CN107311263A - A kind of method of wastewater treatment containing chromium ion and by-product chromium-containing catalyst - Google Patents
A kind of method of wastewater treatment containing chromium ion and by-product chromium-containing catalyst Download PDFInfo
- Publication number
- CN107311263A CN107311263A CN201710552358.9A CN201710552358A CN107311263A CN 107311263 A CN107311263 A CN 107311263A CN 201710552358 A CN201710552358 A CN 201710552358A CN 107311263 A CN107311263 A CN 107311263A
- Authority
- CN
- China
- Prior art keywords
- chromium
- semiconductor material
- waste water
- light
- inorganic semiconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011651 chromium Substances 0.000 title claims abstract description 171
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 68
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000006227 byproduct Substances 0.000 title claims abstract description 18
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 56
- 239000004065 semiconductor Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000002071 nanotube Substances 0.000 claims description 20
- 239000011858 nanopowder Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000001699 photocatalysis Effects 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 2
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical group C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 38
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 20
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 15
- 229910001868 water Inorganic materials 0.000 description 15
- 238000006356 dehydrogenation reaction Methods 0.000 description 14
- 238000013019 agitation Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 239000006228 supernatant Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 238000004088 simulation Methods 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 11
- 229910052700 potassium Inorganic materials 0.000 description 11
- 239000011591 potassium Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000011859 microparticle Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- -1 Pr2O3 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical class Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical class [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention provides a kind of wastewater treatment containing chromium ion and the method for by-product chrome catalysts, 0.74eV is less than with conduction band potential, the inorganic semiconductor material that energy gap is more than 2.1eV is photochemical catalyst, using ultraviolet light or natural light as light source, under light source irradiation, photochemical catalyst is removed into the dynamic Contact of waste water containing chromium ion that solid impurity processing and pH value are 4~9 with passing through, light-catalyzed reaction is carried out to be no less than 30 minutes, the hexavalent chromium in chromate waste water is set to be reduced into insoluble trivalent chromium compound and zerovalent chromium, insoluble trivalent chromium compound and zerovalent chromium is supported on photocatalyst surface formation chromium photocatalyst composite, so as to realize the processing of the waste water containing chromium ion.The present invention can make total chromium concn and Cr (VI) concentration in sewage reach discharge standard and obtain accessory substance chromium-containing catalyst by light-catalyzed reaction, it not only avoid the secondary pollution that subsequent treatment is brought, and technique is simplified, improve economic benefit.
Description
Technical field
The present invention relates to technology of waste water control field, more particularly to a kind of administered using photochemical catalyst photo catalytic reduction is contained
The method of chromium ion waste water.
Background technology
Heavy metal in current water body and soil, especially chromium, are a kind of pollutions larger to environmental threat, it would be highly desirable to solve
Certainly.And in pollution of chromium waste water, chromium is predominantly in the form of Cr VI Cr (VI) and trivalent chromium Cr (III), wherein Cr's (VI)
Toxicity outclass Cr (III), and harm is big, difficult, and the duration is the primary process object that pollution of chromium is administered long.My sewage
There are strict requirements to chromium content in discharge, according to sewage drainage standard GB8978-1996, the concentration requirement of total chromium in sewage
Less than 1.5mg/L, Cr (VI) concentration requirement is less than 0.5mg/L.And for drinking water, the World Health Organization (WHO) and China
Drinking water standard GB 5749-2006 are required to Cr (VI) content less than 0.05mg/L.
During photo catalytic reduction is applied to Organic Pollution and heavy metal ion pollution processing in recent years.For example,
(Yang J, Lee S.Removal of Cr (VI) the and humic acid by using such as Jae-Kyu Yang
TiO2photocatalysis[J].Chemosphere,2006,63(10):1677-1684.) it is used as photocatalysis with titanium dioxide
Agent, under the irradiation of ultraviolet light, reduction removes the Cr (VI) in sewage.Fang Jiang etc. (Jiang F, Zheng Z, Xu Z,
et al.Aqueous Cr(VI)photo-reduction catalyzed by TiO2and sulfated TiO2[J]
.Journal of Hazardous Materials,2006,134(1-3):Titanium dioxide after 94-103.) being acidified with sulfuric acid
It is used as photochemical catalyst reduction Cr (VI).
In addition, in terms of using the photocatalyst treatment pollution of chromium in addition to titanium dioxide, (the Qin B, Zhao such as Bang Qin
Y,Li H,et al.Facet-dependent performance of Cu2O nanocrystal for
photocatalytic reduction of Cr(VI)[J].Chinese Journal of Catalysis,2015,36
(8):1321-1325.) with cuprous oxide as photochemical catalyst, under the irradiation of visible ray, Cr (VI) is reduced.And
(Liu T Y, Zhao L, Tan X, et the al.Effects of physicochemical factors on Cr (VI) such as Liu
removal from leachate by zero-valent iron and alpha-Fe2O3 nanoparticles.[J]
.Water Science&Technology A Journal of the International Association on Water
Pollution Research,2010,61(11):2759-2767.) use α-Fe2O3As photochemical catalyst visible ray irradiation
Under, Cr (VI) clearance can be reached more than 99.0%.
But Cr (VI) can only be reduced to water miscible trivalent chromium by above-mentioned utilized photochemical catalyst, and subsequent treatment is still needed
Coordinate the precipitation method, by pH value regulation to remove trivalent chromium completely, can equally produce chromium mud, bring after-treatment and secondary pollution
The problem of.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide in a kind of reducing waste water by light-catalyzed reaction
The method for the chromium-containing catalyst that Cr (VI) and by-product can be used directly, such a method can be made in sewage by light-catalyzed reaction
Total chromium concn and Cr (VI) concentration reach discharge standard and obtain accessory substance chromium-containing catalyst, not only avoid subsequent treatment institute band
The secondary pollution come, and technique is simplified, improve economic benefit.
The waste water of the present invention containing chromium ion processing and by-product chromium-containing catalyst method, with conduction band potential be less than-
The inorganic semiconductor material that 0.74eV, energy gap are more than 2.1eV is photochemical catalyst, using ultraviolet light or natural light as light source,
The amount of the photochemical catalyst is not less than 10 times of contained hexavalent chromium quality in waste water, under light source irradiation, by photochemical catalyst
With by removing the dynamic Contact of waste water containing chromium ion that solid impurity processing and pH value are 4~9, carrying out light-catalyzed reaction and being no less than
30 minutes, the hexavalent chromium in chromate waste water is set to be reduced into insoluble trivalent chromium compound and zerovalent chromium, insoluble trivalent chromium
Compound and zerovalent chromium are supported on photocatalyst surface formation chromium-photocatalyst composite, so as to realize the waste water containing chromium ion
Processing, the chromium-photocatalyst composite is chromium-containing catalyst.The pH value is 4~9 waste water containing chromium ion, including is passed through
Cross removal solid impurity and handle the waste water containing chromium ion that the pH value directly obtained is 4~9, also including by removing at solid impurity
The pH value obtained after being adjusted after reason with acid or alkali is 4~9 waste water containing chromium ion.
In the above method, the control of the pH value of waste water is the Cr (VI) because in highly acid and the environment of strong basicity 4~9
It is less than the Cr (III) generated after the photochemical catalyst reduction of -0.74eV, energy gap more than 2.1eV by conduction band potential to be difficult to be entered
One step is reduced to Cr (0) and (is converted under strong acidic condition under soluble Cr (III) ion, strong alkaline condition and is converted into Cr (OH)3
Flocculent deposit is converted into soluble Cr (III) ion), and the oxide Cr of trivalent chromium2O3It is amphoteric oxide, in highly acid
Or can be dissolved in the environment of strong basicity, thus Cr (VI) reduzate is difficult to the surface for being supported on photochemical catalyst, causes place
Sewage after reason also needs to carry out after-treatment.
The type of service of above-mentioned photochemical catalyst has inorganic semiconductor material powder, inorganic semiconductor material nanotube, particle diameter
The inorganic semiconductor material that is loaded with of particle, particle diameter not less than 0.1mm of inorganic semiconductor material formation not less than 0.1mm is received
The particle of ground rice body, the plate body for being loaded with inorganic semiconductor material film or the fixed bed for being filled with inorganic semiconductor material.Load
The particle for having inorganic semiconductor material nano-powder uses Fe3O4、CoFe2O4、ZnFe2O4、NiFe2O4, Fe, Co or Ni be as negative
Carrier is carried, the plate body of carrying inorganic semi-conducting material film is made using glass, plastics, ceramics or metal.
The above-mentioned inorganic semiconductor material as photochemical catalyst is ZrO2、Ga2O3、KTaO3、La2O3、MnO、Nd2O3、
Pr2O3、Sm2O3、SnO、SrTiO3、Tb2O3Or Yb2O3。
It is above-mentioned using ultraviolet light or natural light as radiation source, with reference to photocatalysis field Conventional wisdom, art technology
Personnel can voluntarily select suitable intensity of illumination, light source position to carry out light-catalyzed reaction for high concentration chrome wastewater.
Sacrifice agent can be also added during the light-catalyzed reaction, the sacrifice agent is organic pollution capturing agent or neutrality
Photocatalysis hole trapping agents.Addition sacrifice agent can improve the efficiency of light-catalyzed reaction.
The neutral photocatalysis hole trapping agents are methanol, ethanol, formates, sulphite or oxalates；Organic contamination
Thing capturing agent is phenol, glucose, crystal violet or methyl orange.
When photochemical catalyst type of service for inorganic semiconductor material powder, inorganic semiconductor material nanotube, particle diameter not
The inorganic semiconductor material that is loaded with of particle or particle diameter not less than 0.1mm of inorganic semiconductor material formation less than 0.1mm is received
During the particle of ground rice body, photochemical catalyst is added by removing the waste water containing chromium ion that solid impurity processing and pH value are 4~9
In, complete light-catalyzed reaction under stirring or bubbling state.Then, accessory substance chromium-containing catalyst is reclaimed by sedimentation.
When the type of service of photochemical catalyst is to be loaded with the plate body of inorganic semiconductor material film or be filled with inorganic semiconductor
During the fixed bed of material, place it in through removal solid impurity processing and pH value for 4~9 waste water containing chromium ion in, make
The waste water flow through the plate body for being loaded with inorganic semiconductor material film or be filled with inorganic semiconductor material fixed bed it is complete
Into light-catalyzed reaction.Then, by collecting the filler recovery accessory substance chromium-containing catalyst in the plate body or fixed bed that load film layer.
The removal solid impurity processing is that the solid in high concentration chrome wastewater is removed by prior art means such as filtering, centrifugations
Impurity, those skilled in the art can voluntarily select suitable technological means.
It is anti-against water gas shift reaction, ethane dehydrogenation that the accessory substance chromium-containing catalyst can be directly used for catalytic CO
Should, carbon dioxide methanation reaction, dehydrogenating propane reaction, catalyticing combustion process or olefin polymerization process.
The principle of the present invention is as follows：
Under light illumination, photochemical catalyst generation electronics (e-) and hole (h+), Cr (VI) obtains electron reduction for Cr (III), portion
Cr (III) is divided further to be reduced to zeroth order Cr, zeroth order Cr and Cr (III) oxide Cr2O3Photocatalyst surface is supported on to be formed
Chromium-photocatalyst composite, the compound is chromium-containing catalyst, is named as Cr@photochemical catalysts.
Sacrifice agent+h+→CO2+H2O
Cr6++3e-→Crs++3e-→Cr
Cr2O3+ Cr+ photochemical catalysts → Cr@photochemical catalysts
The present invention has the advantages that：
1st, sewage containing chromium ion is handled using the method for the invention, after testing, total chromium in the sewage after processing
Concentration is less than 0.0528mg/L, and Cr (VI) concentration is much smaller than 0.5mg/L, and Cr (VI) clearance is more than 99%, reaches national standard
GB8978-1996 discharge standards.
2nd, partly led more than the inorganic of 2.1eV because the method for the invention is less than -0.74eV, energy gap with conduction band potential
Body material is photochemical catalyst, and the pH value of waste water scope needed for zerovalent chromium and insoluble trivalent chromium compound is reduced into Cr (III)
Carry out preferably, thus sewage containing chromium ion has been handled using the method for the invention, carried out the mistake of light-catalyzed reaction
Zeroth order Cr and Cr (III) oxide that Cr (VI) is reduced into journey constantly loads to the surface of photochemical catalyst so that in sewage
Cr (VI) is constantly reduced, and after the completion of light-catalyzed reaction, zeroth order Cr and Cr (III) oxide that Cr (VI) is reduced into is substantially complete
Full load has arrived the surface of photochemical catalyst, forms chromium-photocatalyst composite, reclaims the sewage after chromium-photocatalyst composite
It is not required to carry out any processing and can reach national standard GB8978-1996 discharge standards, thus simplifies technique.
3rd, the chromium reclaimed-photocatalyst composite is non-toxic, can be directly used for catalytic CO against hydrosphere transformation
Reaction, ethane dehydrogenation reaction, carbon dioxide methanation reaction, dehydrogenating propane reaction, catalyticing combustion process or olefin polymerization process,
Remove the secondary pollution problem that conventional art subsequent treatment is brought from, improve the economic benefit of route for treatment of chromium containing waste water process.
Brief description of the drawings
Fig. 1 is photochemical catalyst nanometer ZrO in embodiment 12With accessory substance Cr@ZrO2Electromicroscopic photograph, wherein, photo (a) is
Nanometer ZrO2, photo (b) is accessory substance Cr@ZrO2。
Fig. 2 is simulated wastewater Cr (VI) concentration curve, the change of total chromium concn during light-catalyzed reaction in embodiment 1
Change curve and ZrO2Surface loads chromium content change curve.
Fig. 3 is ZrO in application examples 12、Cr@ZrO2It is catalyzed yield of ethene versus time curve during ethane dehydrogenation.
Fig. 4 be in embodiment 5 by sacrifice agent of phenol, ZrO2For photochemical catalyst photocatalytic degradation Cr (VI) curve.
Fig. 5 is the photo of leather waste water before and after the processing in embodiment 6, wherein, photo a is the leather waste water of before processing, is shone
Piece b is the leather waste water after processing.
Fig. 6 is photochemical catalyst ZrO in embodiment 82The electromicroscopic photograph of nanotube, wherein photo a are ZrO2Nanotube front；b
For ZrO2The nanotube back side；Photo c, d are respectively ZrO2Nanotube left and right side.
Fig. 7 is accessory substance Cr@ZrO in embodiment 82The electromicroscopic photograph of nanotube, wherein photo a are Cr@ZrO2Nanotube side
Face；Photo b is Cr@ZrO2Nanotube bottom surface.
Fig. 8 is Cr@ZrO in application examples 22Nanotube reacts as catalyst for ethane dehydrogenation, and yield of ethene is with the time
Change curve.
Fig. 9 is nanoscale Ga in embodiment 92O3With accessory substance Cr@Ga2O3Electromicroscopic photograph, wherein, photo a be nanometer
Ga2O3, photo b is accessory substance Cr@Ga2O3。
Figure 10 is Ga in application examples 32O3、Cr@Ga2O3It is used to ethene during being catalyzed ethane dehydrogenation as photochemical catalyst receive
Rate versus time curve.
Figure 11 is the SrTiO in embodiment 113Photo catalytic reduction Cr (VI) generates accessory substance Cr@SrTiO afterwards3Electronic Speculum shine
Piece.
Figure 12 is curves of the SnO in embodiment 12 as photochemical catalyst photocatalytic degradation Cr (VI).
Figure 13 is curves of the MnO in embodiment 13 as photochemical catalyst photocatalytic degradation Cr (VI).
Embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
The present embodiment prepares nanometer ZrO using sol-gel process2Photochemical catalyst, its preparation method is as follows：
Prepare A liquid：The 1.9095g concentrated sulfuric acids (concentration 98wt%), 35mL isopropanols, 10mL are added into the first container successively
Zirconium-n-butylate mixes A liquid；Prepare B liquid：Added successively into second container 17mL isopropanols, the mixing of 4mL deionized waters and
Into B liquid.Under magnetic stirring, B drops are added in A liquid, stops stirring curing 2h after dripping, then use baking oven dry at 80 DEG C
Dry 2h, places into Muffle furnace in 775 DEG C of calcining 3h, that is, obtains the block ZrO of white2.By obtained block ZrO2It is ground
Form ZrO2Nano-powder, shown in its SEM photograph such as Fig. 1 (a).
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 7, then weighs 0.1g ZrO2Powder is added in above-mentioned mixed liquor and will added
ZrO2The mixed liquor of powder irradiates with 500W mercury lamp as light source, under agitation completes light-catalyzed reaction for 120 minutes, then after centrifuge
Sedimentation 5 minutes, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@ZrO2(i.e. Cr2O3It is supported on Cr
ZrO2Chromium-photocatalyst composite of microparticle surfaces formation), shown in its SEM photograph such as Fig. 1 (b), it can see from Fig. 1 (b),
ZrO after light-catalyzed reaction2A large amount of floccules are presented in surface.
In test light catalytic reaction process be in different time points when reaction solution in Cr (VI) contents and total chrome content, and
Nanometer ZrO2The content of the chromium of upper load, test result is as shown in Figure 2.Figure it is seen that by 80min light-catalyzed reactions,
ZrO2Cr in reaction solution (VI) concentration can be reduced to 0.11mg/L, clearance is 99.4%, enables Cr (VI) concentration
Enough reach that total chrome content is 1.18mg/L in national standard GB8978-1996 discharge standards (Cr (VI) is less than 0.5mg/L), reaction solution,
Less than 1.5mg/L, the total chromium discharge standard of sewage in national standard GB8978-1996 is reached.Light-catalyzed reaction is after 120min, ZrO2
The content of upper chromium is ZrO2The 0.384% of quality.
Application examples 1
By the gained byproduct Cr@ZrO of embodiment 12For ethane dehydrogenation reaction, Cr@ZrO2Consumption is 100mg, gas flow
Under the conditions of 17mL/min, as a result as shown in figure 3, the yield of its maximum ethylene can reach 12.98%.
By ZrO2For ethane dehydrogenation reaction, ZrO2Consumption is 100mg, under the conditions of gas flow is 17mL/min, as a result such as
Shown in Fig. 3, the maximum yield of its ethene is 2.19%.
Above-mentioned experiment shows, Cr@ZrO2The catalyst reacted as ethane dehydrogenation, catalytic effect is substantially better than ZrO2。
Embodiment 2
Nanometer ZrO used in the present embodiment2Photochemical catalyst is same as Example 1, and preparation method is identical.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
By 0.5g ZrO2Photochemical catalyst is loaded on a fixed bed, and under 500W Hg lamp irradiation, it is that 8, concentration is to make pH value
1mg/L potassium bichromate solution 200ml circulates through fixed bed, completes light-catalyzed reaction within 55 minutes, then collects and fixes
Filler and drying in bed, obtain chromium-containing catalyst Cr@ZrO2(i.e. Cr2O3ZrO is supported on Cr2The chromium of microparticle surfaces formation-
Photocatalyst composite).
Embodiment 3
Nanometer ZrO used in the present embodiment2Photochemical catalyst is same as Example 1, and preparation method is identical.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml ethanol is as sacrifice agent and mixes for addition
Close uniform, it is 4 to add the concentrated sulfuric acid and adjust the pH value of above-mentioned mixed liquor, then weighs 0.1g ZrO2Powder adds above-mentioned mixed liquor
In and will add ZrO2The mixed liquor of powder irradiates completion photocatalysis in 120 minutes anti-under agitation with 500W mercury lamp as light source
Should, then after centrifugal sedimentation 5 minutes, remove supernatant liquor, take out sediment drying, obtain chromium-containing catalyst Cr@ZrO2(i.e. Cr2O3
ZrO is supported on Cr2Chromium-photocatalyst composite of microparticle surfaces formation).
Embodiment 4
Nanometer ZrO used in the present embodiment2Photochemical catalyst is same as Example 1, and preparation method is identical.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml ethanol is as sacrifice agent and mixes for addition
Close uniform, it is 9 to add sodium hydroxide and adjust the pH value of above-mentioned mixed liquor, then weighs 0.1g ZrO2Powder adds above-mentioned mixing
In liquid and it will add ZrO2The mixed liquor of powder is irradiated 120 minutes with 500W mercury lamp as light source and is completed photocatalysis under agitation
Reaction, then after centrifugal sedimentation 5 minutes, remove supernatant liquor, take out sediment drying, obtain chromium-containing catalyst Cr@ZrO2(i.e.
Cr2O3ZrO is supported on Cr2Chromium-photocatalyst composite of microparticle surfaces formation).
Embodiment 5
Nanometer ZrO used in the present embodiment2Photochemical catalyst is same as Example 1, and preparation method is identical.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml phenol is as sacrifice agent and mixes for addition
Close uniform, the pH value of the mixed liquor of survey is 7, then weighs 0.1g ZrO2Powder adds in above-mentioned mixed liquor and will add ZrO2Powder
The mixed liquor of body is irradiated completed within 120 minutes light-catalyzed reaction under agitation with 500W mercury lamp as light source, then rear centrifugal sedimentation 5
Minute, supernatant liquor is removed, sediment drying is taken out, obtains chromium-containing catalyst Cr@ZrO2(i.e. Cr2O3ZrO is supported on Cr2It is micro-
Chromium-photocatalyst composite that grain surface is formed).ZrO2It is as shown in Figure 4 to Cr (VI) degradation results
Embodiment 6
Nanometer ZrO used in the present embodiment2Photochemical catalyst is same as Example 1, and preparation method is identical.
The present embodiment is handled certain factory's leather waste water, and the concentration of suspension in leather waste water is up to 2000~
4000mg/L, total chrome content is more than 1200mg/L, and suspension is mainly grease, meat mincing, skin slag, lime, hair, silt, blood stains, with
And some different workshop sections waste water mixing when produce albumen wadding, Cr (OH)3Deng floccule.
The operation of the present embodiment is as follows：
The waste water removed first by filtration treatment after the most suspended substances in leather waste water, filtration treatment is shown in Fig. 5
(a), through measurement, Cr (VI) content is 72mg/L in waste water, and the pH value of waste water is 9.
20mL waste water is measured, 0.1g ZrO are then weighed2Photochemical catalyst is added in waste water.With 500W mercury lamp as light source,
Irradiate under agitation 150 minutes and complete light-catalyzed reaction, then using settling methods, place 1 hour, remove supernatant,
Sediment drying is taken out, chromium-containing catalyst Cr@ZrO are obtained2(i.e. Cr2O3ZrO is supported on Cr2Chromium-light of microparticle surfaces formation
Catalyst composites).
To processed Sewage treatment chromium-containing catalyst Cr@ZrO2Detected afterwards, measure Cr (VI) content for 0.32mg/L,
Less than 0.5mg/L, the total chromium emission request of sewage in national standard GB8978-1996 is reached.Reclaim chromium-containing catalyst Cr@ZrO2Afterwards useless
Water is shown in Fig. 5 (b).
Embodiment 7
The present embodiment uses ZrO2Porous particle is photochemical catalyst.
ZrO2Porous particle preparation method：Weigh 6.0g ZrO2Nano powder is (commercially available) to be added in beaker, then into beaker
50ml ammoniacal liquor (ammoniacal liquor of commercial available quality concentration 25%~28%) is added, is stirred 5 minutes, is filtered with aperture for 0.22 micron of micropore
Film suction filtration 20 minutes, then the ZrO that will be obtained after suction filtration2Nano powder is ground to form, the 1.0g naphthalenes powder by grinding and 0.5g fields is added
After the mixing of cyanines powder, the mixed powder is fitted into extruder and extruded with 2.5Mpa constant pressures, extrusion particle diameter is 0.5mm, through cutting
Knife is cut into long 1mm, a diameter of 0.5mm strip particle, and strip particle then is put into baking oven with 2 DEG C/min programming rate
200 DEG C of constant temperature 3h are warming up to, hot pressing is cooled to room temperature and obtains long 1mm, a diameter of 0.5mm ZrO after terminating2Porous particle.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
Measure 20ml potassium bichromates concentration be 10mg/L potassium bichromate solution, add 2ml glucose as sacrifice agent simultaneously
Well mixed, the pH value for measuring above-mentioned mixed liquor is 7, then weighs 0.3g ZrO2Porous particle is added in above-mentioned mixed liquor simultaneously
ZrO will be added2The mixed liquor of porous particle irradiates completion photocatalysis in 38 minutes anti-under agitation with 500W mercury lamp as light source
Should, then settling methods is used afterwards, 1 hour is placed, supernatant liquor is removed, sediment drying is taken out, obtains chromium-containing catalyst
Cr@ZrO2(i.e. Cr2O3ZrO is supported on Cr2Chromium-photocatalyst composite of microparticle surfaces formation).
Embodiment 8
The present embodiment uses ZrO2Nanotube is photochemical catalyst.
ZrO2Nanotube is prepared using anodizing, and its preparation method is：With 1mol/L (NH4)2SO4+ 0.5wt%NH4F
The aqueous solution be anodic oxidation electrolyte, be then under 0.25wt%, voltage are 20v in 15 DEG C, fluorinion concentration, using zirconium piece as
Anode, platinized platinum is negative electrode, and die opening remains 2cm, electrolysis time 2h, and magnetic agitation is added during electrolysis, that is, prepares ZrO2
Nanotube.After anodic oxidation terminates, by ZrO2Nanotube battle array uses deionized water rinsing immediately, then is dried up with nitrogen, is then placed in
In 80 DEG C of dry 5h in baking oven.Dry after terminating, collect ZrO2Nanotube, its electromicroscopic photograph is shown in Fig. 6.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 6, then weighs 0.2g ZrO2Nanotube is added in above-mentioned mixed liquor and will added
Enter ZrO2The mixed liquor of nanotube is irradiated completed within 120 minutes light-catalyzed reaction under agitation with 500W mercury lamp as light source, then after
Centrifugal sedimentation 5 minutes, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@ZrO2(i.e. Cr2O3It is negative with Cr
It is loaded in ZrO2Chromium-photocatalyst composite of nanotube surface formation), its electromicroscopic photograph is shown in Fig. 7.
Application examples 2
By the gained byproduct Cr@ZrO of embodiment 82It is directly used in anti-for ethane dehydrogenation after ethane dehydrogenation reaction and calcining
Should, reaction condition：Air speed 8400mL/ (g.min), gas composition ethane：Carbon dioxide is 1:1.As a result as shown in figure 8, Fig. 8 tables
It is bright, calcining and the byproduct Cr@ZrO not calcined2Equally there is greater activity for ethane dehydrogenation reaction.
Embodiment 9
The present embodiment uses nanometer Ga2O3It is used as photochemical catalyst.
Nanometer Ga2O3Prepared using hydro-thermal method, its preparation method is：1. with deionized water by gallium nitrate and surfactant
Dissolving, it is that 0.01mol/L, surfactant concentration are 3.2 × 10 to form gallium nitrate concentration-3Mol/L solution；2. ammoniacal liquor is used
(commercially available 25%~28% concentrated ammonia liquor) adjusts the pH value of above-mentioned solution to 8；3. the solution adjusted after pH value is put into polytetrafluoroethyl-ne
In the water heating kettle of alkene liner, then water heating kettle is put into automatic programme control baking oven in 140 DEG C of hydro-thermals 10 hours, then takes out water heating kettle
Naturally cool to room temperature；4. the supernatant liquor in water heating kettle is outwelled, bottom mixture is poured into centrifuge tube, 8000r/min from
The heart 5 minutes, siphons away a layer clear liquid, is cleaned afterwards with deionized water, then centrifuges, and is so repeated three times, then clear with absolute ethyl alcohol
Wash once, cleaned afterwards with deionized water；5. the solid sticky thing for centrifuging bottom of the tube is dried 12 together with centrifuge tube at 50 DEG C
Hour；6. dried solid product is poured into porcelain boat, is put into tube furnace, in being baked and banked up with earth at 900 DEG C 3 hours, obtains Ga2O3Nanometer
Powder, its electromicroscopic photograph is shown in Fig. 9 (a).
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 7, then weighs 0.1g Ga2O3Nano powder is added in above-mentioned mixed liquor and will added
Enter Ga2O3The mixed liquor of nano powder is irradiated completed within 160 minutes light-catalyzed reaction under agitation with 500W mercury lamp as light source, then after
Centrifugal sedimentation 5 minutes, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@Ga2O3(i.e. Cr2O3It is negative with Cr
It is loaded in Ga2O3Chromium-photocatalyst composite of microparticle surfaces formation), its electromicroscopic photograph is shown in Fig. 9 (b).
From fig. 9, it can be seen that nanometer Ga2O3Photochemical catalyst shape size is uniform, and outer surface is rougher, there are a large amount of gullies；
Chromium-containing catalyst Cr@Ga2O3Surface becomes relative smooth, and gully structure substantially shoals, and illustrates Cr2O3Ga is supported on Cr2O3It is micro-
Grain surface.
Application examples 3
By the gained byproduct Cr@Ga of embodiment 92O3For ethane dehydrogenation reaction, Cr@Ga2O3Consumption is 100mg, gas stream
Measure as under the conditions of 17mL/min, as a result as shown in Figure 10.
By Ga2O3For ethane dehydrogenation reaction, Ga2O3Consumption is 100mg, under the conditions of gas flow is 17mL/min, as a result
As shown in Figure 10.
From fig. 10 it can be seen that Cr@Ga2O3The catalyst reacted as ethane dehydrogenation, catalytic effect is substantially better than Ga2O3。
Embodiment 10
The present embodiment uses nanometer La2O3It is used as photochemical catalyst.
Nanometer La2O3Prepared using hydro-thermal method, its preparation method is：1. 0.2630gCTAB (cetyl trimethyls are weighed
Ammonium bromide), add 30ml deionized water wiring solution-formings；2. 0.5860g lanthanum chlorides are added to continue to stir, are formed transparent, homogeneous, steady
Fixed solution；3. the ammoniacal liquor that 0.1-0.6ml concentration is 25wt% is added dropwise into above-mentioned solution, solution becomes translucent, glue, then
Continue to stir one hour；4. the solution being stirred is transferred in 50ml water heating kettles, water heating kettle is put into baking oven and added at 80 DEG C
Hot 24h, after heating is finished, autoclave is taken out from baking oven, after the temperature of autoclave is down to room temperature, is centrifuged, and receive
Collect white precipitate therein, white precipitate is washed into the removal of impurity with distilled water and absolute ethyl alcohol alternate repetition, then at 60 DEG C
Dry 2h and obtain La2O3Nano-powder.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 7, then weighs 0.1g La2O3Nano powder is added in above-mentioned mixed liquor and will added
Enter La2O3The mixed liquor of nano powder is irradiated completed within 180 minutes light-catalyzed reaction under agitation with 500W mercury lamp as light source, then after
Centrifugal sedimentation 5 minutes, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@La2O3(i.e. Cr2O3It is negative with Cr
It is loaded in La2O3Chromium-photocatalyst composite of microparticle surfaces formation).
Embodiment 11
The present embodiment uses nanometer SrTiO3It is used as photochemical catalyst.
Nanometer SrTiO3Prepared using hydro-thermal method, its preparation method is：Weigh 0.01mol butyl titanates and be dissolved in and be equipped with
A liquid is made into the beaker of 50ml isopropanols；Weigh 0.01mol strontium nitrates and be dissolved in the beaker equipped with 50mL water and be made into B solution.
B solution is added dropwise in solution A under stirring, 100mL concentration is then added and is well mixed for 2mol/L KOH solution.Will be above-mentioned
Mixing suspension is moved in the high pressure water heating kettle of polytetrafluoroethyllining lining, and water heating kettle is put into baking oven and preheats 1h at 90 DEG C,
190 DEG C of reaction 3h are then heated to, after heating is finished, autoclave is taken out from baking oven, treats that the temperature of autoclave is down to room temperature
Afterwards, centrifuge, and collect precipitation therein, by precipitation distilled water and acetone respectively cleaning 3 times, then in 60 DEG C of dry 24h
Obtain SrTiO3Nano-powder.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 7, then weighs 0.1g SrTiO3Nano powder is added in above-mentioned mixed liquor and incited somebody to action
Add SrTiO3The mixed liquor of nano powder is irradiated 260 minutes with 500W mercury lamp as light source and is completed light-catalyzed reaction under agitation,
Centrifugal sedimentation 5 minutes after again, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@SrTiO3(i.e. Cr2O3
SrTiO is supported on Cr3Chromium-photocatalyst composite of microparticle surfaces formation), its electromicroscopic photograph is as shown in Figure 11.
Embodiment 12
The present embodiment is used as photochemical catalyst using commercially available SnO powder.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 7, then weigh 0.1g SnO powder and add in above-mentioned mixed liquor and will add
The mixed liquor of SnO powder irradiates with 500W mercury lamp as light source, under agitation completes light-catalyzed reaction for 980 minutes, then after centrifuge
Sedimentation 5 minutes, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@SnO (i.e. Cr2O3It is supported on Cr
Chromium-photocatalyst composite that SnO powder surface is formed).SnO is as shown in figure 12 to Cr (VI) degradation results.
Apply example 13
The present embodiment is used as photochemical catalyst using commercially available MnO powder.
The present embodiment is tested with potassium bichromate solution simulation waste water containing chromium ion, is operated as follows：
The potassium bichromate solution that 20ml potassium bichromates concentration is 10mg/L is measured, 2ml methanol is as sacrifice agent and mixes for addition
Close uniform, the pH value for measuring above-mentioned mixed liquor is 7, then weigh 0.1g MnO powder and add in above-mentioned mixed liquor and will add
The mixed liquor of MnO powder irradiates with 500W mercury lamp as light source, under agitation completes light-catalyzed reaction for 830 minutes, then after centrifuge
Sedimentation 5 minutes, removes supernatant liquor, takes out sediment drying, obtains chromium-containing catalyst Cr@MnO (i.e. Cr2O3It is supported on Cr
Chromium-photocatalyst composite that MnO powder surface is formed).MnO is as shown in figure 13 to Cr (VI) degradation results.
Claims (9)
1. a kind of waste water containing chromium ion processing and by-product chromium-containing catalyst method, it is characterised in that with conduction band potential be less than-
The inorganic semiconductor material that 0.74eV, energy gap are more than 2.1eV is photochemical catalyst, using ultraviolet light or natural light as light source,
The amount of the photochemical catalyst is not less than 10 times of contained hexavalent chromium quality in waste water, under light source irradiation, by photochemical catalyst
With by removing the dynamic Contact of waste water containing chromium ion that solid impurity processing and pH value are 4~9, carrying out light-catalyzed reaction and being no less than
30 minutes, the hexavalent chromium in chromate waste water is set to be reduced into insoluble trivalent chromium compound and zerovalent chromium, insoluble trivalent chromium
Compound and zerovalent chromium are supported on photocatalyst surface formation chromium-photocatalyst composite, so as to realize the waste water containing chromium ion
Processing, the chromium-photocatalyst composite is chromium-containing catalyst.
2. the method for wastewater treatment containing chromium ion according to claim 1 and by-product chrome catalysts, it is characterised in that light is urged
The type of service of agent has inorganic semiconductor material powder, inorganic semiconductor material nanotube, particle diameter inorganic not less than 0.1mm
The particle for being loaded with inorganic semiconductor material nano-powder of particle, particle diameter not less than 0.1mm of semi-conducting material formation, load
There is the plate body of inorganic semiconductor material film or be filled with the fixed bed of inorganic semiconductor material.
3. the method for wastewater treatment containing chromium ion according to claim 1 or 2 and by-product chrome catalysts, it is characterised in that make
It is ZrO for the inorganic semiconductor material of photochemical catalyst2、Ga2O3、KTaO3、La2O3、MnO、Nd2O3、Pr2O3、Sm2O3、SnO、
SrTiO3、Tb2O3Or Yb2O3。
4. the method for wastewater treatment containing chromium ion according to claim 1 or 2 and by-product chrome catalysts, it is characterised in that institute
State and sacrifice agent is also added with during light-catalyzed reaction, the sacrifice agent is organic pollution capturing agent or neutral photocatalysis hole
Capturing agent.
5. the method for wastewater treatment containing chromium ion according to claim 4 and by-product chrome catalysts, it is characterised in that described
Neutral photocatalysis hole trapping agents are methanol, ethanol, formates, sulphite or oxalates；Organic pollution capturing agent is benzene
Phenol, glucose, crystal violet or methyl orange.
6. the method for wastewater treatment containing chromium ion according to claim 2 and by-product chrome catalysts, it is characterised in that work as light
The type of service of catalyst is the nothing of inorganic semiconductor material powder, inorganic semiconductor material nanotube, particle diameter not less than 0.1mm
The particle or particle diameter of the formation of machine semi-conducting material are not less than the 0.1mm particle for being loaded with inorganic semiconductor material nano-powder
When, by photochemical catalyst add through removal solid impurity processing and pH value for 4~9 waste water containing chromium ion in, stirring or rouse
Light-catalyzed reaction is completed under blister state.
7. the method for wastewater treatment containing chromium ion according to claim 2 and by-product chrome catalysts, it is characterised in that work as light
The type of service of catalyst is the plate body for being loaded with inorganic semiconductor material film or the fixed bed for being filled with inorganic semiconductor material
When, place it in by removing solid impurity processing and pH value is in 4~9 waste water containing chromium ion, makes waste water flowing
Light-catalyzed reaction is completed by the plate body for being loaded with inorganic semiconductor material film or the fixed bed for being filled with inorganic semiconductor material.
8. the method for wastewater treatment containing chromium ion according to claim 6 and by-product chrome catalysts, it is characterised in that pass through
Sedimentation reclaims chromium-containing catalyst.
9. the method for wastewater treatment containing chromium ion according to claim 7 and by-product chrome catalysts, it is characterised in that pass through
Collect the filler recovery chromium-containing catalyst in the plate body or fixed bed of load film layer.
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