CN117049726A - 一种含氰或腈废水的处理方法 - Google Patents
一种含氰或腈废水的处理方法 Download PDFInfo
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- CN117049726A CN117049726A CN202311050767.0A CN202311050767A CN117049726A CN 117049726 A CN117049726 A CN 117049726A CN 202311050767 A CN202311050767 A CN 202311050767A CN 117049726 A CN117049726 A CN 117049726A
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- wastewater
- cyanide
- chlorine
- weight percent
- nitrile
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- 239000002351 wastewater Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 36
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 16
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000460 chlorine Substances 0.000 claims abstract description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052693 Europium Inorganic materials 0.000 claims description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical group Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 4
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- -1 cyanides oxychloride Chemical class 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 description 2
- 108050008072 Cytochrome c oxidase subunit IV Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- PANJMBIFGCKWBY-UHFFFAOYSA-N iron tricyanide Chemical compound N#C[Fe](C#N)C#N PANJMBIFGCKWBY-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229920006391 phthalonitrile polymer Polymers 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- NKCCODPFBDGPRJ-UHFFFAOYSA-N nitridocarbon(1+) Chemical compound N#[C+] NKCCODPFBDGPRJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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
- C02F1/66—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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/763—Devices for the addition of such compounds in gaseous form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明公开了一种含氰或腈废水的处理方法,包括以下步骤:(1)加入含氯氧化剂;(2)调节含氰或腈废水的pH值至9.0~13.0;(3)然后将步骤(2)的废水送至催化反应器内进行氧化反应。使用本发明处理后的含氰废水中的总氰含量可明显降低,残留ClO‑含量<10mg/L,满足废水ORP<200mv要求;本发明可以在较低的次氯酸钠用量的情况下,通过一级催化反应器实现废水中CN‑的高效处理。
Description
技术领域
本发明涉及有机废水处理领域,具有涉及一种含氰或腈废水的处理方法。
背景技术
含氰废水一般源于选矿、金属加工、有色金属冶炼、炼焦、电镀、电子、制革化工、仪表等工业生产过程。不同的生产性质,废水的成分和性质也不相同。氰化物属于剧毒物,对人体的毒性主要是与高铁细胞色素酶结合,生成氰化高铁细胞色素氧化酶而失去传递氧的作用,引起组织窒息。水中氰化物可分为简单氰化物和络合氰化物两种。络合氰化物的毒性小的多。含有铜氰和银氰络合阴离子的稀溶液,对鱼类的剧毒性,主要是由未离解离子的毒性造成的。铁氰络合离子非常稳定,没有明显的毒性,但在稀溶液中,经阳光直接照射,容易发生迅速的光解作用,产生有毒的HCN。
采用氯氧化氰化物,使其分解成低毒物或无毒物的方法叫氯氧化法。一般含氯药剂有氯气、液氯、漂白粉、次氯酸钙和次氯酸钠等。上述物质在溶液中都依靠生成OCl-,然后进行氧化反应。由于氯氧化法在碱性条件下进行,故又称碱性氯化法。碱性氯化法的原理是在碱性介质中,首先用含氯药剂使废水中的氰化物氧化为氰酸盐,进一步氧化为二氧化碳和氮。碱性氯化法适用于水量和浓度均可变的含氰废水处理。其缺点是处理后有余氯,产生的氯化氰气体毒性很大。由于碱性条件下氯以ClO-形式存在,氧化能力不如酸性条件下HClO强,酸性氯化法是使氯在酸性溶液中水解后主要以HClO形式存在,能加速氧化提高次氯酸的利用率,从而达到了降低氯耗的目的,但该过程会生成HCN和Cl2从废水中逃逸,对环境造成较大的危害。
专利CN106966488A公开了一种次氯酸钠-超声复合处理含氰废水系统,采用二级次氯酸钠破氰的工艺,在第一步破氰的过程中采用超声进行复合,提高氰根的处理深度,减少次氯酸钠的用量,缩短停留时间,但是设备结构复杂,同时无法处理多余的次氯酸钠。
专利CN102502994A公开了一种低浓度含氰废水的处理方法及系统,将膜分离和催化湿式氧化两种技术的结合,将低浓度的含氰废水浓缩后经催化湿式氧化的方法进行处理,但该方法一次投资和运行成本均较高。
发明内容
为解决上述问题,本发明提供了一种含氰或腈废水的处理方法。本发明的方法可将CN-一步法氧化为CO2和N2,无需进行pH调节后二次氧化,且不会残留ClO-,无需进行亚硫酸钠等还原剂进行还原,氧化效率高,ORP值低。
一种含氰或腈废水的处理方法,包括以下步骤:
(1)加入含氯氧化剂;
(2)调节含氰或腈废水的pH值至9.0~13.0。
(3)然后将步骤(2)的废水送至催化反应器内进行氧化反应。
优选的,所述步骤(1)在10~80℃温度下加入含氯氧化剂。
优选的,步骤(2)中,采用无机酸或无机碱调节pH值。
优选的,所述步骤(2)在10~80℃温度下进行。
优选的,所述的含氯氧化剂为次氯酸盐、次氯酸、ClO2、氯气中的一种或多种,所述次氯酸盐选自次氯酸钠、次氯酸钙等中的一种或多种。
优选的,所述的含氯氧化剂的加量与含氰或腈废水中氰酸根CN-摩尔比为1∶1~10∶1。
优选的,步骤(3)在催化剂存在下进行,所述催化剂包括载体、活性组分和助剂,其中,载体为氧化铝、氧化钛中的一种或者两种,活性组分为铁、镍、锰、铜中的一种或者多种,助剂为锑或铕中的一种或者多种。
优选的,以所述的载体的质量计,所述的活性组分含量为:镍0.5-5.0wt%,铁0-5.0wt%,锰0-5.0wt%,铜0-5.0wt%。
优选的,所述的活性组分含量为:镍2.0-4.0wt%,铁0.5-2.0wt%,锰0.5-2.0wt%,铜0.5-2.0wt%。
优选的,以所述的载体质量计,所述的助剂的含量为:锑0-0.05wt%,铕0.01-0.05wt%。
催化剂中,活性组分及助剂主要以氧化物形态存在。
优选的,所述催化剂可采用现有的金属负载催化剂制备方法制备,如浸渍法,本发明中不作特别限定。
优选的,步骤(3)中,废水的体积空速为0.1-10h-1。
优选的,处理前含氰或腈废水中CN-含量10-1000mg/L。
本发明含氰或腈废水可以为生产间苯二甲腈产生的工艺废水。
优选的,步骤(3)中,反应温度为40-50℃,压力为常压。本发明的废水在催化剂反应器内可将CN-一步氧化为CO2和N2,处理后的废水中CN-含量明显降低,ORP值降低。
本发明与现有技术相比,本发明的优势在于:
现有技术中仅采用含氯氧化剂对CN-进行处理,但是氯化过程流程复杂,需多次pH调节,且低pH条件下存在剧毒HCN和Cl2溢出的风险,残余次氯酸钠需亚硫酸钠还原,控制参数要求高,处理效率不稳定。本发明的方法通过催化氧化反应可以诱发次氯酸钠产生羟基自由基,可以彻底的氧化氰根,最大化发挥次氯酸钠药剂使用效果,克服了现有技术对高浓度含氰废水处理困难的不足,本发明的催化剂各组分互相协同,使次氯酸钠分解更彻底,使处理后废水CN-浓度达标,处理效果稳定,相比于双氧水氧化法、臭氧氧化法和电解氧化法存在运行或投资成本的优势。
具体实施方式
下面通过具体实施例对本发明做进一步说明,本发明所述实施例只是作为对本发明的说明,不限制本发明的范围。
原料来源:含氰废水为采用间二甲苯、氨气和空气,在流化床内进行氨氧化反应制备间苯二甲腈的废水,该反应在生成间苯二甲腈的同时,会产生一定量的HCN和H2O,一般形成总氰根浓度300-800mg/L、氨氮浓度10000-15000mg/L,COD浓度8000-10000mg/L的废水。
实施例1
本实施例中具体废水指标如下:
表1
取10L上述废水常温下(30℃)向其中按照含氯氧化剂与氰酸根CN-摩尔比3:1添加NaClO溶液(8wt%),采用2wt%的NaOH水溶液进行pH调节,调节至pH=10.0。将含氯氧化剂处理后的含氰废水送入装有催化剂的固定床反应器。
所述的催化剂的制备方法,将1900g的AlCl3·6H2O溶于10kg的30wt%的TiCl4溶液,然后与20kg的10wt%NaAlO2溶液在35℃下进行中和反应2h,采用氨水调节溶液pH至9,得到的沉淀物用去离子水洗涤,除去其中的Na+和Cl-,120℃下干燥4h,粉碎后过筛得到100~200目粉料,加入120g田箐粉,1000g的3wt%的硝酸充分捏合后,在挤条机上挤成3mm的长条,采用马弗炉中在500℃下焙烧,得到Al2O3-TiO2复合载体。取上述制备的氧化铝-氧化钛载体5kg置于真空浸渍瓶中,进行真空预处理30min,真空度为80KPa。同时取含铁0.1g/ml的硝酸铁水溶液500ml,含镍0.10g/ml的硝酸镍水溶液1000ml,含锑0.01g/ml的硝酸锑水溶液50ml,含铕0.01g/ml的硝酸铕水溶液50ml,加入到乙醇浓度为10wt%的乙醇水溶液中,配制成总体积为2000ml的浸渍液。将上述浸渍液加入到装有球形氧化铝-氧化钛载体的真空浸渍瓶中混合均匀后对球形氧化铝-氧化钛载体进行等体积浸渍,浸渍120min后,取出并置于烘箱内120℃干燥5h,然后在马弗炉内450℃焙烧3h。
所得催化剂中,以其中氧化铝的重量为基准计,各成分的量如下:铁1.0wt%,镍2.0wt%,锑0.01wt%,铕0.01wt%。
所述催化剂各组分如表2所示。
表2实施例1催化剂主要组成
催化反应温度50℃,体积空速为3h-1下,处理后的废水主要指标如下:
表3
实施例2
含氰废水指标如下:
表4
取10L上述废水常温下(30℃)向其中按照含氯氧化剂与氰酸根CN-摩尔比2:1添加NaClO溶液(8wt%),采用2wt%的HCl水溶液进行pH调节,调节至pH=9.5。将含氯氧化剂处理后的含氰废水送入装有催化剂的固定床反应器。
所述的催化剂的制备方法,将1900g的AlCl3·6H2O溶于10kg的30wt%的TiCl4溶液,然后与20kg的10wt%NaAlO2溶液在35℃下进行中和反应2h,采用氨水调节溶液pH至9,得到的沉淀物用去离子水洗涤,除去其中的Na+和Cl-,120℃下干燥4h,粉碎后过筛得到100~200目粉料,加入120g田箐粉,1000g的3wt%的硝酸充分捏合后,在挤条机上挤成3mm的长条,采用马弗炉中在500℃下焙烧,得到Al2O3-TiO2复合载体。取上述制备的氧化铝-氧化钛载体5kg置于真空浸渍瓶中,进行真空预处理30min,真空度为80KPa。同时取含锰0.1g/ml的硝酸锰水溶液500ml,含镍0.40g/ml的硝酸镍水溶液1000ml,含锑0.03g/ml的硝酸锑水溶液50ml,含铕0.02g/ml的硝酸铕水溶液50ml,加入到乙醇浓度为10wt%的乙醇水溶液中,配制成总体积为2000ml的浸渍液。将上述浸渍液加入到装有球形氧化铝-氧化钛载体的真空浸渍瓶中混合均匀后对球形氧化铝-氧化钛载体进行等体积浸渍,浸渍120min后,取出并置于烘箱内120℃干燥5h,然后在马弗炉内450℃焙烧3h。
所得催化剂中,以其中氧化铝的重量为基准计,各成分的量如下:锰1.0wt%,镍4.0wt%,锑0.03wt%,铕0.02wt%。
所述催化剂各组分如表5所示。
表5实施例2催化剂主要组成
催化反应温度50℃,体积空速为3h-1下,处理后的废水主要指标如下:
表6
实施例3
含氰废水指标如下:
表7
取10L上述废水常温下(30℃)向其中按照含氯氧化剂与氰酸根CN-摩尔比1:1添加NaClO溶液(6wt%),采用2wt%的NaOH水溶液进行pH调节,调节至pH=10.0。将含氯氧化剂处理后的含氰废水送入装有催化剂的固定床反应器。
所述的催化剂采用山东烟台百川汇通科技有限公司的球形氧化铝载体。取上述氧化铝载体5kg置于真空浸渍瓶中,进行真空预处理30min,真空度为80KPa。同时取含锰0.1g/ml的硝酸锰水溶液500ml,含镍0.025g/ml的硝酸镍、含锰0.10g/ml的硝酸锰、含铜0.10g/ml的硝酸铜水溶液1000ml,含锑0.02g/ml的硝酸锑水溶液50ml,含铕0.02g/ml的硝酸铕水溶液50ml,加入到乙醇浓度为10wt%的乙醇水溶液中,配制成总体积为2000ml的浸渍液。将上述浸渍液加入到装有球形氧化铝-氧化钛载体的真空浸渍瓶中混合均匀后对球形氧化铝-氧化钛载体进行等体积浸渍,浸渍120min后,取出并置于烘箱内120℃干燥5h,然后在马弗炉内500℃焙烧5h。
所得催化剂中,以其中氧化铝的重量为基准计,各成分的量如下:铁1.0wt%,镍0.5wt%,锰2.0wt%,铜2.0wt%,锑0.02wt%,铕0.02wt%。
所述催化剂各组分如表8所示。
表8实施例3催化剂主要组成
催化反应温度50℃,体积空速为1h-1下,处理后的废水主要指标如下:
表9
实施例4
含氰废水指标如下:
表10
取10L上述废水常温下(30℃)向其中按照含氯氧化剂与氰酸根CN-摩尔比5:1添加NaClO溶液(6wt%),采用2wt%的NaOH水溶液进行pH调节,调节至pH=12.0。将含氯氧化剂处理后的含氰废水送入装有催化剂的固定床反应器。
所述的催化剂采用山东烟台百川汇通科技有限公司的球形氧化铝载体。取上述氧化铝载体5kg置于真空浸渍瓶中,进行真空预处理30min,真空度为80KPa。同时取含铁0.10g/ml的硝酸铁水溶液500ml,含镍0.025g/ml的硝酸镍、含锰0.015g/ml的硝酸锰、含铜0.010g/ml的硝酸铜水溶液1000ml,含铕0.03g/ml的硝酸铕水溶液50ml,加入到乙醇浓度为10wt%的乙醇水溶液中,配制成总体积为2000ml的浸渍液。将上述浸渍液加入到装有球形氧化铝-氧化钛载体的真空浸渍瓶中混合均匀后对球形氧化铝-氧化钛载体进行等体积浸渍,浸渍120min后,取出并置于烘箱内120℃干燥5h,然后在马弗炉内500℃焙烧5h。
所得催化剂中,以其中氧化铝的重量为基准计,各成分的量如下:铁1.0wt%,镍0.5wt%,锰0.3wt%,铜0.2wt%,锑0.03wt%,铕0.02wt%。
所述催化剂各组分如表11所示。
表11实施例4催化剂主要组成
催化反应温度50℃,体积空速为5h-1下,处理后的废水主要指标如下:
表12
对比例1
含氰废水指标如下:
表13
取10L上述废水常温下(30℃)向其中按照含氯氧化剂与氰酸根CN-摩尔比2:1添加NaClO溶液(8wt%),采用2wt%的NaOH水溶液进行pH调节,调节至pH=10.5。将含氯氧化剂处理后的含氰废水送入装有催化剂的固定床反应器。
所述的催化剂的制备方法,将1900g的AlCl3·6H2O溶于10kg的30wt%的TiCl4溶液,然后与20kg的10wt%NaAlO2溶液在35℃下进行中和反应2h,采用氨水调节溶液pH至9,得到的沉淀物用去离子水洗涤,除去其中的Na+和Cl-,120℃下干燥4h,粉碎后过筛得到100~200目粉料,加入120g田箐粉,1000g的3wt%的硝酸充分捏合后,在挤条机上挤成3mm的长条,采用马弗炉中在500℃下焙烧,得到Al2O3-TiO2复合载体。
所述催化剂各组分如表14所示。
表14对比例1催化剂主要组成
催化反应温度50℃,体积空速为3h-1下,处理后的废水主要指标如下:
表15
对比例2
含氰废水指标如下:
表16
取10L上述废水常温下(30℃),采用专利CN102515388B一种高浓度含氰废水处理方法对上述废水进行处理。分三个阶段进行反应,一段采用氢氧化钙进行pH调节至pH=10.5,添加次氯酸钠(有效氯10%)5ml/L,反应时间30min;二段采用2wt%硫酸调节pH至pH=7.0,添加次氯酸钠(有效氯10%)5ml/L,反应时间30min;三段采用2wt%硫酸调节pH至pH=7.0,添加次氯酸钠(有效氯10%)3ml/L,反应时间30min。一段、二段氯化氧化为一个串联反应过程,总去除率为94%,但出水中CN-浓度仍高达33.3mg/L;三段氯化氧化在二段的基础上继续氧化未完全的反应,此段去除率为98%,最终出水CN-浓度为0.67mg/L。在pH=7的条件下,有部分次氯酸钠生成氯气从水相逃逸,水体残余NaClO约100mg/L,需加入亚硫酸钠进行还原。
催化反应温度50℃,体积空速为1h-1下,处理后的废水组成如下:
表17
Claims (8)
1.一种含氰或腈废水的处理方法,其特征在于,包括以下步骤:
(1)加入含氯氧化剂;
(2)调节含氰或腈废水的pH值至9.0~13.0;
(3)然后将步骤(2)的废水送至催化反应器内进行氧化反应。
2.根据权利要求1所述的处理方法,其特征在于,所述步骤(1)在10~80℃温度下加入含氯氧化剂;
优选的,所述的含氯氧化剂为次氯酸盐、次氯酸、ClO2、氯气中的一种或多种,所述次氯酸盐选自次氯酸钠、次氯酸钙中的一种或多种;
优选的,所述的含氯氧化剂的加量与含氰或腈废水中氰酸根CN-摩尔比为1∶1~10∶1。
3.根据权利要求1或2所述的处理方法,其特征在于,步骤(2)中,采用无机酸或无机碱调节pH值;
优选的,所述步骤(2)在10~80℃温度下进行。
4.根据权利要求1-3任一项所述的处理方法,其特征在于,处理前含氰或腈废水中CN-含量为10-1000mg/L;
优选的,含氰或腈废水为生产间苯二甲腈产生的工艺废水。
5.根据权利要求1-4任一项所述的处理方法,其特征在于,步骤(3)在催化剂存在下进行,所述催化剂包括载体、活性组分和助剂,其中,载体为氧化铝、氧化钛中的一种或者两种,活性组分为铁、镍、锰、铜中的一种或者多种,助剂为锑或铕中的一种或者多种。
6.根据权利要求5所述的处理方法,其特征在于,以所述的载体的质量计,所述的活性组分含量为:镍0.5-5.0wt%,铁0-5.0wt%,锰0-5.0wt%,铜0-5.0wt%;
优选的,所述的活性组分含量为:镍2.0-4.0wt%,铁0.5-2.0wt%,锰0.5-2.0wt%,铜0.5-2.0wt%;
优选的,以所述的载体质量计,所述的助剂的含量为:锑0-0.05wt%,铕0.01-0.05wt%;
优选的,催化剂中,活性组分及助剂主要以氧化物形态存在。
7.根据权利要求1-6任一项所述的处理方法,其特征在于,步骤(3)中,废水的体积空速为0.1-10h-1。
8.根据权利要求1-7任一项所述的处理方法,其特征在于,步骤(3)中,反应温度为40-50℃。
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