CN107311263B - Method for treating wastewater containing chromium ions and by-producing chromium-containing catalyst - Google Patents
Method for treating wastewater containing chromium ions and by-producing chromium-containing catalyst Download PDFInfo
- Publication number
- CN107311263B CN107311263B CN201710552358.9A CN201710552358A CN107311263B CN 107311263 B CN107311263 B CN 107311263B CN 201710552358 A CN201710552358 A CN 201710552358A CN 107311263 B CN107311263 B CN 107311263B
- Authority
- CN
- China
- Prior art keywords
- chromium
- photocatalyst
- semiconductor material
- inorganic semiconductor
- wastewater
- 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.)
- Expired - Fee Related
Links
- 239000011651 chromium Substances 0.000 title claims abstract description 153
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 72
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002351 wastewater Substances 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000004065 semiconductor Substances 0.000 claims abstract description 36
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 32
- 239000006227 byproduct Substances 0.000 claims abstract description 18
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 239000002071 nanotube Substances 0.000 claims description 20
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011858 nanopowder Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 9
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 239000008103 glucose Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- 238000012856 packing Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 70
- 239000000243 solution Substances 0.000 description 43
- 239000011259 mixed solution Substances 0.000 description 39
- 238000005303 weighing Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 17
- 238000006356 dehydrogenation reaction Methods 0.000 description 16
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 13
- 229910052753 mercury Inorganic materials 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000635 electron micrograph Methods 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 7
- 239000010985 leather Substances 0.000 description 7
- 239000011859 microparticle Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000010438 heat treatment 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
- 239000002253 acid Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 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
- 238000005406 washing Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling 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
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 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
- 239000008187 granular material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis 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
- 238000001556 precipitation Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 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
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 244000275012 Sesbania cannabina Species 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
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 238000011109 contamination Methods 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 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
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 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
- 238000010335 hydrothermal treatment Methods 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
- 238000011221 initial treatment Methods 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 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
- 239000002105 nanoparticle Substances 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 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
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Images
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 invention provides a method for treating chromium-ion-containing wastewater and producing a byproduct chromium catalyst, which takes an inorganic semiconductor material with a conduction band potential of less than-0.74 eV and a forbidden band width of more than 2.1eV as a photocatalyst, takes ultraviolet light or natural light as a light source, and dynamically contacts the photocatalyst with the chromium-ion-containing wastewater which is treated by removing solid impurities and has a pH value of 4-9 under the irradiation of the light source to carry out a photocatalytic reaction for not less than 30 minutes, so that hexavalent chromium ions in the chromium-containing wastewater are reduced into an insoluble trivalent chromium compound and zero-valent chromium, and the insoluble trivalent chromium compound and the zero-valent chromium are loaded on the surface of the photocatalyst to form a chromium-photocatalyst compound, thereby realizing the treatment of the chromium-ion-containing wastewater. The method can make the total chromium concentration and the Cr (VI) concentration in the sewage reach the discharge standard through the photocatalytic reaction and obtain the byproduct chromium-containing catalyst, thereby not only avoiding the secondary pollution caused by the subsequent treatment, but also simplifying the process and improving the economic benefit.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for treating chromium ion-containing wastewater by photocatalytic reduction of a photocatalyst.
Background
At present, heavy metals in water and soil, especially chromium, are a pollution which has great threat to the environment and need to be solved urgently. In the chromium-polluted wastewater, the main existing forms of chromium are hexavalent chromium Cr (VI) and trivalent chromium Cr (III), wherein the toxicity of Cr (VI) is far better than that of Cr (III), and the chromium-polluted wastewater is high in harm, difficult to treat and long in duration and is the primary treatment object for chromium pollution control. According to the sewage discharge standard GB8978-1996, the concentration requirement of total chromium in sewage is less than 1.5mg/L, and the concentration requirement of Cr (VI) is less than 0.5 mg/L. For drinking water, the content of Cr (VI) is required to be less than 0.05mg/L by the World Health Organization (WHO) and the national drinking water standard GB 5749-.
In recent years, photocatalytic reduction is applied to the process of treating organic pollution and heavy metal ion pollution. For example, Jae-Kyu Yang et al (Yang J, Lee S. Removal of Cr (VI) and humic acid by using TiO2photocatalysis[J]Chemosphere,2006,63(10): 1677-. Fang Jiang et al (Jiang F, Zheng Z, Xu Z, et al. aquous Cr (VI) photo-reduction catalyzed by TiO2and sulfonated TiO2[ J]Journal of Hazardous Materials,2006,134(1-3):94-103.) reduction of Cr (VI) with titanium dioxide acidified with sulfuric acid as photocatalyst.
Furthermore, in the treatment of chromium contamination with photocatalysts other than titanium dioxide, Bang Qin et al (Qin B, ZhaoY, Li H, et al, face-dependent performance of Cu2O nanocrystalline for photocatalytic reduction of Cr (VI) [ J]The chip Journal of Catalysis,2015,36(8):1321-1325.) uses cuprous oxide as photocatalyst to reduce Cr (VI) under the irradiation of visible light. And Liu et al (Liu T Y, ZHao L, Tan X, et al. effects of physical factors on Cr (VI) removal from free salt by zero-value iron and alpha-Fe2O3 nanoparticles, [ J.].Water Science&Technology A Journal of the International Association on WaterPollution Research,2010,61(11):2759-2O3Under the irradiation of visible light, the removal rate of Cr (VI) as a photocatalyst can reach more than 99.0 percent.
However, the above-mentioned utilized photocatalyst can only reduce Cr (VI) into water-soluble trivalent chromium, and the subsequent treatment still needs to be matched with precipitation method, and the pH value is regulated to completely remove trivalent chromium, and can produce chromium mud, and can bring about the problems of secondary treatment and secondary pollution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for reducing Cr (VI) in wastewater through a photocatalytic reaction and preparing a by-product directly usable chromium-containing catalyst.
The method for treating the chromium-ion-containing wastewater and producing the byproduct of the chromium-containing catalyst takes an inorganic semiconductor material with the conduction band potential less than-0.74 eV and the forbidden band width more than 2.1eV as a photocatalyst, ultraviolet light or natural light is used as a light source, the amount of the photocatalyst is not less than 10 times of the mass of hexavalent chromium ions contained in the wastewater, under the irradiation of a light source, the photocatalyst is dynamically contacted with chromium ion-containing wastewater which is subjected to solid impurity removal treatment and has a pH value of 4-9, a photocatalytic reaction is carried out for no less than 30 minutes, hexavalent chromium ions in the chromium-containing wastewater are reduced into insoluble trivalent chromium compounds and zero-valent chromium, the insoluble trivalent chromium compounds and the zero-valent chromium are loaded on the surface of the photocatalyst to form a chromium-photocatalyst compound, thereby realizing the treatment of the wastewater containing the chromium ions, and the chromium-photocatalyst compound is the chromium-containing catalyst. The chromium ion-containing wastewater with the pH value of 4-9 comprises chromium ion-containing wastewater with the pH value of 4-9 directly obtained by removing solid impurities, and also comprises chromium ion-containing wastewater with the pH value of 4-9 obtained by adjusting with acid or alkali after removing solid impurities.
In the method, the pH value of the wastewater is controlled to be 4-9 because Cr (VI) generated after being reduced by a photocatalyst with a conduction band potential of less than-0.74 eV and a forbidden band width of more than 2.1eV is difficult to be further reduced into Cr (0) (converted into soluble Cr (III) ions under a strong acid condition and converted into Cr (OH) ions under a strong alkaline condition in a strong acid and strong alkaline environment3Flocculent precipitate or conversion to soluble Cr (iii) ions), and the oxide Cr of trivalent chromium2O3Is an amphoteric oxide and can be dissolved in strong acid or strong alkaline environment, so that the reduction product of Cr (VI) is difficult to be loaded on the surface of the photocatalyst, and the treated sewage needs to be subjected to secondary treatment.
The photocatalyst is used in the form of inorganic semiconductor material powder, inorganic semiconductor material nanotubes, particles of inorganic semiconductor material having a particle diameter of not less than 0.1mm, particles of inorganic semiconductor material-loaded nanopowder having a particle diameter of not less than 0.1mm, a plate body of inorganic semiconductor material-loaded film, or a fixed bed of inorganic semiconductor material loaded therein. The particles loaded with inorganic semiconductor material nano powder adopt Fe3O4、CoFe2O4、ZnFe2O4、NiFe2O4Fe, Co or Ni is used as a load carrier, and a plate body for loading the inorganic semiconductor material film is made of glass, plastic, ceramic or metal.
The inorganic semiconductor material as the photocatalyst is ZrO2、Ga2O3、KTaO3、La2O3、MnO、Nd2O3、Pr2O3、Sm2O3、SnO、SrTiO3、Tb2O3Or Yb2O3。
The above-mentioned ultraviolet light or natural light is used as the irradiation light source, refer to the conventional knowledge in the field of photocatalysis, and the skilled person can select the proper illumination intensity and light source position to make photocatalytic reaction on the chromium-containing sewage.
And a sacrificial agent can be added in the photocatalytic reaction process, wherein the sacrificial agent is an organic pollutant trapping agent or a neutral photocatalytic hole trapping agent. The addition of a sacrificial agent can increase the efficiency of the photocatalytic reaction.
The neutral photocatalytic hole trapping agent is methanol, ethanol, formate, sulfite or oxalate; the organic pollutant trapping agent is phenol, glucose, crystal violet or methyl orange.
When the photocatalyst is used in the form of particles formed by inorganic semiconductor material powder, inorganic semiconductor material nanotubes, inorganic semiconductor materials with the particle size not less than 0.1mm or particles loaded with inorganic semiconductor material nanopowder with the particle size not less than 0.1mm, the photocatalyst is added into chromium ion-containing wastewater which is treated by removing solid impurities and has the pH value of 4-9, and the photocatalytic reaction is completed under the stirring or bubbling state. Then, the by-product chromium-containing catalyst is recovered by a precipitation method.
When the photocatalyst is used in the form of a plate body supporting an inorganic semiconductor material film or a fixed bed packed with an inorganic semiconductor material, the photocatalyst is placed in chromium ion-containing wastewater which has been subjected to solid impurity removal treatment and has a pH of 4 to 9, and the wastewater is allowed to flow through the plate body supporting an inorganic semiconductor material film or the fixed bed packed with an inorganic semiconductor material to complete a photocatalytic reaction. The byproduct chromium-containing catalyst is then recovered by collecting the packing in the membrane-bearing plate or fixed bed.
The treatment for removing the solid impurities is to remove the solid impurities in the chromium-containing sewage by the prior technical means such as filtration, centrifugation and the like, and a person in the art can select a proper technical means.
The by-product chromium-containing catalyst can be directly used for catalyzing carbon monoxide reverse water-gas shift reaction, ethane dehydrogenation reaction, carbon dioxide methanation reaction, propane dehydrogenation reaction, catalytic combustion process or olefin polymerization process.
The principle of the invention is as follows:
under illumination, the photocatalyst generates electrons (e)-) And a cavity (h)+) Cr (VI) is reduced to Cr (III) by electrons, part of Cr (III) is further reduced to zero-valent Cr, zero-valent Cr and Cr (III) oxide Cr2O3The chromium-photocatalyst composite is loaded on the surface of the photocatalyst to form a chromium-containing catalyst, namely a chromium-containing catalyst named Cr @ photocatalyst.
Sacrificial agent + h+→CO2+H2O
Cr6++3e-→Crs++3e-→Cr
Cr2O3+ Cr + photocatalyst → Cr @ photocatalyst
The invention has the following beneficial effects:
1. the method is used for treating the sewage containing the chromium ions, and the detection shows that the total chromium concentration in the treated sewage is less than 0.0528mg/L, the concentration of Cr (VI) is far less than 0.5mg/L, and the removal rate of Cr (VI) is more than 99 percent, thereby achieving the national standard GB 0.0528-1996 discharge standard.
2. Because the method of the invention takes the inorganic semiconductor material with the potential of a conduction band less than-0.74 eV and the forbidden band width more than 2.1eV as the photocatalyst, and the pH value range of the wastewater required by the reduction of Cr (III) into zero-valent chromium and insoluble trivalent chromium compounds is optimized, the method of the invention is used for treating the wastewater containing chromium ions, the zero-valent Cr and Cr (III) oxide reduced from Cr (VI) is continuously loaded on the surface of the photocatalyst in the process of carrying out the photocatalytic reaction, so that the Cr (VI) in the wastewater is continuously reduced, after the photocatalytic reaction is finished, the zero-valent Cr and Cr (III) oxide reduced from Cr (VI) is basically and completely loaded on the surface of the photocatalyst to form a chromium-photocatalyst compound, and the wastewater after the chromium-photocatalyst compound is recovered can reach the national discharge standard GB8978-1996 without any treatment, thus simplifying the process.
3. The recovered chromium-photocatalyst compound has no toxicity, can be directly used for catalyzing carbon monoxide reverse water-gas shift reaction, ethane dehydrogenation reaction, carbon dioxide methanation reaction, propane dehydrogenation reaction, catalytic combustion process or olefin polymerization process, avoids the problem of secondary pollution caused by subsequent treatment in the traditional technology, and improves the economic benefit of the chromium-containing wastewater treatment process.
Drawings
FIG. 1 shows nano ZrO of photocatalyst in example 12And by-product Cr @ ZrO2Wherein the photograph (a) is nano ZrO2Photograph (b) shows the by-product Cr @ ZrO2。
FIG. 2 is a graph showing the change of Cr (VI) concentration, the change of total chromium concentration and ZrO in the wastewater simulated in example 1 during the photocatalytic reaction2Chromium content on surfaceA curve of variation.
FIG. 3 shows ZrO in application example 12、Cr@ZrO2Ethylene yield over time during catalytic ethane dehydrogenation.
FIG. 4 shows ZrO prepared by using phenol as a sacrificial agent in example 52The curve shows the photocatalytic degradation of Cr (VI) by the photocatalyst.
FIG. 5 is a photograph of leather wastewater before and after the leather wastewater treatment in example 6, wherein photograph a shows leather wastewater before the treatment and photograph b shows leather wastewater after the treatment.
FIG. 6 shows a photocatalyst ZrO in example 82Electron micrograph of nanotube, wherein photograph a is ZrO2Nanotube front side; b is ZrO2The back of the nanotube; pictures c and d are respectively ZrO2The left and right sides of the nanotube.
FIG. 7 is a diagram showing Cr @ ZrO by-produced in example 82Electron micrograph of nanotube, wherein a is Cr @ ZrO2Nanotube sides; photograph b is Cr @ ZrO2The bottom surface of the nanotube.
FIG. 8 is a diagram of Cr @ ZrO in application example 22The nanotube is used as catalyst for ethane dehydrogenation reaction, and the variation curve of ethylene yield along with time.
FIG. 9 shows nanoscale Ga in example 92O3And by-product Cr @ Ga2O3Wherein, the picture a is nano Ga2O3Photograph b shows by-product Cr @ Ga2O3。
FIG. 10 shows Ga in application example 32O3、Cr@Ga2O3The catalyst is used for catalyzing the change curve of ethylene yield along with time in the process of ethane dehydrogenation.
FIG. 11 shows SrTiO of example 113By-product Cr @ SrTiO generated after photocatalytic reduction of Cr (VI)3Electron micrograph of (a).
FIG. 12 is a graph showing the photocatalytic degradation of Cr (VI) by SnO acting as a photocatalyst in example 12.
FIG. 13 is a graph showing photocatalytic degradation of Cr (VI) by MnO as a photocatalyst in example 13.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
In this example, nano ZrO was prepared by sol-gel method2The preparation method of the photocatalyst comprises the following steps:
preparing a solution A: 1.9095g of concentrated sulfuric acid (with the concentration of 98 wt%), 35mL of isopropanol and 10mL of n-butyl zirconium are sequentially added into a first container and mixed to form solution A; preparing a solution B: and adding 17mL of isopropanol and 4mL of deionized water into the second container in sequence, and mixing to obtain solution B. Under the magnetic stirring, dripping the B liquid into the A liquid, stopping stirring and curing for 2h after dripping, drying for 2h at 80 ℃ by using an oven, and calcining for 3h at 775 ℃ in a muffle furnace to obtain white blocky ZrO2. The obtained bulk ZrO2Grinding to form ZrO2The SEM photograph of the nanopowder is shown in fig. 1 (a).
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
measuring 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of methanol as a sacrificial agent, uniformly mixing to obtain a mixed solution with the pH value of 7, and then weighing 0.1g of ZrO2Adding powder into the above mixed solution and adding ZrO2The mixed liquid of the powder takes a mercury lamp of 500W as a light source, the mixed liquid is irradiated for 120 minutes under stirring to complete the photocatalytic reaction, then the mixed liquid is centrifugally settled for 5 minutes, the supernatant fluid is removed, the precipitate is taken out and dried, and the chromium-containing catalyst Cr @ ZrO is obtained2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst composite formed on the surface of the fine particles), the SEM photograph thereof is shown in FIG. 1(b), and it can be seen from FIG. 1(b) that ZrO after the photocatalytic reaction2The surface exhibits a large amount of flocs.
Testing the Cr (VI) content and the total chromium content in the reaction solution at different time points in the photocatalytic reaction process, and testing the nano ZrO content2The content of chromium supported on the support is shown in fig. 2. As can be seen from FIG. 2, ZrO after 80min of photocatalytic reaction2Can reduce the concentration of Cr (VI) in the reaction liquid to 0.11mg/L, the removal rate is 99.4 percent, and the concentration of Cr (VI) can reach the discharge of national standard GB8978-1996According to the standard (Cr (VI) is less than 0.5mg/L), the total chromium content in the reaction liquid is 1.18mg/L and less than 1.5mg/L, and the total chromium discharge standard of sewage in the national standard GB8978-1996 is reached. After the photocatalytic reaction is carried out for 120min, ZrO2The upper chromium content being ZrO20.384% by mass.
Application example 1
The by-product Cr @ ZrO obtained in example 1 was added2For dehydrogenation of ethane, Cr @ ZrO2The result is shown in figure 3, the maximum ethylene yield can reach 12.98% under the conditions of 100mg and 17mL/min of gas flow.
ZrO 2 is mixed with2For dehydrogenation of ethane, ZrO2The maximum yield of ethylene was 2.19% as shown in FIG. 3, when the amount was 100mg and the gas flow rate was 17 mL/min.
The above experiment shows that Cr @ ZrO2As a catalyst for ethane dehydrogenation reaction, the catalyst effect is obviously superior to ZrO2。
Example 2
Nano ZrO used in this example2The photocatalyst was the same as in example 1 and the preparation method was the same.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
0.5g of ZrO2Loading the photocatalyst on a fixed bed, circulating 200ml of potassium dichromate solution with the pH value of 8 and the concentration of 1mg/L through the fixed bed under the irradiation of a 500W mercury lamp for 55 minutes to complete the photocatalytic reaction, collecting the filler in the fixed bed and drying to obtain the chromium-containing catalyst Cr @ ZrO2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the microparticles).
Example 3
Nano ZrO used in this example2The photocatalyst was the same as in example 1 and the preparation method was the same.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L is measured and added with 2ml of ethanolAdding concentrated sulfuric acid to adjust pH to 4, and weighing 0.1g ZrO2Adding powder into the above mixed solution and adding ZrO2The mixed liquid of the powder takes a mercury lamp of 500W as a light source, the mixed liquid is irradiated for 120 minutes under stirring to complete the photocatalytic reaction, then the mixed liquid is centrifugally settled for 5 minutes, the supernatant fluid is removed, the precipitate is taken out and dried, and the chromium-containing catalyst Cr @ ZrO is obtained2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the microparticles).
Example 4
Nano ZrO used in this example2The photocatalyst was the same as in example 1 and the preparation method was the same.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
weighing 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of ethanol as a sacrificial agent, uniformly mixing, adding sodium hydroxide to adjust the pH value of the mixed solution to 9, and weighing 0.1g of ZrO2Adding powder into the above mixed solution and adding ZrO2The mixed liquid of the powder takes a mercury lamp of 500W as a light source, the mixed liquid is irradiated for 120 minutes under stirring to complete the photocatalytic reaction, then the mixed liquid is centrifugally settled for 5 minutes, the supernatant fluid is removed, the precipitate is taken out and dried, and the chromium-containing catalyst Cr @ ZrO is obtained2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the microparticles).
Example 5
Nano ZrO used in this example2The photocatalyst was the same as in example 1 and the preparation method was the same.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
weighing 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of phenol as a sacrificial agent, uniformly mixing, measuring the pH value of the mixed solution to be 7, and then weighing 0.1g of ZrO2Adding powder into the above mixed solution and adding ZrO2The mixed solution of the powder is irradiated for 120 minutes under stirring by using a 500W mercury lamp as a light source to complete the photocatalysisCarrying out chemical reaction, then carrying out centrifugal sedimentation for 5 minutes, removing supernatant, taking out precipitate and drying to obtain the chromium-containing catalyst Cr @ ZrO2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the microparticles). ZrO (ZrO)2The results of Cr (VI) degradation are shown in FIG. 4
Example 6
Nano ZrO used in this example2The photocatalyst was the same as in example 1 and the preparation method was the same.
In the embodiment, the leather wastewater of a certain factory is treated, the concentration of suspended matters in the leather wastewater reaches 2000-4000 mg/L, the total chromium content is more than 1200mg/L, the suspended matters are mainly grease, minced meat, skin residue, lime, wool, silt and blood stains, and protein floc and Cr (OH) generated when the wastewater of different sections is mixed3And the like.
The operation of this example is as follows:
most of the suspended matter in the leather wastewater was removed by filtration, and the wastewater after filtration was shown in FIG. 5(a), and it was measured that the Cr (VI) content in the wastewater was 72mg/L and the pH of the wastewater was 9.
20mL of wastewater was measured out, and then 0.1g of ZrO was weighed out2The photocatalyst is added to the wastewater. Using 500W mercury lamp as light source, irradiating for 150 min under stirring to complete photocatalytic reaction, then adopting gravity settling method, standing for 1 hr, removing supernatant, taking out precipitate and drying to obtain chromium-containing catalyst Cr @ ZrO2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the microparticles).
Recovery of Cr @ ZrO catalyst from treated waste water2And then, detecting to obtain that the Cr (VI) content is 0.32mg/L and less than 0.5mg/L, thereby meeting the requirement of total chromium discharge of sewage in the national standard GB 8978-1996. Recovery of Cr @ ZrO of chromium-containing catalyst2The latter waste water is shown in FIG. 5 (b).
Example 7
ZrO was used in this example2The porous particles are photocatalysts.
ZrO2The preparation method of the porous particles comprises the following steps: 6.0g of ZrO were weighed2Adding the nano powder (sold in the market) into a beaker, adding 50ml of ammonia water (the commercial ammonia water with the mass concentration of 25-28%) into the beaker, stirring for 5 minutes, performing suction filtration for 20 minutes by using a microporous filter membrane with the pore diameter of 0.22 micrometer, and performing suction filtration to obtain ZrO2Grinding into nanometer powder, adding ground naphthalene powder 1.0g and sesbania powder 0.5g, mixing, extruding at 2.5MPa, extruding to obtain granules with diameter of 0.5mm, cutting with cutter to obtain strip-shaped granules with length of 1mm and diameter of 0.5mm, heating to 200 deg.C at 2 deg.C/min for 3 hr, hot pressing, and cooling to room temperature to obtain ZrO with length of 1mm and diameter of 0.5mm2Porous particles.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
measuring 20ml of potassium dichromate solution with potassium dichromate concentration of 10mg/L, adding 2ml of glucose as sacrificial agent, mixing uniformly to obtain a mixed solution with pH of 7, and weighing 0.3g of ZrO2Adding porous particles into the mixed solution and adding ZrO2The mixed solution of the porous particles uses a 500W mercury lamp as a light source, the mixed solution is irradiated for 38 minutes under stirring to complete the photocatalytic reaction, then the mixed solution is placed for 1 hour by adopting a gravity settling method, supernatant is removed, precipitate is taken out and dried, and the chromium-containing catalyst Cr @ ZrO is obtained2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the microparticles).
Example 8
ZrO was used in this example2The nanotubes are photocatalysts.
ZrO2The nanotube is prepared by an anodic oxidation method, and the preparation method comprises the following steps: with 1mol/L (NH)4)2SO4+0.5wt％NH4Using the aqueous solution of F as an anodic oxidation electrolyte, then using a zirconium sheet as an anode and a platinum sheet as a cathode at 15 ℃ and under the conditions that the fluorine ion concentration is 0.25 wt% and the voltage is 20v, keeping the inter-polar distance at 2cm, carrying out electrolysis for 2h, and adding magnetic stirring during electrolysis to prepare the ZrO2A nanotube. After the anodic oxidation is finished, ZrO is added2The nanotube array is immediately washed with deionized water and thenBlowing the mixture by nitrogen, and then drying the mixture for 5 hours in an oven at 80 ℃. After the drying is finished, collecting ZrO2The electron micrograph of the nanotube is shown in FIG. 6.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
measuring 20ml of potassium dichromate solution with potassium dichromate concentration of 10mg/L, adding 2ml of methanol as sacrificial agent, mixing uniformly to obtain mixed solution with pH of 6, and weighing 0.2g of ZrO2Adding nanotube into the above mixed solution and adding ZrO2The mixed solution of the nano-tube takes a 500W mercury lamp as a light source, the mixed solution is irradiated for 120 minutes under stirring to complete the photocatalytic reaction, then the mixed solution is centrifugally settled for 5 minutes, the supernatant fluid is removed, the precipitate is taken out and dried to obtain the chromium-containing catalyst Cr @ ZrO2(i.e., Cr)2O3And Cr is loaded on ZrO2Chromium-photocatalyst complexes formed on the surface of the nanotubes) and the electron micrograph thereof is shown in fig. 7.
Application example 2
The by-product Cr @ ZrO obtained in example 82Directly used for ethane dehydrogenation reaction and calcining and then used for ethane dehydrogenation reaction, and the reaction conditions are as follows: space velocity 8400mL/(g.min), gas composition ethane: the carbon dioxide is 1: 1. The results are shown in FIG. 8, where FIG. 8 shows the by-product Cr @ ZrO, calcined and uncalcined2Also has higher activity for ethane dehydrogenation reaction.
Example 9
This example uses nano Ga2O3As a photocatalyst.
Nano Ga2O3The preparation method adopts a hydrothermal method, and comprises the following steps: dissolving gallium nitrate and surfactant with deionized water to obtain gallium nitrate solution with concentration of 0.01mol/L and surfactant concentration of 3.2 × 10-3A mol/L solution; secondly, ammonia water (commercial 25% -28% strong ammonia water) is used for adjusting the pH value of the solution to 8; thirdly, putting the solution with the adjusted pH value into a hydrothermal kettle with a polytetrafluoroethylene lining, putting the hydrothermal kettle into an automatic program-controlled oven, carrying out hydrothermal treatment for 10 hours at 140 ℃, and taking out the hydrothermal kettle to naturally cool to room temperature; fourthly, pouring the supernatant liquor in the hydrothermal kettle, pouring the mixture at the bottom into a centrifuge tube,centrifuging at 8000r/min for 5 min, sucking away supernatant, washing with deionized water, centrifuging again, repeating for three times, washing with anhydrous ethanol once, and washing with deionized water; fifthly, drying the solid sticky matter at the bottom of the centrifuge tube and the centrifuge tube for 12 hours at 50 ℃; sixthly, pouring the dried solid product into a porcelain boat, putting the porcelain boat into a tube furnace, and baking the porcelain boat for 3 hours at 900 ℃ to obtain Ga2O3The electron micrograph of the nanopowder is shown in FIG. 9 (a).
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
weighing 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of methanol as a sacrificial agent, uniformly mixing to obtain a mixed solution with the pH value of 7, and weighing 0.1g of Ga2O3Adding the nanometer powder into the mixed solution and adding Ga2O3The mixed solution of the nano powder takes a mercury lamp of 500W as a light source, the mixed solution is irradiated for 160 minutes under stirring to complete the photocatalytic reaction, then the mixed solution is centrifugally settled for 5 minutes, the supernatant is removed, the precipitate is taken out and dried, and the chromium-containing catalyst Cr @ Ga is obtained2O3(i.e., Cr)2O3And Cr is supported on Ga2O3A chromium-photocatalyst composite formed on the surface of the fine particles), and an electron micrograph thereof is shown in fig. 9 (b).
As can be seen from FIG. 9, nano Ga2O3The shape and the size of the photocatalyst are uniform, the outer surface is rough, and a large number of gullies exist; chromium-containing catalyst Cr @ Ga2O3The surface becomes relatively smooth and the gully structure becomes shallow, which indicates that Cr is in the surface2O3And Cr is supported on Ga2O3The surface of the particles.
Application example 3
The by-product Cr @ Ga obtained in example 92O3For dehydrogenation of ethane, Cr @ Ga2O3The results are shown in FIG. 10, when the amount is 100mg and the gas flow rate is 17 mL/min.
Ga is mixed with2O3For dehydrogenation of ethane, Ga2O3The results are shown in FIG. 10, when the amount is 100mg and the gas flow rate is 17 mL/min.
As can be seen from FIG. 10, Cr @ Ga2O3As the catalyst for ethane dehydrogenation reaction, the catalytic effect is obviously superior to that of Ga2O3。
Example 10
This example uses nano-La2O3As a photocatalyst.
Nano La2O3The preparation method adopts a hydrothermal method, and comprises the following steps: weighing 0.2630g CTAB (cetyl trimethyl ammonium bromide), and adding 30ml deionized water to prepare solution; adding 0.5860g lanthanum chloride and stirring to form transparent, homogeneous and stable solution; thirdly, 0.1 to 0.6ml of ammonia water with the concentration of 25 weight percent is dripped into the solution, the solution becomes semitransparent and colloidal, and then the stirring is continued for one hour; transferring the stirred solution into a 50ml hydrothermal kettle, putting the hydrothermal kettle into an oven, heating for 24h at 80 ℃, taking the autoclave out of the oven after the heating is finished, cooling the temperature of the autoclave to room temperature, performing centrifugal separation, collecting white precipitate, washing the white precipitate with distilled water and absolute ethyl alcohol alternately and repeatedly to remove impurities, and drying for 2h at 60 ℃ to obtain La2O3And (3) nano powder.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
weighing 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of methanol as a sacrificial agent, uniformly mixing to obtain a mixed solution with the pH value of 7, and weighing 0.1g of La2O3Adding nanometer powder into the above mixed solution, and adding La2O3The mixed solution of the nano powder takes a mercury lamp of 500W as a light source, the mixed solution is irradiated for 180 minutes under stirring to complete the photocatalytic reaction, then the mixed solution is centrifugally settled for 5 minutes, the supernatant is removed, the precipitate is taken out and dried, and the chromium-containing catalyst Cr @ La is obtained2O3(i.e., Cr)2O3And Cr is loaded on La2O3Chromium-photocatalyst complexes formed on the surface of the microparticles).
Example 11
This example uses nano SrTiO3As a photocatalyst.
Nano SrTiO3The preparation method adopts a hydrothermal method, and comprises the following steps: weighing 0.01mol of tetrabutyl titanate, and dissolving in a beaker filled with 50ml of isopropanol to prepare solution A; 0.01mol of strontium nitrate is weighed and dissolved in a beaker filled with 50mL of water to prepare a solution B. The solution B is added dropwise into the solution A under stirring, and then 100mL of 2mol/L KOH solution is added and mixed evenly. Transferring the mixed suspension into a polytetrafluoroethylene-lined high-pressure hydrothermal kettle, putting the hydrothermal kettle into an oven, preheating for 1h at 90 ℃, heating to 190 ℃ for reaction for 3h, taking the autoclave out of the oven after heating is finished, centrifugally separating after the temperature of the autoclave is reduced to room temperature, collecting precipitates in the autoclave, respectively cleaning the precipitates for 3 times by using distilled water and acetone, and drying for 24h at 60 ℃ to obtain SrTiO3And (3) nano powder.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
weighing 20ml potassium dichromate solution with potassium dichromate concentration of 10mg/L, adding 2ml methanol as sacrificial agent, mixing well to obtain pH of the above mixed solution of 7, and weighing 0.1g SrTiO3Adding the nanometer powder into the mixed solution and adding SrTiO3The mixed solution of the nano powder takes a mercury lamp of 500W as a light source, the mixed solution is irradiated for 260 minutes under stirring to complete the photocatalytic reaction, then the mixed solution is centrifugally settled for 5 minutes, the supernatant is removed, the precipitate is taken out and dried, and the chromium-containing catalyst Cr @ SrTiO is obtained3(i.e., Cr)2O3And Cr supported on SrTiO3A chromium-photocatalyst composite formed on the surface of the fine particles), and an electron micrograph thereof is shown in fig. 11.
Example 12
Commercially available SnO powders were used as photocatalysts in this example.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
weighing 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of methanol as a sacrificial agent, uniformly mixing to obtain a mixed solution with the pH value of 7, weighing 0.1g of SnO powder, adding the mixed solution into the mixed solution, taking a 500W mercury lamp as a light source, stirring, and adding the SnO powderIrradiating for 980 min to complete photocatalytic reaction, centrifuging for 5 min, removing supernatant, taking out precipitate, and oven drying to obtain chromium-containing catalyst Cr @ SnO (i.e. Cr)2O3And Cr-photocatalyst composite formed by supporting Cr on the surface of SnO powder). The results of the SnO degradation of Cr (VI) are shown in FIG. 12.
Application example 13
This example uses commercially available MnO powder as the photocatalyst.
In this example, the experiment was performed by using a potassium dichromate solution to simulate chromium ion-containing wastewater, and the operations were as follows:
measuring 20ml of potassium dichromate solution with the potassium dichromate concentration of 10mg/L, adding 2ml of methanol as a sacrificial agent, uniformly mixing to obtain the pH value of the mixed solution of 7, then weighing 0.1g of MnO powder, adding the MnO powder into the mixed solution, irradiating the mixed solution with the MnO powder by using a 500W mercury lamp as a light source under stirring for 830 minutes to complete a photocatalytic reaction, then centrifugally settling for 5 minutes, removing a supernatant, taking out a precipitate and drying to obtain a chromium-containing catalyst Cr @ MnO (namely Cr @ MnO)2O3And Cr supported on the surface of MnO powder to form a chromium-photocatalyst composite). The results of MnO degradation to Cr (VI) are shown in FIG. 13.
Claims (8)
1. A method for treating wastewater containing chromium ions and producing a byproduct of a chromium-containing catalyst is characterized in that an inorganic semiconductor material with a conduction band potential of less than-0.74 eV and a forbidden band width of more than 2.1eV is used as a photocatalyst, ultraviolet light or natural light is used as a light source, the amount of the photocatalyst is not less than 10 times of the mass of hexavalent chromium ions contained in the wastewater, the photocatalyst is dynamically contacted with the chromium-containing ion wastewater which is treated by removing solid impurities and has a pH value of 4-9 under the irradiation of the light source, and a photocatalytic reaction is carried out for not less than 30 minutes to reduce the hexavalent chromium ions in the chromium-containing wastewater into an insoluble trivalent chromium compound Cr2O3And zero-valent chromium, insoluble trivalent chromium compounds Cr2O3And zero-valent chromium is loaded on the surface of the photocatalyst to form a chromium-photocatalyst compound, so that the treatment of the wastewater containing chromium ions is realized, and the chromium-photocatalyst compound is a chromium-containing catalyst;
the inorganic semiconductor material as the photocatalyst is ZrO2、Ga2O3、La2O3MnO, SnO or SrTiO3。
2. The method according to claim 1, wherein the photocatalyst is used in the form of inorganic semiconductor material powder, inorganic semiconductor material nanotubes, particles of inorganic semiconductor material having a particle diameter of not less than 0.1mm, particles of inorganic semiconductor material supported with a particle diameter of not less than 0.1mm, a plate body supported with an inorganic semiconductor material film, or a fixed bed packed with an inorganic semiconductor material.
3. The method for treating chromium-ion-containing wastewater and producing a byproduct chromium catalyst as claimed in claim 1 or 2, wherein a sacrificial agent is added in the photocatalytic reaction process, and the sacrificial agent is an organic pollutant trapping agent or a neutral photocatalytic hole trapping agent.
4. The method of claim 3, wherein the neutral photo-catalytic hole-trapping agent is methanol, ethanol, formate, sulfite or oxalate; the organic pollutant trapping agent is phenol, glucose, crystal violet or methyl orange.
5. The method of claim 2, wherein when the photocatalyst is used in the form of inorganic semiconductor material powder, inorganic semiconductor material nanotubes, particles formed from inorganic semiconductor material having a particle size of not less than 0.1mm, or particles loaded with inorganic semiconductor material nanopowder having a particle size of not less than 0.1mm, the photocatalyst is added to the chromium ion-containing wastewater treated to remove solid impurities and having a pH of 4 to 9, and the mixture is stirred or bubbled to form a suspension system with the wastewater to complete the photocatalytic reaction.
6. The method of claim 2, wherein when the photocatalyst is used in the form of a plate loaded with an inorganic semiconductor material film or a fixed bed loaded with an inorganic semiconductor material, the photocatalyst is placed in the chromium ion-containing wastewater treated to remove solid impurities and having a pH of 4 to 9, and the wastewater is allowed to flow through the plate loaded with an inorganic semiconductor material film or the fixed bed loaded with an inorganic semiconductor material to complete the photocatalytic reaction.
7. The method of claim 5, wherein the chromium-containing catalyst is recovered by sedimentation.
8. The method of claim 6, wherein the chromium-containing catalyst is recovered by collecting the packing in a plate body or a fixed bed supporting the membrane layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710552358.9A CN107311263B (en) | 2017-07-07 | 2017-07-07 | Method for treating wastewater containing chromium ions and by-producing chromium-containing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710552358.9A CN107311263B (en) | 2017-07-07 | 2017-07-07 | Method for treating wastewater containing chromium ions and by-producing chromium-containing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107311263A CN107311263A (en) | 2017-11-03 |
| CN107311263B true CN107311263B (en) | 2020-11-03 |
Family
ID=60177520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710552358.9A Expired - Fee Related CN107311263B (en) | 2017-07-07 | 2017-07-07 | Method for treating wastewater containing chromium ions and by-producing chromium-containing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107311263B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11780786B2 (en) | 2020-09-14 | 2023-10-10 | Chevron Phillips Chemical Company Lp | Transition metal-catalyzed production of alcohol and carbonyl compounds from hydrocarbons |
| US11839870B2 (en) | 2018-09-17 | 2023-12-12 | Chevron Phillips Chemical Company Lp | Modified supported chromium catalysts and ethylene-based polymers produced therefrom |
| US11969718B2 (en) | 2023-02-10 | 2024-04-30 | Chevron Phillips Chemical Company Lp | Modified supported chromium catalysts and ethylene-based polymers produced therefrom |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956519B (en) * | 2019-04-21 | 2021-11-12 | 贵州大学 | Method for removing hexavalent chromium and organic phenol pollutants in water through photochemical synergy |
| US11180435B2 (en) | 2019-09-16 | 2021-11-23 | Chevron Phillips Chemical Company, Lp | Chromium-catalyzed production of alcohols from hydrocarbons |
| CN112774685A (en) * | 2021-01-07 | 2021-05-11 | 杭州齐原叶环保科技有限公司 | Ca-doped Tb2O3/Fe2O3-GO composite material preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2493181A1 (en) * | 1980-11-05 | 1982-05-07 | Centre Nat Rech Scient | Photo:catalysts, esp. for photolysis of water - comprising semiconductor and group VIIa or Gp=VIII metal |
| CN101264953A (en) * | 2008-04-18 | 2008-09-17 | 中国科学院化学研究所 | Photochemical reduction method for treating chromium-containing waste water without additional reducing agent and sacrificial agent |
| CN101982240A (en) * | 2010-09-21 | 2011-03-02 | 淮北师范大学 | Design and preparation of high-activity narrow-band gap photocatalyst capable of selectively oxidizing alcohols and reducing nitro-compounds |
| CN102531095A (en) * | 2010-12-14 | 2012-07-04 | 佳龙科技工程股份有限公司 | Method for removing heavy metal in waste liquid |
| CN104773806A (en) * | 2015-04-08 | 2015-07-15 | 中国科学院化学研究所 | Preparation method of high-reducibility nano material and application of high-reducibility nano material in underground water pollution treatment |
| CN106362718A (en) * | 2016-08-17 | 2017-02-01 | 华南理工大学 | ZrO2/TiO2 composite photocatalyst and its preparation method and use |
-
2017
- 2017-07-07 CN CN201710552358.9A patent/CN107311263B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2493181A1 (en) * | 1980-11-05 | 1982-05-07 | Centre Nat Rech Scient | Photo:catalysts, esp. for photolysis of water - comprising semiconductor and group VIIa or Gp=VIII metal |
| CN101264953A (en) * | 2008-04-18 | 2008-09-17 | 中国科学院化学研究所 | Photochemical reduction method for treating chromium-containing waste water without additional reducing agent and sacrificial agent |
| CN101982240A (en) * | 2010-09-21 | 2011-03-02 | 淮北师范大学 | Design and preparation of high-activity narrow-band gap photocatalyst capable of selectively oxidizing alcohols and reducing nitro-compounds |
| CN102531095A (en) * | 2010-12-14 | 2012-07-04 | 佳龙科技工程股份有限公司 | Method for removing heavy metal in waste liquid |
| CN104773806A (en) * | 2015-04-08 | 2015-07-15 | 中国科学院化学研究所 | Preparation method of high-reducibility nano material and application of high-reducibility nano material in underground water pollution treatment |
| CN106362718A (en) * | 2016-08-17 | 2017-02-01 | 华南理工大学 | ZrO2/TiO2 composite photocatalyst and its preparation method and use |
Non-Patent Citations (2)
| Title |
|---|
| Nano-titania assisted photoreduction of Cr(VI) The role of the different TiO2 polymorphs;G. Cappelletti et al.;《Applied Catalysis B: Environmental 》;20070921;第78卷;摘要 * |
| 剥离MoS_2负载TiO_2的制备与甘油水溶液光催化制氢;周美华等;《高校化学工程学报》;20170630;第31卷(第03期);第610页第1-2段 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11839870B2 (en) | 2018-09-17 | 2023-12-12 | Chevron Phillips Chemical Company Lp | Modified supported chromium catalysts and ethylene-based polymers produced therefrom |
| US11865528B2 (en) | 2018-09-17 | 2024-01-09 | Chevron Phillips Chemical Company Lp | Modified supported chromium catalysts and ethylene-based polymers produced therefrom |
| US11780786B2 (en) | 2020-09-14 | 2023-10-10 | Chevron Phillips Chemical Company Lp | Transition metal-catalyzed production of alcohol and carbonyl compounds from hydrocarbons |
| US11969718B2 (en) | 2023-02-10 | 2024-04-30 | Chevron Phillips Chemical Company Lp | Modified supported chromium catalysts and ethylene-based polymers produced therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107311263A (en) | 2017-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107311263B (en) | Method for treating wastewater containing chromium ions and by-producing chromium-containing catalyst | |
| CN105289693B (en) | A kind of Zn0.5Co0.5Fe2O4/g‑C3N4The preparation method of composite photo-catalyst | |
| CN105540733B (en) | A kind of TiO2Reduced graphene composite material and preparation method and the application in artificial seawater system | |
| CN104828902B (en) | A kind of method of petal-shaped magnetic iron oxide molybdenum sulfide complex catalysts reduction treatment chromate waste water | |
| Gao et al. | Mechanisms for photo assisted Fenton of synthesized pyrrhotite at neutral pH | |
| CN108745289B (en) | Preparation method and application of LDH and SWCNT nanocomposite material | |
| CN108479774B (en) | Zinc oxide composite photocatalyst and preparation method and application thereof | |
| CN108620097A (en) | A kind of preparation method and purposes of silver iodide/bismuth oxybromide heterojunction photocatalyst | |
| CN106423272B (en) | A kind of load type titania/graphene oxide bead and the preparation method and application thereof | |
| CN114192171A (en) | Cu:ZnIn2S4-Ti3C2Preparation method and application of composite photocatalyst | |
| CN108636395A (en) | A kind of composite photo-catalyst of weakly visible photoresponse and its preparation and application | |
| CN111036249A (en) | FexP/Mn0.3Cd0.7S composite photocatalyst and preparation method and application thereof | |
| CN104707560A (en) | Preparation method of modified mesopore TiO2 capable of effectively removing phosphorus in wastewater | |
| Xu et al. | Enhancement in photo-fenton-like degradation of azo dye methyl orange using TiO2/hydroniumjarosite composite catalyst | |
| CN108940310A (en) | A kind of Pd/Fe@Fe3O4Composite catalyst and the preparation method and application thereof | |
| WO2020093517A1 (en) | Photocatalytic material for efficient and selective reduction and removal of nitrate nitrogen in water, and preparation method thereof | |
| CN110918099A (en) | Method for treating hexavalent chromium-containing wastewater through photocatalytic reduction of nickel oxide-nickel cobaltate-black titanium dioxide composite | |
| CN102728299B (en) | A kind of titania-doped compound magnetic nano adsorber and its preparation method, application | |
| CN103506104B (en) | Carbon-doped TiO2 visible light-responding catalytic film on glass carrier and preparation method thereof | |
| CN110540243B (en) | Preparation method of amorphous iron oxyhydroxide and recovery method after organic matter adsorption | |
| CN107081153B (en) | Method for reducing Cr (VI) based on catalyst photocatalysis | |
| CN113292101B (en) | Preparation method and application of high-purity birnessite material | |
| JP2015167882A (en) | Photocatalyst production method, photocatalyst, and hydrogen generation method | |
| CN107335438A (en) | CuOxThe co-modified TiO of NiO2The preparation method of the efficient reduction dechlorination material of photocatalysis | |
| CN105944724A (en) | Cu2O visible-light-induced photocatalyst for wastewater treatment and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201103 Termination date: 20210707 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |