CN106145481A - The apparatus and method of organic industrial sewage are processed based on cavitation technique - Google Patents
The apparatus and method of organic industrial sewage are processed based on cavitation technique Download PDFInfo
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- CN106145481A CN106145481A CN201610771191.0A CN201610771191A CN106145481A CN 106145481 A CN106145481 A CN 106145481A CN 201610771191 A CN201610771191 A CN 201610771191A CN 106145481 A CN106145481 A CN 106145481A
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- waste water
- cavitation
- water
- ozone
- toluene
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000010865 sewage Substances 0.000 title claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002351 wastewater Substances 0.000 claims abstract description 85
- 230000008569 process Effects 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 18
- -1 nitrogenous aromatic compounds Chemical class 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 11
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 150000001448 anilines Chemical class 0.000 claims abstract description 6
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 5
- 238000000638 solvent extraction Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 229910001868 water Inorganic materials 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 19
- 239000003610 charcoal Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 239000011236 particulate material Substances 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract 1
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 238000006385 ozonation reaction Methods 0.000 description 15
- 239000002360 explosive Substances 0.000 description 11
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 10
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006396 nitration reaction Methods 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 239000000015 trinitrotoluene Substances 0.000 description 6
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- GAKLFAZBKQGUBO-UHFFFAOYSA-N 2-methyl-3-nitrophenol Chemical compound CC1=C(O)C=CC=C1[N+]([O-])=O GAKLFAZBKQGUBO-UHFFFAOYSA-N 0.000 description 2
- RUIFULUFLANOCI-UHFFFAOYSA-N 3,5-Dinitrotoluene Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 RUIFULUFLANOCI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010936 aqueous wash Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- VMMLSJNPNVTYMN-UHFFFAOYSA-N dinitromethylbenzene Chemical class [O-][N+](=O)C([N+]([O-])=O)C1=CC=CC=C1 VMMLSJNPNVTYMN-UHFFFAOYSA-N 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- ZILXIZUBLXVYPI-UHFFFAOYSA-N 2,4-dinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C([N+]([O-])=O)=C1 ZILXIZUBLXVYPI-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- KZBOXYKTSUUBTO-UHFFFAOYSA-N 2-methyl-1,4-dinitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=CC=C1[N+]([O-])=O KZBOXYKTSUUBTO-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- CZSSKBQAJULWPY-UHFFFAOYSA-N 2-undecylsulfanylacetic acid Chemical compound CCCCCCCCCCCSCC(O)=O CZSSKBQAJULWPY-UHFFFAOYSA-N 0.000 description 1
- ZIIGSRYPZWDGBT-UHFFFAOYSA-N 610-30-0 Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O ZIIGSRYPZWDGBT-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229940119157 Hydroxy radical scavenger Drugs 0.000 description 1
- AGUIVNYEYSCPNI-UHFFFAOYSA-N N-methyl-N-picrylnitramine Chemical group [O-][N+](=O)N(C)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O AGUIVNYEYSCPNI-UHFFFAOYSA-N 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006172 aromatic nitration reaction Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention relates to process the apparatus and method of organic industrial sewage based on cavitation technique.It is related specifically to for processing the device containing nitrobenzene Yu the industrial wastewater of aminobenzene class produced in the production process of toluene di-isocyanate(TDI) (TDI).This device includes surge tank, for removing the rotary pulsed cavitation device of nitrogenous aromatic compounds from described waste water, in order to the film filter of separation of methylbenzene from treated waste water, Hydrodynamic cavitation device, the Burdick lamp being allowed to remove organic impurities for waste water described in comprehensive purification and ozonator, in order to the carbon filter of the ozone and organic impurities that remove residual from waste water with for removing the cyclone separator of particle from waste water by carrying out liquid-liquid extraction with toluene.
Description
Technical field
The present invention relates to process and there is organic works such as aminobenzene class, nitrobenzene, phenols, aldehydes and nitrogenous organic dyestuff
The device of industry waste water.More particularly, the present invention relate to process the device of the waste water produced in TDI production process: (i) borrows
Help toluene nitrification 2, other isomer of 4-dinitrotoluene (DNT) (2,4-DNT) and dinitrotoluene (DNT) (2,5-, 2,6,3,
4-, 2,3-and 3,5-DNT) and (ii) hydrogenate, by corresponding nitro isomer, the aminoderivative 2,4 di amino toluene that obtains
(2,4-TDA) and 2,6-diaminotoluene (2,6-TDA).Compared with existing technology for treating industrial waste water, in particular for containing
Intractable aminobenzene class, the organic industrial sewage of nitrobenzene class pollutant, this equipment can have easy and simple to handle, be easy to automatically
Change control, reduce sludge quantity, energy-saving and cost-reducing on the premise of, improve organic rate of clearing up, increase COD clearance, and can increase
The biodegradability of subsequent treatment.
Background technology
Produced in the common process of dinitrotoluene (DNT) (DNT) by toluene and sulphuric acid with the mixture (nitration acids) of nitric acid,
The acid reaction water that distills out in sulphuric acid concentration step and from the alkalescence of purification of DNT and acid wash water with aqueous
Waste water formation obtains.In addition to mononitrotoluene and dinitrotoluene (DNT), this technique waste water is possibly together with other nitration by-products；
Such as one nitrocresol, dinitrocreasol and trinitrocresol (also referred to as nitrocresol class), picric acid and nitrobenzoic acid.Must
The reason that these materials remove from aqueous phase mainly must there be two.First, present in the fresh water (FW) concentration of DNT reach or
More than 2.5 weight % and mononitrotoluene (MNT) at concentrations up to 1.5 weight % in the case of, the place of untreated waste water
Put the yield losses that represent required product.Secondly, aromatic nitro compound is the most degradable in biological effluent treatment factory, and
There is the character [US2004262238 (CN1285514 (C), 2006.11.22)] poisonous to antibacterial.
A kind of post processing is from being one, two by aromatic nitration and the alkaline process waste water of trinitro-aromatic compounds
Method, the pH that described alkaline process waste water has is 7.5 to 13, and described method includes step: it is right a) to be derived from by interpolation
The vitriolated aqueous phase obtained in nitrification carries out the concentrated sulphuric acid of post processing and alkaline process waste water is acidified to pH less than 5, this
Define by the mixture A of the organic facies separated and acid water phase composition；B) mixture A is made to connect with fresh downflow sludge
Touch；And c) remove downflow sludge [US2012234773 (A1), (CN102666471 (A), 2012.09.12)].
A kind of removing nitre from the alkaline waste water stream produced the technique by mixed acid technology nitrated aromatic compound
Base aromatic compounds and the method for nitro-phenolic compound, comprising: (a) will be containing nitro-aromatics and nitropheneol
The pH regulator of the aqueous alkaline waste stream of compound is in the range of about 2 to 4.5；B () can realize the oxygen of nitro-phenolic compound
Acidic aqueous stream is made to contact with enough hydrogen peroxide and ferrous ion under conditions of change；C nitropheneol content is reduced by ()
The aqueous wash streams of acidic oxidation be adjusted to about pH ＞ /=4, make aqueous wash streams contact with carbon adsorbent with (d)
[US5356539 (A), (CN1065514 (C), 2001.05.09)].
Publication [20] and [21] show for 2 at 25 DEG C, and (2,4-DNT concentration are 250 hundred to 4-DNT saturated solution
Rate very much) for, 2,4-DNT in two kinds of commercial activated charcoal (Filtrasorb 300 and Filtrasorb 400Salgon)
Aequum be respectively every gram of dry coal be 540 and 1030mg.2, the 4-DNT this gel powder with high adsorptive on coal can interfere significantly on it
The safety of regeneration.In other words, for safety reasons, containing 2, the activated carbon of 4-DNT can not carry out hot recycling.By with properly
Solvent (acetone or methanol) extraction these compounds can be removed about 85% from waste coal.The analysis of extract shows,
In solution, except 2, outside 4-DNT, there is also at least six kinds of other chemical substances.In them four kinds are confirmed as 2,4-dinitro
Base benzylalcohol, 2,4-dinitrobenzal-dehyde, 2,4-dinitrobenzoic acid and 2,4-dinitrobenzoic acid ester.The existence of these compounds
Showing, absorbing 2 by activated carbon, 4-DNT is with suitable chemical oxidation reaction.
The analysis of prior art shows, any one in said method can not realize neutralizing in high degree and include 2,4-DNT
At interior aromatic nitro derivative.In some cases, their use causes the notable consumption of adsorbing material and energy cost.
Document describes the various methods using nitro oxidative degradation, for removing nitration from solution and industrial wastewater
The purpose of compound.The end product of some of these methods is carbon dioxide, water and nitric acid or its salt.
In document, some researchs of report are devoted to research [1-4] and at UV/H in the presence of UV and visible ray2O2's
Under the influence of [5] use the Fenton reagent method that carries out nitro-aromatics decomposition.
Li et al. [3] uses UV/ Fenton reagent to establish the order below of deactivation rate of nitroaromatic explosive: 2-nitre
Base toluene ＞ 4-Methylnitrobenzene (4-nitritoluene) ＞ 2,4-DNT ＞ 2,6-DNT ＞ TNT.The nitroaromatic of above-mentioned series
The deactivation rate of explosive shows, the number increasing the nitryl group on aromatic ring improves the chemical stability in the middle of aforementioned substances
And significantly reduce speed and the completeness of its mineralising.
According to the research carried out by Beltran et al. [9], lack hydroxy radical scavenger, pH is 7-9 and temperature is less than 30
It DEG C it is the optimum condition removing nitro-aromatics.Due to the importance reason of hydroxy radical reaction, the removal in natural water
It is much lower that speed ratio is observed in laboratory ultra-pure water.Have been found that at 20 DEG C between ozone and nitroaromatic hydrocarbon is straight
Connect the speed constant of reaction less than 6M-1s-1.Removing the nitro-aromatics more than 99% is owing to hydroxy radical aoxidizes.That
Single ozonisation of nitro-aromatics can be classified as the high-level oxidation technology of reality.
Ozonisation combines with hydrogen peroxide and causes 2, and the removal level of 6-dinitrotoluene (DNT) is than the feelings of only simple ozonisation
Condition is higher.When by 2,6-dinitrotoluene (DNT) is exposed to UV/O3When UV in the system of oxidation radiates, it is removed and is also carried out than existing
Do not have in the case of irradiation faster.List of references 9,10 shows, in addition to consideration economically, and oxidative system UV/O3It is to lead
Cause purified wastewater the most in high degree and be allowed to remove the effective ways of nitro-derivative.
As shown in list of references 11, employing UV irradiation Direct Resolution explosive is the most inconspicuous.Fenton method can be effectively
Nitroaromatic explosive in decomposition water solution.
According to the mechanism of Fenton's reaction, by Fe (II) and H2O2The hydroxy radical produced rises in the middle of decomposing organic compounds
Important effect [12]:
H2O2+Fe2+→OH·+OH-.+Fe3+, (1)
OH·+Fe2+→OH-.+Fe3+. (2)
When using UV lamp, it simultaneously induces the H producing hydroxy radical2O2Photodissociation and Fe (III) is reduced to Fe
(II)[13].Meanwhile, free radical cause explosive degraded with by abstract hydrogen atoms carry out trinitrotoluene, RDX and
The oxidation of HMX:
RH+OH·→R·+H2O. (3)
Fenton's reaction [14] is effective in the middle of the degraded of seven kinds of explosives, and gives explosive in this research
Degradation kinetics rate equation.The speed of explosive oxidation is along with Fe in Fenton system2+The increase of concentration and significantly increase.
The oxidation rate of explosive follows following order: DNT ＞ PA ＞ AP ＞ TNT ＞ tetryl ＞ RDX ＞ HMX.Possible mechanism of degradation
Reason also supports the above results.Work as Fe2+(compared with when this concentration is higher) when concentration is relatively low, UV light has higher promotion efficiency.
Utilize Fenton reagent, UV/H2O2With the DNT isomer that UV/ Fenton reagent carrys out spent acid in mineralising methylbenzene nitration technique
With 2，4，6-trinitrotoluene (TNT) [15-18].Carry out oxidative degradation test to explain total in spent acid of various performance variables
The impact of the performance of the mineralising of organic compound (TOC), including reaction temperature, the intensity of UV (254nm) irradiation, the dosage of ozone
Concentration with sulphuric acid.It should be noted that is combined with UV irradiation by ozonisation can realize the most complete of organic compound
Mineralising.But, under the experiment condition of this research, the photodissociation of ozone decomposed or ozone will not produce hydroxy radical (OH·)。
According to being determined by gas chromatograph/mass spectrograph (GC/MS) and by gas chromatography/flame ionization detector (GC/
FID) spectrum being further characterized by, gives the multiple oxidative pathway of DNT isomer, and it includes o-, m-, to a nitro first respectively
Benzene (MNT) and 1,3-dinitro benzene.Additionally, the oxidative degradation of 2,4,6-TNT obtains 1，3，5-trinitrobenzene intermediate.
Fig. 1 shows and utilizes light ozonisation 2, and 4-DNT forms environment-friendly type material (CO2、H2O and NO3 -) mechanism.As this machine
Reason, based on the data obtained by gas chromatogram (GC), 2,4-DNT decomposition relate to being formed on aromatic ring containing carbonyl group and carboxylic
The nitro-derivative of base.It is found that and there are in the reactive mixture in these in the 10-15 minute period of head of photochemical catalytic oxidation
Between product.Through the photochemical catalytic oxidation of the most several hours, intermediate was converted into carbon dioxide, water and nitrate ion.To one
Similar oxidation mechanism is give also with trinitrotoluene (TNT).
Persulfate anion is used to combine with ultrasonic irradiation the oxidative degradation of the DNT carried out in waste water, Qi Zhongguan
Observe synergy [19].
No. 4,604,214 United States Patent (USP) discloses in a kind of waste water stream produced from production nitro-aromatics to be removed
Go trinitrocresol and the method for picric acid pollutant.The method relates to the thick dinitrotoluene (DNT) making to be produced by mixed acid technology
Contact with alkaline medium to produce containing water soluble nitro cresol and picric alkali wash water.At enough aqueous acids
Reason washings are to drop to 3-4 by pH.Make water-bearing media can realize big portion with hydrogen peroxide and ferrous ion after adjustment of ph
Trinitrocresol is divided to contact under conditions of being oxidized to carboxylic acid, nitric acid and carbon dioxide.
For now, the most known extraction 2 from aqueous phase, the method for 4-DNT toluene, such as patent document
US2004262238 A1 (CN1285514 C, 2006.11.22), US2012248038 A1 (CN102656137 A,
2012.09.05) and as disclosed in US6506948 B1.Quote these files and disclose proposed method compared to
The feature of perception method and difference.
Therefore, all known technology all can only partly solve the problem of DNT loss, thus from the work of DNT synthesis
The waste water pollution problem of factory the most not yet has been resolved.
Other list of references
[1] Z.M.Li, M.M.Peterson, S.D.Comfort, G.L.Horst, P.J.Shea and B.T.Oh,
Remediating TNT-contaminated soil by soil washing and Fenton oxidation,
Sci.Total Environ.204(1997)107-115.
[2] Z.M.Li, S.D.Comfort and P.J.Shea, Destruction of 2,4,6-
Trinitrotoluene by Fenton oxidation, J.Environ.Qual.26 (1997) 480-487.
[3] Z.M.Li, P.J.Shea and S.D.Comfort, Nitrotoluene destruction by UV-
Catalyzed Fenton oxidation, Chemosphere 36 (1998) 1849-1865.
[4] M.-J.Liou, M.-C.Lu and J.-N.Ohen, Oxidation of explosives by Fenton
And photoFenton process, Water Res.37 (2003) 3172-3179.
[5] P.C.Ho, Photooxidation of 2,4-dinitrotoluene in aqueous solution in
The presence of hydrogen peroxide, Environ.Sci.Technol.20 (1986) 260-267.
[6] R.Dillert, I.Fornefett, U.Siebers and D.Bahnemann, Photocatalytic
Degradation of trinitrotoluene and trinitrobenzene:influence of hydrogen
Peroxide, J.Photochem.Photobiol.A 94 (1996) 231-236.
[7] J.D.Rodgers and N.J.Bunce, Treatment methodsfor the remediation of
Nitroaromatic explosives, Water Res.35 (2001) 2101-2111.
[8] S.Hwang, E.J.Bouwer, S.L.Larson and J.L.Davis, Decolorization of
alkaline TNT hydrolysis effluents using UV/H2O2, J.Hazard.Mater.B108 (2004) 61-
67.
[9] F.J.Beltran, J.M.Encinar and M.A.Alonso, Nitroaromatic hydrocarbon
Ozonation in water.1.Single ozonation, Ind.Eng.Chem.Res.37 (1998) 25-31.
[10] F.J.Beltr á n, J.M.Encinar and M.A.Alonso, Nitroaromatic Hydrocarbon
Ozonation in Water.2.Combined Ozonation with Hydrogen Peroxide or UV
Radiation, Ind.Eng.Chem.Res., 1998,37 (1), pp 32-40.
[11] M.-J.Liou, M.-C.Lu and J.-N.Ohen, Oxidation of explosives by Fenton
And photo-Fenton process, Water Res.37 (2003) 3172-3179.
[12] C.Walling, Fenton's reagent revisited, Acc.Chem.Res.8 (1975), No.4:
125-53.
[13] B.Utset, J.Garcia, J.Casado, X.Domenech and J.Peral, Replacement of
H2O2 by O2In Fenton and photo-Fenton reactions, Chemosphere 41 (2000) 1187-92.
[14] M.-J.Liou, M.-C.Lu and J.-N.Ohen, Oxidation of explosives by Fenton
And photo-Fenton process, Water Res.37 (2003) 3172-3179.
[15] W.-S.Chen, C.-N.Juan and K.-M.Wei, Mineralization of
dinitrotoluenes and trinitrotoluene of spent acid in toluene nitration
Progess by Fenton oxidation, Chemosphere 60 (2005), No.8,1072-1079.
[16] F.J.Beltr á n, J.M.Encinar and M.A.Alonso, Nitroaromatic hydrocarbon
Ozonation in water 1.single ozonation, Ind.Eng.Chem.Res.37 (1998) 25-31.
[17] F.J.Beltr á n, J.M.Encinar and M.A.Alonso, Nitroaromatic hydrocarbon
ozonation in water 2.Combined ozonation with hydrogen peroxide or UV
Radiation, Ind.Eng.Chem.Res.37 (1998) 32-40.
[18] W.-S.Chen, C.-N.Juan and K.-M.Wei, Decomposition of dinitrotoluene
Isomers and 2,4,6-trinitrotoluene in spent acid from toluene nitration
Process by ozonation and photo-ozonation, J.Hazard.Materials 147 (2007), Nos.1-
2,97-104.
[19] W.S.Chen and Y.C.Su, Removal of dinitrotoluenes in wastewater by
Sono-activated persulfate, Ultrason Sonochem.19 (2012), No.4,921-7.
[20] P.C.Ho and C.Stuart Daw, Adsorption and desorption of
Dinitrotoluene on activated carbon, Environ.Sci.Technol.22 (1988), No.8,919-924,
Http:// pubs.acs.org/doi/abs/10.1021/es00173a009.
[21] P.C.Ho and C.Stuart Daw, Adsorption and desorption of
dinitrotoluene on activated carbon.Final Report to the U.S.Army Toxic and
Hazardous Materials Agency.Oak Ridge National Laboratory(1987)
Http:// www.dtic.mil/dtic/tr/fulltext/u2/a466647.pdf.
Summary of the invention
The present invention is compared with existing technology for treating industrial waste water, in particular for containing intractable aminobenzene class, nitro
The organic industrial sewage of benzene pollutant, this equipment can have easy and simple to handle, be easy to Automated condtrol, reduce sludge quantity, joint
On the premise of lowering consumption, improve organic rate of clearing up, increase COD clearance, and the biodegradability of subsequent treatment can be increased.
Providing a kind of device according to the first aspect of the invention, this device includes: at least one is equipped with the buffering of waste water
Tank, described waste water has nitrogenous aromatic compounds before processing in rotary pulsed cavitation device；At least one is rotary pulsed
Cavitation device, for removing nitrogenous aromatic compounds by carrying out liquid-liquid extraction with toluene from described waste water；At least one is centrifuged
Pump, for providing at least one film filter with separation of methylbenzene from treated waste water the waste water processed with toluene；Extremely
A few unit being made up of Hydrodynamic cavitation device, Burdick lamp and ozonator, for locating with ozone-UV by Hydrodynamic cavitation
The reason synthetically waste water described in purification that combines is allowed to remove organic impurities；At least one carbon filter, in order to from waste water
The middle ozone removing residual and organic impurities；At least one centrifugal pump, for providing at least by the waste water of ozone purification
One cyclone separator, for removing particle from waste water.
In one embodiment, can be constructed to be permeable to tank make the waste water by rotary pulsed cavitation device partly purification
Return to form the recirculation circuit of Guan Bi in tank, for processing the waste water through partly processing further.Specifically, should
Device, by using surge tank mode, makes the effluent part after rotary pulsed cavitation device processes return to regulate in tank with shape
Become the recirculation circuit of Guan Bi, so can adjust the circulation time of cavitation step process waste water by adjusting circulating load.
In another embodiment, described surge tank includes that at least one is for the import and at least one use that receive waste water
In introduce acid or alkali with regulation tank in the import of pH of waste water, and also have the chemical combination for providing the ferrum (II) being used as catalyst
The import of thing, described catalyst in the module have Hydrodynamic cavitation device under the effect of ultraviolet radiation and ozone
Organic compound contained in oxidized waste water.
In yet another embodiment, this device can farther include at least one by Hydrodynamic cavitation device, Burdick lamp and smelly
The module that Oxygen Generator is constituted, wherein can be arranged on Burdick lamp and/or ozonator under described Hydrodynamic cavitation device
Trip or its upstream end are to guarantee to remove the organic impurities of residual from described waste water.
In still another embodiment, this device can be furnished with one or more pH sensor being positioned in tank with by tank
Face introducing alkali or acid regulate the pH of waste water.
In another embodiment, one of component of charcoal particulate filter can be Linesless charcoal, activated carbon or thermal expansion graphite.
In another embodiment, can the central shaft of cyclone separator tangential on intake.
Providing the method processing organic industrial sewage according to the second aspect of the invention, it comprises the following steps (1) extremely
(6) any one in:
(1) preparing the stage of waste water before processing in rotary pulsed cavitation device, this stage includes drawing inside tank
Enter alkali or the acid pH with regulation waste water, and introducing is as the compound of the ferrum (II) of catalyst, in Hydrodynamic cavitation module
In organic compound contained in oxidized waste water stream under the effect of ultraviolet radiation and ozone；
(2) by the rank of the toluene nitrogenous aromatic compounds of liquid-liquid extraction from waste water in described rotary pulsed cavitation device
Section；
(3) extracted by the liquid-liquid of toluene from standing rotary pulsed cavitation device by means of film or other filter any
The waste water taken filters out the stage of toluene；
(4) process, by Hydrodynamic cavitation and ozone-UV, the stage that the integrated treatment that combines has the waste water of organic impurities；
(5) by waste water being transmitted ozone and the stage of organic impurities removing residual quantity through charcoal particulate filter；
With
(6) before waste water is discharged to sewer, from waste water, graininess is removed by the slipstream in cyclone separator
The stage of material.
In one embodiment, charcoal particulate filter can use any kind of work of applicable clean solution, solvent, gas
Property charcoal；And/or wherein charcoal particulate filter uses thermal expansion graphite.
In another embodiment, organic industrial sewage can contain aminobenzene class, nitrobenzene, phenols, aldehydes and
The pollutant such as nitrogenous organic dyestuff.Such as, organic industrial sewage can be containing 2,4-DNT, 2,6-DNT, 2,5-DNT, 3,4-
DNT, 2,3-DNT and/or 3,5-DNT；Or can be containing 2,4-TDA, 2,6-TDA, 2,5-TDA, 3,4-TDA, 2,3-TDA
And/or 3,5-TDA；Or can also be the mixture of the above compound.
Accompanying drawing explanation
Fig. 1 shows and utilizes light-ozonisation 2 in prior art, and 4-DNT forms environment-friendly type material (CO2、H2O and NO3 -) machine
Reason.
Fig. 2 shows the block chart of the device being used for DNT (or TDA) waste-water purification according to the present invention.
Fig. 3 a shows under the influence of free radical OH some possible sides of degradation of toluene in Hydrodynamic cavitation reactor
Formula.
Fig. 3 b shows under the influence of free radical O some possible sides of degradation of toluene in Hydrodynamic cavitation reactor
Formula.
Detailed description of the invention
Block chart for the device of DNT (or TDA) waste-water purification is shown in Fig. 2.Here: 1-rotation-pulse cavitation device；
2-tank；3-centrifugal pump；4-film filter；5-Hydrodynamic cavitation device；6-UV lamp；7-ozonator；8-charcoal particulate filter and/or
Thermal expansion graphite；9-centrifugal pump；10-cyclone separator.It is noted that cyclone separator 10 is inserted in charcoal particulate filter and/or
Before thermal expansion graphite (8).
The device operation being allowed to depart from DNT for purified water is as follows.Toluene is added in the waste water containing DNT, and this is molten
Liquid is sent to be connected to the tank 2 of rotary pulsed cavitation device 1, and two components are wherein by the rotation of the rotor blade of pulse cavitation device 1
Turn mixing.If it is necessary to can additionally be added to alkali or acid in tank 2 change the pH of waste water；Ferrum (II) can also be added
Compound, because working as under the influence of the ozone produced by ozonator 7 and the ultraviolet radiation produced by UV lamp 6 in waterpower
When processing waste water in cavitation device 5, the compound of ferrum (II) plays the catalysis of organic compound contained in further oxidized waste water
The effect of agent.
The operation principle of rotation-pulse cavitation device is based on destroying continuous print liquid medium, next making bubble " vanish ".
Component is crushed to nanoscale by this permission, increases the contact area between waste water and the toluene containing DNT simultaneously, so that liquid-
The process of liquid extraction is accelerated.Water-toluene emulsion is made to be exposed in turbulent flow cavitation, the machine produced centrifugal under the influence of translational force
Tool and impulse action, this provides the emulsion of dispersion and homogenizing.Compared with the similar dissolubility in water, DNT in toluene more
Good dissolubility (more than 1680 times) makes process accelerate.And, it is anti-that the temperature suitably selected and pH value also contribute to aggravation chemistry
Should.Kinetic energy is delivered to water-toluene emulsion by the output blade of cavitation device, and is moved into film filter 4 by outlet, toluene with
The DNT extracted separates with water there.Toluene is returned to main line with the DNT of extraction and can be reused；Water
The purification unit being sent to be made up of Hydrodynamic cavitation device 5, UV lamp 6 and ozonator 7 carries out other process.Can by under
State at least one (that is, UV lamp and/or ozonator) in two equipment be arranged on the downstream of described Hydrodynamic cavitation device or its
Upstream end is to guarantee to remove the organic impurities of residual from described waste water.In other words, due to the fact that and realize additional skill
Art effect, i.e. according to the present invention, the nitro-derivative that purified wastewater is allowed to remove including DNT is included by being repeated exposure to
Ozone-oxygen and/or ozone-air mixt use the ozonisation of hydraulics cavitation and the wavelength UV radiation less than 280nm simultaneously
Starting stage.At UV predose, expose water-ozone mixture and processed further by Hydrodynamic cavitation.After UV irradiation, by gained
To water keep be enough to organic pollution is oxidized to CO2With water or the requirement being sufficient for chemical oxygen demand (COD) value time
Between.In substituting setting, Hydrodynamic cavitation device 5, UV lamp 6 and ozonator 7 can be arranged on the upstream of film filter 4
Place.
In an individual manner, Hydrodynamic cavitation reactor provides by realizing the liquid medium considered that cavitation effect processes
Liquid component strength mixing.This program causes the bubble-break formed in liquid medium and is formed as shock wave
Instantaneous power pulse.This effect result in the degree of depth mixing of treated liquid.During bubble-break, bubble radially moves
Dynamic energy is converted to the kinetic energy of accumulation microjet, and it leaves bubble with the highest speed, thus realizes cavitation stirring
Mechanism.When being furnished with the jet-aerator playing ozonator effect according to the present invention, due to ozone-oxygen and/or
The flowing of ozone-bubble and their maximum contact with liquid medium, the intensity of the mixing of air-gas system improves very
To more.Additional bubble stream adds the turbulent flow of medium and the reactivity of ozone due to its dissolubility reason in water.
According to document, ozone dissolubility in water is higher than oxygen；At a temperature of 20 DEG C, its Cmax in water is
570mg/l.Ozone concentration by weight in the admixture of gas leaving new-type ozonator has reached 14%.It is being used for
Removing in the actual industrial system of organic impurities from water, ozone real balance concentration in water is generally compared to still-mode
Obtained will several multiplying factor low.
Under the influence of cavitation in the aqueous solution containing various inertia and reactant gas, it may occur however that various chemistry are anti-
Should.The cavitation initiation of these reactions is reduced to hydrone and the ionizing of active gases and excites and be reduced to H2O molecule
Dissociate.The each of these processes the most about 10-14 second.
Due to the fact that persistent period of final stage that cavitation bubble is vanished is 10-9-10-8S, thus be possible to
The energy having Inert gas molecule to participate in gas phase shifts and fills.Together with this situation, in cavitation chamber, 10-7-
10-6The conversion of the free radical of chemical reactivity gas and the reaction of the restructuring of free radical is related to during s.Cavitation bubble
Vanish and cause H2The decomposition of O molecule and the restructuring of free radical, this causes molecular oxygen, hydrogen peroxide and other compound long-pending in water
Tired.As indicated above, these reagent promote to relate to being present in the presence of the compound and UV radiation of ferrum (II)
The oxidizing process of the oxidation of the organic impurities in water.
Because forming various chemical compounds, there occurs the change of the pH of water caused by cavitation, described various chemicalization
The existence in water for the treatment of conditions, impurity and gas content thereof are depended in the output of compound.Water-molecule dissociation becomes H and OH certainly
Being subsequently resulted in the synthesis of hydrogen peroxide by base, there is the pH reducing water in it.Such as, there is the cavitation in the water of nitrogen-containing compound
The effect thing followed is to form HNO3And HNO2, this improves the acidity of system.Mixed at ozone, ozone-oxygen or ozone-air
In the presence of compound, the most only form HNO3.Similarly, during processing the water containing nitrous acid in Hydrodynamic cavitation reactor
Form HNO3Or its salt.
The experimental result obtained during the work of the present invention by us is concluded that
1. use Hydrodynamic cavitation device to process water and add molecular oxygen concentration in water；Its some mechanism formed are to pass through
Cavitation cause chemical process and relate to H2O molecule resolves into free radical and O and OH in cavitation chamber.Another mechanism is
Molecular oxygen is formed by ozone decomposed under the effect that Hydrodynamic cavitation and UV radiate.
2., when cavitation process, water comes in contact with air, and the dominant mechanism increasing the concentration of oxygen be at aeration and
Cavitation period O2Dissolving.
3. along with O2The increase of the concentration in raw water, the effect of the chemical action of cavitation increases.
4. at gas (such as O3H is formed in the presence of)2O2And O2Dependency in terms of qualitative similarity indicate formation
The concurrency of process.
5. ozone, hydrogen peroxide and free radical O and OH oxidation dissolution toluene in water, in waste water cleaning caudacoria
Still contain a small amount of toluene.Based on document and our experimental data, we have proposed (Fig. 3 a and Fig. 3 b) at free radical OH
Under the influence of (Fig. 3 a) and O (Fig. 3 b) in Hydrodynamic cavitation reactor some possible modes of degradation of toluene.
The next stage that waste water according to the present invention processes is to use charcoal particulate filter 8 to remove the smelly of residual quantity from which
Oxygen and organic impurities and remove particulate material by the slipstream in cyclone separator 10.
Charcoal particulate filter can equipped with any kind of activated carbon of applicable cleaning liquid, solvent and gas or they with heat
The mixture of expanded graphite.
Process the waste water of factory of synthesis DNT meet when being purified in a device in accordance with the invention for pH and
By the environmental requirement of the organic impurity content that COD value is estimated.
Specific embodiments of the present invention allow from the technique by means of concentrated nitric acid and sulphuric acid nitrated aromatic compound
The acid produced or alkaline waste water stream remove nitro-aromatics.
During the exploitation of the present invention, to three kinds produced in by mixed acid technology nitrated aromatic compound
The waste water of type is tested.
The first waste water is formed during nitrification: pH is 5 to 6, and COD is 2000-3000mg/l, inorganic salt ＜
30000mg/l, DNT are 100-200mg/l, and temperature is 50-70 DEG C, particle ＜ 5mg/l.
The second waste water is also formed during nitrification: pH ＜ 0.5, COD are 2000-3000mg/l, inorganic salt ＜
35000mg/l；Nitric acid ＜ 7.9%, nitrous acid ＜ 2.7%, sulphuric acid ＜ 6.4%, DNT are 300-400mg/l, and temperature is 50-70
DEG C, particle ＜ 5mg/l.
3rd waste water produces during hydrogenating: pH is 11 to 12, and COD is 6000-8000mg/l, inorganic salt ＜
5000mg/l, TDA are 200-400mg/l, and temperature is 20-35 DEG C, particle ＜ 50mg/l.
The method according to the invention can be implemented in batch or continuously.Preferably, described side is implemented continuously according to the present invention
Method.
The method according to the invention is described in detail below with reference to following three embodiments.
Embodiment 1.By distilled water and 2,4-DNT premixing is to obtain 50 liters of COD sample water as 450mg/l.Next
Toluene is added in the ratio that every liter of water is 10mg.Including that rotation-pulse cavitation device 1, centrifugal pump 2, film filter 4, waterpower are empty
Change and the device in the loop of device 5, UV lamp 6 and ozonator 7 processes DNT water and the solution of toluene.The process time is 30 points
Clock.COD measured value in the outfan water outlet of device is 50mg/l.
Embodiment 2.By distilled water and 2,4-DNT premixing is to obtain 50 liters of COD sample water as 450mg/l.Including
Rotation-pulse cavitation device 1, centrifugal pump 2, film filter 4, Hydrodynamic cavitation device 5, UV lamp 6 and ozonator 7, charcoal particle filtering
Device in the loop of device 8 and cyclone separator 10 processes DNT water.The process time is 30 minutes.Output at device brings out
The COD measured value of water is 10mg/l.
Embodiment 3.By distilled water and 2,4-TDA premixing is to obtain 50 liters of COD sample water as 450mg/l.Including
Rotation-pulse cavitation device 1, centrifugal pump 2, film filter 4, Hydrodynamic cavitation device 5, UV lamp 6 and ozonator 7, charcoal particle filtering
Device in the loop of device 8 and cyclone separator 10 processes TDA water.The process time is 30 minutes.Output at device brings out
The COD measured value of water is 10mg/l.
Claims (10)
1. a device, this device includes: at least one is equipped with the surge tank of waste water, and described waste water is in rotary pulsed cavitation device
There is before processing nitrogenous aromatic compounds；At least one rotary pulsed cavitation device, for by carrying out liquid-liquid with toluene
Extraction removes nitrogenous aromatic compounds from described waste water；At least one centrifugal pump, provides for the waste water that will process with toluene
To at least one film filter with separation of methylbenzene from treated waste water；At least one by Hydrodynamic cavitation device, Burdick lamp and
The unit that ozonator is constituted, for combining synthetically waste water described in purification by Hydrodynamic cavitation and ozone-UV process
It is allowed to remove organic impurities；At least one carbon filter, in order to remove ozone and the organic impurities of residual from waste water；Extremely
A few centrifugal pump, for providing at least one cyclone separator by the waste water of ozone purification, for removing from waste water
Remove particle.
Device the most according to claim 1, wherein, is constructed to be permeable to surge tank make by rotary pulsed cavitation device part
The waste water of ground purification returns to form the recirculation circuit of Guan Bi in tank, useless through partly process for processing further
Water.
Device the most according to claim 1 and 2, described surge tank includes that at least one is for the import and extremely receiving waste water
Few one for introducing acid or alkali with the import of the pH of waste water in regulation tank, and also have for providing the ferrum being used as catalyst
(II) import of compound, described catalyst in the module have Hydrodynamic cavitation device at ultraviolet radiation and smelly
Organic compound contained in the lower oxidized waste water of the effect of oxygen.
Device the most according to any one of claim 1 to 3, this device farther includes at least one by Hydrodynamic cavitation
The module that device, Burdick lamp and ozonator are constituted, is wherein arranged on described waterpower by Burdick lamp and/or ozonator
The downstream of cavitation device or its upstream end are to guarantee to remove the organic impurities of residual from described waste water.
Device the most according to claim 1, this device be furnished with one or more pH sensor being positioned in tank with by
Inside tank, introducing alkali or acid regulate the pH of waste water.
Device the most according to claim 1, wherein, one of component of charcoal particulate filter is that Linesless charcoal, activated carbon or heat are swollen
Swollen graphite.
Device the most according to claim 1, wherein, cyclone separator central shaft tangential on provide water.
8. the method processing organic industrial sewage, it comprises the following steps any one in (1) to (6):
(1) preparing the stage of waste water before processing in rotary pulsed cavitation device, the described stage includes drawing in surge tank
Enter alkali or the acid pH with regulation waste water, and introducing is as the compound of the ferrum (II) of catalyst, in Hydrodynamic cavitation module
In organic compound contained in oxidized waste water stream under the effect of ultraviolet radiation and ozone；
(2) by the stage of the toluene nitrogenous aromatic compounds of liquid-liquid extraction from waste water in described rotary pulsed cavitation device；
(3) by means of film or other filter any from the liquid-liquid extraction stood rotary pulsed cavitation device by toluene
Waste water filters out the stage of toluene；
(4) process, by Hydrodynamic cavitation and ozone-UV, the stage that the integrated treatment that combines has the waste water of organic impurities；
(5) by waste water being transmitted ozone and the stage of organic impurities removing residual quantity through charcoal particulate filter；With
(6) before waste water is discharged to sewer, from waste water, particulate material is removed by the slipstream in cyclone separator
Stage.
Method the most according to claim 8, wherein, charcoal particulate filter use be suitable for clean solution, solvent, gas appoint
The activated carbon of what type；And/or wherein charcoal particulate filter uses thermal expansion graphite.
The most according to claim 8 or claim 9, method, wherein, organic industrial sewage contains aminobenzene class, nitrobenzene, phenol
Class, aldehydes and nitrogenous organic dyestuff.
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