CN104649510B - Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone - Google Patents
Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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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- 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
- C02F2101/32—Hydrocarbons, e.g. oil
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- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
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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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- 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
- C02F3/30—Aerobic and anaerobic processes
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Abstract
The invention provides a method for treating sewage generated from a process for producing caprolactam by utilizing cyclohexanone, wherein classification pre-treatment is performed aiming at the quality characteristics of the technical sewage of each production unit, and biochemical treatment and advanced treatment are performed uniformly. According to the method, the reasonable and effective classification pre-treatment is performed on the technical sewage of each production unit of a caprolactam device, so that the treatment effect of caprolactam production sewage is improved, and the stability and the discharge index of a subsequent biochemical treatment system are improved; and the investment and the operation cost of a sewage treatment device are largely reduced, the environment pollution is reduced, the operation is simple and feasible, and excellent economic benefit and environmental benefit are provided.
Description
Technical field
The present invention relates to sewage treatment technology field, it is dirty that more particularly, to a kind of Ketohexamethylene method produces caprolactam technique
The processing method of water.
Background technology
Caprolactam (CPL) is the important monomer producing nylon -6 fiber (chinlon) and nylon-6 engineering plastics, extensively should
For fields such as nylon fibre, engineering plastics, plastic sheetings.Most caprolactam production commercial plants are all with ring at present
Hexanone is raw material, main inclusion four big process units：1) hydrogen peroxide plant：This device is with alkyl-anthraquinone and organic solvent for work
Solution, is utilized respectively hydrogen and oxygen is hydrogenated and oxidation reaction, produces hydrogen peroxide；2) pimelinketone device：This device is with benzene
For raw material, selection is carried out to benzene and is hydrogenated to cyclohexene, produce Hexalin through hydration, rectification, then produced with cyclohexanol dehydrogenation
Ketohexamethylene；3) amidoxime gasifying device：With ammonia, hydrogen peroxide, Ketohexamethylene as raw material, reaction in the presence of catalyst produces ring to this device
Hexanone oxime；4) liquid phase rearrangement device：This device with cyclohexanone-oxime as raw material, in the presence of catalyst sulfuric acid, send out by cyclohexanone-oxime
Raw liquid phase rearrangement reaction produces caprolactam.Although this technique productions caprolactam can effectively reduce plant energy consumption and material consumption,
But also bring the reluctant problem of process spent water simultaneously.Major pollutants in Ketohexamethylene method caprolactam technology sewage are
Ketohexamethylene, hexamethylene, Hexalin, benzene, cyclohexanone-oxime, organic acid, caprolactam, ammonia nitrogen etc., have that rate of water added is big, COD is high, B/C
Than low, composition complicated, biochemical treatment hardly possible the problems such as, thus become in petroleum chemical industry reluctant production waste it
One.
In actual production, each workshop section's process spent water mixing unification is generally processed by caprolactam production apparatus,
Often due to hybrid technique sewage biodegradability difference and organic pollution concentration high the problems such as opposite processing system cause huge
Big impact, leads to wastewater treatment efficiency undesirable and high cost.In recent years, produce caprolactam work with to Ketohexamethylene method
The developmental research of skill sewage water treatment method and practical experience accumulation, find in process spent water produced by cyclohexanone oxamidinating unit
Containing ketone Organic substance, sewage B/C is extremely low, and its direct discharge can cause the microorganism mortality in biochemical treatment system, right
The generation destructive effects of biochemical treatment system and impact.Therefore, part caprolactam production apparatus progressively begin with oneself
Amide process spent water hierarchical processing method, is carried out pre- using technology such as advanced oxidations to cyclohexanone oxamidinating cell process waste water
Process, then carry out the method for biochemical treatment with after the mixing of full factory process spent water again.But this method does not have to each production
The process spent water of unit is fully and completely classified classification, the such as part of contaminated water of liquid phase rearrangement production unit, although the water yield
Less, but organic pollutant excessive concentration, COD is up to more than 100000mg/L, if direct discharge still can be to biochemical system
Cause huge impact.
CN 101734825 A discloses a kind of processing method of wastewater generated by cyclohexanone ammoximation process, makes technique first
Sewage carries out advanced oxidation reaction, is then processed using sequencing batch activated sludge processing system (SBR).Cyclohexanone oxamidinating
After advanced oxidation pretreatment, the Organic substance having impact to biochemical system in sewage is oxidized to microorganism cell process sewage
Harmless Organic substance, the biodegradability improving sewage reduces the content of organics in sewage so as to can be with other sewage simultaneously
Enter biochemical system after mixing to be processed.But, because other production unit part of contaminated water COD are too high, pretreated ammonia
After oximate unit sewage and other sewage mixing of full factory, still there is very high ammonia nitrogen and organic concentration.Due to follow-up SBR method
The restriction of process characteristic (sludge concentration is relatively low, the time of staying is short, mass-transfer efficiency is low) is it is impossible to fully meet caprolactam technology dirt
The processing requirement of water, thus it is clearly present the problems such as cost of sewage disposal is too high, investment is excessive and treatment effect is undesirable.
CN 102452762 A is using oxidation and pretreatment-ferrum copper pre-micro-electrolysis disposal-membrane bioreactor (MBR) combination
Technique is processed to caprolactam technology sewage.Oximes process spent water part COD of preprocessed removal and biology poison first
Property material, then carries out MBR biochemical treatment being mixed into remaining caprolactam production sewage.Process with used by CN 101734825 A
Method is compared, although this method effectively increases the treatment effect of wastewater of caprolactam production, the method requires to enter MBR system
Below the hybrid technique COD of sewage 3000mg/L of system is that is to say, that the too high technique of moiety concentrations that produces of liquid phase rearrangement unit
Sewage can cause the impact of MBR system after being directly entered this system, still cannot fully meet the place of caprolactam technology sewage
Reason require, still do not solve existing caprolactam sewage water treatment method complex operation, influent quality has high demands, poor for applicability,
The difficult problem such as cost of sewage disposal is too high, investment is excessive and treatment effect is undesirable.
Content of the invention
The problem to be solved in the present invention is to provide a kind of processing method of Cyclohexanone Production caprolactam technology sewage, solves
Investment present in existing preparing process of caprolactam sewage water treatment method and high cost, treatment effect are undesirable etc. asks
Topic.
For solving above-mentioned technical problem, the technical solution used in the present invention is：A kind of Ketohexamethylene method produces caprolactam work
The processing method of skill sewage, comprises the steps：
1), it is classified pretreatment, oximes cell process sewage carries out pretreatment using advanced oxidation processes；By liquid phase
Rearrangement units process spent water, carries out pretreatment using evaporation and concentration and dope burning process, and main purpose is that will have containing higher
It is concentrated solution and condensed fluid that the sewage of organic pollutants concentration carries out concentrating and separating, and in concentrated solution, organic pollution is dense, needs
Carry out dope burning, and the organic pollution concentration in condensed fluid is relatively low, can directly carry out subsequent biochemical process；By other units
Sewage carry out pretreatment, main mesh with one of grid, ammonia aeration, neutralization, coagulating sedimentation, air supporting or two or more method
Be to remove part bulky grain sewage, suspension and colloid or soluble organic pollution；
2), biochemical treatment, by step 1) carry out biochemical treatment, described biochemical treatment through the sewage of each unit of pretreatment
For in anaerobic biological technique, aerobic biochemical technique, anaerobic-aerobic group technology or anaerobic-aerobic integrated metaplasia metallization processes
Kind it is preferred that by step 1) import comprehensive adjustment pond and carry out homogenizing and all measure through each unit process spent water of pretreatment, wherein warp
The sewage body of pretreated liquid phase rearrangement cell process sewage evaporation lime set, oximes cell process sewage and other units
Long-pending flow-rate ratio is 1:3～10:2～12, and CODcr be respectively 500～4500mg/L, 1000～6000mg/L, 500～
6000mg/L, then the sewage in comprehensive adjustment pond is sent into biochemistry pool.
Preferably, sewage is through step 2) in biochemical treatment after, carry out advanced treatment process, described advanced treatment process
It is to process advanced oxidation to be coupled with biochemical treatment.
Preferably, described advanced treatment process refers to that the water outlet to biochemical treatment carries out advanced oxidation and processes Posterior circle backflow
To the water inlet end of biochemical treatment, outer row's part of contaminated water guarantee sewage disposal system turnover water balance simultaneously.
Preferably, the backflow water yield through advanced oxidation process and the ratio of outer displacement are 2～6, preferably 3～5.
Preferably, step 1) in, described advanced oxidation processes the Fenton oxidation method that refers to, Ozonation, wet type sky
One of gas oxidizing process, supercritical water oxidation method.
Preferably, step 1) in, during described advanced oxidation is processed, add catalyst and oxidant in sewage, wherein urge
Agent is Fe2+、Cu2+、Ni2+、Co2+、Zn2+One of or two or more, described oxidant is that hydrogen peroxide, ozone, oxygen are (empty
Gas), persulfate, one of potassium permanganate or sodium hypochlorite or two kinds of combinations.
Preferably, step 1) in, evaporation and concentration and dope burning process refer to liquid phase rearrangement cell process sewage collecting
Afterwards, it is evaporated concentrating, steam condensate enters biochemistry pool, and dope is sent into incinerator and burned；Described evaporation and concentration work
Skill adopts an effect or multiple-effect evaporation technique.
Preferably, step 1) in, during described advanced oxidation is processed, hydrogen hydrogen peroxide technique sewage is used as oxidant.
Preferably, step 1) in, described advanced oxidation processes and comprises the steps,
A), will be adjusted respectively for the sewage producing in oximes for caprolactam production technology sewage and hydrogen hydrogen peroxide technique
Pond homogenizing is simultaneously introduced pretreatment reaction pond after all measuring, and adds catalyst, carries out advanced oxidation reaction；Preferably, described
In caprolactam oximes production technology sewage, COD is 3000～6000mg/L, produces in described hydrogen hydrogen peroxide technique
Sewage addition is 0～100g/L；
B), the sewage introducing flocculation sedimentation tank through advanced oxidation reaction carries out flocculation precipitation reaction, wherein consolidating in sewage
Body impurity occurs flocculation sediment to be removed in the presence of flocculant, and the sewage after process enters biochemical treatment system and carries out depth
Degree is processed.
Preferably, in the pretreatment reaction pond in step a) also added with cooxidant it is preferred that described catalyst
Measure as 0～60mg/L；The amount of described cooxidant is 0～2g/L it is preferred that the time of advanced oxidation reaction is 20～40 points
Clock.
The present invention has the advantages and positive effects that：It is pre- that the present invention carries out classification classification to each production unit process spent water
Process, specific aim is higher compared with existing similar processing method, thus has advantages below：
1), biochemical treatment system influent quality is no strict with, applied widely；
2), processing method is simply effective, and sewage disposal system is reliable and stable；
3), difficult biochemical sewage is carried out with targetedly advanced oxidation process, effective reducing energy consumption material consumption；
4), high strong sewage is carried out with targetedly evaporation and concentration pretreatment, improve subsequent biochemical system stability and can
By property；
5), effectively improve the toleration that process spent water variation water quality impacts to system；
6), the advanced treatment process that advanced oxidation and biochemical treatment are coupled, effectively improves oxidant utilization, reduces
Operating cost；
7), biochemical treatment system floor space is little, and investment is low；
8), effluent index is superior, non-secondary pollution.
Brief description
Fig. 1 is the process chart of the present invention；
Fig. 2 is the process chart of embodiment one in the present invention；
Fig. 3 is the process chart of embodiment two in the present invention；
Specific embodiment
Below in conjunction with the accompanying drawings, technical scheme is described in further detail.
A kind of Ketohexamethylene method produces the processing method of caprolactam technology sewage, comprises the steps：
1), it is classified pretreatment, oximes cell process sewage is processed it is therefore intended that will be difficult to give birth to using advanced oxidation
Change the target contaminant partial oxidation of degraded, be converted into the intermediate product with preferable biodegradability；By liquid phase rearrangement unit work
Skill sewage, using evaporation and concentration and dope burning process；The sewage grid of other units, ammonia aeration, neutralization, coagulation are sunk
One of shallow lake, air supporting or two or more method are processed, and main purpose is to remove part bulky grain sewage, suspension and glue
Body or soluble organic pollution；
2), biochemical treatment, by step 1) import regulating reservoir and carry out homogenizing and all measure through each unit process spent water of pretreatment,
Liquid phase rearrangement cell process sewage wherein after pretreatment, oximes cell process sewage, other cell process sewage volumes
Flow-rate ratio is 1:3～10:2～12, CODcr are respectively 500～4500,1000～6000,500～6000mg/L, then will adjust
Sewage in pond sends into biochemistry pool, carries out biochemical treatment, and described biochemical treatment is anaerobic biological technique, aerobic biochemical technique, detests
One of oxygen-aerobic combination technique or anaerobic-aerobic integrated metaplasia metallization processes.
After sewage is processed through above-mentioned steps, according to the requirement of draining, decide whether to carry out advanced treatment process, described
Advanced treatment process is to process advanced oxidation to be coupled with biochemical treatment, as shown in figure 1, the water outlet of biochemical treatment is carried out height
Level oxidation processes Posterior circle is back to the water inlet end of biochemical treatment, and outer row's part of contaminated water ensures sewage disposal system Inlet and outlet water simultaneously
Balance.
Embodiment one
The caprolactam production apparatus process spent water of certain chemical enterprise, water outlet CODcr require reach 500mg/L receive pipe will
Ask, its process chart is as shown in Figure 2.
1), it is classified pretreatment
A) difficult biochemical sewage is the pretreatment of oximes cell process sewage (wherein CODcr is 5500mg/L)：First will
Oximes cell process sewage and the mixing of hydrogen peroxide cell process sewage, and add a certain amount of hydrogen peroxide and ferrous sulfate molten
Liquid, its concentration is respectively：Hydrogen peroxide process sewage 50g/L, hydrogen peroxide 120mg/L, ferrous sulfate 10mg/L, after reacting 30 minutes
Flocculant is added to carry out flocculation sediment and sludge condensation into sewage, gained supernatant and solid precipitation deliver to comprehensive adjustment respectively
Pond and sludge dewatering workshop, the mud cake outward transport of generation is processed, and the CODcr of pretreated sewage is 3500mg/L；
B) high strong sewage (i.e. liquid phase rearrangement cell mesh process spent water, its CODcr is 135000mg/L) pretreatment：By liquid
Partly high strong sewage in phase rearrangement units carries out three-effect evaporation and condensation after collecting respectively, and steam condensate delivers to comprehensive adjustment
Pond, bottom of towe dope is sent into incinerator and is burned.The CODcr of tower top lime set is 1500mg/L.
C) other sewage of full factory (its CODcr is 4500mg/L) pretreatment：Other sewage of full factory remove partly big through grid
Granule sewage, suspension and colloid or soluble organic pollution deliver to comprehensive adjustment pond, and the CODcr of pretreated sewage is
4500mg/L.
2), biochemical treatment
By step 1) import regulating reservoir and carry out homogenizing and all measure through each unit process spent water of pretreatment, wherein preprocessed
Liquid phase rearrangement cell process sewage afterwards, oximes cell process sewage, other cell process sewage volume flow ratios are 1:9:
10, by being pumped into Aerobic-anaerobic integration biochemistry pool, water inlet is in the mixed liquor of integrated biochemistry pool inhalant region and high reflux ratio
After rapid mix homogeneously, enter biological selecting area, constantly inoculation has the short of very strong fertility and environment resistant changing capability
Generation prokaryotic micro-organisms, muddy water mixed solution acts on subsequently into aeration zone by the plug-flow of air lifting pushing implement, by controlling end
Micro-oxygen conditions, complete the degraded to pollutant such as COD, ammonia nitrogen, total nitrogens using microorganism, and sewage enters outgassing area afterwards, by water
Internal dissolved gas enter mud-water separation area after fully separating out, and in mud-water separation area, activated sludge is trapped, and supernatant receives pipe
Discharge.Mud in integrated biochemistry pool periodically by being pumped to sludge concentration tank, deliver to respectively by gained supernatant and solid precipitation
Comprehensive adjustment pond and sludge dewatering workshop, the mud cake outward transport that dehydration produces is processed.
Through as above step process, water outlet CODcr requires to reach 500mg/L and receives pipe requirement.
Embodiment two
The caprolactam production apparatus process spent water of certain chemical enterprise, water outlet CODcr requires to reach 60mg/L first grade discharging
Standard requires, and process chart is shown in Fig. 3.
1) pretreatment
A) difficult biochemical sewage (oximes cell process sewage, its CODcr is 4800mg/L) pretreatment：First will be oximes
Cell process sewage and the mixing of hydrogen peroxide cell process sewage, and add a certain amount of hydrogen peroxide and copperas solution, it is dense
Degree is respectively：Hydrogen peroxide process sewage 50g/L, hydrogen peroxide 120mg/L, ferrous sulfate 10mg/L, react 30 minutes backward sewage
Interior addition flocculant carries out flocculation sediment and sludge condensation, gained supernatant and solid precipitation deliver to respectively comprehensive adjustment pond and
Sludge dewatering workshop, the mud cake outward transport of generation is processed, and the CODcr of pretreated sewage is 2800mg/L；
B) high strong sewage (liquid phase rearrangement cell mesh process spent water, its CODcr is 128000mg/L) pretreatment：By liquid phase
Partly high strong sewage in rearrangement units carries out three-effect evaporation and condensation after collecting respectively, and steam condensate delivers to comprehensive adjustment pond,
Bottom of towe dope is sent into incinerator and is burned.The CODcr of tower top lime set is 1300mg/L.
C) other sewage of full factory (CODcr is 5300mg/L) pretreatment：Other sewage of full factory remove partly big through grid
Grain sewage, suspension and colloid or soluble organic pollution deliver to comprehensive adjustment pond, and the CODcr of pretreated sewage is
5300mg/L.
2) biochemical treatment
Complete by step 1) import regulating reservoir and carry out homogenizing and all measure through each unit process spent water of pretreatment, wherein locate through pre-
Liquid phase rearrangement cell process sewage after reason, oximes cell process sewage, other cell process sewage volume flow ratios are 1:
10:9, A is carried out together with the mud flowing back from sedimentation tank by pump2/ O biochemical treatment.Initially enter anaerobic pond, in this mud
Anaerobe carry out anaerobic reaction using the dissolved organic matter in raw sewage；Then together with the mixed liquor of aerobic end backflow
Enter anoxic pond, the denitrifying bacterium in this mud carries out Denitrification using the nitrate of remaining Organic substance and backflow and takes off
Nitrogen；After the completion of denitrification reaction, enter Aerobic Pond, the nitrifier in this mud carries out Nitrification by the mineralized nitrogen in waste water
For nitrate, polyP bacteria carries out aerobic phosphorus absorption simultaneously, and also here is aoxidized remaining Organic substance by aerobic bacteria, after through sedimentation tank
Carry out mud-water separation, water outlet carries out advanced treating, the sludge part of precipitation is returned anaerobic pond, partly discharged with excess sludge.
3) advanced treating
COD of sewage cr after above-mentioned process step is processed is reduced to 150mg/L, wherein still remaining a small amount of dividing greatly
Sub- persistent organic pollutants, can be utilized the sewage treatment process that biochemistry is coupled with Fenton advanced oxidation that bio-chemical effluent is carried out
Advanced treating.Add a certain amount of hydrogen peroxide and copperas solution in biochemical treatment water outlet first, its concentration is respectively：Double
Oxygen water 8mg/L, ferrous sulfate 0.6mg/L, in 30 minutes backward sewage of reaction, addition flocculant carries out flocculation sediment and mud is dense
Contracting, gained supernatant and solid precipitation deliver to comprehensive adjustment pond and sludge dewatering workshop respectively, and the mud cake outward transport of generation is processed.
Fenton oxidation sewage ensures at sewage through comprehensive adjustment pond circulating reflux to biochemical system water inlet end, simultaneously outer row's part of contaminated water
Reason system passes in and out water balance.It is 3.5 through the backflow water yield that advanced oxidation is processed with the ratio of outer displacement.
Through as above step process, water outlet CODcr requires to reach 60mg/L first discharge standard requirement.
Above embodiments of the invention are described in detail, but described content have been only presently preferred embodiments of the present invention,
It is not to be regarded as the practical range for limiting the present invention.All impartial changes made according to the scope of the invention and improvement etc., all should
Still belong within this patent covering scope.
Claims (6)
1. a kind of Ketohexamethylene method produce caprolactam technology sewage processing method it is characterised in that：Comprise the steps：
1), it is classified pretreatment, oximes cell process sewage carries out pretreatment using advanced oxidation processes；By liquid phase rearrangement
Cell process sewage, carries out pretreatment using evaporation and concentration and dope burning process；The sewage grid of other units, ammonia are blown
One of de-, neutralization, coagulating sedimentation, air supporting or two or more method carry out pretreatment；During described advanced oxidation is processed, use
Hydrogen hydrogen peroxide technique sewage is as oxidant；
Described advanced oxidation processes and comprises the steps,
A), by the sewage producing in oximes for caprolactam production technology sewage and hydrogen hydrogen peroxide technique, adjusted pond is equal respectively
Matter is simultaneously introduced pretreatment reaction pond after all measuring, and adds catalyst, carries out advanced oxidation reaction；Described caprolactam amidoxime
In metaplasia production. art sewage, COD is 3000～6000mg/L, and the sewage addition producing in described hydrogen hydrogen peroxide technique is 0
～100g/L；Also added with cooxidant in pretreatment reaction pond, the amount of described catalyst is 0～60mg/L；Described auxiliary oxygen
The amount of agent is 0～2g/L, and the time of advanced oxidation reaction is 20～40 minutes；And the sewage producing in hydrogen hydrogen peroxide technique
Addition, cooxidant all do not include 0g/L, the amount of catalyst does not include 0mg/L；
B), the sewage introducing flocculation sedimentation tank through advanced oxidation reaction carries out flocculation precipitation reaction, and the wherein solid in sewage is miscellaneous
Matter occurs flocculation sediment to be removed in the presence of flocculant, and the sewage after process enters biochemical treatment system and carries out depth
Reason；
2), biochemical treatment, by step 1) carry out biochemical treatment through the sewage of each unit of pretreatment, described biochemical treatment is to detest
One of oxygen biochemical process, aerobic biochemical technique, anaerobic-aerobic group technology or anaerobic-aerobic integrated metaplasia metallization processes, will
Step 1) import comprehensive adjustment pond and carry out homogenizing and all measure through each unit process spent water of pretreatment, liquid wherein after pretreatment
The sewage volume flow ratio that phase rearrangement units process spent water evaporates lime set, oximes cell process sewage and other units is 1:
3～10:2～12, and CODcr is respectively 500～4500mg/L, 1000～6000mg/L, 500～6000mg/L, then will be comprehensive
Sewage in regulating reservoir sends into biochemistry pool.
2. Ketohexamethylene method according to claim 1 produce caprolactam technology sewage processing method it is characterised in that：Dirty
Water is through step 2) in biochemical treatment after, carry out advanced treatment process, described advanced treatment process is to process advanced oxidation
It is coupled with biochemical treatment.
3. Ketohexamethylene method according to claim 2 produce caprolactam technology sewage processing method it is characterised in that：Institute
State advanced treatment process and refer to that the water outlet to biochemical treatment carries out advanced oxidation and processes the water inlet that Posterior circle is back to biochemical treatment
End, outer row's part of contaminated water guarantee sewage disposal system turnover water balance simultaneously.
4. Ketohexamethylene method according to claim 3 produce caprolactam technology sewage processing method it is characterised in that：Warp
The backflow water yield that advanced oxidation is processed is 2～6 with the volume ratio of outer displacement.
5. Ketohexamethylene method according to claim 4 produce caprolactam technology sewage processing method it is characterised in that：Warp
The backflow water yield that advanced oxidation is processed is 3～5 with the volume ratio of outer displacement.
6. Ketohexamethylene method according to claim 1 produce caprolactam technology sewage processing method it is characterised in that：Step
In rapid 1), evaporation and concentration and dope burning process refer to after liquid phase rearrangement cell process sewage collecting, to be evaporated concentrating, and steam
Vapour condensed fluid enters biochemistry pool, and dope is sent into incinerator and burned；Described evaporating and concentrating process adopts an effect or multiple-effect to steam
Send out technique.
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| CN201410811533.8A CN104649510B (en) | 2014-12-22 | 2014-12-22 | Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone |
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| CN104649510B true CN104649510B (en) | 2017-02-22 |
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| CN105502732A (en) * | 2015-12-01 | 2016-04-20 | 上海明诺环境科技有限公司 | Advanced treatment technology for caprolactam wastewater and device |
| CN106976949A (en) * | 2017-04-07 | 2017-07-25 | 华中科技大学 | A kind of oxidation treatment method of Leachate site biological treatment water outlet |
| CN108275825A (en) * | 2017-09-29 | 2018-07-13 | 聊城煤泗新材料科技有限公司 | A kind of caprolactam oximate wastewater treatment method |
| CN107857408B (en) * | 2017-12-08 | 2023-05-19 | 暨南大学 | Purifying device and treatment method for PPCPs in drinking water source |
| CN109626543B (en) * | 2018-11-26 | 2020-09-18 | 华中科技大学 | Method for treating organic wastewater by catalytic oxidation of two-phase oxidant system |
| CN111718058A (en) * | 2019-03-20 | 2020-09-29 | 中石化南京化工研究院有限公司 | Treatment method of caprolactam production waste liquid |
| CN110204128A (en) * | 2019-07-09 | 2019-09-06 | 上海环境保护有限公司 | A kind of caprolactam sewerage advanced treatment process |
| CN110436710A (en) * | 2019-08-14 | 2019-11-12 | 浙江巨能环境工程有限公司 | A kind of nylon 6 produces waste water high-efficiency processing unit and treatment process |
| CN112661343A (en) * | 2019-10-16 | 2021-04-16 | 唐山曹妃甸天川环保科技有限公司 | Advanced treatment system and method for caprolactam production wastewater |
| CN110818186A (en) * | 2019-11-18 | 2020-02-21 | 苏州大成有方数据科技有限公司 | Treatment process of phenol-acetone industrial wastewater |
| CN114906916A (en) * | 2021-02-09 | 2022-08-16 | 中国石油化工股份有限公司 | Pretreatment method of caprolactam ammoximation process production wastewater |
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| CN101618919A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Method for processing waste water produced by caprolactam ammoximation process |
| CN101734825B (en) * | 2008-11-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for treating wastewater generated by cyclohexanone ammoximation process |
| CN103145288A (en) * | 2013-03-15 | 2013-06-12 | 湖南百利工程科技股份有限公司 | Method for processing and recovering hazardous substance in liquid waste in caprolactam production |
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