CN108404929A - A kind of preparation method and applications of magnetic Nano ferrimanganic bimetallic oxide composite catalyst - Google Patents
A kind of preparation method and applications of magnetic Nano ferrimanganic bimetallic oxide composite catalyst Download PDFInfo
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- CN108404929A CN108404929A CN201810140407.2A CN201810140407A CN108404929A CN 108404929 A CN108404929 A CN 108404929A CN 201810140407 A CN201810140407 A CN 201810140407A CN 108404929 A CN108404929 A CN 108404929A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910003144 α-MnO2 Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 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 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 206010001497 Agitation Diseases 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 150000003254 radicals Chemical class 0.000 abstract description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000005415 magnetization Effects 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000003918 potentiometric titration Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyethylene pyrrole Pyrrolidone Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910006648 β-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/393—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Abstract
The invention discloses a kind of preparation method and applications of magnetic Nano ferrimanganic bimetallic oxide composite catalyst.The present invention is by Fe3O4With α MnO2The two combines, and can both overcome the difficulty for being difficult to recycle, and reduces secondary pollution, and can reach higher catalytic activity by the synergistic effect of the two, can effectively activate PS and generate a large amount of free radical cracking Organic substance in water.Magnetic Nano ferrimanganic bimetallic oxide composite catalyst saturation magnetization prepared by the present invention be 39.89emu/g, can be quickly be separated from the water out by external magnetic field.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of magnetic Nano ferrimanganic bimetallic oxide composite catalyzing
The preparation method and applications of agent.
Background technology
Fenton and embryonic stem-like cells the advantage is that the hydroxyl of generation as more one kind is applied in chemical oxidization method
Base free radical (OH) has very strong oxidisability, achievees the purpose that remove pollutant.But since it requires reaction condition in pH value
It is 3 or so, and H2O2It is expensive, preserve it is difficult, it is excessively high so as to cause processing cost.
Based on potentiometric titrations (SO4 -) reaction high-level oxidation technology be widely used to wastewater treatment, due to it
The free radical of the strong oxidizing property of generation can be with efficient oxidation degradation of organic substances.Activate peroxy-monosulfate (PMS) and persulfate
(PS) SO generated4 -·(E0=2.5~3.1V) compared to the .OH (E of traditional Fenton (Fenton) reagent method generation0=1.8~
2.7V), there is higher oxidation-reduction potential, thus be more suitable for aoxidizing hardly degraded organic substance.Based on SO4 -Advanced oxidation skill
Art processing organic wastewater applicable elements are wide in range, efficient, have very high application potential.By heat, ultraviolet light, transition metal from
Son (Fe2+、Co2+、Cu2+Deng) and metal oxide etc. can activate persulfate and generate SO4 -·.Wherein Fe2+In neutrallty condition
Under can effectively be catalyzed persulfate and generate potentiometric titrations, but Fe in neutral conditions2+Oxidizable is Fe3+To lose
Activity.Co2+Although there is higher catalytic performance, its carcinogenesis leads to Co2+It can not extensive use.Currently, persulfate
Catalyticing research is more not easily cause ring since its stable reaction is easily recycled using metal oxide heterogeneous catalysis
It pollutes in border.
MnO2As a kind of excellent catalyst, it can be adapted for a variety of oxidation technology catalytic degradation organic matters.In difference
α-the MnO of crystal form2, β-MnO2, γ-MnO2And unbodied MnO2Middle α-MnO2Higher catalytic activity is shown, and can
SO is generated to activate persulfate4 -·.But nanometer α-MnO2Usually exist in colloidal form in the solution, it is difficult to solid-liquid point
From can not recycle after leading to reaction and cause secondary pollution.Fe3O4There is particle good superparamagnetism, chemical property to stablize,
It can be separated and recovered by magnetic separation in solution.
Currently, the more Mn oxide activation PMS used has good effect, but it is unsatisfactory on the catalytic effect of PS
And it is difficult to recycling and causes secondary pollution.It is same that Fe is used alone3O4PS is activated, catalytic effect is not highly desirable yet.
Invention content
It is an object of the invention to overcome prior art defect, it is compound to provide a kind of magnetic Nano ferrimanganic bimetallic oxide
The preparation method of catalyst.
Another object of the present invention is to provide the applications of above-mentioned magnetic Nano ferrimanganic bimetallic oxide composite catalyst.
Technical scheme is as follows：
A kind of preparation method of magnetic Nano ferrimanganic bimetallic oxide composite catalyst, includes the following steps：
(1) green vitriol and polyvinylpyrrolidone are pressed 2.6~3：1 mass ratio is dissolved in deionized water,
It stirs evenly rapidly；
(2) by the material obtained by step (1) in 68~85 DEG C of oil bath magnetic agitations, being rapidly added NaOH solution makes itself and sulphur
Sour ferrous molar ratio is 1~3：1, sealing 1.5~3.5h of reaction will generate being deposited under 60~65 DEG C of vacuum conditions of black
Fe is made in drying3O4；
(3) by the Fe obtained by step (2)3O4It is ground into powder, the powder and potassium permanganate are then pressed 4：4~7
Mass ratio be dissolved in deionized water, 4~11min of ultrasound be uniformly mixed, the dilute hydrochloric acid that 0.5~2.3mL is then added dropwise shakes
It is even；
(4) material obtained by step (3) is moved into autoclave, it is cold after 100~125 DEG C of 8~12h of heating reaction
But it to room temperature, is then cleaned to supernatant and is in neutrality with deionized water, dried under vacuum condition and obtain the magnetic Nano ferrimanganic
Bimetallic oxide composite catalyst, i.e. magnetic Nano Fe3O4@α-MnO2Catalyst.
In a preferred embodiment of the invention, the step (1) is：By green vitriol and polyethylene pyrrole
Pyrrolidone is dissolved in by 2.78~3: 1 mass ratio in deionized water, is stirred evenly rapidly.
In a preferred embodiment of the invention, the step (2) is：By the material obtained by step (1) 70~
85 DEG C of oil bath magnetic agitations, being rapidly added NaOH solution makes the molar ratio of itself and ferrous sulfate be 2~3: 1, and sealing reaction 2~
3h will generate being deposited under 65 DEG C of vacuum conditions for black and dry, and Fe is made3O4。
In a preferred embodiment of the invention,：The step (3) is：By the Fe obtained by step (2)3O4It carries out
Then the powder and potassium permanganate are dissolved in by 4: 5~6 mass ratio in deionized water by grind into powder, 5~10min of ultrasound
It is uniformly mixed, the dilute hydrochloric acid that 0.7~2.0mL is then added dropwise shakes up.
In a preferred embodiment of the invention, the step (4) is：Material obtained by step (3) is moved into
In autoclave, then 100~120 DEG C of heating reaction 10~12h postcoolings are cleaned with deionized water to supernatant to room temperature
It is in neutrality, is dried under vacuum condition and obtain the magnetic Nano ferrimanganic bimetallic oxide composite catalyst, i.e. magnetic Nano
Fe3O4@α-MnO2Catalyst.
Another technical solution of the present invention is as follows：
A kind of magnetic Nano ferrimanganic bimetallic oxide composite catalyst prepared by above-mentioned preparation method is handling organic dirt
Contaminate the application in waste water.
In a preferred embodiment of the invention, under conditions of room temperature and neutral pH, by the Magnetic nano iron
It is added to together with manganese bimetallic oxide composite catalyst and persulfate in the organic polluting water, the persulfate
A concentration of 2~3mM in organic polluting water, the magnetic Nano ferrimanganic bimetallic oxide composite catalyst is in organic dirt
Contaminate a concentration of 0.8~1.2g/L in waste water.
It is further preferred that the persulfate is sodium peroxydisulfate or potassium peroxydisulfate.
The beneficial effects of the invention are as follows：
1, of the invention by Fe3O4With α-MnO2The two combines, and can both overcome the difficulty for being difficult to recycle, and reduces secondary pollution,
It can reach higher catalytic activity by the synergistic effect of the two again, can effectively activate PS and generate a large amount of free radical drop
Solve Organic substance in water.
2, magnetic Nano ferrimanganic bimetallic oxide composite catalyst and persulfate prepared by preparation method of the invention
It being added together in the waste water containing organic pollution, the two contacts to form a large amount of potentiometric titrations with strong oxidizing property, from
And aoxidizing organic pollution makes its degradation.
3, the magnetic Nano ferrimanganic bimetallic oxide composite catalyst and persulfate that prepared by the present invention act synergistically, nothing
External energy is needed, condition needed for reaction can be reached under room temperature condition of neutral pH, and digestion of metallic ion amount is few, is returned after reaction
Debit just, compared to homogeneous persulfate system can continuously provide potentiometric titrations, in sustaining degradation water
Organic pollution.
4, the magnetic Nano ferrimanganic bimetallic oxide composite catalyst that prepared by preparation method of the invention is more individual
Fe3O4Or individual α-MnO2It can be more effectively catalyzed persulfate, the two plays mutual synergistic effect, being capable of effective activation mistake
Sulfate generates a large amount of free-radical oxidations degradation Organic substance in water.
5, magnetic Nano ferrimanganic bimetallic oxide composite catalyst saturation magnetization prepared by the present invention is
39.89emu/g, can be quickly be separated from the water out by external magnetic field.
Description of the drawings
Fig. 1 is magnetic Nano Fe prepared by the embodiment of the present invention 13O4@α-MnO2The transmission electron microscope photo of catalyst
(amplification factor 100nm).
Fig. 2 is magnetic Nano Fe prepared by the embodiment of the present invention 13O4@α-MnO2The hysteresis loop and recovering effect of catalyst
Figure.
Fig. 3 is the design sketch of bisphenol-A in different system processing water in the embodiment of the present invention 1.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode combination attached drawing.
Embodiment 1
(1) green vitriol and polyvinylpyrrolidone are dissolved in by 2.78~3: 1 mass ratio in deionized water,
It stirs evenly rapidly.
(2) by the material obtained by step (1) in 70~85 DEG C of oil bath magnetic agitations, being rapidly added NaOH solution makes itself and sulphur
Sour ferrous molar ratio is 2~3: 1, and sealing 2~3h of reaction will generate being deposited under 65 DEG C of vacuum conditions for black and dry, makes
Obtain Fe3O4。
(3) by the Fe obtained by step (2)3O4It is ground into powder, the powder and potassium permanganate are then pressed 4: 5~6
Mass ratio be dissolved in deionized water, 5~10min of ultrasound be uniformly mixed, the dilute hydrochloric acid that 0.7~2.0mL is then added dropwise shakes
It is even.
(4) material obtained by step (3) is moved into autoclave, after 100~120 DEG C of 10~12h of heating reaction
It is cooled to room temperature, is then cleaned to supernatant and be in neutrality with deionized water, dried under vacuum condition and obtain the Magnetic nano iron
Manganese bimetallic oxide composite catalyst, i.e., magnetic Nano Fe as shown in Figure 13O4@α-MnO2Catalyst, magnetism is such as Fig. 2 institutes
Show.
The bisphenol-A solution that 100mL contains 30mg/L is added into reactor, sodium peroxydisulfate and this implementation are added into solution
Magnetic Nano Fe made from example3O4@α-MnO2Catalyst, it is respectively 3mM and 1.2g/L to make its concentration.It is examined with high performance liquid chromatography
Treatment effect is surveyed, as shown in figure 3, under the conditions of 25 DEG C and pH value are 7.4.Degradation efficiency of the bisphenol-A after 90min is 92%.
Comparative example
Using the same system in embodiment 1, it is molten into 2 reactors to be separately added into the bisphenol-A that 100mL contains 30mg/L
Sodium peroxydisulfate is added into solution for liquid, and it is respectively 3mM to make its concentration, and Fe is added in 2 reactors respectively3O4With α-MnO2Make
For catalyst.With high performance liquid chromatography detection treatment effect, as shown in figure 3, under the conditions of 25 DEG C and pH value are 7.4.Bisphenol-A exists
Degradation efficiency after 90min is respectively 38.9% and 50.4%.
Those of ordinary skill in the art remain able to it is found that when technical scheme of the present invention changes in following ranges
To same as the previously described embodiments or similar technique effect：
A kind of preparation method of magnetic Nano ferrimanganic bimetallic oxide composite catalyst, includes the following steps：
(1) green vitriol and polyvinylpyrrolidone are dissolved in by 2.6~3: 1 mass ratio in deionized water,
It stirs evenly rapidly；
(2) by the material obtained by step (1) in 68~85 DEG C of oil bath magnetic agitations, being rapidly added NaOH solution makes itself and sulphur
Sour ferrous molar ratio is 1~3: 1, sealing 1.5~3.5h of reaction, will generate being deposited under 60~65 DEG C of vacuum conditions of black
Fe is made in drying3O4；
(3) by the Fe obtained by step (2)3O4It is ground into powder, the powder and potassium permanganate are then pressed 4: 4~7
Mass ratio be dissolved in deionized water, 4~11min of ultrasound be uniformly mixed, the dilute hydrochloric acid that 0.5~2.3mL is then added dropwise shakes
It is even；
(4) material obtained by step (3) is moved into autoclave, it is cold after 100~125 DEG C of 8~12h of heating reaction
But it to room temperature, is then cleaned to supernatant and is in neutrality with deionized water, dried under vacuum condition and obtain the magnetic Nano ferrimanganic
Bimetallic oxide composite catalyst, i.e. magnetic Nano Fe3O4@α-MnO2Catalyst.
A kind of application of above-mentioned magnetic Nano ferrimanganic bimetallic oxide composite catalyst in handling organic polluting water：
Under conditions of room temperature and neutral pH, by the magnetic Nano ferrimanganic bimetallic oxide composite catalyst and persulfate (mistake
Sodium sulphate or potassium peroxydisulfate) it is added to together in the organic polluting water, the persulfate is in organic polluting water
A concentration of 2~3mM, the magnetic Nano ferrimanganic bimetallic oxide composite catalyst is a concentration of in organic polluting water
0.8~1.2g/L.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (8)
1. a kind of preparation method of magnetic Nano ferrimanganic bimetallic oxide composite catalyst, it is characterised in that：Including walking as follows
Suddenly：
(1) green vitriol and polyvinylpyrrolidone are dissolved in by 2.6~3: 1 mass ratio in deionized water, rapidly
It stirs evenly；
(2) by the material obtained by step (1) in 68~85 DEG C of oil bath magnetic agitations, being rapidly added NaOH solution makes itself and sulfuric acid Asia
The molar ratio of iron is 1~3: 1, and sealing 1.5~3.5h of reaction will generate being deposited under 60~65 DEG C of vacuum conditions for black and dry
It is dry, Fe is made3O4；
(3) by the Fe obtained by step (2)3O4It is ground into powder, then the powder and potassium permanganate are pressed to 4: 4~7 matter
Amount ratio is dissolved in deionized water, and 4~11min of ultrasound is uniformly mixed, and the dilute hydrochloric acid that 0.5~2.3mL is then added dropwise shakes up；
(4) material obtained by step (3) is moved into autoclave, 100~125 DEG C of heating 8~12h of reaction postcoolings are extremely
Then room temperature is cleaned to supernatant with deionized water and is in neutrality, dried under vacuum condition and obtain the double gold of the magnetic Nano ferrimanganic
Belong to oxide composite catalyst, i.e. magnetic Nano Fe3O4@α-MnO2Catalyst.
2. preparation method as described in claim 1, it is characterised in that：The step (1) is：By green vitriol and gather
Vinylpyrrolidone is dissolved in by 2.78~3: 1 mass ratio in deionized water, is stirred evenly rapidly.
3. preparation method as described in claim 1, it is characterised in that：The step (2) is：By the material obtained by step (1)
In 70~85 DEG C of oil bath magnetic agitations, being rapidly added NaOH solution makes the molar ratio of itself and ferrous sulfate be 2~3: 1, and sealing is anti-
2~3h is answered, being deposited under 65 DEG C of vacuum conditions for black will be generated and dried, Fe is made3O4。
4. preparation method as described in claim 1, it is characterised in that：The step (3) is：Obtained by step (2)
Fe3O4It is ground into powder, is then dissolved in the powder and potassium permanganate in deionized water by 4: 5~6 mass ratio, ultrasound 5
~10min is uniformly mixed, and the dilute hydrochloric acid that 0.7~2.0mL is then added dropwise shakes up.
5. preparation method as described in claim 1, it is characterised in that：The step (4) is：By the material obtained by step (3)
Be moved into autoclave, 100~120 DEG C heating reaction 10~12h postcoolings to room temperature, then with deionized water clean to
Supernatant is in neutrality, and is dried under vacuum condition and is obtained the magnetic Nano ferrimanganic bimetallic oxide composite catalyst, i.e., magnetic
Nanometer Fe3O4@α-MnO2Catalyst.
6. magnetic Nano ferrimanganic bimetallic oxide prepared by the preparation method in a kind of claim 1 to 5 described in any requirement
Application of the composite catalyst in handling organic polluting water.
7. application as claimed in claim 6, it is characterised in that：Under conditions of room temperature and neutral pH, by the magnetic Nano
It is added to together with ferrimanganic bimetallic oxide composite catalyst and persulfate in the organic polluting water, the persulfuric acid
A concentration of 2~3mM of the salt in organic polluting water, the magnetic Nano ferrimanganic bimetallic oxide composite catalyst is organic
A concentration of 0.8~1.2g/L in pollutant effluents.
8. the use as claimed in claim 7, it is characterised in that：The persulfate is sodium peroxydisulfate or potassium peroxydisulfate.
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