CN109422430A - A kind of processing method of high organic nitrogen waste water - Google Patents
A kind of processing method of high organic nitrogen waste water Download PDFInfo
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- CN109422430A CN109422430A CN201710783930.2A CN201710783930A CN109422430A CN 109422430 A CN109422430 A CN 109422430A CN 201710783930 A CN201710783930 A CN 201710783930A CN 109422430 A CN109422430 A CN 109422430A
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The present invention relates to a kind of processing method of high organic nitrogen waste water, including ozone oxidation, removal and transform portion organic nitrogen and organic matter；Ozone layer destroying pond removes remaining ozone in water, reduces ozone and destroys caused by microorganism；Anoxic treatment technique, removal and the nitrate nitrogen progress anti-nitration reaction for converting the organic nitrogen and organic matter in water, while phegma being taken back, thoroughly remove nitrogen from water；Material filling type MBR unit, thorough decomposing organic matter, most ammonia-nitrogen are converted to nitrate nitrogen and nitrite nitrogen by nitrification, and aminating reaction can also occur herein for fraction organic nitrogen.The anaerobic environment formed inside carrier biofilm simultaneously, can also occur denitrification simultaneously, further reduced the nitrogen in water outlet.High organic nitrogen waste water treatment process of the present invention, it is practical, effective, nitrogen, COD etc. in high organic nitrogen waste water can be effectively removed, realizes the qualified discharge of waste water, there is good environmental benefit and wide application prospect.
Description
Technical field
The present invention relates to a kind of processing method of high organic nitrogen waste water, more specifically include ozone oxidation, anoxic and
The treatment process of material filling type MBR three step process unit provides a kind of reliable processing for the qualified discharge of high organic nitrogen waste water nitrogen
Method.
Background technique
It is seriously affected currently, being generated to human lives by the nitrogen cycle of artificial destruction.People are to nitrogen in sewage
Content control requires to be increasingly stringenter.There are many existence form of nitrogen in water, according to compound form, can be divided into organic nitrogen, ammonia nitrogen
And nitrate nitrogen.Wherein existence form of the organic nitrogen as main nitrogen a kind of in production and living carries out it efficiently to remove tool
There is certain difficulty.
Currently used organic nitrogen removal method has: biological treatment, chemical method and physical method.Utilize anaerobism or hydrolysis acid
The ammonification of organic nitrogen may be implemented in chemical industry skill, then acts on the removal for realizing nitrogen by nitrification and denitrification again.In addition to this,
There is research to attempt the organic nitrogen gone in water removal using algae and plant method, but such method be only limitted to low concentration organic nitrogen it is useless
Water.There are also researchs to remove the organic nitrogen in water removal using chemical oxidization method, and the removal rate of chemical oxidization method is also only capable of reaching 50% left side
It is right；There are also researchs to remove the organic nitrogen in water removal using physical absorption and physics sedimentation, but there is no finally turn nitrogen for physical method
Nitrogen is turned to, but is still present in waste liquid or slag in the form of organic nitrogen or inorganic nitrogen.Every kind of method has its one-sidedness, no
The higher organic nitrogen wastewater treatment of concentration can be reached the emission request to nitrogen at present.
In view of the above problems, practical, effective treatment process is developed, high organic nitrogen waste water water quality after processing is enable
Meet the emission request of standard, realizes stably reaching standard.
Summary of the invention
Present invention seek to address that the deficiencies in the prior art, develop a kind of processing method of high organic nitrogen waste water.
To achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of processing method of high organic nitrogen waste water, comprising the following steps:
1. waste water, which enters ozone oxidation unit, carries out oxidation processes, ammonia nitrogen, nitrate nitrogen are converted by the organic nitrogen in waste water
Or nitrogen, and cyclic annular and long-chain organic matter open loop chain rupture is converted to the easy biochemical degradation organic matter of small molecule, form ozone oxidation
Unit water outlet；
2. ozone oxidation unit, which is discharged, enters ozone destruction unit, remaining ozone in the water outlet of ozone decomposition oxidation unit,
Form ozone destruction unit water outlet；
3. ozone destruction unit water outlet enters anoxic unit, it is anti-to carry out ammonification to the organic nitrogen in ozone destruction unit water outlet
It answers, while denitrification is carried out to nitrate nitrogen, and further make the organic matter open loop chain rupture in ozone destruction unit water outlet, shape
It is discharged at anoxic unit；
4. anoxic unit water outlet enters material filling type MBR unit, aminating reaction is carried out to the organic nitrogen in anoxic unit water outlet,
Nitrification and denitrification occurs in material filling type MBR unit simultaneously, and removes remaining organic matter, contains unreacted nitre state
The sludge reflux of nitrogen to anoxic unit carries out denitrification, the discharge of material filling type MBR unit standard water discharge.
Illustrate concrete methods of realizing of the invention further below:
The present invention is mainly suitable for high organic nitrogen waste water, the water quality characteristics of waste water are as follows: total nitrogen 300-600mg/L, wherein having
Machine nitrogen proportion should be greater than 80%, COD 6000-12000mg/L, pH 6-9.
On the basis of above scheme, oxidation processes described in step 1 are ozone oxidation or O3 catalytic oxidation, Gao Youji
Nitrogen waste water first passes through ozone oxidation or O3 catalytic oxidation processing, and part organic nitrogen is converted to ammonia nitrogen or nitrate nitrogen, or into one
Step is oxidized to N2, while it is organic the organic matter open loop chain rupture of part cyclic or long-chain can be converted to the easy biochemical degradation of small molecule
Object.
On the basis of above scheme, it is 20-40mg/L, residence time that the ozone of the ozone oxidation unit, which adds concentration,
For 20-40min.
On the basis of above scheme, total nitrogen after ozone oxidation unit oxidation processes in high organic nitrogen waste water is from 300-
600mg/L is reduced to 100-300mg/L, and wherein organic nitrogen proportion is declined, and ratio is less than 70%；COD is from 6000-
12000mg/L is reduced to 3000-7000mg/L.
Ozone oxidation unit is discharged after ozone destruction unit, and ozone, ozone layer destroying list have been substantially not present in water
Member water outlet enters anoxic unit.Anoxic unit is substantially carried out the further open loop chain rupture and removal of organic matter, while carrying out organic
Nitrate nitrogen in waste water is converted to nitrogen from waste water and removed by the ammoniation of nitrogen and the denitrification of nitrate nitrogen.
On the basis of above scheme, ozone destruction unit described in step 3 is discharged the residence time in anoxic unit
Generally 6-12h, dissolved oxygen are controlled in 0.2mg/L or less.
Anoxic unit water outlet is directly entered material filling type MBR unit, goes residual organic substances in water removal, least a portion of organic herein
Nitrogen continues ammonification, and most mineralized nitrogens are at nitrate nitrogen.
On the basis of above scheme, the residence time of material filling type MBR unit described in step 4 is 24-36h, described to fill out
MBR membrane cisterna in material formula MBR unit includes membrane module area and packing area, and the filler in the packing area uses composite filling, Gu
The volume at the vacant place except membrane module in MBR membrane cisterna, the filler should subtract shared by membrane module not less than MBR membrane cisterna appearance
70% of volume after volume.
On the basis of above scheme, membrane module area is different with the aeration intensity of packing area, and the membrane module area aeration is strong
Degree is 12-15:1 with processing water, and the control of the aeration intensity of packing area is in 5-8:1.
On the basis of above scheme, the reflux ratio of sludge reflux described in the step 4 is 200-300%.
On the basis of above scheme, the material filling type MBR unit is discharged COD < 60mg/L, and total nitrogen is less than 30mg/L, ammonia
Nitrogen is less than 1mg/L.
The present invention has the following advantages and beneficial effects:
The present invention is handled by the first step that high organic nitrogen waste water is completed in ozone oxidation or O3 catalytic oxidation, can both be incited somebody to action
Partial organic substances open loop chain rupture, the organic matter of removal 50% or so, and nitrogen can be released during open loop chain rupture, it will
50% or so organic nitrogen is converted into ammonia nitrogen and nitrate nitrogen or even direct oxidation as nitrogen removal.
The present invention completes the further removal of organic matter and nitrogen by anoxic unit.Ozone oxidation unit water outlet is by smelly
Oxygen destroys after unit, enters back into anoxic unit.Anoxic unit can even remove remaining a part of organic matter open loop chain rupture,
Can also be by the further ammonification of the organic nitrogen of the remainder in waste water, while anti-nitre will be carried out by the nitrate nitrogen of sludge reflux
Nitrogen in waste water is thoroughly converted to nitrogen removal by change effect.
It is further using material filling type MBR technique after the open loop chain rupture of organic matter and the ammonification of organic nitrogen are basically completed
The organic matter in water removal is removed, and is nitrate nitrogen by mineralized nitrogen.Since pond is provided with filler, there are hypoxia responses inside filler
Area, therefore nitrification and part denitrification has occurred simultaneously in this element, be conducive to further decreasing for organic matter and total nitrogen.
Organic removal rate can reach 95% or more, and nitrogen removal rate can reach 80% or more.
The present invention is the treatment process of high organic nitrogen waste water, and process is simple, effective, and it is useless targetedly to remove high organic nitrogen
Organic matter, total nitrogen in water realize the stably reaching standard discharge of sewage.
Detailed description of the invention
The present invention has following attached drawing:
Fig. 1 is the treatment process schematic diagram of the high organic nitrogen waste water of the present invention.
Specific embodiment
A specific embodiment of the invention is further described in cooperation attached drawing 1 below, embodiments of the present invention packet
It includes but is not limited to the following example.
High organic nitrogen waste water compared with high ammonia nitrogen, high-nitrate state nitrogen waste water for, wherein more process of a step organic nitrogen ammonification,
Therefore ammonification, nitrification, the efficiency of anti-nitration reaction are improved, realizes the removal of nitrogen in process short as far as possible.Ozone oxidation unit
It is detached from part organic nitrogen from organic matter partial organic substances open loop chain rupture as the pretreatment unit of high organic nitrogen waste water,
It is converted to ammonia nitrogen or nitrate nitrogen or even nitrogen.Anoxic unit is entered back by pretreated waste water, anoxic unit continues to give up
Ammonification is not carried out by the organic nitrogen of ammonification in water, and further open loop chain rupture even degradation of organic substances, in addition to this, anoxic unit
It is more important one effect, exactly make the aerobic reflux from material filling type MBR unit waste water occur denitrification, nitrate nitrogen is final
Nitrogen is converted into remove from waste water.Still organic matter and inorganic nitrogen containing higher concentration in anoxic unit water outlet also include one
Partial organic nitrogen, into material filling type MBR processing unit, waste water is completely degraded in this element, organic matter, a large amount of ammonia
Nitrogen is nitrified into nitrate nitrogen and nitrite nitrogen, and a part of organic nitrogen can still carry out ammonification herein.Due to being loaded in MBR membrane cisterna
Composite filling, in addition to the nitration reaction that organic matter degradation and ammonia nitrogen occurs outside carrier biofilm, in the carrier biofilm
Due to the presence of anoxic sublimity denitrification can also occur for portion, realize the removal of nitrogen.In this way, in each processing unit, it can
The removal for enough realizing organic matter and nitrogen, ensure that effluent quality.
A kind of processing method of high organic nitrogen waste water, comprising the following steps:
1. waste water, which enters ozone oxidation unit, carries out oxidation processes, ammonia nitrogen, nitrate nitrogen are converted by the organic nitrogen in waste water
Or nitrogen, and cyclic annular and long-chain organic matter open loop chain rupture is converted to the easy biochemical degradation organic matter of small molecule, form ozone oxidation
Unit water outlet；
2. ozone oxidation unit, which is discharged, enters ozone destruction unit, remaining ozone in the water outlet of ozone decomposition oxidation unit,
Form ozone destruction unit water outlet；
3. ozone destruction unit water outlet enters anoxic unit, it is anti-to carry out ammonification to the organic nitrogen in ozone destruction unit water outlet
It answers, while denitrification is carried out to nitrate nitrogen, and further make the organic matter open loop chain rupture in ozone destruction unit water outlet, shape
It is discharged at anoxic unit；
4. anoxic unit water outlet enters material filling type MBR unit, aminating reaction is carried out to the organic nitrogen in anoxic unit water outlet,
Nitrification and denitrification occurs in material filling type MBR unit simultaneously, and removes remaining organic matter, contains unreacted nitre state
The sludge reflux of nitrogen to anoxic unit carries out denitrification, the discharge of material filling type MBR unit standard water discharge.
The present invention is mainly suitable for high organic nitrogen waste water, the water quality characteristics of waste water are as follows: total nitrogen 300-600mg/L, wherein having
Machine nitrogen proportion should be greater than 80%, COD 6000-12000mg/L, pH 6-9.
On the basis of above scheme, oxidation processes described in step 1 are ozone oxidation or O3 catalytic oxidation, Gao Youji
Nitrogen waste water first passes through ozone oxidation or O3 catalytic oxidation processing, and part organic nitrogen is converted to ammonia nitrogen or nitrate nitrogen, or into one
Step is oxidized to N2, while it is organic the organic matter open loop chain rupture of part cyclic or long-chain can be converted to the easy biochemical degradation of small molecule
Object.
On the basis of above scheme, it is 20-40mg/L, residence time that the ozone of the ozone oxidation unit, which adds concentration,
For 20-40min.
On the basis of above scheme, total nitrogen after ozone oxidation unit oxidation processes in high organic nitrogen waste water is from 300-
600mg/L is reduced to 100-300mg/L, and wherein organic nitrogen proportion is declined, and ratio is less than 70%；COD is from 6000-
12000mg/L is reduced to 3000-7000mg/L.
Ozone oxidation unit is discharged after ozone destruction unit, and ozone, ozone layer destroying list have been substantially not present in water
Member water outlet enters anoxic unit.Anoxic unit is substantially carried out the further open loop chain rupture and removal of organic matter, while carrying out organic
Nitrate nitrogen in waste water is converted to nitrogen from waste water and removed by the ammoniation of nitrogen and the denitrification of nitrate nitrogen.
On the basis of above scheme, ozone destruction unit described in step 3 is discharged the residence time in anoxic unit
Generally 6-12h, dissolved oxygen are controlled in 0.2mg/L or less.
Anoxic unit water outlet is directly entered material filling type MBR unit, goes residual organic substances in water removal, least a portion of organic herein
Nitrogen continues ammonification, and most mineralized nitrogens are at nitrate nitrogen.
On the basis of above scheme, the residence time of material filling type MBR unit described in step 4 is 24-36h, described to fill out
MBR membrane cisterna in material formula MBR unit includes membrane module area and packing area, and the filler in the packing area uses composite filling, Gu
The volume at the vacant place except membrane module in MBR membrane cisterna, the filler should subtract shared by membrane module not less than MBR membrane cisterna appearance
70% of volume after volume.
On the basis of above scheme, membrane module area is different with the aeration intensity of packing area, and the membrane module area aeration is strong
Degree is 12-15:1 with processing water, and the control of the aeration intensity of packing area is in 5-8:1.
On the basis of above scheme, the reflux ratio of sludge reflux described in the step 4 is 200-300%.
On the basis of above scheme, the material filling type MBR unit is discharged COD < 60mg/L, and total nitrogen is less than 30mg/L, ammonia
Nitrogen is less than 1mg/L.
Embodiment 1
Certain gas field amine purification waste water, water quality situation are as follows: pH 8.9, COD 12000mg/L, total nitrogen 600mg/L have
Machine nitrogen is 560mg/L.Waste water initially enters O3 catalytic oxidation unit and is pre-processed, ozone dosage 40mg/L, reaction
Time is 40min, and the COD content in processed waste water is down to 5700mg/L from 12000mg/L, and total nitrogen is down to from 600mg/L
280mg/L, wherein organic nitrogen is 100mg/L.Water outlet enters ozone layer destroying pond, and then into anoxic pond, the anoxic residence time is
12h, dissolved oxygen control are 0.1mg/L.Anoxic water outlet enters material filling type MBR, residence time 36h, reflux ratio 300%.Out
Water COD is 59mg/L, and water outlet total nitrogen is 25mg/L, ammonia nitrogen 0.8mg/L, meets the requirement of local sewage drainage standard.
Embodiment 2
Certain petrochemical industry organic nitrogen waste water, water quality situation are as follows: pH 6.3, COD 6000mg/L, total nitrogen 300mg/L, it is organic
Nitrogen is 260mg/L.Waste water initially enters O3 catalytic oxidation unit and is pre-processed, ozone dosage 20mg/L, when reaction
Between be 20min, the COD content in processed waste water is down to 3300mg/L from 6000mg/L, and total nitrogen is down to 160mg/ from 300mg/L
L, wherein organic nitrogen is 60mg/L.Water outlet enters ozone layer destroying pond, then enters anoxic pond, and the anoxic residence time is 6h, dissolution
Oxygen control is 0.2mg/L.Anoxic water outlet enters material filling type MBR, and the residence time is reflux ratio 200% for 24 hours.Being discharged COD is
50mg/L, water outlet total nitrogen are 20mg/L, ammonia nitrogen 0.5mg/L, meet the requirement of local sewage drainage standard.
Embodiment 3
Certain petrochemical industry organic nitrogen waste water, water quality situation are as follows: pH 7.5, COD 9000mg/L, total nitrogen 450mg/L, it is organic
Nitrogen is 460mg/L.Waste water initially enters ozone oxidation unit and is pre-processed, ozone dosage 30mg/L, and the reaction time is
30min, the COD content in processed waste water are down to 3500mg/L from 9000mg/L, and total nitrogen is down to 100mg/L from 450mg/L,
Middle organic nitrogen is 50mg/L.Water outlet enters ozone layer destroying pond, then enters anoxic pond, and the anoxic residence time is 10h, dissolved oxygen control
It is made as 0.1mg/L.Anoxic water outlet enters material filling type MBR, residence time 30h, reflux ratio 250%.Water outlet COD is 55mg/
L, water outlet total nitrogen are 25mg/L, ammonia nitrogen 0.3mg/L, meet the requirement of local sewage drainage standard.
The content being not described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (10)
1. a kind of processing method of high organic nitrogen waste water, it is characterised in that: the following steps are included:
(1) waste water enters ozone oxidation unit progress oxidation processes, converts ammonia nitrogen, nitrate nitrogen or nitrogen for the organic nitrogen in waste water
Gas, and cyclic annular and long-chain organic matter open loop chain rupture is converted to the easy biochemical degradation organic matter of small molecule, form ozone oxidation unit
Water outlet；
(2) ozone oxidation unit water outlet enters ozone destruction unit, and remaining ozone in the water outlet of ozone decomposition oxidation unit is formed
Ozone destruction unit water outlet；
(3) ozone destruction unit water outlet enters anoxic unit, carries out aminating reaction to the organic nitrogen in ozone destruction unit water outlet,
Denitrification is carried out to nitrate nitrogen simultaneously, and further makes the organic matter open loop chain rupture in ozone destruction unit water outlet, is formed
Anoxic unit water outlet；
(4) anoxic unit water outlet enters material filling type MBR unit, carries out aminating reaction to the organic nitrogen in anoxic unit water outlet, together
When in material filling type MBR unit nitrification and denitrification occurs, and remove remaining organic matter, contain unreacted nitrate nitrogen
Sludge reflux to anoxic unit carry out denitrification, material filling type MBR unit standard water discharge discharge.
2. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: the water quality characteristic of the waste water
Are as follows: total nitrogen 300-600mg/L, wherein organic nitrogen proportion is greater than 80%, COD 6000-12000mg/L, pH 6-9.
3. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: oxidation processes described in step 1
For ozone oxidation or O3 catalytic oxidation.
4. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: the ozone oxidation unit it is smelly
It is 20-40mg/L, residence time 20-40min that oxygen, which adds concentration,.
5. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: ozone oxidation unit oxidation processes
The total nitrogen in high organic nitrogen waste water is reduced to 100-300mg/L from 300-600mg/L afterwards, and wherein organic nitrogen proportion is less than
70%；COD is reduced to 3000-7000mg/L from 6000-12000mg/L.
6. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: ozone layer destroying described in step 3
Residence time of the unit water outlet in anoxic unit is 6-12h, and dissolved oxygen is controlled in 0.2mg/L or less.
7. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: material filling type MBR described in step 4
The residence time of unit is 24-36h, and the MBR membrane cisterna in the material filling type MBR unit includes membrane module area and packing area, described
After filler in packing area uses composite filling, the volume of the filler to subtract volume shared by membrane module not less than MBR membrane cisterna appearance
Volume 70%.
8. the processing method of high organic nitrogen waste water as claimed in claim 7, it is characterised in that: membrane module area aeration intensity
It is 12-15:1 with processing water, the aeration intensity of packing area is controlled in 5-8:1.
9. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: sludge described in the step 4
The reflux ratio of reflux is 200-300%.
10. the processing method of high organic nitrogen waste water as described in claim 1, it is characterised in that: the material filling type MBR unit goes out
Water COD < 60mg/L, total nitrogen are less than 30mg/L, and ammonia nitrogen is less than 1mg/L.
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| CN110467317A (en) * | 2019-08-26 | 2019-11-19 | 广西农垦永新畜牧集团金光有限公司 | A kind of livestock breeding wastewater innocuity disposal system and method |
| CN112850895A (en) * | 2021-01-29 | 2021-05-28 | 安道麦安邦(江苏)有限公司 | Method and device for treating pymetrozine organic nitrogen wastewater |
| CN117602762A (en) * | 2023-12-13 | 2024-02-27 | 江苏南大华兴环保科技股份公司 | Advanced treatment system and method for industrial wastewater |
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