CN104591474A - Unsaturated polyester wastewater treatment and reuse method - Google Patents
Unsaturated polyester wastewater treatment and reuse method Download PDFInfo
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- CN104591474A CN104591474A CN201310529691.XA CN201310529691A CN104591474A CN 104591474 A CN104591474 A CN 104591474A CN 201310529691 A CN201310529691 A CN 201310529691A CN 104591474 A CN104591474 A CN 104591474A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2103/38—Polymers
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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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1263—Sequencing batch reactors [SBR]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Activated Sludge Processes (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses an unsaturated polyester wastewater treatment and reuse method. The method comprises the following steps: rectifying unsaturated polyester wastewater, concentrating and recovering material components with a high boiling point, and condensing material components with a lower boiling point to form organic wastewater; hydrolyzing the organic wastewater formed after condensation; and carrying out secondary aerobic biochemical treatment on the hydrolyzed organic wastewater. The method can thoroughly solve the pollution of the unsaturated polyester wastewater, makes the wastewater harmless, and has the characteristics of stable running of a biochemical treatment system, good biochemical treatment effect, high organic material recovery rate, treatment of a waste with another, small occupied land, economy and practicality, and water obtained after the treatment can be used as technologic supplied water or dilution water.
Description
Technical field
The present invention relates to a kind of process and reuse method of unsaturated polyester waste water, particularly relate to the process of the polyester waste water that the polycondensation stage in a kind of unsaturated polyester resin (UPR) production process produces, process water outlet can be used as technique feedwater or dilution water.
Background technology
Unsaturated polyester resin (UPR) by diprotic acid, dibasic alcohol, chemical polycondensation occurs and obtains, high density unsaturated polyester waste water is mainly at the generation water of alcohol acid anhydride in polycondensation, organic content, up to about 15 wt%, is mainly the intermediate product such as the reaction masses such as ethylene glycol, propylene glycol, glycol ether, phthalic anhydride, cis-butenedioic anhydride and some low molecule polyester monocases.
The method process polyester waste water that early stage polyester enterprise many employings hot Media Oven burns, but not easily balance due to system pressure, there is serious safety problem, the method does not re-use.The cost of the method process polyester waste water adopting hot Media Oven to burn is higher, and useful resources a large amount of in waste water can not be recycled, and causes the huge wasting of resources.CN102285697A discloses a kind of technique of unsaturated polyester resin industry waste water reclaiming, adopts azeotropic distillation separation and recovery technology by the organism Resource recovery in waste water, and the waste water after azeotropy rectification column is separated enters biochemical system.Although the method decreases the concentration of wastewater through organic matter, reduce follow-up intractability, entrainer and wastewater volume are than being 1.5:1, and usage quantity is huge, does not have actual operability.In addition, the waste component after separation is single, and be mainly and produce several organic compound such as raw material used and by product, lack required nitrogen, phosphoric and the inorganic metal element of microorganism growth, Biochemical Treatment is bad.
Because Wastewater by Biochemical Treatment has, efficiency is high, cost is low, reduced investment, simple operation and other advantages, is the prefered method of Industrial Wastewater Treatment.But, and unsaturated polyester waste water that organic concentration very high single for specific examples of such components, biochemical process is adopted to carry out processing and only rely on mixing sanitary sewage to come supplementary nitrogen, phosphorus and inorganic salt be far from being enough, extra people is comprehensive not for adding medicament, and the working cost of wastewater treatment can be increased, uneconomical practicality.In addition, if biological treatment system long-term lacking Cucumber, sludge character will be caused to change, cause stickiness to expand, a series of operation problems such as shock-resistance is poor.
Summary of the invention
For the feature of the deficiencies in the prior art and unsaturated polyester waste water, the invention provides a kind of process and reuse method of unsaturated polyester waste water.The method thoroughly can solve the pollution of unsaturated polyester waste water, make it innoxious, have that biochemical treatment system operates steadily, Biochemical Treatment is good, the organic materials rate of recovery is high, the treatment of wastes with processes of wastes against one another, take up an area the features such as little, economical and practical, process water outlet can be used as technique feedwater or dilution water.
The process of unsaturated polyester waste water of the present invention and reuse method, comprise following content: first rectification process unsaturated polyester waste water, and carry out concentration and recovery to high boiling material component, lower boiling material component is formed with organic waste water after condensation; Then the organic waste water formed after condensation is hydrolyzed process; Organic waste water after finally adopting secondary to support well biochemical treatment hydrolysis.
In the inventive method, described unsaturated polyester waste water is from the polycondensation stage in unsaturated polyester resin production process, organic concentration is about 10 wt% ~ 20 wt%, is mainly the mixed solution of the intermediate product such as the reaction masses such as ethylene glycol, propylene glycol, glycol ether, phthalic anhydride, cis-butenedioic anhydride and some low molecule polyester monocases.
In the inventive method, rectification process condition is for controlling temperature inside rectifying tower 95 DEG C ~ 110 DEG C, and overhead condensation liquid temp is 75 ~ 80 DEG C, and the total reflux time is about 1 ~ 2 h, and distillate volume accounts for 80 ~ 85% of cumulative volume, and liquid-phase reflux ratio is 3 ~ 5:1.Steam with water vapour lower than the organism of 100 DEG C, condensation is formed with organic waste water.
In the inventive method, the organic waste water hydrolysis treatment formed after condensation is carried out in effectively hydrolyzing reactor.Arrange lightweight suspension ball filler in effectively hydrolyzing reactor, packing ratio is 30% ~ 50%.The internal temperature of controlled hydrolysis reactor is 55 ~ 60 DEG C, volumetric loading 5 ~ 10 kgCOD/ (m
3d), hydraulic detention time is 20 ~ 40 h.Hydrolysis treatment utilizes the waste heat of rectification process and using the water outlet after biochemical treatment as dilution water, reflux ratio is 1 ~ 5:1.The hydrolysis treatment effect of the organic waste water formed after adopting the water outlet after biochemical treatment can improve condensation as dilution water.
In the inventive method, the organic waste water formed after solidifying is before being hydrolyzed, and preferably in organic waste water, add appropriate human and animal excreta, with the volumeter of organic waste water, the dosage of ight soil is 5 ~ 40 g/L.Human feces and organic waste water are after hydrolysis treatment, be conducive to human feces in biochemical treatment process, resolve into material that is nitrogenous, phosphorous and trace metal, be used for supplementary nitrogen, phosphoric and other trace metals lacked, normal active and improve the efficiently and smoothly operated of biochemical system further to maintain microorganism.
In the inventive method, one-level aerobic treatment selects high loading sequencing batch biofilm reactor SBBR.Its volumetric loading 5 ~ 10 kgCOD/ (m
3d), aeration time is 10 ~ 20 h.Reactor built-in flow model suspension ball filler, packing ratio is 30% ~ 75%.Microorganic adhesion biofilm growth formation on filler in SBBR reactor, the microbial film that periodic exhaustion comes off and adsorbed a large amount of organic active sludge.SBBR reactor is provided with strengthening sludge drainage system, is regularly discharged by active sludge, promotes biomembranous quick growth.
In the inventive method, secondary aerobic treatment selects MBR membrane bioreactor.Control MBR reactor volume load is 2.0 ~ 5.0 kgCOD/ (m
3d), hydraulic detention time is 5 ~ 10 h, and sludge concentration is 5.0 ~ 8.0 g/L.Adopt Polyolefin Hollow Fiber assembly, run membrane flux 0.2 ~ 0.4 m
3/ (m
2d), operating pressure scope-5 cm Hg ~-40 cm Hg.The effect that MBR reactor utilizes membrane micropore to retain, is trapped in inside reactor by active sludge, and its process water outlet clear, can meet the requirement of technique feedwater or dilution water.
Compared with the prior art, the unsaturated polyester method of wastewater treatment that the inventive method provides can obtain the materials such as highly purified ethylene glycol, propylene glycol, phthalic acid, phthalic anhydride, cis-butenedioic anhydride by rectification process, the waste water that condensation is formed directly does not carry out biochemical treatment but after pyrohydrolysis, adopts two-stage aerobic biochemical treatment, can significantly improve the stability of Biochemical Treatment and maintenance biochemical system.The method can reclaim a large amount of useful resources from unsaturated polyester waste water, turns waste into wealth, and can realize again unsaturated polyester waste water recycling as technique feedwater or dilution water, have good economic benefit and environmental benefit.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of a kind of concrete unsaturated polyester wastewater treatment and reuse of the present invention;
Wherein: 1, rectifying tower, 2, material storage tank, 3, condenser, 4, effluent storage tank, 5, equalizing tank, 6, high-temperature hydrolysis device, 7, gas-holder, 8, high loading SBBR reactor, 9, MBR reactor.
Fig. 2 is the concrete structure schematic diagram of a kind of high loading SBBR of the present invention reactor;
Wherein: 10, water-in, 11, sludge bucket, 12, mud discharging mouth, 13, aeration tube, 14, prosopyle, 15, shell, 16, filler, 17, overflow weir, 18, water outlet.
Embodiment
Fig. 1 is a kind of concrete technical process of the present invention: the unsaturated polyester waste water that polycondensation phase produces is introduced into rectifying tower 1, organism in waste water is mainly the reaction masses such as diethylene glycol, ethylene glycol, propylene glycol, phthalic anhydride, cis-butenedioic anhydride, the boiling point of these organism materials is all high than the boiling point of water, liquid phase oily organism is formed in the bottom of rectifying tower 1, recycling after material storage tank 2 is collected.The unsaturated polyester waste water that the steam that rectifying generates forms lower concentration by condenser 3 enters effluent storage tank 4, and the concentration of reflow treatment water outlet dilution influent COD in equalizing tank 5, increase the basicity of waste water, reflux ratio is 1 ~ 5:1.The nutritive elements such as biochemical treatment required nitrogen, phosphorus and trace metal are lacked due to waste water, the ight soil adding people and animals can decompose generation ammonia nitrogen and phosphoric acid salt in biochemical treatment process, other contained trace elements can meet the normal growth requirement of microorganism, strengthen the stability of biochemical system.After equalizing tank 5 fully mixing, waste water enters high-temperature hydrolysis device, the temperature of reactor is 55 ~ 60 DEG C, in waste water, the organism of the difficult degradation such as some lower boiling ester class, hydro carbons and phenols at high temperature can accelerate hydrolysis, form low molecular organic acid, improve the biodegradability of waste water, the anaerobic gas of generation enters gas-holder 7.Water outlet after pyrohydrolysis process enters in high loading SBBR reactor 8 carries out one-level aerobic treatment, because wastewater biodegradability is fine, and the organism that the active sludge quick adsorption of suspension is a large amount of, discharger subsequently.Water outlet after high loading SBBR reactor for treatment enters MBR reactor 9 and carries out further biochemical treatment, and process water outlet meets reuse standard.
Fig. 2 illustrates a kind of concrete structure schematic diagram of high loading SBBR reactor.This reactor is synthetic glass material, the wide * of its long * is high=and 200 mm*200 mm*320 mm, effective volume is 6.5L.Waste water, after pyrohydrolysis, has good biodegradability, is entered by SBBR reactor lower part water-in 10, after the active sludge of suspension growth carries out quick adsorption to it, by outside mud discharging mouth 12 discharger after being collected by the sludge bucket 11 of sludge drainage system immediately.The microbial film be attached on filler 16 is constantly bred, the oxidation operation in water is made to be decomposed into simple inorganics, when reaching certain thickness, owing to can not get enough oxygen in biological membranous layer, change anaerobic digestion into by aerobic decomposition, microorganism is aging gradually to come off from filler 16 surface.Waste water is from bottom to top by suspended sludge bed and filling batch, and microorganism carries out Adsorption and decomposition to the organism in water, and the water outlet after process is discharged by water outlet 18 through overflow weir 17.In aerobic system, there is competitive relation in the microbial film of apposition growth and the active sludge of suspension growth, therefore, quick discharge active sludge both can discharge the suspended sludge having adsorbed large amount of organic, be conducive to again biomembranous quick growth, thus reduce volume and the oxygen-consumption of structures, reduce working cost.
Further illustrate the inventive method and effect below by embodiment, wherein wt% is massfraction.
Embodiment 1
Treatment process of the present invention is adopted to process the unsaturated polyester resins wastewater that polycondensation phase produces.Unsaturated polyester resin is with diethylene glycol, ethylene glycol, propylene glycol, phthalic anhydride, cis-butenedioic anhydride for main material production, and the quantity discharged of polyester waste water is 30 m
3/ d, in polyester waste water, organic content is about 15 wt%, and wherein the content of dibasic alcohol is about 11.2 ~ 11.8 wt%, and the content of phthalic anhydride and cis-butenedioic anhydride is 2.5 ~ 2.7 wt%, and other light constituent organism are 0.3 ~ 1.2 wt%.This covering device runs 3 months continuously, and concrete operational condition and operation treatment effect are in table 1.
table 1 embodiment 1 main processing units and treatment effect
Embodiment 2
Adopt treatment process of the present invention to process the polyester waste water identical with embodiment 1 at different conditions, this covering device runs 3 months continuously, and concrete operational condition and operation treatment effect are in table 2.
table 2 embodiment 2 main processing units and treatment effect
Embodiment 3
According to the ratio of COD:N:P=400:5:1 before the aerobic SBBR process of pyrohydrolysis process rear stage, waste water per ton adds 10g ight soil, and all the other treatment condition are identical with embodiment 1.After device runs 3 months continuously, water outlet COD is 161 mg/L, BOD
5be 28.7 mg/L, ammonia nitrogen 8.5 mg/L, volatile phenol 3.0 mg/L.
Embodiment 4
According to the ratio of COD:N:P=400:5:1, every L waste water adds 0.87g ammonium chloride and 0.2g potassium primary phosphate, and all the other treatment condition are identical with embodiment 2.After device runs 3 months continuously, water outlet COD is 146 mg/L, BOD
5be 38.2 mg/L, ammonia nitrogen 10.1 mg/L, volatile phenol 2.5 mg/L.
comparative example 1
Adopt the polyester waste water that the method process of conventional rectification+two-stage aerobic process is identical, all the other treatment condition are identical with embodiment 4.After device runs 3 months continuously, water outlet COD is 180 mg/L, BOD
5be 96 mg/L, ammonia nitrogen 15.6 mg/L, volatile phenol 9.1 mg/L, cannot meet reusing sewage standard.
Adopt treatment process of the present invention, the most of organism in unsaturated polyester waste water can be made to be recycled utilization, greatly reduce difficulty and the expense of subsequent disposal.Human and animal excreta and reflow treatment water outlet is added to supplement the nutrients material and regulate the pH of water inlet and basicity and pyrohydrolysis process owing to have employed, the waste water that rectifying condensation is formed meets the prerequisite of biochemical treatment, can complete-reclaiming after high loading SBBR and MBR process.
Claims (13)
1. the process of unsaturated polyester waste water and a reuse method, it is characterized in that comprising following content: first rectification process unsaturated polyester waste water, carry out concentration and recovery to high boiling material component, lower boiling material component is formed with organic waste water after condensation; Then the organic waste water formed after condensation is hydrolyzed process; Organic waste water after finally adopting secondary to support well biochemical treatment hydrolysis.
2. method according to claim 1, is characterized in that: described unsaturated polyester waste water is from the polycondensation stage in unsaturated polyester resin production process, and in unsaturated polyester waste water, organic concentration is 10 wt% ~ 20 wt%.
3. method according to claim 1 and 2, is characterized in that: unsaturated polyester waste water is ethylene glycol, propylene glycol, glycol ether, phthalic anhydride, cis-butenedioic anhydride.
4. method according to claim 1, it is characterized in that: rectification process condition is for controlling temperature inside rectifying tower 95 DEG C ~ 110 DEG C, and overhead condensation liquid temp is 75 ~ 80 DEG C, and the total reflux time is about 1 ~ 2 h, distillate volume accounts for 80 ~ 85% of cumulative volume, and liquid-phase reflux ratio is 3 ~ 5:1.
5. method according to claim 1, is characterized in that: arrange lightweight suspension ball filler in hydrolysis reactor, and packing ratio is 30% ~ 50%.
6. method according to claim 1, is characterized in that: the internal temperature of hydrolysis reactor is 55 ~ 60 DEG C, volumetric loading 5 ~ 10 kgCOD/ (m
3d), hydraulic detention time is 20 ~ 40 h.
7. method according to claim 1, is characterized in that: hydrolysis treatment utilizes the water outlet after biochemical treatment as dilution water, and reflux ratio is 1 ~ 5:1.
8. method according to claim 1, is characterized in that: the organic waste water formed after solidifying is before being hydrolyzed, and in organic waste water, add human and animal excreta, with the volumeter of organic waste water, the dosage of ight soil is 5 ~ 40 g/L.
9. method according to claim 1, is characterized in that: one-level aerobic treatment selects high loading sequencing batch biofilm reactor (SBBR), volumetric loading 5 ~ 10 kgCOD/ (m
3d), aeration time is 10 ~ 20 h.
10. method according to claim 9, is characterized in that: SBBR reactor built-in flow model suspension ball filler, packing ratio is 30% ~ 75%.
11. methods according to claim 1, is characterized in that: secondary aerobic treatment selects MBR membrane bioreactor.
12. methods according to claim 11, is characterized in that: MBR reactor volume load is 2.0 ~ 5.0 kgCOD/ (m
3d), hydraulic detention time is 5 ~ 10 h, and sludge concentration is 5.0 ~ 8.0 g/L.
13. methods according to claim 11 or 12, is characterized in that: MBR reactor adopts Polyolefin Hollow Fiber assembly, run membrane flux 0.2 ~ 0.4 m
3/ (m
2d), operating pressure scope-5 cm Hg ~-40 cm Hg.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310529691.XA CN104591474A (en) | 2013-11-01 | 2013-11-01 | Unsaturated polyester wastewater treatment and reuse method |
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| CN201310529691.XA CN104591474A (en) | 2013-11-01 | 2013-11-01 | Unsaturated polyester wastewater treatment and reuse method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565616A (en) * | 2016-03-04 | 2016-05-11 | 苏州苏沃特环境科技有限公司 | Technology system for treatment and reuse of polyester fiber wastewater |
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2013
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| CN1974508A (en) * | 2006-12-07 | 2007-06-06 | 浙江大学 | Process of recovering glycol and acetaldehyde from waste polyester water |
| JP2010005500A (en) * | 2008-06-24 | 2010-01-14 | Nbl Kk | Water percolation pipe and its use |
| CN102126926A (en) * | 2010-12-23 | 2011-07-20 | 上海聚友化工有限公司 | Method for recycling ethylene glycol and acetaldehyde from polyester waste water |
| CN202390292U (en) * | 2011-12-21 | 2012-08-22 | 江阴明大化工有限公司 | Aeration type high-concentration unsaturated polyester process waste water high-activity processing device |
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| CN105565616A (en) * | 2016-03-04 | 2016-05-11 | 苏州苏沃特环境科技有限公司 | Technology system for treatment and reuse of polyester fiber wastewater |
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