CN106955708A - A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water - Google Patents
A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water Download PDFInfo
- Publication number
- CN106955708A CN106955708A CN201710270854.5A CN201710270854A CN106955708A CN 106955708 A CN106955708 A CN 106955708A CN 201710270854 A CN201710270854 A CN 201710270854A CN 106955708 A CN106955708 A CN 106955708A
- Authority
- CN
- China
- Prior art keywords
- tio
- persulfate
- feco
- water
- organic
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000000126 substance Substances 0.000 title claims abstract description 13
- 230000003213 activating effect Effects 0.000 title claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 229910002546 FeCo Inorganic materials 0.000 claims abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 13
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 4
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 5
- -1 iron ion Chemical class 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 229910001429 cobalt ion Inorganic materials 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229910003321 CoFe Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water, realized especially by following steps：TiO is prepared first2Porous microsphere；Then FeCo/TiO is prepared2；Finally by FeCo/TiO2It is sufficiently mixed with the aqueous solution containing organic matter, adds persulfate while being irradiated with ultraviolet, in FeCo/TiO2SO is produced with activation under the synergy of ultraviolet light4 ﹣And OH, so that majority of organic pollutants in degrading waste water.Handling process of the present invention is simple, only need single step reaction, organic wastewater qualified discharge can be made, cobalt ions and iron ion dissolution rate are extremely low, reduce environmental pollution, under acidic, neutral and alkaline conditions, it is higher to the organic matter degradation efficiency in waste water, realize the stable processing of the organic wastewater in the case of a variety of pH value.
Description
Technical field
The present invention relates to a kind of FeCo/TiO2Persulfate Fourier Series expansion technique processing organic wastewater is activated, belongs to environmental protection
Field.
Background technology
With various detergent, agricultural chemicals, a large amount of uses of chemical fertilizer and sanitary sewage, the increase of discharged volume of industrial waste water,
Exacerbate water pollution.Especially poisonous, harmful and difficult degradation the organic pollution of organic matter turns into the difficult point of water process.Base
In SO4 ﹣High-level oxidation technology be it is fast-developing in recent years get up new technology, because of its efficient process hardly degraded organic substance and
The characteristics of environmental pollution is small and get the attention.With the active material hydroxyl radical free radical of traditional high-level oxidation technology
(OH) compare, SO4 ﹣It is a kind of free radical of high activity, SO4 ﹣·(E0=2.5~oxidation-reduction potential 3.1) compares OH
(E0=1.8~2.7) high；SO4 ﹣Life-span (half-life period is 4s) it is long compared with OH (life-span be less than 1 μ s), be conducive to and pollutant
Contact, increase chance of the free radical to contaminant degradation；Overcome OH only have could aoxidize in acid condition it is organic
The shortcoming of thing；There is more preferable selectivity to target contaminant.Have oxidant good stability, dissolubility high in use,
The advantages of activation method is various, applied widely, anti-inorganic salts interference performance is strong.
SO4 ﹣High-level oxidation technology is to produce SO by activating persulfate4 ﹣·.Conventional activation method includes ultraviolet
The chemical method such as the physical means such as light, heat, microwave and transition metal ions.Wherein, Co2+To the activation effect of persulfate most
It is good.But metal ion Co2+It is toxic, secondary pollution and bio-toxicity can be caused, health problem is brought, thus limit the system
Extensive use.Accordingly, it would be desirable to by Co2+It is fixed on certain carrier and forms complex carrier, metal ion is lost in, simultaneously
Also it can be recycled, i.e., produces SO using heterogeneous catalysis system catalysis4 ﹣Oxidation of organic compounds.Therefore to Co2+Enter
Row load, finds suitable carrier, is one of most popular, most active problem in studying at present.
The content of the invention
It is an object of the invention to provide a kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water, purpose exists
Catalyst (the metal ion Co in the homogeneous persulfate activation system of solution2+) reclaim difficulty and easily cause secondary environmental pollution
Problem, meanwhile, coupling photocatalysis reinforcing organic matter degradation effect.
The object of the invention is achieved by the following technical programs.
A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water, it is characterised in that this method includes：
TiO is prepared first2Porous microsphere；Then FeCo/TiO is prepared2；Finally by FeCo/TiO2With containing the water-soluble of organic matter
Liquid is sufficiently mixed, and adds persulfate while being irradiated with ultraviolet, in FeCo/TiO2Produced with being activated under the synergy of ultraviolet light
Raw SO4 ﹣And OH, so that majority of organic pollutants in degrading waste water, specifically includes following steps：
First, TiO is prepared2Porous microsphere：
(1) butyl titanate and absolute ethyl alcohol are sufficiently mixed, butyl titanate used is 1 with absolute ethyl alcohol mass ratio:1
~1:2.Mixed liquor A is made.
(2) certain volume absolute ethyl alcohol separately is taken, after 1M salt acid for adjusting pH to 2~3, is added to made from step (1) and mixes
Close in liquid A, the mass ratio of absolute ethyl alcohol and mixed liquor A is 1:1.5~1:2.5, electromagnetic agitation 30min is allowed to be sufficiently mixed, and obtains
To TiO2Sol B.
(3) by TiO2After sol B is mixed with phenol, it is added in normal heptane decentralized medium, is being sufficiently stirred for lower dropwise addition first
Aldehyde.Wherein, TiO2The mass ratio of sol B and phenol is 5:1~10:1, TiO2The mass ratio of sol B and normal heptane is 1:1~1:
1.5,TiO2The mass ratio of sol B and formaldehyde is 2:1~10:1, it is warming up to 60~70 DEG C and is reacted, to mixing after about 1.5h
Liquid is filtered, and is cleaned repeatedly with ethanol, obtains milky polymer, is TiO2Complex microsphere C.
(4) after complex microsphere C is dried, polymer is decomposed through 500 DEG C of calcination process 2h, TiO is obtained2Porous microsphere.
2nd, FeCo/TiO is prepared2：Prepare cobalt nitrate and nitric acid iron mixed solution, TiO prepared by step one2Porous microsphere
Add in above-mentioned mixed solution, wherein, iron, the load capacity of cobalt are respectively the 20~50% of titania weight, 20~50%.Electricity
Magnetic stirs 5h, and then 80 DEG C of stirring in water bath evaporations are near dry, through 500 DEG C of high-temperature roasting 5h after drying.It is then placed in cold in drying basin
But to room temperature, FeCo/TiO is obtained2。
3rd, uviol lamp is placed into organic wastewater or on organic wastewater surface, by the 0.1~1% of organic wastewater quality
Ratio adds FeCo/TiO2, persulfate is added in 0.1~1% ratio of organic wastewater quality, is aerated, reaction 2~
12h。
Beneficial effects of the present invention：
(1) present invention utilizes the titanium dioxide (FeCo/TiO of load iron cobalt using persulfate as oxidant2)) in
Heavy metal ion activates persulfate, produces potentiometric titrations SO4 ﹣·；Under the irradiation of ultraviolet light, persulfate is activated,
Produce potentiometric titrations SO4 ﹣, FeCo/TiO2In TiO2Generation light-catalyzed reaction produces hydroxyl radical free radical OH.
SO4 ﹣Under OH collective effect, organic matter is thoroughly degraded.
(2) present invention utilizes nontoxic TiO2As carrier, loaded metal ion iron and cobalt, in the mistake of activation persulfate
Cheng Zhong, digestion of metallic ion is very low, reduces the secondary pollution of environment.And composite catalyst FeCo/TiO2Efficiently, stably, can
Recycling.
(3) FeCo loads can form shallow seismic method, effectively capture light induced electron, realize effectively dividing for photo-generated carrier
From raising photocatalysis efficiency, so as to improve TiO2Photocatalytic activity, strengthens organic matter degradation effect.
(4) present invention realizes the stable processing of the waste water in the case of a variety of pH value, thus need not adjust waste water in addition
PH value, saves substantial amounts of processing cost.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of the titanium dioxide of load iron cobalt.
Fig. 2 is the X-ray diffractogram of the titanium dioxide of load iron cobalt.
Fig. 3 is the titanium dioxide activation ammonium persulfate-sodium bisulfate degradation of phenol waste water design sketch using iron cobalt.
Embodiment
For ease of understanding, with reference to specific embodiments and the drawings, the present invention will be further described.
Embodiment 1
(1) 25mL butyl titanates and 32.2mL absolute ethyl alcohols are sufficiently mixed.32.2mL absolute ethyl alcohols separately are taken, hydrochloric acid is used
It is added to after regulation pH to 2~3 in the mixed liquor of above-mentioned butyl titanate and absolute ethyl alcohol, electromagnetic agitation 30min is allowed to abundant
Mixing, obtains TiO2Colloidal sol.
(2) 80mL TiO are taken2After colloidal sol is mixed with 12g phenol, it is added in 100mL normal heptane decentralized media, abundant
Stirring is lower to be added dropwise 16mL formaldehyde, and being warming up to 60~70 DEG C is reacted, and mixed liquor is filtered after about 1.5h, and anti-with ethanol
Multiple cleaning, obtains milky polymer, as TiO2Complex microsphere, makes polymer point after drying through 500 DEG C of calcination process 2h
Solution, that is, obtain TiO2Porous microsphere.
(3) Co (NO that 50mL contains 0.12mol/L are prepared3)2·6H2O and 0.125mol/L Fe (NO3)3·9H2O's
Predecessor mixed solution, by 1g TiO2Dipping wherein, closely do, after drying by electromagnetic agitation 5h, then 80 DEG C of stirring in water bath evaporations
Through 500 DEG C of high-temperature roasting 5h.It is then placed in drying basin and is cooled to room temperature, obtains CoFe/TiO2Composite catalyst.
(4) it is that uviol lamp is placed on the phenolic waste water surface that 100mg/L, pH are 6 in 50ml concentration, adds 0.075gFeCo/
TiO2, 0.15g ammonium persulfate-sodium bisulfates are added, are aerated, 2h is reacted, the clearance of phenol reaches 93.1%.
Embodiment 2
(1) 12.5mL butyl titanates and 16.1mL absolute ethyl alcohols are sufficiently mixed.16.1mL absolute ethyl alcohols separately are taken, salt is used
Acid for adjusting pH is to being added in the mixed liquor of above-mentioned butyl titanate and absolute ethyl alcohol after 2~3, and electromagnetic agitation 30min is allowed to fill
Divide mixing, obtain TiO2Colloidal sol.
(2) 40mL TiO are taken2After colloidal sol is mixed with 6g phenol, it is added in 50mL normal heptane decentralized media, is fully stirring
Lower dropwise addition 8mL formaldehyde is mixed, 60~70 DEG C is warming up to and is reacted, mixed liquor is filtered after about 1.5h, and with ethanol repeatedly
Cleaning, obtains milky polymer as TiO2Complex microsphere, polymer is decomposed after drying through 500 DEG C of calcination process 2h,
Obtain TiO2Porous microsphere.
(3) Co (NO that 25mL contains 0.12mol/L are prepared3)2·6H2O and 0.125mol/L Fe (NO3)3·9H2O's
Predecessor mixed solution, by 0.5g TiO2Dipping wherein, closely do, drying by electromagnetic agitation 5h, then 80 DEG C of stirring in water bath evaporations
By 500 DEG C of high-temperature roasting 5h.It is then placed in drying basin and is cooled to room temperature, obtains CoFe/TiO2Composite catalyst.
(4) it is that the rhodamine wastewater surface that 200mg/L, pH are 10 places uviol lamp in 100ml concentration, adds
0.1gFeCo/TiO2, 0.2g sodium peroxydisulfates are added, are aerated, 3h is reacted, the clearance of rhodamine B reaches 99.3%.
With experimental result, the present invention will be further described below.
(1) Micro-Structure Analysis
It will be seen from figure 1 that CoFe/TiO2Profile based on spheroid, particle is uniform, and particle diameter is at 1 μm or so.
Figure it is seen that and TiO2X-ray diffractogram compare, catalyst CoFe/TiO2X-ray diffractogram increase
Characteristic peak, wherein, peak value is respectively 35.74 °, 37.28 °, 53.89 ° and 62.73 °, correspondence (311), (222), (422) and
(440) CoFe in crystal face, with standard card JCPDS 01-11212O4Characteristic peak it is consistent.In addition, catalyst has part
Fe2O3Peak, peak value is at 33.19 °, 35.66 ° and 54.12 °.Illustrate that iron cobalt is successfully supported on TiO2On.
(2) treatment effect explanation
50mL phenolic waste waters are taken in conical flask, the catalysis of 3g/L ammonium persulfate-sodium bisulfate and 1.5g/L is then added
Agent CoFe/TiO2.Respectively under no light, natural lighting, UVA (wavelength 365nm) and UVB (wavelength 308nm) illumination condition, lead to
Enter air to carry out after aeration agitation, reaction different time, determine phenolic waste water concentration, calculate phenol clearance, the data obtained is such as
Shown in Fig. 3.
From the figure 3, it may be seen that under any illumination condition, the clearance of phenol increases with the increase in reaction time, and nothing
Clearance under illumination condition under the conditions of the clearance of phenol and natural lighting is consistent substantially, this explanation natural lighting condition
The degraded of Pyrogentisinic Acid does not have much affect.When reaching 120min between when reacted, the clearance of phenol is slightly higher under UVA illumination conditions
In under natural lighting and non-illuminated conditions；And under UVB illumination conditions, with the increase in reaction time, phenol clearance is always
Higher than non-illuminated conditions, natural lighting condition and UVA illumination conditions.Illustrate ultraviolet light to CoFe/TiO2Activate persulfate drop
Solution phenol has synergy.
It should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, although ginseng
The present invention is described in detail according to previous embodiment, for a person skilled in the art, it still can be to preceding
State the technical scheme described in embodiment to modify, or which part technical characteristic is replaced on an equal basis.
Within the spirit and principles of the invention, any modifications, equivalent substitutions and improvements done etc., should be included in
Within protection scope of the present invention.
Claims (5)
1. a kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water, it is characterised in that prepare TiO first2It is porous
Microballoon；Then FeCo/TiO is prepared2；Finally by FeCo/TiO2It is sufficiently mixed with the aqueous solution containing organic matter, adds persulfate
Irradiated simultaneously with ultraviolet, in FeCo/TiO2SO is produced with activation under the synergy of ultraviolet light4 ﹣And OH, so as to degrade
Majority of organic pollutants in waste water, specifically includes following steps：
(1) TiO, is prepared2Porous microsphere：
(1) butyl titanate and absolute ethyl alcohol are sufficiently mixed, butyl titanate used is 1 with absolute ethyl alcohol mass ratio:1~1:
2, mixed liquor A is made；
(2) certain volume absolute ethyl alcohol separately is taken, after 1M salt acid for adjusting pH to 2~3, is added to mixed liquor A made from step (1)
In, the mass ratio of absolute ethyl alcohol and mixed liquor A is 1:1.5~1:2.5, electromagnetic agitation 30min is allowed to be sufficiently mixed, and obtains TiO2
Sol B；
(3) by TiO2After sol B is mixed with phenol, it is added in normal heptane decentralized medium, is being sufficiently stirred for lower dropwise addition formaldehyde, rises
Warm to 60~70 DEG C are reacted, and mixed liquor is filtered after about 1.5h, and are cleaned repeatedly with ethanol, obtain milky poly-
Compound, is TiO2Complex microsphere C；
(4) by TiO2After complex microsphere C drying, polymer is decomposed through 500 DEG C of calcination process 2h, TiO is obtained2Porous microsphere；
(2) FeCo/TiO, is prepared2：Cobalt nitrate and nitric acid iron mixed solution are prepared, TiO prepared by step (4)2Porous microsphere
Add in above-mentioned mixed solution, electromagnetic agitation 5h, then 80 DEG C of stirring in water bath evaporations are near dry, through 500 DEG C of high-temperature roastings after drying
5h, is then placed in drying basin and is cooled to room temperature, obtains FeCo/TiO2；
(3) uviol lamp, is placed into organic wastewater or on organic wastewater surface, by 0.1~1% ratio of organic wastewater quality
Example adds FeCo/TiO2, persulfate is added in 0.1~1% ratio of organic wastewater quality, is aerated, reaction 2~
12h, in FeCo/TiO2SO is produced with activation under the synergy of ultraviolet light4 ﹣And OH, so as to largely have in degrading waste water
Organic pollutants.
The processing method of Organic substance in water, its feature 2. activation persulfate Fourier Series expansion technique according to claim 1 is degraded
It is：Persulfate is selected from sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, monopersulfate sodium, single over cure in the step (3)
Potassium hydrogen phthalate or ammonium persulfate-sodium bisulfate.
The method of Organic substance in water 3. activation persulfate Fourier Series expansion technique according to claim 1 is degraded, it is characterised in that：
The pH value of the reaction system is 3~11.
The method of Organic substance in water 4. activation persulfate Fourier Series expansion technique according to claim 1 is degraded, it is characterised in that：
In step (3), TiO2The mass ratio of sol B and phenol is 5:1~10:1, TiO2The mass ratio of sol B and normal heptane is 1:1~
1:1.5, TiO2The mass ratio of sol B and formaldehyde is 2:1~10:1.
The method of Organic substance in water 5. activation persulfate Fourier Series expansion technique according to claim 1 is degraded, it is characterised in that：
In step (2), iron, the load capacity of cobalt are respectively the 20~50% of titania weight, 20~50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710270854.5A CN106955708A (en) | 2017-04-24 | 2017-04-24 | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710270854.5A CN106955708A (en) | 2017-04-24 | 2017-04-24 | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106955708A true CN106955708A (en) | 2017-07-18 |
Family
ID=59485019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710270854.5A Pending CN106955708A (en) | 2017-04-24 | 2017-04-24 | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106955708A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640205A (en) * | 2018-05-31 | 2018-10-12 | 合肥宸翊商贸有限公司 | A kind of water remediation floating plate of high light transmission |
| CN108726659A (en) * | 2018-05-31 | 2018-11-02 | 合肥宸翊商贸有限公司 | A kind of preparation method of the floating plate of promotion water remediation |
| CN108726628A (en) * | 2018-05-31 | 2018-11-02 | 合肥宸翊商贸有限公司 | A kind of floating plate for promoting water remediation |
| CN108751324A (en) * | 2018-05-31 | 2018-11-06 | 合肥宸翊商贸有限公司 | A kind of water remediation material |
| CN110002572A (en) * | 2019-04-19 | 2019-07-12 | 天津工业大学 | A kind of Ag2O/TiO2The method for activating persulfate purification phenol wastewater |
| CN110090657A (en) * | 2019-06-04 | 2019-08-06 | 中南大学 | A kind of sepiolite composite catalyst and preparation method thereof, novel Fenton-like and its application |
| CN110240253A (en) * | 2019-07-23 | 2019-09-17 | 大连民族大学 | A method of utilizing remaining alkali Heat Treatment purified cotton black liquor |
| CN110605133A (en) * | 2019-08-22 | 2019-12-24 | 中国科学院山西煤炭化学研究所 | Nitrogen-doped titanium-carbon composite catalyst and preparation method and application thereof |
| CN111233075A (en) * | 2018-11-28 | 2020-06-05 | 株式会社日本光电科技 | Ultraviolet treatment method and system |
| CN111359634A (en) * | 2020-03-18 | 2020-07-03 | 同济大学 | Iron-doped cobalt disulfide nanoparticles and preparation method thereof |
| CN111533210A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Method for treating dye wastewater by using UV (ultraviolet) to heat and activate persulfate |
| CN112158908A (en) * | 2020-08-06 | 2021-01-01 | 浙江工业大学 | Ultraviolet-light-based reinforced sulfur-modified alpha-Fe2O3Method for degrading typical PPCPs in water by persulfate |
| CN113264583A (en) * | 2021-04-23 | 2021-08-17 | 江苏大地益源环境修复有限公司 | Process and equipment based on electric persulfate activation technology |
| US11192805B2 (en) | 2018-05-29 | 2021-12-07 | Florida Polytechnic University Board of Trustees | Synergistic chemical oxidative and photocatalytic enhancer system (scopes) for wastewater remediation |
| JP2022063837A (en) * | 2020-10-12 | 2022-04-22 | 台灣中油股▲ふん▼有限公司 | Processing method of waste water simultaneously containing ammonia-nitrogen of high concentration and organic constructs |
| CN114426359A (en) * | 2021-12-17 | 2022-05-03 | 南京师范大学 | Method for treating wastewater containing chlorinated organic phosphate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525177A (en) * | 2008-12-16 | 2009-09-09 | 中国海洋大学 | Method of using active persulphate for processing difficult-biodegradability organic waste water |
| CN103896388A (en) * | 2014-03-26 | 2014-07-02 | 华南理工大学 | Method for treating organic wastewater by using double catalysts to heterogeneously activate persulfates |
-
2017
- 2017-04-24 CN CN201710270854.5A patent/CN106955708A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525177A (en) * | 2008-12-16 | 2009-09-09 | 中国海洋大学 | Method of using active persulphate for processing difficult-biodegradability organic waste water |
| CN103896388A (en) * | 2014-03-26 | 2014-07-02 | 华南理工大学 | Method for treating organic wastewater by using double catalysts to heterogeneously activate persulfates |
Non-Patent Citations (2)
| Title |
|---|
| PANNEERSELVAM SATHISHKUMAR ET AL.: "CoFe2O4/TiO2 nanocatalysts for the photocatalytic degradation of Reactive Red 120 in aqueous solutions in the presence and absence of electron acceptors", 《PANNEERSELVAM SATHISHKUMAR ET AL.》 * |
| 石可瑜: "纳米晶粒TiO2多孔微球的合成与表征", 《催化学报》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11192805B2 (en) | 2018-05-29 | 2021-12-07 | Florida Polytechnic University Board of Trustees | Synergistic chemical oxidative and photocatalytic enhancer system (scopes) for wastewater remediation |
| CN108640205A (en) * | 2018-05-31 | 2018-10-12 | 合肥宸翊商贸有限公司 | A kind of water remediation floating plate of high light transmission |
| CN108726659A (en) * | 2018-05-31 | 2018-11-02 | 合肥宸翊商贸有限公司 | A kind of preparation method of the floating plate of promotion water remediation |
| CN108726628A (en) * | 2018-05-31 | 2018-11-02 | 合肥宸翊商贸有限公司 | A kind of floating plate for promoting water remediation |
| CN108751324A (en) * | 2018-05-31 | 2018-11-06 | 合肥宸翊商贸有限公司 | A kind of water remediation material |
| CN111233075A (en) * | 2018-11-28 | 2020-06-05 | 株式会社日本光电科技 | Ultraviolet treatment method and system |
| CN110002572A (en) * | 2019-04-19 | 2019-07-12 | 天津工业大学 | A kind of Ag2O/TiO2The method for activating persulfate purification phenol wastewater |
| CN110090657B (en) * | 2019-06-04 | 2020-01-14 | 中南大学 | Sepiolite composite catalyst, preparation method thereof, novel Fenton-like system and application thereof |
| CN110090657A (en) * | 2019-06-04 | 2019-08-06 | 中南大学 | A kind of sepiolite composite catalyst and preparation method thereof, novel Fenton-like and its application |
| CN110240253A (en) * | 2019-07-23 | 2019-09-17 | 大连民族大学 | A method of utilizing remaining alkali Heat Treatment purified cotton black liquor |
| CN110605133A (en) * | 2019-08-22 | 2019-12-24 | 中国科学院山西煤炭化学研究所 | Nitrogen-doped titanium-carbon composite catalyst and preparation method and application thereof |
| CN111359634A (en) * | 2020-03-18 | 2020-07-03 | 同济大学 | Iron-doped cobalt disulfide nanoparticles and preparation method thereof |
| CN111533210A (en) * | 2020-04-29 | 2020-08-14 | 南京中微纳米功能材料研究院有限公司 | Method for treating dye wastewater by using UV (ultraviolet) to heat and activate persulfate |
| CN112158908A (en) * | 2020-08-06 | 2021-01-01 | 浙江工业大学 | Ultraviolet-light-based reinforced sulfur-modified alpha-Fe2O3Method for degrading typical PPCPs in water by persulfate |
| JP2022063837A (en) * | 2020-10-12 | 2022-04-22 | 台灣中油股▲ふん▼有限公司 | Processing method of waste water simultaneously containing ammonia-nitrogen of high concentration and organic constructs |
| JP7177220B2 (en) | 2020-10-12 | 2022-11-22 | 台灣中油股▲ふん▼有限公司 | At the same time, a method for treating wastewater containing high concentrations of ammonium nitrogen and organic constituents |
| CN113264583A (en) * | 2021-04-23 | 2021-08-17 | 江苏大地益源环境修复有限公司 | Process and equipment based on electric persulfate activation technology |
| CN113264583B (en) * | 2021-04-23 | 2023-03-17 | 江苏大地益源环境修复有限公司 | Process and equipment based on electric persulfate activation technology |
| CN114426359A (en) * | 2021-12-17 | 2022-05-03 | 南京师范大学 | Method for treating wastewater containing chlorinated organic phosphate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955708A (en) | A kind of method for activating persulfate Fourier Series expansion technique degraded Organic substance in water | |
| CN106807376B (en) | Magnetic nano composite catalyst and preparation method and application thereof | |
| CN104258885B (en) | A kind of preparation method of sheet hydroxyl cupric phosphate nano material | |
| CN108212158B (en) | Fenton catalyst and preparation method and application thereof | |
| CN109999890A (en) | A kind of ferro-cobalt bimetallic original position doping MCM-41 catalyst and its preparation method and application | |
| CN108212192A (en) | A kind of light-fenton catalyst and preparation method thereof | |
| Tang et al. | A novel S-scheme heterojunction in spent battery-derived ZnFe2O4/g-C3N4 photocatalyst for enhancing peroxymonosulfate activation and visible light degradation of organic pollutant | |
| CN106582812A (en) | Composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and preparation method thereof | |
| CN104368325A (en) | Preparation method of formaldehyde-photodegrading honeycomb activated carbon | |
| Liu et al. | Nitrogen doped Cu/Fe@ PC derived from metal organic frameworks for activating peroxymonosulfate to degrade Rhodamine B | |
| CN103071493A (en) | Preparation method of hollow Ag/Zno microsphere photocatalyst | |
| CN108176400A (en) | The method of Atrazine in a kind of nano zero valence iron/graphene complex activation persulfate removal water body | |
| CN105642248A (en) | Formaldehyde filter screen composite material for air purifier and preparation method thereof | |
| CN109574333A (en) | A kind of copper modification nitrogen-doped titanium dioxide material and its preparation method and application | |
| CN104226287A (en) | Preparation method of nano titanium dioxide photocatalyst thin film | |
| Xiao et al. | Graphitic carbon nitride for photocatalytic degradation of sulfamethazine in aqueous solution under simulated sunlight irradiation | |
| CN101550497B (en) | Method of preparing zinc oxide composite coated with nano-silver particles by one step wet heating | |
| CN104549400A (en) | Visible light response type TiO2 nanotube array, as well as preparation method and applications thereof | |
| CN102145950A (en) | Method for processing printing and dying wastewater | |
| CN102701315A (en) | Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton | |
| CN110327928A (en) | A kind of photochemical catalyst and preparation method thereof of efficient degradation organic pollutant | |
| CN108246329B (en) | N-doped graphene-cerium oxide composite catalyst and application thereof in acidic degradation-resistant wastewater treatment | |
| CN107555526A (en) | A kind of method of composite visible light catalyst processing waste water containing chrome | |
| CN105883915A (en) | Nano-crystal titanium dioxide microspheres and application thereof as ozonation catalyst | |
| CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170718 |