CN109626545B - Method for degrading acid orange 7 by using carbon-containing ferro-manganese bimetallic catalyst - Google Patents
Method for degrading acid orange 7 by using carbon-containing ferro-manganese bimetallic catalyst Download PDFInfo
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- CN109626545B CN109626545B CN201811539182.4A CN201811539182A CN109626545B CN 109626545 B CN109626545 B CN 109626545B CN 201811539182 A CN201811539182 A CN 201811539182A CN 109626545 B CN109626545 B CN 109626545B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910000616 Ferromanganese Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000000593 degrading effect Effects 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000013082 iron-based metal-organic framework Substances 0.000 claims description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
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- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical compound [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 239000007800 oxidant agent Substances 0.000 abstract description 10
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- 238000007885 magnetic separation Methods 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 12
- 235000013980 iron oxide Nutrition 0.000 description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 9
- 239000012488 sample solution Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 230000005653 Brownian motion process Effects 0.000 description 1
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- 108091006149 Electron carriers Proteins 0.000 description 1
- MAQAUGBCWORAAB-UHFFFAOYSA-N [C+4].[O-2].[Fe+2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Fe+2].[O-2].[O-2] MAQAUGBCWORAAB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
- C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for degrading acid orange 7 by using a carbon-containing ferro-manganese bimetallic catalyst, belonging to the technical field of water pollution treatment. The method for degrading acid orange 7 specifically comprises the following steps: s1, preparing a carbon-containing ferro-manganese bimetallic catalyst; s2, uniformly mixing a certain amount of acid orange 7 and peroxymonosulfate to prepare a mixed solution; and S3, adding the prepared carbon-containing ferro-manganese bimetallic catalyst into the mixed solution in the step S2, and stirring, wherein the carbon-containing ferro-manganese bimetallic catalyst degrades acid orange 7. In the method, the iron and manganese in the carbon-containing iron-manganese bimetallic catalyst synergistically play a role, the reaction of circularly catalyzing peroxymonosulfate by each catalyst is mutually promoted, the utilization efficiency of the catalyst and the oxidant is high, and the effect of degrading the acid orange 7 is good; meanwhile, the catalyst in the method has wide pH application range, and the catalyst material has magnetism, so that the magnetic separation method is convenient to recycle, and secondary pollution is avoided.
Description
Technical Field
The invention relates to the technical field of water pollution treatment, in particular to a method for degrading acid orange 7 by using a carbon-containing ferro-manganese bimetallic catalyst.
Background
Printing and dyeing wastewater is generated in the industries such as coating industry, textile industry, leather manufacturing industry and the like, and azo dyes characterized by azo bonds (N ═ N) are more and more widely applied in the printing and dyeing industry along with the improvement of synthesis technology, and the generated wastewater has the characteristics of large amount, strong toxicity, carcinogenesis, mutation, difficult degradation and the like. Most of the dye waste water contains aromatic functional groups and has complex structure composition, and the dye waste water can cause great harm to aquatic organisms and human health if being directly discharged without being treated; therefore, the degradation technology of the waste water is also receiving more and more attention. Acid orange 7 is a typical azo dye, and the prior art cannot effectively degrade and remove the acid orange 7.
Disclosure of Invention
In view of the above, the invention provides a method for degrading acid orange 7 by activating PMS with a carbon-containing ferro-manganese bimetallic catalyst, which solves the problems of low utilization efficiency of the catalyst and the oxidant, difficult recovery, and a wide pH application range in the traditional advanced oxidation method.
A method for degrading acid orange 7 by using a carbon-containing ferro-manganese bimetallic catalyst comprises the following steps:
s1, preparing a carbon-containing ferro-manganese bimetallic catalyst;
s2, uniformly mixing a certain amount of acid orange 7 and peroxymonosulfate to prepare a mixed solution;
and S3, adding the prepared carbon-containing ferro-manganese bimetallic catalyst into the mixed solution in the step S2, and stirring, wherein the carbon-containing ferro-manganese bimetallic catalyst degrades acid orange 7.
Further, the step S1 is specifically:
s1.1, preparing an organic iron-based MOFS: dissolving fumaric acid and ferric chloride hexahydrate in deionized water according to the molar ratio of 1:1, and placing the mixed solution in a hydrothermal synthesis reaction kettle to perform heating reaction at 85 ℃ for 12 hours to synthesize the iron-based MOFS;
s1.2, iron oxide containing carbon Fe2O3Preparation of @ C: centrifugally drying the iron-based MOFS prepared in the step S1.1, and calcining the dried iron-based MOFS at 600 ℃ for 4 hours in a nitrogen atmosphere to obtain the carbon-containing iron oxide Fe2O3@C；
S1.3, in the presence of iron oxides containing carbon Fe2O3@ C loaded with Mn3O4: and (2) mixing the following components in percentage by mass: 1 potassium permanganate and iron oxide containing carbon Fe2O3And putting the @ C into a 60% ethanol aqueous solution, putting the mixture into a reaction kettle, heating the mixture at 160 ℃ for reaction for 12 hours, naturally cooling the mixture, centrifugally separating the obtained precipitate, washing the precipitate with deionized water for 2 times, and drying the precipitate to obtain the carbon-containing ferro-manganese bimetallic catalyst.
Furthermore, in the step S3, the adding amount of the carbon-containing ferro-manganese bimetallic catalyst is 0.1g/L-0.5 g/L.
Further, the decolorizing efficiency of the carbon-containing iron-manganese bimetallic catalyst for catalyzing peroxymonosulfate to degrade acid orange 7 in 40 minutes is more than or equal to 98%.
Furthermore, the method is applicable to the pH value of 3-11 and the temperature of 20-50 ℃.
Compared with the prior art, the invention has the beneficial effects that: in the method for degrading acid orange 7 by using the carbon-containing ferro-manganese bimetallic catalyst, ferro-manganese synergistically plays a role in mutually promoting the reaction of respectively circularly activating peroxymonosulfate; in the method, the utilization efficiency of the catalyst and the oxidant is high, and the effect of degrading the acid orange 7 is good; meanwhile, the method has wide pH application range, and the catalyst material has magnetism, so that the magnetic separation method is convenient to recycle, and secondary pollution is avoided.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1 is a flow chart of a method for degrading acid orange 7 in an example of the present invention;
FIG. 2 is a flow chart of a method for preparing a carbonaceous ferro-manganese bimetallic catalyst in an example of the present invention;
FIG. 3 is a FESEM image of an organic iron-based MOFS prepared in an example of the present invention;
FIG. 4 is a representation of the iron oxide containing carbon Fe prepared in an example of the present invention2O3FESEM image of @ C;
fig. 5(a) and 5(b) are FESEM images of carbonaceous ferro-manganese bimetallic catalysts prepared in examples of the present invention;
FIG. 6 shows the production of Fe in the examples of the present invention2O3@C、Mn3O4And a carbonaceous ferro-manganese bimetallic catalyst Mn3O4/Fe2O3The XRD pattern of @ C;
FIG. 7 shows a carbon-containing Fe-Mn bimetallic catalyst Mn in an example of the present invention3O4/Fe2O3Graph of magnetic recovery effect of @ C;
FIG. 8 shows a carbon-containing Fe-Mn bimetallic catalyst Mn in an example of the present invention3O4/Fe2O3XRD patterns before and after use of the @ C material;
FIG. 9 is a graph of the removal rate of acid orange 7 with different catalyst dosages as used in the examples of the present invention;
FIG. 10 is a graph of the removal rate of acid orange 7 with different dosages of oxidizing agent added in accordance with an embodiment of the present invention;
FIG. 11 is a graph of acid orange 7 removal at various pH conditions in accordance with an example of the present invention;
FIG. 12 is a graph of acid orange 7 removal at different temperature conditions in accordance with an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Referring to fig. 1 and fig. 2, an embodiment of the present invention provides a method for degrading acid orange 7 by using a carbon-containing ferro-manganese bimetallic catalyst, which includes the following specific steps:
s1, preparing a carbon-containing ferro-manganese bimetallic catalyst;
the step S1 specifically includes:
s1.1, preparing an organic iron-based MOFS: weighing 1.741g of trans-succinic acid and 4.050g of ferric chloride hexahydrate, wherein the molar ratio of the trans-succinic acid to the ferric chloride hexahydrate is 1: 1; dissolving the weighed fumaric acid and ferric chloride hexahydrate in 80mL of deionized water, and magnetically stirring for 30 minutes at the rotating speed of 250 r/min; placing the obtained mixed solution in a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and heating and reacting for 12 hours in a common oven at the temperature of 85 ℃ to synthesize iron-based MOFS; and washing the prepared iron-based MOFS precipitate of the light pink powder with deionized water for 2-3 times, and drying for later use.
The FESEM image of the product organic iron-based MOFS prepared in the step S1.1 is shown in fig. 3, and it can be seen that the iron-based MOFS is in a fusiform shape and has a smooth surface.
S1.2, iron oxide containing carbon Fe2O3Preparation of @ C: weighing 2g of the light pink iron-based MOFS prepared in the step S1.1, placing the mixture in a tube furnace in nitrogen atmosphere, and calcining the mixture for 4 hours at the temperature of 600 ℃ to obtain magnetic black powder with a fusiform shape and a rough surface, namely Fe iron oxide containing carbon2O3@C。
Step S1.2 of preparing iron oxide Fe containing carbon2O3FESEM image of @ C As shown in FIG. 4, it can be seen that the carbonized iron-based MOFS retained the original fusiform form, the smooth surface was transformed into a rough surface with a large number of pores, and the length of the crystals was between about 500 and 1000 nm.
S1.3, in the presence of iron oxides containing carbon Fe2O3@ C loaded with Mn3O4: weighing 2g of potassium permanganate and 1g of the carbon-containing iron oxide Fe prepared in step S1.22O3@ C is put into 70ml ethanol water solution with the mass fraction of 60 percent, mechanically stirred for 30 minutes, and the rotating speed is controlled at 250 r/min; and then transferring the mixed solution into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, heating and reacting for 12h at 160 ℃, naturally cooling, centrifugally separating the obtained black solid, washing for 2 times by using deionized water, and drying for 8h at 60 ℃ in a vacuum drying oven to obtain the carbon-containing ferro-manganese bimetallic catalyst.
FESEM images of the carbonaceous ferromanganese bimetallic catalyst prepared in step S1.3 are shown in fig. 5(a) and 5 (b).
It should be noted that in example 1 of the present invention, the iron-based metal framework organic compound is used as a sacrificial precursor, and is calcined in a nitrogen atmosphere to make the product retain the original fusiform form, the carbonized iron-based MOFS are transformed from a smooth surface to a rough surface with a large number of pores, and the length of the crystal is between about 500-1000 nm.
FIG. 6 shows Fe as an intermediate product in the preparation of a catalyst2O3@ C and Mn3O4And the final product containing a carbon-containing ferro-manganese bimetallic catalyst Mn3O4/Fe2O3The XRD pattern of @ C; from the figure, Fe can be seen2O3The @ C material being 15.00 deg., 18.39 deg., 23.84 deg. at 2 theta angles, respectivelyDiffraction peaks at 26.11 °, 30.27 °, 35.60 °, 37.28 ° 43.34 ° and 62.73 ° compared to γ -Fe in the standard XRD database2O3The diffraction peaks of (JCPDS cardno.25-1402) are coincident, indicating that the intermediate product Fe containing carbon iron oxide is prepared2O3The iron oxide in @ C is gamma-Fe2O3。
The presence of Fe3C was also observed due to the nanoscale gamma-Fe formed by the calcination of the metal core2O3Fe3C is formed by the close contact with carbon, wherein the carbon can provide adsorption active sites in catalytic reaction, act as an electron carrier, coat metal ions and effectively reduce the dissolution of the metal ions so as to improve the stability of the catalyst; additionally gamma-Fe2O3The magnetic property of the material can make the catalytic material easily separated from the solution, thereby improving the recycling value of the catalyst, and the magnetic recovery effect of the material is shown in figure 7.
Example 1 of the invention in Fe by solvothermal reaction2O3@ C surface loading Mn3O4Increasing the catalytic active sites of the catalyst material, as shown in fig. 6, the carbon-containing ferro-manganese bimetallic catalyst material has diffraction peaks at 2 theta angles of 18.02 degrees, 28.97 degrees, 31.03 degrees, 32.41 degrees, 36.04 degrees, 38.10 degrees, 44.37 degrees and 60.03 degrees respectively, and the diffraction peaks correspond to Mn in a standard XRD database3O4(JCPDS card No.18-0803) shows high coincidence of diffraction peaks, which indicates that example 1 of the present invention succeeds in preparing a sacrificial precursor (Fe) for iron carbide-based MOFS2O3@ C) based on Mn3O4The morphology of the final catalyst material is shown in fig. 5(a) and 5 (b).
S2, uniformly mixing a certain amount of acid orange 7 and peroxymonosulfate to prepare a mixed solution;
and S3, adding the prepared carbon-containing ferro-manganese bimetallic catalyst into the mixed solution in the step S2, and stirring, wherein the carbon-containing ferro-manganese bimetallic catalyst degrades acid orange 7.
It should be noted that iron and manganese can respectively activate PMS to generate active species to attack and degrade acid orange 7, and a synergistic effect exists between the double metals, so that respective catalytic cycling reactions can be mutually promoted, and the catalytic activity of the catalyst is effectively improved; the possible reactions for activating PMS by the catalyst material in example 1 of the present invention are shown in the following formulas 1 to 5:
Fe2++HSO5 -→Fe3++SO4 -·+OH- (1)
Fe3++HSO5 -→Fe2++SO5 -·+H+ (2)
Mn2++HSO5 -→Mn3++SO4 -·+OH- (3)
Mn3++HSO5 -→Mn2++SO5 -·+H+ (4)
Fe(Ⅲ)-OH+Mn(Ⅱ)-OH→Fe(Ⅱ)-OH+Mn(Ⅲ)-OH (5)
finally, by comparing the XRD patterns of the catalyst material before and after use in example 1 of the present invention, as shown in fig. 8, it can be seen that the XRD pattern of the catalyst is not changed after use, which indicates that the catalyst has no structural change after use, is highly stable and can be recycled.
Example 2
First, influence of catalyst addition
The difference of the addition amount of the carbon-containing ferro-manganese bimetallic catalyst to Mn of the invention3O4/Fe2O3The effect of the @ C/PMS system in degrading acid orange 7.
The experimental process specifically comprises the following steps:
a250 mL beaker equipped with a mechanical stirring paddle was charged with 100mL of 35mg/L azo dye acid orange 7 solution, followed by 1mL of 0.1M peroxymonosulfate solution to fix the initial PMS concentration at 1mM, with the initial pH unadjusted (pH 6.17), and finally various doses of the carbonaceous ferro-manganese bimetallic catalyst prepared in example 1 were added to initiate the degradation reaction.
Taking 2mL of the mixed sample solution at 0min, 1min, 3min, 7min, 10min, 20min, 30min and 40min, adding 2mL of methanol to quench the residual free radicals, continuously inhibiting the reaction, and measuring the absorbance of acid orange 7 in the mixed sample solution at the position of 484nm of the characteristic visible light absorption wavelength of the acid orange 7 by a spectrophotometer; the removal rates for different periods of time for degrading acid orange 7 with different catalyst dosages are shown in fig. 9.
By analyzing the graph of fig. 9, it can be found that the reaction system of the embodiment of the invention has about 98% degradation effect on acid orange 7 within 40 minutes of reaction under the condition that the adding amount of the catalyst is 0.1g/L-0.5 g/L; with the increase of the adding amount of the catalyst, the provided surface catalytic active sites are increased, the reaction probability of the catalyst and PMS is increased, and the efficiency of removing acid orange 7 by the system is gradually increased; the removal efficiency of the acid orange 7, the dissolution rate of metal ions in the reaction solution, the catalyst addition cost and the like are comprehensively considered, and the catalyst addition amount is recommended to be 0.1g/L-0.3g/L in the system.
Second, Effect of concentration of oxidizing agent (PMS)
The concentration of oxidant (PMS) is an important factor affecting the degradation of acid orange 7. The embodiment of the invention researches the concentration of PMS on Mn in the invention3O4/Fe2O3The effect of the @ C/PMS system in degrading acid orange 7.
The experimental process specifically comprises the following steps:
a250 mL beaker equipped with a mechanical stirring paddle was charged with 100mL of a 35mg/L solution of the azo dye acid orange 7, various doses of PMS oxidant were added, and 0.03g of the catalyst prepared in example 1 was added, the initial catalyst concentration was fixed at 0.3g/L, the initial pH was not adjusted (pH 6.17), and the degradation reaction was initiated.
Taking 2mL of the mixed sample solution at 0min, 1min, 3min, 7min, 10min, 20min, 30min and 40min, adding 2mL of methanol to quench the residual free radicals, continuously inhibiting the reaction, and measuring the absorbance of acid orange 7 in the sample at the position of 484nm of the characteristic visible light absorption wavelength of the acid orange 7 by a spectrophotometer; the removal rate of acid orange 7 in the mixed sample solution by adding different doses of PMS is shown in FIG. 10.
From the analysis of fig. 10, it can be seen that when the concentration of PMS is increased from 0.125mM to 1.25mM, the degradation efficiency of acid orange 7 is significantly enhanced, because PMS with high concentration is more easily adsorbed on the surface of the heterogeneous catalyst, and further diffuses to the active sites inside the catalyst through the fine pores, so that a large amount of active free radicals are generated to oxidatively degrade acid orange 7, and the degradation efficiency is increased; however, in the presence of high-concentration PMS, high-concentration active groups are easy to react with each other to generate SO with weaker oxidizing capability5 -And the like, so that the degradation efficiency is not promoted by greatly increasing the concentration of PMS; meanwhile, the unreacted PMS also has certain environmental risks. The concentration of PMS oxidant is recommended to be between 0.125mM and 1mM by comprehensively considering the addition cost of PMS oxidant, the degradation efficiency of acid orange 7 and environmental protection factors.
Third, influence of initial pH of solution
The pH value of the solution is a key factor for determining the catalytic degradation effect of acid orange 7, and the degradation conditions of acid orange 7 under different initial pH values (3, 5, 7, 9 and 11) of the system are studied in the embodiment of the invention, and the result is shown in FIG. 11.
The experimental process specifically comprises the following steps:
to a 250mL beaker equipped with a mechanical stirring paddle was added 100mL of a 35mg/L solution of the azo dye acid orange 7 at an initial pH of 0.1M H2SO4And 0.05M of H2SO, 0.1M NaOH and 0.05M NaOH are respectively adjusted to 3, 5, 7, 9 and 11; a further 1mL of 0.1M peroxymonosulfate solution and 0.03g of catalyst were added to initiate the degradation reaction.
Taking 2mL of the sample at 0min, 1min, 3min, 5min, 7min and 10min, adding 2mL of methanol to quench the residual free radicals in the sample, continuously inhibiting the reaction, and measuring the absorbance of the sample at 484nm of the characteristic visible light absorption wavelength of acid orange 7 by using a spectrophotometer; the removal rates of acid orange 7 at different pH and different time for the mixed sample solutions are shown in FIG. 11.
From the analysis of FIG. 11, it can be found that in the case of pH 7 or less, the decoloring efficiency of acid orange 7 gradually increases as the pH of the mixed sample solution decreases, because of the acid barUnder the condition, the elution amount of metal ions in the heterogeneous catalyst is increased, and the generation efficiency of system free radicals is improved by a homogeneous catalysis system of PMS; the embodiment of the invention observes that under the condition that the initial pH of the reaction solution is 9, the catalytic efficiency of the system is higher than that under the condition that the initial pH of the reaction solution is 7, because under the alkaline condition, the metal ions on the surface of the catalyst are easier to form macromolecular metal-OH-HSO5 -Superoxide complex, which weakens the S-O bond and further promotes HSO5 -(main active ingredient of PMS). As can be seen from fig. 11, even under the condition that the initial pH of the reaction solution was 11, the acid orange 7 was able to complete degradation and decoloration within 10 minutes. Examples of the invention illustrate Mn3O4/Fe2O3The @ C/PMS system for degrading acid orange 7 has a wide pH application range, and can cope with complex working environments under different process conditions.
Fourth, influence of reaction temperature
Temperature has a great influence on the progress of the chemical reaction. FIG. 12 shows the temperature of the reaction solution versus Mn of the present invention3O4/Fe2O3The effect of the @ C/PMS system on the efficiency of degrading acid orange 7.
The experimental process specifically comprises the following steps:
in a 250mL beaker equipped with a mechanical stirring paddle, 100mL of a 35mg/L solution of the azo dye acid orange 7 was added, 1mL of a 0.1M solution of peroxymonosulfate and 0.03g of catalyst were added, the initial pH was not adjusted (pH 6.17), and the degradation reaction was started at a temperature in the range of 23-45 ℃.
And 2mL of the mixed sample solution is taken at 0min, 0.5min, 1min, 1.5min, 2min, 2.5min, 3min, 4min, 5min and 7min, 2mL of methanol is added to quench the residual free radicals in the mixed sample solution, the reaction is continuously inhibited, and the absorbance of the acid orange 7 in the mixed sample solution is measured at the position of 484nm of the characteristic visible light absorption wavelength of the acid orange 7 by a spectrophotometer.
Under the condition that other conditions are not changed, the degradation efficiency of the acid orange 7 is increased along with the temperature increase of the reaction liquid in the range of 23-45 ℃. This is because the heat provided by the temperature rise can activate a part of PMS to generate active free radicals, and each group is enhancedThe Brownian motion increases the collision probability of the free radicals and the acid orange 7, and reduces the activation energy of the free radicals generated by the PMS. In the actual industrial wastewater treatment, the printing and dyeing wastewater generally has higher water temperature, so the Mn in the invention3O4/Fe2O3The @ C/PMS system degraded acid orange 7 can be well suitable for printing and dyeing wastewater treatment.
The invention discloses a method for degrading acid orange 7 by using a carbon-containing ferro-manganese bimetallic catalyst, wherein ferro-manganese used as the catalyst in the method can play a role in a synergistic manner and mutually promote the reactions of respectively circularly activating peroxymonosulfate; the method has high utilization efficiency of the catalyst and the oxidant and good effect of degrading the acid orange 7; meanwhile, the method has wide pH application range, and the catalyst material has magnetism, so that the magnetic separation method is convenient to recycle, and secondary pollution is avoided.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A method for degrading acid orange 7 by using a carbon-containing ferro-manganese bimetallic catalyst is characterized by comprising the following steps:
s1, preparing a carbon-containing ferro-manganese bimetallic catalyst;
s1.1, preparing an organic iron-based MOFS: dissolving fumaric acid and ferric chloride hexahydrate in deionized water, and placing the mixed solution in a hydrothermal synthesis reaction kettle to perform heating reaction at 85 ℃ for 12 hours to synthesize the iron-based MOFS;
s1.2, preparing carbon-containing iron oxide: centrifugally drying the iron-based MOFS prepared in the step S1.1, and calcining the dried iron-based MOFS at 600 ℃ for 4 hours in a nitrogen atmosphere to obtain the carbon-containing iron oxide Fe2O3@C；
S1.3, loading Mn on carbon-containing iron oxide3O4: adding potassium permanganate and carbon-containing iron oxide into 60% ethanolPlacing the aqueous solution in a reaction kettle, heating the aqueous solution at 160 ℃ for 12h, reacting the aqueous solution for 12h, naturally cooling the aqueous solution, and centrifugally separating, washing and drying the obtained precipitate to obtain the carbon-containing ferro-manganese bimetallic catalyst;
s2, uniformly mixing a certain amount of acid orange 7 and 0.125mM-1mM of peroxymonosulfate to prepare a mixed solution;
s3, adding the prepared carbon-containing ferro-manganese bimetallic catalyst into the mixed solution in the step S2, and stirring, wherein the carbon-containing ferro-manganese bimetallic catalyst degrades acid orange 7; the addition amount of the carbon-containing ferro-manganese bimetallic catalyst is 0.1g/L-0.5 g/L;
the decolorizing efficiency of the carbon-containing iron-manganese bimetallic catalyst for catalyzing peroxymonosulfate to degrade acid orange 7 in 40 minutes is more than or equal to 98 percent.
2. The method for degrading acid orange 7 by using the carbonaceous ferro-manganese bimetallic catalyst according to claim 1, wherein the pH value for the method for degrading acid orange 7 is 3-11.
3. The method for degrading acid orange 7 by using the carbonaceous ferro-manganese bimetallic catalyst according to claim 1, wherein the temperature for degrading acid orange 7 is 20-50 ℃.
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