CN115739178B - Preparation method and application of phenolic foam supported manganese ferrite catalyst - Google Patents
Preparation method and application of phenolic foam supported manganese ferrite catalyst Download PDFInfo
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- CN115739178B CN115739178B CN202211097335.0A CN202211097335A CN115739178B CN 115739178 B CN115739178 B CN 115739178B CN 202211097335 A CN202211097335 A CN 202211097335A CN 115739178 B CN115739178 B CN 115739178B
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- 239000006260 foam Substances 0.000 title claims abstract description 97
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 51
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 43
- 239000011572 manganese Substances 0.000 title claims abstract description 43
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 37
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000004939 coking Methods 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 7
- 229920000053 polysorbate 80 Polymers 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000007667 floating Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006385 ozonation reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a preparation method of a phenolic foam supported manganese ferrite catalyst, which combines a traditional manganese ferrite catalyst with a phenolic foam carrier, solves the problems that manganese ferrite is easy to agglomerate and unstable due to strong magnetism on the surface of the manganese ferrite, and solves the problems that the catalyst is difficult to recover in nano-size, extremely easy to dissolve, easy to run off and the like because the nano-manganese ferrite catalyst is supported on phenolic foam with relatively large size. The phenolic foam has a good porous structure and can be used as an excellent self-floating material, and the reaction suspension bed is formed by utilizing the good self-floating performance of the material and the arrangement of aeration at the bottom of the reaction device, so that the catalyst can fully contact ozone, and the ozone utilization rate is improved.
Description
Technical Field
The invention relates to the technical field of sewage treatment catalysts, in particular to a preparation method and application of a phenolic foam supported manganese ferrite catalyst.
Background
The catalytic ozonation technology is to combine a catalyst to degrade organic matters efficiently on the basis of ozone oxidation. Catalytic ozonation is classified into homogeneous ozonation and heterogeneous ozonation. The homogeneous ozone oxidation is to utilize transition metal ion as catalyst to catalyze ozone to produce hydroxyl radical to react with organic matter and degrade the organic matter. The homogeneous ozone oxidation catalyst has the defects of easy loss, difficult recovery, possible dissolution and the like, and is still to be promoted in research and development. Non-uniform ozone oxidation is mainly transition metal, transition metal oxide and supported metal, and mainly adopts synergistic action of adsorption and catalysis or adopts solid catalyst to catalyze ozone to generate high-activity free radical. The catalyst has relatively wide application, and has the problems of low catalytic efficiency, small specific surface area and the like. At present, ferrite nano-catalysts are easy to run off and difficult to recycle.
Disclosure of Invention
The invention combines the advantages of homogeneous ozone catalysis and heterogeneous ozone catalysis, provides a catalyst of manganese ferrite supported by phenolic foam, has stable ferrite structure and outstanding catalytic performance; the phenolic foam has good heat resistance and low temperature resistance, has uniform pore diameter, and can be used as a good catalyst carrier; the manganese ferrite catalyst is attached to phenolic foam, and the floating catalyst based on carbonized phenolic foam loaded ferrite is provided, so that COD and cyanide in coking wastewater can be degraded more efficiently.
A preparation method of a phenolic foam supported manganese ferrite catalyst comprises the following steps:
(1) Preparing a phenolic foam carrier, namely mixing and stirring phenolic resin, a surfactant and normal hexane, adding a phosphoric acid solution, continuously stirring, and introducing the mixture into a mold for foaming after the solution is uniformly stirred to obtain phenolic foam;
(2) Cleaning the phenolic foam prepared in the step (1), cutting the phenolic foam into cuboid blocks, drying the cuboid blocks, and then placing the cuboid blocks in a tube furnace for carbonization at 750 ℃ for 2 hours; obtaining carbonized phenolic foam;
(3) MnCl is added to 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O, modifier and urea are dissolved in ultrapure water, and are fully mixed and dispersed by ultrasonic until the O, the modifier and the urea are completely dissolved;
(4) Mixing the phenolic foam cut in the step (2) and the mixed solution obtained in the step (3), putting the mixture into a high-pressure reaction kettle, heating the mixture for reaction for 4 hours, and repeatedly washing the mixture with deionized water and absolute ethyl alcohol after the reaction is finished;
(5) And (3) drying the catalyst obtained in the step (4) in a vacuum drying oven at 80 ℃, and continuously calcining the catalyst in a muffle furnace at a high temperature of 550 ℃ for 5 hours to obtain the manganese ferrite-loaded phenolic foam catalyst.
The method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein the surfactant in the step (1) is one or more of non-ionic surfactants of tween 80, tween 60 and DC 193.
Further, in the step (1), phenolic resin, a surfactant and n-hexane are mixed according to a mass ratio of 100:6:5, mixing to obtain a mixed resin solution, wherein the mass ratio of the mixed resin solution to phosphoric acid is (5): 1, mixing uniformly.
Further, the modifier in the step (3) is one or two of polystyrene or cetyl trimethyl ammonium bromide.
Further, mnCl in the step (3) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 The mol ratio of O, hexadecyl trimethyl ammonium bromide and urea is 5-8:8-12-:0.5-0.6:25.
further, the temperature rise rate of the high-temperature calcination in the muffle furnace in the step (5) is 2 ℃ min < -1 >, and then the calcination is maintained.
And (3) mixing the phenolic foam cut in the step (2) and the mixed solution in the step (3), placing the mixed solution in a high-pressure reaction kettle, placing the high-pressure reaction kettle in a forced air drying box, and reacting for 4 hours at 110-150 ℃.
Further, the concentration of the phosphoric acid solution was 3mol/L.
The phenolic foam supported manganese ferrite catalyst is used in catalyzing ozone to treat coking waste water.
The invention has the beneficial effects that:
(1) The invention combines the traditional manganese ferrite catalyst with the phenolic foam carrier, and solves the problem that manganese ferrite is easy to agglomerate and unstable because of strong magnetism on the surface of the manganese ferrite.
(2) According to the invention, the nano manganese ferrite catalyst is loaded on phenolic foam with relatively large size, so that the problems of difficult recovery of the nano size of the catalyst, easy dissolution, easy loss and the like are solved.
(3) The invention combines heterogeneous catalyst with suspended phenolic foam, so that the catalyst is wholly renewable and has good industrial application prospect, and the cost is saved.
(4) The phenolic foam has a good porous structure and can be used as an excellent self-floating material, and the reaction suspension bed is formed by utilizing the good self-floating performance of the material and the arrangement of aeration at the bottom of the reaction device, so that the catalyst can fully contact ozone, and the ozone utilization rate is improved.
(5) The method provided by the invention has the advantages of simplicity, low cost, low energy consumption, low equipment requirement, easiness in production and good industrial application prospect.
Drawings
FIG. 1 shows the XRD pattern of the product at 130 ℃
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A preparation method of a phenolic foam supported manganese ferrite catalyst comprises the following steps:
(1) Preparing a phenolic foam carrier, namely mixing and stirring phenolic resin, a surfactant and normal hexane, adding a phosphoric acid solution, continuously stirring, and introducing the mixture into a mold for foaming after the solution is uniformly stirred to obtain phenolic foam;
(2) Cleaning the phenolic foam prepared in the step (1), cutting the phenolic foam into cuboid blocks, drying the cuboid blocks, and then placing the cuboid blocks in a tube furnace for carbonization at 750 ℃ for 2 hours; obtaining carbonized phenolic foam;
(3) MnCl is added to 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O, modifier and urea are dissolved in ultrapure water, and are fully mixed and dispersed by ultrasonic until the O, the modifier and the urea are completely dissolved;
(4) Mixing the phenolic foam cut in the step (2) and the mixed solution obtained in the step (3), putting the mixture into a high-pressure reaction kettle, heating the mixture for reaction for 4 hours, and repeatedly washing the mixture with deionized water and absolute ethyl alcohol after the reaction is finished;
(5) And (3) drying the catalyst obtained in the step (4) in a vacuum drying oven at 80 ℃, and continuously calcining the catalyst in a muffle furnace at a high temperature of 550 ℃ for 5 hours to obtain the manganese ferrite-loaded phenolic foam catalyst.
The method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein the surfactant in the step (1) is one or more of non-ionic surfactants of tween 80, tween 60 and DC 193.
Further, in the step (1), phenolic resin, a surfactant and n-hexane are mixed according to a mass ratio of 100:6:5, mixing to obtain a mixed resin solution, wherein the mass ratio of the mixed resin solution to phosphoric acid is (5): 1, mixing uniformly.
Further, the modifier in the step (3) is one or two of polystyrene or cetyl trimethyl ammonium bromide.
Further, mnCl in the step (3) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 The mol ratio of O, hexadecyl trimethyl ammonium bromide and urea is 5-8:8-12-:0.5-0.6:25.
further, the temperature rise rate of the high-temperature calcination in the muffle furnace in the step (5) is 2 ℃ min < -1 >, and then the calcination is maintained.
And (3) mixing the phenolic foam cut in the step (2) and the mixed solution in the step (3), placing the mixed solution in a high-pressure reaction kettle, placing the high-pressure reaction kettle in a forced air drying box, and reacting for 4 hours at 110-150 ℃.
Further, the concentration of the phosphoric acid solution was 3mol/L. The phosphoric acid can be used as an acid curing agent in the process of preparing the phenolic foam, and the acid curing agent has the advantages of short curing induction period, high curing degree and short foaming period. However, if the acid concentration is too high, the heat generation amount is increased, so that corrosion to production equipment is likely to occur, and control is not easy.
Example 1:
preparation and carbonization of phenolic foam carrier: weighing a certain mass of phenolic resin, tween 80 and 6% of normal hexane, and mixing according to a certain mass ratio. Stirring the mixed solution for 25min according to 3500r/min, adding the diluted phosphoric acid solution according to a certain proportion, and continuing stirring. After the solution is stirred uniformly, the solution is led into a die. Foaming at 80 deg.c and normal pressure to obtain phenolic foam. The prepared phenolic foam was washed, and the phenolic foam was cut into rectangular blocks of 1cm×2cm×3 cm. After the foam is dried, the foam is placed in a tube furnace for carbonization at 750 ℃ for 2 hours.
Preparation of phenolic foam supported ferrite catalyst: 5mmol MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.548mmol CTAB and 25mmol urea were dissolved in 50mL ultra pure water, and the solution was thoroughly mixed and dispersed by ultrasonic until it was completely dissolved.
And (3) placing the prepared solution and the cut phenolic foam into a high-pressure reaction kettle, and placing the high-pressure reaction kettle into a blast drying box to react for 4 hours at 130 ℃. After the reaction is finished, waiting for the high-pressure reaction kettle to naturally cool to room temperature, and repeatedly washing the reacted catalyst by deionized water and absolute ethyl alcohol.
The washed catalyst was dried overnight at 80 ℃ in a vacuum oven. Continuously calcining in a muffle furnace at 550 ℃ for 5 hours at a temperature rising rate of 2 ℃ for 2 min -1 . Obtaining the phenolic foam catalyst of the loaded manganese ferrite. The catalyst obtained under this condition was designated as catalyst A.
Example 2:
preparation and carbonization of phenolic foam carrier: weighing a certain mass of phenolic resin, tween 80 and 6% of normal hexane, and mixing according to a certain mass ratio. Stirring the mixed solution for 25min according to 3500r/min, adding the diluted phosphoric acid solution according to a certain proportion, and continuing stirring. After the solution is stirred uniformly, the solution is led into a die. Foaming at 80 deg.c and normal pressure to obtain phenolic foam. The prepared phenolic foam was washed, and the phenolic foam was cut into rectangular blocks of 1cm×2cm×3 cm. After the foam is dried, the foam is placed in a tube furnace for carbonization at 750 ℃ for 2 hours.
Preparation of phenolic foam supported ferrite catalyst: 5mmol MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.548mmol CTAB and 25mmol urea were dissolved in 50mL ultra pure water, and the solution was thoroughly mixed and dispersed by ultrasonic until it was completely dissolved.
And (3) placing the prepared solution and the cut phenolic foam into a high-pressure reaction kettle, and placing the high-pressure reaction kettle into a blast drying box to react for 4 hours at 120 ℃. After the reaction is finished, waiting for the high-pressure reaction kettle to naturally cool to room temperature, and repeatedly washing the reacted catalyst by deionized water and absolute ethyl alcohol.
The washed catalyst was dried overnight at 80 ℃ in a vacuum oven. Continuously calcining in a muffle furnace at 550 ℃ for 5 hours at a temperature rising rate of 2 ℃ for 2 min -1 . Obtaining the phenolic foam catalyst of the loaded manganese ferrite. The catalyst obtained under this condition was designated as catalyst B.
Example 3:
preparation and carbonization of phenolic foam carrier: weighing a certain mass of phenolic resin, tween 80 and 6% of normal hexane, and mixing according to a certain mass ratio. Stirring the mixed solution for 25min according to 3500r/min, adding the diluted phosphoric acid solution according to a certain proportion, and continuing stirring. After the solution is stirred uniformly, the solution is led into a die. Foaming at 80 deg.c and normal pressure to obtain phenolic foam. The prepared phenolic foam was washed, and the phenolic foam was cut into rectangular blocks of 1cm×2cm×3 cm. After the foam is dried, the foam is placed in a tube furnace for carbonization at 750 ℃ for 2 hours.
Preparation of phenolic foam supported ferrite catalyst: 5mmol MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.6mmol CTAB and 25mmol urea were dissolved in 50mL ultra pure water, and the solution was thoroughly mixed and dispersed by ultrasonic until it was completely dissolved.
And (3) placing the prepared solution and the cut phenolic foam into a high-pressure reaction kettle, and placing the high-pressure reaction kettle into a blast drying box to react for 4 hours at 110 ℃. After the reaction is finished, waiting for the high-pressure reaction kettle to naturally cool to room temperature, and repeatedly washing the reacted catalyst by deionized water and absolute ethyl alcohol.
The washed catalyst was dried overnight at 80 ℃ in a vacuum oven. The high-temperature calcination is continued in a muffle furnace at 550 ℃ for 5 hours, and the temperature rising rate is 2 ℃ min < -1 >. Obtaining the phenolic foam catalyst of the loaded manganese ferrite. The catalyst obtained under this condition was designated as catalyst C.
Example 4:
preparation and carbonization of phenolic foam carrier: weighing a certain mass of phenolic resin, tween 80 and 6% of normal hexane, and mixing according to a certain mass ratio. Stirring the mixed solution for 25min according to 3500r/min, adding the diluted phosphoric acid solution according to a certain proportion, and continuing stirring. After the solution is stirred uniformly, the solution is led into a die. Foaming at 80 deg.c and normal pressure to obtain phenolic foam. And cleaning the prepared phenolic foam, and after the foam is dried, placing the phenolic foam in a tube furnace for carbonization at 750 ℃ for 2 hours.
Preparation of phenolic foam supported ferrite catalyst: 5mmol MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.6mmol CTAB and 25mmol urea were dissolved in 50mL ultra pure water, and the solution was thoroughly mixed and dispersed by ultrasonic until it was completely dissolved.
The carbonized phenolic foam was cut into a rectangular block of 1 cm. Times.2 cm. Times.3 cm. And (3) placing the prepared solution and the cut phenolic foam into a high-pressure reaction kettle, and placing the high-pressure reaction kettle into a blast drying box to react for 4 hours at 140 ℃. After the reaction is finished, waiting for the high-pressure reaction kettle to naturally cool to room temperature, and repeatedly washing the reacted catalyst by deionized water and absolute ethyl alcohol.
The washed catalyst was dried in a vacuum oven at 80℃overnightAnd (5) drying. Continuously calcining in a muffle furnace at 550 ℃ for 5 hours at a temperature rising rate of 2 ℃ for 2 min -1 . Obtaining the phenolic foam catalyst of the loaded manganese ferrite. The catalyst obtained under this condition was designated as catalyst D.
Comparative example 1:
in order to make the reaction effect more visual, the coking wastewater is treated by ozone alone as a comparison example, and the treatment effect of degrading COD and removing cyanide is taken as a reference, compared with the treatment effect of catalyzing the ozone to treat the coking wastewater by using the catalyst disclosed by the invention. The experimental conditions were all the same.
Comparative example 2
The treatment effect of the manganese ferrite for treating the coking wastewater is used as a reference, and the treatment effect of degrading COD and removing cyanide is compared with the treatment effect of the catalyst for catalyzing ozone for treating the coking wastewater. The experimental conditions were all the same.
In order to prove the application effect of the catalyst in treating pollutants in coking wastewater, the invention takes COD and cyanide in the coking wastewater as target pollutants, takes carbonized phenolic foam supported ferrite as the catalyst through ozone oxidation, catalyzes and degrades the target pollutants, and evaluates the performance of the catalyst. 300mL of wastewater and 0.3g of the catalyst of practical examples 1-4 described above were charged into a reaction apparatus, ozone gas flow rate: 1.0L min -1 The reaction time was 1.5h, which was introduced into the bottom of the reactor. Taking 1-1.5 mL of sample every 15min, and immediately introducing 5min of high-purity N 2 For removing residual dissolved ozone in the sample. Wherein, the ozone adding conditions of the comparative examples are the same. And comparing the treatment effect of the target pollutant.
Table 1 effects of examples 1, 2, 3, 4 catalysts and comparative examples on removal of COD and cyanide from coking wastewater
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| COD removal rate | 84.31％ | 79.61％ | 77.56％ | 78.42％ | 68.63％ | 75.4％ |
| Phenol removal rate | 77.31％ | 70.53％ | 69.76％ | 71.53％ | 60.35％ | 72.3％ |
| Quinoline removal rate | 71.16％ | 66.55％ | 65.49％ | 67.55％ | 55.57％ | 72.1％ |
| Pyridine removal rate | 68.34％ | 62.66％ | 60.57％ | 62.83％ | 53.14％ | 70.6％ |
Example 5
Recovery of manganese ferrite catalyst
From the above table, the catalytic performance is improved after the manganese ferrite is attached to the phenolic foam, and the phenolic foam has excellent temperature resistance and a uniform porous structure, so that the manganese ferrite can be used as a novel catalyst carrier. The porous structure of the phenolic foam ensures that the manganese ferrite catalyst can be uniformly dispersed on the surface of the phenolic foam, improves the specific surface area, ensures that the active components are more fully combined with sewage, and improves the degradation efficiency of pollutants. Meanwhile, the manganese ferrite in the single nano state can have the problems of dissolution and the like in the catalytic process, and the manganese ferrite catalyst is more beneficial to recovery after being combined with a carrier. .
As can be seen from the data in Table 1, the removal efficiency of COD, phenol, quinoline and pyridine is greatly improved after the catalyst is added. Examples 1, 2, 3 and 4 found that the catalyst formed at 130 ℃ in example 1 had higher removal rate of COD, phenol, quinoline and pyridine by changing the reaction temperature at the time of preparing the catalyst, so that the reaction temperature of 130 ℃ was the optimal reaction condition. And then, compared with the effect of treating coking wastewater by using the ozone and the nano-catalyst, the degradation rate of pollutants is improved by about 10% -15% after the active component is combined with the phenolic foam carrier, and the combination of the manganese ferrite catalyst and the phenolic foam carrier is proved to be capable of improving the degradation efficiency.
The above-described embodiments are only illustrative of one of the preferred modes of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the design of the present invention.
Claims (9)
1. The preparation method of the phenolic foam supported manganese ferrite catalyst is characterized by comprising the following steps of:
(1) Preparing a phenolic foam carrier, namely mixing and stirring phenolic resin, a surfactant and normal hexane, adding a phosphoric acid solution, continuously stirring, and introducing the mixture into a mold for foaming after the solution is uniformly stirred to obtain phenolic foam;
(2) Cleaning the phenolic foam prepared in the step (1), cutting the phenolic foam into cuboid blocks, drying the cuboid blocks, and then placing the cuboid blocks in a tube furnace for carbonization at 750 ℃ for 2 hours; obtaining carbonized phenolic foam;
(3) MnCl is added to 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O, modifier and urea are dissolved in ultrapure water, and are fully mixed and dispersed by ultrasonic until the O, the modifier and the urea are completely dissolved;
(4) Mixing the phenolic foam cut in the step (2) and the mixed solution obtained in the step (3), putting the mixture into a high-pressure reaction kettle, heating the mixture for reaction for 4 hours, and repeatedly washing the mixture with deionized water and absolute ethyl alcohol after the reaction is finished;
(5) And (3) drying the catalyst obtained in the step (4) in a vacuum drying oven at 80 ℃, and continuously calcining the catalyst in a muffle furnace at a high temperature of 550 ℃ for 5 hours to obtain the manganese ferrite-loaded phenolic foam catalyst.
2. The method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein the surfactant in the step (1) is one or more of non-ionic surfactants of tween 80, tween 60 and DC 193.
3. The preparation method of the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein in the step (1), phenolic resin, a surfactant and n-hexane are mixed according to a mass ratio of 100:6:5, mixing to obtain a mixed resin solution, wherein the mass ratio of the mixed resin solution to phosphoric acid is (5): 1, mixing uniformly.
4. The method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein the modifier in the step (3) is one or two of polystyrene or cetyl trimethyl ammonium bromide.
5. The method for preparing a phenolic foam supported manganese ferrite catalyst according to claim 1, wherein in the step (3), mnCl 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 The mol ratio of O, hexadecyl trimethyl ammonium bromide and urea is 5-8:8-12-:0.5-0.6:25.
6. the method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein the heating rate of high-temperature calcination in the muffle furnace in the step (5) is 2 ℃ min -1 And then held.
7. The preparation method of the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein in the step (4), the phenolic foam cut in the step (2) and the mixed solution in the step (3) are mixed and placed into a high-pressure reaction kettle, and the high-pressure reaction kettle is placed into a blast drying box to react for 4 hours at the temperature of 110-150 ℃.
8. The method for preparing a phenolic foam supported manganese ferrite catalyst according to claim 3, wherein the concentration of the phosphoric acid solution is 3mol/L.
9. The application of the phenolic foam supported manganese ferrite catalyst is characterized by being used for catalyzing ozone to treat coking wastewater.
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