CN103288294B - Treatment method of polyether-containing wastewater - Google Patents
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Abstract
The invention relates to a treatment method of polyether-containing wastewater, which mainly solves the problems of high COD (chemical oxygen demand), incapacity of realizing up-to-standard discharge for polyether wastewater with low BOD/COD (biochemical oxygen demand/chemical oxygen demand) ratio, the large floor area of a treatment system, low treatment efficiency, and high subsequent treatment capacity due to the high dosage of sludge, existing in the prior art. According to the treatment method disclosed by the invention, the problems are solved well by adopting the following technical scheme: the polyether-containing wastewater having a BOD/COD being not greater than 0.1, and a COD being not less than 1500 mg/L is discharged after being treated by an adjusting pool, a biochemical pool, an activated sludge pool and a secondary sedimentation pool, so that in the discharged wastewater, the COD is not greater than 250 mg/L, the suspended solid SS content is not greater than 250 mg/L, and the ammonia-nitrogen content NH3-N is not greater than 7 mg/L; and the concentration of activated sludge in the activated sludge pool is 1000-3800 mg/L, the dissolved oxygen DO in water is 0.5-3.0 mg/L, and the biochemical aeration pressure is 0.6-1.2 kgf/m<2>. The treatment method can be used for industrial production for polyether-containing wastewater treatment.
Description
Technical field
The present invention relates to a kind for the treatment of process containing Polyester wastewater.
Background technology
Polyether glycol (PPG) is the important source material of synthesis 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.Polyethers for raw material, in its production process, can produce a large amount of high density Polyester wastewater with glycerol, vinylbenzene, vinyl cyanide, oxyethane, propylene oxide etc.In these waste water, not only containing a large amount of low molecular polymerization single polymerization monomer, but also containing a large amount of polyphosphazene polymer ethoxylated polyhydric alcohols.Due to the organism that polyether glycol itself and most of raw materials for production thereof are all difficult degradations, cause organic constituents complexity in factory effluent, concentration is high, strong toxicity, biodegradability are poor, waste water is difficult to qualified discharge.
Polyetherpolyols production wastewater mainly comes from the de-low molecule waste water of PPG synthesizing section, flushing waste water, vacuum pump system draining and sanitary sewage, and the principal pollutant of waste water are COD.Existing treatment process mainly adopts physico-chemical pretreatment to add the technological line of subsequent biochemical process.Document " Inner Mongol environmental science; 2007.4 " discloses the method for a kind of coagulating sedimentation-acidication-biological adsorption-UBF-catalytic oxidation one oxidation ditch-absorbing process process polyether polyol wastewater, utilize coagulating sedimentation to carry out pre-treatment polyether polyol wastewater, and then processed further 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, and the method for use heating removes the larger molecular organics in polyether polyol wastewater.But these two kinds of pretreatment processs are owing to lacking specific aim, to COD clearance only 5-10% less than, thus cause technical process complicated operation, processing cost high.Document CN102372402A discloses a kind for the treatment of process of polyether polyol wastewater.Its concrete steps are: (1) regulates polyether polyol wastewater pH value to be 2-6 by acid solution, then carries out pre-treatment, and after controlling pre-treatment, the B/C of waste water is than being 0.42-0.65; (2) regulate after the pH value of step (1) pretreated waste water is 7-8 with alkaline solution, enter in the biochemistry strengthening pond adding biological reinforced mud, control dissolved oxygen concentration, pH value, ORP value and the hydraulic detention time in biochemical strengthening pond, and add nitrogen and phosphorus liquid and trace element, carry out stirring or plug-flow operation, make this pond mud carry out bioselection; (3) water outlet through biochemical strengthening pond process 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 and phosphorus liquid and trace element, carry 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 " disclose a kind of O
1/ A/O
2the operation method of method process high density Polyester wastewater, enters multistage contact-oxidation pool and carries out one-level Aerobic biological process after oil trap oil removing by the high-concentration waste water of BOD/COD=0.15-0.39.Point A, B, C tri-sections in multistage contact-oxidation pool, be provided with soft-filler in pond, filler is fluffy flocculent structure.A section mainly removes easy biochemical partial organic substances, and B section, C section principal degradation can the long-chain larger molecular organicses such as biochemical, PPG, POP that degradation rate is slower.The object of anoxic section carries out acidification hydrolization, fragmented into by the long-chain macromolecule organic substance decomposing of failing to degrade through the process of multistage catalytic oxidation and be easily degraded to small organic molecule, improve 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 qualified discharge after the further process in two-stage biological contact oxidation pond again.But these two kinds of methods above-mentioned are not suitable for the Polyester wastewater that COD is high, BOD/COD ratio is low especially, and treatment system is taken up an area many, and processing efficiency is low, and mud consumption causes greatly subsequent disposal amount large.
Summary of the invention
Technical problem to be solved by this invention be prior art there is the high and BOD/COD of COD cannot qualified discharge than low Polyester wastewater, treatment system is taken up an area many, processing efficiency is low, and mud consumption causes greatly the problem that subsequent disposal amount is large, provides a kind for the treatment of process containing Polyester wastewater newly.The method can make BOD/COD≤0.1, COD >=1500 mg/litre containing Polyester wastewater qualified discharge, and take up an area few, processing efficiency is high, and mud consumption is few.
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 containing Polyester wastewater, by BOD/COD≤0.1, the discharging by after the process that comprises equalizing tank, biochemistry pool, activated sludge tank and second pond containing Polyester wastewater of 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 activated sludge tank, the concentration of active sludge is 1000-3800 mg/litre, water oxygen level DO=0.5-3.0 mg/litre, and biochemical aeration pressure is 0.6-1.2kgf/m
2.
In technique scheme, preferably, in described activated sludge tank, the concentration of active sludge is 1800-3600 mg/litre, water oxygen level DO=0.8-2.5 mg/litre, and biochemical aeration pressure is 0.65-1.0kgf/m
2.
In technique scheme, preferably, add basic cpd and phosphorus source in equalizing tank, 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, basic cpd, phosphorus source or nitrogenous source is added off and on or continuously.More preferably, in equalizing tank, basic cpd, phosphorus source or nitrogenous source is added continuously.
In technique scheme, preferably, the material increasing bacterium and contain Polyester wastewater contact area is provided with in described biochemistry pool.More preferably, described material is selected from filler or filter screen.Most preferably, described material is selected from filler; Described filler is fluidization; The plot ratio of filler is 20-80%, preferred 30-50%.
In technique scheme, preferably, in described biochemistry pool, biochemical aeration pressure is 0.1-1.2kgf/m
2.More preferably, biochemical aeration pressure is 0.6-1.0kgf/m
2.
In technique scheme, preferably, ammonia-nitrogen content NH in biochemistry pool is controlled
3-N≤25 mg/litre, water oxygen level DO=1.0-5.0 mg/litre.
In technique scheme, preferably, flocculation agent is added in described second pond, 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 adjust ph, adds phosphorus source, nitrogenous source, for bacterium provides suitable acid or alkali environment and nutritive medium, thus makes bacterium can continue, play a role equably.In biochemistry pool, most of organic cod is removed.In activated sludge tank, COD is removed further.Second pond in order to be separated water outlet and mud, and reduces the phosphorus content in water outlet, meets environmental requirement.
The present invention by adopting high pressure biochemical aeration in activated sludge tank, makes mushroom can under reaction under high pressure condition, and metabolism is accelerated, and improves waste treatment capacity; High pressure aeration also can reduce the floor space of activated sludge tank; Activated sludge concentration is low, can reduce the treatment capacity of mud.Adopt the inventive method treatments B OD/COD≤0.1, COD >=1500 mg/litre containing Polyester wastewater, the COD of waste discharge can be made to be reduced to 60-80 mg/litre, total COD clearance reaches more than 93%, suspension content SS is reduced to 20 mg/litre, ammonia-nitrogen content is reduced to 2 mg/litre, and the treatment time can reduce 50%, and floor space can reduce 50%, mud handling capacity can reduce 50%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
The water yield containing Polyester wastewater and the water quality of process are as shown in table 1.
Table 1
| The water yield | Rice 3/ sky | 3040 |
| PH value | - | 6.8 |
| COD | Mg/litre | 3600 |
| BOD/COD | - | 0.1 |
The above-mentioned Polyester wastewater that contains is by discharging after the process of equalizing tank, biochemistry pool, activated sludge tank and second pond.
Wherein, added NaOH and potassium primary phosphate every 1 hour to equalizing tank interval, the pH value in equalizing tank is 9.2, total phosphorous TP=8 mg/litre.
Be provided with filter screen in biochemistry pool, biochemical aeration pressure is 0.2kgf/m
2, ammonia in biochemistry pool-nitrogen content NH
3-N=10 mg/litre, water oxygen level DO=2.1 mg/litre.
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 0.65kgf/m
2.Activated sludge tank takes up an area 154m
2.
Add flocculation agent sodium polyacrylate in described second pond, the concentration of sodium polyacrylate in second pond is 6.25 × 10
-3g/L.
In waste water after second pond process, COD=150 mg/litre, suspension content SS=160 mg/litre, ammonia-nitrogen content NH
3-N=2.8 mg/litre.
Whole treating processes lasts 3 days.
[embodiment 2]
Described in table 1 containing Polyester wastewater by discharging after the process of equalizing tank, biochemistry pool, activated sludge tank and second pond.
Wherein, added NaOH and potassium primary phosphate every 1 hour to equalizing tank interval, the pH value in equalizing tank is 10.2, total phosphorous TP=18 mg/litre.
Be provided with filter screen in biochemistry pool, biochemical aeration pressure is 0.5kgf/m
2, ammonia in biochemistry pool-nitrogen content NH
3-N=10.5 mg/litre, water oxygen level DO=2.5 mg/litre.
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.Activated sludge tank takes up an area 154m
2.
Add flocculation agent sodium polyacrylate in described second pond, the concentration of sodium polyacrylate in second pond is 6.25 × 10
-3g/L.
In waste water after second pond process, COD=100 mg/litre, suspension content SS=120 mg/litre, ammonia-nitrogen content NH
3-N=2.0 mg/litre.
Whole treating processes lasts 2.5 days.
[embodiment 3]
Described in table 1 containing Polyester wastewater by discharging after the process of equalizing tank, biochemistry pool, activated sludge tank and second pond.
Wherein, added NaOH and potassium primary phosphate every 1 hour to equalizing tank interval, the pH value in equalizing tank is 12.2, total phosphorous TP=12 mg/litre.
Be provided with filler in biochemistry pool, filler is fluidization, and the plot ratio of filler is 35%, and biochemical aeration pressure is 0.75kgf/m
2, ammonia in biochemistry pool-nitrogen content NH
3-N=10.5 mg/litre, water oxygen level DO=2.5 mg/litre.
In activated sludge tank, the concentration of active sludge is 3200 mg/litre, water oxygen level DO=1.8 mg/litre, and biochemical aeration pressure is 0.85kgf/m
2.Activated sludge tank takes up an area 154m
2.
Add flocculation agent sodium polyacrylate in described second pond, the concentration of sodium polyacrylate in second pond is 6.25 × 10
-3g/L.
In waste water after second pond process, COD=98 mg/litre, suspension content SS=25 mg/litre, ammonia-nitrogen content NH
3-N=2.0 mg/litre.
Whole treating processes lasts 2.8 days.
[embodiment 4]
Described in table 1 containing Polyester wastewater by discharging after the process of water collecting basin, equalizing tank, biochemistry pool, activated sludge tank and second pond.
Wherein, the gravity drainage of plant area collected by water collecting basin.
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.
Be provided with filler in biochemistry pool, filler is fluidization, and the plot ratio of filler is 70%.Biochemical aeration pressure is 0.95kgf/m
2, ammonia in biochemistry pool-nitrogen content NH
3-N=10.5 mg/litre, water oxygen level DO=3 mg/litre.
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 1.0kgf/m
2.Activated sludge tank takes up an area 154m
2.
Add flocculation agent sodium polyacrylate and polyacrylamide in described second pond, 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 process, COD=70 mg/litre, suspension content SS=20 mg/litre, ammonia-nitrogen content NH
3-N=1.8 mg/litre.
Whole treating processes lasts 2 days.
[embodiment 5]
The water yield containing Polyester wastewater and the water quality of process are as shown in table 2.
Table 2
| The water yield | Rice 3/ sky | 3040 |
| PH value | - | 7 |
| COD | Mg/litre | 4000 |
| BOD/COD | - | 0.045 |
Described in table 2 containing Polyester wastewater by discharging after the process of equalizing tank, biochemistry pool, activated sludge tank and second pond.
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.
Be provided with filler in biochemistry pool, filler is fluidization, and the plot ratio of filler is 38%.Biochemical aeration pressure is 1.0kgf/m
2, ammonia in biochemistry pool-nitrogen content NH
3-N=12 mg/litre, water oxygen level DO=4 mg/litre.
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.Activated sludge tank takes up an area 154m
2.
Add flocculation agent sodium polyacrylate, polyacrylamide and chitosan in described second pond, 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 process, COD=75 mg/litre, suspension content SS=20 mg/litre, ammonia-nitrogen content NH
3-N=2 mg/litre.
Whole treating processes lasts 1.9 days.
[comparative example 1]
Described in table 1 containing Polyester wastewater by discharging after the process of equalizing tank, biochemistry pool, activated sludge tank and second pond.
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.
In biochemistry pool, filler or filter screen are not set.Biochemical aeration pressure is 0.5kgf/m
2, ammonia in biochemistry pool-nitrogen content NH
3-N=30 mg/litre, water oxygen level DO=10 mg/litre.
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.Activated sludge tank takes up an area 310m
2.
Do not add flocculation agent in described second pond, be only settling bowl.
In waste water after second pond process, COD=500 mg/litre, suspension content SS=250 mg/litre, ammonia-nitrogen content NH
3-N=15 mg/litre.
Whole treating processes lasts 4.5 days.
Claims (10)
1. the treatment process containing Polyester wastewater, BOD/COD≤0.1, containing after Polyester wastewater passes through the system process be made up of equalizing tank, biochemistry pool, activated sludge tank and second pond of COD>=1500 mg/litre are discharged, 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 activated sludge tank, the concentration of active sludge is 1000 ~ 3800 mg/litre, water oxygen level DO=0.5 ~ 3.0 mg/litre, and biochemical aeration pressure is 0.6 ~ 1.2kgf/m
2;
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., according to claim 1 containing the treatment process of Polyester wastewater, it is characterized in that in described activated sludge tank, the concentration of active sludge is 1800 ~ 3600 mg/litre, water oxygen level DO=0.8 ~ 2.5 mg/litre, and biochemical aeration pressure is 0.65 ~ 1.0kgf/m
2.
3., according to claim 1 containing the treatment process of Polyester wastewater, it is characterized in that 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.
4., according to claim 1 containing the treatment process of Polyester wastewater, it 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.
5., according to claim 1 containing the treatment process of Polyester wastewater, it is characterized in that also in equalizing tank, adding 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.
6. according to claim 1 or 5, contain the treatment process of Polyester wastewater, it is characterized in that off and on or in equalizing tank, add basic cpd, phosphorus source and nitrogenous source continuously.
7., according to claim 6 containing the treatment process of Polyester wastewater, it is characterized in that in equalizing tank, adding basic cpd, phosphorus source and nitrogenous source continuously.
8., according to claim 1 containing the treatment process of Polyester wastewater, it is characterized in that being provided with in described biochemistry pool increases bacterium and the material containing Polyester wastewater contact area; Biochemical aeration pressure is 0.1 ~ 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;
Flocculation agent is added in described second pond, 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., according to claim 8 containing the treatment process of Polyester wastewater, it is characterized in that biochemical aeration pressure is 0.6 ~ 1.0kgf/m
2; Described material is selected from filler or filter screen;
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.
10., according to claim 9 containing the treatment process of Polyester wastewater, it is characterized in that described material is selected from filler; Described filler is fluidization; The plot ratio of filler is 20 ~ 80%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4970005A (en) * | 1990-06-01 | 1990-11-13 | Arco Chemical Technology, Inc. | Method for treatment of wastewater containing polyether polyols |
| DD299370A7 (en) * | 1990-05-14 | 1992-04-16 | Basf Schwarzheide Gmbh,De | PROCESS FOR THE BIOLOGICAL TREATMENT OF POLYETHERAL-CARBONATED WASTEWATERS |
| CN1644537A (en) * | 2004-12-16 | 2005-07-27 | 南开大学 | Polyether polyatomic alcohol producing sewage recovering and utilizing treatment |
| CN102372402A (en) * | 2011-10-09 | 2012-03-14 | 南京工业大学 | Method for treating polyether polyol wastewater |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2568635Y (en) * | 2002-02-28 | 2003-08-27 | 于利军 | Easy-to-move membrane bioreator |
| CN101525205B (en) * | 2009-04-28 | 2012-07-04 | 北京清大国华环保科技有限公司 | Pressure type membrane bioreactor technique of suspension bed and device |
-
2013
- 2013-05-07 CN CN201310165161.1A patent/CN103288294B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD299370A7 (en) * | 1990-05-14 | 1992-04-16 | Basf Schwarzheide Gmbh,De | PROCESS FOR THE BIOLOGICAL TREATMENT OF POLYETHERAL-CARBONATED WASTEWATERS |
| US4970005A (en) * | 1990-06-01 | 1990-11-13 | Arco Chemical Technology, Inc. | Method for treatment of wastewater containing polyether polyols |
| CN1644537A (en) * | 2004-12-16 | 2005-07-27 | 南开大学 | Polyether polyatomic alcohol producing sewage recovering and utilizing treatment |
| CN102372402A (en) * | 2011-10-09 | 2012-03-14 | 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. |