CN111115933A - Flameless torch type ultra-clean discharge process for high-ammonia nitrogen wastewater containing VOCs - Google Patents
Flameless torch type ultra-clean discharge process for high-ammonia nitrogen wastewater containing VOCs Download PDFInfo
- Publication number
- CN111115933A CN111115933A CN201911232261.5A CN201911232261A CN111115933A CN 111115933 A CN111115933 A CN 111115933A CN 201911232261 A CN201911232261 A CN 201911232261A CN 111115933 A CN111115933 A CN 111115933A
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- Prior art keywords
- wastewater
- tower
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- ammonia nitrogen
- Prior art date
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- 239000002351 wastewater Substances 0.000 title claims abstract description 128
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 45
- 238000010521 absorption reaction Methods 0.000 claims abstract description 41
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 39
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 14
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims abstract description 3
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- 239000000701 coagulant Substances 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 8
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- 239000003344 environmental pollutant Substances 0.000 claims description 7
- -1 flocculant Substances 0.000 claims description 7
- 231100000719 pollutant Toxicity 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 208000028659 discharge Diseases 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- 239000012071 phase Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
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- 150000008282 halocarbons Chemical class 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- 239000002250 absorbent Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
-
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- 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
-
- 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
- C02F1/043—Details
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- 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
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
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- 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
- C02F1/5281—Installations for water purification using chemical agents
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- 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
- C02F2001/007—Processes including a sedimentation step
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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- 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
- C02F2103/06—Contaminated groundwater or leachate
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- 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
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- 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
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
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- 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
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- 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
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- 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
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- 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
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1205—Particular type of activated sludge processes
- C02F3/1215—Combinations of activated sludge treatment with precipitation, flocculation, coagulation and separation of phosphates
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- 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
- C02F3/28—Anaerobic digestion processes
- C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a flameless torch type ultra-clean discharge process for high-ammonia nitrogen wastewater containing VOCs; the wastewater is pretreated by the pretreatment unit and then enters a stripping tower to recover ammonia nitrogen, and simultaneously VOCs in the wastewater are separated, and the ammonia nitrogen is recovered in an ammonia water tank in the form of ammonia water under the action of a condenser; VOCs in gas phase are heated by a second preheater and then enter an oxidation tower, and are subjected to decomposition and oxidation reaction under the action of a catalyst to generate exhaust gas products containing carbon dioxide, sulfur dioxide, water and the like; heating the high-temperature exhaust gas product in a second preheater to enter VOCs in the tower, after heat exchange, spraying and washing the VOCs in an absorption tower by ammonia water in an ammonia water tank, discharging the tail gas in an ultra-clean manner, and spraying and washing the washing liquid into a crystallizer to evaporate and crystallize to obtain ammonium salt; waste liquid discharged from the bottom of the stripping tower is preheated by the first preheater and then passes through the post-treatment unit, so that ultra-clean discharge of the waste water is realized.
Description
Technical Field
The invention belongs to the technical field of ultra-clean discharge of waste water and waste gas and environment protection, and particularly relates to a flameless torch type ultra-clean discharge process for high ammonia nitrogen waste water containing VOCs.
Background
Volatile Organic Compounds (VOCs) are substances with complex composition and wide distribution, and have great harm to the environment. With the coming of policy of "action plan for preventing and treating air pollution", the control of VOCs is also enhanced unprecedentedly. Especially, the VOCs dissipated by waste water, waste liquid and waste residue need to be treated and then be discharged in an ultra-clean way. For example, VOCs released in the processes of petrochemical wastewater collection, transportation, storage and treatment are one of the main sources of VOCs discharged by petrochemical enterprises, enter the atmosphere in an unorganized discharge form through the contact surface between wastewater and air, and are also commonly used in sewage treatment plants, pharmaceutical factories, organic synthesis industries and the like. The high ammonia nitrogen wastewater mainly comes from coking, petrochemical, pharmaceutical and garbage treatment industries and the like, and has the harm of causing water eutrophication, causing water black and odorous and even generating toxic action on people and organisms. The ammonia nitrogen content discharged from water body is used as one of key indexes for limiting requirements in the policy of water pollution prevention and control action plan.
VOCs generally refer to a large class of organic compounds having a boiling point range of 50-260 ℃, a saturated vapor pressure of more than 133.32Pa at room temperature, and existing in the air as vapor at room temperature. The main components of the catalyst are hydrocarbons, halogenated hydrocarbons, chlorocarbons, sulfur hydrocarbons, oxygen-containing hydrocarbons, low-boiling polycyclic aromatic hydrocarbons and the like. It has fire and explosion risks, is toxic and carcinogenic to human bodies, and can cause ecological environment damages such as ozone layer cavities, greenhouse effect, photochemical smog and the like. The common recovery techniques mainly include condensation, adsorption, absorption and membrane separation. The condensation method is suitable for recovering VOCs with high concentration and high boiling point; the adsorption method is suitable for recovering medium-low concentration and high-flux VOCs; the absorption method is suitable for recovering large-gas-quantity and medium-concentration VOCs; the membrane separation method has the advantages of simple process, low energy consumption, high recovery rate and the like. For VOCs with complex components and difficult recycling, the combustion method is adopted at present, and the treatment efficiency is high and thorough. Wherein, the direct flame combustion is carried out, the temperature is about 1100 ℃, and the direct flame combustion method is only suitable for the condition that VOCs contain higher heat value. If the catalyst is utilized to reduce the temperature in the combustion process, the retention time is reduced, and the requirement on the heat value of VOCs is also reduced, the catalyst can be regarded as a flameless torch combustion process in a broad sense, and finally the products of catalytic oxidation combustion are inorganic substances such as carbon dioxide, sulfur dioxide, water and the like.
Common treatment methods for ammonia nitrogen wastewater include a biological method, a breakpoint chlorination method, an ion exchange method, a stripping method and the like. Wherein the biological method, the breakpoint chlorination method and the ion exchange method are suitable for treating wastewater with medium and low ammonia nitrogen concentration. The ammonia nitrogen concentration of the wastewater is higher (more than 5000mg/L), the wastewater pretreatment is carried out by a stripping method, the removal effect is better, and the treatment cost is relatively more economic. The main process flow is as follows: firstly, the pH value of the wastewater is adjusted, and ammonia nitrogen ions in the wastewater are converted into free ammonia according to the ion balance.
NH4 ++OH-→NH3+H2O
When the pH value of the wastewater is about 7, the ammonia nitrogen is mostly NH4 +The form exists. The free ammonia fraction gradually increases as the pH increases above 11. The ammonia is extracted by the introduced air or steam, and various byproducts are produced by absorbing water, sulfuric acid or hydrochloric acid, so that the effective recycling of the ammonia nitrogen is realized. The total ammonia nitrogen removal rate can reach 70-95%, and the ammonia nitrogen concentration of the treated wastewater can be less than 10 mg/L.
High ammonia nitrogen wastewater containing VOCs is common in petrochemical and garbage treatment industries, and the environmental hazard brought by unorganized discharge of VOCs in the process is generally not considered for the treatment of the wastewater at present. In regions with strict environmental policies, the common treatment idea is to independently remove VOCs and ammonia nitrogen pollutants and then realize ultra-clean discharge. The process has high energy consumption, insufficient resource utilization efficiency of ammonia nitrogen and VOCs, and high total wastewater treatment cost. With the stricter national control on the environmental emission of VOCs, a more efficient, energy-saving, recycling and low-cost treatment process for the wastewater is urgently needed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a flameless torch type ultra-clean discharge process for high ammonia nitrogen wastewater containing VOCs; the high ammonia nitrogen wastewater containing VOCs generated in the industries of petrochemical industry, garbage disposal and the like is treated by the high ammonia nitrogen wastewater containing VOCs flameless torch type ultra-clean discharge system, so that ultra-clean discharge is realized.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a flameless torch type ultra-clean discharge system for VOCs-containing high ammonia nitrogen wastewater mainly comprises a pretreatment unit 1, a stripping unit, a flameless torch unit, an evaporative crystallization unit and a post-treatment unit 10; the pretreatment unit 1, the stripping unit, the flameless torch unit and the evaporative crystallization unit are sequentially connected, and the post-treatment unit 10 is connected with the stripping unit through a pipeline;
the pretreatment unit 1 is used for pretreating high ammonia nitrogen wastewater containing VOCs to reduce heavy metal ions, suspended matters, chroma, hardness and COD in the wastewater;
the stripping unit is used for recovering ammonia nitrogen and separating VOCs;
the flameless torch unit is used for ultra-clean decomposition and oxidation of VOCs;
the evaporation crystallization unit is used for washing and absorbing the ammonia water and the purified gas recovered by the stripping unit, and concentrating to obtain crystalline salt;
the post-treatment unit 10 is used for post-treating the wastewater separated by the stripping unit to realize ultra-clean discharge of the wastewater.
As a further preferred option of the application, the stripping unit is provided with a stripping tower 3, the front end of the stripping tower 3 is connected with a first preheater 2, a cold process inlet of the first preheater 2 is connected with a pretreatment unit pipeline, and a cold process outlet is connected with a feed inlet of the stripping tower 3; the hot process inlet is connected with a wastewater outlet of the stripping tower 3; the hot process outlet is connected with a pipeline of the post-processing unit 10; the bottom of the stripping tower 3 is also provided with a steam inlet; the pipeline at the top of the stripping tower 3 is connected with the shell side of a condenser 4; an outlet at one side of the bottom of the shell pass of the condenser 4 is connected with a return pipeline of the stripping tower 3, an outlet at the other side of the shell pass is connected with an ammonia water tank, and a pipeline at the upper end of the shell pass is connected with a flameless torch unit; the pipe pass of the condenser 4 is connected with circulating water; the flameless torch unit is provided with a second preheater 6 and an oxidation tower 7, a cold path inlet pipeline of the second preheater 6 is connected with the condenser 4, a cold path outlet is connected with a feed inlet of the oxidation tower 7, a purified gas outlet of the oxidation tower 7 is connected with a hot path inlet of the second preheater 6, and a hot path outlet of the second preheater 6 is connected with a purified gas inlet of the evaporative crystallization unit;
the evaporation crystallization unit is provided with an absorption tower 8 and a crystallizer 9, the side surface of the bottom of the absorption tower 8 is provided with a purified gas inlet, the top of the absorption tower 8 is provided with a purified gas outlet, and the side surface of the top of the absorption tower 8 is connected with an ammonia water tank pipeline; an air inlet is arranged on the bottom side surface of the absorption tower 8; the bottom of the absorption tower 8 is connected with a crystallizer 9 through a pipeline.
As a further preferred option of the present application, the pretreatment unit 1 mainly comprises a regulating reservoir, a dosing reservoir and a clarification tank, wherein the regulating reservoir, the dosing reservoir and the clarification tank are connected in sequence; the adjusting tank is used for homogenizing and equalizing the inflow water and adjusting the impact and fluctuation load of the fed wastewater; the chemical medicines such as coagulant, flocculant, acid and alkali are added into the wastewater in the dosing tank, wherein the acid and alkali are used for reaction precipitation of hardness ions such as calcium and magnesium and heavy metal ions in the wastewater and system pH adjustment, and the coagulant and the flocculant are used for coagulation precipitation of suspended substances SS in the wastewater; and the clarification tank is used for removing suspended substances SS in the wastewater after the dosing reaction, and dewatering equipment is used in combination to obtain mud cakes.
As a further preference of the application, a pipeline is connected with a filter behind the clarification tank, and preferably, the filter is a multi-media filter; the multi-media filter combined clarification tank is used for removing suspended substances SS in wastewater. Under the condition that the feed wastewater contains high chroma and COD at the same time, the chroma and the COD content can be removed after the pretreatment unit treatment, and the subsequent wastewater pollutant removal load is reduced.
As a further optimization of the application, the feed inlet of the stripping tower 3 is provided with a waste water distributor, and the steam inlet of the stripping tower 3 is provided with a steam distributor.
As a further preference of the present application, a catalyst bed layer is arranged in the oxidation tower.
As a further preferred embodiment of the present application, a single-layer or multi-layer spraying system is arranged at the upper part of the absorption tower 8, and a demister is arranged at the top; preferably, the absorption tower 8 is further provided with an internal circulation system.
As a further preference herein, the post-treatment unit 10 is a biochemical treatment tank and/or an advanced oxidation system.
As the further preferred of this application, still be provided with the unorganized VOCs collecting system that discharges behind the biochemical treatment pond, the unorganized VOCs collecting system that discharges is equipped with the draught fan, the draught fan passes through 6 cold stroke imports of pipeline access second preheater.
A flameless torch type ultra-clean discharge process for high ammonia nitrogen wastewater containing VOCs comprises the following steps: the wastewater is pretreated by a pretreatment unit 1 and then enters a stripping tower 3 to recover ammonia nitrogen, and simultaneously VOCs in the wastewater are separated, and the ammonia nitrogen is recovered in an ammonia water tank 5 in an ammonia water form under the action of a condenser 4; VOCs in gas phase are heated by a second preheater 6 and then enter a flameless torch 7 to be decomposed and oxidized under the action of a catalyst to generate exhaust gas products containing carbon dioxide, sulfur dioxide, water and the like; heating the high-temperature exhaust gas product in a second preheater 6 to enter VOCs in the tower, after heat exchange, spraying and washing the product in an absorption tower 8 by ammonia water in an ammonia water tank, discharging the tail gas in an ultra-clean manner, and spraying and washing the product in a crystallizer 9 to evaporate and crystallize to obtain ammonium salt; waste liquid discharged from the bottom of the stripping tower 3 is preheated by the first preheater 2 and then passes through the post-treatment unit 10, so that ultra-clean discharge of the waste water is realized.
The invention provides a flameless torch type ultra-clean discharge process for high-ammonia-nitrogen wastewater containing VOCs, which aims at the high-ammonia-nitrogen wastewater containing VOCs generated in the industries of petrifaction, garbage treatment and the like, wherein the types of the VOCs comprise one or more components such as hydrocarbons, halogenated hydrocarbons, chlorocarbons, sulfur hydrocarbons, oxygenated hydrocarbons, low-boiling polycyclic aromatic hydrocarbons and the like, the mass fraction of the VOCs is 1-10%, and the ammonia nitrogen content is higher than 5000 mg/L. According to the specific water quality condition, or contains a certain amount of suspended solids SS, heavy metal ions, hardness ions such as calcium and magnesium and the like.
The wastewater firstly enters a pretreatment unit, and the specific treatment process is flexibly selected according to the quality of the inlet water. Comprises one or more devices such as a regulating tank, a dosing tank, a high-density clarification tank, a multi-medium filter and the like.
The adjusting tank is used for homogenizing and equalizing the inflow water and adjusting the impact and fluctuation load of the fed wastewater. The chemical medicines such as coagulant, flocculant, acid and alkali are added into the wastewater in the dosing tank, wherein the acid and alkali are used for reaction precipitation of hardness ions such as calcium and magnesium and heavy metal ions in the wastewater and system pH adjustment, and the coagulant and the flocculant are used for coagulation precipitation of suspended substances SS in the wastewater. And the high-density clarification tank is used for removing suspended substances SS in the wastewater after the dosing reaction, and dewatering equipment is used in combination to obtain mud cakes. The multi-medium filter is combined with a high-density clarification tank and is used for removing suspended substances SS in the wastewater. Under the condition that the feed wastewater contains high chroma and COD at the same time, after the feed wastewater is treated by the pretreatment unit, part of chroma and COD content can be removed, and the subsequent wastewater pollutant removal load is reduced.
And (3) adjusting the pH value of the wastewater after the pretreatment unit to be more than 11, heating the wastewater to 70-80 ℃ by a preheater, and entering a stripping tower to realize the separation process of ammonia distillation and VOCs. Low-pressure steam is supplied from outside as a heat source and enters the tower from a steam inlet distributor at the bottom of the stripping tower. The feeding wastewater enters the tower through a wastewater distributor at a feed inlet at the upper part of the stripping tower. The form in the tower can be plate type or packing type, and the waste water is uniformly distributed from top to bottom and effectively transfers heat and mass with the steam from the bottom of the tower. After multiple gas-liquid phase equilibrium, the ammonia concentration in the wastewater is reduced, and the ammonia concentration in the gas phase is increased. Due to the volatility of the VOCs, the wastewater is heated such that the VOCs are transferred from the aqueous phase to the gas phase. And (3) sending the mixed gas phase substance to a condenser through a tower top pipeline, condensing ammonia and water vapor into ammonia water by circulating water, refluxing part of the ammonia water into the tower from the tower top, and conveying the rest ammonia water (with the concentration of 15-20%) into an ammonia water tank for storage. Along with the continuous progress of the stripping reaction, the ammonia concentration in the waste water at the bottom of the tower is lower and can be reduced to be within 5 mg/L. And controlling the operating temperature of the condenser to be 40-70 ℃ to enable the VOCs to be in a gas phase state, and introducing the gas phase state to a flameless torch oxidation tower for treatment through a pipeline at the upper end of the shell pass of the condenser. The temperature of the wastewater at the bottom of the stripping tower is 100-110 ℃, and the wastewater is used as a heat source, heated by a first preheater and then enters a post-treatment unit.
The method comprises the following steps of heating the stripped gas-phase VOCs to 200-250 ℃ through a second preheater before the gas-phase VOCs enter a flameless torch oxidation tower, wherein a catalyst bed layer is arranged in the oxidation tower, the catalyst mainly comprises alumina, silicon oxide, a molecular sieve and the like as carriers, transition metal oxides of manganese, chromium, cobalt, nickel and the like as active components, the loading capacity of the catalyst is 5-15%, and the particle size of the catalyst is 3-5 mm. The reaction temperature in the tower is about 600 ℃, the pressure is 0.1-0.5 MPa, the preheated gas-phase VOCs undergo adiabatic catalytic combustion reaction in an oxygen-containing atmosphere, and the gas-phase VOCs undergo decomposition and oxidation processes to generate stable inorganic substances such as carbon dioxide, sulfur dioxide, water and the like. The temperature of the exhaust gas product is 300-500 ℃, and the exhaust gas product is heated by a preheater and enters a tower gas-phase VOCs, and then is introduced into an absorption tower through a pipeline for treatment.
In the absorption tower, the discharged gas product generated by combustion of the VOCs flameless torch enters from the side surface of the lower part of the tower body, and ammonia water serving as an absorbent is pumped from an ammonia water tank to the side surface of the upper part of the absorption tower through a pipeline to enter. The upper part of the tower is provided with a single-layer or multi-layer spraying system, and the ammonia water is uniformly sprayed from top to bottom through a spraying head and performs gas-liquid mass and heat transfer reaction with the exhaust gas from the bottom of the tower. The absorption tower is internally provided with a spraying internal circulation, so that the reaction sufficiency in the absorption process is increased. And (4) the sprayed and absorbed exhaust gas is subjected to moisture removal and ammonia escape through a top demister, and then is subjected to ultra-clean emission. And introducing air into the tower bottom to oxidize the washing liquid subjected to the absorption reaction into high-valence ammonium salt concentrated liquid. By means of the higher temperature of the discharged gas entering the tower, the washing liquid at the bottom of the tower can be heated, evaporated and concentrated, and the processing load of a rear-end crystallizer is reduced. And (3) enabling the concentrated ammonium salt solution at the tower bottom to enter a crystallizer through a pipeline, and obtaining one or more mixed ammonium salts containing ammonium carbonate, ammonium sulfate, ammonium chloride and the like after evaporation crystallization, centrifugal separation, drying and packaging, wherein the mixed ammonium salts can be used as excellent fertilizers to realize resource utilization. The crystallizer can adopt a forced external circulation mode, a DTB (draw texturing and drying) or an Olso mode, and the spraying amount of the ammonia water is determined according to the composition and the content of VOCs (volatile organic compounds) in the feed wastewater.
The post-treatment unit is used for the condition that the wastewater at the bottom of the stripping tower does not meet the ultra-clean discharge, and a biochemical and advanced oxidation treatment unit is usually adopted to further remove the residual pollutants such as ammonia nitrogen and COD in the wastewater until the wastewater is ultra-clean and discharged. In the treatment of the post-treatment unit, a small amount of VOCs discharged in an unorganized way can be generated, such as VOCs emitted by an aerobic pool and an anaerobic pool in a biochemical treatment process, and the like, equipment is adopted at each generation point for covering and sealing, an induced draft fan system is added, and the VOCs are collected and then are uniformly conveyed to an oxidation tower through a pipeline for flameless torch clean discharge treatment. Finally realizing the ultra-clean discharge of waste water and waste gas.
Drawings
FIG. 1 is a flow chart of an ultra-clean discharge treatment method for the flameless torch treatment of high ammonia nitrogen wastewater containing VOCs according to the invention;
FIG. 2 is a flow chart of a pretreatment unit of a flameless torch treatment ultra-clean discharge treatment system for high ammonia nitrogen wastewater containing VOCs according to the invention;
FIG. 3 is a schematic structural diagram of a high-density clarification tank of a flameless torch treatment ultra-clean discharge treatment system for high-ammonia nitrogen wastewater containing VOCs in the invention;
in the figure, 1-pretreatment unit; 11-a regulating reservoir; 12-a medicine adding pool; 13-high density clarification tank; 131-a coagulation tank; 132-a flocculation tank; 133-a precipitation tank; 134-sloping plate; 135-a dewatering device; 14-a multi-media filter; 2-a first preheater; 3-a stripping tower; 4-a condenser; 5-ammonia water tank; 6-a second preheater; 7-an oxidation tower; 8-an absorption tower; 9-a crystallizer; 10-post-processing unit.
Detailed Description
In order that the present invention may be more clearly understood, the following detailed description is given in conjunction with the examples. The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example 1:
fig. 1 shows an embodiment of the present invention, wherein fig. 1 is a schematic structural diagram of the present invention. Referring to fig. 1, a flameless torch type ultra-clean discharge system for high ammonia nitrogen wastewater containing VOCs mainly comprises a pretreatment unit 1, a stripping unit, a flameless torch unit, an evaporative crystallization unit and a post-treatment unit 10; the pretreatment unit 1, the stripping unit, the flameless torch unit and the evaporative crystallization unit are sequentially connected, and the post-treatment unit 10 is connected with the stripping unit through a pipeline; the pretreatment unit 1 is used for pretreating high ammonia nitrogen wastewater containing VOCs to reduce heavy metal ions, suspended matters, chroma, hardness and COD in the wastewater; the stripping unit is used for recovering ammonia nitrogen and separating VOCs; the flameless torch unit is used for ultra-clean decomposition and oxidation of VOCs; the evaporation crystallization unit is used for washing and absorbing the ammonia water and the purified gas recovered by the stripping unit, and concentrating to obtain crystalline salt; the post-treatment unit 10 is used for post-treating the wastewater separated by the stripping unit to realize ultra-clean discharge of the wastewater.
The pretreatment unit 1 comprises an adjusting tank 11, a dosing tank 12, a high-density clarification tank 13 and a multi-media filter 14, wherein the adjusting tank 11, the dosing tank 12, the high-density clarification tank 13 and the multi-media filter 14 are connected in sequence; the adjusting tank 11 is used for homogenizing and equalizing the inflow water and adjusting the impact and fluctuation load of the fed wastewater; the chemical dosing tank 12 is used for dosing chemical drugs such as coagulant, flocculant, acid and alkali into the wastewater, wherein the acid and alkali are used for reaction precipitation of hardness ions such as calcium and magnesium and heavy metal ions in the wastewater and system pH adjustment, and the coagulant and the flocculant are used for coagulation precipitation of suspended substances SS in the wastewater; the high-density clarification tank 13 is used for removing suspended substances SS in the wastewater after the dosing reaction, and a dewatering device 135 is used in combination to obtain mud cakes; the multi-media filter 14 is combined with the high-density clarification tank 13 and used for removing suspended substances SS in the wastewater. Under the condition that the feed wastewater contains high chroma and COD at the same time, the chroma and the COD content can be removed after the pretreatment unit treatment, and the subsequent wastewater pollutant removal load is reduced.
The stripping unit is provided with a stripping tower 3, the front end of the stripping tower 3 is connected with a first preheater 2, a cold process inlet of the first preheater 2 is connected with a pipeline of the pretreatment unit 1, a cold process outlet is connected with a feed inlet of the stripping tower 3, and the feed inlet of the stripping tower 3 is provided with a waste water distributor; the hot process inlet is connected with a wastewater outlet of the stripping tower 3; the hot process outlet is connected with a pipeline of the post-processing unit 10; the bottom of the stripping tower 3 is also provided with a steam inlet, and the steam inlet of the stripping tower 3 is provided with a steam distributor; the pipeline at the top of the stripping tower 3 is connected with the shell side of a condenser 4; an outlet at one side of the bottom of the shell pass of the condenser 4 is connected with a return pipeline of the stripping tower 3, an outlet at the other side of the shell pass is connected with an ammonia water tank, and a pipeline at the upper end of the shell pass is connected with a flameless torch unit; the pipe pass of the condenser 4 is connected with circulating water;
the flameless torch unit is provided with a second preheater 6 and an oxidation tower 7, a cold path inlet pipeline of the second preheater 6 is connected with the condenser 4, a cold path outlet is connected with a feed inlet of the oxidation tower 7, a purified gas outlet of the oxidation tower 7 is connected with a hot path inlet of the second preheater 6, and a hot path outlet of the second preheater 6 is connected with a purified gas inlet of the evaporative crystallization unit; and a catalyst bed layer is arranged in the oxidation tower.
The evaporation crystallization unit is provided with an absorption tower 8 and a crystallizer 9, the side surface of the bottom of the absorption tower 8 is provided with a purified gas inlet, the top of the absorption tower 8 is provided with a purified gas outlet, and the side surface of the top of the absorption tower 8 is connected with an ammonia water tank pipeline; an air inlet is arranged on the bottom side surface of the absorption tower 8; the bottom of the absorption tower 8 is connected with a crystallizer 9 through a pipeline. A single-layer or multi-layer spraying system is arranged at the upper part of the absorption tower 8, and a demister is arranged at the top; preferably, the absorption tower 8 is further provided with an internal circulation system. The post-treatment unit 10 is an Upflow Anaerobic Sludge Blanket (UASB).
Example 2:
the treatment capacity of percolate of a certain refuse incineration plant is 150m3The water quality index of the water quality index organic acid is 10000-20000 mg/L, and the COD iscr20000-40000 mg/L, BOD510000-20000 mg/L of NH3N is 5000-8000 mg/L, suspended substance SS is 3000-8000 mg/L, total hardness is 3000-5000 mg/L, and pH is 6-8. Wherein the concentration of each heavy metal ion is 20-50 mg/L Fe, 3-5 mg/L Zn, 3-5 mg/L Cr and 2-3 mg/L Mn.
The temperature of the fed wastewater is 5-35 ℃, the wastewater firstly enters an adjusting tank 11 in a pretreatment unit 1 for homogenization, and the influence caused by water quality fluctuation is reduced; then enters a medicine adding pool 12, NaOH and Na are added into the medicine adding pool2CO3The solution and medicine adding tank 12 is provided with a stirrerA mixer; the wastewater enters a high-density clarification tank 13 from a dosing tank 12, polymeric ferric chloride and polyacrylamide are respectively added into a coagulation tank 131 and a flocculation tank 132 and are stirred to form larger alum flocs, and the larger alum flocs enter a precipitation tank 133 to realize suspended matter coalescence and sedimentation; part of the sludge at the bottom of the settling tank 133 is condensed and then flows back to the coagulation tank 131, and the rest is discharged by a pump and sent to sludge treatment; the upper layer waste liquid flows out to the multi-medium filter 14 through the inclined plate 134, the filler adopts anthracite, quartz sand, active carbon and the like, the concentration of heavy metal ions in the waste water at the outlet of the multi-medium filter 14 is reduced to be below the discharge standard, namely CODcrAnd BOD5The removal rate reaches 30-60%, the total hardness is less than 100mg/L, the suspended matter SS is less than 10mg/L, and the pH value is 11-12.
The wastewater is heated to about 75 ℃ by the first preheater 2 and then enters the stripping tower 3; the stripping tower adopts a packing form (stainless steel pall ring), wastewater is uniformly distributed from top to bottom through a wastewater distributor at an inlet, and steam (0.2MPa) at the bottom of the stripping tower enters the stripping tower through an inlet steam distributor and is in thermal contact with the wastewater from bottom to top; the gas phase ammonia, VOCs and water vapor extracted by the steam are collected above the stripping tower 3 and enter a condenser 4 through a pipeline; the operation temperature of the condenser 4 is 60 ℃, ammonia is dissolved in water after being condensed to form ammonia water, about 5 percent of ammonia water flows back into the stripping tower 3, the rest ammonia water enters the ammonia water tank 5 for storage, and the temperature of the ammonia water is controlled to be about 25 ℃; gas-phase VOCs at the upper part of the shell pass of the condenser 4 enter a second preheater 6 in front of a flameless torch oxidation tower 7, and after reaction in the oxidation tower 7, the product of the exhaust gas is heated to about 200 ℃ and then enters the oxidation tower 7 for adiabatic catalytic combustion; the active components of the catalyst mainly comprise manganese oxide and cobalt oxide, the manganese oxide and cobalt oxide are loaded on alumina, the loading capacity is about 10%, the particle size is about 5mm, the reaction pressure in the tower is about 0.4MPa, the reaction temperature is about 600 ℃, and products generated in an oxygen-containing atmosphere are stable inorganic substances such as carbon dioxide, sulfur dioxide, water and the like; the product temperature of the outlet discharge gas is about 500 ℃, and the outlet discharge gas enters the absorption tower 8 for leaching after being preheated to enter the tower VOCs.
The upper part of the absorption tower 8 is provided with a multilayer spraying system, ammonia water with the concentration of about 15 percent stored in an ammonia water tank is uniformly sprayed from top to bottom through a spraying head, and is subjected to gas-liquid mass and heat transfer reaction with the exhaust gas product from the bottom of the tower, and the exhaust gas product after being washed is discharged after moisture and ammonia escape through a demister arranged at the top of the tower and reaches the air discharge standard. The leaching solution after the absorption reaction is dropped to the bottom of the tower, and is oxidized into concentrated solution of ammonium salt which takes ammonium carbonate as the main part and contains a small amount of ammonium sulfate and ammonium chloride under the condition of introducing air into the bottom of the tower; the absorption tower 8 is internally provided with a washing liquid internal circulation to ensure that the absorption reaction is full, and meanwhile, the leaching liquid exchanges heat with the high-temperature exhaust gas entering the tower to realize the evaporation concentration process of the ammonium salt concentrated solution; and (3) feeding the concentrated solution of the ammonium salt at the tower bottom into a forced external circulation crystallizer 9, and obtaining mixed ammonium salt mainly containing ammonium carbonate after evaporation crystallization, centrifugal separation, drying and packaging.
The temperature of the wastewater outlet at the bottom of the stripping tower 3 is about 105 ℃, the fed wastewater is heated by the first preheater 2 and then enters the post-treatment unit 10, and sequentially enters an up-flow anaerobic sludge bed (UASB) and an improved activated sludge process (SBR) for treatment, and the residual COD in the wastewatercrAnd BOD5The removal rate reaches more than 90 percent and 92 percent and contains NH3And the content of the-N internal pollutants is reduced to be below the emission standard, so that ultra-clean emission is realized.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The meaning of "and/or" as used herein is intended to include both the individual components or both.
The term "connected" as used herein may mean either a direct connection between components or an indirect connection between components via other components.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.
Claims (10)
1. A flameless torch type ultra-clean discharge system for VOCs-containing high-ammonia nitrogen wastewater is characterized by mainly comprising a pretreatment unit (1), a stripping unit, a flameless torch unit, an evaporative crystallization unit and a post-treatment unit (10); the pretreatment unit (1), the stripping unit, the flameless torch unit and the evaporative crystallization unit are sequentially connected, and the post-treatment unit (10) is connected with the stripping unit through a pipeline;
the pretreatment unit (1) is used for pretreating the high ammonia nitrogen wastewater containing VOCs to reduce heavy metal ions, suspended matters, chroma, hardness and COD in the wastewater;
the stripping unit is used for recovering ammonia nitrogen and separating VOCs;
the flameless torch unit is used for ultra-clean decomposition and oxidation of VOCs;
the evaporation crystallization unit is used for washing and absorbing the ammonia water and the purified gas recovered by the stripping unit, and concentrating to obtain crystalline salt;
the post-treatment unit (10) is used for post-treating the wastewater separated by the stripping unit to realize ultra-clean discharge of the wastewater.
2. The flameless torch type ultra-clean discharge system for high ammonia nitrogen wastewater containing VOCs in claim 1,
the stripping unit is provided with a stripping tower (3), the front end of the stripping tower (3) is connected with a first preheater (2), a cold path inlet of the first preheater (2) is connected with a pretreatment unit pipeline, and a cold path outlet is connected with a feed inlet of the stripping tower (3); the hot process inlet is connected with a wastewater outlet of the stripping tower (3); the hot process outlet is connected with a pipeline of the post-treatment unit (10); the bottom of the stripping tower (3) is also provided with a steam inlet; the pipeline at the top of the stripping tower (3) is connected with the shell side of the condenser (4); an outlet at one side of the bottom of the shell pass of the condenser (4) is connected with a reflux pipeline of the stripping tower (3), an outlet at the other side is connected with an ammonia water tank, and a pipeline at the upper end of the shell pass is connected with a flameless torch unit; the pipe pass of the condenser (4) is connected with circulating water;
the flameless torch unit is provided with a second preheater (6) and an oxidation tower (7), a cold path inlet pipeline of the second preheater (6) is connected with the condenser (4), a cold path outlet is connected with a feed inlet of the oxidation tower (7), a purified gas outlet of the oxidation tower (7) is connected with a hot path inlet of the second preheater (6), and a hot path outlet of the second preheater (6) is connected with a purified gas inlet of the evaporative crystallization unit;
the evaporation crystallization unit is provided with an absorption tower (8) and a crystallizer (9), the side surface of the bottom of the absorption tower (8) is provided with a purified gas inlet, the top of the absorption tower (8) is provided with a purified gas outlet, and the side surface of the top of the absorption tower (8) is connected with an ammonia water tank pipeline; an air inlet is arranged on the bottom side surface of the absorption tower (8); the bottom of the absorption tower (8) is connected with a crystallizer (9) through a pipeline.
3. The flameless torch type ultra-clean discharge system for high-ammonia nitrogen wastewater containing VOCs (volatile organic chemicals) according to claim 1 or 2, characterized in that the pretreatment unit (1) mainly comprises a regulating tank, a dosing tank and a clarification tank, wherein the regulating tank, the dosing tank and the clarification tank are connected in sequence; the adjusting tank is used for homogenizing and equalizing the inflow water and adjusting the impact and fluctuation load of the fed wastewater; the chemical medicines such as coagulant, flocculant, acid and alkali are added into the wastewater in the dosing tank, wherein the acid and alkali are used for reaction precipitation of hardness ions such as calcium and magnesium and heavy metal ions in the wastewater and system pH adjustment, and the coagulant and the flocculant are used for coagulation precipitation of suspended substances SS in the wastewater; and the clarification tank is used for removing suspended substances SS in the wastewater after the dosing reaction, and dewatering equipment is used in combination to obtain mud cakes.
4. The flameless torch type ultra-clean discharge system for high ammonia nitrogen wastewater containing VOCs according to claim 3, characterized in that a pipeline is connected with a filter after the clarification tank, preferably, the filter is a multi-media filter; the multi-media filter combined clarification tank is used for removing suspended substances SS in the wastewater; under the condition that the feed wastewater contains high chroma and COD at the same time, the chroma and the COD content can be removed after the pretreatment unit treatment, and the subsequent wastewater pollutant removal load is reduced.
5. The flameless torch type ultra-clean discharge system for high-ammonia nitrogen wastewater containing VOCs according to claim 2, characterized in that the feed inlet of the stripping tower (3) is provided with a wastewater distributor, and the steam inlet of the stripping tower (3) is provided with a steam distributor.
6. The flameless torch type ultra-clean discharge system for high-ammonia nitrogen wastewater containing VOCs according to claim 2, characterized in that a catalyst bed layer is arranged in the oxidation tower.
7. The flameless torch type ultra-clean discharge system for high-ammonia nitrogen wastewater containing VOCs (volatile organic compounds) according to claim 2, characterized in that a single-layer or multi-layer spraying system is arranged at the upper part of the absorption tower (8), and a demister is arranged at the top; preferably, the absorption tower (8) is also provided with an internal circulation system.
8. The flameless torch type ultra-clean discharge system for high ammonia nitrogen wastewater containing VOCs according to claim 2, wherein the post-treatment unit (10) is a biochemical treatment tank and/or an advanced oxidation system.
9. The flameless torch type ultra-clean discharge system for high-ammonia-nitrogen wastewater containing VOCs according to claim 8, wherein a collection system for non-tissue discharge VOCs is further arranged behind the biochemical treatment tank, the collection system for non-tissue discharge VOCs is provided with an induced draft fan, and the induced draft fan is connected to a cold process inlet of the second preheater (6) through a pipeline.
10. A flameless torch type ultra-clean discharge process for high ammonia nitrogen wastewater containing VOCs is characterized by comprising the following steps:
the wastewater is pretreated by a pretreatment unit (1), enters a stripping tower (3) to recover ammonia nitrogen, and simultaneously VOCs (volatile organic compounds) in the wastewater are separated, and the ammonia nitrogen is recovered in an ammonia water tank (5) in an ammonia water form under the action of a condenser (4); VOCs in gas phase are heated by a second preheater (6) and then enter an oxidation tower (7) to be decomposed and oxidized under the action of a catalyst, so that exhaust gas products containing carbon dioxide, sulfur dioxide, water and the like are generated; heating the high-temperature exhaust gas product in a second preheater (6) to enter VOCs in the tower, after heat exchange, spraying and washing the product in an absorption tower (8) by ammonia water in an ammonia water tank, discharging the tail gas in an ultra-clean manner, and allowing the sprayed and washed product to enter a crystallizer (9) for evaporation and crystallization to obtain ammonium salt; waste liquid discharged from the bottom of the stripping tower (3) is preheated by the first preheater (2) and then passes through the post-treatment unit (10), so that ultra-clean discharge of the waste water is realized.
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| CN201911232261.5A CN111115933A (en) | 2019-12-05 | 2019-12-05 | Flameless torch type ultra-clean discharge process for high-ammonia nitrogen wastewater containing VOCs |
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