CN103043846A - Acrylic fiber waste water treatment method - Google Patents
Acrylic fiber waste water treatment method Download PDFInfo
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- CN103043846A CN103043846A CN2011103078771A CN201110307877A CN103043846A CN 103043846 A CN103043846 A CN 103043846A CN 2011103078771 A CN2011103078771 A CN 2011103078771A CN 201110307877 A CN201110307877 A CN 201110307877A CN 103043846 A CN103043846 A CN 103043846A
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Abstract
An acrylic fiber waste water treatment method. An acrylic fiber waste water treatment method is provided which comprises the following steps: (a) performing ultrasonic hydrolysis treatment of acrylic fiber waste water; (b) treating the acrylic fiber waste water treated by ultrasonic hydrolysis in step (a) in a biological reaction tank; and (c) performing Fenton treatment of the acrylic fiber waste water obtained in step (b). Through ultrasonic hydrolysis pretreatment of the acrylic fiber waste water, oligomers and long-chain macromolecules which are difficult to bio-degrade in the waste water are decomposed and degraded; the COD index of the waste water is decreased obviously; and the biodegradability is improved. Effluent from ultrasonic hydrolysis flows into the integrated biological reaction tank for biological reactions such as denitrification and decarbonization so as to remove most COD and ammonia nitrogen. Effluent from the integrated biological reaction tank is subjected to the Fenton process to remove residual organic matter difficult to degrade so as to ensure the effluent quality.
Description
Technical field
The present invention relates to a kind for the treatment of process of Nitrilon waste water, be specifically related to a kind of Nitrilon waste water treatment process that comprises the ultrasonic wave hydrolysis.
Background technology
Nitrilon waste water is a kind of high concentrated organic wastewater, and it contains multiple pollutant, especially contains low-molecular(weight)polymer, so environmental pollution is large and be difficult to processing, thereby has seriously hindered the development of acrylic fibers industry.It is one of emphasis of petrochemical complex Pollution abatement and control that Nitrilon waste water is processed.
Owing to introducing and the more high reason of oligomer of organic additive in the acrylic fiber production process process causes Nitrilon waste water biodegradability extreme difference, BOD
5/ COD value is 0.1～0.2, has Pollutant levels height, N/C is high, toxicity is high and B/C is low " three high one is low " characteristics.Studies show that in Nitrilon waste water, readily biodegradable class, biodegradable class, the shared massfraction of difficult for biological degradation class three class organic pollutants are respectively 52.28%, 7.09%, 40.63%.Difficult for biological degradation reaches and accounts for about half of total organic matter amount than the difficult for biological degradation organic pollution materials, directly processes this waste water to comparatively difficulty up to standard with biological process.And because a large amount of existence of organonitrogen and ammonia nitrogen cause existing biochemical processing process can not reach good wastewater treatment efficiency.Therefore need be aided with suitable pre-treatment measure, with reduce hardly degraded organic substance content, make great efforts to improve the biodegradability of waste water.
Both at home and abroad Nitrilon waste water is processed and carried out a large amount of experimental studies, treatment process mainly contains: chemical method (chemical coagulation, chemical oxidation and internal electrolysis); Biological process (SBR method, biological contact oxidation process, pressurization aerobic biochemical process, acidization pre-treatment, biological filtering tower combined working and the special bacterial classification of interpolation); Physico-chemical processes (millipore filtration and absorption).These methods are widely applied in acrylic fiber production process enterprise, and have obtained preferably effect, but the problem that exists is also a lot, and main manifestations is: (1) water outlet is difficult to up to standard, and except COD, ammonia-nitrogen content is higher in the water outlet; (2) overstand causes initial investment and working cost too high.In addition, problem that the microbial film of millipore filtration stops up and the iron carbon bed of interior electrolysis scabs all affects the steady running for the treatment of system.
Therefore, take suitable measure that Nitrilon waste water is carried out pre-treatment, reduce the Pollutant levels that biochemistry is harmful to or the degradation effect that improves organic pollutant, to guarantee efficiently carrying out of subsequent biological treatment, optimize effluent quality, become the key point that Nitrilon waste water is processed.
Patent CN1061949C discloses a kind of wet spinning acrylic fibers industry integrated waste water treatment method.This patent is according to the water quality characteristics of acrylic fibers industry waste water, waste water is divided into three strands, adopt first mixed condensed gas flotation process to process Nitrilon waste water, after adopting biological contact oxidation process to process spinning recovery waste water, again above-mentioned two strands of treated waste water are mixed with vinyl cyanide, sodium cyanide waste water and carry out the processing of A/O biochemical denitrification, remove COD, NaSCN, NH in the waste water thereby reach
3The purpose of the pollutents such as-N.
Chinese patent CN101638278A discloses a kind of pretreatment process of acrylic fiber chemical wastewater, this invention is carried out interior electrolysis treatment and the processing of Fenton reagent oxidation to the acrylic fiber chemical wastewater that the pH value is adjusted to less than 6, in order to the heavy metal ion in the preliminary removal acrylic fiber chemical wastewater, ammonia nitriding compound and organism, and the oxidation operation of bio-refractory is decomposed into the organism of easy biochemical degradation.Adopt the method for this invention to improve through pretreated organism bio-degradable, for follow-up biochemical treatment provides good prerequisite.
But there are many defectives in above-mentioned technology:
(1) existing pressurized hydrolysis-biochemical treatment process, the alkaline hydrolysis process is little to the action effect of oligopolymer, and oligopolymer also is difficult to remove by biochemical process, and produces soda acid pollution and ammonia and nitrogen pollution problem.
(2) adopt the techniques such as coagulation-precipitation, coagulation-air supporting as pretreatment technology, water outlet BOD
5/ COD value is lower, and the bio-degradable ability is still very poor, causes follow-up biochemical treatment, is difficult to reach the qualified discharge of sewage; The transfer of pollutent, by methods such as coagulation-precipitation, coagulation-air supporting, magnetic resin absorption with oligopolymer in the waste water with the mud cake form from wherein separating, hazardous and noxious substances is transferred to solid phase by liquid phase in its waste water, has produced secondary pollution, contaminate environment.
(3) existing multistage anaerobic/, aerobic treatment route, pollutent in the Nitrilon waste water can produce restraining effect to anaerobe, and high and low polymers molecular weight is large, difficulty is biodegradable, oligopolymer has very strong adhesive, the filler of anaerobic pond and Aerobic Pond parcel, microbial film is gone to pot, cause sewage work's processing efficiency sharply to descend.
(4) traditional biochemical processing process (for example, A/O treatment process etc.) treatment scheme is long, and floor space is large, and investment is large, and processing costs is high.
(5) consideration of ammonia nitrogen problem is comprehensive not, can't guarantee normally carrying out of nitration denitrification reaction, uses shipwreck with up to standard, and except COD content height, ammonia-nitrogen content is higher in the water outlet.
Therefore, the technology of the processing Nitrilon waste water of domestic industrial application all can not reach ideal effect at present, is difficult to the COD in the Nitrilon waste water is down to below the 250mg/L, and has a lot of defectives in the technology application process.Any single treatment process all is difficult to the treatment effect that reaches higher, two or more rationally effective combination process becomes the direction of research and probe, finally reaches the purpose of improving the Nitrilon waste water effluent quality with the advantage by the performance the whole bag of tricks.
Summary of the invention
The object of the present invention is to provide a kind of method of processing Nitrilon waste water, the advantage such as it has, and cost is low, effluent quality is high (such as low COD value and high B/C value) and technique are simple.
One aspect of the present invention provides a kind of method of processing Nitrilon waste water, and described method comprises the steps:
(a) Nitrilon waste water is carried out the ultrasonic wave hydrolysis treatment;
(b) Nitrilon waste water through the ultrasonic wave hydrolysis treatment that step (a) is obtained is processed with biological reaction tank; And
(c) Nitrilon waste water that step (b) is obtained carries out Fenton to be processed.
In a preferred embodiment of the present invention, the condition of described ultrasonic wave hydrolysis is as follows: frequency is 10-750kHz, preferred 10-200kHz, more preferably 10-100kHz, most preferably 20-50kHz; Acoustic intensity is 1-100W/cm
2, be preferably 1-80W/cm
2, 5-50W/cm more preferably
2, most preferably be 5-20W/cm
2Hydraulic detention time is 0.5-10h, is preferably 1-5h, and more preferably 1-4h most preferably is 1.5-3h.
In a preferred embodiment of the present invention, carry out preferably the pH value of Nitrilon waste water being regulated before the ultrasonic wave hydrolysis, for example the pH value is preferably 10-14, and more preferably 11-13 most preferably is about 12.
In a preferred embodiment of the present invention, described biological reaction tank is the integral biological reaction tank.
In a preferred embodiment of the present invention, described integral biological reaction tank comprises built-in aeration tube; Preferably, the body of described aeration tube comprises aeration porose area and non-aeration porose area; Described solarization air cap district is positioned at the tube wall of 180 ° of-300 ° of positions, angle, the body cross section center of circle; Described solarization air cap is distinguished and is furnished with a plurality of solarization air caps that run through tube body wall; Described non-aeration porose area is positioned at the tube wall except the aeration zone on the body.
In a preferred embodiment of the present invention, the integral biological reaction tank comprises the highly effective air power set; Preferably, described highly effective air power set comprises:
-a plurality of airlift unit, and described airlift unit comprises:
-be located at the airlift air feed port on top, airlift unit;
-be located at the gas manifold of side, airlift unit; Described gas manifold connects the airlift aeration tube; Arrange a plurality of so that air enters the airlift ventage of airlift aeration tube from gas manifold between described gas manifold and the described airlift aeration tube;
The side of-described airlift aeration tube arranges a plurality of self-closing production wells;
-contraminated zone, described contraminated zone be located at the airlift aeration tube around so that described aeration tube in gas be distributed in described contraminated zone by the self-closing production well.
In a preferred embodiment of the present invention, described integral biological reaction tank operating parameter is as follows: pH is 6-10, is preferably 6.5-9, and more preferably 6.5-8.5 most preferably is 7-8.5; Hydraulic detention time is 5-100h, is preferably 5-80h, and more preferably 10-60h most preferably is 15-40h; Dissolved oxygen concentration 0-5.0mg/L is preferably 0.1-3.0mg/L, and more preferably 0.1-2.0mg/L most preferably is 0.1-0.5mg/L; Sludge concentration is 1-50g/L, is preferably 2-40g/L, and more preferably 5-20g/L most preferably is 6-10g/L.
In a preferred embodiment of the present invention, it is as follows that described Fenton processes operating parameter: reaction conditions is normal temperature and pressure, and initial pH is 3-6, is preferably 3-5, and more preferably 3.5-4.5 most preferably is 3.5-4; Reaction times is 1-4h, is preferably 1-3h, more preferably 1-2h; H
2O
2With the COD mass ratio be 1-3, be preferably 1-2, more preferably 1.5-2; Add the amount of ferrous sulfate, i.e. H
2O
2And FeSO
4Mol ratio is 3-6, is preferably 3-5, more preferably 4-5.
The present invention provides a kind of technique for preparing acrylic fibers on the other hand, and described technique comprises the method for processing Nitrilon waste water of the present invention.
A further aspect of the invention provides a kind of Nitrilon waste water, and described Nitrilon waste water obtains by method of the present invention; Preferably, the COD of described Nitrilon waste water is less than or equal to 150mg/L, and ammonia nitrogen concentration is less than or equal to 20mg/L; More preferably; The COD of described Nitrilon waste water is 10-150mg/L, and ammonia nitrogen concentration is 5-20mg/L; Most preferably; The COD of described Nitrilon waste water is 40-100mg/L, and ammonia nitrogen concentration is 10-18mg/L.
The present invention proposes a kind of combination process of processing Nitrilon waste water, that is: adopt the combination process of ultrasonic wave hydrolysis-integral biological reaction tank-unit such as Fenton oxidation to process Nitrilon waste water.By Nitrilon waste water being carried out ultrasonic wave hydrolysis pre-treatment, with the oligopolymer in the waste water and be difficult to that biodegradable long-chain macromolecule decomposes and degraded, obviously reduce the COD index of such waste water, improve its biodegradability.The water outlet of ultrasonic wave hydrolysis enters the integral biological reaction tank, carries out denitrogenation, de-carbon biological respinse, removes most COD and ammonia nitrogen (comprise organic compounds containing nitrogen transform and form).The water outlet of integral biological reaction tank is by the hardly degraded organic substance of Fenton technique oxidation removal remnants, to guarantee effluent quality.
Description of drawings
Fig. 1 is the schema of the processing Nitrilon waste water of Comparative Examples 1.
Fig. 2 is the schema that the embodiment of the invention 1 is processed Nitrilon waste water.
Fig. 3 is that the ultrasonic wave hydrolysis is for the impact of COD.
Embodiment
" scope " disclosed herein is with the form of lower limit and the upper limit.Can be respectively one or more lower limits, and one or more upper limit.Given range limits by a selected lower limit and a upper limit.The border that selected lower limit and the upper limit define special scope.All can carry out by this way restricted portion and comprise with capable of being combined, and namely any lower limit can be combined to form a scope with any upper limit.For example, listed the scope of 60-120 and 80-110 for special parameter, be interpreted as that the scope of 60-110 and 80-120 also expects.In addition, if the minimum extent value 1 and 2 of listing, and if listed maximum range value 3,4 and 5, the scope below then can all expect: 1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless have other the explanation, the content range of each component of composition with and preferable range between can mutually be combined to form new technical scheme.
In the present invention, unless other explanations are arranged, the technical characterictic of each technical scheme can be combined to form new technical scheme mutually.For concise and to the point purpose, the applicant has omitted the specific descriptions of these combinations in specification sheets, but can think that the open scope of this specification sheets has specifically comprised these technical schemes that obtain by combination.
In the present invention, unless other explanations are arranged, the multicomponent mixture of " its combination " described each element of expression, for example two kinds, three kinds, four kinds and until the multicomponent mixture of maximum possible.
In the present invention, unless other explanations are arranged, all " parts " and percentage ratio (%) all refer to weight percentage.
In the present invention, unless other explanations are arranged, the percentage ratio sum of each component is 100% in all compositions.
In the present invention, unless other explanations are arranged, the breviary that numerical range " a-b " expression a closes to the arbitrary real array between the b represents that wherein a and b are real numbers.For example the whole real numbers between " 0-5 " have all been listed in numerical range " 0-5 " expression herein, and " 0-5 " just the breviary of these combinations of values represents.
In the present invention, unless other explanations are arranged, integer numerical range " a-b " expression a represents that to the breviary of the combination of the arbitrary integer between the b wherein a and b are integers.For example integer numerical range " 1-N " expression 1,2 ... N, wherein N is integer.
Mention in this manual all documents (comprising patent disclosure text and non-patent publication us) and all be inserted in this in full by reference, as the part of this specification sheets.For the purpose of concise and to the point, this specification sheets no longer is described the full text of above-mentioned document, but does not represent that the content of above-mentioned document is not open in this manual.
If do not explicitly point out, then used term " a kind of " refers to " at least a " among the present invention.
One aspect of the present invention provides a kind of method of processing Nitrilon waste water, and described method comprises the steps:
(a) Nitrilon waste water is carried out the ultrasonic wave hydrolysis treatment;
(b) Nitrilon waste water through the ultrasonic wave hydrolysis treatment that step (a) is obtained is processed with biological reaction tank; And
(c) Nitrilon waste water that step (b) is obtained carries out Fenton to be processed.
Pollutent in the ultrasonic degradation waste water is the physical and chemical changes that comes from ultrasonic cavitation effect and cause thus.Ultrasonic wave produces two kinds of effects:
When (1) sound field is propagated, produce violent vibration in waste water.This violent vibration shows powerful hydromeehanics shearing force in macroscopic view, makes carbon bond generation fracture on the macromolecular main chain, thereby plays the effect of degraded macromolecular.
(2) cavitation effect impels that steeping in water for reconstitution is estranged to be split and chain reaction, forms free oxygen and H thereby produce oxyradical
2O
2Free radical and H that organism soluble in water and cavitation effect produce
2O
2React, thereby organic pollutant is directly decomposed or oxidative degradation.
Therefore, Nitrilon waste water is through ultrasonic wave hydrolysis, oligopolymer wherein and be difficult to that biodegradable long-chain macromolecule decomposes and degraded, thus obviously reduced the COD index of Nitrilon waste water.The B/C value of water inlet can be brought up to 0.2-0.4 from being less than or equal to 0.1, thereby improves its biodegradability.
In the present invention, how carrying out the ultrasonic wave hydrolysis treatment is conventional to those skilled in the art, but those of ordinary skills go out can be used for concrete grammar of the present invention in conjunction with the prior art direct derivation again according to description of the invention.In a preferred embodiment of the present invention, the condition of described ultrasonic wave hydrolysis is as follows: frequency is 10-750kHz, preferred 10-200kHz, more preferably 10-100kHz, most preferably 20-50kHz; Acoustic intensity is 1-100W/cm
2, be preferably 1-80W/cm
2, 5-50W/cm more preferably
2, most preferably be 5-20W/cm
2Hydraulic detention time is 0.5-10h, is preferably 1-5h, and more preferably 1-4h most preferably is 1.5-3h.
In a preferred embodiment of the present invention, carry out preferably the pH value of Nitrilon waste water being regulated before the ultrasonic wave hydrolysis, for example the pH value is preferably 10-14, and more preferably 11-13 most preferably is about 12.
In the present invention, COD slightly reduced and the biodegradability raising after Nitrilon waste water was hydrolyzed through ultrasonic wave, then entered biological reaction tank and processed.In the present invention, described biological reaction tank is conventional, and those of ordinary skill in the art can directly obtain concrete biological reaction tank in conjunction with prior art again according to description of the invention.In a preferred embodiment of the present invention, described biological reaction tank is the integral biological reaction tank.
In a preferred embodiment of the present invention, the integral biological reaction tank comprises built-in aeration tube.An example of described aeration tube can be referring to CN201436285U (it is inserted in this in full by reference), for example embodiment 1 of CN201436285U and 2 described disclosed aeration tubes.The terminal dissolved oxygen of integral biological reaction tank preferably is controlled at 0.5mg/L, and the in-built wired dissolved oxygen analytic instrument of reaction tank.According to the signal of line dissolved oxygen analytic instrument, regulate blower fan tolerance to reduce energy consumption.Preferably, comprise the double oxygen and the aerobic zone that alternately occur in the integral biological reaction tank, so that top condition nitrated, that denitrification carries out simultaneously to be provided, thereby reduce the ammonia nitrogen concentration in the waste water.More preferably, the integral biological reaction tank uses the highly effective air power set.An example of described highly effective air power set is referring to CN201530745U (it is inserted in this in full by reference), for example the embodiment 1 disclosed highly effective air power set of CN201530745U.Reflux by vast scale, mixed solution is back to feed-water end from end, directly the high-concentration waste water of feed-water end is carried out dilution for many times, so that the organic concentration gradient is little in the whole reaction tank, the each several part oxygen requirement is more or less the same, and improves the efficient of biological respinse.
In the present invention, another example of described aeration tube is as follows: the body of aeration tube comprises aeration porose area and non-aeration porose area; Described solarization air cap district is positioned at the tube wall of 180 ° of-300 ° of positions, angle, the body cross section center of circle; Described solarization air cap is distinguished and is furnished with a plurality of solarization air caps that run through tube body wall; Described non-aeration porose area is positioned at the tube wall except the aeration zone on the body.
In the present invention, another example of described highly effective air power set comprises:
-a plurality of airlift unit, and described airlift unit comprises:
-be located at the airlift air feed port on top, airlift unit;
-be located at the gas manifold of side, airlift unit; Described gas manifold connects the airlift aeration tube; Arrange a plurality of so that air enters the airlift ventage of airlift aeration tube from gas manifold between described gas manifold and the described airlift aeration tube;
The side of-described airlift aeration tube arranges a plurality of self-closing production wells;
-contraminated zone, described contraminated zone be located at the airlift aeration tube around so that described aeration tube in gas be distributed in described contraminated zone by the self-closing production well.
In the present invention, the processing condition of described integral biological reaction tank are conventional, and those of ordinary skill in the art can directly obtain its processing condition in conjunction with prior art again according to description of the invention.In a preferred embodiment of the present invention, integral biological reaction tank operating parameter is as follows: pH is 6-10, is preferably 6.5-9, and more preferably 6.5-8.5 most preferably is 7-8.5; Hydraulic detention time is 5-100h, is preferably 5-80h, and more preferably 10-60h most preferably is 15-40h; Dissolved oxygen concentration 0-5.0mg/L is preferably 0.1-3.0mg/L, and more preferably 0.1-2.0mg/L most preferably is 0.1-0.5mg/L; Sludge concentration is 1-50g/L, is preferably 2-40g/L, and more preferably 5-20g/L most preferably is 6-10g/L.
In the present invention, the Fenton processing is conventional.Usually, Fenton processes and refers to H
2O
2At Fe
2+Katalysis under decompose to produce the OH of strong oxidizing property, again by the adduction between free radical and the organic compound, replacement, transfer transport, scission of link etc., can non-selectivity oxygenolysis organism.It is strong that the Fenton processing has oxidisability, do not produce the advantage of secondary pollution.Adopt the Fenton method as the advanced treatment of Nitrilon waste water among the present invention, process the water outlet of integral biological reaction tank, organic loading is low, has directly reduced investment and the running cost of high-level oxidation technology, and has further improved effluent quality, makes the final qualified discharge of water outlet.
In a preferred embodiment of the present invention, it is as follows that Fenton processes operating parameter: reaction conditions is normal temperature and pressure, and initial pH is 3-6, is preferably 3-5, and more preferably 3.5-4.5 most preferably is 3.5-4; Reaction times is 1-4h, is preferably 1-3h, more preferably 1-2h; H
2O
2With the COD mass ratio be 1-3, be preferably 1-2, more preferably 1.5-2; Add the amount of ferrous sulfate, i.e. H
2O
2And FeSO
4Mol ratio is 3-6, is preferably 3-5, more preferably 4-5.
In a preferred embodiment of the present invention, above-mentioned steps (a), (b) and order (c) are (a), (b) and then (c).
Process Nitrilon waste water through ultrasonic wave hydrolysis-integral biological reaction tank-Fenton combination process, realize the sewage qualified discharge, solved in the present Nitrilon waste water processing long flow path, complicated operation, the problem that outlet effect is below standard.
The present invention adopts ultrasonic wave hydrolysis-integral biological reaction tank-Fenton combination process to process Nitrilon waste water, flow process is simple, easy to operate, effective degradation of organic substances and ammonia nitrogen, and has a stronger impact resistance, it is strong to invest its degradation property and shock resistance, and outlet effect is good, and COD and ammonia nitrogen concentration all are better than national grade one discharge standard in the water outlet.
Further illustrate the present invention below in conjunction with embodiment.Should be appreciated that following embodiment only is used for illustration purpose, is not limited to the present invention.
Embodiment
Comparative Examples 1
Step 1 is passed in the equalizing tank regulating water quality and the water yield with certain acrylic fiber production process factory Nitrilon waste water.
Step 2 passes into the Nitrilon waste water after step 1 is regulated in the contact-oxidation pool.Arrange soft cellulose filler in the contact-oxidation pool, hydraulic detention time is 18h, adopts blast aeration, the about 3-4mg/L of dissolved oxygen concentration.After contact-oxidation pool was processed, effluent COD concentration was about 600-800mg/L.Because the bonding of the oligopolymer in Nitrilon waste water filler affects the biofilm effect, after the long-time running, the processing efficiency of sewage work reduces.
Step 3, contact-oxidation pool water outlet are sent into anoxic/aerobic (A/O) reaction tank, and dissolved oxygen in anoxic tank concentration is less than 0.3mg/L, and hydraulic detention time is 8h, and the about 2-3mg/L of Aerobic Pond dissolved oxygen concentration, hydraulic detention time are 24h, sludge concentration 3-5g/L.After the A/O reaction tank was processed, water outlet COD maintained 200-400mg/L, and ammonia nitrogen concentration 30-40mg/L can not qualified discharge, and the oxygenation energy consumption is higher in the biological treatment, and the biological reaction tank floor space is large.
Certain acrylic fiber production process factory production equipment sewage effluent water quality table of table 1
Embodiment 1
Step 1 is passed into certain acrylic fiber production process factory in the equalizing tank regulating water quality and the water yield.Simultaneously add sodium hydroxide in equalizing tank, the pH value of regulating Nitrilon waste water is about 12.
Step 2 will be passed into through the Nitrilon waste water that step 1 was processed in the ultrasonic wave hydrolytic tank.Hyperacoustic frequency is 22kHz, and acoustic intensity is 10W/cm
2, the reaction times is 2h, reaction conditions is normal temperature and pressure.Open loop, chain-breaking reaction occur in the larger molecular organics molecule in the sewage under the extreme physical condition of ultrasonic generation, it is converted into easily is biodegradable small-molecule substance.
Below in conjunction with table 2 and Fig. 3 the pretreating effect among the embodiment is described.
Table 2 Nitrilon waste water adopts different pretreatments Inlet and outlet water water quality
Reference table 2 and Fig. 3 adopt separately alkaline hydrolysis to process, and the COD average removal rate is 20.67%, and water outlet B/C index brings up to 0.11 by 0.091, and biodegradability is not improved.And through the ultrasonic wave hydrolysis, the COD average removal rate is 32.18%, and water outlet B/C index brings up to 0.22 by 0.091, and biodegradability is significantly improved.As seen the polymer unwinds of some macromole, carbochain having been grown by ul-trasonic irradiation becomes the short polymkeric substance of small molecules, carbochain, has obviously improved the biodegradability of Nitrilon waste water, for subsequent biological treatment is laid a good foundation.
Step 3 is hydrolyzed pretreated Nitrilon waste water through ultrasonic wave and is passed into the integral biological reaction tank.In water inlet, add phosphoric acid salt.Described phosphoric acid salt is selected from potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC, and the COD of water inlet and phosphatic weight ratio are 100: (0.5-2).
The biochemical treatment condition is: sludge concentration 8g/L, and dissolved oxygen concentration 0.5mg/L, hydraulic detention time 20h, pH are 7.5.After the integral biological reaction tank was processed, effluent COD concentration maintained in the 150-90mg/L scope.
Step 4 passes into the described Nitrilon waste water of processing through the integral biological reaction tank in the Fenton reagent oxidation pond, and the organism of difficult degradation remaining in the sewage is carried out oxygenolysis.
Wherein, the treatment condition in Fenton reagent oxidation pond are: the H of adding
2O
2With the COD mass ratio be 2; The H that adds
2O
2And FeSO
4Mol ratio is 5; Reaction times is 1 hour; Reaction conditions is normal temperature and pressure.Add Fe in the waste water
2+, H
2O
2After, Fe
2+And H
2O
2Between chain reaction occurs, in reaction, produce active extremely strong free radical (such as OH), by the adduction between free radical and the organic compound, replacement, transfer transport, scission of link etc., make the hardly degraded organic substance oxidative degradation in the water body become low toxicity or non-toxic substance, even directly be degraded into CO again
2, H
2O and other inorganic salt are near permineralization.After the Fenton method was processed, acrylon sewage COD was reduced to 60mg/L by 150-90mg/L.
Adopt embodiment 1 method to compare with Comparative Examples 1, the results are shown in Table 3.
Table 3 Nitrilon waste water adopts the analysis of different process treatment effect
By as seen from Table 3, water outlet COD can be reduced to 60mg/L behind the method for the embodiment 1 processing Nitrilon waste water, ammonia nitrogen is reduced to 15mg/L.
Claims (10)
1. method of processing Nitrilon waste water, described method comprises the steps:
(a) Nitrilon waste water is carried out the ultrasonic wave hydrolysis treatment;
(b) Nitrilon waste water through the ultrasonic wave hydrolysis treatment that step (a) is obtained is processed with biological reaction tank; And
(c) Nitrilon waste water that step (b) is obtained carries out Fenton to be processed.
2. the method for claim 1 is characterized in that, the condition of described ultrasonic wave hydrolysis is as follows: frequency is 10-750kHz, preferred 10-200kHz, more preferably 10-100kHz, most preferably 20-50kHz; Acoustic intensity is 1-100W/cm
2, be preferably 1-80W/cm
2, 5-50W/cm more preferably
2, most preferably be 5-20W/cm
2Hydraulic detention time is 0.5-10h, is preferably 1-5h, and more preferably 1-4h most preferably is 1.5-3h.
3. the method for claim 1 is characterized in that, carries out preferably the pH value of Nitrilon waste water being regulated before the ultrasonic wave hydrolysis, and for example the pH value is preferably 10-14, and more preferably 11-13 most preferably is about 12.
4. the method for claim 1 is characterized in that, described biological reaction tank is the integral biological reaction tank.
5. method as claimed in claim 4 is characterized in that, described integral biological reaction tank comprises built-in aeration tube; Preferably, the body of described aeration tube comprises aeration porose area and non-aeration porose area; Described solarization air cap district is positioned at the tube wall of 180 ° of-300 ° of positions, angle, the body cross section center of circle; Described solarization air cap is distinguished and is furnished with a plurality of solarization air caps that run through tube body wall; Described non-aeration porose area is positioned at the tube wall except the aeration zone on the body.
6. method as claimed in claim 4 is characterized in that, the integral biological reaction tank comprises the highly effective air power set; Preferably, described highly effective air power set comprises:
-a plurality of airlift unit, and described airlift unit comprises:
-be located at the airlift air feed port on top, airlift unit;
-be located at the gas manifold of side, airlift unit; Described gas manifold connects the airlift aeration tube; Arrange a plurality of so that air enters the airlift ventage of airlift aeration tube from gas manifold between described gas manifold and the described airlift aeration tube;
The side of-described airlift aeration tube arranges a plurality of self-closing production wells;
-contraminated zone, described contraminated zone be located at the airlift aeration tube around so that described aeration tube in gas be distributed in described contraminated zone by the self-closing production well.
7. method as claimed in claim 4 is characterized in that, described integral biological reaction tank operating parameter is as follows: pH is 6-10, is preferably 6.5-9, and more preferably 6.5-8.5 most preferably is 7-8.5; Hydraulic detention time is 5-100h, is preferably 5-80h, and more preferably 10-60h most preferably is 15-40h; Dissolved oxygen concentration 0-5.0mg/L is preferably 0.1-3.0mg/L, and more preferably 0.1-2.0mg/L most preferably is 0.1-0.5mg/L; Sludge concentration is 1-50g/L, is preferably 2-40g/L, and more preferably 5-20g/L most preferably is 6-10g/L.
8. the method for claim 1 is characterized in that, it is as follows that described Fenton processes operating parameter: reaction conditions is normal temperature and pressure, and initial pH is 3-6, is preferably 3-5, and more preferably 3.5-4.5 most preferably is 3.5-4; Reaction times is 1-4h, is preferably 1-3h, more preferably 1-2h; H
2O
2With the COD mass ratio be 1-3, be preferably 1-2, more preferably 1.5-2; Add the amount of ferrous sulfate, i.e. H
2O
2And FeSO
4Mol ratio is 3-6, is preferably 3-5, more preferably 4-5.
9. technique for preparing acrylic fibers, described technique comprises the method for processing Nitrilon waste water claimed in claim 1.
10. Nitrilon waste water, described Nitrilon waste water obtains by method claimed in claim 1; Preferably, the COD of described Nitrilon waste water is less than or equal to 150mg/L, and ammonia nitrogen concentration is less than or equal to 20mg/L; More preferably; The COD of described Nitrilon waste water is 10-150mg/L, and ammonia nitrogen concentration is 5-20mg/L; Most preferably; The COD of described Nitrilon waste water is 40-100mg/L, and ammonia nitrogen concentration is 10-18mg/L.
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