CN103288291B - Polyester wastewater treatment method - Google Patents
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- CN103288291B CN103288291B CN201310165017.8A CN201310165017A CN103288291B CN 103288291 B CN103288291 B CN 103288291B CN 201310165017 A CN201310165017 A CN 201310165017A CN 103288291 B CN103288291 B CN 103288291B
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Abstract
The invention relates to a polyether wastewater treatment method for mainly solving the problem of the prior art that the polyester wastewater with low COD (Chemical Oxygen Demand) and high BOD (Biochemical Oxygen Demand)/COD cannot be discharged up to the standard, the treatment system takes up large space and the treatment efficiency is low. The polyether wastewater treatment method disclosed by the invention discharges the polyester-containing wastewater of which the BOD/COD is not larger than 0.1 mg/L and the COD is not smaller than 1500 mg/L after treatment of a regulation tank, a biochemical tank, an activated sludge tank and a secondary sedimentation tank, so that the COD of the discharged wastewater is not larger than 250 mg/L, the content SS of suspended solids is not larger than 250 mg/L, and the content of NH3-N is not larger than 7 mg/L, wherein the biochemical tank is internally provided with a material for increasing the contact area between bacteria and the polyester-containing wastewater; the biochemical aeration pressure is 0.6-1.2 kgf/m<2>; the MH3-N content in the biochemical tank is controlled to be not larger than 25 mg/L, the oxygen content DO in the water is within 1.0-5.0 mg/L, so the technical scheme well solves the problem and can be used in industrial production of polyester wastewater treatment.
Description
Technical field
The present invention relates to a kind for the treatment of process of polyethers waste water.
Background technology
Polyether glycol (PPG) is the important source material of synthetic rigid urethane foam, also can be used as paper industry defoamer, crude oil demulsifier, lubricant, quenching medium, emulsion foaming agent, rubber lubricant and dedicated solvent etc.It is raw material that polyethers be take glycerol, vinylbenzene, vinyl cyanide, oxyethane, propylene oxide etc., in its production process, can produce a large amount of high density polyethers waste water.In these waste water, not only contain a large amount of low molecular polymerization single polymerization monomers, but also contain a large amount of polyphosphazene polymer ethoxylated polyhydric alcohols.Because polyether glycol itself and most of raw materials for production thereof are all the organism of difficult degradation, cause that in factory effluent, organic constituents is complicated, concentration is high, strong toxicity, biodegradability be poor, waste water is difficult to qualified discharge.
Polyether glycol factory effluent mainly comes from de-low molecule waste water, flushing waste water, vacuum pump system draining and the sanitary sewage of PPG synthesizing section, and the principal pollutant of waste water are COD.Existing treatment process mainly adopts physico-chemical pretreatment to add the technological line of follow-up biochemical treatment.Document " Inner Mongol environmental science; 2007.4 " discloses the method that a kind of coagulating sedimentation-acidication-biological adsorption-UBF-catalytic oxidation one oxidation ditch-absorbing process is processed polyether glycol waste water, utilize coagulating sedimentation to carry out pre-treatment polyether glycol waste water, and then further process by the processing method of absorption.Document " Treatment of Industrial Water, 2006.4 " discloses a kind of Design of polyhydric alcohol conjugated polyether wastewater treatment engineering, by the method for heating, removes the larger molecular organics in polyether glycol waste water.But these two kinds of pretreatment processs are owing to lacking specific aim, to COD clearance only 5-10% less than, thereby cause technical process complicated operation, processing cost high.Document CN102372402A discloses a kind for the treatment of process of polyether glycol waste water.Its concrete steps are: (1) regulates polyether glycol waste water ph by acid solution is 2-6, then carries out pre-treatment, and after control pre-treatment, the B/C of waste water is than being 0.42-0.65; (2) with alkaline solution, regulate after the pH value of step (1) pretreated waste water is 7-8, enter in the biochemistry strengthening pond that adds biological reinforced mud, control dissolved oxygen concentration, pH value, ORP value and hydraulic detention time in biochemical strengthening pond, and add nitrogen phosphorus nutrition liquid and trace element, stir or plug-flow operation, make this pond mud carry out bioselection; (3) water outlet of processing through biochemical strengthening pond enters preliminary sedimentation tank, and the sludge reflux after mud-water separation acts on biochemical strengthening pond; Supernatant liquor enters Aerobic Pond, carries out aeration operation, controls dissolved oxygen concentration, pH value, ORP value and hydraulic detention time in Aerobic Pond, and adds nitrogen phosphorus nutrition liquid and trace element, carries out wastewater treatment; (4) waste water through aerobic treatment enters second pond, and supernatant liquor is discharged, and sludge reflux enters Aerobic Pond.Document " petrochemical complex environment protection, 2003(26) 3 " discloses a kind of O
1/ A/O
2method is processed the operation method of high density polyethers waste water, the high-concentration waste water of BOD/COD=0.15-0.39 is entered after oil trap oil removing to multistage contact-oxidation pool and carries out the processing of one-level aerobe.In multistage contact-oxidation pool, minute A, B, C are tri-sections, are provided with soft-filler in pond, and filler is fluffy flocculent structure.A section is mainly removed easy biochemical partial organic substances, and B section, the main degraded of C section can biochemical, the slower long-chain larger molecular organicses such as PPG, POP of degradation rate.The object of anoxic section is to carry out acidification hydrolization, and the long-chain macromolecule organic substance decomposing that processing fails to degrade through multistage catalytic oxidation is fragmented into and is easily degraded to small organic molecule, improves the biodegradability of waste water, for follow-up two-stage biological contact oxidation creates conditions.The high concentration water of and anaerobic treatment aerobic through one-level and sewage of low concentration be qualified discharge after the further processing in two-stage biological contact oxidation pond again.But above-mentioned these two kinds of methods are not suitable for the polyethers waste water that COD is high, BOD/COD ratio is low especially, and treatment system occupation of land is many, and processing efficiency is low.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the high and BOD/COD of COD cannot qualified discharge than low polyethers waste water, and treatment system is taken up an area many, and the problem that processing efficiency is low provides a kind for the treatment of process of new polyethers waste water.The method can make BOD/COD≤0.1, COD >=1500 mg/litre containing polyethers discharged wastewater met the national standard, and take up an area less, processing efficiency is high.
In order to solve the problems of the technologies described above, the technical scheme that the present invention takes is as follows: a kind for the treatment of process of polyethers waste water, by discharging after comprising the processing of equalizing tank, biochemistry pool, activated sludge tank and second pond containing polyethers waste water of BOD/COD≤0.1, COD>=1500 mg/litre, make COD≤250 mg/litre in waste discharge, suspension content SS≤250 mg/litre, ammonia-nitrogen content NH
3-N≤7 mg/litre; Wherein, in described biochemistry pool, be provided with and increase bacterium and the material that contains polyethers waste water contact area; Biochemical aeration pressure is 0.6-1.2kgf/m
2; Control ammonia-nitrogen content NH in biochemistry pool
3-N≤25 mg/litre, water oxygen level DO=1.0-5.0 mg/litre.
In technique scheme, preferably, biochemical aeration pressure is 0.65-1.0kgf/m
2.
In technique scheme, preferably, described material is selected from filler or filter screen.More preferably, described material is selected from filler; Described filler is fluidization; The plot ratio of filler is 20-50%.
In technique scheme, preferably, in equalizing tank, add basic cpd and phosphorus source, the pH value in regulating and controlling pond is 9-13, total phosphorous TP≤20 mg/litre.More preferably, the pH value in regulating and controlling pond is 9.2-12.5, total phosphorous TP=1.5-18 mg/litre.
In technique scheme, preferably, described basic cpd is selected from least one in sodium hydroxide, potassium hydroxide or sodium carbonate; Described phosphorus source is selected from least one in potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC.
In technique scheme, preferably, also in equalizing tank, add nitrogenous source, make the ammonia-nitrogen content NH in equalizing tank
3-N=20-115 mg/litre; Described nitrogenous source is selected from least one in urea, ammonium chloride or ammonium nitrate.
In technique scheme, preferably, in equalizing tank, add basic cpd, phosphorus source or nitrogenous source off and on or continuously.More preferably, in equalizing tank, add basic cpd, phosphorus source or nitrogenous source continuously.
In technique scheme, preferably, in described activated sludge tank, the concentration of active sludge is 1000-5000 mg/litre, water oxygen level DO=0.5-3.0 mg/litre, and biochemical aeration pressure is 0.1-1.2kgf/m
2.
In technique scheme, preferably, in described second pond, add flocculation agent, described flocculation agent is selected from least one in aluminium salt inorganic flocculating agent, molysite inorganic flocculating agent, starch-phosphate, starch xanthate, chitin, microbial flocculant, polyacrylamide, sodium polyacrylate, chitosan, polyvinylamine or polyvinyl sulfonate, and the concentration of flocculation agent in second pond is 0.35 * 10
-3-25 * 10
-3grams per liter.More preferably, described flocculation agent is selected from least one in polyacrylamide, sodium polyacrylate, chitosan, polyvinylamine or polyvinyl sulfonate, and the concentration of flocculation agent in second pond is 2.5 * 10
-3-10 * 10
-3grams per liter.
In the inventive method, equalizing tank, in order to regulate pH value, adds phosphorus source, nitrogenous source, for bacterium provides suitable acid or alkali environment and nutritive medium, thereby makes bacterium can continue, play a role equably.In biochemistry pool, most of organic cod is removed.In activated sludge tank, COD is further removed.Second pond is in order to separated water outlet and mud, and the phosphorus content in reduction water outlet, meets environmental requirement.
The present invention increases bacterium and the material that contains polyethers waste water contact area by arranging in biochemistry pool, has increased contact area, and bacterium is fully contacted with waste water; The present invention has also adopted the technical scheme of high pressure biochemical aeration, has accelerated speed of response on the one hand, has improved processing efficiency, due to the degree of depth of high pressure aeration source with biochemistry pool, has reduced floor space on the other hand.Adopt the inventive method treatments B OD/COD≤0.1, COD >=1500 mg/litre containing polyethers waste water, can make the COD of waste discharge be reduced to 60-80 mg/litre, total COD clearance reaches more than 90%, suspension content SS is reduced to 20 mg/litre, ammonia-nitrogen content is reduced to 2 mg/litre, take up an area and reduce 50%, processing efficiency improves 1 times, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
The water yield and the water quality containing polyethers waste water processed are as shown in table 1.
Table 1
| The water yield | Rice 3/ day | 3040 |
| PH value | - | 6.8 |
| COD | Mg/litre | 3600 |
| BOD/COD | - | 0.1 |
Above-mentioned containing discharging after the processing of polyethers waste water by equalizing tank, biochemistry pool, activated sludge tank and second pond.
Wherein, every 1 hour, to equalizing tank, intermittently add NaOH and potassium primary phosphate, the pH value in equalizing tank is 9.2, total phosphorous TP=8 mg/litre.
In biochemistry pool, be provided with filter screen, biochemical aeration pressure is 0.65kgf/m
2, ammonia-nitrogen content NH in biochemistry pool
3-N=10 mg/litre, water oxygen level DO=2.1 mg/litre.Biochemistry pool takes up an area 154m
2.
In activated sludge tank, the concentration of active sludge is 1050 mg/litre, water oxygen level DO=1.8 mg/litre, and biochemical aeration pressure is 0.2kgf/m
2.
In described second pond, add flocculation agent sodium polyacrylate, the concentration of sodium polyacrylate in second pond is 6.25 * 10
-3g/L.
In waste water after second pond is processed, COD=150 mg/litre, suspension content SS=160 mg/litre, ammonia-nitrogen content NH
3-N=2.8 mg/litre.
Whole treating processes is lasted 3 days.
[embodiment 2]
Discharging containing after the processing of polyethers waste water by equalizing tank, biochemistry pool, activated sludge tank and second pond described in table 1.
Wherein, every 1 hour, to equalizing tank, intermittently add NaOH and potassium primary phosphate, the pH value in equalizing tank is 10.2, total phosphorous TP=18 mg/litre.
In biochemistry pool, be provided with filter screen, biochemical aeration pressure is 0.9kgf/m
2, ammonia-nitrogen content NH in biochemistry pool
3-N=10.5 mg/litre, water oxygen level DO=2.5 mg/litre.Biochemistry pool takes up an area 154m
2.
In activated sludge tank, the concentration of active sludge is 1050 mg/litre, water oxygen level DO=1.8 mg/litre, and biochemical aeration pressure is 0.95kgf/m
2.
In described second pond, add flocculation agent sodium polyacrylate, the concentration of sodium polyacrylate in second pond is 6.25 * 10
-3g/L.
In waste water after second pond is processed, COD=100 mg/litre, suspension content SS=120 mg/litre, ammonia-nitrogen content NH
3-N=2.0 mg/litre.
Whole treating processes is lasted 2.5 days.
[embodiment 3]
Discharging containing after the processing of polyethers waste water by equalizing tank, biochemistry pool, activated sludge tank and second pond described in table 1.
Wherein, every 1 hour, to equalizing tank, intermittently add NaOH and potassium primary phosphate, the pH value in equalizing tank is 12.2, total phosphorous TP=12 mg/litre.
In biochemistry pool, be provided with filler, filler is fluidization, and the plot ratio of filler is 75%, and biochemical aeration pressure is 0.75kgf/m
2, ammonia-nitrogen content NH in biochemistry pool
3-N=10.5 mg/litre, water oxygen level DO=2.5 mg/litre.Biochemistry pool takes up an area 154m
2.
In activated sludge tank, the concentration of active sludge is 3400 mg/litre, water oxygen level DO=1.8 mg/litre, and biochemical aeration pressure is 0.95kgf/m
2.
In described second pond, add flocculation agent sodium polyacrylate, the concentration of sodium polyacrylate in second pond is 6.25 * 10
-3g/L.
In waste water after second pond is processed, COD=98 mg/litre, suspension content SS=25 mg/litre, ammonia-nitrogen content NH
3-N=2.0 mg/litre.
Whole treating processes is lasted 2.8 days.
[embodiment 4]
Discharging containing after the processing of polyethers waste water by water collecting basin, equalizing tank, biochemistry pool, activated sludge tank and second pond described in table 1.
Wherein, water collecting basin is collected the gravity drainage of plant area.
In equalizing tank, add NaOH, potassium primary phosphate and urea continuously, the pH value in equalizing tank is 11, total phosphorous TP=15 mg/litre.
In biochemistry pool, be provided with filler, filler is fluidization, and the plot ratio of filler is 40%.Biochemical aeration pressure is 0.95kgf/m
2, ammonia-nitrogen content NH in biochemistry pool
3-N=10.5 mg/litre, water oxygen level DO=3 mg/litre.Biochemistry pool takes up an area 154m
2.
In activated sludge tank, the concentration of active sludge is 1800 mg/litre, water oxygen level DO=2 mg/litre, and biochemical aeration pressure is 0.95kgf/m
2.
In described second pond, add flocculation agent sodium polyacrylate and polyacrylamide, the concentration of sodium polyacrylate in second pond is 5 * 10
-3g/L, the concentration of polyacrylamide in second pond is 0.4375 * 10
-3g/L.
In waste water after second pond is processed, COD=70 mg/litre, suspension content SS=20 mg/litre, ammonia-nitrogen content NH
3-N=1.8 mg/litre.
Whole treating processes is lasted 2 days.
[embodiment 5]
The water yield and the water quality containing polyethers waste water processed are as shown in table 2.
Table 2
| The water yield | Rice 3/ day | 3040 |
| PH value | - | 7 |
| COD | Mg/litre | 4000 |
| BOD/COD | - | 0.045 |
Discharging containing after the processing of polyethers waste water by equalizing tank, biochemistry pool, activated sludge tank and second pond described in table 2.
Wherein, add NaOH, SODIUM PHOSPHATE, MONOBASIC and ammonium nitrate continuously in equalizing tank, the pH value in equalizing tank is 11.5, total phosphorous TP=12 mg/litre.
In biochemistry pool, be provided with filler, filler is fluidization, and the plot ratio of filler is 38%.Biochemical aeration pressure is 1.0kgf/m
2, ammonia-nitrogen content NH in biochemistry pool
3-N=12 mg/litre, water oxygen level DO=4 mg/litre.Biochemistry pool takes up an area 154m
2.
In activated sludge tank, the concentration of active sludge is 2000 mg/litre, water oxygen level DO=2 mg/litre, and biochemical aeration pressure is 1.1kgf/m
2.
In described second pond, add flocculation agent sodium polyacrylate, polyacrylamide and chitosan, the concentration of sodium polyacrylate in second pond is 5 * 10
-3g/L, the concentration of polyacrylamide in second pond is 0.45 * 10
-3g/L, the concentration of chitosan in second pond is 3.125 * 10
-3g/L.
In waste water after second pond is processed, COD=75 mg/litre, suspension content SS=20 mg/litre, ammonia-nitrogen content NH
3-N=2 mg/litre.
Whole treating processes is lasted 1.9 days.
[comparative example 1]
Discharging containing after the processing of polyethers waste water by equalizing tank, biochemistry pool, activated sludge tank and second pond described in table 1.
Wherein, add potassium primary phosphate off and in equalizing tank, the pH value in equalizing tank is 6.9, total phosphorous TP=30 mg/litre.
Filler or filter screen are not set in biochemistry pool.Biochemical aeration pressure is 0.5kgf/m
2, ammonia-nitrogen content NH in biochemistry pool
3-N=30 mg/litre, water oxygen level DO=10 mg/litre.Biochemistry pool takes up an area 3100m
2.
In activated sludge tank, the concentration of active sludge is 4000 mg/litre, water oxygen level DO=5.0 mg/litre, and biochemical aeration pressure is 0.5kgf/m
2.
In described second pond, not adding flocculation agent, is only settling bowl.
In waste water after second pond is processed, COD=500 mg/litre, suspension content SS=250 mg/litre, ammonia-nitrogen content NH
3-N=15 mg/litre.
Whole treating processes is lasted 4.5 days.
Claims (9)
1. the treatment process of a polyethers waste water, by discharging after comprising the processing of equalizing tank, biochemistry pool, activated sludge tank and second pond containing polyethers waste water of BOD/COD≤0.1, COD>=1500 mg/litre, make COD≤250 mg/litre in waste discharge, suspension content SS≤250 mg/litre, ammonia-nitrogen content NH
3-N≤7 mg/litre; Wherein, in described biochemistry pool, be provided with and increase bacterium and the material that contains polyethers waste water contact area; Biochemical aeration pressure is 0.6～1.2kgf/m
2; Control ammonia-nitrogen content NH in biochemistry pool
3-N≤25 mg/litre, water oxygen level DO=1.0～5.0 mg/litre;
Described material is selected from filler or filter screen;
In equalizing tank, add basic cpd and phosphorus source, the pH value in regulating and controlling pond is 9～13, total phosphorous TP≤20 mg/litre.
2. the treatment process of polyethers waste water according to claim 1, is characterized in that biochemical aeration pressure is 0.65～1.0kgf/m
2.
3. the treatment process of polyethers waste water according to claim 1, is characterized in that described material is selected from filler; Described filler is fluidization; The plot ratio of filler is 20～50%.
4. the treatment process of polyethers waste water according to claim 1, is characterized in that the pH value in regulating and controlling pond is 9.2～12.5, total phosphorous TP=1.5～18 mg/litre; Described basic cpd is selected from least one in sodium hydroxide, potassium hydroxide or sodium carbonate; Described phosphorus source is selected from least one in potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC.
5. the treatment process of polyethers waste water according to claim 1, is characterized in that also in equalizing tank, adding nitrogenous source, makes the ammonia-nitrogen content NH in equalizing tank
3-N=20～115 mg/litre; Described nitrogenous source is selected from least one in urea, ammonium chloride or ammonium nitrate.
6. according to the treatment process of polyethers waste water described in claim 1 or 5, it is characterized in that off and on or in equalizing tank, add basic cpd, phosphorus source or nitrogenous source continuously.
7. the treatment process of polyethers waste water according to claim 6, is characterized in that in equalizing tank, adding basic cpd, phosphorus source or nitrogenous source continuously.
8. the treatment process of polyethers waste water according to claim 1, is characterized in that in described activated sludge tank, and the concentration of active sludge is 1000～5000 mg/litre, water oxygen level DO=0.5～3.0 mg/litre, and biochemical aeration pressure is 0.1～1.2kgf/m
2;
In described second pond, add flocculation agent, described flocculation agent is selected from least one in aluminium salt inorganic flocculating agent, molysite inorganic flocculating agent, starch-phosphate, starch xanthate, chitin, microbial flocculant, polyacrylamide, sodium polyacrylate, chitosan, polyvinylamine or polyvinyl sulfonate, and the concentration of flocculation agent in second pond is 0.35 * 10
-3～25 * 10
-3grams per liter.
9. the treatment process of polyethers waste water according to claim 8, is characterized in that in described activated sludge tank, and the concentration of active sludge is 1500～3800 mg/litre, and biochemical aeration pressure is 0.6～0.95kgf/m
2;
Described flocculation agent is selected from least one in polyacrylamide, sodium polyacrylate, chitosan, polyvinylamine or polyvinyl sulfonate, and the concentration of flocculation agent in second pond is 2.5 * 10
-3～10 * 10
-3grams per liter.
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|---|---|---|---|
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| CN105417846B (en) * | 2015-11-13 | 2018-01-09 | 淄博正大聚氨酯有限公司 | The method for handling PPG technique waste water |
| CN107487952B (en) * | 2017-09-22 | 2020-09-29 | 长沙华时捷环保科技发展股份有限公司 | Combined treatment method for beneficiation wastewater containing xanthate residues |
| CN110862154A (en) * | 2019-11-29 | 2020-03-06 | 江南大学 | Treatment method of polyether polyol production tail water |
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| CN102372402B (en) * | 2011-10-09 | 2014-04-09 | 南京工业大学 | Method for treating polyether polyol wastewater |
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Address after: 215633 Beijing Road 20, Yangzi Chemical Industrial Park, Jiangsu, Suzhou Patentee after: Changhua chemical Polytron Technologies Inc Address before: 215633 Beijing Road 20, Yangzi Chemical Industrial Park, Jiangsu, Suzhou Patentee before: Jiangsu Changhua Polyurethane Science & Technology Co., Ltd. |
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