CN104649510A - 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 PDF

Info

Publication number
CN104649510A
CN104649510A CN201410811533.8A CN201410811533A CN104649510A CN 104649510 A CN104649510 A CN 104649510A CN 201410811533 A CN201410811533 A CN 201410811533A CN 104649510 A CN104649510 A CN 104649510A
Authority
CN
China
Prior art keywords
sewage
treatment
biochemical
carry out
produces
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410811533.8A
Other languages
Chinese (zh)
Other versions
CN104649510B (en
Inventor
吕威鹏
赵斌
李树华
赵敏伟
梁军湘
郭启迪
李�荣
杨克俭
段瑾
陈雁军
张媛
王绍伟
孙承宇
潘建通
迟金宝
张雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BEIJING BHT ENVIRONMENT TECHNOLOGY Co Ltd
China Tianchen Engineering Corp
Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd
Original Assignee
BEIJING BHT ENVIRONMENT TECHNOLOGY Co Ltd
China Tianchen Engineering Corp
Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BEIJING BHT ENVIRONMENT TECHNOLOGY Co Ltd, China Tianchen Engineering Corp, Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd filed Critical BEIJING BHT ENVIRONMENT TECHNOLOGY Co Ltd
Priority to CN201410811533.8A priority Critical patent/CN104649510B/en
Publication of CN104649510A publication Critical patent/CN104649510A/en
Application granted granted Critical
Publication of CN104649510B publication Critical patent/CN104649510B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes

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

A kind of pimelinketone method produces the treatment process of caprolactam technology sewage
Technical field
The present invention relates to sewage treatment technology field, particularly relate to the treatment process that a kind of pimelinketone method produces caprolactam process spent water.
Background technology
Hexanolactam (CPL) is the important monomer producing nylon-6 fiber (polyamide fibre) and nylon-6 engineering plastics, is widely used in the fields such as nylon fibre, engineering plastics, plastics film.Current most caprolactam production full scale plant is all take pimelinketone as raw material, mainly comprise four large process units: 1) hydrogen peroxide plant: this device with alkyl-anthraquinone and organic solvent for working solution, utilize hydrogen and oxygen to carry out hydrogenation and oxidizing reaction respectively, produce hydrogen peroxide; 2) pimelinketone device: this device take benzene as raw material, carries out selec-tive hydrogenation to benzene and generates tetrahydrobenzene, produces hexalin, then produce pimelinketone with cyclohexanol dehydrogenation through hydration, rectifying; 3) oximes device: this device is with ammonia, hydrogen peroxide, pimelinketone for raw material, and cyclohexanone-oxime is produced in reaction under the effect of catalyzer; 4) liquid phase rearrangement device: this device take cyclohexanone-oxime as raw material, under the effect of catalyst sulfuric acid, hexanolactam is produced in the reaction of cyclohexanone-oxime generation liquid phase rearrangement.Although this explained hereafter hexanolactam can effectively reduce plant energy consumption and material consumption, also bring the reluctant problem of process spent water simultaneously.Principal pollutant in pimelinketone method caprolactam technology sewage are pimelinketone, hexanaphthene, hexalin, benzene, cyclohexanone-oxime, organic acid, hexanolactam, ammonia nitrogen etc., large by rate of water added, COD is high, B/C than low, form the problems such as complicated, biochemical treatment is difficult, thus become one of reluctant production waste in petroleum chemical industry.
In actual production, each workshop section's process spent water mixing unification processes by caprolactam production apparatus usually, often due to hybrid technique sewage biodegradability difference and organic contamination substrate concentration height etc. problem huge impact is caused to biochemical treatment system, cause wastewater treatment efficiency undesirable and high cost.In recent years, along with development research and the practical experience accumulation of pimelinketone method being produced to caprolactam technology sewage water treatment method, find in the process spent water that cyclohexanone oxamidinating unit produces containing ketone organism, sewage B/C is extremely low, its direct discharge can cause the microorganism mortality in biochemical treatment system, on generation destructive effects and the impact of biochemical treatment system.Therefore, part caprolactam production apparatus progressively starts to adopt caprolactam technology sewage hierarchical processing method, namely adopt the technology such as advanced oxidation to carry out pre-treatment to cyclohexanone oxamidinating cell process waste water, and then and the process spent water mixing of full factory after carry out the method for biochemical treatment.But this method does not carry out fully and completely classify and grading to the process spent water of each productive unit, the such as part of contaminated water of liquid phase rearrangement productive unit, although the water yield is less, but organic pollutant excessive concentration, COD is up to more than 100000mg/L, if directly discharge still can cause huge impact to biochemical system.
CN 101734825 A discloses a kind for the treatment of process of wastewater generated by cyclohexanone ammoximation process, first makes process spent water carry out advanced oxidation reaction, then adopts sequencing batch activated sludge treatment system (SBR) to process.Cyclohexanone oxamidinating cell process sewage is after advanced oxidation pre-treatment, the organism of impact is had to be oxidized to the organism harmless to microorganism to biochemical system in sewage, the biodegradability of raising sewage reduces the organic content in sewage simultaneously, enters biochemical system process with other sewage after can mixing.But, because other productive units part of contaminated water COD is too high, after pretreated oximes unit sewage and other sewage of full factory mix, still there is very high ammonia nitrogen and organic concentration.Due to the restriction of follow-up SBR method process characteristic (sludge concentration is lower, the residence time is short, mass-transfer efficiency low), the processing requirements of caprolactam technology sewage cannot be met completely, thus obviously exist cost of sewage disposal too high, invest the problems such as excessive and treatment effect is undesirable.
CN 102452762 A adopts oxidation and pre-treatment-iron copper pre-micro-electrolysis disposal-membrane bioreactor (MBR) combination process to process caprolactam technology sewage.First remove oximes process spent water part COD and bio-toxicity material through pre-treatment, then carry out MBR biochemical treatment being mixed into all the other caprolactam production sewage.Compared with CN 101734825 A treatment process used, although this method effectively improves the treatment effect of wastewater of caprolactam production, but the method requires below the hybrid technique COD of sewage 3000mg/L entering MBR system, that is the impact of MBR system can be caused after the process spent water that the moiety concentrations of liquid phase rearrangement unit generation is too high directly enters this system, or the processing requirements of caprolactam technology sewage cannot be met completely, still existing hexanolactam sewage water treatment method complicated operation is not solved, influent quality requires high, poor for applicability, cost of sewage disposal is too high, invest the difficult problems such as excessive and treatment effect is undesirable.
Summary of the invention
The problem to be solved in the present invention is to provide a kind for the treatment of process of Cyclohexanone Production caprolactam technology sewage, solves the problems such as the investment that exists in existing preparing process of caprolactam sewage water treatment method and high cost, treatment effect be undesirable.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of pimelinketone method produces the treatment process of caprolactam technology sewage, comprises the steps:
1), classification pre-treatment, by oximes cell process sewage, adopt advanced oxidation processes carry out pre-treatment; By liquid phase rearrangement cell process sewage, evaporation concentration and dope burning process is adopted to carry out pre-treatment, main purpose is concentrated solution and phlegma by carrying out concentrating and separating containing the sewage of higher organic contamination substrate concentration, in concentrated solution, organic pollutant is dense, dope burning need be carried out, and organic contamination substrate concentration in phlegma is lower, subsequent biochemical process directly can be carried out; One or more methods in the sewage grid of other unit, ammonia aeration, neutralization, coagulating sedimentation, air supporting are carried out pre-treatment, and main purpose removes part macrobead sewage, suspension and colloid or insoluble organic pollutant;
2), biochemical treatment, by step 1) carry out biochemical treatment through the sewage of pretreated each unit, described biochemical treatment is anaerobic biological technique, aerobic biochemical technique, one in anaerobic-aerobic combination process or anaerobic-aerobic integrated biochemical process, preferably, by step 1) import comprehensive adjustment pond through pretreated each cell process sewage and carry out homogeneous and all measure, wherein liquid phase rearrangement cell process sewage evaporation lime set after pretreatment, the sewage volume flow ratio of oximes cell process sewage and other unit is 1:3 ~ 10:2 ~ 12, and CODcr is respectively 500 ~ 4500mg/L, 1000 ~ 6000mg/L, 500 ~ 6000mg/L, again 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 is coupled at advanced oxidation process and biochemical treatment.
Preferably, described advanced treatment process refers to and carries out to the water outlet of biochemical treatment the feed-water end that advanced oxidation process Posterior circle is back to biochemical treatment, and outer row's part of contaminated water ensures Sewage treatment systems Inlet and outlet water balance simultaneously.
Preferably, be 2 ~ 6 through the backflow water yield of advanced oxidation process and the ratio of outer water displacement, preferably 3 ~ 5.
Preferably, step 1) in, described advanced oxidation process refers to the one in Fenton oxidation method, Ozonation, wet air oxidation, supercritical water oxidation method.
Preferably, step 1) in, in described advanced oxidation process, add catalyzer and oxygenant in sewage, wherein catalyzer is Fe 2+, Cu 2+, Ni 2+, Co 2+, Zn 2+in one or more, described oxygenant be in hydrogen peroxide, ozone, oxygen (air), persulphate, potassium permanganate or clorox one or both combination.
Preferably, step 1) in, evaporation concentration and dope burning process refer to that carry out evaporation concentration, steam condensate enters biochemistry pool by after liquid phase rearrangement cell process sewage collecting, and dope is sent into incinerator and burned; Described evaporating and concentrating process adopts effect or a multiple-effect evaporation technique.
Preferably, step 1) in, in described advanced oxidation process, use Hydrogen Peroxide Production process spent water as oxygenant.
Preferably, step 1) in, described advanced oxidation process comprises the steps,
A), by the sewage produced in oximes for hexanolactam production technique sewage and Hydrogen Peroxide Production technique after equalizing tank homogeneous is all measured, introduce pretreatment reaction pond respectively simultaneously, and add catalyzer, carry out advanced oxidation reaction; Preferably, in the oximes production technique sewage of described hexanolactam, COD is 3000 ~ 6000mg/L, and the sewage addition produced in described Hydrogen Peroxide Production technique is 0 ~ 100g/L;
B), through advanced oxidation reaction sewage introduce flocculation sedimentation tank carry out flocculation precipitation reaction, there is flocculation sediment and removed in the solid impurity wherein in sewage, the sewage after process enters biochemical treatment system and carries out advanced treatment under the effect of flocculation agent.
Preferably, step a) in pretreatment reaction pond in be also added with secondary oxidizer, preferably, the amount of described catalyzer is 0 ~ 60mg/L; The amount of described secondary oxidizer is 0 ~ 2g/L, and preferably, the time of advanced oxidation reaction is 20 ~ 40 minutes.
The advantage that the present invention has and positively effect are: the present invention carries out classify and grading pre-treatment to each productive unit process spent water, and specific aim is stronger compared with existing similar treatment process, thus has the following advantages:
1), to biochemical treatment system influent quality without strict demand, applied widely;
2), treatment process is simply effective, and Sewage treatment systems is reliable and stable;
3), to difficult biochemical sewage carry out advanced oxidation process targetedly, effectively reduce energy and material consumption;
4), to high strong sewage carry out evaporation concentration pre-treatment targetedly, improve stability and the reliability of subsequent biochemical system;
5) tolerance that process spent water variation water quality impacts system, is effectively improved;
6), advanced oxidation and biochemical treatment carry out the advanced treatment process that is coupled, effectively improves oxidant utilization, reduce running cost;
7), biochemical treatment system floor space is little, invests low;
8), effluent index is superior, non-secondary pollution.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the process flow sheet of embodiment one in the present invention;
Fig. 3 is the process flow sheet of embodiment two in the present invention;
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is described in further detail.
Pimelinketone method produces a treatment process for caprolactam technology sewage, comprises the steps:
1), classification pre-treatment, by oximes cell process sewage, adopt advanced oxidation process, object is to be difficult to the target contaminant partial oxidation of biochemical degradation, is converted into the intermediate product with better biodegradability; By liquid phase rearrangement cell process sewage, adopt evaporation concentration and dope burning process; One or more methods in the sewage grid of other unit, ammonia aeration, neutralization, coagulating sedimentation, air supporting processed, main purpose removes part macrobead sewage, suspension and colloid or insoluble organic pollutant;
2), biochemical treatment, by step 1) import equalizing tank through pretreated each cell process sewage and carry out homogeneous and all measure, wherein liquid phase rearrangement cell process sewage after pretreatment, oximes cell process sewage, other cell process sewage volume flow ratios are 1:3 ~ 10:2 ~ 12, CODcr is respectively 500 ~ 4500, 1000 ~ 6000, 500 ~ 6000mg/L, again the sewage in equalizing tank is sent into biochemistry pool, carry out biochemical treatment, described biochemical treatment is anaerobic biological technique, aerobic biochemical technique, one in anaerobic-aerobic combination process or anaerobic-aerobic integrated biochemical process.
Sewage is after above-mentioned steps processes, according to the requirement of draining, determine whether carry out advanced treatment process, described advanced treatment process is coupled at advanced oxidation process and biochemical treatment, as shown in Figure 1, the water outlet of biochemical treatment is carried out the feed-water end that advanced oxidation process Posterior circle is back to biochemical treatment, outer row's part of contaminated water ensures Sewage treatment systems Inlet and outlet water balance simultaneously.
Embodiment one
The caprolactam production apparatus process spent water of certain chemical enterprise, water outlet CODcr requires that reaching 500mg/L receives pipe requirement, and its process flow sheet as shown in Figure 2.
1), classification pre-treatment
A) pre-treatment of difficult biochemical sewage and oximes cell process sewage (wherein CODcr is 5500mg/L): first by oximes cell process sewage and the mixing of hydrogen peroxide cell process sewage, and add a certain amount of hydrogen peroxide and copperas solution, its concentration is respectively: hydrogen peroxide process sewage 50g/L, hydrogen peroxide 120mg/L, ferrous sulfate 10mg/L, react and within 30 minutes, add flocculation agent in backward sewage and carry out flocculation sediment and sludge condensation, gained supernatant liquor and solid precipitation deliver to comprehensive adjustment pond and sludge dewatering workshop respectively, the mud cake outward transport process produced, 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) pre-treatment: carry out three-effect evaporation and condensation after being collected respectively by high for the part in liquid phase rearrangement unit strong sewage, steam condensate delivers to comprehensive adjustment pond, and dope at the bottom of tower is sent into incinerator and burned.The CODcr of tower top lime set is 1500mg/L.
C) full factory other sewage (its CODcr is 4500mg/L) pre-treatment: other sewage of full factory remove part macrobead sewage, suspension and colloid through grid or insoluble organic pollutant delivers to comprehensive adjustment pond, and the CODcr of pretreated sewage is 4500mg/L.
2), biochemical treatment
By step 1) import equalizing tank through pretreated each cell process sewage and carry out homogeneous and all measure, wherein liquid phase rearrangement cell process sewage after pretreatment, 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 after integrated biochemistry pool inhalant region mixes rapidly with the mixed solution of high reflux ratio, enter biological selecting area, constantly inoculation has the short generation prokaryotic micro-organisms of very strong fecundity and environment resistant changing capability, then muddy water mixed solution enters aeration zone by the plug-flow effect of air lifting pushing implement, by controlling end micro-oxygen conditions, microorganism is utilized to complete COD, ammonia nitrogen, the degraded of the pollutents such as total nitrogen, sewage enters outgas district afterwards, mud-water separation district is entered after fully being separated out by dissolved gas in water body, in mud-water separation district, active sludge is trapped, tube drainage received by supernatant liquor.Mud in integration biochemistry pool is regularly by being pumped to sludge thickener, and gained supernatant liquor and solid precipitation deliver to comprehensive adjustment pond and sludge dewatering workshop respectively, the mud cake outward transport process that dehydration produces.
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 the requirement of 60mg/L first discharge standard, and process flow sheet is shown in Fig. 3.
1) pre-treatment
A) difficult biochemical sewage (oximes cell process sewage, its CODcr is 4800mg/L) pre-treatment: first by oximes cell process sewage and the mixing of hydrogen peroxide cell process sewage, and add a certain amount of hydrogen peroxide and copperas solution, its concentration is respectively: hydrogen peroxide process sewage 50g/L, hydrogen peroxide 120mg/L, ferrous sulfate 10mg/L, react and within 30 minutes, add flocculation agent in backward sewage and carry out flocculation sediment and sludge condensation, gained supernatant liquor and solid precipitation deliver to comprehensive adjustment pond and sludge dewatering workshop respectively, the mud cake outward transport process produced, 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) pre-treatment: carry out three-effect evaporation and condensation after being collected respectively by high for the part in liquid phase rearrangement unit strong sewage, steam condensate delivers to comprehensive adjustment pond, and dope at the bottom of tower is sent into incinerator and burned.The CODcr of tower top lime set is 1300mg/L.
C) full factory other sewage (CODcr is 5300mg/L) pre-treatment: other sewage of full factory remove part macrobead sewage, suspension and colloid through grid or insoluble organic pollutant delivers to comprehensive adjustment pond, and the CODcr of pretreated sewage is 5300mg/L.
2) biochemical treatment
Complete in step 1) import equalizing tank through pretreated each cell process sewage and carry out homogeneous and all measure, wherein liquid phase rearrangement cell process sewage after pretreatment, oximes cell process sewage, other cell process sewage volume flow ratios are 1:10:9, carry out A by pump together with the mud refluxed from settling tank 2/ O biochemical treatment.First enter anaerobic pond, the anerobe in this mud utilizes the dissolved organic matter in raw waste water to carry out anaerobic reaction; Then enter anoxic pond together with the mixed solution refluxed with aerobic end, the denitrifying bacteria in this mud utilizes the nitrate of remaining organism and backflow to carry out denitrification denitrogenation; After denitrification reaction completes, enter Aerobic Pond, nitrifier in this mud carries out polyP bacteria while that the mineralized nitrogen in waste water being nitrate by nitrification and carries out aerobic suction phosphorus, remaining organism is also oxidized by aerobic bacteria at this, mud-water separation is carried out finally by settling tank, advanced treatment is carried out in water outlet, and the sludge part of precipitation returns anaerobic pond, and part is discharged with excess sludge.
3) advanced treatment
COD of sewage cr after above-mentioned treatment step process is reduced to 150mg/L, wherein still remaining a small amount of macromole Persistent organic pollutants, and the biochemical sewage treatment process be coupled with Fenton advanced oxidation can be utilized to carry out advanced treatment to bio-chemical effluent.First in biochemical treatment water outlet, a certain amount of hydrogen peroxide and copperas solution is added, its concentration is respectively: hydrogen peroxide 8mg/L, ferrous sulfate 0.6mg/L, react and within 30 minutes, add flocculation agent in backward sewage and carry out flocculation sediment and sludge condensation, gained supernatant liquor and solid precipitation deliver to comprehensive adjustment pond and sludge dewatering workshop respectively, the mud cake outward transport process of generation.Fenton oxidation sewage is through comprehensive adjustment pond pump around circuit to biochemical system feed-water end, and outer row's part of contaminated water ensures Sewage treatment systems Inlet and outlet water balance simultaneously.Be 3.5 through the backflow water yield of advanced oxidation process and the ratio of outer water displacement.
Through as above step process, water outlet CODcr requires to reach the requirement of 60mg/L first discharge standard.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the scope of the invention change and improve, and all should still belong within this patent covering scope.

Claims (10)

1. pimelinketone method produces a treatment process for caprolactam technology sewage, it is characterized in that: comprise the steps:
1), classification pre-treatment, by oximes cell process sewage, adopt advanced oxidation processes carry out pre-treatment; By liquid phase rearrangement cell process sewage, evaporation concentration and dope burning process is adopted to carry out pre-treatment; One or more methods in the sewage grid of other unit, ammonia aeration, neutralization, coagulating sedimentation, air supporting are carried out pre-treatment;
2), biochemical treatment, by step 1) carry out biochemical treatment through the sewage of pretreated each unit, described biochemical treatment is anaerobic biological technique, aerobic biochemical technique, one in anaerobic-aerobic combination process or anaerobic-aerobic integrated biochemical process, preferably, by step 1) import comprehensive adjustment pond through pretreated each cell process sewage and carry out homogeneous and all measure, wherein liquid phase rearrangement cell process sewage evaporation lime set after pretreatment, the sewage volume flow ratio of oximes cell process sewage and other unit is 1:3 ~ 10:2 ~ 12, and CODcr is respectively 500 ~ 4500mg/L, 1000 ~ 6000mg/L, 500 ~ 6000mg/L, again the sewage in comprehensive adjustment pond is sent into biochemistry pool.
2. pimelinketone method according to claim 1 produces the treatment process of caprolactam technology sewage, it is characterized in that: sewage is through step 2) in biochemical treatment after, carry out advanced treatment process, described advanced treatment process is coupled at advanced oxidation process and biochemical treatment.
3. pimelinketone method according to claim 2 produces the treatment process of caprolactam technology sewage, it is characterized in that: described advanced treatment process refers to and carries out to the water outlet of biochemical treatment the feed-water end that advanced oxidation process Posterior circle is back to biochemical treatment, outer row's part of contaminated water ensures Sewage treatment systems Inlet and outlet water balance simultaneously.
4. pimelinketone method according to claim 3 produces the treatment process of caprolactam technology sewage, it is characterized in that: be 2 ~ 6 through the backflow water yield of advanced oxidation process and the volume ratio of outer water displacement, and preferably 3 ~ 5.
5. the pimelinketone method according to any one of Claims 1 to 4 produces the treatment process of caprolactam technology sewage, it is characterized in that: step 1) in, described advanced oxidation process refers to the one in Fenton oxidation method, Ozonation, wet air oxidation, supercritical water oxidation method.
6. the pimelinketone method according to any one of Claims 1 to 4 produces the treatment process of caprolactam technology sewage, it is characterized in that: step 1) in, in described advanced oxidation process, add catalyzer and oxygenant in sewage, wherein catalyzer is Fe 2+, Cu 2+, Ni 2+, Co 2+, Zn 2+in one or more, described oxygenant be in hydrogen peroxide, ozone, oxygen, persulphate, potassium permanganate or clorox one or both combination.
7. pimelinketone method according to claim 1 produces the treatment process of caprolactam technology sewage, it is characterized in that: step 1) in, evaporation concentration and dope burning process refer to after liquid phase rearrangement cell process sewage collecting, carry out evaporation concentration, steam condensate enters biochemistry pool, and dope is sent into incinerator and burned; Described evaporating and concentrating process adopts effect or a multiple-effect evaporation technique.
8. the pimelinketone method according to any one of claim 1 ~ 7 produces the treatment process of caprolactam technology sewage, it is characterized in that: step 1) in, in described advanced oxidation process, use Hydrogen Peroxide Production process spent water as oxygenant.
9. pimelinketone method according to claim 8 produces the treatment process of caprolactam technology sewage, it is characterized in that: step 1) in, described advanced oxidation process comprises the steps,
A), by the sewage produced in oximes for hexanolactam production technique sewage and Hydrogen Peroxide Production technique after equalizing tank homogeneous is all measured, introduce pretreatment reaction pond respectively simultaneously, and add catalyzer, carry out advanced oxidation reaction; Preferably, in the oximes production technique sewage of described hexanolactam, COD is 3000 ~ 6000mg/L, and the sewage addition produced in described Hydrogen Peroxide Production technique is 0 ~ 100g/L;
B), through advanced oxidation reaction sewage introduce flocculation sedimentation tank carry out flocculation precipitation reaction, there is flocculation sediment and removed in the solid impurity wherein in sewage, the sewage after process enters biochemical treatment system and carries out advanced treatment under the effect of flocculation agent.
10. pimelinketone method according to claim 9 produces the treatment process of caprolactam technology sewage, it is characterized in that: step a) in pretreatment reaction pond in be also added with secondary oxidizer, preferably, the amount of described catalyzer is 0 ~ 60mg/L; The amount of described secondary oxidizer is 0 ~ 2g/L, and preferably, the time of advanced oxidation reaction is 20 ~ 40 minutes.
CN201410811533.8A 2014-12-22 2014-12-22 Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone Active CN104649510B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410811533.8A CN104649510B (en) 2014-12-22 2014-12-22 Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410811533.8A CN104649510B (en) 2014-12-22 2014-12-22 Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone

Publications (2)

Publication Number Publication Date
CN104649510A true CN104649510A (en) 2015-05-27
CN104649510B CN104649510B (en) 2017-02-22

Family

ID=53241222

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410811533.8A Active CN104649510B (en) 2014-12-22 2014-12-22 Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone

Country Status (1)

Country Link
CN (1) CN104649510B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109626543A (en) * 2018-11-26 2019-04-16 华中科技大学 A kind of method of two-phase oxidizer system catalytic oxidation treatment organic wastewater
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
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
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN101734825A (en) * 2008-11-20 2010-06-16 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN101734825A (en) * 2008-11-20 2010-06-16 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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109626543A (en) * 2018-11-26 2019-04-16 华中科技大学 A kind of method of two-phase oxidizer system catalytic oxidation treatment organic wastewater
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
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

Also Published As

Publication number Publication date
CN104649510B (en) 2017-02-22

Similar Documents

Publication Publication Date Title
CN104649510B (en) Method for treating sewage generated from process for producing caprolactam by utilizing cyclohexanone
CN106746175A (en) A kind of kitchen garbage, waste-water processing method
WO2010133177A1 (en) Landfill leachate wastewater treatment system and process thereof
CN104961306B (en) A kind of processing method of vaccary breeding wastewater
CN104671613B (en) A kind for the treatment of process of percolate from garbage filling field
CN101311132A (en) Waste water recycling comprehensive processing process
CN103641277B (en) Acrylonitrile waste water treatment method
CN106430845A (en) Kitchen garbage wastewater treatment apparatus
CN110803835A (en) Recycling treatment method for quaternary ammonium salt wastewater
CN111268872A (en) Pesticide wastewater treatment process and treatment device thereof
CN103663875A (en) Method for improving denitrification rate of acrylonitrile waste water
CN106517669B (en) The positive osmosis treatment system of black smelly water A/O and treatment process
CN111170545A (en) Pesticide wastewater treatment system and process
CN109205954A (en) Light electrolysis catalysis oxidation, biochemical treatment high-concentration waste hydraulic art
CN105621805A (en) Refuse incineration plant leachate up-to-standard discharge treatment system and method
CN107473370B (en) Sewage treatment system and method combining membrane bioreactor and phosphorus recovery process
CN104098221B (en) A kind for the treatment of process of hexanolactam sewage
CN112960869A (en) Treatment system and treatment method for industrial sewage generated in preparation of adiponitrile by direct hydrocyanation of butadiene
CN107814461A (en) The processing unit and method of a kind of cyanide containing wastewater
CN111995177A (en) Method for full-quantitative treatment of landfill leachate through electron beam irradiation
CN107151082B (en) Zero-discharge treatment system and method for DMF (dimethyl formamide) -containing wastewater
CN105036337A (en) Method for accelerating ammonification speed of chemical engineering waste water containing organic nitrogen
CN207418548U (en) A kind of sewage recycling processing unit
CN104876334B (en) Short-range nitrification/denitrification dephosphorization-series device and method for synchronously recovering phosphorus
CN108101219A (en) A kind of high ammonia nitrogen organic wastewater treatment process of continuous flow and its device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant