CN112456676A - Method for treating organic wastewater - Google Patents
Method for treating organic wastewater Download PDFInfo
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- CN112456676A CN112456676A CN202011226059.4A CN202011226059A CN112456676A CN 112456676 A CN112456676 A CN 112456676A CN 202011226059 A CN202011226059 A CN 202011226059A CN 112456676 A CN112456676 A CN 112456676A
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- organic wastewater
- manganese
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- liquid
- organic
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- 239000002351 wastewater Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 99
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 70
- 239000011572 manganese Substances 0.000 claims abstract description 69
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 54
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 239000007791 liquid phase Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000006479 redox reaction Methods 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 239000012066 reaction slurry Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- 238000002386 leaching Methods 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 43
- 239000000126 substance Substances 0.000 abstract description 31
- 239000000047 product Substances 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000011084 recovery Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000005416 organic matter Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 229910001437 manganese ion Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 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 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- -1 salt ions Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009279 wet oxidation reaction 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
-
- 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
-
- 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
- C02F2103/343—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 pharmaceutical industry, e.g. containing antibiotics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for treating organic wastewater. The method comprises the following steps: carrying out redox reaction on the organic wastewater and a manganese oxide-containing material in the presence of acid to obtain reaction slurry containing divalent manganese; carrying out solid-liquid separation on the reaction slurry to obtain a liquid-phase product containing divalent manganese; removing the solvent in the liquid-phase product to obtain a precipitated material; and oxidizing and roasting the separated material to separate out residual organic matters in the material to obtain a metal salt product containing divalent manganese. The treatment method can be used for resourcefully treating the organic wastewater, particularly the high-concentration organic wastewater, can effectively utilize the chemical energy of organic pollutants in the wastewater, has the advantages of high treatment efficiency, mild operation conditions and the like, and has good economy.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating organic wastewater.
Background
High concentration organic waste water often refers to some waste water with COD more than or equal to 10000mg/L, sometimes the COD of the waste water is even as high as hundreds of thousands of milligrams per liter. The water quality components in the high-concentration organic wastewater are complex, the high-concentration organic wastewater contains toxic and harmful substances, and often contains high-content salt, the high-concentration organic wastewater has strong acidity and basicity and poor direct biochemical activity, and the problem of reasonable treatment is a common problem of sewage treatment in the world at present. The waste water is generated in various industrial fields, and the common waste water comprises coking industry, pharmaceutical industry, petroleum/oil industry, textile/printing and dyeing industry, organic preparation chemical industry, paint industry and the like. The continuous high-yield of the high-concentration organic wastewater has large harm pressure to the environment, and is one of key objects for preventing and controlling environmental pollution.
At present, the methods for treating wastewater with high organic pollutant content mainly include physical chemical methods, chemical methods and biochemical methods.
The existing physical and chemical treatment method mainly utilizes a porous adsorbent with large specific surface area to adsorb organic pollutants, and can also add a coagulant to destabilize and separate the pollutants from the wastewater. The separation process is mainly based on the pressure difference, concentration difference and potential difference to drive the pollutant selectively permeating semi-permeable membrane to carry out membrane separation. In addition, there is a method of separating organic contaminants and the like by contact adhesion of the atomized wastewater to carbonaceous particles. However, these physical separation methods do not provide high removal rates of organic contaminants from wastewater and require subsequent chemical or biochemical treatment.
Chemical methods are generally used for treating high-concentration organic wastewater, and a high-temperature incineration method, an ozone oxidation method, a Fenton reagent method, a photocatalytic oxidation decomposition method, an electrochemical micro-electrolysis oxidation method, a microwave catalytic wet oxidation method, a chlorine dioxide oxidation method, and the like have been reported. However, the chemical treatment is mostly carried out by adding an oxidant, so that the chemical treatment has high cost and large investment, the treatment effect is relatively limited, and the stability of the treatment effect of the system is poor, so that the application of the chemical treatment in the wastewater with high organic matter concentration is limited. The incineration method can efficiently treat high-concentration organic wastewater, but the energy consumption is relatively large, and the application is less in China. For example, in patent CN102168857A, high-concentration salt-containing organic waste liquid waste oil is treated at 1200-1300 ℃, so that the applicability is strong, the waste liquid heat energy recovery amount is large, and although the resource can be effectively and circularly utilized, the temperature is high and the energy consumption is high.
The biochemical method mainly focuses on two aspects in the organic wastewater treatment, one is a biodegradation process flow, such as the combined use of an anaerobic and aerobic biological oxidation process, and the other is a membrane bioreactor, such as a film similar to aerobic sludge granules or enriched biological populations. However, the biological treatment of wastewater is significantly limited by the limit of the concentration of toxic substances in wastewater, and is difficult to apply to high-concentration organic wastewater, and even if the wastewater is treated by a biological method after the concentration of the wastewater is reduced by diluting with water, the defects of difficult degradation of partial organic matters, complex treatment process, slow rate, long period and the like exist.
The requirements of China on environment and production are more and more stringent, new requirements are provided in industrial water quality discharge standards, new wastewater discharge requirements are difficult to meet only by the existing treatment method, particularly the problem of deep degradation of wastewater treated by low-concentration and difficultly-degradable organic pollutants treated by the existing process is solved, even if the wastewater is treated by methods such as stronger active oxidants or multi-stage biological oxidation, the deep degradation effect of the difficultly-degradable pollutants is still limited, and the treatment cost is high. Therefore, there is an urgent need to develop and explore a more efficient, economical and secondary pollution-free method for treating wastewater with high organic concentration.
Based on the existing treatment technology of the wastewater with high organic matter concentration, the wastewater resource treatment is an effective way for treating the wastewater with high organic matter concentration and improving the value. For example, in patent CN108793551A, the soluble sub-salt is used as V2O5The organic matter is quickly and deeply oxidized under the catalysis of SBA-15. However, the method recycles solid salt, neglects the utilization of chemical energy of organic pollutants, and has high requirement on oxidation pressure which reaches 2.5-10.0 MPa.
For the above reasons, it is necessary to provide an organic wastewater treatment method which can utilize high-concentration organic matters in wastewater as resources, can effectively utilize chemical energy of organic pollutants, and has mild operation conditions.
Disclosure of Invention
The invention mainly aims to provide a method for treating organic wastewater, which aims to solve the problems of insufficient chemical energy utilization of organic pollutants, harsh operating conditions and the like in the resource treatment of high-concentration organic wastewater in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for treating organic wastewater, comprising the steps of: carrying out redox reaction on the organic wastewater and a manganese oxide-containing material in the presence of acid to obtain reaction slurry containing divalent manganese; carrying out solid-liquid separation on the reaction slurry to obtain a liquid-phase product containing divalent manganese; removing the solvent in the liquid-phase product to obtain a precipitated material; and oxidizing and roasting the separated material to separate out residual organic matters in the material to obtain a metal salt product containing divalent manganese.
Further, the organic wastewater is acidic, neutral or weakly alkaline wastewater, the COD concentration in the organic wastewater is more than or equal to 10000mg/L, and the preferred COD concentration in the organic wastewater is 10000-200000 mg/L.
Further, the liquid-solid weight ratio of the organic wastewater to the manganese oxide-containing material is (2-10): 1; preferably, the weight ratio of COD in the organic wastewater to tetravalent manganese in the manganese oxide-containing material is (0.1-0.3): 1.
Further, the acid is selected from sulfuric acid, hydrochloric acid, nitric acid or industrial waste acid, preferably the acid is sulfuric acid; preferably, the dosage of the acid is 1-2 times of the theoretical dosage required by leaching the metal ions in the manganese oxide-containing material.
Further, the material containing manganese oxide is selected from pyrolusite, manganese nodule, MnO containing2One or more of waste materials; preferably, the particle size of the manganese oxide-containing material is less than or equal to 0.01 mm.
Further, the oxidation-reduction reaction is carried out in a stirring state, and the stirring speed is 300-600 r/min; preferably, the temperature of the oxidation-reduction reaction is 25-200 ℃, more preferably 70-90 ℃, and the time of the oxidation-reduction reaction is 0.5-4 h.
Further, volatile gas is obtained in the oxidation-reduction reaction process, and the treatment method further comprises the following steps: the volatile gas is absorbed by dilute acid, water or organic wastewater after adding acid.
Further, the step of removing the solvent from the liquid phase product comprises: carrying out reduced pressure distillation on the liquid-phase product to obtain a precipitated material; the distillation temperature in the reduced pressure distillation process is 40-60 ℃, and the distillation time is 2-12 h.
Further, in the process of oxidizing and roasting the precipitated material, roasting temperature is 600-650 ℃, and roasting time is 0.5-2 h; preferably, the oxidizing roasting process produces flue gas, and the treatment method further comprises returning the flue gas to the redox reaction step.
Further, after obtaining the metal salt product, the processing method further comprises: dissolving a metal salt product in water to obtain a dissolved solution; adjusting the pH value of the dissolving solution to 5.5-7.5 to obtain a purified solution; adjusting the pH value of the purified solution to be alkalescent, and then recrystallizing to obtain a manganous salt and a manganese-extracted solution; and recovering salts in the manganese extraction solution.
The invention provides a method for treating organic wastewater, which comprises the following steps: carrying out redox reaction on the organic wastewater and a manganese oxide-containing material in the presence of acid to obtain reaction slurry containing divalent manganese; carrying out solid-liquid separation on the reaction slurry to obtain a liquid-phase product containing divalent manganese; removing the solvent in the liquid-phase product to obtain a precipitated material; and oxidizing and roasting the separated material to separate out residual organic matters in the material to obtain a metal salt product containing divalent manganese. The treatment method provided by the invention can effectively utilize the chemical energy of the organic pollutants in the organic wastewater, and the organic pollutants are used as reducing agents for reducing the organic pollutants containing the manganese oxide materials, organic matters which are relatively easy to degrade are subjected to oxidative degradation in the process, tetravalent manganese in the manganese oxide materials is reduced into bivalent manganese, and enters a liquid phase under the action of acid. After redox reaction, separating a liquid phase product and further removing a solvent, separating out residual refractory organics and metal salt in the liquid phase, and oxidizing and roasting the separated-out product to decompose the residual refractory organics by roasting, wherein the residual refractory organics is a metal salt product containing divalent manganese.
The treatment method can be used for resourcefully treating the organic wastewater, particularly the high-concentration organic wastewater, can effectively utilize the chemical energy of organic pollutants in the wastewater, has the advantages of high treatment efficiency, mild operation conditions and the like, and has good economy.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the recycling treatment of high-concentration organic wastewater in the prior art has the problems of insufficient chemical energy utilization of organic pollutants, harsh operating conditions and the like.
The wastewater with high organic matter concentration contains a large amount of organic pollutants, has high chemical energy, is a potential chemical energy source capable of being oxidized and utilized, and can be used as a reduction active agent of some materials, such as manganese oxide ore materials and the like. The method is one of the methods for promoting the reclamation of the waste water and improving the economic value of the waste water. However, the use of high organic matter concentration wastewater as a reducing agent for manganese oxide ore materials and the like has a problem that the decomposition of organic matter is not complete, the concentration of residual organic matter in a leaching solution is high, and the subsequent wet purification is affected.
The invention provides a method for treating organic wastewater based on the above, which comprises the following steps: carrying out redox reaction on the organic wastewater and a manganese oxide-containing material in the presence of acid to obtain reaction slurry containing divalent manganese; carrying out solid-liquid separation on the reaction slurry to obtain a liquid-phase product containing divalent manganese; removing the solvent in the liquid-phase product to obtain a precipitated material; and oxidizing and roasting the separated material to separate out residual organic matters in the material to obtain a metal salt product containing divalent manganese.
The treatment method provided by the invention can effectively utilize the chemical energy of the organic pollutants in the organic wastewater, and the organic pollutants are used as reducing agents for reducing the organic pollutants containing the manganese oxide materials, organic matters which are relatively easy to degrade are subjected to oxidative degradation in the process, tetravalent manganese in the manganese oxide materials is reduced into bivalent manganese, and enters a liquid phase under the action of acid. After redox reaction, separating liquid phase product and further removing solvent (the solvent is the solvent of wastewater, mainly water), separating out residual refractory organics and metal salt in the liquid phase, then carrying out oxidation roasting on the separated out product, roasting and decomposing the residual refractory organics, and obtaining the residual metal salt product containing bivalent manganese.
In the actual operation process, after the organic wastewater is mixed with the manganese oxide-containing material and the acid in the reactor, the oxidation activity of the manganese oxide in the manganese oxide-containing material is utilized to compete for the electron energy contained in the organic pollutants in the organic wastewater, the organic pollutants are oxidized and degraded, and electrons are released (the oxidation degradation product is CO)2And H2O), while tetravalent manganese in the manganese oxide material is reduced to divalent manganese and leached into solution. In addition to oxidatively degraded organicBesides, the solution contains some refractory organic pollutants, and the components in the liquid-phase product form mixed solids along with the removal of the solvent, and the refractory organic pollutants are precipitated by the metal salt containing the divalent manganese. The refractory organics can be decomposed by oxidizing roasting (CO is the main product)2And H2O), and finally obtaining the metal salt product containing the divalent manganese.
The treatment method can be used for resourcefully treating the organic wastewater, particularly the high-concentration organic wastewater, can effectively utilize the chemical energy of organic pollutants in the wastewater, has the advantages of high treatment efficiency, mild operation conditions and the like, and has good economy. In addition, the method utilizes oxidation reduction, solid-liquid separation, solvent removal and oxidizing roasting, fully utilizes the chemical energy of the organic pollutants, and simultaneously thoroughly removes the refractory organic pollutants remained and mixed in the divalent manganese-containing metal salt, so that the metal salt can more fully separate metal ions through wet impurity removal separation, and the influence of the refractory pollutants on the wet separation is avoided. In addition, in the process, organic pollutants are fully oxidized and degraded, pollutants which are difficult to degrade are fully oxidized and roasted, no secondary pollution is generated in the process, and the flow is simple.
The indissolvable components of the wastewater or the leaching slag of the manganese oxide-containing material obtained in the oxidation reduction process can be recycled for other uses, the water collected in the solvent removing process can also be recycled for use, roasting smoke can be generated in the roasting process, and the roasting smoke can be discharged after being absorbed by the manganese oxide-containing material. In particular, the possible organic substances of the waste water contain S, and SO is produced2Can be absorbed and oxidized; secondly, the decomposition of macromolecular organic substances during the roasting process may generate reducing gases such as CO and H2S, etc., which can be absorbed by Mn (+ 4); thirdly, organic matters in the wastewater may contain volatile gas and can be adsorbed and recycled or oxidized; fourthly, the solid part of dust in the flue gas can be adsorbed by the materials with large surface area, and the like.
The treatment process is not limited by the states of components such as solid content, inorganic ion components, pH value and the like in the organic wastewater. In a preferred embodiment, the organic wastewater is acidic (e.g. pH 5-7), neutral or weakly alkaline (e.g. 7-8.2), and the COD concentration in the organic wastewater is not less than 10000mg/L, preferably 10000-200000 mg/L. Through oxidation-reduction reaction, more than 80% of organic pollutants in the organic wastewater can be oxidized and degraded in the reaction process, pollutants difficult to treat are degraded, the COD concentration can be lower than 3000mg/L, after the obtained reaction slurry is subjected to solid-liquid separation, the content of bivalent manganese ions in a liquid phase product can reach more than 25g/L, even more than 60g/L, and the concentrated crystallization value is high. In the actual treatment process, when the COD concentration in the organic wastewater is too high, such as higher than 50000mg/L, and the COD concentration in the liquid-phase product after the corresponding redox reaction step is still higher, such as higher than 10000mg/L, a manganese oxide-containing material and an acid can be further added into the liquid-phase product after the first reaction, and secondary or even multiple conversion and utilization can be carried out until the COD concentration is degraded to a lower concentration, so that bivalent manganese ions are fully enriched in the liquid-phase product, and the chemical energy of organic pollutants can be more fully converted and utilized.
In order to enable organic pollutants in the organic wastewater to react with manganese oxide in the manganese oxide-containing material more fully so as to achieve the purposes of utilizing chemical energy and improving resource utilization effect, in a preferred embodiment, the solid-liquid weight ratio of the organic wastewater to the manganese oxide-containing material is (2-10): 1; preferably, the weight ratio of COD in the organic wastewater to tetravalent manganese in the manganese oxide-containing material is (0.1-0.3): 1. This is advantageous in that the redox reaction proceeds more sufficiently to promote oxidation of COD by tetravalent manganese as much as possible.
The acid is added to provide conditions for leaching of the manganous and other metals in the material, and in a preferred embodiment the acid is selected from sulphuric acid, hydrochloric acid, nitric acid or spent industrial acid, preferably the acid is sulphuric acid; preferably, the dosage of the acid is 1-2 times of the theoretical dosage required by leaching the metal ions in the manganese oxide-containing material. The use of the acid of the type mentioned above, with its amount controlled within the above range, is more advantageous for leaching of divalent manganese ions and other metal ions. Meanwhile, the method is also beneficial to promoting the oxidation-reduction reaction of organic pollutants in the organic wastewater and manganese oxide in the materials.
In a preferred embodiment, the manganese oxide-containing material is selected from pyrolusite, nodules of manganese, MnO-containing materials2One or more of waste materials (such as spent catalyst, etc.). By using the material containing manganese oxide, on one hand, the chemical energy in the wastewater can be effectively utilized through the oxidation-reduction reaction with the organic pollutants in the organic wastewater, and on the other hand, convenient conditions are provided for resource recovery of manganese and other metals in the materials. These materials contain some leachable valuable metals such as iron and the like in addition to manganese, and these valuable metals can also be eluted by oxidation-reduction under acid conditions, and after subsequent solid-liquid separation, solvent removal, and oxidizing roasting, these metals can also be separated by further wet means to obtain corresponding metal products. Preferably, the manganese oxide-containing material is pyrolusite. It should be noted that the manganese oxide-containing material adopted by the method is not limited by the manganese grade and impurity components in the material, and the effect of the method can be realized by high-grade and low-grade manganese oxide-containing materials.
Preferably, the particle size of the manganese oxide-containing material is less than or equal to 0.01mm, and the particle size is controlled within the range, so that the contact and reaction of organic pollutants in the organic wastewater and the manganese oxide are facilitated, and the reaction efficiency is improved. More preferably, the oxidation-reduction reaction is carried out in a stirring state, and the stirring speed is 300-600 r/min; preferably, the temperature of the oxidation-reduction reaction is 25-200 ℃, more preferably 70-90 ℃, and the time of the oxidation-reduction reaction is 0.5-4 h. When the reaction is carried out under the conditions, the organic pollutants can be more fully oxidized and degraded, and the reaction efficiency and the conversion rate are higher.
In a preferred embodiment, a volatile gas is obtained during the redox reaction, and the processing method further comprises: the volatile gas is absorbed by dilute acid, water or wastewater to be treated after adding acid. The reaction process of the organic wastewater usually generates volatile gases along with ammonia gas, and the volatile gases are favorably absorbed by dilute acid (dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid or industrial wastewater), water or organic wastewater after acid addition (such as organic wastewater to be treated after the addition of sulfuric acid, hydrochloric acid and nitric acid). In a specific operation, the above-mentioned redox process can be carried out in a temperature-controllable leaching agitation reactor, and more preferably, a volatile gas-recoverable reactor having a gas circulation control and recovery device is used. Therefore, volatile gases such as ammonia gas, volatile phenol/alcohol and the like generated in the reaction process can be connected with the reaction device by adopting a closed pipeline, and the gas flowing direction is controlled by the pipeline to regulate and control the gas.
The above-mentioned process for removing the solvent may be carried out in a form commonly used in the art. Of course, in order to improve the solvent removal efficiency, in a preferred embodiment, the step of removing the solvent from the liquid phase product comprises: carrying out reduced pressure distillation on the liquid-phase product to obtain a precipitated material; the distillation temperature in the reduced pressure distillation process is 40-60 ℃, and the distillation time is 2-12 h. Along with the reduced pressure distillation, the metal salt and the refractory organic pollutants in the liquid phase product are gradually concentrated and deposited, and finally concentrated and crystallized to form mixed solid powder. And recovering distilled water generated in the distillation process by using a return water collecting device. In addition, volatile gases, such as volatile ammonia components, are also generated during the vacuum distillation, and preferably recovered with dilute acid, water or wastewater to be treated after adding acid.
In a preferred embodiment, in the process of oxidizing and roasting the precipitated material, the roasting temperature is 600-650 ℃, and the roasting time is 0.5-2 hours. Under the condition of the medium-temperature roasting, the degradation of the organic pollutants difficult to degrade is more thorough. During the oxidizing calcination, it is preferable to blow air into the reaction system so that the reaction proceeds more sufficiently. Preferably, the oxidizing roasting process produces flue gas, and the treatment method further comprises returning the flue gas to the redox reaction step. Thus, reducing gases such as SO in the flue gas2,H2S and the like can be absorbed by Mn oxide for secondary oxidation and CO is discharged2And H2And O. After the oxidizing roasting, the metal salt product can be subjected to subsequent treatment or application after being cooled.
As mentioned above, after the manganese oxide-containing material is used, some valuable metals are also leached into the liquid phase along with the oxidation-reduction reaction, and the corresponding metal salt product obtained also includes some other valuable metal salts besides the divalent manganese salt. In order to more fully separate these valuable metals, in a preferred embodiment, after obtaining the metal salt product, the treatment process further comprises: dissolving a metal salt product in water to obtain a dissolved solution; adjusting the pH value of the dissolved solution to 5.5-7.5 to separate heavy metal ions (heavy metal ions form hydroxide precipitates) such as Cu, Co, Ni, Fe, Pb and the like in the dissolved solution to obtain a purified solution; adjusting the pH of the purified solution to be alkalescent (for example, 7.5-8.5, and the pH is greater than that of the former dissolved solution), and then recrystallizing to obtain a divalent manganese salt and a manganese-extracted solution; and (4) recovering salts in the manganese-extracted liquid, for example, recovering by adopting a concentration fractional crystallization method to obtain salts such as Na/K/Mg and the like. For example, firstly, the basic magnesium carbonate method is adopted to extract magnesium, and then Na/K separation and recovery are carried out. Sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide and the like can be adopted in the process of adjusting the pH value, and salt ions in the solution after manganese extraction are correspondingly adopted.
In a specific application process, the heat required by each step in the treatment method can be provided by waste heat in an industrial process, preferably by waste heat of flue gas in the oxidizing roasting process, and specific operations can be understood and implemented by those skilled in the art, and are not described herein again.
In summary, the method provided by the invention for treating organic wastewater, especially high-concentration organic wastewater, has the following advantages:
1) the organic wastewater is used as a medicament, so that the economic and utilization values of the organic wastewater are increased.
2) The high-concentration organic wastewater has high utilization rate of chemical resources and high recovery rate of organic pollutants and inorganic components.
3) The organic pollutants in the organic wastewater are thoroughly treated, the pollutants difficult to treat are fully degraded, the easily degradable components are utilized based on the oxidation-reduction reaction, then the components difficult to treat are roasted at the medium temperature for oxidative decomposition, and the degradation emission of the organic pollutants in the process is CO2And H2O；
4) Based on the characteristic of high concentration of organic pollutants in the wastewater, the organic pollutants are used as chemical energy substances to be reduced and leached to obtain a liquid phase product with high divalent manganese concentration, so that the value of the solvent removal process is increased.
5) The method has the advantages of wide application range, low property requirements on organic wastewater and manganese oxide-containing materials, simple process flow and particular suitability for organic wastewater with COD concentration more than or equal to 10000 mg/L.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) Taking high-salt high-COD organic wastewater (the NaCl content is 16.8 wt%, the COD concentration is 20000mg/L and the pH value is 8.2) of a chemical plant, adding the wastewater and low-grade pyrolusite (the Mn grade is 22.2% and the Fe grade is 6.7%) into a process atmosphere-adjustable constant-temperature stirring reaction kettle according to the liquid-solid ratio of 3:1, wherein the weight ratio of the COD and tetravalent manganese in the organic wastewater is 0.2:1, and adding hydrochloric acid to adjust the pH value of a solution to 1.0 (the addition amount of the hydrochloric acid is 1.2 times of the theoretical required amount of leaching of divalent manganese and iron), thereby obtaining raw material slurry. The raw material slurry is stirred and leached for 2 hours under the conditions that the temperature is 70 ℃ and the stirring speed is 400r/min, so as to obtain reaction slurry. Filtering the reaction slurry to obtain a liquid phase product, wherein the COD concentration is reduced to 2400mg/L, and the Mn concentration is reduced to2+The concentration is 56g/t, the leaching slag is used for preparing silicon-based materials, and volatile gas is generated in the recovery process of the organic wastewater added with hydrochloric acid to be treated.
(2) And (2) introducing the liquid-phase product obtained in the step (1) into a distillation device, distilling for 5 hours at 50 ℃ under the condition of induced air and reduced pressure to obtain a solid component containing refractory organic matters and metal salts, and recovering reduced-pressure distilled water.
(3) And (3) cooling the solid component obtained in the step (2), roasting at 650 ℃ for 2h, introducing air in the process to fully oxidize and decompose the organic pollutants, and circularly introducing the roasted flue gas into the step (1) for absorption to obtain the metal salt component without organic matters.
(4) Soaking the metal salt obtained in the step (3) in water according to the liquid-solid mass ratio of 2:1 to obtain a dissolved solution, wherein metal ions in the dissolved solution mainly comprise manganese ions and iron ions, and the pH value is reduced to 2.0 after the water soaking; regulating deviceAdjusting the pH value of the whole dissolving solution to 7.0, and obtaining a purified solution, wherein the removal rate of iron precipitate is 99.9%; adjusting the pH value of the purified liquid to 8.0, and recrystallizing to obtain MnCl with the purity of 99.9%2And a manganese extraction solution. Electrolytic Mn is prepared by adopting an electrolysis mode, and salt products such as NaCl and the like are recovered by concentrating and crystallizing the solution after electrolytic manganese extraction. After the low-grade pyrolusite is treated, the recovery rate of manganese is 98 percent, and the recovery rate of iron is 37 percent.
Example 2
(1) Taking high-COD coking wastewater (COD concentration is 50000mg/L, total ammonia concentration is 5000mg/L and pH is 7.2) in a coking section of a certain coking plant, adding the wastewater and high-grade pyrolusite (Mn grade is 46.2%) into a pressurized reaction kettle with adjustable process atmosphere according to a liquid-solid ratio of 5:1, wherein the weight ratio of the COD and tetravalent manganese in the organic wastewater is 0.15:1, and adding sulfuric acid to adjust the pH of a solution to 0.5 (the addition of the sulfuric acid is 1.5 times of the theoretical required amount for leaching the divalent manganese), so as to obtain raw material slurry. The raw material slurry is stirred and leached for 1h at the temperature of 140 ℃ and the stirring speed of 300r/min, so as to obtain reaction slurry. And filtering the reaction slurry to obtain a liquid-phase product, wherein the COD concentration is reduced to 23000mg/L, the Mn concentration is 66g/t, and the recovery rate of ammonia recovered by volatilization of ammonia components is 85%. Aiming at the liquid phase product, carrying out secondary reduction leaching at 90 ℃ for 2h by taking the liquid-solid ratio of the liquid phase product to pyrolusite as 10:1 to obtain the total Mn content2+103g/L and COD concentration of 3000mg/L, volatile components are recovered in the leaching process. The coking wastewater is high ammonia nitrogen wastewater, ammonia gas is volatilized in the leaching process, and the ammonia gas is led out by a pipeline and collected into another container after being condensed.
(2) And (2) introducing the secondary liquid phase product obtained in the step (1) into a distillation device, distilling for 6h at 60 ℃ under the condition of induced air and reduced pressure to obtain a solid component containing refractory organic matters and metal salts, and recovering reduced pressure distilled water.
(3) And (3) cooling the solid component obtained in the step (2), roasting at 600 ℃ for 4h, introducing air in the process to fully oxidize and decompose the organic pollutants, and circularly introducing the roasted flue gas into the step (1) for absorption to obtain the metal salt component without organic matters.
(4) Soaking the metal-free salt obtained in the step (3) in water according to the liquid-solid mass ratio of 1:1 to obtain a dissolved solution, wherein metal ions in the dissolved solution mainly comprise manganese ions, a small amount of copper ions and zinc ions are additionally contained, and the pH value is reduced to 2.0 after the water soaking; adjusting the pH value of the dissolving solution to 6.5 to recover heavy metal copper and zinc, wherein the recovery rate of the heavy metal is more than 99%, and obtaining a purified solution; adjusting the pH value of the purified liquid to 8.5, recrystallizing to obtain a manganese sulfate monohydrate product with the purity of 99.3 percent, wherein the manganese recovery rate is 97.8 percent.
Example 3
(1) Taking high-COD liquid medicine (the COD concentration is 150000mg/L, the solid component content is 2.3 percent, and the pH is 5) of a pharmaceutical factory, adding the wastewater and multi-metal nodules (the grades of Mn, Ni, Cu, Co and Fe are respectively 20.2 percent, 1.31 percent, 1.26 percent, 0.22 percent and 9.8 percent) into a pressurized reaction kettle with adjustable process atmosphere according to the liquid-solid ratio of 2:1, wherein the weight ratio of COD to tetravalent manganese in the organic wastewater is 0.3:1, and adding sulfuric acid to adjust the pH of the solution to 1.0 (the addition amount of the sulfuric acid is 1.5 times of the leaching theoretical required amount of divalent manganese, Ni, Cu, Co and Fe) to obtain raw material slurry. The raw material slurry is stirred and leached for 1h at the temperature of 90 ℃ and the stirring speed of 500r/min, so as to obtain reaction slurry. Filtering the reaction slurry to obtain a liquid-phase product, wherein the COD concentration is reduced to 60000mg/L, the Mn concentration is 52g/t, the nickel-copper-cobalt leaching rate reaches 99%, the silicate minerals with large specific surface area of the leaching slag have good adsorption performance on solid components and organic pollutants, and the slag is used for preparing an adsorption material; then, adding polymetallic nodule into the primary liquid-phase product at a liquid-solid ratio of 6:1, and carrying out secondary reduction leaching at 90 ℃ for 2 hours to obtain the total Mn content2+63g/L and a COD concentration of 30000 mg/L. Then, carrying out three times of reduction leaching on the secondary liquid phase product with the liquid-solid ratio of 5:1 at 90 ℃ for 2h to obtain the total Mn content2+72g/L，Ni+4.6g/L，Cu2+4.2g/L，Co2+0.9g/L，Fe3+8.0g/L and a COD concentration of 9000mg/L for the third liquid phase product.
(2) And (2) introducing the tertiary liquid phase product obtained in the step (1) into a distillation device, carrying out reduced pressure distillation at 40 ℃ for 12h to obtain a solid component containing refractory organic matters and metal salts, and collecting reduced pressure distilled water.
(3) And (3) cooling the solid component obtained in the step (2), roasting at 650 ℃ for 2h, introducing air in the process to fully oxidize and decompose the organic pollutants, and circularly introducing the roasted flue gas into the step (1) for absorption to obtain the metal salt component without organic matters.
(4) Soaking the metal salt obtained in the step (3) in water according to a liquid-solid mass ratio of 0.8:1 to obtain a dissolved solution, wherein metal ions in the dissolved solution mainly comprise manganese ions, iron ions, nickel ions, copper ions and cobalt ions, the pH value is reduced to 4.0 after the water soaking, a small amount of dilute sulfuric acid is added to adjust the pH value to 6.5-7.0 for depositing heavy metals, the total recovery rates of nickel, copper, cobalt and iron respectively reach 98.5%, 96.2%, 98.7% and 32.2%, and a purified solution is obtained after removing the heavy metals; adjusting the pH value of the purified liquid to 7.5, recrystallizing to obtain a manganese sulfate monohydrate product with the purity of 99.1 percent, wherein the recovery rate of manganese is 99 percent.
Example 4
(1) Taking certain high-COD garbage percolate (the COD concentration is 40000mg/L and the pH value is 8.2), adding the percolate and waste manganese slag (the Mn grade is 18.4%) containing Mn (IV) into a process atmosphere-adjustable constant-temperature stirring reaction kettle according to the liquid-solid ratio of 6:1, wherein the weight ratio of the COD to tetravalent manganese in organic wastewater is 0.2:1, and adding sulfuric acid to adjust the pH value of a solution to 1.2 (the addition amount of the sulfuric acid is 1.3 times of the theoretical required amount for leaching divalent manganese), thus obtaining raw material slurry. The raw material slurry is stirred and leached for 4 hours at the temperature of 120 ℃ and the stirring speed of 500r/min, so as to obtain reaction slurry. Filtering the reaction slurry to obtain a liquid phase product, wherein the COD concentration is reduced to 800mg/L, and Mn is added2+The concentration was 77 g/t.
(2) And (2) introducing the liquid-phase product obtained in the step (1) into a distillation device, distilling for 5 hours at 40 ℃ under the condition of induced air and reduced pressure to obtain a solid component containing refractory organic matters and metal salts, and recovering reduced-pressure distilled water.
(3) And (3) cooling the solid component obtained in the step (2), roasting at 600 ℃ for 4h, introducing air in the process to fully oxidize and decompose the organic pollutants, and circularly introducing the roasted flue gas into the step (1) for absorption to obtain the metal salt component without organic matters.
(4) Soaking the metal salt obtained in the step (3) in water according to the liquid-solid mass ratio of 3:1 to obtain a dissolved solution, wherein metal ions in the dissolved solution mainly comprise manganese ions, lead ions, zinc ions, copper ions and cadmium ions, and the pH value is reduced to 2.0 after the water soaking; adjusting the pH value of the dissolved solution to 6.7, and recovering heavy metals such as lead, zinc, copper, cadmium and the like to obtain a purified solution; adjusting the pH value of the purified liquid to 8.0, and recrystallizing to obtain a manganese sulfate monohydrate product with the purity of 99.2 percent and a manganese extraction liquid. Electrolytic Mn is prepared by adopting an electrolysis mode, and the solution after electrolytic manganese extraction is concentrated and crystallized to recover salt products such as sodium sulfate and the like. After the waste manganese slag is treated, the recovery rate of manganese is 98%, and the recovery rates of lead, zinc, copper and cadmium are respectively 96.6%, 96.7%, 98.4% and 94.3%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for treating organic wastewater is characterized by comprising the following steps:
carrying out redox reaction on the organic wastewater and a manganese oxide-containing material in the presence of acid to obtain reaction slurry containing divalent manganese;
carrying out solid-liquid separation on the reaction slurry to obtain a liquid-phase product containing divalent manganese;
removing the solvent in the liquid-phase product to obtain a precipitated material;
and carrying out oxidizing roasting on the precipitated materials to decompose residual organic matters in the precipitated materials to obtain a metal salt product containing bivalent manganese.
2. The method for treating organic wastewater according to claim 1, wherein the organic wastewater is acidic, neutral or weakly alkaline wastewater, the COD concentration in the organic wastewater is not less than 10000mg/L, and preferably the COD concentration in the organic wastewater is 10000-200000 mg/L.
3. The method for treating organic wastewater according to claim 2, wherein the liquid-solid weight ratio of the organic wastewater to the manganese oxide-containing material is (2-10): 1; preferably, the weight ratio of COD in the organic wastewater to tetravalent manganese in the manganese oxide-containing material is (0.1-0.3): 1.
4. The method for treating organic wastewater according to any one of claims 1 to 3, wherein the acid is selected from sulfuric acid, hydrochloric acid, nitric acid, or industrial waste acid, preferably the acid is sulfuric acid; preferably, the dosage of the acid is 1-2 times of the theoretical dosage required by leaching the metal ions in the manganese oxide-containing material.
5. The method for treating organic wastewater according to any one of claims 1 to 3, wherein the manganese oxide-containing material is selected from pyrolusite, manganese nodule, MnO-containing material2One or more of waste materials; preferably, the particle size of the manganese oxide-containing material is less than or equal to 0.01 mm.
6. The method for treating organic wastewater according to any one of claims 1 to 3, wherein the redox reaction is carried out under stirring at a stirring speed of 300 to 600 r/min; preferably, the temperature of the oxidation-reduction reaction is 25-200 ℃, more preferably 70-90 ℃, and the time of the oxidation-reduction reaction is 0.5-4 h.
7. The method for treating organic wastewater according to any one of claims 1 to 3, wherein a volatile gas is obtained during the oxidation-reduction reaction, and the method further comprises: and (3) absorbing the volatile gas by using dilute acid, water or the organic wastewater after adding acid.
8. The method for treating organic wastewater according to any one of claims 1 to 3, wherein the step of removing the solvent in the liquid-phase product comprises: carrying out reduced pressure distillation on the liquid-phase product to obtain the precipitated material; the distillation temperature in the reduced pressure distillation process is 40-60 ℃, and the distillation time is 2-12 h.
9. The method for treating organic wastewater according to any one of claims 1 to 3, wherein in the process of oxidizing roasting the precipitated material, the roasting temperature is 600 to 650 ℃, and the roasting time is 0.5 to 2 hours; preferably, the oxidizing roasting process results in flue gas, and the treatment method further comprises returning the flue gas to the redox reaction step.
10. The method for treating organic wastewater according to any one of claims 1 to 3, wherein after obtaining the metal salt product, the method further comprises:
dissolving the metal salt product with water to obtain a dissolved solution;
adjusting the pH value of the dissolving solution to 5.5-7.5 to obtain a purified solution;
adjusting the pH value of the purified solution to be alkalescent, and then recrystallizing to obtain a manganous salt and a manganese-extracted solution;
and recovering salts in the manganese extraction liquid.
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