CN102936078B - Method for treating wastewater of dry-spinning acrylic fibers - Google Patents
Method for treating wastewater of dry-spinning acrylic fibers Download PDFInfo
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- CN102936078B CN102936078B CN201110234171.7A CN201110234171A CN102936078B CN 102936078 B CN102936078 B CN 102936078B CN 201110234171 A CN201110234171 A CN 201110234171A CN 102936078 B CN102936078 B CN 102936078B
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Abstract
The invention relates to a method for treating wastewater of dry-spinning acrylic fibers, and belongs to the field of wastewater treatment. The method comprises the following steps of (1) adjusting a pH value of the wastewater to a preset value; (2) performing a first grade aerobic biochemical treatment on the wastewater treated by the first step (1) in a first grade aerobic biochemical treatment pool; (3) performing ozone catalytic oxidation treatment on the wastewater treated by the first step (2); and (4) performing a second grade aerobic biochemical treatment on the wastewater treated by the first step (3) in a second grade aerobic biochemical treatment pool, precipitating and discharging the supernatant. The method has the advantages of good treatment effect, short flow, simple operations and stable operations, and is particularly suitable for treating the wastewater of the dry-spinning acrylic fibers.
Description
Technical field
The present invention relates to a kind of method of processing organic waste water, especially relate to the method for processing acrylic fibers waste water by dry process.
Background technology
Dry acrylic fiber production technique is that to take vinyl cyanide, methyl acrylate, Sodium styrene sulfonate be main raw material, through aqueous suspension polymerization, produces polymer, and the dimethyl formamide (DMF) of take is solvent, the dry-spinning process that the hot nitrogen of take is heating carrier.
Acrylic fibers waste water by dry process mainly comprises three classes: factory effluent, ground flushing water and sanitary sewage.Its water quality characteristics is: COD value is high, generally in 1500mg/L left and right; Pollutant kind is many, complicated component; Poisonous, hard-degraded substance content is large; Intractability is large, is typical high concentration hard-degraded organic waste water.
At present, overwhelming majority Acrylic Fibers Plant adopts pre-treatment-anaerobic-aerobic technique to process acrylic fibers waste water by dry process, the COD value of wastewater effluent is reduced to 500mg/L left and right, then be mixed into sewage work with other waste water and merge processing, this makes waste water downstream treating processes produce following problem: the toxic organic compound containing in (1) acrylic fibers waste water by dry process can affect the normal operation of biochemical treatment system, some pollutent can not get effectively processing and enters receiving water body with water outlet, affects receiving water body water quality; (2) hardly degraded organic substance (as part of auxiliary) has increased the difficulty of waste water downstream treatment system, causes disposed of sewage COD value to be difficult to up to standard.
Chinese patent CN1293159A discloses a kind of method of processing acrylic fibers waste water by dry process, and the technique of its use is: flocculation-anaerobic nitrification-anaerobic-aerobic-sand filtration-charcoal absorption.Chinese patent CN1170784C discloses a kind of method of processing acrylic fibers waste water by dry process, and the technique of its use is: air supporting-adsorption biodegradation-sulfate reduction-biological desulphurization-product methane three-phase series-anaerobic-aerobic.Chinese patent CN1210214C discloses a kind of method of processing acrylic fibers waste water by dry process, and the technique of its use is: coagulating sedimentation-active sludge-micro-electrolysis-anaerobic acidification-anoxic-aerobic process.
Adopt aforesaid method to process acrylic fibers waste water by dry process, water outlet all can reach acrylic fiber industry national grade one discharge standard (COD < 160mg/L).But also there is larger problem in aforesaid method: contain many poisonous, hard-degraded substances in (1) acrylic fibers waste water by dry process, the efficiency of microbiological deterioration pollutent is lower, cause whole processing technological flow long, complicated operation, management inconvenience, wastewater effluent water quality is unstable; (2) for patent CN1170784C, sulfate reduction and product methane phase in anaerobic reactor, operational condition is harsh, industrial implementation is difficult; (3) in wastewater treatment process, need to add multiple nutrients material, need the regularly a large amount of excess sludge of discharge, increased cost for wastewater treatment.Therefore be badly in need of a kind of method of processing acrylic fibers waste water by dry process.
Summary of the invention
For existing the problems referred to above in prior art, the present invention proposes a kind of method of processing acrylic fibers waste water by dry process, this treatment process has easy and simple to handle, and technical process is short, stable, the advantage that COD removal efficiency is high.
The method according to this invention, it comprises the following steps:
1) the pH value of waste water is adjusted to preset value;
2) by through described 1) waste water after processing carries out one-level aerobic treatment in one-level aerobic treatment pond;
3) by through described 2) waste water after processing carries out catalytic ozonation processing;
4) by through described 3) waste water after processing carries out secondary aerobic treatment in secondary aerobic treatment pond, discharges supernatant liquor after precipitation.
The method according to this invention, first enters acrylic fibers waste water by dry process pH value equalizing tank, regulates its pH value.In one embodiment, with alkali, the pH value of waste water is adjusted to 7.0-8.5, described alkali is preferably sodium hydroxide.
The method according to this invention, carries out biochemical treatment by regulating waste water after pH value to be drained in one-level aerobic biochemical pool.In view of in acrylic fibers waste water by dry process poisonous, hardly degraded organic substance content is high, COD value is higher, and in one embodiment, the active sludge using is ordinary activated sludge, this ordinary activated sludge is the mud producing in petrochemical wastewater treating processes, after domestication is cultivated, obtains.
The microorganism of biochemical treatment need to maintain the necessary nitrogen of biological activity, phosphoric, in acrylic fibers waste water by dry process, contain more nitrogenous compound, therefore do not need to supplement nitrogen, but in waste water, contain hardly phosphorus, therefore need to supplement P contained compound, to meet the needs of microorganism growth.In one embodiment, in one-level aerobic biochemical pool, add phosphorus containg substances, be preferably potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC.In a preferred embodiment, the phosphatic amount adding counts 100 with the mass ratio of influent waste water COD and phosphoric: 1.0-100: 5.0, be preferably 100: 2.0-100: 3.0.
In order further to improve the effect of one-level aerobic treatment, in one embodiment, in described one-level aerobic biochemical pool, be tied filler, to fix suspended sludge wherein, increase the sludge concentration of system.In one embodiment, spendable filler is divided into: soft-filler and semi soft packing.Wherein the matter material of soft-filler is synthon, tensile strength 6.8-7.1 gram/monofilament, and elongation < 4%, specific surface area 50-110m
2/ m
3, porosity > 97%.The matter material of semi soft packing is polypropylene, polyethylene, and axial cord is plastic ties or fiber rope.Specific surface area 50-110m
2/ m
3, porosity > 97%.By this filler, in pond, the microorganic adhesion of 60-80% is fixed on filling surface, and 20-40% is suspended in waste water.
The method according to this invention, one-level aerobic treatment condition is: retention time of sewage 24-48h, sludge concentration 5-8g/L, dissolved oxygen concentration 3-5mg/L, temperature 18-35 ℃, pH value 7.0-8.5.After one-level aerobic treatment, the easily biodegradable organics in waste water is degraded, and the COD in waste water significantly reduces.
Preferably, acrylic fibers waste water by dry process is after one-level aerobic treatment, wastewater effluent is entered in the first second pond and carries out solid-liquid separation, and the suspended sludge in water outlet turns back in one-level aerobic biochemical pool and continues to use after precipitating, concentrating, and supernatant liquor is entered to ozone (O
3) catalytic oxidation unit processes, so that the larger molecular organics that is wherein difficult to biochemical degradation is oxidized to small organic molecule, even exhaustive oxidation decomposes.In one embodiment, described catalytic ozonation carries out in closed reactor, and the flow of ozone is 50-100mg/L, and aeration time is 20min-1h.
The catalyzer using in catalytic ozonation technology can be divided into two classes: be 1) homogeneous catalyst, comprise transition metal ion, as Fe
2+, Fe
3+, Cu
2+deng; 2) be heterogeneous catalyst, comprise solid metal, metal oxide etc., as hydrous iron oxide (FeOOH), Manganse Dioxide etc.Homogeneous catalyst has the advantages such as reactive behavior is high, speed is fast, but because metal ion is dissolved in the water, cause loss and the pollution to environment of catalyzer, and need it to carry out certain subsequent disposal after catalytic ozonation reaction, thereby increased the cost of water treatment.And heterogeneous catalyst is to be added in water with solid form, to compare with homogeneous catalyst, it has the separation of being easy to, recycling, has both avoided loss and the environmental pollution of catalyzer, has reduced again the cost of water treatment.
Heterogeneous catalyst-hydrous iron oxide is extensively present in occurring in nature, and its physicochemical property are stable, and specific surface area is higher and the adsorbed hydroxyl content is high, solubleness is extremely low.Under neutrallty condition, hydrous iron oxide surface band zero charge, can catalysis ozone decomposes and generates hydroxyl radical free radical, and meanwhile, hydrous iron oxide is cheap and easy to get, recoverable, can, to environment, be not a kind of catalyzer that is suitable for O3 catalytic oxidation.Waste water, after catalytic ozonation, can improve its biodegradability on the one hand, on the other hand, also can remove partial organic substances, reduces the organic loading of follow-up biochemical treatment.In one embodiment, in catalytic ozonation, the catalyzer using is hydrous iron oxide, and its granularity is 50-200 order, and its concentration in waste water is 500-1000mg/L.In a preferred embodiment, when waste water is carried out to catalytic ozonation, carry out mechanical stirring, be beneficial to the carrying out of catalytic oxidation.
After catalytic ozonation, the oxidized small organic molecule that resolves into of organism in waste water, its BOD/COD, between 0.3-0.4, is applicable to using biochemical process to process.
The method according to this invention, enters the water outlet in described settling tank in secondary aerobic biochemical pool, further carries out biochemical treatment.In one embodiment, the active sludge using is ordinary activated sludge, identical with the active sludge of one-level aerobic biochemical pool.
In secondary aerobic treatment process, also need to supplement the element that maintains microorganism active.In one embodiment, in secondary aerobic biochemical pool, add phosphorus containg substances, be preferably potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC.In a preferred embodiment, the phosphatic amount adding counts 100 with the mass ratio of influent waste water COD and phosphoric: 1.0-100: 5.0, be preferably 100: 2.0-100: 3.0.
The method according to this invention, secondary aerobic treatment condition is: retention time of sewage 12-24h, sludge concentration 3-5g/L, dissolved oxygen concentration 3-5mg/L, temperature 18-35 ℃, pH value 6.5-8.0.
Finally, the waste water after secondary aerobic treatment is entered in the second second pond and realizes solid-liquid separation.The supernatant liquor of discharging is as clear as crystal, and COD clearance is between 90-95%, and water outlet COD is less than 160mg/L, reaches acrylic fiber industry national grade one discharge standard.
The invention has the advantages that, first acrylic fibers waste water by dry process is carried out to one-level biochemical treatment, and then carry out catalytic ozonation, can significantly reduce the usage quantity of catalytic ozonation reagent, Reaction time shorten, reduces costs, also more friendly to environment.In addition, the present invention has adopted one-level aerobic biochemical-catalytic ozonation-secondary aerobic biochemical method to process acrylic fibers waste water by dry process, COD clearance is between 90-95%, water outlet COD is less than 160mg/L, and have advantages of that treatment scheme is short, easy and simple to handle, stable, be particularly suitable for processing acrylic fibers waste water by dry process.
Accompanying drawing explanation
Hereinafter by the embodiment based on different and with reference to accompanying drawing, the present invention is described in more detail.Wherein:
Fig. 1 is the process flow diagram for the treatment of in accordance with the present invention acrylic fibers waste water by dry process.
Embodiment
Below in conjunction with accompanying drawing, a kind of method of processing acrylic fibers waste water by dry process of the present invention is described further.
Fig. 1 is the process flow diagram for the treatment of in accordance with the present invention acrylic fibers waste water by dry process.First need acrylic fibers waste water by dry process 10 to be processed is drained in pH value equalizing tank 1, then adds alkaline matter 11, the pH value of waste water 10 is adjusted to preset value.Then described waste water is drained in one-level aerobic biochemical pool 2, adds phosphorus containg substances 12 to carry out one-level aerobic treatment simultaneously.Afterwards, waste water is entered in the first second pond 3, precipitate, and supernatant liquor is drained in catalytic ozonation unit 4, add catalytic ozonation reagent 13 simultaneously, under the acting in conjunction of ozone and catalyzer, the larger molecular organics of the bio-refractory in waste water is oxidized to biodegradable small organic molecule.Then, the supernatant liquor in catalytic ozonation unit 4 entered in secondary aerobic biochemical pool 5 and add phosphorus containg substances 14, carrying out secondary aerobic treatment.Finally, waste water is drained in the second second pond 6, realizes solid-liquid separation, the water outlet 20 of second pond is discharged.
Embodiment 1:
By acrylic fibers waste water by dry process, its water quality characteristic is COD:1442.3mg/L, pH value: 5.5, enter pH value equalizing tank, and adding concentration is 25% sodium hydroxide solution, and pH value is adjusted to 7.5-8.0.Then described waste water is entered in one-level aerobic biochemical reaction tank, add potassium primary phosphate, its add-on is for to count 100: 2 with the mass ratio of influent waste water COD and phosphoric, and at sludge concentration 6-7g/L, dissolved oxygen concentration 4-5mg/L, temperature 20-30 ℃, processes 36h under pH value 7.5-8.0.Afterwards, waste water is entered in the first second pond and precipitated, and supernatant liquor is drained into catalytic ozonation reactor, in reactor, add the hydroxyl oxidize iron catalyst of granularity between 50-200 order, its concentration is 500mg/L, ozonizer exports ozone flow between 50-60L/h simultaneously, aeration 30min under continuous mechanical stirring.Then the waste water after catalytic ozonation is drained in secondary aerobic biochemical pool, add potassium primary phosphate, its add-on is for to count 100: 2 with the mass ratio of influent waste water COD and phosphoric, and at sludge concentration 3-4g/L, dissolved oxygen concentration 3-4mg/L, temperature 20-30 ℃, processes 24h under pH value 6.5-7.0.Then the waste water after processing precipitates in the second second pond, realizes solid-liquid separation, and water outlet is discharged.In treating processes, the COD of waste water changes in Table 1.
Table 1
Embodiment 2:
By acrylic fibers waste water by dry process, its water quality characteristic is COD:1263.7mg/L, pH value: 6.0, enter in pH value equalizing tank, and adding concentration is 25% sodium hydroxide solution, and pH value is adjusted to 8.0-8.5.Then described waste water is entered in one-level aerobic biochemical reaction tank, add SODIUM PHOSPHATE, MONOBASIC, its add-on is for to count 100: 3 with the mass ratio of influent waste water COD and phosphoric, and at sludge concentration 5-6g/L, dissolved oxygen concentration 4-5mg/L, temperature 20-30 ℃, processes 24h under pH value 8.0-8.5.Afterwards, waste water is entered in the first second pond and precipitated, and supernatant liquor is drained into catalytic ozonation reactor, in reactor, add the hydroxyl oxidize iron catalyst of granularity between 50-200 order, its concentration is 1000mg/L, ozonizer exports ozone flow between 70-80L/h simultaneously, aeration 1h under continuous mechanical stirring.Then the waste water after catalytic ozonation is drained in secondary aerobic biochemical pool, add SODIUM PHOSPHATE, MONOBASIC, its add-on is for to count 100: 3 with the mass ratio of influent waste water COD and phosphoric, and at sludge concentration 3-4g/L, dissolved oxygen concentration 3-4mg/L, temperature 20-30 ℃, processes 12h under pH value 6.5-7.0.Then the waste water after processing precipitates in the second second pond, realizes solid-liquid separation, and water outlet is discharged.In treating processes, the COD of waste water changes in Table 2.
Table 2
Embodiment 3:
By acrylic fibers waste water by dry process, its water quality characteristic is COD:1339mg/L, pH value: 6.3, enter in pH value equalizing tank, and adding concentration is 25% sodium hydroxide solution, and pH value is adjusted to 7.5-8.5.Then described waste water is entered in one-level aerobic biochemical reaction tank, add potassium primary phosphate, its add-on is for to count 100: 1 with the mass ratio of influent waste water COD and phosphoric, and at sludge concentration 6-8g/L, dissolved oxygen concentration 4-5mg/L, temperature 20-30 ℃, processes 48h under pH value 7.5-8.5.Afterwards, waste water is entered in the first second pond and precipitated, and supernatant liquor is drained into catalytic ozonation reactor, in reactor, add the hydroxyl oxidize iron catalyst of granularity between 50-200 order, its concentration is 800mg/L, ozonizer exports ozone flow between 90-100L/h simultaneously, aeration 20min under continuous mechanical stirring.Then the waste water after catalytic ozonation is drained in secondary aerobic biochemical pool, add potassium primary phosphate, its add-on is for to count 100: 1 with the mass ratio of influent waste water COD and phosphoric, and at sludge concentration 3-4g/L, dissolved oxygen concentration 3-4mg/L, temperature 20-30 ℃, processes 18h under pH value 6.5-7.0.Then the waste water after processing precipitates in the second second pond, realizes solid-liquid separation, and water outlet is discharged.In treating processes, the COD of waste water changes in Table 3.
Table 3
By above-described embodiment, can see, method of the present invention can reach good effect to the processing of acrylic fibers waste water by dry process.Acrylic fibers waste water by dry process is after above-mentioned processing, and water outlet COD, lower than 160mg/L, reaches acrylic fiber industry national grade one discharge standard.In addition, present method also have advantages of that treatment scheme is short, cost is low, easy and simple to handle, stable.
Although invention has been described with reference to preferred embodiment, without departing from the scope of the invention, can carry out various improvement and can replace material wherein with equivalent it.The present invention is not limited to disclosed specific embodiment in literary composition, but comprises all technical schemes that fall within the scope of claim.
Claims (10)
1. a method of processing acrylic fibers waste water by dry process, it comprises the following steps:
1) the pH value of waste water is adjusted to preset value;
2) by through described 1) waste water after processing carries out one-level aerobic treatment in one-level aerobic treatment pond;
3) by through described 2) waste water after processing carries out catalytic ozonation processing;
4) by through described 3) waste water after processing carries out secondary aerobic treatment in secondary aerobic treatment pond, discharges supernatant liquor after precipitation,
In catalytic ozonation, the catalyzer using is hydrous iron oxide, and its granularity is 50-200 order, and its concentration in waste water is 500-1000mg/L,
Described 1) in use alkali that the pH value of waste water is adjusted to 7.0-8.5, described alkali is sodium hydroxide.
2. method according to claim 1, is characterized in that, described 2) and 4) in the active sludge that uses be ordinary activated sludge.
3. method according to claim 1, is characterized in that, described 2) and 4) in aerobic biochemical treatment tank, add phosphoric acid salt.
4. method according to claim 3, is characterized in that, described phosphoric acid salt is potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC.
5. according to the method described in claim 3 or 4, it is characterized in that, described 2) and 4) in the phosphatic amount that adds with the mass ratio of influent waste water COD and phosphoric, count 100:1.0-100:5.0.
6. method according to claim 5, is characterized in that, described mass ratio is counted 100:2.0-100:3.0.
7. according to the method described in any one in claim 1 to 4, it is characterized in that, described 2) in aerobic treatment condition be: retention time of sewage 24-48h, sludge concentration 5-8g/L, dissolved oxygen concentration 3-5mg/L, temperature 18-35 ℃, pH value 7.0-8.5.
8. method according to claim 1, is characterized in that, described 4) in aerobic treatment condition be: retention time of sewage 12-24h, sludge concentration 3-5g/L, dissolved oxygen concentration 3-5mg/L, temperature 18-35 ℃, pH value 6.5-8.0.
9. method according to claim 1, is characterized in that, described 3) catalytic ozonation in closed reactor, carry out, the flow of ozone is 50-100mg/L, aeration time is 20min-1h.
10. method according to claim 1, is characterized in that, described 2) in one-level aerobic treatment pond in be tied filler.
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