CN102795740B - High-efficiency denitrification method of acrylonitrile production wastewater - Google Patents
High-efficiency denitrification method of acrylonitrile production wastewater Download PDFInfo
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- CN102795740B CN102795740B CN2012101221962A CN201210122196A CN102795740B CN 102795740 B CN102795740 B CN 102795740B CN 2012101221962 A CN2012101221962 A CN 2012101221962A CN 201210122196 A CN201210122196 A CN 201210122196A CN 102795740 B CN102795740 B CN 102795740B
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 46
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000005273 aeration Methods 0.000 claims abstract description 37
- 239000010802 sludge Substances 0.000 claims abstract description 35
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 241000894006 Bacteria Species 0.000 claims abstract description 13
- 238000005276 aerator Methods 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000002054 inoculum Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000005265 energy consumption Methods 0.000 claims description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical group N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 238000009434 installation Methods 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000004062 sedimentation Methods 0.000 abstract 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229920002972 Acrylic fiber Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 5
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic nitrile Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- TWHASHYLEGKHEX-UHFFFAOYSA-N [N].N.N#CC#N Chemical compound [N].N.N#CC#N TWHASHYLEGKHEX-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000003851 biochemical process Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920013649 Paracril Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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Abstract
The invention discloses a high-efficiency denitrification method of acrylonitrile production wastewater, which comprises steps as follows: acrylonitrile production wastewater is introduced into an anoxic tank for treatment, effluent water of the anoxic tank enters an aeration tank for treatment, effluent water of the aeration tank is subjected to mud-water separation via a secondary sedimentation tank and enters an oxidation reaction tank for oxidation treatment, and effluent water of the oxidation reaction tank enters a sedimentation tank for sedimentation; the anoxic tank, aeration tank and secondary sedimentation tank contain activated sludge containing rich cyanide degradation bacteria; the effective volume ratio of the anoxic tank to the aeration tank is 1:1-1:1.5; the aeration tank is provided with an HS forced-cut aerator; and the air quantity for aeration is 10-15m<3>/min/1000m<3>. The invention also discloses a biochemical denitrification treatment method of acrylonitrile production wastewater, and an activated sludge containing rich cyanide degradation bacteria and a preparation method thereof, which are related to the high-efficiency denitrification method. The high-efficiency denitrification method of acrylonitrile production wastewater has the advantages of simple process, investment saving and low operating cost, and is simple to operate; and the treated wastewater can achieve Grade 1 in GB8978-1996.
Description
Technical field
The present invention relates to water-treatment technology field, be specifically related to a kind of efficient denitrification method of Wastewater from Acrylonitrile Production, and the active sludge of the concentration of cyanide degradation bacteria of using in the method and preparation method thereof, and a kind of biochemical denitrification treatment process of Wastewater from Acrylonitrile Production.
Background technology
In recent years along with the development of vinyl cyanide derived product acrylic fibers, acrylonitrile-butadiene-styrene (ABS)/vinylbenzene (ABS/AS), acrylamide, paracril and the aspects such as nitrile rubber, adiponitrile and hexanediamine, particularly the continually developing and applying of downstream fine chemistry industry new product, the vinyl cyanide demand in the world constantly increases.Vinyl cyanide is a kind of volatile, hypertoxic organic compound, and EPA and China have listed it in the priority pollutants list in succession.
The method of both at home and abroad acrylic nitrile waste water being processed mainly contains: evaporation concentration method, biochemical process, ferrous sulfate method, superoxide method, hydrolysis method, Ozonation, liquid-film method, ion exchange method, active carbon adsorption etc.For concentration, lower acrylic nitrile waste water generally takes biochemical process to process.The acrylic nitrile waste water biologic treating technique is still not overripened at present, and the operation successful experience is less.Grand celebration Acrylic Fibers Plant sewage disposal main flow employing table exposes to the sun and adds the contact oxidation, and influent COD is diluted to 800-1000mgL
-1, water outlet COD<200mgL
-1, NH
3-N is about 150mgL
-1.Sewage disposal main flow in chemical fibre factory, Fushun is aeration tower-anaerobic biological-catalytic oxidation-charcoal tower, and influent COD is 1200mgL
-1, water outlet COD is 500-600mgL
-1, variation water quality is large, large on the biochemical treatment impact, fluctuation of service.Kingsoft petrochemical industry Acrylic Fibers Plant sewage disposal main flow is the tower filter, and influent COD is 1000-2000mgL
-1, water outlet is 500-700mgL
-1.Anqing Petrochemical Company acrylic fibers company limited has adopted A/O art breading acrylon sewage to be processed, but treatment effect is unsatisfactory, and water outlet COD is 103.5mgL
-1, ammonia nitrogen is 31.3mgL
-1.The treatment effect of Lanzhou Petrochemical Acrylic Fibers Plant is relatively good, and water outlet COD is 102mg/L, and ammonia nitrogen is 1.02mgL
-1Yet, in its water inlet, have 1/3 to be the easy sanitary sewage of biological treatment, and treatment process is hydrolysis-A/O technique-catalytic oxidation, more loaded down with trivial details.
Summary of the invention
Technical problem to be solved by this invention is to have overcome that the treatment process technology of existing biological treatment Wastewater from Acrylonitrile Production immaturely causes fluctuation of service, treatment effect is undesirable or the defect such as technique is loaded down with trivial details, a kind of efficient denitrification method of Wastewater from Acrylonitrile Production is provided, the biochemical denitrification treatment process of Wastewater from Acrylonitrile Production, and the active sludge of the concentration of cyanide degradation bacteria of using in the method and preparation method thereof.The efficient denitrification method of Wastewater from Acrylonitrile Production of the present invention is that a kind of flow process is simple, reduced investment, processing efficiency are high, be applicable to the method that project scale is processed Wastewater from Acrylonitrile Production.
The invention provides a kind of preparation method of active sludge of concentration of cyanide degradation bacteria, it comprises the steps: 1. the Wastewater from Acrylonitrile Production after dilution to be passed in biological treatment system and processed as water inlet, active sludge is inoculated in described biological treatment system, and the inoculum size of active sludge is 10-15gL
-1, and adding organic carbon source, the dosage of organic carbon source is 50-150mgCODL
-1D
-1The useful volume that L in the inoculum size of described active sludge and the dosage of organic carbon source is described biological treatment system; Described biological treatment system is the A/O system, comprise the anoxic pond (A pond), aeration tank (O pond) and the second pond that connect successively, the ratio of the useful volume of described anoxic pond and described aeration tank is 1: 1-1: 1.5, HS is installed in described aeration tank and cuts by force aerator, the aeration air quantity of this aerator is 10-15m
3/ min/1000m
32. the extension rate of described dilution is at front 6-8 in week, is reduced to gradually 5 times from 10 times, makes to bring up to gradually 10.0mgL into total cyanogen (TCN) content in water
-1NH in the water outlet of described biological treatment system
3-N content≤5.0mgL
-1The time, described extension rate is narrowed down to 1 times gradually from 5 times, get final product.
In the present invention, the factory effluent that contains the pollutents such as a large amount of vinyl cyanide, vinylformic acid, acetonitrile, propenal, prussiate that described Wastewater from Acrylonitrile Production is the conventional indication in this area.COD, TKN, NH in described Wastewater from Acrylonitrile Production
3The index such as-N and TCN can be different because of engineering, mainly take COD in the present invention as 1200-3000mgL
-1, TKN is 200-500mgL
-1, NH
3-N is 100-250mgL
-1With TCN be 3-10mgL
-1Factory effluent as embodiment preferably, but be not limited to this.
In the present invention, the active sludge that described active sludge is various routines in this area, as the active sludge of common municipal wastewater treatment plant.
In the present invention, described anoxic pond is generally followed stir process when processing, and by agitator is installed, realizes that active sludge does not sink to the bottom.Described agitator is preferably underwater propeller, and described underwater propeller is preferably 1KW/1000m by energy consumption
3Type selecting.
In the present invention, the mode of operation of described biological treatment system is identical with the A/O system of this area, be roughly: enter into anoxic pond and process, the water outlet of anoxic pond enters into aeration tank and processes, the water outlet of aeration tank is discharged after the second pond mud-water separation, and the sludge reflux of second pond is to the feed-water end of anoxic pond.
In the present invention, described aeration tank preferably adopts the plug-flow tank type, is provided with gallery in pond.The total length of described gallery is preferably 5-20 with the ratio of width: 1.
In the present invention, it is that Shanghai Xin Yuan Genie et Environnement produces that described HS cuts by force aerator, and model is that HS cuts by force aerator.
In the present invention, the sludge reflux of described second pond is this area routine operation to the reflux ratio of anoxic pond feed-water end, and preferably reflux ratio is 1.0-2.0, guarantees that the sludge concentration in described biological treatment system maintains 5.0-8.0gVSSL
-1.
In the present invention, described organic carbon source is the organic carbon source of easily degrading, as glucose.
Step 2. in, if extension rate be reduced to 5 times afterwards the water inlet in total cyanogen content do not reach 10.0mgL
-1, can make it meet this total cyanogen content by adding prussiate.Described prussiate can be the inorganic cyanide salt of various routines, as sodium cyanide.
Extension rate of the present invention refers to dilute the business of front strength of solution divided by the strength of solution gained after diluting.
The present invention also provides the active sludge of the concentration of cyanide degradation bacteria obtained by above-mentioned preparation method.The active sludge of the concentration of cyanide degradation bacteria of the present invention prussiate of not only can degrading, can also degrade as hazardous and noxious substances such as propenal.
The present invention also provides a kind of biochemical denitrification treatment process of Wastewater from Acrylonitrile Production, it comprises the steps: Wastewater from Acrylonitrile Production is passed in described anoxic pond and processes, the water outlet of described anoxic pond enters into described aeration tank and processes, the water outlet of described aeration tank is discharged after described second pond mud-water separation, the sludge reflux of described second pond is to the feed-water end of described anoxic pond, nitrification liquid in described aeration tank is back to the feed-water end of described anoxic pond, the active sludge that contains described concentration of cyanide degradation bacteria in described anoxic pond, aeration tank and second pond; The ratio of the useful volume of described anoxic pond and described aeration tank is 1: 1-1: 1.5, and HS to be installed in described aeration tank and to cut by force aerator, the aeration air quantity of this aerator is 10-15m
3/ min/1000m
3.
Wherein, described anoxic pond is generally followed stir process when processing, and by agitator is installed, realizes that active sludge does not sink to the bottom.Described agitator is preferably underwater propeller, and described underwater propeller is 1KW/1000m by energy consumption
3Type selecting.
Wherein, described aeration tank preferably adopts the plug-flow tank type, is provided with gallery in pond.The total length of described gallery is preferably 5-20 with the ratio of width: 1.
Wherein, it is that Shanghai Xin Yuan Genie et Environnement produces that described HS cuts by force aerator, and model is that HS cuts by force aerator.
In the present invention, the sludge reflux of described second pond is this area routine operation to the reflux ratio of anoxic pond feed-water end, and preferably reflux ratio is 1.0-2.0, guarantees that the sludge concentration in described biological treatment system maintains 5.0-8.0gVSSL
-1.
The present invention also provides a kind of efficient denitrification method of Wastewater from Acrylonitrile Production, it comprises the steps: to adopt the biochemical denitrification treatment process of described Wastewater from Acrylonitrile Production to carry out the biochemical denitrification processing to Wastewater from Acrylonitrile Production, waste water after processing enters the oxidizing reaction pond and carries out oxide treatment, the water outlet in oxidizing reaction pond enters settling tank and carries out precipitation process, gets final product.
Wherein, described oxide treatment adopts the oxidation treatment method of this area routine to carry out, and preferably adds clorox and carries out oxide treatment.The dosage of described clorox is the conventional dosage in this area, is preferably 10-100mgL
-1.The treatment time of described oxide treatment is this area conventional processing time, is preferably 1.0-4.0h.When carrying out described oxide treatment, preferably stirred.
Wherein, described settling tank is preferably pressed surface load 0.5-0.75m
3/ m
2/ h design.
The efficient denitrification treatment process main units in the specific implementation of Wastewater from Acrylonitrile Production of the present invention can be anoxic pond, aeration tank, second pond, oxidizing reaction pond and settling tank, wherein, the anoxic pond operated by rotary motion has agitator, and aeration tank is provided with HS and cuts by force aerator.
Raw material of the present invention, equipment and assembly be commercially available obtaining all.On the basis that meets this area general knowledge, in the present invention, the optimum condition of each above-mentioned technical characterictic can arbitrary combination obtain preferred embodiments of the present invention.
Positive progressive effect of the present invention is:
1, simple, the reduced investment of the efficient denitrification method flow of Wastewater from Acrylonitrile Production of the present invention, working cost are low, easy and simple to handle.
2, Wastewater from Acrylonitrile Production (being that biochemical denitrification is processed) after improving the A/O art breading, COD<300mgL
-1, NH
3-N<5.0mgL
-1, TCN<1.0mgL
-1.
3, Wastewater from Acrylonitrile Production is after " hypochlorite oxidation-precipitation " processed, water outlet COD, NH
3-N and TCN are less than respectively 100mgL
-1, 1.0mgL
-1With 0.5mgL
-1, reach the GB8978-1996 primary standard.
The accompanying drawing explanation
The process flow sheet of the efficient denitrification method that Fig. 1 is Wastewater from Acrylonitrile Production of the present invention.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.
In following embodiment, NH
3The detection method of-N, COD, TCN and SS is all carried out " water and effluent monitoring analytical procedure ", China Environmental Science Press, the third edition, 1989 by national standard; Be specially: NH
3-N examination criteria is GB7478-87; The TCN examination criteria is GB7486-87; The COD examination criteria is GB11914-89; The SS examination criteria is GB11901-89.
Embodiment 1
Get equivalent amount of active mud, ammonium sulfate in 8 250mL Erlenmeyer flasks, and (the CN-starting point concentration is respectively 0,0.05,0.1,0.2,0.5,1.0,2.0,5.0 and 10.0mgL to add appropriate NaCN
-1), it is 150mL that the interpolation deionized water makes the mixed solution final volume.In Erlenmeyer flask, MLVSS is 1.2gL
-1, NH in mixed solution
3-N starting point concentration is 10.0mgL
-1, CN
-Starting point concentration is respectively 0,0.05,0.1,0.2,0.5,1.0,2.0,5.0 and 10.0mgL
-1.Drip saturated Na
2CO
3, making pH of mixed is 8.5-9.0.Erlenmeyer flask is placed in to shaking table (200rpm) vibration, every the 1h sampling, is placed in the centrifugal 3min of whizzer (4000rpm), in supernatant liquor, drip 1M HCl to pH<2 stopped reactions, measure NH
3The concentration of-N and total cyanogen.
When not adding CN, mud can be by ammonia nitrogen from 10.0mgL in 6h
-1Degrade to 0.2mgL
-1Below, rate of nitrification is 1.26mgNH
3-NgVSS
-1H
-1.0.04mg CN-g VSS
-1Prussiate on nitrated almost not impact.When NaCN concentration is 0.17mg CN
-G
-1During VSS, NH
3The lag phase of 1h appears in the degraded initial stage of-N, after lag phase, and NH
3-N just starts degraded.Along with the raising of CN concentration, also extend gradually lag phase.When the CN dosage is 0.83mg CN
-GVSS
-1The time, nitration reaction has been stagnated 6h; When the CN dosage is 1.67mg CN
-GVSS
-1The time, nitration reaction has been stagnated 7h; When the CN dosage is 8.33mg CN
-GVSS
-1The time, ammonia nitrogen is almost not degraded in 24h.
There is regular phenomenon in batch test-results: nitrification CN concentration in free-water is greater than 0.08mg CN
-GVSS
-1In time, can stop carrying out, and only has after the CN degraded is to 0 and could start reaction; When the CN dosage is 8.33mg CN
-GVSS
-1The time, ammonia nitrogen shows fully suppressed, unchanged in 24h, because CN in 24h is completely degraded, does not cause.We think thus, and the startup gordian technique of Wastewater from Acrylonitrile Production biological treatment engineering is at first degrade CN and hazardous and noxious substances.
Embodiment 2
The sbr reactor device that testing apparatus is 5L, seed sludge is general municipal sewage sludge, inoculation mud amount 22g, VSS/SS=60%.Process of the test can be divided into two stages: the stage 1.: the enrichment process of cyanogen degradation bacteria.The ammonia nitrogen influent concentration is 20mgL
-1, the COD influent concentration is 800-1200mgL
-1, the CN influent concentration in 12 days by 5mgL
-1Gradient is increased to 50mgL gradually
-1.Stage is 2.: process containing the cyanogen ammonia nitrogen waste water.The CN influent concentration remains 50mgL
-1, the COD influent concentration is maintained 1200mgL
-1, the ammonia nitrogen influent concentration is increased to 120mgL gradually
-1.
Water inlet NaCN concentration is by 5mg CN
-L
-1(the 1st day and the 2nd day) increases to 40mgCN-L gradually
-1(the 7th day), add glucose and ammonium sulfate, makes respectively into the total COD of water and total NH
3-N is 800mgL
-1And 20mgL
-1, water outlet COD is at 50mgL
-1Below, water outlet NH
3-N is at 0.2mgL
-1Below, water outlet CN is lower than 0.5mgL
-1, system stability, operating performance is better.When reactor moves to the 8th day, water inlet NaCN concentration increases to 50mg CN
-L
-1, the total cyanogen concentration of water outlet is increased to 7.5mgL
-1, water outlet NH
3-N also is increased to 4.4mgL
-1.Continue operation after 2 days under this concentration, the water outlet ammonia nitrogen is lower than 0.2mgL
-1.Move continuously afterwards about 1 week, water inlet CN is 50mgL
-1, influent ammonia nitrogen is 20mgL
-1, influent COD is 1200mgL
-1, water outlet CN is 0.5mgL
-1, the water outlet ammonia nitrogen is 0.2mgL
-1, water outlet COD is 50mgL
-1Left and right.The microorganism of having tamed out gradually the CN that can degrade in mud is described.
Afterwards, start to process containing the cyanogen ammonia nitrogen waste water.Within the 20th day, ammonia nitrogen concentration is increased to 30mgL
-1, the water outlet ammonia nitrogen also is increased to 5.7mgL
-1, but continue water inlet two days later, be down to again 0.2mgL
-1Left and right.Influent ammonia nitrogen gradient raising gradually afterwards, each raising all can be accompanied by the raising of of short duration water outlet ammonia nitrogen concentration, returns to again subsequently 0.2mgL
-1Below.
The 40th day, influent COD was 1200mgL
-1, influent ammonia nitrogen is 120mgL
-1, COD/NH3-N is 10: 1, water inlet CN is 50mgL
-1, water outlet COD is less than 50mgL
-1, ammonia nitrogen is less than 0.2mgL
-1, CN is less than 0.5mgL
-1.
Embodiment 3
Shandong petrochemical industry Acrylic Fibers Plant waste water treatment engineering, treatment scheme is shown in Fig. 1.
Contain the pollutents such as a large amount of vinyl cyanide, vinylformic acid, acetonitrile, propenal, prussiate in waste water, bacteria metabolism is had to restraining effect, be difficult to biological degradation, this project composite wastewater water yield is 500-800m
3D
-1, COD, TKN, NH
3-N and TCN are respectively 1250-3000mgL
-1, 200-500mgL
-1, 100-250mgL
-1With 3-10mgL
-1.
Main units has, (1) anoxic pond (A pond), pool size: 48 * 20 * 5.5m, useful volume: 4300m
3, inside establish two of underwater propellers (stirring action), single-machine capacity is 2.4KW; (2) aeration tank (O pond), pool size: 48 * 16 * 5.5m, useful volume: 3800m
3, minute two gallerys, the long 48m of gallery, wide 8m, be equipped with HS and cut by force aerator in aeration tank, linear arrangement, aeration intensity is 10-15m
3/ min/1000m
3(3) second pond, be of a size of Ф 14 * 5.5m, and useful volume is 750m
3, return sludge ratio 1.0; (4) oxidizing reaction pond, be of a size of Ф 5.0 * 5.5m, and useful volume is 98m
3(5) settling tank, be of a size of Ф 14 * 5.5m, and useful volume is 750m
3(surface load is 0.5m
3/ m
2/ h).
Wherein A pond, O pond and second pond form biological treatment system.
Disposable seed sludge 15gSSL in biological treatment system
-1.
First 2 weeks, by after 10 times of wastewater dilutions, enter biological treatment system, influent COD, NH
3-N and TCN are respectively 125-300mgL
-1, 10-25mgL
-1With 0.3-1.0mgL
-1, the glucose dosage is 150mgCODL
-1D
-1, water outlet NH
3-N is 5.0-8.0mgL
-1
The 3rd week starts, 5 times of water inlets afterwards of wastewater dilution, influent COD, NH
3-N is respectively 250-600mgL
-1, 20-50mgL
-1, drop into NaCN and make TCN be increased to 2.0-10.0mgL
-1
Continue operation 4 weeks, water outlet TCN and NH
3-N is respectively 1.0mgL
-1And 5.0mgL
-1Left and right.Now in the O pond, the mean value of sludge concentration MLSS and MLVSS is respectively 9.70 and 6.07gL
-1
Reduce gradually extension rate to waste water not redilution, now influent COD, NH
3-N and TCN are respectively 1200-3000mgL
-1, 200-500mgL
-1With 4-10mgL
-1, flow is 700-800m
3D
-1.Biological treatment system water outlet COD, NH have been moved since 2 years
3-N and TCN are respectively lower than 300mgL
-1, 5.0mgL
-1With 1.0mgL
-1.
The biological treatment system water outlet is entered to the hypochlorite oxidation reaction tank and carry out oxide treatment, the clorox dosage is 20mgL
-1, then enter settling tank and precipitated, water outlet COD, NH after precipitation
3-N and TCN are lower than 100mgL
-1, 1.0mgL
-1With 0.5mgL
-1, reach the GB8978-1996 primary standard.
Claims (14)
1. the preparation method of the active sludge of a concentration of cyanide degradation bacteria, it comprises the steps: 1. the Wastewater from Acrylonitrile Production after dilution to be passed in biological treatment system and processed as water inlet, active sludge is inoculated in described biological treatment system, and the inoculum size of active sludge is 10-15gL
-1, and adding organic carbon source, the dosage of organic carbon source is 50-150mgCODL
-1D
-1The useful volume that L in the inoculum size of described active sludge and the dosage of organic carbon source is described biological treatment system; Described biological treatment system comprises anoxic pond, aeration tank and the second pond connected successively, the ratio of the useful volume of described anoxic pond and described aeration tank is 1:1-1:1.5, HS is installed in described aeration tank and cuts by force aerator, the aeration air quantity of this aerator is 10-15m
3/ min/1000m
32. the extension rate of described dilution is at front 6-8 in week, is reduced to gradually 5 times from 10 times, makes to bring up to gradually 10.0mgL into the total cyanogen content in water
-1NH in the water outlet of described biological treatment system
3-N content≤5.0mgL
-1The time, described extension rate is narrowed down to 1 times gradually from 5 times, get final product.
2. preparation method as claimed in claim 1, is characterized in that: described anoxic pond installation agitator.
3. preparation method as claimed in claim 2, it is characterized in that: described agitator is underwater propeller.
4. preparation method as claimed in claim 3, it is characterized in that: described underwater propeller is 1kW/1000m by energy consumption
3Type selecting.
5. preparation method as claimed in claim 1 is characterized in that: described aeration tank adopts the plug-flow tank type, is provided with gallery in pond.
6. preparation method as claimed in claim 5, it is characterized in that: the total length of described gallery is 5-20:1 with the ratio of width.
7. preparation method as claimed in claim 1, it is characterized in that: the sludge reflux of described second pond to the reflux ratio of anoxic pond feed-water end is 1.0-2.0, guarantees that the sludge concentration in described biological treatment system maintains 5.0-8.0gVSSL
-1.
8. preparation method as claimed in claim 1, it is characterized in that: described organic carbon source is glucose; Step 2. in, if extension rate be reduced to 5 times afterwards the water inlet in total cyanogen content do not reach 10.0 mgL
-1, add prussiate and make it meet this total cyanogen content.
9. preparation method as claimed in claim 8, it is characterized in that: described prussiate is sodium cyanide.
10. the active sludge of the concentration of cyanide degradation bacteria obtained by the described preparation method of any one in claim 1～9.
11. the biochemical denitrification treatment process of a Wastewater from Acrylonitrile Production, it comprises the steps: Wastewater from Acrylonitrile Production is passed in anoxic pond and processes, the water outlet of anoxic pond enters into aeration tank and processes, the water outlet of aeration tank is discharged after the second pond mud-water separation, the sludge reflux of second pond is to the feed-water end of anoxic pond, nitrification liquid in aeration tank is back to the feed-water end of anoxic pond, the active sludge that contains concentration of cyanide degradation bacteria claimed in claim 10 in described anoxic pond, aeration tank and second pond; Described anoxic pond, aeration tank or second pond are described with claim 1～7 any one.
12. the biochemical denitrification treatment process of Wastewater from Acrylonitrile Production as claimed in claim 11 is characterized in that: the waste water after biochemical denitrification is processed enters the oxidizing reaction pond and carries out oxide treatment, and the water outlet in oxidizing reaction pond enters settling tank and carries out precipitation process, gets final product.
13. the biochemical denitrification treatment process of Wastewater from Acrylonitrile Production as claimed in claim 12 is characterized in that: described oxide treatment employing adds clorox to be carried out, and the dosage of described clorox is 10-100mgL
-1The treatment time of described oxide treatment is 1.0-4.0h.
14. the biochemical denitrification treatment process of Wastewater from Acrylonitrile Production as claimed in claim 12 is characterized in that: described settling tank is pressed surface load 0.5-0.75m
3/ m
2/ h design.
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| CN105271605B (en) * | 2014-07-11 | 2017-08-29 | 中国石油化工股份有限公司 | The processing method of acrylic nitrile waste water |
| CN110184219B (en) * | 2019-05-30 | 2021-06-04 | 中国石油大学(华东) | Nitrile degrading bacterium and application thereof in production of acrylic acid |
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| CN1188743A (en) * | 1997-07-04 | 1998-07-29 | 化学工业部第三设计院 | Comprehensive effluent disposal technology for wet spinning acrylic fibers industry |
| CN1385380A (en) * | 2001-05-11 | 2002-12-18 | 中国石油化工股份有限公司 | Method for treating acrylonitrile and acrylic waste water |
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| KR0136162B1 (en) * | 1994-12-30 | 1998-04-25 | 김만제 | Cultivation process of microorganism having nitrification ability of ammonia nitrogen in waste water |
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|---|---|---|---|---|
| CN1188743A (en) * | 1997-07-04 | 1998-07-29 | 化学工业部第三设计院 | Comprehensive effluent disposal technology for wet spinning acrylic fibers industry |
| CN1385380A (en) * | 2001-05-11 | 2002-12-18 | 中国石油化工股份有限公司 | Method for treating acrylonitrile and acrylic waste water |
| CN101306903A (en) * | 2007-05-18 | 2008-11-19 | 中国石油化工股份有限公司 | Biochemical treatment process for high-concentration ammonia-nitrogen-containing waste water |
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