temperature is set as
50 DEG C, absorbent is room temperature, and in Membrane Materials process, concentrated sulphuric acid to be added is to ensure the quality hundred of sulphuric acid in absorbent
Dividing concentration more than 5%, 30min records NH3-N concentration is reduced to 37mg/L, pH=9.84, and absorbing liquid obtains
The purest ammonium salt, and be acid, can be used in the step of waste water tune pH to 3 of step (1).
Water outlet COD=220mg/L, NH3-N=37mg/L, can be used for the bottom water of paranitrochlorobenzene ammonolysis technique
Use
Embodiment two
Amino benzene analog waste water, deep blue purple color, COD=5100mg/L, TOC=2400mg/L, pH=9.1, ammonia nitrogen is 2100mg/L,
Total nitrogen is 4600mg/L.
(1) photocatalysis: take amino benzene analog waste water regulation pH to 5, be added thereto to wastewater quality 5.0% in batches
Hydrogen peroxide, under mercury lamp prolonged exposure, keep reaction temperature be 25 DEG C, aerated reaction 4 hours.Light is urged
Change effluent quality: COD=110mg/L, NH3-N=3900mg/L, pH=5.8.
(2) deamination film: add liquid caustic soda (mass concentration is the sodium hydroxide solution of 30%) in photocatalysis water outlet
Regulation pH to 11.5, waste water flow velocity is 0.25m/s, configures 10% sulfuric acid solution and inhales gaseous free ammonia
Receive, absorbing liquid flow velocity 0.1m/s.Wastewater temperature is 60 DEG C, and absorbent is room temperature, and Membrane Materials to be mended in processing
Adding concentrated sulphuric acid to ensure the mass percentage concentration more than 5% of sulphuric acid in absorbent, 40min records NH3-N concentration
Being reduced to 28mg/L, pH=9.5, absorbing liquid obtains the purest ammonium salt.
Water outlet COD=121mg/L, NH3-N=28mg/L, can be used for production.
Embodiment three
Certain ammonolysis mother liquor waste water, is mainly composed of NH3·H2O、NH4Cl, 2,4-dinitroaniline, chloro two
Nitroaniline compound etc., deep isabelline relatively transparent liquid, distribute pungent ammonia taste.Its pH=9.38,
COD=1941mg/L, NH3-N=2985mg/L, TN=4800mg/L, solid content is 3.11%.
(1) Fe-C light electrolysis: the pH regulator of waste water to 2, Fe powder and activated carbon dosage are respectively useless
The 2.0% and 0.2% of water quality, reacts 3h.Adding alkali regulation wastewater pH is 8.5, and stirring flocculation 0.5h filters
Obtain effluent quality: COD=400mg/L, NH3-N=4400mg/L.
(2) ultrafiltration-nanofiltration: step (1) water outlet regulation pH to 11.7, pass sequentially through under room temperature ultrafilter membrane and
NF membrane, COD about 50mg/L in the water outlet obtained, ammonia nitrogen about 4310mg/L.
(3) deamination film: the water outlet of step (2) is heated to 50 DEG C, passes through deamination with the flow velocity of 0.3m/s
Film, 10% sulfuric acid solution (room temperature, 25 DEG C) flows through at deamination film opposite side with the speed of 0.1m/s, absorbs
Gaseous free ammonia.Absorption process detects the concentration of sulphuric acid, when concentration is less than 5%, adds concentrated sulphuric acid, keep
The sulfuric acid concentration of absorbent is more than 5%, and reaction 30min records water outlet NH3-N concentration is reduced to 59mg/L,
PH=9.2, absorbing liquid obtains the purest ammonium salt.
Water outlet COD=67mg/L, NH3-N=59mg/L, can be used for production.
Embodiment four
In H-acid and in waste water, containing LOMAR PWA EINECS 246-676-2 Ammonia Organic substance and ammonium sulfate, its pH=10, COD=21941
Mg/L, NH3-N=10785mg/L, TN=4800mg/L, solid content is 17.11%.
(1) wet oxidation: waste water is heated to 230 DEG C, pressure is 3MPa, with oxygen as oxidant, high temperature
Reaction under high pressure 1h, adds 0.2% kieselguhr in the water outlet obtained, after agitation and filtration, obtain filtrate, filtrate
COD is 3860mg/L, and ammonia nitrogen is 13377mg/L, and total nitrogen is 120mg/L.
(2) light Fenton: the liquid regulation pH to 4 that step (1) obtains, is added thereto to 0.2% ferrous sulfate
After, adding hydrogen peroxide, the dosage of hydrogen peroxide and the mass ratio of waste water are 3% (on the basis of the quality of waste water),
Under mercury lamp prolonged exposure, keep temperature 30 DEG C, aerated reaction 2 hours, obtain treatment fluid 1.
(3) ultrafiltration-nanofiltration: step (2) water outlet pH regulator is to 11.7, after simple filtration, under room temperature successively
By ultrafilter membrane and NF membrane, COD about 50mg/L in the water outlet obtained, ammonia nitrogen about 14310mg/L, total nitrogen
Less than 10mg/L.
(4) deamination film: the water outlet of step (3) is heated to 40 DEG C, passes through deamination with the flow velocity of 0.3m/s
Film, 10% sulfuric acid solution (room temperature, 25 DEG C) flows through at deamination film opposite side with the speed of 0.1m/s, absorbs
Gaseous free ammonia.Absorption process detects the concentration of sulphuric acid, when concentration is less than 5%, adds concentrated sulphuric acid, keep
The sulfuric acid concentration of absorbent is more than 5%, and reaction 30min records water outlet NH3-N concentration is reduced to 59mg/L,
PH=9.2, absorbing liquid obtains the purest ammonium salt.
(5) salt recycles: the aobvious acidity of deamination film water outlet, COD is 61mg/L.Deamination film water outlet is by steaming
Evaporating salinity in the treatment fluid after membrance concentration is 30%, is processed by bipolar membrane electrodialysis, obtains the sulphuric acid of 10%
With 9% sodium hydroxide.
Claims (10)
1. a process technique for ammonolysis waste water, described ammonolysis waste water refers to the waste water produced during Organic substance generation ammonolysis reaction, it is characterised in that said method comprising the steps of:
(1) pretreatment: ammonolysis waste water carries out pretreatment, described pretreatment is the process of decomposing organic matter, and the process step of described decomposing organic matter includes one or both in Fe-C light electrolysis, photochemical catalytic oxidation;
(2) Membrane Materials: pretreated waste water regulation step (1) obtained is to alkalescence, 15-60 DEG C it is warming up to after filtration, being processed by Membrane Materials and remove free ammonia, in Membrane Materials, absorbent for absorbing free ammonia is water or the sulphuric acid of mass fraction 5%-10% or hydrochloric acid.
2. the method for claim 1, it is characterised in that in described step (2), when described absorbent is water, the absorbing liquid obtained is ammonia;When absorbent is sulphuric acid or the hydrochloric acid of mass fraction 5%-10%, the absorbing liquid obtained is ammonium sulfate or ammonium chloride solution.
3. the method for claim 1, it is characterized in that in described step (1), the operating procedure of described Fe-C light electrolysis is: regulate the pH value of pending waste water to 2-3.5, Fe powder and activated carbon dosage are respectively 0.5-3.0% and 0.1-0.3% of wastewater quality, stirring at normal temperature reaction 1-5h, then adjust pH value to flocculate to 8-10, after filtration, obtain the waste water after Fe-C microelectrolysis processing.
4. the method for claim 1, it is characterized in that in described step (1), the operating procedure of described photochemical catalytic oxidation is: by pending waste water regulation pH value to 3-6, it is added thereto to hydrogen peroxide, the mass ratio adding quality and waste water of hydrogen peroxide is (0.2-1%) × (the COD numerical value ÷ 1000 in waste water), under mercury lamp prolonged exposure, keeps temperature 20-50 DEG C, aerated reaction 2-5 hour, obtains the waste water after Treatment by Photocatalysis Oxidation.
5. the method for claim 1, it is characterised in that in described step (2), during described Membrane Materials processes, the flow velocity of waste water is 0.01-0.5m/s, the flow velocity 0.01-0.5m/s of absorbent.
6. the method for claim 1, it is characterised in that in described step (2), described absorbent is sulphuric acid or the hydrochloric acid of mass fraction 5%-10%.
7. method as claimed in claim 6, it is characterised in that in described step (2), during Membrane Materials, the mass percentage concentration keeping absorbent is more than 5%.
8. the method for claim 1, it is characterized in that in described step (1), also including in described pretreatment that wet oxidation processes, described pretreatment includes the one in Fe-C light electrolysis, photochemical catalytic oxidation or ammonolysis waste water carries out Fe-C light electrolysis, photochemical catalytic oxidation successively or ammonolysis waste water carries out Fe-C light electrolysis, wet oxidation process, photochemical catalytic oxidation successively or successively ammonolysis waste water is carried out wet oxidation process, photochemical catalytic oxidation;The COD of waste water is processed to below 500mg/L by pretreatment stage.
9. the method for claim 1, it is characterised in that in described step (2), carries out membrane filtration before Membrane Materials in advance.
10. the method for claim 1, it is characterised in that in described step (1), described pretreatment for carry out Fe-C light electrolysis, photochemical catalytic oxidation successively by ammonolysis waste water, and described pretreatment comprises the following steps:
(1-A) light electrolysis: by the pH regulator of pending waste water to 2-3.5, Fe powder and activated carbon dosage are respectively 0.5-3.0% and 0.1-0.3% of wastewater quality, stirring at normal temperature reaction 1-5h, the filtrate being filtrated to get adds adsorbent, after filtration, obtains the waste water after Fe-C microelectrolysis processing;
(1-B) light Fenton: the waste water after Fe-C microelectrolysis processing is regulated pH to 3-6, it is added thereto to hydrogen peroxide, the mass ratio adding quality and waste water of hydrogen peroxide is 0.2-1% × (the COD numerical value in waste water divided by 1000), under mercury lamp prolonged exposure, keep temperature 20-50 DEG C, aerated reaction 2-5 hour, then pH value is adjusted to flocculate to 8-10, filter, filtrate adds the 0.01-0.2% activated carbon of filtrate quality and adsorbs, and obtains the waste water after Treatment by Photocatalysis Oxidation after filtration.
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