CN108395051A - Stable and efficient coking wastewater short-cut nitrification method - Google Patents
Stable and efficient coking wastewater short-cut nitrification method Download PDFInfo
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- CN108395051A CN108395051A CN201710068953.5A CN201710068953A CN108395051A CN 108395051 A CN108395051 A CN 108395051A CN 201710068953 A CN201710068953 A CN 201710068953A CN 108395051 A CN108395051 A CN 108395051A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 238000004939 coking Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010802 sludge Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 10
- 238000006396 nitration reaction Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 5
- 230000001546 nitrifying effect Effects 0.000 claims description 5
- 238000010899 nucleation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002918 waste heat Substances 0.000 abstract 2
- 238000004821 distillation Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 208000028659 discharge Diseases 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000009825 accumulation Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention discloses a stable and efficient coking wastewater shortcut nitrification method, which reasonably utilizes waste heat resources of chemical ammonia distillation wastewater to maintain temperature conditions required by a reaction system, realizes effective recycling of the waste heat resources of a steel mill, saves the thermal energy consumption for heating for maintaining the temperature required by the shortcut nitrification reaction under the conventional conditions, finally realizes stable and efficient shortcut nitrification in MBR, not only greatly reduces the operation cost of wastewater treatment, but also lays a foundation for the subsequent denitrification and the final standard discharge of coking wastewater.
Description
Technical field
The invention belongs to industrial waste water treatment more particularly to a kind of coking wastewater short distance nitrations of stability and high efficiency
Method.
Background technology
Coking wastewater is the waste water that High T-emperature Carbonization is formed in the process and in gas purification, chemical products subtractive process,
Complicated component, pollutant concentration is high, coloration is high, toxicity is big, and property is highly stable, and biodegradability is poor, is discharged ammonia nitrogen and COD occupies height
Under not, recently as the increasingly stringent of environmental protection standard, the total nitrogen of sewage discharge is also limited, coking wastewater is reached
More stringent requirements are proposed for mark discharge.
In recent years, by constantly studying and putting into practice, domestic and foreign scholars have found many technologies for administering coking wastewater, main
There are biological treatment, method of chemical treatment, physicochemical treatment method and achieves certain treatment effect.The current coking in China is useless
Water treatment technology is applied to mainly have anaerobic-aerobic process (A/O), the aerobic (A/O of anaerobic-aerobic-in engineering2), anaerobism-lack
Oxygen-aerobic method (A2/ O), the anaerobism-level-one aerobic-anaerobic-aerobic (A of two level2/O2) etc., coking wastewater index is substantially steady after processing
It is scheduled on the secondary discharge standard of GB8978-1996, especially COD and NH3The two indexs of-N are difficult to reach emission request simultaneously.
Traditional bio-denitrification technology think the ammoniacal nitrogen in water to be completely removed just have to by completely nitrify with
Denitrification process, the i.e. terminal using nitrate as nitrification and denitrifying starting point.Many scholars are anti-to short distance nitration in recent years
Nitrification denitrogenation technology has carried out numerous studies, and short-cut nitrification and denitrification technology in the nitrification stage due to reducing NO2 --NO3 -It is anti-
Answer process, the dosage of organic carbon source that can generally reduce 40%, oxygen demand can at least reduce by 25%, not only shorten the reaction time,
Reduce reactor volume, reduce investment and operating cost, and reduce energy consumption, improves nitric efficiency and traditional
Sewage water denitrification technology is compared, and is had wide development space, has been caused the extensive concern of domestic and international researcher.
It is new by looking into, some relevant patents and article are retrieved, such as " energy-saving process for treating high ammonia nitrogen waste water "
(CN101195513), this method first makes waste water convert triumphant formula nitrogen to ammonia nitrogen by pretreatment, subsequently into short distance nitration pond
In, Ammonia Nitrification was controlled in the nitrite nitrogen stage, then micro-electrolysis reactor is utilized to substitute anaerobic denitrifying or ammoxidation
Technique carries out denitrogenation processing, then makees subsequent processing with bioanalysis or Fenton oxidation method, materialization oxidizing process, and nitrogen removal rate reaches
60%-75%.This method is mainly used for high NH_3-N treating, still undesirable to hardly degraded organic substance processing." the processing of coking wastewater
Coking wastewater is passed through oil separator, regulating reservoir, iron carbon-Fenton oxidation pond, up-flow by method " (CN 101781067A), this patent
Formula anaerobic mud bed reactor, hydrolysis multi-function pool, anoxic pond, complex enzyme/activated sludge pond and secondary settling tank, then discharge water outlet.This
Processing structures needed for kind method are more, and complex process takes up a large area, and operating cost is also higher.A kind of " Treatment of Coking Effluent
Process " (CN200810234318.0), this method are made of physicochemical treatment unit and biochemical treatment unit, wherein at materialization
Reason unit is made of micro-electrolysis reactor, sedimentation basin, and micro-electrolysis reactor is to fill out with waste iron filing, copper scrap bits and lightweight bulk material
Material.Biochemical treatment unit is made of inside circulation triphase fluidized bed reactor, is realized using immobilized active sludge bead while de-
Nitrogen removes carbon.Although water outlet volatile phenol, ammonia nitrogen, coloration can reach integrated wastewater discharge standard primary standard, COD treatment effects
It is unsatisfactory, it is only capable of reaching integrated wastewater discharge standard secondary standard." one kind obtaining stable nitrite by sewage denitrification
The method of accumulation " (CN101602545A), this method are adjusted the carbon-nitrogen ratio of sewage with methanol or other additional carbons, utilize pH value
Variation characteristic instruction activated sludge process denitrification process, the nitrate in sewage is changed into nitrite by final realize,
To obtain stable nitrite accumulation.But this method needs additional carbon, increases the processing cost of sewage, and obtain
Nitrite accumulation amount is 25% or so of the initial nitrate total amount of reaction, and accumulation is not very high.
In conclusion coking wastewater realizes final qualified discharge, the Nitrogen removal effect for obtaining stability and high efficiency early period is extremely closed
It is important, it is therefore necessary to develop a kind of high treating effect, technological process is simple, and equipment operation and investment cost all compare conjunction
It is important will finally to realize coking wastewater the sustainable development of qualified discharge and coal chemical enterprise has for the bio-denitrification technology of reason
Realistic meaning.
Invention content
In view of the foregoing drawbacks, the technical problems to be solved by the invention provide a kind of coking wastewater short distance nitre of stability and high efficiency
Change method, by the short distance for reasonably making biochemical section acquisition stability and high efficiency using the useless residual heat resources of steel mill and control reaction condition
Nitrification effect reduces cost for wastewater treatment, and base is established for the denitrification denitrogenation and final qualified discharge of follow-up coking wastewater
Plinth..
To achieve the goals above, the technical solution adopted by the present invention is such：
A kind of coking wastewater short-range nitration method of stability and high efficiency, it is characterised in that：The water of coking wastewater to be dealt with
Matter is COD：2500-3500mg/L, NH4 +-N：100-300mg/L, pH：7-8, the coking wastewater through gravity oil-removing is in heat exchanger
Heat exchange, 15-25 DEG C of coking wastewater temperature, 90-95 DEG C of distilled ammonia wastewater, the coking wastewater inflow after heating are carried out with distilled ammonia wastewater
In aerobic membrane bioreactor, 35-45 DEG C of control coking wastewater temperature, the distilled ammonia wastewater of cooling comes back to coking wastewater system
In；The seed sludge of MBR is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 4000-5000mg/L of sludge seeding is opened
Dynamic stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist；Then control reactor
In dissolved oxygen concentration be 0.5-0.9mg/L, pH 8-9, the hydraulic detention time of reactor is 18-22h, NH of intaking4 +- N's
Volumetric loading is 0.24-0.32gNH4 +-N/(L·d)；With the increase of running time, the NO in water outlet3 -- N concentration gradually subtracts
It is few, NO2 -The concentration of-N gradually increases, and runs 8-12 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio can reach
90% or more, the short distance nitration effect of stability and high efficiency is obtained, base has been established for subsequent denitrification denitrogenation and Anammox
Plinth.
The beneficial effects of the invention are as follows：Rationally maintained needed for reaction system using the residual heat resources of chemical industry distilled ammonia wastewater
Temperature condition realizes steel mill's residual heat resources effective recycling, saves under normal condition as needed for maintenance short distance nitration reaction
Temperature and the thermal energy consumption heated, the short distance nitration of stability and high efficiency is finally realized in MBR, is not only greatly reduced at waste water
The operating cost of reason, and lay a good foundation for subsequent denitrification denitrogenation and the final qualified discharge of coking wastewater.
Description of the drawings
Fig. 1 is present invention process flow chart.
Specific implementation mode
With reference to embodiment, the present invention is described in detail.
Embodiment 1：
Coking wastewater (temperature is 15 DEG C) through gravity oil-removing carries out in heat exchanger with distilled ammonia wastewater (temperature is 90 DEG C)
Heat exchange, it is 35 DEG C to control the coking wastewater temperature after heat exchange, and the coking wastewater after heating flows into aerobic membrane bioreactor
In, the seed sludge of reactor is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 4000mg/L of sludge seeding starts
Stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist.Then in control reactor
Dissolved oxygen concentration be 0.5mg/L, pH 8, control reactor hydraulic detention time be 18h, intake NH4 +The volumetric loading of-N
For 0.24gNH4 +-N/(L·d).With the increase of running time, the NO in water outlet3 -- N concentration gradually decreases, NO2 -The concentration of-N
It gradually increases, runs 8 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio reaches 91%, obtains stability and high efficiency
NO2 -The accumulation of-N creates good flow condition for subsequent denitrification denitrogenation and being smoothed out for Anammox reaction.
Embodiment 2：
Coking wastewater (temperature is 20 DEG C) through gravity oil-removing carries out in heat exchanger with distilled ammonia wastewater (temperature is 93 DEG C)
Heat exchange, it is 40 DEG C to control the coking wastewater temperature after heat exchange, and the coking wastewater after heating flows into aerobic membrane bioreactor
In, the seed sludge of reactor is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 4500mg/L of sludge seeding starts
Stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist.Then in control reactor
Dissolved oxygen concentration be 0.7mg/L, pH 8.5, control reactor hydraulic detention time be 20h, intake NH4 +The volume of-N is negative
Lotus is 0.28gNH4 +-N/(L·d).With the increase of running time, the NO in water outlet3 -- N concentration gradually decreases, NO2 -- N's is dense
Degree gradually increases, and runs 10 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio reaches 93%, obtains stability and high efficiency
NO2 -The accumulation of-N creates good into water bar for being smoothed out of reacting of subsequent denitrification denitrogenation and Anammox
Part.
Embodiment 3：
Coking wastewater (temperature is 25 DEG C) through gravity oil-removing carries out in heat exchanger with distilled ammonia wastewater (temperature is 95 DEG C)
Heat exchange, it is 45 DEG C to control the coking wastewater temperature after heat exchange, and the coking wastewater after heating flows into aerobic membrane bioreactor
In, the seed sludge of reactor is derived from the nitrifying sludge of chemical plant aerobic tank, and initial a concentration of 5000mg/L of sludge seeding starts
Stage reactors show preferable NH4 +- N removal effects are discharged mainly with NO3 -- N forms exist.Then in control reactor
Dissolved oxygen concentration be 0.9mg/L, pH 9.0, control reactor hydraulic detention time be 22h, intake NH4 +The volume of-N is negative
Lotus is 0.32gNH4 +-N/(L·d).With the increase of running time, the NO in water outlet3 -- N concentration gradually decreases, NO2 -- N's is dense
Degree gradually increases, and runs 12 days, the NO of membrane bioreactor water outlet2 --N/NOxN ratio reaches 94%, obtains stability and high efficiency
NO2 -The accumulation of-N creates good into water bar for being smoothed out of reacting of subsequent denitrification denitrogenation and Anammox
Part.
Claims (1)
1. a kind of coking wastewater short-range nitration method of stability and high efficiency, it is characterised in that：The water quality of coking wastewater to be dealt with
For COD：2500-3500mg/L, NH4 +-N：100-300mg/L, pH：7-8, the coking wastewater through gravity oil-removing in heat exchanger with
Distilled ammonia wastewater progress heat exchange, 15-25 DEG C of coking wastewater temperature, 90-95 DEG C of distilled ammonia wastewater, the coking wastewater after heating flow into
In aerobic membrane bioreactor, 35-45 DEG C of control coking wastewater temperature, the distilled ammonia wastewater of cooling comes back to coking wastewater system
In；The seed sludge of MBR is derived from the nitrifying sludge of chemical plant aerobic tank, initial a concentration of 4000-5000mg/L of sludge seeding；With
It is 0.5-0.9mg/L to control the dissolved oxygen concentration in reactor afterwards, and the hydraulic detention time of pH 8-9, reactor are 18-22h,
Water inlet NH4 +The volumetric loading of-N is 0.24-0.32gNH4 +-N/(L·d)；Operation 8-12 days, membrane bioreactor water outlet
NO2 --N/NOxN ratio reaches 90% or more.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710068953.5A CN108395051A (en) | 2017-02-08 | 2017-02-08 | Stable and efficient coking wastewater short-cut nitrification method |
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| Publication Number | Publication Date |
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Family
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| CN201710068953.5A Pending CN108395051A (en) | 2017-02-08 | 2017-02-08 | Stable and efficient coking wastewater short-cut nitrification method |
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| CN1562799A (en) * | 2004-04-02 | 2005-01-12 | 浙江大学 | Method for fast starting up procedure for nitrifying wastewater of containing ammonia in short range |
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