CN105797728B - A kind of magnetic Nano CuxO‑Fe2O3The preparation method and applications of ozone catalyst - Google Patents
A kind of magnetic Nano CuxO‑Fe2O3The preparation method and applications of ozone catalyst Download PDFInfo
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- CN105797728B CN105797728B CN201610229363.1A CN201610229363A CN105797728B CN 105797728 B CN105797728 B CN 105797728B CN 201610229363 A CN201610229363 A CN 201610229363A CN 105797728 B CN105797728 B CN 105797728B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002351 wastewater Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 claims abstract description 16
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000013019 agitation Methods 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000011943 nanocatalyst Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 230000033558 biomineral tissue development Effects 0.000 abstract description 4
- 238000001802 infusion Methods 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- 238000006385 ozonation reaction Methods 0.000 description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229920005479 Lucite® Polymers 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- -1 small molecule aldehyde Chemical class 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 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 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 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 description 2
- 235000011082 potassium citrates Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 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
- B01J23/70—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
- B01J23/745—Iron
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention relates to a kind of Cu x O‑Fe2O3The preparation method and applications of nano material, the invention belongs to Sewage advanced treatment and environmental catalysis technical field.Cu is prepared by infusion process x O‑Fe2O3Nano material, it is added to as catalyst in hardly degraded organic substance waste water, catalysis ozone reaction, promotes the degraded of organic pollution, drastically increase the mineralization rate of organic matter；Cu x O‑Fe2O3Nano material size is small, the good dispersion in nano material system, and Cu x O‑Fe2O3With magnetic, reacted catalyst can be efficiently separated with water, reclaimed by means of external magnetic field, and catalyst stability reuses remain in that high catalytic activity afterwards three times well.The Cu that the present invention adds x O‑Fe2O3Catalyst can significantly improve removal efficiency of the ozone to pollutant, under the conditions of pH is 3~11, can obtain preferable catalytic effect, and the dosage of catalyst is small, recycling performance is stable, is had broad prospects in water process.
Description
Technical field
Present invention relates particularly to a kind of magnetic Nano material CuxO-Fe2O3The preparation method of ozone catalyst and its it is being catalyzed
Ozone removes the application in Pollutants in Wastewater, belongs to Sewage advanced treatment and environmental catalysis technical field, suitable for difficult degradation
The processing of organic wastewater.
Background technology
Ozone has very high oxidation-reduction potential (2.07V), due to its Strong oxdiative ability, is received in water treatment field
Extensive concern.But there is also deficiency, the reaction of ozone and organic matter would generally generate small molecule aldehyde or carboxylic acid, not further with
Ozone reaction, cause the mineralization rate of ozone oxidation organic matter low.Compared with independent ozone oxidation reaction, catalytic ozonation
As a kind of high-level oxidation technology, dominant mechanism be in the presence of a catalyst catalysis ozone decompose produce reaction rate faster,
The stronger hydroxyl radical free radical (oxidation-reduction potential 2.80V) of oxidisability, can degrading waste water processing in a variety of difficult degradations production
Thing, it is the research heat in advanced treatment of wastewater field in recent years so as to realize the efficient sewerage processing in the case of low-ozone dosage
Point.Catalytic ozonation technology is divided into two classes by the difference of used catalyst：One kind is using metal ion as the homogeneous of catalyst
Catalytic ozonation reacts；Another kind of reacted using the heterogeneous catalytic ozonation of solid catalyst.
Heterogeneous catalysis ozonation technique is a kind of emerging high-level oxidation technology, with homogeneous catalysis ozonation technique phase
Than having the advantages that catalyst is not allowed to be easy to run off, do not introduce secondary pollution, repeatable utilization, there is more preferable application prospect.It is non-
Most widely used catalyst mainly has four types in homogeneous catalysis ozonization：(1) metal-oxide catalyst；
(2) loaded catalyst；(3) mineral type or modified mineral type catalyst；(4) active carbon type catalyst.Wherein using most extensive
Catalyst be some typical transition metal oxide and carried noble metal oxides, mainly pass through the surface of catalyst
Active group promotes ozone decomposed generation oxygen-content active species or formation two kinds of approach of complex compound to carry out degradation of contaminant.These gold
The dissolution that category oxide generally has metal ion causes loss of active component, in the case where pH is neutrallty condition, ineffective, pH is fitted
With scope it is small the shortcomings of.It is high and stably to prepare catalytic activity, the few catalyst of stripping quantity is the side for needing to be continually striving at present
To.
The Cu prepared using infusion processxO-Fe2O3, due to the reduction corrosion of middle iron and the oxygen of copper under preparation process high temperature
Change and constantly occur, reaction particles size constantly diminishes, and magnetic Nano material is belonged to after calcining.The synthetic method of this catalyst with
And the catalyst is used for catalysis ozone reaction and had not been reported.Magnetic Nano material, one side size is small, good dispersion, favorably
In the activity for improving catalyst；On the other hand due to quick separating, again recovery, profit can be realized using external magnetic field with magnetic
With.Therefore iron copper composite catalyst can be prepared using infusion process to be used in catalytic ozonation.
The content of the invention
Prepare that cost is high, is difficult to recovery and use the invention aims to solving in heterogeneous catalysis nano particle,
A kind of the problems such as pH scope of applications are limited, easy dissolution is lost in, it is desirable to provide magnetic Nano CuxO-Fe2O3The system of ozone catalyst
Preparation Method and its application.
The Cu of the present inventionxO-Fe2O3Oxidation rate is slow when catalyst not only overcomes the independent ozone to remove pollutant and mineralization rate
Efficiency is low, and homogeneous catalyst can not recycle and reuse, introduce secondary pollution problems.Also overcome current metal oxidation
The problems such as thing catalyst effect is unstable, the pH scope of applications are small, the hardly possible of particularly nano particle reclaims.Do not have in preparation process
There is the expensive heavy metal of addition, cost is low, while iron, copper belong to conventional transition metal element, and toxicity is low.CuxO-Fe2O3Catalysis
Agent provides a kind of efficient, lasting method for the removal of pollutant in water body.
The present invention can be achieved through the following technical solutions：
Magnetic Nano Cu proposed by the present inventionxO-Fe2O3The preparation method of ozone catalyst, is comprised the following steps that：
(1) by Cu (NO3)2Soluble in water, stirring makes its dissolving, is made into the Cu (NO that concentration is 0.1~0.2mol/L3)2It is molten
Liquid, dispersant is configured to 1mol/L solution, obtains dispersant solution, it is standby；
(2) 5.6g~11.2g iron powders are added to the Cu (NO obtained by step (1)3)2In solution, then add 0.1 ‰~
Dispersant solution obtained by the step of 1 ‰ volume (1), 1~2h of mechanical agitation at 120 DEG C；The iron, copper mol ratio is controlled to be
0.5:1~2:1；
(3) mixture of gained dries 2~4h at 100~120 DEG C after mechanical agitation, obtains solid；
(4) dried solid is calcined into 1~2h at 450~550 DEG C, obtains CuxO-Fe2O3Magnetic Nano material.
In the present invention, dispersant described in step (1) is citrate, including its common soluble-salt form, citric acid
It is any in ammonium, sodium citrate or potassium citrate etc..
The Cu obtained using preparation method of the present inventionxO-Fe2O3Ozone catalyst is heterogeneous catalysis, in preparation process
In, the corrosion of iron and the reduction of copper are carried out simultaneously, and during continuous corrosion with oxidation, the size of catalyst constantly subtracts
Small, centre is iron-clad, and outer layer is sequentially distributed Fe2O3、Cu、Cu2O、CuO；CuxO-Fe2O3Ozone catalyst forms：Iron mainly with
Fe、Fe2O3Form exist, copper is with Cu, Cu2O, CuO forms are present.
The magnetic Nano Cu that preparation method of the present invention obtainsxO-Fe2O3Ozone catalyst removes waste water in catalysis ozone
Application in middle pollutant, is comprised the following steps that：
(1) add waste water into reactor, the pH for adjusting waste water is 3~11；
(2) Cu is added into waste waterxO-Fe2O3Ozone catalyst, with gross mass content meter, CuxO-Fe2O3Ozone catalyst
It is 100~200mg/L to add concentration, and ozone is passed through into reactor, carries out catalytic oxidation, reacts knot after 30~120min
Beam, sampling analysis water quality；
(3)CuxO-Fe2O3The recovery of nano material：After reaction terminates, using external magnetic field by CuxO-Fe2O3Ozone catalytic
Agent is effectively reclaimed, and is easy to CuxO-Fe2O3The recycling of ozone catalyst, overcome what nanocatalyst was difficult to separate and recover to lack
Point.
In the present invention, the ozone that concentration is 2~4mg/min is passed through in step (2) in reactor.
In the present invention, described CuxO-Fe2O3Catalyst is by X-ray diffractometer (XRD), X-ray photoelectron spectroscopic analysis
(XPS) it is Fe, Fe to characterize composition2O3、Cu、Cu2O, CuO, catalyst are by using iron as shell, outer layer is sequentially distributed Fe2O3、Cu、
Cu2O、CuO；Prepared CuxO-Fe2O3Catalyst shape is nano-scale particle.
The inventive method can be used alone, and can also be used in combination with other water treatment technologies.The present invention is single with tradition
Only ozonation technology and homogeneous catalysis ozonation technology are compared, and have some following advantage：
1.CuxO-Fe2O3Preparation method carried out simultaneously with the reduction of zeroth order iron rot and copper so that the reaction of catalyst
It is active high.Preparing raw material is easy to get, and synthesis cycle is short.
2.CuxO-Fe2O3The pH of O3 catalytic oxidation reaction is applied widely, can be obtained in the range of being 3~11 in pH
Good effect, its application is expanded.
3. by using heterogeneous catalysis CuxO-Fe2O3, the present invention significantly improves the clearance and significantly of pollutant
Improve the mineralization rate of Recalcitrant chemicals so that most of even all of TOC is converted into CO2And H2O, therefore go well
Except Recalcitrant chemicals in waste water.
4. nano material CuxO-Fe2O3There is good dispersiveness in water, and to the absorption property of Pollutants in Wastewater
Very small, catalytic action is contacted with each other essentially from ozone, catalyst, pollutant, and hydroxyl is produced in catalyst surface ozone decomposed
Base free radical cracking pollutant.Therefore, less catalyst amountses can obtains good catalysis ozone effect.
5.CuxO-Fe2O3Nano material has magnetic, and quick separating, recovery can be realized by externally-applied magnetic field.With compared with
Good mechanical strength, after reaction, copper-based of iron will not introduce the secondary pollution of water body without dissolution.Reacted in catalysis ozone
Under the conditions of reuse repeatedly after still there is stable catalytic effect.
Brief description of the drawings
Fig. 1 is Cu in embodiment 1xO-Fe2O3SEM figure.
Fig. 2 is repefral concentration clearance figure in embodiment 4.When ■ represents independent ozonization in figure
DMP removal curve, ◆ the removal curve of DMP during catalyst CuO effects is indicated, ▲ indicate catalyst Fe2O3During effect
DMP removal curve, ● indicate catalyst CuxO-Fe2O3DMP removal curve during effect.
Fig. 3 is the clearance figure of repefral (DMP) in embodiment 9.■, which is represented, in figure catalyst action
When DMP removal curve, ◆ table PO4 3-In the presence of removal curve of the catalyst action to DMP, ▲ represent and be catalyzed in the presence of tBuOH
Agent acts on the removal curve to DMP.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the present invention will be further described.Embodiments of the invention are given below,
But the application not limited to this of the present invention.
Embodiment 1
(1)CuxO-Fe2O3Preparation：By Cu (NO3)2·3H2O is soluble in water, and stirring and dissolving forms 0.1mol/L Cu
(NO3)2Solution, 5.6g iron powder and the ammonium citrate dispersant of 0.1 ‰ volumes are then added into the 100mL solution, 120
At DEG C after mechanical agitation 1h, solid particle and solution are dried into 3h at 110 DEG C, solid is finally calcined into 1h at 500 DEG C, obtained
To CuxO-Fe2O3Magnetic Nano material.Its SEM photograph is shown in Fig. 1, and catalyst is uniform ellipsoidal particle, and size is 60nm left
It is right.
(2) CuO preparation：By Cu (NO3)2·3H2O is soluble in water, and stirring and dissolving forms 0.1mol/L Cu (NO3)2It is molten
Liquid, the ammonium citrate dispersant of 0.1 ‰ volumes is then added into the 100mL solution, will at 120 DEG C after mechanical agitation 1h
Solid particle dries 3h with solution at 110 DEG C, and solid finally is calcined into 1.5h at 500 DEG C, obtains CuO.
(3)Fe2O3Preparation：5.6g iron powder is added into 100mL ultra-pure waters and the ammonium citrate of 0.1 ‰ volumes disperses
Agent, at 120 DEG C after mechanical agitation 1h, solid particle and solution are dried into 3h at 110 DEG C, finally by solid at 500 DEG C
1.5h is calcined, obtains Fe2O3。
Embodiment 2
By Cu (NO3)2·3H2O is soluble in water, and stirring and dissolving forms 0.2mol/L Cu (NO3)2Solution, then to 100mL
5.6g iron powder and the sodium citrate dispersant of 0.5 ‰ volumes are added in the solution, will at 120 DEG C after mechanical agitation 1.5h
Solid particle dries 4h with solution at 100 DEG C, and solid finally is calcined into 2h at 450 DEG C, obtains CuxO-Fe2O3Magnetic Nano
Material.
Embodiment 3
CuxO-Fe2O3Preparation：By Cu (NO3)2·3H2O is soluble in water, and stirring and dissolving forms 0.1mol/L Cu (NO3)2
Solution, 11.2g iron powder and the potassium citrate dispersant of 1 ‰ volumes, the machine at 120 DEG C are then added into the 100mL solution
After tool stirring 2h, solid particle and solution are dried into 2h at 120 DEG C, solid is finally calcined into 2h at 550 DEG C, obtained
CuxO-Fe2O3Magnetic Nano material.
Embodiment 4
Using repefral as target contaminant, it is 5.70 to prepare water sample pH, and concentration is 50mg/L simulation
Waste water.2L simulated wastewaters are taken to be separately added into 100mg/L's in 2.5L internal diameters 80mm, high 500mm lucite reactor
CuxO-Fe2O3、CuO、Fe2O3, be passed through 4mg/min ozone at room temperature, mechanical agitation, reaction time 30min, reaction 5,
10th, 30min samplings detection repefral concentration and TOC.Compare the Cu that independent ozone obtains with embodiment 1xO-
Fe2O3、CuO、Fe2O3In differential responses time DMP concentration clearance.Result is obtained as shown in Fig. 2 CuxO-Fe2O3、CuO、
Fe2O3Catalysis ozone degradation effect is apparently higher than independent ozone, and the Cu in catalyst in threexO- Fe2O3Urged with highest
Change activity.The heterogeneous catalysis Cu of synthesisxO-Fe2O3During oxidative degradation repefral, reaction rate is fast, reaction
Repefral clearance reaches 92% when carrying out 10min.
Embodiment 5
Dyeing and Printing Wastewater Biological Treatment secondary clarifier effluent 2L is taken in 2.5L internal diameters 80mm, high 500mm lucite reactor,
Water sample pH=8.50, initial COD are 94.21mg/L.It is separately added into Cu prepared by 150mg/L embodiment 1xO- Fe2O3, room
2mg/min ozone, mechanical agitation, reaction time 40min, in reaction 5,10,20,40min sampling detections are passed through under temperature
COD.Compare independent ozone and CuxO-Fe2O3In differential responses time COD reduction.It is as shown in the table to obtain result, in difference
Point in time sampling, catalysis ozone will be good than the degradation effect of independent ozone.React after 20min individually that ozone COD is no longer
Reduce, and catalysis ozone reaction COD with the reaction time be gradually reduced, at the end of 40min is reacted.COD is
42.94mg/L, reach one-level emission standard A.
Embodiment 6
Certain industrial park waste water 2L is taken in 2.5L internal diameters 80mm, high 500mm lucite reactor, water sample pH=
7.00th, initial COD is 420.72mg/L.It is separately added into Cu prepared by 200mg/L embodiment 1xO-Fe2O3, it is passed through at room temperature
3mg/min ozone, mechanical agitation, reaction time 40min, in reaction 5,10,20,40min sampling detections COD.Compare list
Only ozone and CuxO-Fe2O3In differential responses time COD reduction.Obtain that result is as shown in the table, taken at different time points
Sample, catalysis ozone will be good than the degradation effect of independent ozone.Catalysis ozone reaction COD gradually subtracts with the progress in reaction time
Small, at the end of 40min is reacted, COD reduces 75%.
Embodiment 7
Using repefral as target contaminant, the simulated wastewater that water sample concentration is 50mg/L is prepared.Take 4 parts
2L simulated wastewaters in 2.5L internal diameters 80mm, high 500mm lucite reactor, 4 parts of water samples adjust respectively pH for 4,5.7,7,
9 and add embodiment 2 preparation 100mg/L CuxO-Fe2O3, 4mg/min ozone is passed through at room temperature, mechanical agitation, is reacted
Sampling detection repefral concentration and TOC after time is 60min.Test result indicates that it is 50mg/ to initial concentration
L, pH is the DMP waste water from 4,5.7,7,9 respectively, and concentration removal rate quickly, reaches 100% within 60min, and TOC
It is as shown in the table for clearance, in the range of 4~9, CuxO-Fe2O3It is respectively provided with good catalytic effect；CuxO-Fe2O3In acid condition
The effect of lower catalysis ozone is more preferable.
Embodiment 8
Using oxalic acid as target contaminant, the simulated wastewater that water sample concentration is 50mg/L is prepared.Take 5 parts of 2L simulated wastewaters in
2.5L internal diameters 80mm, in high 500mm lucite reactor, 5 parts of water samples adjust pH 5,7,9,11 and to add embodiment respectively
3 100mg/L prepared CuxO-Fe2O3, 3mg/min ozone is passed through at room temperature, and mechanical agitation, the reaction time is after 60min
Sampling detection concentration of oxalic acid.Test result indicates that it is that 50mg/L, pH are given up from 5,7,9,11 oxalic acid respectively to initial concentration
Water, it is as shown in the table for oxalic acid clearance, reaction time 60min, and to the catalytic degradation effect of oxalic acid, it is as shown in the table, in 5~11 models
In enclosing, CuxO-Fe2O3Good catalytic effect is respectively provided with, the concentration clearance of oxalic acid is above 45%；In faintly acid weakly acidic pH
Under the conditions of good catalytic activity.
Embodiment 9
Using repefral as target contaminant, 3 parts of 2L water samples are prepared, add 100mg phthalic acids two
Methyl esters, then sequentially add 10mL ultra-pure waters, 5mol/L Na3PO4, 5mol/L TBA, regulation pH be 7.00.Take 3 parts of 2L moulds
Intend waste water in 2.5L internal diameters 80mm, high 500mm lucite reactor, be separately added into 100mg/L CuxO-Fe2O3, room temperature
Under be passed through 4mg/min ozone, mechanical agitation, reaction time 120min, reaction 5,10,20,30,40,60,90,
120min sampling detection repefral concentration.The present embodiment has investigated 25mmol/L PO4 3-, BtOH pairs of the tert-butyl alcohol
CuxO-Fe2O3The influence of catalysis ozone reaction.Shown in experimental result Fig. 3.PO is added in reaction4 3-, after BtOH, hence it is evident that inhibit
DMP degraded.Due to PO4 3-The original oh group of catalyst surface is instead of, the avtive spot for showing catalyst surface is hydroxyl
Base group, the tert-butyl alcohol are the Indirect indicators of hydroxyl radical free radical.Therefore CuxO- Fe2O3Catalysis ozone reaction mechanism is that promotion is smelly
Oxygen decomposes with catalyst surface hydroxy combining and produces hydroxyl radical free radical.
Embodiment 10
Using repefral as target contaminant, the simulated wastewater that water sample concentration is 50mg/L is prepared.Take 1 part
In 2.5L internal diameters 80mm, high 500mm lucite reactor, regulation pH is 7 and adds the preparation of embodiment 1 2L simulated wastewaters
150mg/L CuxO-Fe2O3,2mg/min ozone, mechanical agitation are passed through at room temperature, sampling inspection after the reaction time is 120min
Survey repefral concentration and TOC.Catalyst is 150mg/L CuxO-Fe2O3, will react the catalyst after terminating and uses
Magnet separation, recovery, in 60 DEG C of dry 2h, obtain the catalyst that can be reused, so recycling 3 times.Experimental result
Such as following table reuse three times, the DMP of catalysis ozone can reach 100%, TOC clearances and be kept approximately constant.As a result show,
CuxO-Fe2O3 catalytic ozonation degradation DMP waste water has obviously catalytic effect, and catalytic performance is steady after multiplicating
It is fixed.
| Access times | 1 | 2 | 3 |
| TOC clearances (%) | 47.33 | 46.96 | 45.23。 |
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (5)
- A kind of 1. magnetic Nano Cu x O-Fe2O3The preparation method of ozone catalyst, it is characterised in that comprise the following steps that：（1）By Cu (NO3)2Soluble in water, stirring makes its dissolving, is made into the Cu (NO that concentration is 0.1 ~ 0.2 mol/L3)2Solution, will Dispersant is configured to 1 mol/L solution, obtains dispersant solution, standby；（2）The g iron powders of 5.6 g ~ 11.2 are added to step（1）Cu (the NO of gained3)2In solution, 0.1 ‰ ~ 1 ‰ bodies are then added Long-pending step（1）The dispersant solution of gained, the h of mechanical agitation 1 ~ 2 at 120 DEG C；It is 0.5 to control iron, copper mol ratio:1~2: 1；（3）The mixture of gained dries 2 ~ 4 h at 100 ~ 120 DEG C after mechanical agitation, obtains solid；（4）Dried solid is calcined into 1 ~ 2 h at 450 ~ 550 DEG C, obtains Cu x O-Fe2O3Magnetic Nano material.
- 2. preparation method according to claim 1, it is characterised in that step（1）Described in dispersant be citrate.
- 3. preparation method according to claim 1, it is characterised in that the Cu that the preparation method obtains x O-Fe2O3Ozone is urged Agent is heterogeneous catalysis Cu x O-Fe2O3, centre is iron-clad, and outer layer is sequentially distributed Fe2O3、Cu、Cu2O、CuO；Cu x O-Fe2O3 Ozone catalyst forms：Iron is mainly with Fe, Fe2O3Form exist, copper is with Cu, Cu2O, CuO forms are present.
- A kind of 4. magnetic Nano Cu that preparation method obtains as claimed in claim 1 x O-Fe2O3Ozone catalyst is in catalysis ozone Remove the application in Pollutants in Wastewater, it is characterised in that comprise the following steps that：（1）Add waste water into reactor, the pH for adjusting waste water is 3 ~ 11；（2）Cu is added into waste water x O-Fe2O3Ozone catalyst, with gross mass content meter, Cu x O-Fe2O3Ozone catalyst adds Concentration is 100 ~ 200 mg/L, and ozone is passed through into reactor, carries out catalytic oxidation, reacts and terminate after 30 ~ 120 min, Sampling analysis water quality；（3）Cu x O-Fe2O3The recovery of nano material：After reaction terminates, using external magnetic field by Cu x O-Fe2O3Ozone catalyst has Effect recovery, is easy to Cu x O-Fe2O3The recycling of ozone catalyst, overcome nanocatalyst be difficult to separation and recovery the shortcomings that.
- 5. application according to claim 4, it is characterised in that step（2）The smelly of 2 ~ 4 mg/min is passed through in middle reactor Oxygen.
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