CN111392865A - Method for treating organic amine wastewater - Google Patents
Method for treating organic amine wastewater Download PDFInfo
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- CN111392865A CN111392865A CN202010276348.9A CN202010276348A CN111392865A CN 111392865 A CN111392865 A CN 111392865A CN 202010276348 A CN202010276348 A CN 202010276348A CN 111392865 A CN111392865 A CN 111392865A
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- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000002351 wastewater Substances 0.000 title claims abstract description 61
- 150000001412 amines Chemical class 0.000 title claims abstract description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 44
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 35
- 241000894006 Bacteria Species 0.000 claims abstract description 34
- 230000002195 synergetic effect Effects 0.000 claims abstract description 11
- 241001148471 unidentified anaerobic bacterium Species 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 244000005700 microbiome Species 0.000 claims abstract description 6
- 241001453382 Nitrosomonadales Species 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000010802 sludge Substances 0.000 claims description 35
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- WBNQDOYYEUMPFS-UHFFFAOYSA-N N-nitrosodiethylamine Chemical compound CCN(CC)N=O WBNQDOYYEUMPFS-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000001546 nitrifying effect Effects 0.000 abstract description 8
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001651 autotrophic effect Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 241001148470 aerobic bacillus Species 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000053 physical method Methods 0.000 description 4
- 238000011020 pilot scale process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 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 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
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- 231100000719 pollutant Toxicity 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- -1 tire manufacturing Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
- C02F3/305—Nitrification and denitrification treatment characterised by the denitrification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
- C02F3/303—Nitrification and denitrification treatment characterised by the nitrification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
- C02F3/307—Nitrification and denitrification treatment characterised by direct conversion of nitrite to molecular nitrogen, e.g. by using the Anammox process
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
Abstract
The invention relates to a method for treating organic amine wastewater, which decomposes organic amine by using anaerobic bacteria to cause the organic amine to generate ammoniation reaction to generate micromolecular acid and inorganic ammonia, and realizes NO by using a denitrifying bacteria-anaerobic ammonia oxidizing bacteria synergetic symbiotic system3 ‑Reduction to NO2 ‑And the removal of BOD in the system is realized; the denitrification process is completed by using anaerobic ammonium oxidizing bacteria, namely NH3-N as electron donor, NO2 ‑Is an electron acceptor, and anaerobic ammoxidation reaction is carried out to realize denitrification; the heterotrophic microorganism and the autotrophic microorganism are used as strains to realize the deep removal of BOD and NH in the sewage3Conversion of-N to NO3 ‑，Finally, the sewage is discharged after reaching standards. The invention can solve the problems of carbon-nitrogen ratio imbalance and carbon in the organic amine wastewater treatment processThe problem of serious shortage of sources; the reflux nitrifying liquid is utilized to the anaerobic ammonia oxidation process section to provide NO for the anaerobic ammonia oxidation process section3 ‑And NO2 ‑As an electron acceptor, the method completes the processes of ammonia oxidation and short-range denitrification, and greatly reduces the operation cost.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment methods, and particularly relates to a treatment method of organic amine wastewater.
Background
In 2018, the discharge amount of industrial wastewater in China is up to 175 hundred million tons. The substandard emission of industrial wastewater becomes a primary factor influencing the water resource safety in China, wherein the organic amine wastewater has more serious threat to the environmental pollution. The organic amine wastewater mainly comes from leather, tire manufacturing, fine chemical engineering and other production enterprises, and belongs to high-nitrogen low-carbon wastewater with high concentration, strong toxicity and difficult biodegradation.
At present, the treatment method for organic amine-containing wastewater at home and abroad mainly comprises a physical method, a chemical method and a biochemical method. The physical method and the chemical method utilize basic physical properties and chemical properties to achieve the purposes of recovery, separation and degradation. The physical methods mainly comprise a rectification method, an extraction method, stripping, gas stripping and the like, and are generally suitable for organic amine wastewater with higher concentration; the chemical method comprises methods such as ion exchange method and AOPs, and the physical method and the chemical method are difficult to reach the emission standard and are usually used as pretreatment process sections of biochemical treatment. The organic amine has poor biodegradability, and a large amount of free ammonia is easily generated in the biochemical process, so that the microorganism is poisoned to stop degradation. The conventional organic amine wastewater denitrification process at present mainly comprises anaerobic-anoxic-aerobic (A)2O) denitrification process. A. the2the/O denitrification process has the advantages of simple flow, mature technology and the like, but the process has low pollutant concentration tolerance, low denitrification capability and larger required tank volume, thus leading to high capital construction cost; in addition, the C/N of the organic amine wastewater is usually far less than 5, the stable operation of the system is maintained, a large amount of carbon source needs to be added into the anoxic tank to generate denitrification reaction, so that NO is generated2 -、NO3 -Conversion to N2Thereby resulting in system operating costs much higher than other industrial sewage costs of the same order of magnitude. If a new process which is tolerant of high pollutant concentration and can be stably operated under the condition of lower C/N can be found, huge economic benefits can be generated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for treating organic amine wastewater, wherein a denitrifying bacteria-anaerobic ammonia oxidation bacteria symbiotic system and an aerobic bacteria-nitrifying bacteria symbiotic system are used for treating the organic amine wastewater by an anaerobic-anaerobic ammonia oxidation-aerobic (A-DN/ANAMMOX-O) process, so that the problems of unbalanced carbon-nitrogen ratio and serious shortage of carbon source are solved; the reflux nitrifying liquid is utilized to the anaerobic ammonia oxidation process section to provide NO for the anaerobic ammonia oxidation process section3 -And NO2 -As an electron acceptor, the catalyst completes the processes of ammonia oxidation and denitrification, thereby greatly reducing the operation cost.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the method for treating the organic amine wastewater is characterized by comprising the following steps of:
(1) the organic amine wastewater enters a regulating tank to remove impurities, uniform water quality and stabilize water flow;
(2) adding anaerobic active strains into the anaerobic reactor at one time, enabling the wastewater treated in the step (1) to enter the anaerobic reactor through a lift pump, decomposing organic amine by anaerobic bacteria in the anaerobic reactor, and carrying out ammoniation reaction on the organic amine to generate micromolecular acid and inorganic ammonia;
(3) adding short-range denitrifying bacteria-anaerobic ammonium oxidation bacteria synergistic symbiotic bacteria into a short-range denitrifying/anaerobic ammonium oxidation reactor, overflowing the wastewater treated in the step (2) into the short-range denitrifying/anaerobic ammonium oxidation reactor, and enabling denitrifying bacteria in the short-range denitrifying/anaerobic ammonium oxidation reactor to react with NO3 -As an electron acceptor, BOD as an electron donor, and short-range denitrification reaction to produce NO2 -And CO2(ii) a NH generated by anaerobic ammonia oxidizing bacteria in anaerobic reactor3-N as electron donor with NO2 -As electron acceptor, anaerobic ammoxidation reaction is completed to degrade NH3-N；CO2Provides a carbon source for the anaerobic ammonium oxidation reaction.
(4) Adding heterotrophic aerobic bacteria and nitrifying bacteria into an aerobic reactor to form cooperative symbiotic bacteria, overflowing the wastewater treated in the step (3) into the aerobic reactor, deeply removing BOD in the wastewater by using a heterotrophic microorganism-autotrophic microorganism cooperative symbiotic system in the aerobic reactor, and removing NH in the wastewater3Conversion of-N to NO3-(ii) a Part of mixed liquor in the aerobic reactor flows back to the short-cut denitrification/anaerobic ammonia oxidation reactor through a reflux pump to provide an electron acceptor for denitrification reaction;
(5) and (4) overflowing the wastewater treated in the step (4) into a sedimentation tank for mud-water separation, so that the mixed liquid is clarified and discharged after reaching the standard.
Preferably, the organic amine wastewater contains one or more of ammonia-containing organic matters or inorganic matters, wherein the organic amine mainly comprises methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, ethylenediamine, triethylamine, hydrazine, aniline, N-dimethylformamide, N-dimethylacetamide, piperazine, pyridine, imidazole, pyrimidine, urea, N-dimethylnitrosamine, N-diethylnitrosamine, amino acids, and hydrochlorides, sulfates and nitrates of the organic matters, and the inorganic ammonia mainly comprises NH3、NH3·H2O、NH4Cl、(NH4)2SO4、NH4NO3And (NH)4)2CO。
Preferably, the retention time of the organic amine wastewater in the step (1) entering a regulating tank is 0.1-5 days.
Preferably, the reaction temperature of the anaerobic reactor in the step (2) is in the range of 5-55 ℃, the pH value is in the range of 5-9.5, the sludge concentration is in the range of 1000-20000 mg/L, and the volume load is in the range of 0.3-5.0 kg (COD)/m (m)3*d)。
Preferably, in the step (3), the reaction temperature in the short-cut denitrification/anaerobic ammonia oxidation reactor is 5-55 ℃, the pH value is 6-9, and the sludge isThe concentration is 1000-20000 mg/L, the dissolved oxygen concentration is 0-2 mg/L, the volume load is 0.1-5.0 kg (COD)/(m)3D). TN volume loading in the range from 0.1 to 5.0kg (TN)/(m)3*d)。
Preferably, in the step (4), the reaction temperature of the aerobic reactor is in the range of 5-55 ℃, the pH value is in the range of 6-9, the sludge concentration is in the range of 10-20000 mg/L, the dissolved oxygen concentration is in the range of 0.2-9 mg/L, and the volume load is in the range of 0.1-5 kg (COD)/(m)3*d),NH3The volume load of-N is in the range of 0.1 to 5kg (NH)3-N)/(m3*d)。
Preferably, in the step (4), alkali liquor is added into the aerobic reactor for stabilizing the pH of the reaction system, wherein the alkali liquor is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate and calcium bicarbonate or a mixture water solution in any proportion.
Preferably, in the step (4), part of the mixed liquor in the aerobic reactor flows back to the short-cut denitrification/anaerobic ammonia oxidation reactor, wherein the reflux ratio is 0.3-10.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the method adopts a short-range denitrifying bacteria-anaerobic ammonium oxidation bacteria symbiotic system and a heterotrophic aerobic bacteria-nitrifying bacteria symbiotic system to treat the organic amine wastewater by an anaerobic-short-range denitrifying/anaerobic ammonium oxidation-aerobic process, and solves the problems of unbalanced carbon-nitrogen ratio and serious insufficient carbon source; the reflux nitrifying liquid is utilized to the anaerobic ammonia oxidation process section to provide NO for the anaerobic ammonia oxidation process section3 -And NO2 -As an electron acceptor, the method completes the anaerobic ammonia oxidation and denitrification processes, and greatly reduces the operation cost.
Drawings
FIG. 1 is a schematic view showing the structure of a processing system used in the processing method of the present invention.
Detailed Description
The technical solutions in the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A self-made pilot test system for an A-DN/ANAMMOX-O combined treatment process is characterized in that the daily treatment capacity is 50L/d, organic amine wastewater (mainly comprising N, N-Dimethylformamide (DMF), wherein CDMF is 10000 mg/L), the pH of the wastewater is 9, TN is 2300 mg/L. an anaerobic process section is formed by domesticating activated sludge in an oxidation ditch process with anaerobic bacteria, the effective volume is 75L, the reaction temperature is 30 ℃, the pH is 7.3, the sludge concentration is 5000 mg/L. an anaerobic ammonia oxidation process section is formed by domesticating anaerobic ammonia oxidizing bacteria and denitrifying bacteria, a symbiotic system is formed, the effective volume of pilot test equipment is 75L, the reaction temperature is 40 ℃, the pH is 7.8, the sludge concentration is 8000 mg/L, an aerobic process section is formed by domesticating autotrophic bacteria and nitrifying bacteria, a synergistic symbiotic system is formed, the effective volume of pilot test equipment is 75L, the reaction temperature is 38 ℃, the pH is 5000-7.8, the aerobic process section is L, and the bacteria are formed by domesticating heterotrophic bacteria and the aerobic process is a sodium carbonate2CO3) And adjusting the pH value of the reaction system. The treated effluent CODCr＝220mg/L，NH3-N＝8mg/L，TN＝67mg/L，pH＝8.5。
Example 2
A pilot-scale system of a self-made A-DN/ANAMMOX-O combined treatment process has the daily treatment capacity of 50L/d, organic amine wastewater (the main components of Dimethylamine (DMA), sodium acetate (NaAc) and other small molecular compounds, wherein the concentration of DMA is 6000 mg/L and 2800 mg/L), and COD in the wastewaterCr7350 mg/L, pH 11, TN 1780 mg/L, anaerobic process segment, anaerobic bacteria acclimatized and inoculated from activated sludge in oxidation ditch process, effective volume 75L, reaction temperature 25 deg.C, pH 7.8, sludge concentration 8500 mg/L, anaerobic ammonia oxidation process segment, bacterial strain acclimatized from anaerobic ammonia oxidation bacteria-denitrifying bacteria to form symbiotic system, pilot plant effective volume 75L, reaction temperature 30 deg.C, pH 7.5, sludge concentration 6500 mg/L, aerobic process segment, bacterial strain selected from heterotrophic aerobic process segmentThe bacteria-nitrifying bacteria are trained to form a synergistic symbiotic system, the effective volume of pilot plant is 75L, the reaction temperature is 35 ℃, the pH value is 7.5-8, the sludge concentration is 5000 mg/L, and potassium bicarbonate (KHCO) is adopted in the reaction process3) And adjusting the pH value of the reaction system. The treated effluent CODCr＝380mg/L，NH3-N＝6.8mg/L，TN＝49mg/L，pH＝8.3。
Example 3
A pilot-scale system of a self-made A-DN/ANAMMOX-O combined treatment process has the daily treatment capacity of 20L/d, and organic amine wastewater (the main components of Urea (Urea) and phenol, ethyl acetate, ethanol and other small molecular compounds, wherein the concentration of the Urea is 4600 mg/L) is COD in the wastewaterCr6770 mg/L, pH 7.7, TN content 2245 mg/L. anaerobic process segment, wherein anaerobic bacteria are domesticated and inoculated from active sludge in oxidation ditch process, effective volume 75L, reaction temperature 20 ℃, pH 7.6, sludge concentration 8500 mg/L. anaerobic ammonia oxidation process segment, strains are domesticated from anaerobic ammonia oxidation bacteria-denitrifying bacteria to form symbiotic system, pilot plant effective volume 75L, reaction temperature 25 ℃, pH 8.2, sludge concentration 4500 mg/L, aerobic process segment, strains are domesticated from heterotrophic aerobic bacteria-nitrifying bacteria to form synergistic symbiotic system, pilot plant effective volume 75L, reaction temperature 25 ℃, pH 7.8-8.3, sludge concentration 5000 mg/L, sodium hydroxide (NaOH) is used in the reaction process to adjust the pH value of the reaction system, COD value of treated effluent waterCr＝270mg/L，NH3-N＝7.2mg/L，TN＝55mg/L，pH＝7.8。
Example 4
The self-made pilot-scale system of the A-DN/ANAMMOX-O combined treatment process has the daily treatment capacity of 50L/d, and organic amine wastewater (the main components of Aniline (AB) and ammonium chloride (NH)4Cl), and benzoic acid, ethyl acetate and other small molecule compounds, wherein aniline is 1350 mg/L), the COD of the wastewaterCr6770 mg/L3-N (2100 mg/L) 2845 mg/L, pH 7.5, anaerobic process, anaerobic bacteria acclimatized and inoculated from activated sludge in oxidation ditch process, effective volume 75L, reaction temperature 35 deg.C, pH 7.3, sludge concentration 12500 mg/L, anaerobic ammonia oxidation process, and strain with anaerobic ammoniaOxidizing bacteria and denitrifying bacteria are domesticated to form a symbiotic system, the effective volume of pilot plant equipment is 75L, the reaction temperature is 35 ℃, the pH is 7.8, the sludge concentration is 8500 mg/L, an aerobic process section is formed, strains are trained from self-contained heterotrophic aerobic bacteria and nitrifying bacteria to form a synergistic symbiotic system, the effective volume of pilot plant equipment is 75L, the reaction temperature is 38 ℃, the pH is 7.5-8, the sludge concentration is 6000 mg/L, and calcium hydroxide (Ca (OH) is adopted in the reaction process2) And adjusting the pH value of the reaction system. The treated effluent CODCr＝367mg/L，NH3-N＝6.8mg/L，TN＝66mg/L，pH＝7.5。
Example 5
A pilot-scale system of a self-made A-DN/ANAMMOX-O combined treatment process has daily treatment capacity of 80L/d, organic amine wastewater (main components of piperazine, N, N-dimethylacetamide (DMAc), acetic acid, ethanol and other small molecular compounds, wherein the main components comprise 750 mg/L of piperazine and 2250 mg/L of DMAc), and COD (chemical oxygen demand) of the wastewaterCr8570 mg/L content is 1845 mg/L, pH 7.5, anaerobic process section, anaerobic bacteria are domesticated and inoculated from activated sludge in oxidation ditch process, effective volume is 75L, reaction temperature is 38 ℃, pH 7.5, sludge concentration is 12500 mg/L, strain is domesticated from anaerobic ammonia oxidation bacteria-denitrifying bacteria to form symbiotic system, pilot plant effective volume is 75L, reaction temperature is 38 ℃, pH 7.8, sludge concentration is 12500 mg/L, aerobic process section, strain is domesticated from heterotrophic aerobic bacteria-nitrifying bacteria to form synergistic symbiotic system, pilot plant effective volume is 75L, reaction temperature is 38 ℃, pH 7.5-8, sludge concentration is 7500 mg/L, sodium carbonate (Na) is adopted in reaction process (Na is Na) is added2CO3) And adjusting the pH value of the reaction system. The treated effluent CODCr＝331mg/L，NH3-N＝7.1mg/L，TN＝63mg/L，pH＝8.4。
Comparative example 1
Self-made anaerobic-anoxic-aerobic (A)2O) combined treatment process pilot system, daily treatment capacity 50L/d, organic amine wastewater (main component N, N-Dimethylformamide (DMF), wherein DMF 2000 mg/L, limited by aerobic basin load), pH 9, TN 460 mg/L, anaerobic process section, anaerobic bacteria oxidation ditch processThe method is characterized in that medium activated sludge is domesticated and inoculated, the effective volume is 75L, the reaction temperature is 30 ℃, the pH is 7.3, the sludge concentration is 5000 mg/L, an anoxic process section is adopted, strains are domesticated and inoculated by the activated sludge in an oxidation ditch process, the effective volume is 75L, the reaction temperature is 30 ℃, the pH is 7.3, the sludge concentration is 5000 mg/L, a supplementary carbon source is glucose, the effective concentration in a tank is 900 mg/L, an aerobic nitrification process section is adopted, the strains are domesticated by autotrophic aerobic bacteria and nitrifying bacteria to form a synergistic symbiotic system, the effective volume of pilot plant is 75L, the reaction temperature is 38 ℃, the pH is 7.0-7.8, the sludge concentration is 3000 mg/L, and sodium carbonate (Na) is adopted in the reaction process2CO3) And adjusting the pH value of the reaction system. The treated effluent CODCr＝320mg/L，NH3-N＝8mg/L，TN＝65mg/L，pH＝8.5。
Comparative example 2
A pilot system of a self-made anaerobic ammonization-aerobic nitrification-anaerobic denitrification-contact oxidation combined treatment process has the daily treatment capacity of 10L/d (limited by the impact resistance of an aerobic pool), organic amine wastewater (the main components of Dimethylamine (DMA), sodium acetate (NaAc) and other small molecular compounds, wherein the concentration of DMA is 6000 mg/L and 2800 mg/L), and COD (chemical oxygen demand) of the wastewaterCr7350 mg/L, pH 11, TN 1780 mg/L, anaerobic process, in which anaerobic bacteria are acclimatized and inoculated to active sludge in oxidation ditch process, effective volume 75L, reaction temperature 30 deg.C, pH 7.3, sludge concentration 5000 mg/L, aerobic nitrification process, in which the strain is acclimatized from self-contained heterotrophic aerobic bacteria-nitrifying bacteria to form synergistic symbiotic system, pilot plant effective volume 75L, reaction temperature 38 deg.C, pH 7.0-7.8, sludge concentration 3000 mg/L, and sodium carbonate (Na) is used in the reaction process2CO3) Adjusting the pH value of a reaction system, acclimatizing and inoculating denitrifying bacteria to activated sludge in an oxidation ditch process in a denitrifying process section, wherein the effective volume is 75L, the reaction temperature is 30 ℃, the pH is 7.3, the sludge concentration is 3000 mg/L, a supplementary carbon source selects glucose, the effective concentration in a pool is 1100 mg/L, a contact oxidation process section is provided, a biological membrane is an aerobic bacteria culture biofilm, the effective volume of a pilot plant is 75L, the reaction temperature is 38 ℃, the pH of the denitrifying bacteria is controlled to be 8.0-8.5, and the reduced concentration of the biological membrane is 3000 mg/LODCr＝280mg/L，NH3-N＝7mg/L，TN＝65mg/L，pH＝8.2。
Examples 1 to 5 organic wastewater treatment was carried out by the following steps, including:
(1) the organic amine wastewater enters a regulating tank to remove impurities, uniform water quality and stabilize water flow;
(2) adding anaerobic active bacteria into an anaerobic reactor, and enabling the wastewater treated in the step (1) to enter the anaerobic reactor through a lift pump, decomposing organic amine by anaerobic bacteria in the anaerobic reactor, and performing ammoniation reaction on the organic amine to generate micromolecular acid and inorganic ammonia;
(3) adding short-range denitrifying bacteria-anaerobic ammonium oxidation bacteria synergistic symbiotic bacteria into a short-range denitrifying/anaerobic ammonium oxidation reactor, overflowing the wastewater treated in the step (2) into the short-range denitrifying/anaerobic ammonium oxidation reactor, and enabling denitrifying bacteria in the short-range denitrifying/anaerobic ammonium oxidation reactor to react with NO3 -As an electron acceptor, BOD as an electron donor, and short-range denitrification reaction to produce NO2 -And CO2(ii) a Completion of NH produced by anaerobic reactor by anaerobic ammonia oxidizing bacteria3-N as electron donor, with NO2-Degradation of NH by anammox reaction as electron acceptor4 +-N；
(4) Adding heterotrophic aerobic bacteria and nitrifying bacteria into an aerobic reactor to form cooperative symbiotic bacteria, overflowing the wastewater treated in the step (3) into the aerobic reactor, deeply removing BOD in the wastewater by using a heterotrophic microorganism-autotrophic microorganism cooperative symbiotic system in the aerobic reactor, and removing NH in the wastewater3Conversion of-N to NO3-(ii) a Part of mixed liquor in the aerobic reactor flows back to the short-cut denitrification/anaerobic ammonia oxidation reactor through a reflux pump to provide an electron acceptor for denitrification reaction;
(5) and (4) overflowing the wastewater treated in the step (4) into a sedimentation tank for mud-water separation, so that the mixed liquid is clarified and discharged after reaching the standard.
Compared with the comparative examples 1 and 2, the process disclosed by the invention does not need to add a large amount of carbon sources in the treatment process, has a good wastewater treatment effect and a high treatment speed, and can reduce the operation cost through the comparison of the examples 1 to 5.
The above description is only a preferred embodiment of the present invention, and therefore, the scope of the present invention should not be limited by the description of the preferred embodiment, and all equivalent changes and modifications made in the claims and the specification should be included in the scope of the present invention.
Claims (8)
1. The method for treating the organic amine wastewater is characterized by comprising the following steps of:
(1) the organic amine wastewater enters a regulating tank to remove impurities, uniform water quality and stabilize water flow;
(2) enabling the wastewater treated in the step (1) to enter an anaerobic reactor through a lift pump, decomposing organic amine by anaerobic bacteria in the anaerobic reactor, and carrying out an ammoniation reaction on the organic amine to generate micromolecular acid and inorganic ammonia;
(3) overflowing the wastewater treated in the step (2) into a short-cut denitrification/anaerobic ammonia oxidation reactor, wherein denitrifying bacteria in the short-cut denitrification/anaerobic ammonia oxidation reactor use NO3 -As an electron acceptor, BOD as an electron donor, and short-range denitrification reaction to produce NO2 -And CO2(ii) a NH generated by anaerobic ammonia oxidizing bacteria in anaerobic reactor3-N as electron donor with NO2 -As electron acceptor, anaerobic ammoxidation reaction is completed to degrade NH3-N；
(4) Overflowing the wastewater treated in the step (3) into an aerobic reactor, deeply removing BOD in the wastewater by using a heterotrophic microorganism-autotrophic microorganism synergistic symbiotic system in the aerobic reactor, and carrying out NH treatment on the wastewater3Conversion of-N to NO3 -(ii) a Part of mixed liquor in the aerobic reactor flows back to the short-cut denitrification/anaerobic ammonia oxidation reactor through a reflux pump to provide an electron acceptor for denitrification reaction;
(5) and (4) overflowing the wastewater treated in the step (4) into a sedimentation tank for mud-water separation, so that the mixed liquid is clarified and discharged after reaching the standard.
2. The method for treating organic amine waste water according to claim 1The method is characterized in that the organic amine wastewater contains one or more of ammonia-containing organic matters or inorganic matters, wherein the organic amine mainly comprises methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, ethylenediamine, triethylamine, hydrazine, aniline, N-dimethylformamide, N-dimethylacetamide, piperazine, pyridine, imidazole, pyrimidine, urea, N-dimethylnitrosamine, N-diethylnitrosamine, amino acids, hydrochlorides, sulfates and nitrates of the organic matters, and the inorganic ammonia mainly comprises NH3、NH3·H2O、NH4Cl、(NH4)2SO4、NH4NO3And (NH)4)2CO3。
3. The method for treating organic amine wastewater according to claim 1, wherein the retention time of the organic amine wastewater in the conditioning tank in the step (1) is 0.1-5 days.
4. The method for treating organic amine wastewater according to claim 1, wherein the reaction temperature of the anaerobic reactor in the step (2) is in the range of 5 to 55 ℃, the pH value is in the range of 5 to 9.5, the sludge concentration is in the range of 1000 to 20000 mg/L, and the volume load is in the range of 0.3 to 5.0kg (COD)/m3*d)。
5. The method for treating organic amine wastewater according to claim 1, wherein in the step (3), the reaction temperature in the short-cut denitrification/anammox reactor is in the range of 5 to 55 ℃, the pH value is in the range of 6 to 9, the sludge concentration is in the range of 1000 to 20000 mg/L, and the dissolved oxygen concentration is in the range of 0 to 2 mg/L, and the volume loading is in the range of 0.1 to 5.0kg (COD)/m (m) (m:)3D). TN volume loading in the range from 0.1 to 5.0kg (TN)/(m)3*d)。
6. The method for treating organic amine wastewater according to claim 1, wherein the reaction temperature of the aerobic reactor in the step (4) is in the range of 5 to 55 ℃, the pH value is in the range of 6 to 9, and the sludge concentration is in the range of 10 to 20000 mg/L, dissolved oxygen concentration range of 0.2-9 mg/L volume load range of 0.1-5 kg (COD)/(m)3*d),NH3The volume load of-N is in the range of 0.1 to 5kg (NH)3-N)/(m3*d)。
7. The method for treating organic amine wastewater as defined in claim 1, wherein in step (4), an alkali solution is added to the aerobic reactor for stabilizing the pH of the reaction system, and the alkali solution is one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate and calcium bicarbonate or a mixture of any proportion of the above solutions.
8. The method for treating organic amine wastewater according to claim 1, wherein in the step (4), part of the mixed liquor in the aerobic reactor is refluxed into the short-cut denitrification/anammox reactor, wherein the reflux ratio is 0.3-10.
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