CN115739178A - Preparation method and application of phenolic foam loaded manganese ferrite catalyst - Google Patents
Preparation method and application of phenolic foam loaded manganese ferrite catalyst Download PDFInfo
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- CN115739178A CN115739178A CN202211097335.0A CN202211097335A CN115739178A CN 115739178 A CN115739178 A CN 115739178A CN 202211097335 A CN202211097335 A CN 202211097335A CN 115739178 A CN115739178 A CN 115739178A
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- 239000006260 foam Substances 0.000 title claims abstract description 98
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 52
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 45
- 239000011572 manganese Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 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 38
- 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 24
- 239000000203 mixture Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 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 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 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
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000003837 high-temperature calcination 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
- 238000005406 washing Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000007667 floating Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 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 10
- 238000003763 carbonization Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 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
- 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
- 238000007605 air drying Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 239000011148 porous material Substances 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
- 239000000126 substance Substances 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
Images
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
Abstract
The invention discloses a preparation method of a phenolic foam loaded manganese ferrite catalyst, which combines the traditional manganese ferrite catalyst with a phenolic foam carrier, solves the problems of easy agglomeration and instability of the manganese ferrite due to strong magnetism on the surface of the manganese ferrite, and solves the problems of difficult recovery of the nano size of the catalyst, easy dissolution, easy loss and the like when the nano manganese ferrite catalyst is loaded on phenolic foam with larger size. The phenolic foam has a good porous structure and can be used as an excellent self-floating material, and a reaction suspension bed is formed by utilizing the good self-floating performance of the material and the aeration arrangement at the bottom of the reaction device, so that the catalyst can fully contact with 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 loaded manganese ferrite catalyst.
Background
The catalytic ozonization technology combines a catalyst on the basis of ozone oxidation to efficiently degrade organic matters. Catalytic ozonation is divided into homogeneous ozonation and heterogeneous ozonation. Homogeneous phase ozone oxidation is to utilize transition metal ions as a catalyst to catalyze ozone to generate hydroxyl radicals to perform a series of reactions with organic matters so as to degrade the organic matters. The homogeneous ozone oxidation catalyst has the defects of easy loss, difficult recovery, possibility of dissolution and the like, and needs to be improved in research and development. The heterogeneous ozone oxidation mainly comprises transition metals, transition metal oxides and supported metals, and mainly comprises the synergistic action of adsorption and catalysis or a solid catalyst for catalyzing ozone to generate high-activity free radicals. The catalyst is relatively widely applied, and simultaneously has the problems of low catalytic efficiency, small specific surface area and the like. At present, the ferrite nano-catalyst is easy to run off and is difficult to recover.
Disclosure of Invention
The invention combines the advantages of homogeneous ozone catalysis and heterogeneous ozone catalysis, provides a catalyst of phenolic foam loaded manganese ferrite, and the ferrite has stable structure and outstanding catalytic performance; the phenolic foam has good heat resistance and low temperature resistance, has uniform pore size 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 (chemical oxygen demand) and cyanide in coking wastewater can be degraded more efficiently.
A preparation method of a phenolic foam loaded manganese ferrite catalyst comprises the following steps:
(1) Preparing a phenolic foam carrier, namely mixing and stirring phenolic resin, a surfactant and n-hexane, adding a phosphoric acid solution, continuously stirring, and introducing the solution into a mould 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 carbonizing the cuboid blocks in a tubular furnace at 750 ℃ for 2 hours; obtaining carbonized phenolic foam;
(3) Mixing MnCl 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 Dissolving O, a modifier and urea in ultrapure water, fully mixing and ultrasonically dispersing the ultrapure water until the ultrapure water is completely dissolved;
(4) Mixing the cut phenolic foam in the step (2) and the mixed solution 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 by using deionized water and absolute ethyl alcohol after the reaction is finished;
(5) And (5) 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 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 step (1) is one or more of nonionic surfactants tween 80, tween 60 and DC 193.
Further, in the step (1), the mass ratio of the phenolic resin to the surfactant to n-hexane is 100:6:5, mixing to obtain a mixed resin solution, wherein the mixed resin solution and phosphoric acid are mixed according to the mass ratio of 5:1 and mixing uniformly.
Further, the modifier in the step (3) is one or a mixture of polystyrene and hexadecyl trimethyl ammonium bromide.
Further, mnCl is adopted in the step (3) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 The mol ratio of O, cetyl trimethyl ammonium bromide and urea is 5-8: 25.
further, in the step (5), the heating rate of the high-temperature calcination in the muffle furnace is 2 ℃ min-1, and then the temperature is maintained.
Further, in the step (4), the cut phenolic foam in the step (2) and the mixed solution in the step (3) are mixed and placed in a high-pressure reaction kettle, and the high-pressure reaction kettle is placed in a forced air drying oven and reacts for 4 hours at the temperature of 110-150 ℃.
Further, the concentration of the phosphoric acid solution is 3mol/L.
An application of a phenolic foam loaded manganese ferrite catalyst in catalyzing ozone to treat coking wastewater.
The invention has the beneficial effects that:
(1) The invention combines the traditional manganese ferrite catalyst with the phenolic foam carrier, and solves the problems of easy agglomeration and instability of the manganese ferrite due to strong magnetism on the surface of the manganese ferrite.
(2) The invention loads the nano manganese ferrite catalyst on the phenolic foam with larger size, and solves the problems of difficult nano size recovery, easy dissolution, easy loss and the like of the catalyst.
(3) The invention combines the heterogeneous catalyst with the suspendable phenolic foam, so that the catalyst can be integrally recycled, the cost is saved, and the invention has good industrial application prospect.
(4) The phenolic foam has a good porous structure and can be used as an excellent self-floating material, and a reaction suspension bed is formed by utilizing the good self-floating performance of the material and the aeration arrangement at the bottom of the reaction device, so that the catalyst can fully contact with ozone, and the ozone utilization rate is improved.
(5) The method has the advantages of simplicity, low cost, low energy consumption, low equipment requirement, easiness in production and good industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of the product at 130 deg.C
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a phenolic foam loaded manganese ferrite catalyst comprises the following steps:
(1) Preparing a phenolic foam carrier, namely mixing and stirring phenolic resin, a surfactant and n-hexane, adding a phosphoric acid solution, continuously stirring, and introducing the solution into a mould 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 carbonizing the cuboid blocks in a tubular furnace at 750 ℃ for 2 hours; obtaining carbonized phenolic foam;
(3) Mixing MnCl 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 Dissolving O, a modifier and urea in ultrapure water, and fully mixing and ultrasonically dispersing until the O, the modifier and the urea are completely dissolved;
(4) Mixing the cut phenolic foam in the step (2) and the mixed solution 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 by using deionized water and absolute ethyl alcohol after the reaction is finished;
(5) And (4) 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 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 step (1) is one or more of nonionic surfactants tween 80, tween 60 and DC 193.
Further, in the step (1), the mass ratio of phenolic resin to surfactant to n-hexane is 100:6:5, mixing to obtain a mixed resin solution, wherein the mixed resin solution and phosphoric acid are mixed according to the mass ratio of 5:1 and mixing uniformly.
Further, the modifier in the step (3) is one or a mixture of polystyrene and hexadecyl trimethyl ammonium bromide.
Further, mnCl is adopted 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): 25.
further, in the step (5), the heating rate of the high-temperature calcination in the muffle furnace is 2 ℃ min-1, and then the heating is maintained.
Further, in the step (4), the phenolic foam cut in the step (2) and the mixed solution in the step (3) are mixed and placed in a high-pressure reaction kettle, and the high-pressure reaction kettle is placed in an air-blowing drying oven and reacts for 4 hours at the temperature of 110-150 ℃.
Further, the concentration of the phosphoric acid solution is 3mol/L. Phosphoric acid can be used as an acid curing agent in the process of preparing phenolic foam, and the acid curing agent has short curing induction period, high curing degree and short foaming period. However, if the acid concentration is too high, the calorific value is also increased, and the corrosion of production equipment is likely to occur, and the control is difficult.
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. And stirring the mixed solution for 25min at 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 introduced into a mold. Foaming at 80 ℃ under normal pressure to obtain the phenolic foam. The prepared phenolic foam is cleaned, and the phenolic foam is cut into cuboid blocks of 1cm multiplied by 2cm multiplied by 3 cm. After the foam is dried, the foam is placed in a tubular furnace for carbonization at 750 ℃ for 2h.
Preparation of phenolic foam loaded ferrite catalyst: adding 5mmol of MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.548mmol of CTAB and 25mmol of urea are dissolved in 50mL of ultrapure waterIn (3), fully mixing and ultrasonically dispersing the mixture until the mixture is completely dissolved.
And (3) putting the prepared solution and the cut phenolic foam into a high-pressure reaction kettle, and placing the high-pressure reaction kettle in a forced air drying oven to react for 4 hours at the temperature of 130 ℃. After the reaction is finished, the high-pressure reaction kettle is naturally cooled to room temperature, and the catalyst after the reaction is repeatedly washed by deionized water and absolute ethyl alcohol.
The washed catalyst was dried in a vacuum oven at 80 ℃ overnight. Continuously calcining at 550 ℃ in a muffle furnace for 5 hours at the temperature rise rate of 2 ℃ and min -1 . Obtaining the phenolic foam catalyst loaded with the manganese ferrite. The catalyst obtained under these conditions 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. And stirring the mixed solution for 25min at 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 introduced into a mold. Foaming at 80 ℃ under normal pressure to obtain the phenolic foam. The prepared phenolic foam is cleaned, and the phenolic foam is cut into cuboid blocks with the length of 1cm multiplied by 2cm multiplied by 3 cm. After the foam is dried, the foam is placed in a tubular furnace for carbonization at 750 ℃ for 2h.
Preparation of phenolic foam supported ferrite catalyst: 5mmol of MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.548mmol of CTAB and 25mmol of urea are dissolved in 50mL of ultrapure water, and the mixture is fully mixed to be dispersed by ultrasonic until the mixture is 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 in a forced air drying oven to react for 4 hours at the temperature of 120 ℃. After the reaction is finished, the high-pressure reaction kettle is naturally cooled to room temperature, and the catalyst after the reaction is repeatedly washed by deionized water and absolute ethyl alcohol.
The washed catalyst was dried in a vacuum oven at 80 ℃ overnight. Continuously calcining at 550 ℃ in a muffle furnace for 5h at the temperature rise rate of 2 ℃ min -1 . Obtaining the phenolic aldehyde loaded with the manganese ferriteA foam catalyst. The catalyst obtained under these conditions was designated as catalyst B.
Example 3:
preparation and carbonization of phenolic foam carrier: weighing certain mass of phenolic resin, tween 80 and 6% of n-hexane, and mixing according to a certain mass ratio. And stirring the mixed solution for 25min at 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 introduced into a mould. Foaming at 80 ℃ under normal pressure to obtain the phenolic foam. The prepared phenolic foam is cleaned, and the phenolic foam is cut into cuboid blocks with the length of 1cm multiplied by 2cm multiplied by 3 cm. After the foam is dried, the foam is placed in a tubular furnace for carbonization at 750 ℃ for 2h.
Preparation of phenolic foam loaded ferrite catalyst: adding 5mmol of MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.6mmol CTAB and 25mmol urea are dissolved in 50mL of ultrapure water, and the solution is ultrasonically dispersed by thorough mixing until the solution is 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 in a forced air drying oven to react for 4 hours at the temperature of 110 ℃. After the reaction is finished, the high-pressure reaction kettle is naturally cooled to room temperature, and the catalyst after the reaction is repeatedly washed by deionized water and absolute ethyl alcohol.
The washed catalyst was dried in a vacuum oven at 80 ℃ overnight. And continuously calcining at 550 ℃ in a muffle furnace for 5h at the temperature rise rate of 2 ℃ min-1. Obtaining the phenolic foam catalyst loaded with the manganese ferrite. The catalyst obtained under these conditions 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. And stirring the mixed solution for 25min at 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 introduced into a mould. Foaming at 80 ℃ under normal pressure to obtain the phenolic foam. And cleaning the prepared phenolic foam, drying the foam, and then placing the foam in a tubular furnace for carbonization at 750 ℃, wherein the reaction time is 2h.
Preparation of phenolic foam loaded ferrite catalyst: adding 5mmol of MnCl 2 ·4H 2 O、10mmol Fe(NO 3 ) 3 ·9H 2 O, 0.6mmol CTAB and 25mmol urea are dissolved in 50mL of ultrapure water, and the mixture is fully mixed and ultrasonically dispersed until the mixture is completely dissolved.
Cutting the carbonized phenolic foam into rectangular blocks of 1cm multiplied by 2cm multiplied by 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 in a forced air drying oven to react for 4 hours at the temperature of 140 ℃. After the reaction is finished, the high-pressure reaction kettle is naturally cooled to room temperature, and the catalyst after the reaction is repeatedly washed by deionized water and absolute ethyl alcohol.
The washed catalyst was dried in a vacuum oven at 80 ℃ overnight. Continuously calcining at 550 ℃ in a muffle furnace for 5 hours at the temperature rise rate of 2 ℃ and min -1 . Obtaining the phenolic foam catalyst loaded with the manganese ferrite. The catalyst obtained under these conditions was designated as catalyst D.
Comparative example 1:
in order to ensure that the reaction effect is more visual, the coking wastewater treated by the single ozone is taken as a comparative example, and the treatment effects of degrading COD and removing cyanide are taken as references to be compared with the treatment effect of the coking wastewater treated by the catalyst catalyzed by the ozone. The experimental conditions were the same.
Comparative example 2
The single use of manganese ferrite for coking wastewater treatment is compared with the treatment effect of using the catalyst of the invention to catalyze ozone for coking wastewater treatment by taking the treatment effects of COD degradation and cyanide removal as reference. The experimental conditions were the same.
In order to prove the application effect of the catalyst in the treatment of coking wastewater pollutants, COD and cyanide in the coking wastewater are taken as target pollutants, carbonized phenolic foam loaded ferrite is taken as the catalyst through ozone oxidation, the target pollutants are catalytically degraded, and the performance of the catalyst is evaluated. To the reaction apparatus were charged 300mL of wastewater and 0.3g of the catalyst of the above example 1-4, ozone gas flow rate: 1.0L min -1 The mixture is introduced into the bottom of the reactor, and the reaction time is 1.5h. Taking 1-1.5 mL of sample every 15min, immediately introducing high-purity N for 5min 2 And the device is used for removing residual dissolved ozone in the sample. Wherein, the ozone adding conditions of the comparative example are the same. And comparing the treatment effect on the target pollutants.
Table 1 examples 1, 2, 3, 4 catalysts and comparative examples the effect of removing 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％ |
| Removal rate of quinoline | 71.16％ | 66.55％ | 65.49％ | 67.55％ | 55.57％ | 72.1％ |
| Removal rate of pyridine | 68.34％ | 62.66％ | 60.57％ | 62.83％ | 53.14％ | 70.6％ |
Example 5
Recovery of manganese ferrite catalyst
As can be seen from the table above, the catalytic performance of the manganese ferrite 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. Due to the porous structure of the phenolic foam, the manganese ferrite catalyst can be uniformly dispersed on the surface of the phenolic foam, the specific surface area is increased, the active component is more fully combined with sewage, and the degradation efficiency of pollutants is improved. Meanwhile, the manganese ferrite in a single nanometer state has the problems of dissolution and the like in the catalysis 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 by changing the reaction temperature at the time of preparing the catalyst, it was found that in example 1, the removal rate of COD, phenol, quinoline and pyridine by the catalyst formed at 130 ℃ was higher, and thus the reaction temperature of 130 ℃ was the optimum reaction condition. Compared with the effect of treating the coking wastewater by using the single ozone and the single nano-catalyst, the degradation rate of the active component and the phenolic foam carrier to pollutants is improved by about 10-15%, and the combination of the manganese ferrite catalyst and the phenolic foam carrier is proved to improve the degradation efficiency.
The above-described embodiments are only intended to describe one of the preferred embodiments of the present invention, and should not be construed as limiting the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (9)
1. The preparation method of the phenolic foam loaded 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 solution into a mould 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 carbonizing the cuboid blocks in a tubular furnace at 750 ℃ for 2 hours; obtaining carbonized phenolic foam;
(3) Mixing MnCl 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 Dissolving O, a modifier and urea in ultrapure water, fully mixing and ultrasonically dispersing until the O, the modifier and the urea are completely dissolved;
(4) Mixing the cut phenolic foam in the step (2) with the mixed solution 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 by using deionized water and absolute ethyl alcohol after the reaction is finished;
(5) And (5) 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 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 step (1) is one or more of nonionic surfactants 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), the mass ratio of phenolic resin to surfactant to n-hexane is 100:6:5, mixing to obtain a mixed resin solution, wherein the mixed resin solution and phosphoric acid are mixed according to the mass ratio of 5:1 and mixing uniformly.
4. The method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein the modifier in step (3) is one or a mixture of polystyrene and cetyltrimethylammonium bromide.
5. The method for preparing the phenolic foam supported manganese ferrite catalyst according to claim 1, wherein in the step (3), mnCl is adopted 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 The mol ratio of O, hexadecyl trimethyl ammonium bromide and urea is (5-8): 25.
6. the method for preparing the phenolic foam loaded manganese ferrite catalyst according to claim 1, wherein in the step (5), the temperature rise rate of high-temperature calcination in a muffle furnace is 2 ℃ min -1 And then held.
7. The preparation method of the phenolic foam loaded manganese ferrite catalyst according to claim 1, wherein in the step (4), the cut phenolic foam in the step (2) and the mixed solution in the step (3) are mixed and placed in a high-pressure reaction kettle, and the high-pressure reaction kettle is placed in an air-blowing drying oven and reacts for 4 hours at 110-150 ℃.
8. The method for preparing the 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 loaded manganese ferrite catalyst is characterized in that the phenolic foam loaded manganese ferrite catalyst is used for catalyzing ozone to treat coking wastewater.
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