CN103641277B - Acrylonitrile waste water treatment method - Google Patents
Acrylonitrile waste water treatment method Download PDFInfo
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- CN103641277B CN103641277B CN201310681566.0A CN201310681566A CN103641277B CN 103641277 B CN103641277 B CN 103641277B CN 201310681566 A CN201310681566 A CN 201310681566A CN 103641277 B CN103641277 B CN 103641277B
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title abstract description 24
- 238000004065 wastewater treatment Methods 0.000 title abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 61
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 239000010802 sludge Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 241000276438 Gadus morhua Species 0.000 claims description 50
- 235000019516 cod Nutrition 0.000 claims description 50
- -1 acrylic nitrile Chemical class 0.000 claims description 44
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 16
- 238000011068 load Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 8
- 238000006396 nitration reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000004059 degradation Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000005755 formation reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 43
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 230000035695 Efflux Effects 0.000 abstract 2
- 238000004062 sedimentation Methods 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 11
- 230000037250 Clearance Effects 0.000 description 10
- 230000035512 clearance Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 229920002972 Acrylic fiber Polymers 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 229960004643 Cupric oxide Drugs 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000001146 hypoxic Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 235000019600 saltiness Nutrition 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 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
- 241000894006 Bacteria Species 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- WOFDVDFSGLBFAC-UHFFFAOYSA-N Lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005111 flow chemistry technique Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000001502 supplementation Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Abstract
The invention relates to an acrylonitrile waste water treatment method, which is mainly used for solving the problems of low efficiency of removing COD (Chemical Oxygen Demand) and TN (Total Nitrogen), yielding water of non-compliance, long process flow and high operation cost of acrylonitrile waste water treatment in the prior art. The acrylonitrile waste water treatment method provided by the invention comprises the following steps: (1) firstly feeding the acrylonitrile waste water into a short-cut nitrification and denitrification tank; (2) dividing the efflux of the short-cut nitrification and denitrification tank into two branches, and feeding one branch into an anaerobic tank, returning the mixed liquid of the anaerobic tank to the short-cut nitrification and denitrification tank, and feeding the other branch into the sedimentation tank; (3) returning one part of sludge at the bottom of the sedimentation tank to the short-cut nitrification and denitrification tank, and discharging one part as sludge, and feeding the supernatant into an advanced oxidation pond; (4) feeding the efflux of the advanced oxidation pond into a biological aerated filter to obtain the waste water for discharge which is up to the A-level standard of Integrated Wastewater Discharge Standard GB8978-1996; the technical scheme can be used for well solving the problems; therefore, the acrylonitrile waste water treatment method can be applied to industrial treatment of the acrylonitrile waste water.
Description
Technical field
The present invention relates to a kind for the treatment of process of acrylic nitrile waste water.
Background technology
Vinyl cyanide is mainly used in the productions such as acrylic fibers, paracril, adiponitrile, acrylamide, ABS resin, also can be used for the production of hexanolactam, polyhydric alcohol polymer, it has broad application prospects in fields such as synthon, synthetic rubber, plastics, China and even the whole world are to the demand strong growth of vinyl cyanide, and production device for acrylic nitrile will constantly start.The production method of vinyl cyanide has cyanoethanol method, acetylene method, propylene ammmoxidation process and propane ammoxidation method four kinds, what current domestic and international application was maximum is propylene ammmoxidation process, namely with propylene, ammonia and air for main raw material, under the effect of certain reaction conditions and catalyzer, generate vinyl cyanide and water, by product is mainly acetonitrile and prussic acid.Reaction product, after the series of measures such as absorption, extraction and stripping are separated, still containing organism such as vinyl cyanide, prussic acid, acetonitrile, pyridine, vinylformic acid, propenal, anti-maleic nitrile and cyanalcohols in factory effluent, and reacts residual ammonia.The key character of acrylic nitrile waste water is that high chemical oxygen demand (hereinafter referred to as COD), high total nitrogen (hereinafter referred to as TN) and high prussiate are (hereinafter referred to as CN
-); Toxicity is high, and intractability is large.
For this kind of acrylic nitrile waste water, early stage more employing burning method, because burning method process is comparatively simple, incineration temperature is 850 ~ 1100 DEG C, the most thorough to the destruction of pollutent; But burn the high-temp waste gas produced directly to be discharged in air, there is serious energy consumption waste and problem of environmental pollution.Conventional method first adopts the physics such as multiple-effect evaporation, hydrogen peroxide oxidation, wet oxidation or Fenton reagent or chemical process to carry out pre-treatment to acrylic nitrile waste water, removes vinyl cyanide and prussiate, reduce it to after the toxicity of microorganism, then take Biochemical method.
Acrylic nitrile waste water after pre-treatment, COD and TN still very high (COD up to 3500mg/L, TN up to 550mg/L, TN is mainly organonitrogen and ammonia nitrogen), adopt existing biological method process to there is difficulty, efficiency is lower, needs to utilize service water or low concentration wastewater dilution aftertreatment.As: adopt Wastewater Treated by Activated Sludge Process after Shanghai acrylonitrile installation water reuse service water is diluted to COD < 1000mg/L, water outlet COD is 300 ~ 500mg/L, ammonia nitrogen < 150mg/L; Anqing acrylonitrile installation waste water and Nitrilon waste water are mixed to after COD is about 700mg/L and adopt the process of A/O method, water outlet COD < 170mg/L; It is 650-800mg/L, TN is after 60-70mg/L that grand celebration acrylonitrile installation waste water and Nitrilon waste water are mixed to COD, adopts pure oxygen aeration+contact oxidation method process, water outlet COD and NH
3-N is substantially up to standard; After Jilin acrylonitrile installation water reuse low concentration wastewater is diluted to COD < 1800mg/L, adopt the process of SBR method, water outlet COD is 800 ~ 900mg/L, NH
3-N < 300mg/L, can not be up to standard; Biological multiplication method process is adopted, water outlet COD < 300mg/L, NH after transformation
3-N < 50mg/L, still below standard.Therefore, although carried out diluting (2 ~ 5 times) to acrylic nitrile waste water, COD and NH of water outlet
3the requirement of-N does not all reach " integrated wastewater discharge standard " (GB8978-1996) primary standard, can not direct outer row.In addition, owing to not specifying the index of TN in GB8978-1996, although above user have employed the treatment process with denitrification functions, water outlet TN is not all examined.
Along with the pay attention to day by day of China's environmental pollution, improve the pollution exhaust criteria of all kinds of manufacturing enterprise, especially country and provincial standard have put into effect total nitrogen discharge index successively, if " urban wastewater treatment firm pollutant emission standard " (GB18918-2002) regulation one-level/secondary total nitrogen index is 15/20mg/L, " Shanghai City integrated wastewater discharge standard " (DB31/199-2009) regulation one-level/secondary total nitrogen index is 25/35mg/L, and " Liaoning Province's integrated wastewater discharge standard " (DB21/1627-2008) total nitrogen index is 15mg/L.Removing COD and TN due to biological process is most economical, method the most thoroughly, so, the bioremediation of development of new, or based on the combination treatment method of biological treatment, the COD clearance of raising acrylic nitrile waste water and nitric efficiency, significant.In recent years, disclose several biologic treating technique for acrylic nitrile waste water successively, but have that treatment scheme is longer, processing efficiency is lower or the problem such as running cost is higher.
Chinese patent CN102190408B(201110096473.2) adopt preaeration reaction tank-hydrolysis acidification pool-oxygen compatibility pool-mono-section Aerobic Pond-bis-section Aerobic Pond-second pond combination process process vinyl cyanide, acrylic fiber production process comprehensive wastewater, COD is 4500 ~ 6100mg/L, when TN is 380 ~ 523mg/L, water outlet COD is 450 ~ 638mg/L, and total nitrogen is 38 ~ 56mg/L.COD clearance is 86% ~ 92%, TN clearance is 85% ~ 93%.The advantage of this technology is that TN clearance is higher, but water outlet COD is higher, still needs further biochemical treatment.
Chinese patent CN202016935U(201120121780.7) disclose one containing nitrile wastewater denitrification treatment apparatus, adopting anaerobic pond-settling tank-oxygen compatibility pool-Aerobic Pond combination process process COD to be 3000 ~ 5000mg/L, TN is 600 ~ 800mg/L, CN
-be 10 ~ 20mg/L containing nitrile waste water, water outlet COD < 62.8mg/L, NH
3-N < 3.66mg/L, TN < 32.5mg/L.The advantage of this technology is COD, NH
3the clearance of-N and TN is all higher, and water outlet reaches GB8978-1996 first discharge standard substantially.Shortcoming needs in oxygen compatibility pool, add a large amount of carbon source (methyl alcohol etc.), and to meet the carbon-nitrogen ratio needed for nitric nitrogen denitrification, running cost is very high.Because anaerobic pond is 50% ~ 70% to the clearance of COD, but to TN and NH
3-N does not have removal effect substantially, and TN can only remove at oxygen compatibility pool-Aerobic Pond (i.e. A/O method).When adopting A/O method to remove TN, require that the carbon-nitrogen ratio in sewage is greater than 4, just can reach higher nitric efficiency.
Chinese patent CN202529945U(201120523601.2) adopt alkaline hydrolysis-aerobic biochemical-Fenton advanced oxidation-acidication-aerobic biochemical combination process process vinyl cyanide and acrylic fibers device waste water, in this technology, 1. mainly for the removal of COD, to NH
3-N and TN examines; 2., after mixing with polymeric wastewater and filature wastewater, the COD of waste water is less than 1000mg/L; 3. advanced oxidation need be removed COD and reaches 350mg/L, and running cost is higher.
Chinese patent CN102718362(201210205190.1) a kind of bioremediation of Wastewater from Acrylonitrile Production, the flow process adopted is: homogeneous equalizing tank-hypoxia response district-aerobic reactor zone-nitration reaction district-second pond, in anoxic, aerobic and nitration reaction district, all filler is installed, and adds carbon source in front end, nitration reaction district.It is not right that the subject matter of the method is that carbon source adds position, and nitration reaction district is also aerobic reaction, and the carbon source added is easy to by aerobic degradation, and the hypoxia response district carrying out denitrification denitrogenation can not get supplementing of carbon source.In addition, the residence time of each reaction zone is all wrong according to COD carry calculation.The object that should process according to each district calculates respectively: hypoxia response district adopts nitric nitrogen carry calculation, and aerobic reactor zone adopts COD carry calculation, and nitration reaction district adopts ammonia nitrogen loading to calculate.
Chinese patent CN102399044A(201110371133.6) a kind of Wastewater from Acrylonitrile Production integrated processing method in, biological treatment part have employed two sections of conventional A/O techniques, be 85% and 90% to the clearance of COD and ammonia nitrogen, enter the COD of ultrafiltration and reverse osmosis up to 132 and 118mg/L, pose a big pressure to ultrafiltration and reverse osmosis membrane, cleaning and the frequency of maintenance of system are higher.
Chinese patent CN103159374A(201110424220.3) a kind for the treatment of process to the organic waste water containing vinyl cyanide material, adopt (1) materializing strategy; (2) anoxic/aerobic (A/O) biochemical treatment; (3) waste water comprising vinyl cyanide material of deep oxidation treatment combination flow processing CODcr≤1000mg/L, the COD149mg/L of final process water outlet, BOD19mg/L, colourity < 20, pH6 ~ 9, reach sewage second-level emission request substantially.The influent concentration that this technology is suitable for is lower, and removal efficiency is low, and effluent quality does not reach the requirement of GB8978-1996 primary standard.
Chinese patent CN103086576A(201310064394.2) a kind of vinyl cyanide, in acrylic fiber production process comprehensive effluent disposal technology, acrylic nitrile waste water with after pretreated lower concentration Nitrilon waste water mixes, adopt one-stage hydrolysis acidifying-anoxic pond-one-level aerobic-second pond-secondary acidication-secondary is aerobic-nitrification tank-second pond combination process process.Its advantage is COD and NH of water outlet
3-N reaches GB8978-1996 first discharge standard, and TN is less than 30mg/L.But its influent concentration is low, be only 1/4 ~ 1/5 of acrylic nitrile waste water, treatment scheme is long, and construction investment and running cost are all higher.
Summary of the invention
Technical problem to be solved by this invention overcomes prior art process acrylic nitrile waste water to have that removal efficiency is lower, water outlet is not up to standard, and the problem that technical process is long, running cost is high, provides a kind of new acrylic nitrile waste water treatment process.The method is used for, in the process of the fine waste water of propylene, having the advantages that COD and TN removal efficiency is high, standard water discharge, flow process are simple, running cost is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind for the treatment of process of acrylic nitrile waste water, comprises the following steps:
(1) be 1500 ~ 3500 mg/litre by COD, TN is 200 ~ 550 mg/litre, NH
3-N is that first the acrylic nitrile waste water of 20 ~ 80 mg/litre enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge, carries out the anti-nitration reaction of nitrated and nitric nitrogen of organic matter degradation, ammonia nitrogen;
(2) effluent in described short-cut nitrification and denitrification pond is divided into two-way, and a road enters anoxic pond, mixes with the hydrocarbon polymer adding anoxic pond, and the mixed solution of formation returns to short-cut nitrification and denitrification pond as anoxic pond phegma, and another road enters settling tank;
(3) part for the mud bottom described settling tank returns to short-cut nitrification and denitrification pond as described settling tank returned sluge, and a part is as mud discharging, and the supernatant liquor on settling tank top enters advanced oxidation pond, with catalyzer and oxidising agent;
(4) effluent in advanced oxidation pond enters after BAF contacts with porous filter-material, obtains COD≤60 mg/litre, TN≤50 mg/litre, NH
3the discharge of wastewater up to standard of-N≤10 mg/litre, the mud that BAF produces is as mud discharging.
In technique scheme, preferably, described short-cut nitrification and denitrification pond adopts DO instrument and interlock of fan; In short-cut nitrification and denitrification pond, DO accurately controls in 0.3 ~ 0.5 mg/litre, and pH controls 7.5 ~ 8.0, and temperature is 10 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000 mg/litre; The part being entered anoxic pond by short-cut nitrification and denitrification pond utilizes pump to promote, and controls to promote 2 ~ 5 times that flow is flooding quantity; The part being entered settling tank by short-cut nitrification and denitrification pond is run by gravity, without the need to controlling flow; Short-cut nitrification and denitrification pond adopts at least one in airlift, submersible agitator, pump to realize the internal recycle of mixed solution in pond, and inner circulating reflux flow quantity is 10 ~ 30 times of flooding quantity.
In technique scheme, preferably, the hydrocarbon polymer adding anoxic pond described in is selected from least one in methyl alcohol, ethanol; The carbon-nitrogen ratio controlling mixed solution in anoxic pond is that (3 ~ 5): 1, DO is less than 0.3 mg/litre, and pH is 7.0 ~ 7.8, and temperature is 15 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000mg/L; Install submersible agitator in anoxic pond, the mixed liquor flows by gravity of anoxic pond is back to short-cut nitrification and denitrification pond.
In technique scheme, preferably, the hydraulic load of described settling tank is 0.5 ~ 1.0m
3/ m
2.h, settling tank base sludge is back to the flow in short-cut nitrification and denitrification pond is 50 ~ 100% of flooding quantity.
In technique scheme, preferably, described catalyzer is heterogeneous catalyst, and more preferably, heterogeneous catalyst is the oxide compound of activated carbon supported copper or manganese, or at least one in the oxide compound of activated alumina supported copper or manganese; Oxygenant is ozone, and ozone dosage is 40 ~ 80 mg/litre; In advanced oxidation pond, dwell time of sewage is 1 ~ 2h.
In technique scheme, preferably, the effluent in described advanced oxidation pond enters after BAF contacts with porous filter-material, discharged wastewater met the national standard, mud discharge after dehydration of back flush discharge; Described porous filter-material is selected from least one in porous ceramic grain or porous porcelain grain, and filtrate height is 3.0 ~ 4.5m, and the volumetric loading of BAF is 0.2 ~ 0.5kgCOD/m
3.d.
In technique scheme, preferably, there is inner circulating reflux liquid in described anoxic pond, realized by submersible agitator, and agitator power is every cubic metre of anoxic pond volume 4 ~ 8W.
In technique scheme, preferably, the standard of described discharge of wastewater is " integrated wastewater discharge standard " GB8978-1996 primary standard.
In the inventive method, first acrylic nitrile waste water enters short-cut nitrification and denitrification pond, with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge short mix.The effect of internal recycle: one is the water inlet of diluting high-concentration, reduces acrylic nitrile waste water to the toxicity of microorganism; Two is that the nitric nitrogen that Ammonia Nitrification generates is back to the more sufficient inlet segment of carbon source, improves denitrification rate.Remaining for denitrification hydrocarbon polymer is utilized or is degraded by the effect of anoxic pond mixed-liquor return in short-cut nitrification and denitrification pond.Active sludge is reclaimed in the effect of clarifier sludge backflow, maintains sludge concentration higher in biological reaction tank, improves the clearance of pollutent.In control pond, DO is 0.3 ~ 0.5mg/L, pH is 7.5 ~ 8.0, and reach the top condition needed for short-cut nitrification and denitrification reaction, denitrification flora can utilize NO
2-carry out denitrification as electron acceptor(EA), namely nitrosification microorganism is by NH
4 +-N is converted into NO
2 --N, directly carries out anti-nitration reaction, by NO by denitrifying microorganism immediately
2 --N is reduced to N
2release.
The effluent in short-cut nitrification and denitrification pond is divided into two-way, and a road enters anoxic pond, and another road enters settling tank.The effect of anoxic pond is intensified anti-nitrated, raising nitric efficiency, is realized: control the optimum regime of mixed solution needed for denitrification in anoxic pond, namely DO is less than 0.3mg/L, and pH value is 7.0 ~ 7.8, and temperature is 15 ~ 35 DEG C by following measures; Add the hydrocarbon polymer of lower molecular weight, provide denitrification required sufficient carbon source; The mixed solution entering anoxic pond utilizes pump to promote, and avoids air-lift unit that the DO of anoxic pond is raised, is unfavorable for denitrification.Compared with the preposition anoxic pond of conventional A/O technique, more easily control DO value and pH value, external carbon hydrogen compound more easily utilize by denitrifying bacteria, therefore have higher denitrification efficiency.The flow entering anoxic pond is determined according to DO value in short-cut nitrification and denitrification pond end nitrate and anoxic pond, 2 ~ 5 times that get flooding quantity.After complete denitrification, the mixed solution run by gravity of anoxic pond is back to short-cut nitrification and denitrification pond, is utilized adding excessive hydrocarbon polymer or degrades in short-cut nitrification and denitrification pond.The effect of settling tank is mud-water separation, prevents mud from entering advanced oxidation pond on the one hand, increases oxidant consumption amount; Recyclable active sludge on the other hand, maintains sludge concentration higher in biological reaction tank, improves the clearance of pollutent.The supernatant liquor of settling tank drains into advanced oxidation pond and processes further, and the mud of bottom is promoted by pump or airlift, is back to front end, short-cut nitrification and denitrification pond, a small amount of mud discharging.
Part hardly degraded organic substance is removed in the effect in advanced oxidation pond, or makes it resolve into small organic molecule; Adopt ozone as oxygenant, can avoid adopting Fenton oxidation method to need first acid adding to be adjusted to acidity, add alkali again and be adjusted to alkalescence and cause equipment corrosion, increase the problems such as sewage saltiness; Load heterogeneous catalyst in pond, improve ozone oxidation speed, eliminate ozone to the selectivity of hardly degraded organic substance.Still containing a small amount of ozone in the water outlet in advanced oxidation pond, ozone can kill the microorganism of BAF, so its water outlet must enter BAF again after 1 ~ 2h ozone is cleared up.Because BAF is built with porous filtrate, microorganic adhesion, at filter material surface, can make sewage, air fully contacts with microorganism, has and removes COD, NH
3the multi-functional of-N, TN and SS, is specially adapted to the advanced treatment of low concentration wastewater, makes water outlet qualified discharge; The sludge quantity that BAF produces is little, discharges with back flushing draining, through concentrated and discharge after dewatering.
Adopt disposal methods acrylic nitrile waste water of the present invention, the water outlet COD≤60mg/L after process, NH
3-N≤5mg/L, reaches or is better than " integrated wastewater discharge standard " GB8978-1996 primary standard; TN≤50mg/L, meets TN emission request.Owing to have employed short-cut nitrification and denitrification technique in the present invention, organic matter degradation, nitrification and denitrification process is completed in same pond, reduce by the oxygen requirement of about 25% than traditional A/O technique, the carbon source of about 40%, reaction times shortens about 63%, reaches the object of saving energy consumption and improving removal efficiency.Owing to adding external anoxic pond in the present invention, enhance denitrification effect, improve TN clearance.Owing to have employed catalytic ozonation technique in the present invention, be applicable to the removal of various refractory organic, improve the biodegradability of sewage, do not increase the saltiness of sewage, be conducive to effluent reuse.Owing to have employed BAF as second stage aerobic treatment facility in the present invention, soon, it integrates bio-oxidation and retains suspended solids, saves post precipitation pond for easy biofilm, biological startup.Method of the present invention is by organics removal and total nitrogen is most economical, based on the simplest bioremediation, be aided with high-level oxidation technology, have the advantages that removal efficiency is high, flow process is simple, running cost is low, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention:
In figure, the implication of each label is: 1-short-cut nitrification and denitrification pond, 2-anoxic pond, 3-settling tank, 4-advanced oxidation pond, 5-BAF, 6-waste water feed line, 7-anoxic pond inner circulating reflux, 8-oxygenant pipeline, the outer draining of 9-, the outer comb line of 10-BAF mud, 11-mud arranges main pipe line outward, the outer comb line of 12-clarifier sludge, 13-settling tank base sludge pipeline, 14-short-cut nitrification and denitrification pond inner circulating reflux, 15-settling tank return sludge line, 16-hydrocarbon polymer adds pipeline.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment
Embodiment
[embodiment 1]
Certain acrylic nitrile waste water water quality: COD is 3000mg/L, NH
3-N is 40mg/L, TN is 495mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is 25 times of flooding quantity; In control pond, DO is 0.4mg/L, pH is 7.8, and temperature is 20 DEG C, and sludge concentration is 6000mg/L.
The effluent in short-cut nitrification and denitrification pond is divided into two-way: a route pump promotes and enters anoxic pond, it promotes 3.5 times that flow is flooding quantity, methyl alcohol is added in pond, dosage is that 3:1 calculates by carbon-nitrogen ratio, and the DO of anoxic pond is 0.1mg/L, pH is 7.5, temperature is 25 DEG C, sludge concentration is 6000mg/L, establishes submersible agitator to realize the internal recycle of mixed solution in anoxic pond, and agitator power is every cubic metre of anoxic pond volume 4W; Another road run by gravity enters settling tank, and the hydraulic load of settling tank is 0.75m
3/ m
2.h, return sludge ratio is 80%, and the supernatant liquor of settling tank enters advanced oxidation pond, and wherein COD is 125mg/L, NH
3-N is 5.5mg/L, TN is 39mg/L.
Advanced oxidation pond is built with catalyzer, and catalyzer is activated alumina loaded copper oxide, and cupric oxide charge capacity is 15%(weight), ozone dosage is 50mg/L, and dwell time of sewage is 2h, and the COD of water outlet is 85mg/L, NH
3-N and TN is constant.
The water outlet in advanced oxidation pond enters BAF after ozone is cleared up, and porous filter-material is porous ceramic grain, and packed height is 4m, and volumetric loading is 0.5kgCOD/m
3.d, final outflow water water quality: COD is 53.4mg/L, NH
3-N is 3.5mg/L, TN is 39mg/L, reaches " integrated wastewater discharge standard " GB8978-1996 primary standard.
[embodiment 2]
Certain acrylic nitrile waste water water quality: COD is 3500mg/L, NH
3-N is 45mg/L, TN is 520mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is 30 times of flooding quantity; In control pond, DO is 0.5mg/L, pH is 8.1, and temperature is 30 DEG C, and sludge concentration is 8000mg/L.
The effluent in short-cut nitrification and denitrification pond is divided into two-way: a route pump promotes and enters anoxic pond, its flow is 2.8 times of flooding quantity, methyl alcohol is added in pond, dosage is that 4:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.3mg/L, pH is 7.8, and temperature is 35 DEG C, sludge concentration is 8000mg/L, and in anoxic pond, agitator power is every cubic metre of anoxic pond volume 6W; Another road run by gravity enters settling tank, and the hydraulic load of settling tank is 0.50m
3/ m
2.h, return sludge ratio is 100%, and the supernatant liquor of settling tank enters advanced oxidation pond, and wherein COD is 147mg/L, NH
3-N is 6.7mg/L, TN is 48mg/L.
Advanced oxidation pond is built with activated carbon supported manganese dioxide-catalyst, and manganese dioxide load amount is 5%(weight), ozone dosage is 80mg/L, and dwell time of sewage is 2h, and the COD of water outlet is 90mg/L, NH
3-N and TN is constant.
The water outlet in advanced oxidation pond enters BAF after ozone is cleared up, and porous filter-material is porous ceramic grain, and packed height is 4.5m, and volumetric loading is 0.3kgCOD/m
3.d, final outflow water water quality: COD is 56.5mg/L, NH
3-N is 3.8mg/L, TN is 48mg/L.
[embodiment 3]
Certain acrylic nitrile waste water mixes water quality with other waste water: COD is 1500mg/L, NH
3-N is 33mg/L, TN is 220mg/L.
First acrylic nitrile waste water enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge; Adopt airlift to make mixed solution internal recycle, internal recycle flow is 10 times of flooding quantity; In control pond, DO is 0.3mg/L, pH is 7.5, and temperature is 25 DEG C, and sludge concentration is 4000mg/L.
The effluent in short-cut nitrification and denitrification pond is divided into two-way: a route pump promotes and enters anoxic pond, its flow is 5 times of flooding quantity, ethanol is added in pond, dosage is that 5:1 calculates by carbon-nitrogen ratio, the DO of anoxic pond is 0.2mg/L, pH is 7.3, and temperature is 30 DEG C, sludge concentration is 4000mg/L, and in anoxic pond, agitator power is every cubic metre of anoxic pond volume 4W; Another road run by gravity enters settling tank, and the hydraulic load of settling tank is 1.00m
3/ m
2.h, return sludge ratio is 50%, and the supernatant liquor of settling tank enters advanced oxidation pond, and wherein COD is 119mg/L, NH
3-N is 5.3mg/L, TN is 28.6mg/L.
Advanced oxidation pond is built with activated alumina load manganese dioxide-catalyst, and manganese dioxide load amount is 5%(weight), ozone dosage is 40mg/L, and dwell time of sewage is 2h, and the COD of water outlet is 80mg/L, NH
3-N and TN is constant.
The water outlet in advanced oxidation pond enters BAF after ozone is cleared up, and porous filter-material is porous porcelain grain, and packed height is 3.0m, and volumetric loading is 0.25kgCOD/m
3.d, final outflow water water quality: COD is 45mg/L, NH
3-N is 0.8mg/L, TN is 28.6mg/L.
Claims (9)
1. a treatment process for acrylic nitrile waste water, comprises the following steps:
(1) be 1500 ~ 3500 mg/litre by COD, TN is 200 ~ 550 mg/litre, NH
3-N is that first the acrylic nitrile waste water of 20 ~ 80 mg/litre enters short-cut nitrification and denitrification pond, mixes with inner circulating reflux liquid, anoxic pond phegma and settling tank returned sluge, carries out the anti-nitration reaction of nitrated and nitric nitrogen of organic matter degradation, ammonia nitrogen;
(2) effluent in described short-cut nitrification and denitrification pond is divided into two-way, and a road enters anoxic pond, mixes with the hydrocarbon polymer adding anoxic pond, and the mixed solution of formation returns to short-cut nitrification and denitrification pond as anoxic pond phegma, and another road enters settling tank;
(3) part for the mud bottom described settling tank returns to short-cut nitrification and denitrification pond as described settling tank returned sluge, and a part is as mud discharging, and the supernatant liquor on settling tank top enters advanced oxidation pond, with catalyzer and oxidising agent;
(4) effluent in advanced oxidation pond enters after BAF contacts with porous filter-material, obtains COD≤60 mg/litre, TN≤50 mg/litre, NH
3the discharge of wastewater up to standard of-N≤10 mg/litre, the mud that BAF produces is as mud discharging.
2. the treatment process of acrylic nitrile waste water according to claim 1, is characterized in that described short-cut nitrification and denitrification pond adopts the control mode of DO instrument and interlock of fan; In short-cut nitrification and denitrification pond, DO accurately controls in 0.3 ~ 0.5 mg/litre, and pH controls 7.5 ~ 8.0, and temperature is 10 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000 mg/litre; The part being entered anoxic pond by short-cut nitrification and denitrification pond utilizes pump to promote, and controls to promote 2 ~ 5 times that flow is flooding quantity; The part being entered settling tank by short-cut nitrification and denitrification pond is run by gravity, without the need to controlling flow; Short-cut nitrification and denitrification pond adopts at least one in airlift, submersible agitator, pump to realize the internal recycle of mixed solution in pond, and inner circulating reflux flow quantity is 10 ~ 30 times of flooding quantity.
3. the treatment process of acrylic nitrile waste water according to claim 1, the hydrocarbon polymer adding anoxic pond described in it is characterized in that is selected from least one in methyl alcohol, ethanol; The carbon-nitrogen ratio controlling mixed solution in anoxic pond is that (3 ~ 5): 1, DO is less than 0.3 mg/litre, and pH is 7.0 ~ 7.8, and temperature is 15 ~ 35 DEG C, and sludge concentration is 4000 ~ 8000mg/L; Install submersible agitator in anoxic pond, the mixed liquor flows by gravity of anoxic pond is back to short-cut nitrification and denitrification pond.
4. the treatment process of acrylic nitrile waste water according to claim 1, is characterized in that the hydraulic load of described settling tank is 0.5 ~ 1.0m
3/ m
2h, the flow that settling tank base sludge is back to short-cut nitrification and denitrification pond is 50 ~ 100% of flooding quantity.
5. the treatment process of acrylic nitrile waste water according to claim 1, is characterized in that described catalyzer is heterogeneous catalyst; Oxygenant is ozone, and ozone dosage is 40 ~ 80 mg/litre; In advanced oxidation pond, dwell time of sewage is 1 ~ 2h.
6. the treatment process of acrylic nitrile waste water according to claim 1, is characterized in that the effluent in described advanced oxidation pond enters after BAF contacts with porous filter-material, discharged wastewater met the national standard, mud discharge after dehydration of back flush discharge; Described porous filter-material is selected from least one in porous ceramic grain or porous porcelain grain, and filtrate height is 3.0 ~ 4.5m, and the volumetric loading of BAF is 0.2 ~ 0.5kgCOD/m
3d.
7. the treatment process of acrylic nitrile waste water according to claim 1, it is characterized in that described anoxic pond exists inner circulating reflux liquid, realized by submersible agitator, agitator power is every cubic metre of anoxic pond volume 4 ~ 8W.
8. the treatment process of acrylic nitrile waste water according to claim 1, is characterized in that the standard of described discharge of wastewater is for " integrated wastewater discharge standard " GB8978-1996 primary standard.
9. the treatment process of acrylic nitrile waste water according to claim 5, is characterized in that described heterogeneous catalyst is the oxide compound of activated carbon supported copper or manganese, or at least one in the oxide compound of activated alumina supported copper or manganese.
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| EP3354624B1 (en) * | 2014-11-28 | 2019-07-10 | Evonik Degussa GmbH | Method for the treatment of contaminated waste water derived from the preparation of isophoronnitrile |
| CN108975497A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | The processing method of acrylic nitrile waste water |
| CN110540336A (en) * | 2018-05-29 | 2019-12-06 | 中国石油化工股份有限公司 | treatment method and application of ammoximation wastewater |
| CN108658381A (en) * | 2018-05-31 | 2018-10-16 | 西安石油大学 | A kind of waste acidifying liquid in oil field processing method |
| CN110723861A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Acrylonitrile sewage treatment method |
| CN109265581B (en) * | 2018-08-31 | 2020-07-24 | 北京化工大学 | Nitrocellulose nitrile rubber and preparation method and application thereof |
| CN114436473A (en) * | 2022-01-26 | 2022-05-06 | 北京铭泽源环境工程有限公司 | Full-flow nylon 66 salt production wastewater treatment method |
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| KR0165170B1 (en) * | 1996-05-31 | 1999-01-15 | 안덕기 | Elimination method of nitrogen from waste water containing acrylonitrile butadiene styrene(abs) |
| CN102718362A (en) * | 2012-06-20 | 2012-10-10 | 哈尔滨工程大学 | Biological treatment method for wastewater produced by acrylonitrile |
| CN102936077A (en) * | 2011-08-15 | 2013-02-20 | 中国石油化工股份有限公司 | Treatment method of polyacrylonitrile fiber production sewage |
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| JP2004175848A (en) * | 2002-11-25 | 2004-06-24 | Taiho Ind Co Ltd | Biodegradable resin molding having denitrifying action |
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| KR0165170B1 (en) * | 1996-05-31 | 1999-01-15 | 안덕기 | Elimination method of nitrogen from waste water containing acrylonitrile butadiene styrene(abs) |
| CN102936077A (en) * | 2011-08-15 | 2013-02-20 | 中国石油化工股份有限公司 | Treatment method of polyacrylonitrile fiber production sewage |
| CN102718362A (en) * | 2012-06-20 | 2012-10-10 | 哈尔滨工程大学 | Biological treatment method for wastewater produced by acrylonitrile |
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