CN110294569A - A kind of processing method of polyurethane production waste water - Google Patents

A kind of processing method of polyurethane production waste water Download PDF

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Publication number
CN110294569A
CN110294569A CN201910516443.9A CN201910516443A CN110294569A CN 110294569 A CN110294569 A CN 110294569A CN 201910516443 A CN201910516443 A CN 201910516443A CN 110294569 A CN110294569 A CN 110294569A
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waste water
water
anaerobic
treatment
processing method
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赵选英
程夫苓
杨峰
朱强
郑刚
张永栋
戴建军
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JIANGSU NANDA HUAXING ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd.
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Jiangsu Nanda Huaxing Environmental Protection & Technology Co Ltd
Nanjing University Yancheng Environmental Protection Technology and Engineering Research Institute
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/122Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
    • 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
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • 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
    • C02F1/722Oxidation by peroxides
    • 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
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • 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
    • C02F2101/34Organic compounds containing oxygen
    • 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
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic 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
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a kind of processing methods of polyurethane production waste water, belong to water-treatment technology field.It pre-processes waste water using Formose Reaction, then uses the biochemical treatment of anaerobic-aerobic, finally carries out advanced treating to waste water using advanced oxidation processes;Anaerobic pond is two or more, and as COD concentration >=6000mg/L in pretreated waste water, the anaerobic pond is worked in the form of concatenated;As COD concentration < 6000mg/L in treated waste water, the anaerobic pond works in form in parallel.The processing method can successfully manage the big situation of waste water water during polyurethane production, variation water quality, overcome the problem that effect is unstable in polyurethane waste shipwreck biochemical treatment in the prior art and actual process.

Description

A kind of processing method of polyurethane production waste water
Technical field
The invention belongs to water-treatment technology fields, more specifically to a kind of processing method of polyurethane production waste water.
Background technique
Polyurethane full name is polyurethanes, is on main chain containing the macromolecular compound for repeating carbamate groups General name, the raw material by changing polyurethane form, can significantly change, and obtain the product of different soft and hard degree, including paint applies Material, foamed plastics, elastomer etc..China be in the world polyurethane production and sale the first big country, soft bubble, hard bubble, elastomer, The polyurethane materials such as spandex, synthetic leather slurry are all widely used in industries such as traffic, furniture, building, clothes.
Polyurethane can generate a large amount of waste water in process of production, compared to other waste water, polyurethane production waste water have with Lower three outstanding features: one, Pollutants in Wastewater content is generally higher and complicated component, direct emission can be such that environment soda acid loses Weighing apparatus;Two, Pollutants in Wastewater is mostly the compounds such as aldehydes, organic acid and atent solvent, and stability is good, it is difficult to it degrades, biochemistry drop It is longer to solve the time, while the formaldehyde toxicity of its higher concentration contained is larger, not only results in microorganism death and meeting in water Inhereditary material in damaging cells is suspecious carcinogen, deteriorates, influences if not administered direct emission and will lead to water quality Ecological environment;Three, waste water displacement, change of water quality fluctuation are big, for example COD in water body concentration (unit: mg/L) can be thousands of Fluctuating change in tens of thousands of ranges.It is all to be filled to after Product Process waste water synthesis into end-o f-pipe -control in traditional treatment process It sets and is handled together, stringent differentiation is not carried out to the materializing strategy rate of substance in waste water and biochemical degradability.It is poly- Often containing the formaldehyde of higher concentration in urethane waste water, there is toxic action to microorganism, will cause microorganism death, at biochemistry Reason failure.Once technique waste water is certain containing the waste water for being difficult to brokenly ring degradation material if it exists synthesis, not only increases operating cost Whole treatment effeciency is also reduced, into when biochemical treatment, once it is not up to standard, it is even more difficult to trace to the source, and due to some difficult to degrade The presence of substance causes biochemical tail water water outlet COD not up to standard, and common processing method is that MBR biomembrane is handled, but its There are film productions it is at high cost, operating cost is high and is also easy to produce fouling membrane the shortcomings that.
Cause the biodegradability of waste water can be poor for three above feature, so that waste water has to pass through at sufficient anaerobism After reason improves B/C value, just can be carried out aerobic biochemical and reach purified treatment effect, and due to biochemical treatment due to operating cost is low, The features such as operating method is simple, it has also become processing industrial wastewater more wide spectrum and method with strong applicability.But it is very important , formaldehyde of the polyurethane production waste water containing higher concentration itself, toxicity can cause inhibiting effect to biochemical treatment system, It is not only difficult to achieve the purpose that wastewater biological is degraded, instead it could even be possible to causing microorganism death that biological treatment system is caused to collapse It bursts.
Through retrieving, Chinese invention patent, application number: 201510781430.6, the applying date: 2015.11.13 discloses one The method of kind processing high-concentration formaldehyde wastewater, the program filter pre- place before anaerobism, aerobic treatment step, using iron filings layer The means that sodium hydroxide and calcium hydroxide are reacted are added in reason, are pre-processed to waste water, reduce the biochemical treatment stage The concentration of COD and formaldehyde in influent quality reduce the intake pressure of biological treatment stage, are discharged in water sample after final process Content of formaldehyde 1mg/L is dropped to by 10000~20000mg/L, COD content is dropped within 100mg/L by 1000~5000mg/L, Realize effectively removing for Pollutants in Wastewater.But there are the following problems for the technology: firstly, it is necessary to which iron filings layer is arranged to draw Enter ferrous ion, the later period also needs to add coagulant iron ion and is passed through flocculation aid chlorine, not only generates in biochemical process big Amount glar and chlorine can be reacted with the humus acid in water generates harmful halides, reacts with ammonia and generates chlorine ammonia Deng influence biochemical effects and chlorine can cause intense stimulus, dangerous environmental protection;Secondly, in view of polyurethane production waste water water, Change of water quality fluctuates big practical factor, and above scheme can not adjust the ability of its processing according to water, water quality load variations.
Big practical factor is fluctuated for polyurethane production waste water water, change of water quality, generally, using anaerobic treatment of waste water When, if the COD concentration of anaerobism water inlet is excessive, in order to obtain preferable water treatment efficiency, general anaerobic biochemical treatment time as far as possible It can be than being up to several days, it is possible to lead to the accelerated ageing of sludge;If also, the waste water water that need to be handled is big, and needs to consider The factor for the treatment of effeciency, how the relationship between effective Balance Treatment effect and treatment effeciency and processing cost is especially tired It is difficult.
Therefore, in view of the above-mentioned problems, need propose it is a kind of it is at low cost, comprehensive treatment effect is good, have adapt to water load, Variation water quality changes processing mode greatly.
Summary of the invention
1. to solve the problems, such as
For polyurethane, the present invention is intended to provide a kind of processing method of polyurethane production waste water, can successfully manage poly- ammonia The big situation of waste water water, variation water quality in ester production process.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of processing method of polyurethane production waste water carries out micro- life firstly, pretreated waste water is sent into anaerobic pond The Anaerobic Treatment of object;Then, the Aerobic Process for Treatment and advanced oxidation processing of microorganism are successively carried out to the waste water after Anaerobic Treatment;
Anaerobic pond is two or more, as COD concentration >=6000mg/L in pretreated waste water, the anaerobism Pond is worked in the form of concatenated;As COD concentration < 6000mg/L in treated waste water, the anaerobic pond is in form in parallel Work.
Above-mentioned pretreatment mode can use physical treatment mode, and waste water is pumped into the primary heavy pond of reaction, water is added Treatment agent removes the solid types suspended matters such as base fabric fine, soft fur, the silt to fall off, mitigates the load of subsequent biochemical processing;It can also be with Using the Formose Reaction of chemical treatments, such as methanol.Above-mentioned advanced oxidation mode can be electrocatalytic oxidation, Fenton Oxidation and ozone oxidation etc..
Waste water after pretreatment, into anaerobic reaction processing is carried out in anaerobic reation pool, anaerobic reaction is divided into hydrolysis rank Section, acidification stage produce acetic acid stage and methane phase stage, and complicated macromolecular is passed through tentatively in waste water, organic matter drop Solution is transformed into the simple small organic molecule of structure, and BOD/COD value improves, and is readily biodegradable them, is subsequent aerobic life Object degradation provides guarantee;Then, further biochemical treatment is carried out to waste water using Aerobic Process for Treatment, to reach efficient process Effect, finally, to ensure that effluent quality carries out deeper processing to waste water using advanced oxidation processes.
It is worth noting that inventor draws a conclusion by repetition test, for polyurethane waste water, as COD < in waste water When 6000mg/L, this waste water BOD/COD value is generally 0.3~0.5, good biodegradability;As COD < 6000mg/L in waste water When, waste water BOD/COD value generally can be lower than 0.3, influence Biochemical Treatment;Simultaneously it is considered that itself water of polyurethane waste water Volume production go out, change of water quality fluctuate big feature, be provided with two or more anaerobic ponds, when anaerobic reaction water inlet in COD content compared with Anaerobic pond concatenated form is selected when height is more than 6000mg/L, biochemical treatment time of the waste water in each anaerobic pond is constant (most More 48h), but the time of biochemical treatment can be extended by the series connection of multiple anaerobic ponds, it thus can be to avoid in an anaerobism Extend the biochemical treatment time (if it exceeds COD concentration 6000mg/ in waste water to obtain preferable treatment effect in reaction tank L, in order to obtain preferable treatment effect, the general anaerobic biochemical treatment time can be long, and approximately 4 days or so), and then cause Sludge age is elongated, and sludge excessive oxidation causes sludge aging;The macromolecular substances that first anaerobic pond is not switched on are at second A new anaerobic biochemical reaction is carried out in anaerobic pond, its macromolecular is opened;When COD content cannot surpass in anaerobic reaction water inlet When crossing 6000mg/L, selects the mode of anaerobic pond parallel connection to handle waste water, water process amount not only can be improved, but also can be improved Treatment effeciency.
Under normal circumstances, two anaerobic pond series/parallels can meet to a certain extent relevant treatment and require, certainly, If the special such as COD excessive concentration of situation, waste water water are excessive, that can increase accordingly the number of anaerobic pond.
Specifically, the processing method of above-mentioned kind of polyurethane production waste water, comprising the following steps:
Step 1: the waste water of collection is sent into first Formose Reaction tank by Wastewater Pretreatment, carries out the glycan processing of methanol;
Step 2: by glycan treated water outlet be sent into conditioning tank, while be added other low concentration wastewaters carry out water quality tune Section, and the pH of water body is adjusted as alkalinity;
Step 3: by the water outlet after conciliation water quality, it is sent into anaerobic pond, carries out the Anaerobic Treatment of microorganism;
Step 4: by the water outlet after Anaerobic Treatment, it is sent into aerobic tank, carries out the Aerobic Process for Treatment of microorganism;
Step 5: by the water outlet after Aerobic Process for Treatment, it is sent into coagulative precipitation tank, carries out coagulating kinetics;
Step 6: by the water outlet after coagulating kinetics, it is sent into ozone tower, carries out oxidation processes.
Carrying out pretreatment to waste water using Formose Reaction has following two points benefit: first: Formose Reaction generates formose, And formose is easier to biological decomposition;Second, the glycan of formation can provide carbon source for anaerobic reaction, realize and recycle.
Preferably, in the step 1: basic catalyst being added in water body, adjusts pH value, is heated to, carries out formaldehyde Formose Reaction;PH value is preferably adjusted to 10~13,60~90 DEG C is heated to, carries out the Formose Reaction of formaldehyde.
Preferably, in the step 2, adjusting water body is to be in neutrality alkalinity, and pH value is preferably 7~9.
Preferably, in the step 3, if there are two anaerobic ponds, described two anaerobic ponds can be with the work of serial or parallel connection Make mode to handle the water outlet after water quality adjustment;The single anaerobic pond to waste water carry out Anaerobic Treatment time be 12~ 48h。
Preferably, as COD concentration >=6000mg/L in the water outlet after water quality adjustment, described two anaerobic ponds are with concatenated Form handles the water outlet after water quality adjustment;As COD concentration < 6000mg/L in the water outlet after water quality adjustment, described two A anaerobic pond is handled the water outlet after water quality adjustment in form in parallel.
Preferably, in the step 5, coagulating sedimentation agent be one of aluminium system, iron series or ferro-aluminum system inorganic coagulant or A variety of, on the basis of volume of intaking, dosage is 80~150mg/L.
Preferably, it in the step 6, is added in water outlet into hydrogen peroxide and catalyst after coagulating kinetics, and lead to Enter ozone;On the basis of volume of intaking, the addition volume ratio of the hydrogen peroxide is 0~1%, the addition volume ratio of the catalyst It is 20%, the concentration that is passed through of the ozone is 4.0~6.0mg/min.The zoneofoxidation hydraulic detention time is 10~30min.
Preferably, the catalyst is one or more of titanium dioxide, manganese dioxide and aluminium oxide catalyst.
Concentration of formaldehyde is 4000~10000mg/L in the polyurethane waste water not carried out before any processing, and COD concentration is 10000~60000mg/L, ammonia nitrogen concentration are 2000~7000mg/L.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) organic according to polyether polyol, formaldehyde, melamine, urea and dicyandiamide etc. is mainly contained in production waste water The characteristics of pollutant, uses the pretreatment mode that low energy consumption, added amount of chemical is few to production waste water to improve the biochemical of waste water Property, it uses and formaldehyde is catalytically conveted to carbohydrate admixture using calcium hydroxide as the Formose Reaction of catalyst, processed waste water can be made Biodegradability enhancing, be convenient for subsequent biochemical treatment;
(2) simultaneously it is considered that polyurethane waste water itself water output, change of water quality fluctuate big feature, there are two settings Or multiple anaerobic ponds, when in anaerobic reaction water inlet COD content it is higher more than 6000mg/L when select the concatenated form of anaerobic pond, it is useless Biochemical treatment time of the water in each anaerobic pond is constant (most 48h), but can extend life by the series connection of multiple anaerobic ponds The time for changing processing, thus it can extend biochemistry to avoid in an anaerobic reation pool in order to obtain preferable treatment effect Handle the time;COD content in waste water is if it exceeds 6000mg/L, in order to obtain preferable treatment effect, at general anaerobic biological Managing the time can be long, approximately 4d or so), and then cause sludge age elongated, sludge excessive oxidation causes sludge aging;It will The macromolecular substances that first anaerobic pond is not switched on carry out a new anaerobic biochemical reaction in second anaerobic pond, it is big Molecule is opened;When COD content is no more than 6000mg/L in anaerobic reaction water inlet, the mode of selection anaerobic pond parallel connection carries out waste water Processing not only can be improved water process amount, but also improve treatment effeciency;
(3) according to still making that adapter tube standard cannot be reached containing some intractable small organic molecules in bio-chemical effluent, Advanced treating is carried out to biochemical tail water using catalytic ozonation, catalytic ozonation has some small-molecule substances good Removal effect, and it is swift in response, process is simple, does not have secondary pollution problem.
Detailed description of the invention
Fig. 1 is the process flow diagram of wastewater treatment of the present invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Firstly the need of explanation, other described waste water refer to:
Initial rainwater: due to rainfall initial stage, it is useless that rainwater has dissolved a large amount of sour gas in air, vehicle exhaust, factory The pollution gas such as gas, behind ground of landing, and due to washing away roofing, asphalt concrete road etc., so that containing in early period rainwater A large amount of polluter, early period, the pollution level of rainwater was higher, or even the pollution level beyond ordinary municipal sewage, rarely had at present The effective treating method of initial rainwater is usually allowed to be discharged into sewer.Such sewage mainly contain a small amount of grease, formaldehyde, Urea, polyether polyol etc.;
Sanitary sewage: a large amount of sanitary sewage complicated component only has by the ability that special sewage treatment plant is handled Limit, sanitary sewage described herein is mainly excrement, bath water, washing water and food and drink water etc.;Such sewage mainly contain cellulose, Starch, carbohydrate and fat protein etc. further include the inorganic salinity such as some chlorides, phosphorus;
Other waste water: in production the waters such as some vacuum pump waste water, equipment, ground flushing water and exhaust-gas treatment waste water it is big, Complicated component, biodegradability are higher;Such waste water mainly contains the organic matters such as a small amount of amine organic matter, formaldehyde, urea.
Embodiment 1
A kind of processing method of polyurethane production waste water is present embodiments provided, has carried out high-concentration formaldehyde in this method Removal, the process object is the incombustible polyether polyol polymer project waste water of Jiangxi polyurethane enterprise, of the invention Process flow is as shown in Figure 1, each component content of waste water sample is as shown in table 1 before and after the processing.
1 wastewater treatment pollutant concentration of table
Produce workshop section's wastewater treatment: including first Formose Reaction-biochemical reaction-catalytic ozonation reaction treatment, the processing Process specific steps are as follows:
Step 1: being collected separately collecting pit for production waste water, is promoted after water, water quality adjustment and gravity stream enters to be equipped with Aerator and mud discharging device biology condensation reaction device, aeration replace stirring, calcium hydroxide are added thereto, at 70 DEG C of constant temperature Lower stirring 40min.
Above-mentioned water outlet is passed through collecting pit, pH to 11 is adjusted with liquid alkaline, is heated to 70 DEG C of progress Formose Reactions.Wherein initial stage Rainwater refers to that ground 10~15mm thickness has formed the precipitation of rainwash, and other concentration waste water COD concentration exist in the present embodiment 1000mg/L。
Step 2: and mix other waste water vacuum pump waste water, equipment, ground flushing water, sanitary sewage, exhaust-gas treatment waste water Water, water quality adjustment are carried out in collecting pit, the pH that regulating step one is discharged is 8.
Step 3: the water outlet of step 2 is introduced into anaerobic biological pond by water leading cylinder and carries out anaerobic biochemical reaction;Because of reality Variation water quality is larger in production, and water quality detection equipment is equipped in anaerobic pond, as pretreated waste water COD >=6000mg/L, The series connection of two anaerobic ponds carries out, when pretreated waste water COD < 6000mg/L, by two anaerobic ponds be switched to parallel form into Row work.
Step 4: anaerobic biological water outlet enters aerobic tank and carries out aerobic biochemical, wherein the hydraulic retention of anaerobic biochemical reaction Time is that for 24 hours, the hydraulic detention time of aerobic biochemical reaction is 5d.
Step 5: the water outlet of step 4 aerobic biochemical is passed through primary sedimentation tank, primary sedimentation tank water outlet enters coagulative precipitation tank, is added PAC, PAM carry out flocculation sedimentation (100mg/L), and after precipitation and separation, top clarified solution enters coagulative precipitation tank, and lower part concentration is dirty Mud passes back into anaerobic pond, reflux ratio 0.5:1.
Step 6: precipitating water outlet enters ozone tower by elevator pump and carries out catalytic ozonation reaction, and caltalyst is added Product is passed through speed 5.0mg/min than the catalyst titanium dioxide for 20%, ozone, adds 0.5% hydrogen peroxide, reacts 30min.
Catalytic ozonation treated water outlet access garden pipe network is to being uniformly processed;The garden adapter tube Standard is water outlet COD value≤500mg/L in garden pipe network, and concentration of formaldehyde≤45mg/L, ammonia nitrogen concentration≤45mg/L, total salt is dense Degree≤5000mg/L.
The sludge generated in wastewater treatment process carries out filters pressing by plate and frame filter press, send to fixed-end forces center.
Embodiment 2
Workshop section's wastewater treatment is produced in the present embodiment: at first Formose Reaction-biochemical reaction-catalytic ozonation reaction Reason, the treatment process specific steps are as follows:
Collecting pit is collected separately by waste water is produced in step 1, is promoted after water, water quality adjustment and gravity stream enters to be equipped with Aerator and mud discharging device biology condensation reaction device, aeration replace stirring, basic catalyst are added thereto, in constant temperature 90 40min is stirred at DEG C.
Above-mentioned water outlet is passed through collecting pit, pH to 13 is adjusted with calcium hydroxide, is heated to 90 DEG C of progress Formose Reactions.
Step 2: it is useless that other waste water vacuum pump waste water, equipment, ground flushing water, sanitary sewage, exhaust-gas treatment is added in mixing Water and initial rainwater, carry out water, water quality adjustment in collecting pit, and the pH that regulating step one is discharged is 9.
Step 3: the water outlet of step 2 is introduced into anaerobic biological pond by water leading cylinder and carries out anaerobic biochemical reaction;Because of reality Variation water quality is larger in production, is monitored at any time to water quality, and in pretreated waste water when COD >=6000mg/L, two are detested The series connection of oxygen pond carries out, and as anaerobism influent COD < 6000mg/L, two anaerobic pond parallel connections are carried out.
Step 4: anaerobic biological water outlet enters aerobic tank and carries out aerobic biochemical, wherein the hydraulic retention of anaerobic biochemical reaction Time is 48h, and the hydraulic detention time of aerobic biochemical reaction is 5d.
Step 5: the water outlet of step 4 aerobic biochemical is passed through primary sedimentation tank, primary sedimentation tank water outlet enters coagulative precipitation tank, is added PAC, PAM (adding concentration 80mg/L) carry out flocculation sedimentation, and after precipitation and separation, top clarified solution enters coagulative precipitation tank, under Portion's thickened sludge passes back into anaerobic pond, reflux ratio 0.5:1.
Step 6: precipitating water outlet enters ozone tower by elevator pump and carries out catalytic ozonation reaction, and volume ratio is added and is The concentration that is passed through of 20% catalyst manganese dioxide, ozone is 4.0mg/min, adds 0.5% hydrogen peroxide, reacts 10min.It is smelly Water outlet access garden pipe network after oxygen catalytic oxidation treatment is to be uniformly processed;The standard of the garden adapter tube is garden Water outlet COD value≤500mg/L in pipe network, concentration of formaldehyde≤45mg/L, ammonia nitrogen concentration≤45mg/L, total salt concentration≤ 5000mg/L.Each component content of waste water sample is as shown in table 2 before and after the processing.
The sludge generated in wastewater treatment process carries out filters pressing by plate and frame filter press, send to fixed-end forces center.
2 wastewater treatment pollutant concentration of table
Embodiment 3
Workshop section's wastewater treatment is produced in the present embodiment: at first Formose Reaction-biochemical reaction-catalytic ozonation reaction Reason, the treatment process specific steps are as follows:
Collecting pit is collected separately by waste water is produced in step 1, is promoted after water, water quality adjustment and gravity stream enters to be equipped with Aerator and mud discharging device biology condensation reaction device, aeration replace stirring, basic catalyst are added thereto, in constant temperature 60 40min is stirred at DEG C.
Above-mentioned water outlet is passed through collecting pit, pH to 10 is adjusted with calcium hydroxide, is heated to 60 DEG C of progress Formose Reactions.
Step 2: it is useless that other waste water vacuum pump waste water, equipment, ground flushing water, sanitary sewage, exhaust-gas treatment is added in mixing Water and initial rainwater, carry out water, water quality adjustment in collecting pit, and the pH that regulating step one is discharged is 7.
The water outlet of step 2 is introduced anaerobic biological pond by water leading cylinder and carries out anaerobic biochemical reaction by step 3;Because of water quality Content of organics is lower, so COD concentration < 6000mg/L in pretreated waste water, two anaerobic pond parallel connections are carried out.
Step 4: anaerobic biological water outlet enters aerobic tank and carries out aerobic biochemical, wherein the hydraulic retention of anaerobic biochemical reaction Time is 12h, and the hydraulic detention time of aerobic biochemical reaction is 5d.
Step 5: the water outlet of step 4 aerobic biochemical is passed through primary sedimentation tank, primary sedimentation tank water outlet enters coagulative precipitation tank, is added PAC, PAM (adding concentration 150mg/L) carry out flocculation sedimentation, and after precipitation and separation, top clarified solution enters coagulative precipitation tank, under Portion's thickened sludge passes back into anaerobic pond, reflux ratio 0.5:1.
Step 6: precipitating water outlet enters ozone tower by elevator pump and carries out catalytic ozonation reaction, and caltalyst is added For product than the alumina catalyst for being 20%, the concentration that is passed through of ozone is 6.0mg/min, adds 0.5% hydrogen peroxide, reacts 30min.Catalytic ozonation treated water outlet access garden pipe network is to being uniformly processed;The mark of the garden adapter tube Standard is water outlet COD value≤500mg/L in garden pipe network, concentration of formaldehyde≤45mg/L, ammonia nitrogen concentration≤45mg/L, total salt concentration ≤5000mg/L.Each component content of waste water sample is as shown in table 3 before and after the processing.
The sludge generated in wastewater treatment process carries out filters pressing by plate and frame filter press, send to fixed-end forces center.
3 wastewater treatment pollutant concentration of table
Embodiment 4
Substantially with embodiment 1, difference place is only that the present embodiment:
Step 4: by the water outlet after Anaerobic Treatment, it is sent into aerobic tank, carries out the Aerobic Process for Treatment of microorganism;Step 4 it is good Complete MBR equipment is added in oxygen pond to handle the water outlet after Anaerobic Treatment.Ozone catalytic is substituted using MVR biology film process Oxidation processes.
Remaining is with embodiment 1, and each component content of waste water sample is as shown in table 4 before and after the processing.
4 wastewater treatment pollutant concentration of table
Although film easily blocks it should be noted that few using MVR biological membrane wastewater treatment occupied area, and it is right Polyurethane production wastewater through organic matter removal rate is significantly lower than catalytic ozonation processing.
Embodiment 5
Substantially with embodiment 1, difference place is only that the present embodiment:
Step 5: by the water outlet after Aerobic Process for Treatment, it is sent into coagulative precipitation tank, carries out coagulating kinetics;Through precipitation and separation Afterwards, lower part thickened sludge passes back into anaerobic pond, reflux ratio 0.5:1, and top clarified solution enters conditioning tank, adjusts pH3, be discharged into Enter micro cell 3h, iron carbon dust dosage is the 0.5% of wastewater volume.
Step 6: by the water outlet after coagulating kinetics, it is sent into Fenton oxidation pond, carries out oxidation processes.Water outlet enters fragrant Pause oxidation pond 3h, and hydrogen peroxide dosage is the 0.5% of wastewater volume, and water outlet enters neutralization precipitation pond, and adjusting pH is 7, is added PAC, PAM carry out flocculation sedimentation, and precipitating water outlet enters garden sewage network.Each component content of waste water sample such as table 5 before and after the processing It is shown.
5 wastewater treatment pollutant concentration of table
It should be noted that a large amount of iron cements can be generated using light electrolysis-Fenton oxidation processing, need as fixed-end forces, And to polyurethane production wastewater through organic matter removal rate significantly lower than catalytic ozonation processing.
Comparative example 1
Substantially with embodiment 1, difference place is only that this comparative example:
Only with an anaerobic reation pool, anaerobic pond hydraulic detention time is for 24 hours, to handle waste water;
Other are the same as embodiment 1.Embodiment 1 is significantly lower than to polyurethane production wastewater through organic matter removal rate.Specific water outlet water Matter is as shown in table 6.
6 wastewater treatment pollutant concentration of table
Comparative example 2
Substantially with embodiment 1, difference place is only that this comparative example:
Only with an anaerobic reation pool, anaerobic pond hydraulic detention time is 48h, carries out handling other same embodiments to waste water 1.Embodiment 1 is significantly lower than to polyurethane production wastewater through organic matter removal rate.Specific effluent quality is as shown in table 7.
7 wastewater treatment pollutant concentration of table
The foregoing is merely highly preferred embodiment of the present invention, are not intended to restrict the invention.It is all in principle of the invention and Any modification, equivalent substitution, improvement and etc. done within spirit, should be included within the scope of the present invention.

Claims (10)

1. a kind of processing method of polyurethane production waste water, it is characterised in that: pretreated waste water is sent into anaerobic pond, is carried out The Anaerobic Treatment of microorganism;Aerobic Process for Treatment, the advanced oxidation processing of microorganism are successively carried out to the waste water after Anaerobic Treatment;
The anaerobic pond at least two, as COD concentration >=6000mg/L in pretreated waste water, anaerobic pond is with concatenated Form work;As COD concentration < 6000mg/L in pretreated waste water, anaerobic pond works in form in parallel.
2. the processing method of polyurethane production waste water according to claim 1, it is characterised in that: specifically include following step It is rapid:
Step 1: the waste water of collection is sent into first Formose Reaction tank by Wastewater Pretreatment, carries out the glycan processing of methanol;
Step 2: by glycan treated water outlet be sent into conditioning tank, while be added other low concentration wastewaters carry out water quality adjustment, and The pH for adjusting water body is alkalinity;
Step 3: by the water outlet after conciliation water quality, it is sent into anaerobic pond, carries out the Anaerobic Treatment of microorganism;
Step 4: by the water outlet after Anaerobic Treatment, it is sent into aerobic tank, carries out the Aerobic Process for Treatment of microorganism;
Step 5: by the water outlet after Aerobic Process for Treatment, it is sent into coagulative precipitation tank, carries out coagulating kinetics;
Step 6: by the water outlet after coagulating kinetics, it is sent into ozone tower, carries out oxidation processes.
3. the processing method of polyurethane production waste water according to claim 2, it is characterised in that: in the step 1: Basic catalyst is added in water body, adjusts pH, heating carries out the Formose Reaction of formaldehyde.
4. the processing method of polyurethane production waste water according to claim 3, it is characterised in that: in the step 2, adjust Water-saving body is neutral or alkalinity.
5. the processing method of polyurethane production waste water according to claim 3, it is characterised in that: in the step 3, if There are two anaerobic pond, two anaerobic ponds can be handled the water outlet after water quality adjustment with the working method of serial or parallel connection.
6. the processing method of polyurethane production waste water according to claim 5, it is characterised in that: the anaerobic pond is to waste water Anaerobic Treatment time be 12~48h.
7. the processing method of polyurethane production waste water according to claim 3, it is characterised in that: in the step 5, mix Solidifying precipitating reagent is one of aluminium system, iron series or ferro-aluminum system inorganic coagulant or a variety of.
8. the processing method of polyurethane production waste water according to claim 3, it is characterised in that: in the step 6, It is added in water outlet into hydrogen peroxide and catalyst after coagulating kinetics, and is passed through ozone.
9. the processing method of polyurethane production waste water according to claim 8, it is characterised in that: the catalyst is dioxy Change one or more of titanium, manganese dioxide and aluminium oxide catalyst.
10. the processing method of polyurethane production waste water according to claim 1 or 2, it is characterised in that: the polyurethane is raw Production formaldehyde in waste water concentration be 4000~10000mg/L, COD concentration be 10000~60000mg/L, ammonia nitrogen concentration be 2000~ 7000mg/L。
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