CN114426349A - Pretreatment method of ammoximation wastewater - Google Patents
Pretreatment method of ammoximation wastewater Download PDFInfo
- Publication number
- CN114426349A CN114426349A CN202010984632.1A CN202010984632A CN114426349A CN 114426349 A CN114426349 A CN 114426349A CN 202010984632 A CN202010984632 A CN 202010984632A CN 114426349 A CN114426349 A CN 114426349A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- sedimentation
- ammoximation
- pretreatment method
- photocatalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 144
- 238000002203 pretreatment Methods 0.000 title claims abstract description 16
- 238000004062 sedimentation Methods 0.000 claims abstract description 68
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 61
- 230000015271 coagulation Effects 0.000 claims abstract description 33
- 238000005345 coagulation Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000701 coagulant Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims description 50
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 40
- 238000007254 oxidation reaction Methods 0.000 claims description 40
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 34
- 239000003513 alkali Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000006385 ozonation reaction Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 230000006641 stabilisation Effects 0.000 claims description 10
- 238000011105 stabilization Methods 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000033558 biomineral tissue development Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 230000000087 stabilizing effect Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- -1 cyclohexylazo Chemical group 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Natural products NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WTFDXZSHRKYAOB-UHFFFAOYSA-N anthracene-9,10-dione;toluene Chemical compound CC1=CC=CC=C1.C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 WTFDXZSHRKYAOB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
-
- 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
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a pretreatment method of ammoximation wastewater, which comprises the following steps of carrying out coagulation sedimentation on the ammoximation wastewater under a weak acid condition to obtain wastewater after the coagulation sedimentation, wherein the coagulation sedimentation comprises the following steps: s101: adding metal salt or a polymer thereof into the ammoximation wastewater, and performing first sedimentation to obtain wastewater after the first sedimentation; s102: adjusting the pH value of the wastewater after the first sedimentation to be weakly acidic, and performing second sedimentation to obtain wastewater after the second sedimentation; s103: and adding a coagulant into the wastewater after the second sedimentation, performing third sedimentation, and filtering to obtain the wastewater after the coagulation sedimentation. After the treatment of the treatment method, the organic nitrogen in the ammoximation high organic nitrogen wastewater can be fully mineralized, the biodegradability of the wastewater is improved, and favorable conditions are created for standard discharge after the subsequent biological treatment of the wastewater.
Description
Technical Field
The invention relates to the field of industrial wastewater treatment, in particular to a pretreatment method of ammoximation wastewater.
Background
Caprolactam is a raw material for producing nylon-6, and the production and demand of which have been increasing in recent years due to the expansion and development of the application fields of nylon fibers, engineering plastics, films and artificial leathers. The caprolactam production process has long flow, large circulating materials, a plurality of byproducts and intermediate products, and the wastewater has complex components and high toxicity and belongs to high-concentration nitrogen-containing organic wastewater, which is one of the production wastewater which is difficult to treat in the current petrochemical industry.
In the production of caprolactam, the important step is to prepare cyclohexanone oxime from cyclohexanone, namely cyclohexanone is subjected to ammoxidation by directly using hydrogen peroxide under the action of a titanium-silicon catalyst to generate cyclohexanone oxime, COD (chemical oxygen demand) of wastewater produced by the ammoxidation process is up to 2000-12000 mg/L, and total nitrogen in the wastewater consists of ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and organic nitrogen, wherein the ammonia nitrogen is converted into the nitrate nitrogen through biochemical aerobic nitrification, and the nitrate nitrogen and the nitrite nitrogen can be removed through anoxic denitrification, so that a key pollutant influencing the standard reaching of the total nitrogen in the wastewater is the organic nitrogen.
The wastewater from caprolactam production mostly adopts a multi-stage treatment mode. The first stage treatment is to remove precipitate or oil by physical methods such as screening, precipitation or floating. The secondary treatment is mainly to remove organic matters in a dissolved state and a colloidal state by a biochemical method, and comprises anaerobic, anoxic and aerobic treatment methods, or different methods are combined to treat wastewater. According to the actual operation conditions of several caprolactam production and polymerization enterprises in China in recent years, the organic matters in the wastewater treated by the anoxic/aerobic process can reach the standard, but the total nitrogen is difficult to reach the standard. The method has the advantages that the composition content of organic nitrogen in the ammoximation wastewater is high, the organic nitrogen is complex and difficult to treat, and the main reason that the total nitrogen of caprolactam wastewater is difficult to reach the standard is provided, even the phenomenon that the ammonia nitrogen in outlet water is higher than that in inlet water appears in the tail end process of part of caprolactam wastewater treatment engineering which actually runs, so that a novel and technically feasible process is necessary to be developed to carry out pretreatment on the organic nitrogen in the ammoximation wastewater, the organic nitrogen is mineralized to the maximum extent in the pretreatment stage, the phenomena that the slow conversion of the organic nitrogen in the main treatment process affects the total nitrogen and the ammonia nitrogen in the outlet water are avoided, and the total nitrogen of the wastewater is ensured to be discharged up to the standard.
Disclosure of Invention
The invention provides a method for treating wastewater generated in a caprolactam production process, in particular to a method for pretreating organic nitrogen in ammoximation wastewater, aiming at the problems that ammoximation wastewater has high COD (chemical oxygen demand), high nitrogen, high organic nitrogen content and poor biodegradability.
The ammoximation wastewater has the characteristics of high COD, high nitrogen, high organic nitrogen content, poor biodegradability and the like. The organic matters in the ammoximation wastewater mainly comprise: the peroxycyclohexylamine, the cyclohexylazo, the anthraquinone toluene and the cyclohexanone oxime are all nitrogen-containing organic matters, have certain polarity and can be settled under an acidic condition. Firstly, adding a proper amount of aluminum or iron salt or polymer to change the surface electrochemical characteristics of the nitrogen-containing organic matters, destroying the stability of particles of the nitrogen-containing organic matters, adding acid to adjust the pH value of the wastewater to be acidic to strengthen the sedimentation of the nitrogen-containing organic matters in the wastewater, adding a nonionic coagulant to react, partially removing organic nitrogen in the ammoximation wastewater, effectively removing suspended matters in the wastewater, and improving the light transmittance of the ammoximation wastewater; then, adding alkali to adjust the pH value of the wastewater to be neutral and slightly alkaline, removing partial organic nitrogen in the wastewater through photocatalytic ozone oxidation, and simultaneously improving the biodegradability of the wastewater.
The first aspect of the present invention provides a method for pretreating ammoximation wastewater, comprising S1: carrying out coagulation sedimentation on the ammoximation wastewater under a weak acid condition to obtain wastewater after coagulation sedimentation, wherein the coagulation sedimentation comprises the following steps:
s101: adding metal salt or a polymer thereof into the ammoximation wastewater, and performing first sedimentation to obtain wastewater after the first sedimentation;
s102: adjusting the pH value of the wastewater after the first sedimentation to be weakly acidic, and performing second sedimentation to obtain wastewater after the second sedimentation;
s103: and adding a coagulant into the wastewater after the second sedimentation, performing third sedimentation, and filtering to obtain the wastewater after the coagulation sedimentation.
According to some embodiments of the invention, the pretreatment method further comprises the steps of:
s2: adjusting the pH value of the wastewater after coagulation sedimentation to be alkalescent to obtain wastewater after alkali adjustment;
s3: and carrying out photocatalytic ozone oxidation on the wastewater after alkali adjustment.
According to some embodiments of the present invention, the ammoximation wastewater comprises at least one of cyclohexylamine peroxide, cyclohexylazo, anthraquinone toluene and cyclohexanone oxime.
According to some embodiments of the invention, the ammoximation wastewater has COD of 2000-6000mg/L, pH of 7.0-10.0, TOC of 500-2000mg/L, BOD5/COD<0.1, 500-1500mg/L of total nitrogen and 100-1000mg/L of organic nitrogen.
According to some embodiments of the invention, the metal salt or polymer thereof is selected from at least one of an aluminum salt and a polymer thereof and an iron salt and a polymer thereof.
According to some embodiments of the invention, the metal salt or polymer thereof is selected from at least one of polyaluminum chloride, aluminum sulfate, ferrous sulfate, and ferric chloride.
According to some embodiments of the invention, the metal salt or polymer thereof is added at a concentration of 10 to 200 mg/L.
According to the invention, the Al produced after dissolution of the aluminium or iron salt or polymer in water3+、Fe2+Or Fe3+Can cause the change of the surface electrochemical characteristics of part of the nitrogen-containing organic matters in the ammoximation wastewater, so that the stability of the nitrogen-containing organic matter particles is deteriorated and the coagulation and sedimentation are generated.
According to some embodiments of the invention, the coagulant is selected from non-ionic polyacrylamides.
According to some embodiments of the invention, the coagulant is dosed at a concentration of 10-100 mg/L.
According to some embodiments of the invention, the time of the first sedimentation is 10-30min in S101.
According to some embodiments of the present invention, in S101, the temperature of the first sedimentation is not particularly required, and the normal temperature or room temperature does not substantially affect the effect.
According to some embodiments of the invention, the temperature of the first sedimentation is 15 to 35 ℃ in S101.
According to some embodiments of the invention, the time of the second sedimentation is 10-30min in S102.
According to some embodiments of the present invention, in S102, the temperature of the second sedimentation is not particularly required, and the normal temperature or room temperature does not substantially affect the effect.
According to some embodiments of the invention, the temperature of the second sedimentation is 15 to 35 ℃ in S102.
According to some embodiments of the invention, the time of the third settling is 10-120min in S103.
According to some embodiments of the present invention, in S103, the temperature of the third sedimentation is not particularly required, and the normal temperature or room temperature does not substantially affect the effect.
According to some embodiments of the invention, the temperature of the third sedimentation is 15 to 35 ℃ in S103.
According to some embodiments of the present invention, in S102, the pH of the wastewater after the first settling is adjusted using concentrated hydrochloric acid having a mass concentration of 36 to 38%.
According to some embodiments of the invention, in S102, the pH is adjusted to 4.5-6.5, which may be, for example, 4.8, 5.0, 5.3, 5.5, 5.8, 6.0, 6.2, and any value in between.
According to a preferred embodiment of the present invention, in S102, the pH is adjusted to 4.5-5.5.
According to some embodiments of the invention, in S1, the weak acid condition is a pH of 4.5-6.5, which may be, for example, 4.8, 5.0, 5.3, 5.5, 5.8, 6.0, 6.2, and any value in between.
According to a preferred embodiment of the present invention, in S1, the weak acid condition is a pH of 4.5 to 5.5.
According to some embodiments of the invention, in S2, the pH of the waste water after coagulation sedimentation is adjusted to be weakly alkaline by using a sodium hydroxide solution with a mass concentration of 40-50%.
According to some embodiments of the invention, in S102, the pH is adjusted to 7.5-9.5.
According to some embodiments of the invention, in S3, the photocatalytic ozonation, the ultraviolet light has a wavelength ranging from 200 to 300 nm.
According to some embodiments of the invention, the photocatalytic ozonation catalyst is selected from transition metal supported catalysts on titania.
According to some specific embodiments of the present invention, the wastewater after alkali adjustment enters a photocatalytic ozonation column to perform a photocatalytic ozonation reaction. An ultraviolet lamp is arranged in the photocatalytic ozonation column, and the wavelength range of ultraviolet light generated by the ultraviolet lamp is 200-300 nm; the photocatalytic ozone oxidation column is filled with a catalyst for photocatalytic ozone oxidation, and the catalyst is a spherical catalyst taking titanium dioxide as a carrier and loading a small amount of transition metal.
According to some embodiments of the invention, the photocatalytic ozonation is performed for a period of 20-120 min.
According to some embodiments of the present invention, the temperature of the photocatalytic ozonation is not particularly required, and the normal temperature or room temperature does not substantially affect the effect.
According to some embodiments of the invention, the method further comprises flowing the photocatalytic ozonated effluent through a stabilization tank for oxygen removal.
According to some embodiments of the invention, the time of the oxygen removal treatment is greater than 120 min.
According to some embodiments of the present invention, the oxygen removal treatment is performed to remove the effect of residual ozone on the subsequent process after photocatalytic ozone oxidation.
According to some specific embodiments of the present invention, the photocatalytic ozonation effluent flows through the stabilization tank, so that residual ozone in the wastewater is sufficiently degraded into oxygen and completely escapes, and the influence of residual dissolved oxygen in the wastewater on the subsequent process (oxygen deficiency) is avoided. The stabilizing pool is formed by connecting at least two same pool bodies in series, the residence time of a single stabilizing pool is more than 60min, and the residence time of the whole stabilizing pool process is more than 120 min.
In a second aspect of the invention, there is provided the use of the pretreatment method according to the first aspect in the treatment of organic nitrogen wastewater, for example in caprolactam production wastewater.
The inventor of the invention discovers through intensive research that nitrogen-containing organic matters in ammoximation wastewater have certain polarity and can slowly settle under the action of a certain electric field or under the condition of lower pH, firstly, a proper amount of aluminum or iron salt or polymer is added to change the surface electrochemical characteristics of the nitrogen-containing organic matters, destroy the stability of nitrogen-containing organic matter particles, add acid to adjust the pH of the wastewater to acidity to strengthen the settlement of the nitrogen-containing organic matters in the wastewater, and add a nonionic coagulant for reaction, thereby realizing partial removal of organic nitrogen in the ammoximation wastewater and effective removal of suspended matters in the wastewater, and improving the light transmittance; and then the residual organic nitrogen compounds in the wastewater are oxidized and degraded by photocatalysis ozone, so that the mineralization of the organic nitrogen is realized, the biodegradability of the wastewater is greatly improved, and favorable conditions are created for the low-cost and high-efficiency treatment of the wastewater by a biochemical method.
The invention has the beneficial effects that: by the method provided by the invention, the final removal rate of organic nitrogen in the effluent is more than 70 percent after the wastewater is treated by the processes of 'reinforced coagulation sedimentation in a weak acid environment, alkali adjustment, photocatalytic ozone oxidation and residual ozone removal in a stabilization tank'. The pH value is only adjusted to about 5 by the intensified coagulation sedimentation in the weak acid environment, the acid consumption is reduced, the removal of 20-40% of nitrogenous organic matters is realized, suspended matters in the wastewater are removed, and the light transmittance of the wastewater is improved; the photocatalytic ozonation can realize selective oxidation of nitrogen-containing organic matters by selecting the wavelength range of ultraviolet light, preferentially oxidize and degrade the nitrogen-containing organic matters, can realize mineralization of organic nitrogen in the ammoximation wastewater of more than 90 percent, simultaneously keeps the capability of improving the biodegradability of the wastewater, but is shorter and obviously reduced in ozone consumption compared with the reaction time of an ozonation process, and can control the removal degree of the nitrogen-containing organic matters in the ammoximation wastewater by adjusting the treatment time or the ozone consumption according to the requirements of a subsequent treatment process at the treatment stage.
Drawings
FIG. 1 is a schematic view of a process for pretreating ammoximation wastewater according to the present invention.
Detailed Description
The pretreatment method of organic nitrogen in ammoximation wastewater provided by the invention can be realized by the following steps:
(1) and (4) enhancing coagulation and sedimentation in a weak acid environment. Adding a certain amount of aluminum or iron salt or polymer into the ammoximation wastewater, and starting stirring. The salt or polymer of aluminum or iron can be polyaluminium chloride, aluminum sulfate, ferrous sulfate, ferric chloride and the like, and the adding concentration is 10-200 mg/L. Al generated by dissolving the salt or polymer of aluminum or iron in water3+、Fe2+Or Fe3+Can cause the change of the surface electrochemical characteristics of part of the nitrogen-containing organic matters in the ammoximation wastewater, so that the stability of the nitrogen-containing organic matter particles is deteriorated and coagulation sedimentation occurs, and the reaction time of the step is 10-30 min. Then concentrated hydrochloric acid with the mass concentration of 36-38% is used for adjusting the pH value of the wastewater to 4.5-6.5, and further sedimentation is carried out. Adding coagulant after 10-30min, reacting for a period of time, and filtering. The coagulant is nonionic polyacrylamide, the adding concentration is 10-100mg/L, and the reaction time is 10-120 min.
(2) And (5) adjusting alkali. Adjusting the pH value of the coagulation effluent to 7.5-9.5 by alkali. The alkali is sodium hydroxide solution with the mass concentration of 40-50%.
(3) And (4) carrying out photocatalytic ozone oxidation. And the wastewater after alkali adjustment enters a photocatalytic ozone oxidation column to carry out photocatalytic ozone oxidation reaction. An ultraviolet lamp is arranged in the photocatalytic ozonation column, and the wavelength range of ultraviolet light generated by the ultraviolet lamp is 200-300 nm; the oxidation column is filled with a catalyst for photocatalytic ozone oxidation, and the catalyst is a spherical catalyst which takes titanium dioxide as a carrier and loads a small amount of transition metal. The reaction time is 20-120 min.
(4) And (5) stabilizing the pool. The water discharged by photocatalytic ozonation flows through the stabilization tank, so that residual ozone in the wastewater is fully degraded into oxygen and completely escapes, and the influence of residual dissolved oxygen in the wastewater on a subsequent process (oxygen deficiency) is avoided. The stabilizing pool is formed by connecting two same pool bodies in series, the residence time of a single stabilizing pool is more than 60min, and the residence time of the whole stabilizing pool process is more than 120 min.
For easy understanding of the present invention, the present invention will be described in detail with reference to examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.
The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1
Certain petrochemical plant caprolactam apparatus for producing discharges the ammoximation waste water, and waste water quality is characterized by: COD3080mg/L, pH8.5, total nitrogen 1284mg/L, organic nitrogen 600mg/L, BOD5The COD was 0.005. The wastewater is treated as follows:
the method comprises the following steps: and (3) performing enhanced coagulation sedimentation in a weak acid environment, adding 100mg/L of polyaluminium chloride into the wastewater, and stirring for reaction for 25 min. Then concentrated hydrochloric acid with the mass concentration of 36% is used for adjusting the pH value of the wastewater to 5.0, and further sedimentation is carried out. Adding 30mg/L nonionic polyacrylamide coagulant after 25min, reacting for 1 hour, and filtering. The organic nitrogen in the produced water is 414mg/L, and the removal rate of the organic nitrogen is 31 percent.
Step two: and (5) adjusting alkali. Adjusting the pH value of the coagulation effluent to 8.0 by alkali. The alkali is sodium hydroxide solution with the mass concentration of 50%.
Step three: and (4) carrying out photocatalytic ozone oxidation. And (3) allowing the wastewater after alkali adjustment to enter a photocatalytic ozone oxidation column to perform photocatalytic ozone oxidation reaction for 45 min. An ultraviolet lamp is arranged in the photocatalytic ozonation column, and the wavelength range of ultraviolet light generated by the ultraviolet lamp is 200-300 nm; the oxidation column is filled with a catalyst for photocatalytic ozone oxidation, and the catalyst is a spherical catalyst which takes titanium dioxide as a carrier and loads a small amount of transition metal. The effluent enters a stabilization tank and stays for 120 min. The organic nitrogen in the produced water is 41mg/L, the COD is 2247mg/L and the BOD is50.48 of COD, 90 percent of organic nitrogen removal rate, remarkable mineralization of organic nitrogen in wastewater and growth of biomassThe chemical property is obviously improved, and favorable conditions are created for subsequent biological treatment.
Example 2
Certain petrochemical plant caprolactam apparatus for producing discharges the ammoximation waste water, and waste water quality is characterized by: COD2810mg/L, pH7.8, total nitrogen 944mg/L, organic nitrogen 242mg/L, BOD5The COD was 0.001. The wastewater is treated as follows:
the method comprises the following steps: and (3) performing enhanced coagulation sedimentation in a weak acid environment, adding 120mg/L of polyaluminium chloride into the wastewater, and stirring for reacting for 20 min. Then concentrated hydrochloric acid with the mass concentration of 36% is used for adjusting the pH value of the wastewater to 5.0, and further sedimentation is carried out. After 30min, 35mg/L of non-ionic polyacrylamide coagulant is added, reaction is carried out for 1 hour, and filtration is carried out. The organic nitrogen in the produced water is 174mg/L, and the removal rate of the organic nitrogen is 28 percent.
Step two: and (5) adjusting alkali. Adjusting the pH value of the coagulation effluent to 8.5 by alkali. The alkali is sodium hydroxide solution with the mass concentration of 50%.
Step three: and (4) carrying out photocatalytic ozone oxidation. And (3) allowing the wastewater after alkali adjustment to enter a photocatalytic ozone oxidation column for photocatalytic ozone oxidation reaction for 30 min. An ultraviolet lamp is arranged in the photocatalytic ozonation column, and the wavelength range of ultraviolet light generated by the ultraviolet lamp is 200-300 nm; the oxidation column is filled with a catalyst for photocatalytic ozone oxidation, and the catalyst is a spherical catalyst which takes titanium dioxide as a carrier and loads a small amount of transition metal. The effluent enters a stabilization tank and stays for 100 min. The organic nitrogen in the produced water is 37mg/L, COD2014mg/L and BOD5The COD is 0.48, the removal rate of organic nitrogen is 79 percent, the mineralization of the organic nitrogen in the wastewater is obvious and the biodegradability is obviously improved, and favorable conditions are created for the subsequent biological treatment.
Example 3
Certain petrochemical plant caprolactam apparatus for producing discharges the ammoximation waste water, and waste water quality is characterized by: COD3080mg/L, pH8.5, total nitrogen 1284mg/L, organic nitrogen 600mg/L, BOD5The COD was 0.005. The wastewater is treated as follows:
the method comprises the following steps: and (3) performing enhanced coagulation sedimentation in a weak acid environment, adding 100mg/L of polyaluminium chloride into the wastewater, and stirring for reaction for 25 min. Then concentrated hydrochloric acid with the mass concentration of 36% is used for adjusting the pH value of the wastewater to 5.5, and further sedimentation is carried out. Adding 30mg/L nonionic polyacrylamide coagulant after 25min, reacting for 1 hour, and filtering. The organic nitrogen in the produced water is 451mg/L, and the removal rate of the organic nitrogen is 25 percent.
Step two: and (5) adjusting alkali. Adjusting the pH value of the coagulation effluent to 8.0 by alkali. The alkali is sodium hydroxide solution with the mass concentration of 50%.
Step three: and (4) carrying out photocatalytic ozone oxidation. And (3) allowing the wastewater after alkali adjustment to enter a photocatalytic ozone oxidation column to perform photocatalytic ozone oxidation reaction for 45 min. An ultraviolet lamp is arranged in the photocatalytic ozonation column, and the wavelength range of ultraviolet light generated by the ultraviolet lamp is 200-300 nm; the oxidation column is filled with a catalyst for photocatalytic ozone oxidation, and the catalyst is a spherical catalyst which takes titanium dioxide as a carrier and loads a small amount of transition metal. The effluent enters a stabilization tank and stays for 120 min. The organic nitrogen in the produced water is 49mg/L, the COD is 2239mg/L and the BOD5The COD is 0.48, the removal rate of organic nitrogen is 89 percent, the mineralization of the organic nitrogen in the wastewater is obvious and the biodegradability is obviously improved, and favorable conditions are created for the subsequent biological treatment.
Example 4
Certain petrochemical plant caprolactam apparatus for producing discharges the ammoximation waste water, and waste water quality is characterized by: COD3080mg/L, pH8.5, total nitrogen 1284mg/L, organic nitrogen 600mg/L, BOD5The COD was 0.005. The wastewater is treated as follows:
the method comprises the following steps: and (3) performing enhanced coagulation sedimentation in a weak acid environment, adding 100mg/L of polyaluminium chloride into the wastewater, and stirring for reaction for 25 min. Then concentrated hydrochloric acid with the mass concentration of 36% is used for adjusting the pH value of the wastewater to 6.0, and further sedimentation is carried out. Adding 30mg/L nonionic polyacrylamide coagulant after 25min, reacting for 1 hour, and filtering. 497mg/L of organic nitrogen in the produced water, and the removal rate of the organic nitrogen is 17 percent.
Step two: and (5) adjusting alkali. Adjusting the pH value of the coagulation effluent to 8.0 by alkali. The alkali is sodium hydroxide solution with the mass concentration of 50%.
Step three: and (4) carrying out photocatalytic ozone oxidation. And (3) allowing the wastewater after alkali adjustment to enter a photocatalytic ozone oxidation column to perform photocatalytic ozone oxidation reaction for 45 min. An ultraviolet lamp is arranged in the photocatalytic ozonation column, and the wavelength range of ultraviolet light generated by the ultraviolet lamp is 200-300 nm; oxidation by oxygenThe column is filled with a catalyst for photocatalytic ozone oxidation, and the catalyst is a spherical catalyst which takes titanium dioxide as a carrier and loads a small amount of transition metal. The effluent enters a stabilization tank and stays for 120 min. 60mg/L of organic nitrogen, 2291mg/L of COD and BOD in produced water5The COD is 0.45, the removal rate of organic nitrogen is 88 percent, the mineralization of the organic nitrogen in the wastewater is obvious and the biodegradability is obviously improved, and favorable conditions are created for the subsequent biological treatment.
Comparative example 1
The caprolactam apparatus of production who handles in example 1 discharges the ammoximation waste water, and waste water quality is characterized by: COD3080mg/L, pH8.5, total nitrogen 1284mg/L, organic nitrogen 599mg/L, BOD5The COD was 0.005. The conventional flocculation treatment is carried out on the wastewater, and the steps are as follows:
the method comprises the following steps: adding 100mg/L polyaluminium chloride, and stirring to react for 25 min;
step two: adjusting the pH value of the wastewater to 9 by using sodium hydroxide with the mass concentration of 40%;
step three: adding 30mg/L nonionic polyacrylamide coagulant after 25min, reacting for 1 hour, and filtering. The organic nitrogen in the produced water is 543mg/L, and the removal rate of the organic nitrogen is 9.3 percent.
Comparing the treatment results of step one in the example 1 and the comparative example 1, the treatment effect of the coagulation sedimentation in the weakly acidic environment is obviously better than the flocculation treatment effect under the conventional condition under the same dosage and reaction time condition.
Comparative example 2
The caprolactam apparatus of production who handles in example 1 discharges the ammoximation waste water, and waste water quality is characterized by: COD3080mg/L, pH8.5, total nitrogen 1284mg/L, organic nitrogen 599mg/L, BOD5The COD was 0.005. The wastewater was treated as follows:
the method comprises the following steps: pre-settling, adding 100mg/L of polyaluminium chloride into the wastewater, and stirring for reacting for 20 min;
step two: intensified sedimentation, namely adjusting the pH value of the wastewater to 3 by using concentrated hydrochloric acid with the mass concentration of 36-38%;
step three: adding 30mg/L nonionic polyacrylamide coagulant after 25min, reacting for 1 hour, and filtering. The organic nitrogen in the produced water is 163mg/L, and the removal rate of the organic nitrogen is 72.8 percent.
Comparing the treatment results of the step one in the example 1 and the comparative example 2, under the same dosage and reaction time conditions, the organic nitrogen overall removal effect of the comparative example 2 is better than that of the step one in the example 1, but not only the acid amount is much larger (the acid amount is adjusted to pH3.0 from pH8.5), but also more alkali is needed for pH adjustment, the overall organic nitrogen removal effect is better after the subsequent alkali adjustment and the photocatalytic ozone oxidation in the example 1, the wastewater biodegradability is obviously improved, and favorable conditions are created for the subsequent biological treatment.
Comparative example 3
The caprolactam apparatus of production who handles in example 1 discharges the ammoximation waste water, and waste water quality is characterized by: COD3080mg/L, pH8.5, total nitrogen 1284mg/L, organic nitrogen 599mg/L, BOD5/COD 0.005. The wastewater was treated as follows:
the method comprises the following steps: and (3) performing enhanced coagulation sedimentation in a weak acid environment, adding 100mg/L of polyaluminium chloride into the wastewater, and stirring for reaction for 25 min. Then concentrated hydrochloric acid with the mass concentration of 36% is used for adjusting the pH value of the wastewater to 5, and further sedimentation is carried out. Adding 30mg/L nonionic polyacrylamide coagulant after 25min, reacting for 1 hour, and filtering. The organic nitrogen in the produced water is 414mg/L, and the removal rate of the organic nitrogen is 31 percent.
Step two: and (5) adjusting alkali. Adjusting the pH value of the coagulation effluent to 8.0 by alkali. The alkali is sodium hydroxide solution with the mass concentration of 50%.
Step three: catalyzing ozone oxidation. And (3) allowing the wastewater after alkali adjustment to enter a catalytic ozone oxidation column for catalytic ozone oxidation reaction, wherein the reaction time is 45 min. The oxidation column is filled with a catalyst for catalyzing ozone oxidation, and the catalyst is a spherical catalyst which takes titanium dioxide as a carrier and loads a small amount of transition metal. The effluent enters a stabilization tank and stays for 120 min. The organic nitrogen removal rate of the produced water is 302mg/L, COD 1809mg/L, BOD5/COD 0.20, and the organic nitrogen removal rate is 27 percent.
Comparing example 1 with comparative example 3, step three of comparative example 3 changes photocatalytic ozonation into catalytic ozonation, and the removal mineralization rate of organic nitrogen is obviously reduced, and the effect of pre-treating organic nitrogen is not effectively achieved.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for pretreating ammoximation wastewater, comprising S1: carrying out coagulation sedimentation on the ammoximation wastewater under a weak acid condition to obtain wastewater after coagulation sedimentation, wherein the coagulation sedimentation comprises the following steps:
s101: adding metal salt or a polymer thereof into the ammoximation wastewater, and performing first sedimentation to obtain wastewater after the first sedimentation;
s102: adjusting the pH value of the wastewater after the first sedimentation to be weakly acidic, and performing second sedimentation to obtain wastewater after the second sedimentation;
s103: and adding a coagulant into the wastewater after the second sedimentation, performing third sedimentation, and filtering to obtain the wastewater after the coagulation sedimentation.
2. The pretreatment method of claim 1, further comprising the steps of:
s2: adjusting the pH value of the wastewater after coagulation sedimentation to be alkalescent to obtain wastewater after alkali adjustment;
s3: and carrying out photocatalytic ozone oxidation on the wastewater after alkali adjustment.
3. The pretreatment method according to claim 1 or 2, wherein the metal salt or a polymer thereof is at least one selected from the group consisting of an aluminum salt and a polymer thereof, and an iron salt and a polymer thereof, preferably at least one selected from the group consisting of polyaluminum chloride, aluminum sulfate, ferrous sulfate, and ferric chloride, and more preferably, the metal salt or a polymer thereof is added at a concentration of 10 to 200 mg/L.
4. The pretreatment method according to any one of claims 1 to 3, wherein the coagulant is selected from nonionic polyacrylamides, and preferably the dosing concentration of the coagulant is 10 to 100 mg/L.
5. The pretreatment method according to any one of claims 1 to 4, wherein in S101, the time of the first sedimentation is 10 to 30 min; and/or
In S102, the time of the second sedimentation is 10-30 min; and/or
In S103, the time of the third sedimentation is 10-120 min.
6. The pretreatment method according to any one of claims 1 to 5, wherein in S102, concentrated hydrochloric acid having a mass concentration of 36 to 38% is used to adjust the pH of the wastewater after the first sedimentation; preferably, the pH is adjusted to 4.5-6.5, preferably 4.5-5.5.
7. The pretreatment method according to any one of claims 1 to 6, wherein in S1, the weak acid condition is a pH of 4.5 to 6.5, preferably 4.5 to 5.5; and/or
In S2, adjusting the pH value of the wastewater after coagulation sedimentation to be alkalescent by adopting a sodium hydroxide solution with the mass concentration of 40-50%; preferably, the pH is adjusted to 7.5-9.5.
8. The pretreatment method according to any one of claims 1 to 7, wherein in the photocatalytic ozonation at S3, the wavelength of ultraviolet light is in the range of 200 to 300 nm; and/or
The catalyst for photocatalytic ozonation is selected from a catalyst taking titanium dioxide as a carrier and loading transition metal; and/or
The time of the photocatalytic ozone oxidation is 20-120 min.
9. The pretreatment method of any one of claims 1 to 8, further comprising flowing the photocatalytic ozonated effluent through a stabilization tank for an oxygen removal treatment, preferably for a time period greater than 120 min.
10. Use of a pretreatment method according to any one of claims 1 to 9 in organic nitrogen wastewater treatment, for example in caprolactam production wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010984632.1A CN114426349A (en) | 2020-09-18 | 2020-09-18 | Pretreatment method of ammoximation wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010984632.1A CN114426349A (en) | 2020-09-18 | 2020-09-18 | Pretreatment method of ammoximation wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114426349A true CN114426349A (en) | 2022-05-03 |
Family
ID=81309090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010984632.1A Pending CN114426349A (en) | 2020-09-18 | 2020-09-18 | Pretreatment method of ammoximation wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426349A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330182A (en) * | 2003-04-16 | 2004-11-25 | Sanyo Electric Co Ltd | Treating method of water to be treated containing organic material and nitrogen compound |
| US8252183B1 (en) * | 2011-10-28 | 2012-08-28 | Kent Bioenergy Corporation | Treating nitorogen-contaminated wastewaters |
| CN103011527A (en) * | 2012-12-29 | 2013-04-03 | 上海安赐机械设备有限公司 | Enhanced oxidation-MBR (membrane bioreactor) treatment method of caprolactam production wastewater |
| CN103708648A (en) * | 2013-12-26 | 2014-04-09 | 清华大学 | Method for realizing reduction-Fenton oxidation coupled treatment of azo dyeing wastewater |
| CN105502732A (en) * | 2015-12-01 | 2016-04-20 | 上海明诺环境科技有限公司 | Advanced treatment technology for caprolactam wastewater and device |
| CN110540316A (en) * | 2018-05-29 | 2019-12-06 | 中国石油化工股份有限公司 | Pretreatment method and application of ammoximation wastewater |
| 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 |
-
2020
- 2020-09-18 CN CN202010984632.1A patent/CN114426349A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004330182A (en) * | 2003-04-16 | 2004-11-25 | Sanyo Electric Co Ltd | Treating method of water to be treated containing organic material and nitrogen compound |
| US8252183B1 (en) * | 2011-10-28 | 2012-08-28 | Kent Bioenergy Corporation | Treating nitorogen-contaminated wastewaters |
| CN103011527A (en) * | 2012-12-29 | 2013-04-03 | 上海安赐机械设备有限公司 | Enhanced oxidation-MBR (membrane bioreactor) treatment method of caprolactam production wastewater |
| CN103708648A (en) * | 2013-12-26 | 2014-04-09 | 清华大学 | Method for realizing reduction-Fenton oxidation coupled treatment of azo dyeing wastewater |
| CN105502732A (en) * | 2015-12-01 | 2016-04-20 | 上海明诺环境科技有限公司 | Advanced treatment technology for caprolactam wastewater and device |
| CN110540316A (en) * | 2018-05-29 | 2019-12-06 | 中国石油化工股份有限公司 | Pretreatment method and application of ammoximation wastewater |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 刘少武等: "《硫酸生产技术》", 30 June 1993, 东南大学出版社 * |
| 朱玉霜等: "《浮选药剂的化学原理（修订版）》", 中南工业大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101734825B (en) | Method for treating wastewater generated by cyclohexanone ammoximation process | |
| CN101618919A (en) | Method for processing waste water produced by caprolactam ammoximation process | |
| Tian et al. | Treatment of pharmaceutical wastewater for reuse by coupled membrane-aerated biofilm reactor (MABR) system | |
| CN112794555A (en) | Novel method for treating wastewater by reinforced coagulation | |
| CN111362462A (en) | Advanced treatment method for papermaking wastewater | |
| CN107352742B (en) | Electrochemical composite oxidation process and system for refractory sewage | |
| CN111732249A (en) | Pretreatment process of integrated Fenton equipment integrated system | |
| CN105152459A (en) | Process for treating wastewater produced in regeneration of SCR denitration catalyst | |
| JPH04349997A (en) | Treatment of organic waste water | |
| CN113648833A (en) | Novel low-pressure high-recovery-rate nanofiltration system and method | |
| CN112960861A (en) | Biological denitrification treatment process for stainless steel pickling wastewater | |
| CN111138040A (en) | Landfill leachate treatment method | |
| CN110540336A (en) | treatment method and application of ammoximation wastewater | |
| JPH01199694A (en) | Waste water treatment by activated sludge method | |
| CN114426349A (en) | Pretreatment method of ammoximation wastewater | |
| Wang et al. | Biological aerated filter treated textile washing wastewater for reuse after ozonation pre-treatment | |
| CN110540316A (en) | Pretreatment method and application of ammoximation wastewater | |
| CN111908728A (en) | Treatment method of refractory organic silicon wastewater with high salt content | |
| HU205330B (en) | Process for purifying sewage containing organic material, by increased removal of phosphorus and nitrogen | |
| Galil et al. | Biological nutrient removal in membrane biological reactors | |
| CN111847795A (en) | System and method for recycling and treating PTA reclaimed water | |
| CN106396242A (en) | Difficultly-degradable wastewater treatment method | |
| Li et al. | Navigating the complexity of pharmaceutical wastewater treatment by “effective strategy, emerging technology, and sustainable solution” | |
| CN114426368A (en) | Treatment method and application of ammoximation wastewater | |
| CN110776193A (en) | Nylon 6 wastewater treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220503 |
|
| RJ01 | Rejection of invention patent application after publication |