CN105562036A - Preparation method and application of iron-sulfur heterogeneous Fenton-like catalyst - Google Patents
Preparation method and application of iron-sulfur heterogeneous Fenton-like catalyst Download PDFInfo
- Publication number
- CN105562036A CN105562036A CN201510928121.7A CN201510928121A CN105562036A CN 105562036 A CN105562036 A CN 105562036A CN 201510928121 A CN201510928121 A CN 201510928121A CN 105562036 A CN105562036 A CN 105562036A
- Authority
- CN
- China
- Prior art keywords
- solution
- fenton
- iron
- catalyst
- ferrous
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 title abstract 4
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 title abstract 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002351 wastewater Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 14
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 14
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical group [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 claims description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 6
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- -1 hydroxyl radical free radical Chemical class 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 5
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000010525 oxidative degradation reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003918 potentiometric titration Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229960005191 ferric oxide Drugs 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method and application of an iron-sulfur heterogeneous Fenton-like catalyst. The preparation method comprises the following steps of adding a dispersing agent into a ferrous solution, and performing uniform stirring; sequentially and slowly pouring solutions of hydrosulfide and sulfide into the solution, keeping the pH of the solution to be 5.0 to 5.5, and performing stirring for 10 to 20min; slowly adding a solution of sulfite into the solution, keeping the pH value to be 5.0 to 5.5, and performing stirring for 5 to 10min to obtain precursor sol; transferring the precursor sol into a sealed glass bottle, and performing constant temperature (25 DEG C) aging reaction in dark to obtain black precipitates, i.e. the final catalyst. The pH of wastewater is regulated to 7.0 to 11.0, a mixed solution of hydrogen peroxide/persulfate and the synthesized heterogeneous fenton-like catalyst are added into the wastewater, and stirring reaction is performed for 10 to 120min to finish the degrading of organic pollutants in the wastewater. A preparation process of the prepared iron-sulfur heterogeneous Fenton-like catalyst is simple, conditions are mild, and when being used, the prepared iron-sulfur heterogeneous Fenton-like catalyst is large in applicable pH range, and has a good deep treatment effect on industrial wastewater.
Description
Technical field
The present invention relates to a kind of preparation method of iron sulphur multiphase-fenton fenton catalyst and the application in advanced treatment of industrial waste water thereof.
Background technology
Fenton oxidation technology, as a kind of common high-level oxidation technology, has been widely used in the advanced treating of waste water.Its cardinal principle passes through Fe
2+with H
2o
2produce the organic pollution that hydroxyl radical free radical carrys out difficult degradation in oxidative degradation water.Such as, but traditional homogeneous phase Fenton's reaction exists certain defect, can produce a large amount of iron oxide deposits, applicable pH scope is lower than 3, Fe
2+catalysis H
2o
2produce hydroxyl radical free radical and can not remove all contaminants completely.The catalysis of multiphase-fenton Fenton is arisen at the historic moment, and its target is that the sludge output in order to solve the existence of homogeneous phase Fenton is large, and the problem that applicable pH range is narrow.
At present, conventional multiphase-fenton fenton catalyst has ferriferous oxide, ferriferous oxide and ultrasonic ultraviolet coupling, on porous support carrying transition metal etc.These methods can both overcome the deficiency of homogeneous phase Fenton's reaction to a certain extent, but there is the low problem of oxidation efficiency in the class Fenton of ferriferous oxide catalysis, although ferriferous oxide and ultrasonic ultraviolet coupling improve the cost that oxidation efficiency but adds water treatment, and the catalyst preparation process of support type is general comparatively complicated, need high-temperature calcination or doping precious metal.Publication number is the preparation method that patent discloses Gd, Pr, Yb doping class fenton catalyst and the application thereof of CN102407128, and the method is passed through Gd (NO
3)
3or Pr (NO
3)
3or Yb (NO
3)
3be added drop-wise to Fe (NO
3)
3and NH
4vO
3make presoma in solution, then obtain catalyst through water under high pressure thermal response.This type of fenton catalyst can widen Fenton's reaction pH scope 2 ~ 11, but Gd, Pr, Yb are noble metal, and the cost of Kaolinite Preparation of Catalyst is higher.Document [Wang Chongtai, Sun Zhenfan, China hero, Hua Shuyan, magnify general, virgin leaf Xiang .Keggin sections replaces heteropolyanion PW_ (11) O_ (39) Fe (III) (H_2O) ~ (4-) photocatalytic degradation nitrobenzene [J]. chemical journal, 2010,11:1037-1042.] be referred to a kind of photocatalysis Fenton-type reagent of novelty, but photocatalysis needs uviol lamp as light source, part actual waste water turbidity is comparatively large, is difficult to printing opacity, so the Application comparison difficulty of photocatalysis in actual waste water.Therefore widen the pH scope of class Fenton's reaction and to reduce catalyst genotoxic potential extremely important, multiphase-fenton fenton catalyst also should have good application to the actual waste water of complicated component especially industrial wastewater in addition simultaneously.
Summary of the invention
The present invention adapts to pH narrow range for solving existing multiphase-fenton fenton catalyst, and the problem of preparation process complexity, proposes a kind of preparation method and application of iron sulphur multiphase-fenton fenton catalyst.
The preparation method of a kind of iron sulphur multiphase-fenton fenton catalyst that the present invention proposes, concrete steps are as follows:
(1) obtain solution:
Ferrous salt is soluble in water, stir and make it dissolve, be made into the ferrous iron solution that concentration is 0.06 ~ 0.1mol/L;
Sulfohydrate and sulfide are distinguished soluble in water, is made into the solution that concentration is 0.1 ~ 0.5mol/L respectively;
Sulphite is made into the sulfite solution that concentration is 0.05 ~ 0.1mol/L;
Dispersant is mixed with the dispersant solution that concentration is 1mol/L;
(2) to step (1) obtain ferrous iron solution in add 0.1 ‰ ~ 1 ‰ volumes the dispersant solution that obtains of step (1), and to stir on magnetic stirring apparatus;
(3) under magnetic stirring, sulfohydrate solution step (1) obtained, sulfide solution are slowly poured in the solution that step (2) prepares successively, drip NaOH solution simultaneously, regulate the pH of solution, it is made to maintain 5.0 ~ 5.5, magnetic agitation 10 ~ 20min;
(4) slowly joined by the sulfite solution that step (1) obtains in the solution that step (3) obtains, drip HCl, maintain pH 5.0 ~ 5.5, magnetic agitation 5 ~ 10min, obtains precursor sol;
(5) be transferred in sealed glass jars by the precursor colloidal sol that step (4) obtains, lucifuge constant temperature (25 DEG C) aging reaction 5 ~ 10 days, obtain black precipitate, this black precipitate is final catalyst.
In the present invention, ferrous is 1:1 ~ 1:3 with the mol ratio of sulfohydrate.
In the present invention, ferrous is 4:1 ~ 2:1 with the mol ratio of sulfide.
In the present invention, ferrous is 5:1 ~ 1:1 with the mol ratio of sulphite.
In the present invention, described ferrous salt is any one in frerrous chloride, iron ammonium sulfate, green vitriol or ferrous nitrate etc.; Described dispersant is citrate, comprises its common soluble salt: as natrium citricum, potassium citrate, ammonium citrate etc.; Sulfohydrate is any one in NaHS, potassium bisulfide or ammonium hydro sulfide etc., and sulfide is any one in vulcanized sodium, potassium sulfide or ammonium sulfide etc.; Sulphite is any one in sodium sulfite, potassium sulfite or ammonium sulfite etc.
The iron sulphur multiphase-fenton fenton catalyst that the present invention proposes is in the application in advanced treatment of industrial waste water, and concrete steps are as follows:
(1) pH value of waste water is regulated: the pH value of the pretreated waste water containing organic pollution is adjusted to 7.0 ~ 11.0;
(2) in the waste water regulating pH value, add hydrogen peroxide/persulfate mixed liquor, mix under magnetic agitation effect;
(3) add multiphase-fenton fenton catalyst 0.04 ~ 2g/L to containing in the organic polluting water of oxidant of step (2) gained, magnetic agitation reaction 10min ~ 120min, namely completes the degraded to organic pollutants.
In the present invention, ferrous is 5:1 ~ 1:5 with the mol ratio of hydrogen peroxide, and hydrogen peroxide mass concentration is 10% ~ 30%.
In the present invention, ferrous is 10:1 ~ 5:1 with the mol ratio of persulfate, and persulfate mass concentration used is 5% ~ 50%.
In the present invention, persulfate used comprises its common soluble salt: in sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate etc. any one.
In catalyst preparation process, ferrous ion and negative divalent hybrid reaction generate Fe
xs
ycolloid particle, under the effect of dispersant, is dispersed in solution, after adding sulphite, the element sulphur meeting of the negative divalence of part and the element sulphur of positive tetravalence return middle reaction to generate the sulphur of negative monovalence, and the sulphur of two kinds of valence states exists simultaneously, is conducive to the catalytic activity improving catalyst.Under suitable pH condition, pass through the aging of certain hour, ferrous iron can be combined with element sulphur and the growth of crystal occurs further, and the class fenton catalyst finally obtained, iron and sulphur all exist with the form of structure state.
Traditional Fenton and class Fenton's reaction generally use hydrogen peroxide as oxidant, and iron catalyzing hydrogen peroxide can produce hydroxyl radical free radical, and hydroxyl radical free radical has very high oxidation-reduction potential (E
0=2.8V), most organic matter of can degrading, but in actual applications, also there is the organic matter that a part of hydroxyl radical free radical can not be degraded.By adding a certain amount of persulfate, can oxidative degradation can not the pollutant of oxidative degradation by hydroxyl radical free radical further, improve the treatment effect to complex industrial waste water, principle is as follows: the iron catalysis persulfate of structure state can produce potentiometric titrations, potentiometric titrations is the another kind of high oxidative group being different from hydroxyl radical free radical, its oxidation-reduction potential E
0=2.5V-3.1V, potentiometric titrations is considered to be oxidized most organic matters under ideal conditions, makes it decompose.In addition, the reaction rate of iron sulphur multiphase-fenton fenton catalyst catalysis persulfate degradation of contaminant of the present invention is slower than hydrogen peroxide, but mineralization ability is higher than hydrogen peroxide, therefore adds persulfate and can improve reaction mineralization ability.
Compared with existing Fenton, class Fenton method, major advantage of the present invention is as follows:
(1) catalyst preparation process is simple, does not need the conditions such as high temperature, can synthesize under normal temperature and pressure.Needed raw material containing toxic heavy-metal elements, does not belong to environmentally friendly catalyst.
(2) the iron sulphur multiphase-fenton fenton catalyst of synthesizing is spheric granules, and particle diameter reaches micron order, is 1 ~ 1.5 μm, and specific area is large, is conducive to structure state iron and sulphur fully and oxidising agent, improves catalytic efficiency.
(3) in the present invention, structure state sulphur has stronger reproducibility, and the ferric iron being converted into solubilised state after avoiding structure state iron and hydrogen peroxide/persulfate to react loses catalytic activity; Its principle makes the ferric iron of solubilised state again be converted into the ferrous iron of structure state by redox reaction, recovers the catalytic activity of iron ion.This process can save the consumption of catalyst, improves catalytic efficiency.
(4) the multiphase-fenton fenton catalyst of synthesizing can adapt to neutrality and alkaline pH.In catalyst, iron is structure state iron, affects less by pH value of solution, and structure state S is by promoting that the circulation of iron also can reduce the impact of pH on catalyst.
(5) catalyst application is when advanced treatment of industrial waste water, a certain amount of persulfate is also added except selecting hydrogen peroxide, the hydroxyl radical free radical first oxidative degradation majority of organic pollutants that catalyzing hydrogen peroxide generates, the potentiometric titrations generated by catalysis persulfate again, further by organic pollution mineralising, improve the treatment effect of the industrial wastewater to complicated component.
Accompanying drawing explanation
Fig. 1 is the multiphase-fenton fenton catalyst Electronic Speculum figure that embodiment 1 is synthesized.
Fig. 2 is the multiphase-fenton fenton catalyst Electronic Speculum figure of the 2-in-1 one-tenth of embodiment.
Fig. 3 is the multiphase-fenton fenton catalyst Electronic Speculum figure that embodiment 6 is synthesized.
Fig. 4 is the acid scarlet change in concentration figure of embodiment 5.
Detailed description of the invention
Embodiment 1
(1) green vitriol is soluble in water, stir and make it dissolve, be made into the solution that concentration is 0.06mol/L; Distinguish soluble in water by NaHS and vulcanized sodium, be made into the solution that concentration is 0.2mol/L, sodium sulfite being made into concentration is 0.08mol/L solution, and dispersant ammonium citrate being mixed with concentration is 1mol/L solution for standby.
(2) in ferrous solution, add the dispersant of 0.1 ‰ volumes, and stir on magnetic stirring apparatus.
(3) under magnetic stirring, NaHS, sodium sulfide solution are slowly poured into successively in the solution that step (2) prepares, drip NaOH solution simultaneously, regulate the pH of solution, make it maintain 5.0 ~ 5.5, magnetic agitation 10min.
(4) slowly added by sodium sulfite solution in the solution that step (3) obtains, drip HCl, maintain pH 5.0 ~ 5.5, magnetic agitation 10min, obtains precursor sol.
(5) be transferred in sealed glass jars by precursor colloidal sol, lucifuge constant temperature (25 DEG C) aging reaction 5 days, obtain black precipitate, this black precipitate is final catalyst.
In described catalyst synthetic reaction, the mol ratio of ferrous iron and NaHS is 1:1; The mol ratio of ferrous iron and sulfide is 3:1; The mol ratio of ferrous iron and sulphite is 5:1.
As can be seen from accompanying drawing 1, catalyst is uniform spherical particle.
Embodiment 2
(1) green vitriol is soluble in water, stir and make it dissolve, be made into the solution that concentration is 0.1mol/L; Distinguish soluble in water by NaHS and vulcanized sodium, be made into the solution that concentration is 0.3mol/L, sodium sulfite being made into concentration is 0.1mol/L solution, and dispersant ammonium citrate being mixed with concentration is 1mol/L solution for standby.
(2) in ferrous solution, add the dispersant of 0.1 ‰ volumes, and stir on magnetic stirring apparatus.
(3) under magnetic stirring, NaHS, sodium sulfide solution are slowly poured into successively in the solution that step (2) prepares, drip NaOH solution simultaneously, regulate the pH of solution, make it maintain 5.0 ~ 5.5, magnetic agitation 15min.
(4) slowly added by sodium sulfite solution in the solution that step (3) obtains, drip HCl, maintain pH 5.0 ~ 5.5, magnetic agitation 10min, obtains precursor sol.
(5) be transferred in sealed glass jars by precursor colloidal sol, lucifuge constant temperature (25 DEG C) aging reaction 10 days, obtain black precipitate, this black precipitate is final catalyst.
In described catalyst synthetic reaction, the mol ratio of ferrous iron and NaHS is 1:3; The mol ratio of ferrous iron and sulfide is 2:1; The mol ratio of ferrous iron and sulphite is 5:1.
As can be seen from accompanying drawing 2, catalyst is uniform spherical particle, and because iron concentration is higher, and the aging reaction time is long, there is part caking phenomenon.
Embodiment 3
Get Dyeing and Printing Wastewater Biological Treatment secondary clarifier effluent 200mL in 250mL beaker, this water sample COD is 128mg/L, pH=7.2.In water sample, add hydrogen peroxide 2mM, sodium peroxydisulfate 0.5mM, add the multiphase-fenton Fenton activator 0.5g/L prepared by embodiment 1 wherein, stirring reaction 60min.After reaction terminates, COD is 45mg/L, reaches one-level emission standard A.
Embodiment 4
Get paper waste second pond bio-chemical effluent 200mL in 250mL beaker, this water sample COD is 116mg/L, pH=8.12.In water sample, add hydrogen peroxide 3mM, sodium peroxydisulfate 1mM, add the multiphase-fenton Fenton activator 1g/L prepared by embodiment 2 wherein, stirring reaction 60min.After reaction terminates, COD is 50mg/L, reaches one-level emission standard A.
Embodiment 5
Using acidic bright red paint as target contaminant, preparation simulated wastewater, wherein the concentration of acid scarlet is 50mg/L.Get 200mL simulated wastewater in 250mL beaker, hydrogen peroxide 1mM is added in water sample, sodium peroxydisulfate 0.2mM, add the multiphase-fenton Fenton activator 0.04g/L prepared by embodiment 1 wherein, stirring reaction 90min, reaction 5,10,30,60,90min time sampling detect the concentration of acid scarlet in water, obtain result as shown in Figure 4.As can be seen from the figure, during the multiphase-fenton fenton catalyst oxidative degradation acid scarlet of synthesis, reaction rate is fast, and when 10min is carried out in reaction, dyestuff is removed 75%, and acid scarlet clearance remains stable.
Embodiment 6
(1) green vitriol is soluble in water, stir and make it dissolve, be made into the solution that concentration is 0.08mol/L; Distinguish soluble in water by NaHS and vulcanized sodium, be made into the solution that concentration is 0.2mol/L, sodium sulfite being made into concentration is 0.05mol/L solution, and dispersant ammonium citrate being mixed with concentration is 1mol/L solution for standby.
(2) in ferrous solution, add the dispersant of 1 ‰ volumes, and stir on magnetic stirring apparatus.
(3) under magnetic stirring, NaHS, sodium sulfide solution are slowly poured into successively in the solution that step (2) prepares, drip NaOH solution simultaneously, regulate the pH of solution, make it maintain 5.0 ~ 5.5, magnetic agitation 10min.
(4) slowly added by sodium sulfite solution in the solution that step (3) obtains, drip HCl, maintain pH 5.0 ~ 5.5, magnetic agitation 10min, obtains precursor sol.
(5) be transferred in sealed glass jars by precursor colloidal sol, lucifuge constant temperature (25 DEG C) aging reaction 7 days, obtain black precipitate, this black precipitate is final catalyst.
In described catalyst synthetic reaction, the mol ratio of ferrous iron and NaHS is 1:1; The mol ratio of ferrous iron and sulfide is 4:1; The mol ratio of ferrous iron and sulphite is 8:1.
As can be seen from accompanying drawing 3, catalyst is uniform spherical particle.
Embodiment 7
With 2,4-Dichlorophenol as target contaminant, preparation simulated wastewater, wherein the concentration of 2,4-Dichlorophenols is 50mg/L.Get 6 parts of 200mL simulated wastewaters in 6 250mL beakers, regulate the pH=8 of solution, hydrogen peroxide 2mM is added in water sample, sodium peroxydisulfate 0.5mM, respectively to the multiphase-fenton Fenton activator 0.04 wherein added prepared by embodiment 2, 0.1, 0.2, 0.5, 1, 2g/L, stirring reaction 120min, staticly settle after the completion of reaction, get supernatant by 0.45 μm of filter membrane, 2 are detected with high performance liquid chromatography, the concentration of 4-Dichlorophenol, experimental result shows as following table, iron sulphur multiphase-fenton fenton catalyst catalyzing hydrogen peroxide/persulfate parachlorophenol compounds clearance prepared by the present invention is high.Under the condition that oxidant consumption is certain, the consumption increasing catalyst can improve pollutants removal rate.
。
Embodiment 8
With 2,4-Dichlorophenol as target contaminant, preparation simulated wastewater, wherein the concentration of 2,4-Dichlorophenols is 50mg/L.Get three parts of 200mL simulated wastewaters and be placed in 250mL beaker respectively, three parts of water samples adjust pH be 7,8,9,10,11 and add hydrogen peroxide 2mM in water sample respectively, sodium peroxydisulfate 0.5mM, add the multiphase-fenton Fenton activator 0.5g/L prepared by embodiment 6 wherein, stirring reaction 60min, staticly settles after the completion of reaction, get supernatant by 0.45 μm of filter membrane, detect the concentration of 2,4-Dichlorophenol with high performance liquid chromatography, experimental result shows as following table.Multiphase-fenton fenton catalyst prepared by the present invention is high to 2,4-chlorophenesic acid clearance under higher pH condition, illustrates that the reaction of catalyst hydrogen peroxide/persulfate removal water pollutant affects less by pH.
。
Claims (9)
1. a preparation method for iron sulphur multiphase-fenton fenton catalyst, it is characterized in that, concrete steps are as follows:
(1) obtain solution:
Ferrous salt is soluble in water, stir and make it dissolve, be made into the ferrous iron solution that concentration is 0.06 ~ 0.1mol/L;
Sulfohydrate and sulfide are distinguished soluble in water, is made into the solution that concentration is 0.1 ~ 0.5mol/L respectively;
Sulphite is made into the sulfite solution that concentration is 0.05 ~ 0.1mol/L;
Dispersant is mixed with the dispersant solution that concentration is 1mol/L;
(2) to step (1) obtain ferrous iron solution in add 0.1 ‰ ~ 1 ‰ volumes the dispersant solution that obtains of step (1), and to stir on magnetic stirring apparatus;
(3) under magnetic stirring, sulfohydrate solution step (1) obtained, sulfide solution are slowly poured in the solution that step (2) prepares successively, drip NaOH solution simultaneously, regulate the pH of solution, it is made to maintain 5.0 ~ 5.5, magnetic agitation 10 ~ 20min;
(4) slowly joined by the sulfite solution that step (1) obtains in the solution that step (3) obtains, drip HCl, maintain pH 5.0 ~ 5.5, magnetic agitation 5 ~ 10min, obtains precursor sol;
(5) be transferred in sealed glass jars by the precursor colloidal sol that step (4) obtains, lucifuge constant temperature (25 DEG C) aging reaction 5 ~ 10 days, obtain black precipitate, this black precipitate is final catalyst.
2. the preparation method of a kind of iron sulphur multiphase-fenton fenton catalyst according to claim 1, is characterized in that the mol ratio of ferrous iron solution and sulfohydrate solution is 1:1 ~ 1:3.
3. the preparation method of a kind of iron sulphur multiphase-fenton fenton catalyst according to claim 1, is characterized in that the mol ratio of ferrous iron solution and sulfide solution is 4:1 ~ 2:1.
4. the preparation method of a kind of iron sulphur multiphase-fenton fenton catalyst according to claim 1, is characterized in that the mol ratio of ferrous iron solution and sulfite solution is 5:1 ~ 1:1.
5. the preparation method of a kind of iron sulphur multiphase-fenton fenton catalyst according to claim 1, is characterized in that described ferrous salt is any one in frerrous chloride, iron ammonium sulfate, green vitriol or ferrous nitrate; Described dispersant is citrate, comprises its common soluble salt: as natrium citricum, potassium citrate, ammonium citrate; Sulfohydrate is any one in NaHS, potassium bisulfide or ammonium hydro sulfide, and sulfide is any one in vulcanized sodium, potassium sulfide or ammonium sulfide; Sulphite is any one in sodium sulfite, potassium sulfite or ammonium sulfite.
6. the iron sulphur multiphase-fenton fenton catalyst that obtains of preparation method, in the application in advanced treatment of industrial waste water, is characterized in that concrete steps are as follows as claimed in claim 1:
(1) pH value of waste water is regulated: the pH value of the pretreated waste water containing organic pollution is adjusted to 7.0 ~ 11.0;
(2) in the waste water regulating pH value, add hydrogen peroxide/persulfate mixed liquor, mix under magnetic agitation effect;
(3) add multiphase-fenton fenton catalyst 0.04 ~ 2g/L to containing in the organic polluting water of oxidant of step (2) gained, magnetic agitation reaction 10min ~ 120min, namely completes the degraded to organic pollutants.
7. application according to claim 6, it is characterized in that ferrous is 5:1 ~ 1:5 with the mol ratio of hydrogen peroxide, hydrogen peroxide mass concentration is 10% ~ 30%.
8. application according to claim 6, it is characterized in that ferrous is 10:1 ~ 5:1 with the mol ratio of persulfate, persulfate mass concentration used is 5% ~ 50%.
9. application according to claim 6, is characterized in that persulfate used comprises its common soluble salt: in sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510928121.7A CN105562036B (en) | 2015-12-15 | 2015-12-15 | A kind of preparation method and application of iron sulphur multiphase-fenton fenton catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510928121.7A CN105562036B (en) | 2015-12-15 | 2015-12-15 | A kind of preparation method and application of iron sulphur multiphase-fenton fenton catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105562036A true CN105562036A (en) | 2016-05-11 |
| CN105562036B CN105562036B (en) | 2017-12-26 |
Family
ID=55872989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510928121.7A Active CN105562036B (en) | 2015-12-15 | 2015-12-15 | A kind of preparation method and application of iron sulphur multiphase-fenton fenton catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105562036B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720930A (en) * | 2017-11-20 | 2018-02-23 | 华东理工大学 | The Industrial Wastewater Treatment reagent and its reaction method of a kind of sulfur compound |
| CN108786852A (en) * | 2018-07-11 | 2018-11-13 | 常州大学 | A kind of preparation method for light Fenton's reaction material |
| CN109231565A (en) * | 2018-10-24 | 2019-01-18 | 辽宁大学 | A method of degradation waste water containing Iopromide |
| CN109589980A (en) * | 2018-10-29 | 2019-04-09 | 华中科技大学 | A kind of preparation method of composite catalyst, and products thereof and application |
| CN109626544A (en) * | 2018-12-07 | 2019-04-16 | 华南农业大学 | A method of based on environmental hormone bisphenol-A in ferriferrous sulfide activation persulfate degradation water body |
| CN109897973A (en) * | 2019-04-03 | 2019-06-18 | 东北师范大学 | A method of utilizing nickel in molysite deposition recycling nickel-containing waste water |
| CN112479341A (en) * | 2020-10-26 | 2021-03-12 | 中国科学院南京土壤研究所 | Preparation method and application of spherical nano iron-sulfur composite material |
| CN113976145A (en) * | 2021-11-23 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Sulfur-modified iron-cobalt oxide nanosheet Fenton catalyst and preparation method and application method thereof |
| CN114100638A (en) * | 2021-11-25 | 2022-03-01 | 浙江理工大学 | Preparation method and application of iron-carbon intercalation molybdenum disulfide catalyst |
| CN115368901A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Composition with function of enhancing nano calcium peroxide to repair polluted soil and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070384A1 (en) * | 2004-12-27 | 2006-07-06 | Council Of Scientific And Industrial Research | Eco-friendly photo-fenton catalyst-immobilized fe(iii) over hy-zeolite |
| CN101862662A (en) * | 2010-06-17 | 2010-10-20 | 中国石油大学(华东) | Multi-doped half-load type Fenton-assisting titanium dioxide photochemical catalyst as well as preparation method and application method |
| CN102698754A (en) * | 2012-05-28 | 2012-10-03 | 北京化工大学 | Nanometer iron oxide/carbon sphere compound catalyst and preparation method and application thereof |
| CN103708647A (en) * | 2013-12-27 | 2014-04-09 | 同济大学 | Deep treatment method for industrial wastewater through natural pyrite catalyzed H2O2 oxidation |
-
2015
- 2015-12-15 CN CN201510928121.7A patent/CN105562036B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070384A1 (en) * | 2004-12-27 | 2006-07-06 | Council Of Scientific And Industrial Research | Eco-friendly photo-fenton catalyst-immobilized fe(iii) over hy-zeolite |
| CN101862662A (en) * | 2010-06-17 | 2010-10-20 | 中国石油大学(华东) | Multi-doped half-load type Fenton-assisting titanium dioxide photochemical catalyst as well as preparation method and application method |
| CN102698754A (en) * | 2012-05-28 | 2012-10-03 | 北京化工大学 | Nanometer iron oxide/carbon sphere compound catalyst and preparation method and application thereof |
| CN103708647A (en) * | 2013-12-27 | 2014-04-09 | 同济大学 | Deep treatment method for industrial wastewater through natural pyrite catalyzed H2O2 oxidation |
Non-Patent Citations (4)
| Title |
|---|
| CHEN LI-WEI ET AL.: "A novel Fenton-like system with hydrogen peroxide,hydroxylamine and Fe(III) for the degradation of benzoic acid", 《黑龙江大学自然科学学报》 * |
| ROBER LIU ET AL.: "Degradation and sludge production of textile dyes by Fenton and photo-Fenton processes", 《DYES AND PIGMENTS》 * |
| ZI-PENG XING ET AL.: "Treatment of antibiotic fermentation wastewater by combined polyferric sulfate coagulation,Fenton and sedimentation process", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 赵英等: "Fenton试剂对硫化物的处理效果研究", 《哈尔滨商业大学学报（自然科学版）》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720930A (en) * | 2017-11-20 | 2018-02-23 | 华东理工大学 | The Industrial Wastewater Treatment reagent and its reaction method of a kind of sulfur compound |
| CN108786852A (en) * | 2018-07-11 | 2018-11-13 | 常州大学 | A kind of preparation method for light Fenton's reaction material |
| CN109231565A (en) * | 2018-10-24 | 2019-01-18 | 辽宁大学 | A method of degradation waste water containing Iopromide |
| CN109589980A (en) * | 2018-10-29 | 2019-04-09 | 华中科技大学 | A kind of preparation method of composite catalyst, and products thereof and application |
| CN109589980B (en) * | 2018-10-29 | 2020-12-18 | 华中科技大学 | Preparation method of composite material catalyst, product and application thereof |
| CN109626544B (en) * | 2018-12-07 | 2020-12-11 | 华南农业大学 | Method for degrading environmental hormone bisphenol A in water body based on ferroferric sulfide activated persulfate |
| CN109626544A (en) * | 2018-12-07 | 2019-04-16 | 华南农业大学 | A method of based on environmental hormone bisphenol-A in ferriferrous sulfide activation persulfate degradation water body |
| CN109897973A (en) * | 2019-04-03 | 2019-06-18 | 东北师范大学 | A method of utilizing nickel in molysite deposition recycling nickel-containing waste water |
| CN112479341A (en) * | 2020-10-26 | 2021-03-12 | 中国科学院南京土壤研究所 | Preparation method and application of spherical nano iron-sulfur composite material |
| CN112479341B (en) * | 2020-10-26 | 2022-06-17 | 中国科学院南京土壤研究所 | Preparation method and application of spherical nano iron-sulfur composite material |
| CN115368901A (en) * | 2021-05-18 | 2022-11-22 | 中国石油化工股份有限公司 | Composition with function of enhancing nano calcium peroxide to repair polluted soil and application thereof |
| CN113976145A (en) * | 2021-11-23 | 2022-01-28 | 中国科学院合肥物质科学研究院 | Sulfur-modified iron-cobalt oxide nanosheet Fenton catalyst and preparation method and application method thereof |
| CN114100638A (en) * | 2021-11-25 | 2022-03-01 | 浙江理工大学 | Preparation method and application of iron-carbon intercalation molybdenum disulfide catalyst |
| CN114100638B (en) * | 2021-11-25 | 2023-08-29 | 浙江理工大学 | Preparation method and application of iron-carbon intercalated molybdenum disulfide catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105562036B (en) | 2017-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105562036A (en) | Preparation method and application of iron-sulfur heterogeneous Fenton-like catalyst | |
| CN104609531B (en) | Method for preparing citrate nano zero-valent iron and method of activated persulfate thereof for treating organic wastewater | |
| CN104743633B (en) | A kind of light helps the method for bismuth ferrite activation potassium hydrogen persulfate degradation of organic waste water | |
| CN104624209B (en) | Modified ferrous oxide activator as well as preparation method and application thereof | |
| CN105084511A (en) | Method for degrading organic waste water by activating persulfate through manganese-cobalt composite oxide | |
| CN104891719A (en) | Method for pre-treating organic industrial wastewater based on ferric-carbon micro-electrolysis activated persulfate | |
| Shokri et al. | Treatment of aqueous solution containing acid red 14 using an electro peroxone process and a box-Behnken experimental design | |
| CN101525190A (en) | Efficient wastewater treating process based on Fenton reaction | |
| CN108176403B (en) | Co-loaded activated carbon fiber3O4Method for preparing catalytic material | |
| CN103787537B (en) | A kind for the treatment of process of sewage and application thereof | |
| CN102963950B (en) | Method for treating printing and dyeing wastewater by steel slag | |
| CN103357413A (en) | Method for preparing binary-oxide composite solid acid catalyst and method for treating degradation-resistant organic pollutants by catalyzing oxidization of H2O2 | |
| CN103787448A (en) | Denitrification method combining denitrification agent and ultraviolet light | |
| CN103058321A (en) | Photochemical method of intensively degrading organic matters | |
| CN103084216B (en) | A kind of microwave catalyst of degradation of organic waste water and catalytic oxidation degradation method thereof | |
| CN104828902A (en) | Method for treating chrome-containing wastewater by catalytic reduction of petaloid magnetic iron oxide/molybdenum sulfide composite | |
| CN101318749B (en) | Photocatalysis oxidation method for treating waste water of anthraquinone dye | |
| CN109231565A (en) | A method of degradation waste water containing Iopromide | |
| CN110510727A (en) | A method of utilizing ultraviolet oxidation sodium sulfite degradating organic dye | |
| CN104445576B (en) | A kind of organic pollutant oxidation treatment method based on sulphur oxyradical | |
| CN104743652A (en) | Method for processing degradation-resistant organic wastewater and multi-element catalyst adopted by method | |
| CN110902804A (en) | Method for removing pollutants in wastewater by utilizing thermally-assisted benzoquinone wastewater to catalyze persulfate | |
| CN104016515A (en) | Method for treating printing and dyeing wastewater by photocatalytic oxidation | |
| CN105344379A (en) | Hydrotalcite-loaded iron phthalocyanine visible light-fenton catalyst, preparation method and application thereof | |
| CN114904529A (en) | Photocatalytic material for degrading pyridine, modified photocatalytic filler, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |