CN116969630A - Treatment method of high ammonia nitrogen wastewater - Google Patents
Treatment method of high ammonia nitrogen wastewater Download PDFInfo
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- CN116969630A CN116969630A CN202310929310.0A CN202310929310A CN116969630A CN 116969630 A CN116969630 A CN 116969630A CN 202310929310 A CN202310929310 A CN 202310929310A CN 116969630 A CN116969630 A CN 116969630A
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- acid
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 238000010405 reoxidation reaction Methods 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000011949 solid catalyst Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 239000002910 solid waste Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 238000001256 steam distillation Methods 0.000 abstract description 3
- 238000010979 pH adjustment Methods 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000855 fermentation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic primary amine Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical compound FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 description 1
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 208000036448 RPGR-related retinopathy Diseases 0.000 description 1
- 201000000467 X-linked cone-rod dystrophy 1 Diseases 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- 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)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a treatment method of high ammonia nitrogen wastewater, and belongs to the field of wastewater treatment. The diazotization wastewater is subjected to acidification layering, steam distillation, catalytic oxidation, pH adjustment, micro-electrolysis, reoxidation, pH readjustment, condensation, precipitation, filtration, triple effect evaporation, anaerobic fermentation and aerobic oxidation, so that the purpose of thoroughly removing ammonia nitrogen can be achieved, and the ammonia nitrogen and total nitrogen data reach qualified indexes. The invention does not need to add special equipment in the original physical and chemical sewage treatment system, has simple separation process, and can treat the high ammonia nitrogen wastewater generated after the qualified diazotization reaction which cannot be treated originally until reaching the standard and being discharged.
Description
Technical Field
The invention relates to a method for treating high ammonia nitrogen wastewater, belonging to the field of wastewater treatment in fine chemical industry.
Background
Diazotisation refers to the reaction of a primary amine with nitrous acid at low temperature to form diazonium salts. The reaction of generating diazonium salt by the action of aromatic primary amine and nitrous acid belongs to diazotization reaction, wherein the aromatic primary amine is often called as diazotization component, and nitrous acid is a diazotizing agent, because nitrous acid is unstable, sodium nitrite and hydrochloric acid or sulfuric acid are usually used for enabling nitrous acid generated during the reaction to react with aromatic primary amine immediately, so that the decomposition of nitrous acid is avoided, and diazonium salt is generated after the diazotization reaction; aliphatic, aromatic and heterocyclic primary amines can be diazotized.
In actual diazotization production, high ammonia nitrogen wastewater generated in the production process is very difficult to treat, the high ammonia nitrogen wastewater can not meet the emission standard by adopting common treatment, water pollution can be caused by forced emission, the environment is extremely influenced, the ecological balance is influenced, and the high ammonia nitrogen wastewater has great harm to human health.
In view of the general high ammonia nitrogen wastewater treatment modes, such as: the distillation filtration desalting method can not effectively remove azo compounds and ammonia nitrogen because the azo compounds and the ammonia nitrogen are easy to distill out; although the incineration method can oxidize azo compounds and ammonia, the waste gas contains nitrogen oxides, and the waste gas needs to be neutralized and absorbed by alkali, and nitrogen-containing waste water is also produced, and the equipment cost and the treatment cost are high, so that the incineration method is not preferable.
The invention relates to wastewater generated by a diazotization reaction process, which is used for analyzing data: pH=8, COD 4 ten thousand mg/L, ammonia nitrogen 1.5 ten thousand mg/L, fluoride ion 50mg/L, total nitrogen 3 ten thousand mg/L, and salt 10%. The traditional pretreatment process comprises the following steps: the water data are distilled out by pH adjustment, micro-electrolysis, oxidation, pH readjustment, condensation, precipitation, filtration and three-effect evaporation system: pH=7, COD 3 ten thousand mg/L, ammonia nitrogen 1 ten thousand mg/L, fluoride ion 40mg/L, total nitrogen 2.5 ten thousand mg/L. The treated wastewater can not reach the acceptable range of the biochemical system, so the treatment can not be continued.
Disclosure of Invention
Aiming at the technical problems, the invention provides a treatment process of a treatment method of high ammonia nitrogen wastewater. The method mainly adopts the processes of acidification layering, steam distillation, catalytic oxidation and other pretreatment, and the analysis data of the wastewater generated before the biochemical system treatment are as follows: ph=5.6, cod=1236 mg/L, ammonia nitrogen 4mg/L, fluoride ion 16mg/L, total nitrogen 16.2mg/L. Then biochemical treatment is carried out, and the analysis result is obtained after anaerobic, aerobic and secondary precipitation water outlet: ph=7, cod=100 mg/L, ammonia nitrogen 2mg/L, fluoride 4mg/L, salt 0.1%, total nitrogen 15mg/L. Other indexes reach the sewage discharge standard, and legal discharge can be carried out.
The invention relates to a treatment method of high ammonia nitrogen wastewater, which comprises the following steps:
a: adding inorganic acid into diazotization wastewater for layering to obtain an upper acidified water layer and a lower oil layer;
b: distilling the acidified waste water layer at 90-110 deg.c to eliminate residual oil layer;
c: cooling, adding a solid catalyst, carrying out oxidation reaction with hydrogen peroxide, and cooling to normal temperature to obtain catalytic oxidation wastewater;
d: the wastewater after catalytic oxidation is subjected to a pretreatment process to obtain filtrate;
e: the filtrate enters a three-effect evaporation system, and kettle liquid is obtained after fractional evaporation and water removal;
f: and carrying out biochemical treatment on the distilled water to obtain qualified wastewater.
Further, in the step a of the above technical scheme, the diazotizing wastewater is: the pH=6-9 of the wastewater, COD1-4 ten thousand mg/L, ammonia nitrogen 0.5-2 ten thousand mg/L, fluoride ion 5-50mg/L, total nitrogen 1-3 ten thousand mg/L and salt content 5-15%.
Further, in the step a of the above technical scheme, the inorganic acid is an inorganic strong acid other than nitric acid and phosphoric acid, including one or more of sulfuric acid, hydrochloric acid, perchloric acid, hydrobromic acid or hydroiodic acid. Sulfuric acid and hydrochloric acid are preferred. The lower oil layer can be recycled.
Further, in the step A of the technical scheme, the mass ratio of the inorganic acid to the diazonium wastewater is 1-5:100; preferably 1-3:100. the mass ratio of the oil layer to the wastewater is 1-3:100; preferably 1-2:100.
further, in the above-mentioned step B, the temperature is preferably 90 to 105℃and the heating means is preferably indirect steam heating (jacket) steam distillation to reduce the amount of water.
Further, in the step C of the above technical scheme, the solid catalyst is made by attaching a transition metal oxide to a silica carrier; the mass ratio of the usage amount to the wastewater is 0.01-0.5:100; preferably 0.01-0.3:100.
further, in the step C of the technical scheme, the mass ratio of the hydrogen peroxide to the wastewater is 0.5-3:100; preferably 0.5-2:100. the oxidation reaction temperature is 30-80 ℃, preferably 30-60 ℃, and finally the temperature is reduced to 10-30 ℃.
Further, in the step D of the above technical solution, the pretreatment process is: through the steps of pH value adjustment, micro-electrolysis, hydrogen peroxide reoxidation, pH readjustment, condensation, precipitation, filtration and the like.
Further, in the step D of the above technical scheme, the pH is adjusted to: neutralizing the excessive acid by using an inorganic base, wherein the inorganic base comprises one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide or barium hydroxide; preferably sodium hydroxide or calcium hydroxide.
Further, in the step D of the technical scheme, the mass ratio of the inorganic base to the wastewater is 0.5-5:100; when the hydrogen peroxide is reoxidized, the mass ratio of the hydrogen peroxide to the wastewater is 0.5-3:100; preferably 0.5-2:100.
in the step E, the kettle liquid is cooled and filtered to obtain solid waste containing salt, and the obtained filtered mother liquid is recycled.
Further, in the step F of the above technical scheme, the biochemical treatment is: anaerobic, aerobic and secondary sedimentation water.
Further, in the step F of the above technical scheme, the qualified wastewater detection data is: pH=6.5-7.5, COD <152mg/L, ammonia nitrogen <1.2mg/L, fluoride ion <1.87mg/L, total nitrogen <22mg/L, and salt content <0.21%.
Advantageous effects of the invention
1. The method has the advantages of easily available raw materials, small operation difficulty and low cost in actual production, particularly in the diazotization process with a large amount of wastewater. The main reaction process is expressed as:
C n H n+1 N m +H 2 O 2 +H + →CO 2 +H 2 O+N 2
2. the raw materials required in the treatment process of the invention are conventional raw materials required in the wastewater treatment process except the catalyst, the types of other raw materials are not increased, the reaction operation conditions are mild, the requirements on reaction equipment are not high, the treatment can be performed by using enamel equipment, special treatment equipment is not increased, and the treatment process is easy to realize.
Detailed Description
The invention will be further described with reference to specific embodiments, and features and advantages of the invention will be apparent from the description. The examples are merely exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the present invention may be made without departing from the scope of the invention, but these changes and substitutions fall within the scope of the invention. In the following examples, unless otherwise specified, all experimental methods used are conventional and all materials, reagents and the like are commercially available from biological or chemical companies.
The preparation method of the self-made transition metal catalyst comprises the following steps: adding 200-mesh column chromatography silica gel with the mass 0.8 times of that of the 8% manganese chloride aqueous solution into the 8% manganese chloride aqueous solution under stirring, and dropwise adding the solution 1:3 mass percent of 5 percent nitric acid, stirring for 2 hours, heating to 150 ℃, and evaporating to dryness. And then washing 3 times with purified water with the mass 2 times of that of the solid each time, and drying at 110 ℃ for 12 hours until the weight is constant, thus obtaining the manganese dioxide/silicon dioxide catalyst.
The preparation process is shown in the following reaction equation:
MnCl 2 +2HNO 3 →Mn(NO 3 ) 2 +2HCl
although the direct use of the commercial manganese dioxide powder has an accelerating effect on the decomposition of hydrogen peroxide, the decomposition speed of hydrogen peroxide is too high, and the hydrogen peroxide is decomposed into oxygen after not participating in the oxidation reaction, so that the effect is not achieved. The self-made catalyst is to enable a small amount of manganese dioxide to be attached to the silicon dioxide, so that the catalysis effect of the manganese dioxide is slowed down, the advantage of large surface area of the silicon dioxide is fully exerted, and the hydrogen peroxide can fully exert the effect.
Adding 910kg of 30% hydrochloric acid and 350kg of o-fluoroaniline into a 3000L reaction kettle to form salt for 2 hours at 50-60 ℃, slowly dripping 900kg of 30% sodium nitrite solution at 0-10 ℃ for 10 hours, and then adding 450kg of copper bromide solid in batches at 9 at 25-35 ℃ to complete the reaction. 550kg of separated oil layer is distilled to obtain o-fluorobromobenzene, the obtained water layer is neutralized to pH=6-8 by 1.12t15% sodium hydroxide, and 431kg of solid copper hydroxide and copper oxide (recovered copper) are removed by plate frame filtration. The amount of the waste water was 2.7t. Namely the high ammonia nitrogen salt-containing wastewater to be treated. Detection result: pH=8, COD 4 ten thousand mg/L, ammonia nitrogen 1.5 ten thousand mg/L, fluoride ion 50mg/L, total nitrogen 3 ten thousand mg/L, and salt 10%.
Example 1
539g of wastewater was added to the autoclave at room temperature, and 7g of concentrated sulfuric acid was added slowly in portions with stirring to adjust ph=1.9. Standing for 30min, separating 12.5g oil layer, distilling water layer at 90-105deg.C, separating oil layer 0.4g, returning water phase to the treatment kettle, cooling to 60deg.C, adding 0.5g self-made solid catalyst under stirring, slowly dropwise adding 3g hydrogen peroxide, keeping the temperature for 0.5 hr, and cooling to 25deg.C. Neutralization with 15g of 30% sodium hydroxide solution, ph=3.
Adding iron and carbon at normal temperature for micro-electrolysis, then dropwise adding 3g of hydrogen peroxide for oxidation, adding 2.5g of calcium hydroxide for regulating pH=7, adding a trace flocculant for precipitation and filtration, filtering solids, heating and distilling filtrate for evaporating to dryness to obtain 431g of water, 77g of waste salt, carrying out anaerobic and aerobic biological bacteria culture treatment on the water for overnight, and settling to obtain 427g of qualified water sample.
The analytical data were: pH=7.3, COD 92.3mg/L, ammonia nitrogen 1mg/L, fluoride ion 3mg/L, salt content 0.1%, total nitrogen 12mg/L and total phosphorus 0.15mg/L.
Example 2
546g of wastewater was added to the autoclave at room temperature, and 7.5g of concentrated sulfuric acid was added slowly in portions with stirring to adjust ph=1.7. Standing for 30min, separating out 11.8g oil layer, heating the water layer at 90-105deg.C for distillation, separating out 0.6g oil layer, returning the water phase to the treatment kettle, cooling the kettle to 60deg.C, adding 0.5g self-made transition metal catalyst under stirring, slowly dropwise adding 3g hydrogen peroxide, keeping the temperature for 0.5 hr after dropwise addition, and cooling to 25deg.C. 15g of 30% sodium hydroxide solution was used for neutralization to ph=3.
Adding iron and carbon at normal temperature for micro-electrolysis, then dropwise adding 3g of hydrogen peroxide for oxidation, adding 1.9g of magnesium hydroxide for regulating pH=7, adding a trace flocculant for precipitation and filtration, filtering solids, heating and distilling filtrate for evaporating to dryness to obtain 454g of water, and carrying out anaerobic and aerobic biological bacteria culture treatment on the water for overnight to obtain 439g of qualified water sample after sedimentation.
The analytical data were: pH=6.9, COD 79.9mg/L, ammonia nitrogen 2mg/L, fluoride ion 5mg/L, salt 0.1%, total nitrogen 13mg/L, total phosphorus 0.09mg/L.
Example 3
At normal temperature, 5t of wastewater was added to the treatment tank, 75kg of concentrated sulfuric acid was slowly added in portions with stirring, and ph=2.1 was adjusted. Standing for 30min, separating 10kg of oil layer, heating the water layer at 90-105deg.C for distillation, separating 0.49kg of oil layer, returning the water phase to the treatment kettle, cooling to 60deg.C, adding 1.2kg of self-made transition metal catalyst under stirring, slowly dropwise adding 4.5kg of hydrogen peroxide, keeping the temperature for 0.5 hr after dropwise addition, and cooling to 25deg.C. The mixture was neutralized to ph=3.8 with 17.5kg of 30% sodium hydroxide solution.
Adding iron and carbon at normal temperature for micro-electrolysis, then dropwise adding 3.2kg of hydrogen peroxide for oxidation, adding 2.4kg of magnesium hydroxide for regulating pH=7, adding a trace amount of flocculating agent for precipitation and filtration, filtering solids, heating and distilling filtrate for evaporating to dryness to obtain 4.58t of water, performing anaerobic and aerobic biological bacteria culture treatment on the water for overnight with 0.59t of waste salt, and settling to obtain 4.52t of treated water.
The analytical data were: pH=6.8, COD 103.5mg/L, ammonia nitrogen 2.5mg/L, fluoride ion 3.72mg/L, salt content 0.15%, total nitrogen 19mg/L and total phosphorus 0.04mg/L.
Example 4
At normal temperature, 8t of wastewater was added to the treatment tank, 10.4kg of concentrated sulfuric acid was slowly added in portions with stirring, and ph=1.9 was adjusted. Standing for 30min, separating 15.4kg of oil layer, heating the water layer at 90-105deg.C for distillation, separating 1.0kg of oil layer, returning the water phase to the treatment kettle, cooling the kettle to 60deg.C, adding 2kg of self-made transition metal catalyst under stirring, slowly dropwise adding 5.6kg of hydrogen peroxide, keeping the temperature for 0.5 hr after dropwise addition, and cooling to 25deg.C. 25kg of 30% sodium hydroxide solution was used for neutralization to ph=4.41.
Adding iron and carbon at normal temperature for micro-electrolysis, then dropwise adding 4.9kg of hydrogen peroxide for oxidation, adding 3.15kg of magnesium hydroxide for regulating pH=7, adding a trace amount of flocculating agent for precipitation and filtration, filtering solids, heating and distilling filtrate for evaporating to dryness to obtain 7.35t of water, waste salt 0.62t, carrying out anaerobic and aerobic biological bacteria culture treatment on the water overnight, and settling to obtain 7.29t of treated water.
The analytical data were: pH=7.3, COD 119.2mg/L, ammonia nitrogen 1.54mg/L, fluoride ion 3.58mg/L, salt content 0.2%, total nitrogen 22mg/L, total phosphorus 0.12mg/L.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (10)
1. The method for treating the high ammonia nitrogen wastewater is characterized by comprising the following steps of:
a: adding inorganic acid into diazotization wastewater for layering to obtain an upper acidified water layer and a lower oil layer;
b: distilling the acidified waste water layer at 90-110 deg.c to eliminate residual oil layer;
c: cooling, adding a solid catalyst, carrying out oxidation reaction with hydrogen peroxide, and cooling to normal temperature to obtain catalytic oxidation wastewater;
d: the wastewater after catalytic oxidation is subjected to a pretreatment process to obtain filtrate;
e: the filtrate enters a three-effect evaporation system, and kettle liquid is obtained after fractional evaporation and water removal;
f: and carrying out biochemical treatment on the distilled water to obtain qualified wastewater.
2. The method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step A, the diazotization wastewater is: the pH value of the wastewater is=6-9, the COD is 1-4 ten thousand mg/L, the ammonia nitrogen is 5000-2 ten thousand mg/L, the fluoride ion is 5-50mg/L, the total nitrogen is 1-3 ten thousand mg/L, and the salt content is 5-15%.
3. The method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step A, the inorganic acid is inorganic strong acid except nitric acid and phosphoric acid, and comprises one or more of sulfuric acid, hydrochloric acid, perchloric acid, hydrobromic acid or hydroiodic acid; the mass ratio of the inorganic acid to the diazonium wastewater is 1-5:100; the mass ratio of the oil layer to the wastewater is 1-3:100.
4. the method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step C, the solid catalyst is prepared by attaching transition metal oxide on a silica carrier; the mass ratio of the usage amount to the wastewater is 0.01-0.5:100.
5. the method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step C, the mass ratio of the hydrogen peroxide to the wastewater is 0.5-3:100.
6. the method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step D, the pretreatment process is as follows: the method comprises the steps of pH value adjustment, micro-electrolysis, hydrogen peroxide reoxidation, pH readjustment, condensation, precipitation and filtration.
7. The method for treating high ammonia nitrogen wastewater according to claim 6, wherein: in step D, the pH is adjusted to neutralize excess acid with an inorganic base including one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, or barium hydroxide.
8. The method for treating high ammonia nitrogen wastewater according to claim 6, wherein: in the step D, the mass ratio of the inorganic alkali to the wastewater is 0.5-5:100; when the hydrogen peroxide is reoxidized, the mass ratio of the hydrogen peroxide to the wastewater is 0.5-3:100.
9. the method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step E, the kettle liquid is cooled and filtered to obtain salt-containing solid waste, and the obtained filtered mother liquid is recycled.
10. The method for treating high ammonia nitrogen wastewater according to claim 1, wherein: in the step F, the biochemical treatment is as follows: anaerobic, aerobic and secondary sedimentation water.
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