CN114643059B - Fenton catalyst for water treatment and preparation method thereof - Google Patents
Fenton catalyst for water treatment and preparation method thereof Download PDFInfo
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- CN114643059B CN114643059B CN202210559903.8A CN202210559903A CN114643059B CN 114643059 B CN114643059 B CN 114643059B CN 202210559903 A CN202210559903 A CN 202210559903A CN 114643059 B CN114643059 B CN 114643059B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 18
- 239000002245 particle Substances 0.000 claims abstract description 123
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 32
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 28
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- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052788 barium Inorganic materials 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
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- 239000000243 solution Substances 0.000 claims description 58
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- 238000002844 melting Methods 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
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- 230000008018 melting Effects 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 8
- 229940031182 nanoparticles iron oxide Drugs 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003960 organic solvent Substances 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
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- 230000003197 catalytic effect Effects 0.000 abstract description 35
- 239000011148 porous material Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 13
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- 230000015556 catabolic process Effects 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- B01J35/23—
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- B01J35/51—
-
- B01J35/60—
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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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to the technical field of water treatment and Fenton catalysts, in particular to a porous heterogeneous Fenton catalyst for water treatment, which is prepared by taking cerium oxide modified mesoporous iron oxide particles, a porous carrier, magnetic hercynite or hercynite, activated alumina, barium azodicarboxylate particles, a slow-release pore-forming agent, an optional high-temperature binder and other components as main raw materials, bonding the raw materials by a bonding solution, granulating the raw materials, and then carrying out thermoforming, loading and other steps. The Fenton catalyst particles prepared by the method have high porosity, catalytic activity and mechanical strength, and are suitable for treating organic wastewater by a Fenton reaction.
Description
Technical Field
The invention relates to the technical field of water treatment and Fenton catalysts, in particular to a heterogeneous Fenton catalyst loaded by a porous material and a preparation method and application thereof.
Background
The fenton oxidation technology is a commonly used wastewater treatment technology, which generates high-activity hydroxyl radicals by catalyzing hydrogen peroxide to decompose, and the hydroxyl radicals have high oxidability and nonspecific selectivity and can effectively degrade various organic pollutants which are difficult to degrade biologically. Therefore, the Fenton oxidation can effectively degrade organic matters in the wastewater, and is an environment-friendly wastewater treatment technology. However, the common Fenton oxidation has the defects of incapability of recycling the catalyst, low reaction rate, low utilization rate of hydrogen peroxide, high byproduct iron mud, high post-treatment cost and the like.
The heterogeneous Fenton technology is an advanced water treatment technology developed based on a common Fenton technology, and overcomes the defects of the Fenton oxidation technology by means of a high-efficiency supported Fenton catalyst. By means of the high-efficiency supported Fenton catalyst, pollutants are converted into biodegradable low-molecular substances or carbon dioxide, water and the like, no sludge is generated, no secondary pollution is generated, and the method is an oxidation technology for treating organic wastewater with a very promising prospect. However, most of the currently developed heterogeneous fenton catalysts are supported solids containing iron oxide catalytic components, and the iron oxide is easy to agglomerate due to the magnetism and nanoparticle properties of the iron oxide, so that the uniform distribution of active sites is not facilitated, and the degradation rate is not high. In addition, the reaction of treating pollutants by the heterogeneous Fenton catalyst occurs at the contact interface of a solid phase and a liquid phase, the carrier used as the catalyst is usually a natural porous material, the pores are small, the porosity is not high, the mass transfer resistance of the two-phase reaction interface is large under the large fluid pressure, and the reaction efficiency is low; and the catalyst has poor stability, cannot be continuously or circularly used for a long time, needs frequent updating and leads to increased cost. The prior art cannot completely avoid the defects.
In the prior art, patent application CN103285887A discloses a preparation method of a diatomite-supported solid super strong acid Fenton catalyst, which comprises the steps of soaking natural diatomite for 10-14 h by using 0.1-1 mol/L inorganic acid, carrying out acidification treatment on the natural diatomite, activating at the temperature of 200-400 ℃ for 1-4 h to obtain activated natural diatomite, roasting at the temperature of 400-600 ℃ for 1-6 h to carry out heat treatment on a precursor, and obtaining the diatomite-supported solid super strong acid Fenton catalyst.
CN 105688917A discloses a porous ceramsite Fenton catalyst and a preparation method thereof, and the preparation method comprises the following steps: (1) according to the weight portion, 20-60 portions of municipal sludge, 10-20 portions of clay, 10-20 portions of kaolin, 10-20 portions of fly ash, 2-5 portions of silicon source, 2-5 portions of copper-containing compound and 2-5 portions of iron-containing compound are taken as raw materials; uniformly mixing all components in the raw materials, and extruding to obtain a ceramsite blank; the silicon source is one or more of water glass, gas-phase silicon dioxide and silicon powder; (2) drying and sintering the ceramsite blank, and cooling to obtain a porous ceramsite carrier; the sintering is to heat the dried ceramsite blank to 300-600 ℃ and preserve heat for 10-40min, and then to 950-1150 ℃ and preserve heat for 10-40 min. According to the method, the porous ceramsite is obtained by high-temperature sintering, a large amount of pores are easily sealed by a molten body, the catalytic efficiency cannot be improved, and the municipal sludge component is unclear and cannot be used as a stable and efficient catalyst preparation source.
CN1147356A spray-drying the catalyst slurry, pre-roasting for 5 hours, coating the catalyst slurry on an alumina carrier, and roasting for 5 hours at 390 ℃ to obtain the finished spherical catalyst. CN 114011416A discloses a porous material loaded multi-metal composite Fenton-like catalyst, a preparation method and application thereof, and the catalyst comprises a porous material and a loaded metal oxide, wherein the mole percentage of iron oxide in the metal oxide is more than 50%.
In summary, the existing supported heterogeneous fenton catalyst generally has one or a series of defects as follows:
1) the existing porous material loaded metal Fenton catalyst is limited in specific surface area by virtue of the structural characteristics of the porous material, so that more reaction contact surfaces cannot be exposed, and more catalytic active sites cannot be provided.
2) Because the catalyst forming method mainly comprises medium-temperature calcination (the activity of a catalytic component is obviously reduced by high-temperature calcination at about one thousand ℃, so that the calcination temperature is usually about six hundred ℃, although the prepared catalyst has various pore structures and specific surface areas, the mechanical strength is generally poor, and the catalyst is easy to crack under the pressure generated by the flow of fluids such as waste water and the like in the long-term operation reaction process, so that the uniform flow and the stable catalytic performance of the fluids are influenced.
3) The existing supported catalyst is mainly prepared by impregnation loading, belongs to surface loading (an impregnation method is to precipitate active metal oxides on the outer surface of a porous material and the inner surface of a pore channel), has low loading capacity of a catalytic component, is easy to fall off and run off (particularly, the catalyst carrier is easy to absorb water and swell to reduce the hardness and soften the particle structure and is easy to run off or even inactivate in long-term soaking), and cannot ensure that the catalytic active component is highly and uniformly dispersed in the catalyst. Even if there are few catalytic components doped in the carrier skeleton, the exposed active sites are few, and the catalytic activity and the utilization rate of hydrogen peroxide cannot be high. And has poor catalytic stability in long-term use.
However, in the prior art, a fenton catalyst filler which can overcome or improve the defects is not available.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a porous heterogeneous Fenton catalyst with high porosity and a preparation method thereof, and the prepared heterogeneous Fenton catalyst particles have high porosity, catalytic activity and mechanical strength, strong flushing resistance and high stability, and are suitable for treating organic wastewater by heterogeneous Fenton reaction.
The specific technical scheme of the invention is as follows.
In a first aspect, the invention provides a porous heterogeneous Fenton catalyst, which is prepared from cerium oxide modified mesoporous iron oxide particles, a porous carrier, and hercynite (magnetic hercynite or hercynite FeAl)2O4) The composite material is prepared by using active aluminum oxide, barium azodicarboxylate particles (preferably with the particle size not more than 50 microns), a slow-release pore-forming agent (preferably calcium sulfate particles with the particle size of 0.05-0.5 mm) and a high-temperature binder (preferably low-melting-point glass powder or polyamide wax micro powder with the particle size of 5-15 microns) as basic raw materials, bonding by using a bonding solution, granulating, and then carrying out thermal forming, loading and the like.
Wherein the porous carrier is selected from at least one of zeolite powder, kaolin and montmorillonite powder.
Among them, the high-temperature binder is preferably a low-melting glass frit, more preferably one having an initial melting temperature of about 500 ℃ (for example, 450 ℃ C. and 550 ℃ C.), and is commercially available, and is preferably added in an amount of 0.5 to 5 wt.%.
The cerium oxide modified mesoporous iron oxide particles are composed of mesoporous iron oxide supported cerium oxide. The preferable specific surface area of the mesoporous iron oxide is not less than 80m2Per gram of mesoporous ferric oxide (ordered mesopores, pore diameter of 3-10nm, particle size of about 50 nm) or ferroferric oxide. The mesoporous iron oxide can be prepared according to the general method in the field, and can also be obtained commercially.
Wherein the adhesive solution is prepared by reacting iron salt solution with ammonia water to generate sol solution of sol, and adding thermal decomposition pore-forming adhesive (selected from polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone).
Preferably, the preparation raw material of the porous heterogeneous Fenton catalyst comprises the following basic raw materials in parts by weight: 100 parts of porous carrier, 5-10 parts of hercynite, 3-5 parts of cerium oxide modified mesoporous iron oxide particles, 10-20 parts of activated alumina and 1-3 parts of barium azodicarboxylate particles; 5-15 parts of slow-release pore-forming agent particles and 2-5 parts of high-temperature binder. Wherein, the porous carrier is composed of natural zeolite powder, kaolin and montmorillonite powder, wherein the weight proportion of the natural zeolite powder is preferably not less than 50%.
In a second aspect, the present invention also provides a method for preparing the heterogeneous fenton catalyst, comprising the steps of:
s1) selecting clean and dry raw material powder according to the parts by weight: 100 parts of porous carrier, 5-10 parts of hercynite (magnetic hercynite (also called spinel type ferrite or magnetic spinel) or hercynite), 3-5 parts of cerium oxide modified mesoporous iron oxide particles, 10-20 parts of activated alumina, 1-3 parts of barium azodicarboxylate particles, 5-15 parts of calcium sulfate particles and a proper amount of high-temperature binder (preferably 2-5 parts); uniformly mixing the porous carrier, the hercynite and the activated alumina according to the proportion, then grinding (until the particle size is less than 0.2mm, preferably 0.1-0.15 mm), sieving, and mixing with the cerium oxide modified mesoporous iron oxide particles, the barium azodicarboxylate particles (preferably 1-10 microns), the calcium sulfate particles (preferably 0.1-0.3 mm) and the high-temperature binder to obtain a solid mixed raw material;
s2), under the stirring condition, ammonia water is dripped into 10-20wt% ferric nitrate aqueous solution for reaction to generate sol; after complete precipitation (e.g., pH stabilized at about 8), adding an appropriate amount of thermally decomposable pore-forming binder (preferably 0.5-2wt% by mass) and mixing to obtain a treatment solution, wherein the operation is preferably carried out under stirring in a water bath at 30-50 ℃. And cooling to room temperature after the completion to obtain an adhesive solution for later use.
Wherein the thermal decomposition pore-forming adhesive is selected from at least one of polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone.
Mixing the solid mixed raw material powder with the binding solution, fully wetting and uniformly stirring, and then granulating in a granulator. Wherein the solid content of the slurry is controlled to be suitable for granulation (preferably 50-70%), and granulating in a granulator to obtain spherical granules or cylindrical granules, preferably spherical granules with a diameter of 1-5 mm.
S3) subjecting the resultant pellets to heat treatment in a muffle furnace, the steps being as follows:
firstly, raising the temperature from room temperature to 150 ℃ at the speed of 2-3 ℃/min, preheating for 10-15min, then raising the temperature to 250-280 ℃ at the speed of 1-1.5 ℃/min, and preserving the heat for 30-60 min;
then, the temperature is raised to 550-600 ℃ at the rate of 3-5 ℃/min, the calcination is carried out for 1-3h at the temperature, and then the temperature is lowered to about 100 ℃ at the rate of 5-6 ℃/min for discharging. And removing broken and incomplete particles to obtain a catalyst preform.
Wherein the preheating of the heat treatment step can cause the thermally decomposable organic pore-forming binder to be thermally decomposed sufficiently. Meanwhile, the barium azodicarboxylate can be fully decomposed to form pores at 250-280 ℃ and subsequent higher temperature, thereby greatly improving the porosity.
S4) immersing the obtained catalyst preform in 0.5-1M FeCl3Solution (FeCl)3·6H2O is dissolved in deionized water), and the ultrasonic dispersion is uniform; under the heating condition of 60-70 ℃ water bath or oil bath, dropwise adding ammonia water solution (15-25 wt%) while stirring until iron ions are fully precipitated, and then filtering and separating solid particles; and (5) drying. Specifically, the mixture is put into an oven with the temperature of 60 ℃ to be dried for 10-12 h.
S5) placing the dried particles in a tubular furnace, introducing nitrogen to replace the atmosphere, heating to 660-680 ℃ at the heating rate of 5-6 ℃/min, and calcining for 1-2 h; and cooling to room temperature after calcination, washing with deionized water, fully drying and drying to obtain the heterogeneous Fenton catalyst particles.
Wherein the cerium oxide modified mesoporous iron oxide particles are prepared by the following steps:
adding mesoporous iron oxide nanoparticles with the particle size of about 50-100nm into a composite organic solvent containing n-butanol, and simultaneously dropwise adding Ce (Ce: (n-butyl alcohol)) at room temperature under the stirring conditionNO3)3Adding the solution and ammonia water into the organic composite solvent, and adding Ce (NO)3)3And continuously dropwise adding ammonia water after the dropwise addition of the solution is finished until the pH value is stabilized at 9-10, and then reacting for 2-3h under the stirring or oscillation condition. Standing and aging at room temperature for 10-12h after the reaction is finished, performing solid-liquid separation, fully washing with deionized water and absolute ethyl alcohol, performing vacuum drying, and calcining at 660-680 ℃ for 2-3h in a muffle furnace in a nitrogen atmosphere to obtain the cerium oxide doped modified mesoporous iron oxide nanoparticles. Wherein the iron oxide nanoparticles are mixed with Ce (NO)3)3The mass ratio of the raw materials is 10: 0.1-1.
Compared with the method that only the iron oxide is adopted as the catalytic component, the cerium oxide modified mesoporous iron oxide can obviously improve the catalytic activity of the catalyst under the illumination condition due to the optical activity of the cerium oxide. In addition, compared with common iron oxide, the mesoporous iron oxide can be doped and adsorbed with cerium oxide more easily, and the cerium oxide loading effect is improved.
In a third aspect, the invention further provides the heterogeneous fenton catalyst particles prepared by the method, and application of the heterogeneous fenton catalyst particles in wastewater treatment, especially wastewater containing organic matters, wherein the source of the heterogeneous fenton catalyst particles can be dye wastewater, pharmaceutical and chemical wastewater or papermaking wastewater and the like. When in use, the compound is combined with hydrogen peroxide to form a Fenton-like system, and the wastewater is oxidized.
Compared with the prior art, the invention has the following beneficial technical effects:
1) in the preparation of the catalyst, the mode of doping and combining the carrier powder and the metal catalytic components (cerium oxide modified mesoporous iron oxide and hercynite) is adopted, and compared with the prior art which only adopts a loading mode, the catalytic components can be introduced into the catalyst; meanwhile, the porosity of the catalyst is improved by means of slow-release pore-forming and heat treatment pore-forming in the preparation of the catalyst, so that the internally doped catalytic component is exposed, and more reaction sites are provided.
2) The system construction of open pores with different sizes and multiple levels inside the catalyst particles is one of the innovations of the invention. Except for adopting the conventional thermal decomposition pore-forming agent (high molecular organic polymer) and the water-insoluble barium azodicarboxylate (the gas production is large, the released gas is nontoxic, and the particle size can be adjusted to obtain pores with required sizes), the invention also innovatively adopts the slow-release pore-forming agent-calcium sulfate particles, and the calcium sulfate is used as a filler to be doped in the catalyst particles to form uniform occupying distribution.
Because the calcium sulfate is high-temperature resistant, the calcium sulfate is basically not decomposed in the roasting process, so that the calcium sulfate can completely exist in a formed catalyst product; meanwhile, due to the characteristic of slightly water-soluble property, the catalyst can be slowly dissolved, reduced and completely disappeared in the long-term running and using process of the catalyst for water treatment, so that more pores are generated in the catalyst, and the catalytic components doped in the catalyst are exposed, so that more catalytic sites are generated. Therefore, unlike the similar fenton catalysts of the prior art, the catalyst of the present invention can ensure the following beneficial technical effects during use: along with the operation time, the porosity and the catalytic performance are gradually improved to a certain extent, so that the performance reduction trend of the catalyst is reduced (due to factors such as catalytic component loss, pore blockage and the like, all the similar catalysts have the performance reduction trend). Namely, the invention can improve the operation stability of the catalyst, prolong the regeneration period of the catalyst and further prolong the service life of the catalyst.
3) The improvement of the structural strength of the catalyst particles is another major innovation of the present invention. Different from the prior art that a porous material is directly adopted as a load carrier, the invention crushes the carrier material, mixes the crushed carrier material with a catalytic component, and recombines the mixture to be used as a material for preparing the catalyst, thereby being beneficial to containing a pore-forming agent to generate an additional pore structure (the micro pores of the material are combined with the additional pore-forming pores, so that the porosity of the catalyst is improved, and the porosity exceeds 60 percent).
However, this also brings with it another disadvantage: compared with the direct use of particles such as molecular sieves, the particles recombined in the invention are easy to cause low structural strength of the formed catalyst and easy to expand, soften or even crack in the long-term use process to cause loss of the catalytic component on the premise of low calcination temperature (generally not exceeding 700 ℃ in the prior art so as to avoid reduction of the activity of the catalytic component caused by high temperature) due to low adhesion among the particles, pore generation caused by pore-forming treatment and other factors.
In order to solve the technical problems, the invention adopts high-temperature adhesive such as low-melting-point glass powder (lead-free), in particular to the glass powder with the initial melting temperature of about 500 ℃, thereby obviously improving the strength of the particles. Thereby opening the application that the heterogeneous Fenton catalyst can be added with glass powder to enhance the particle strength. Generally, the glass powder is not a porous carrier, and is not used for preparing heterogeneous Fenton catalysts because the glass powder causes pore blockage after melting. However, the invention adopts the artificial pore-forming mode of the granular solid inorganic pore-forming agent barium azodicarboxylate and the pore-forming inhibitor, thereby greatly reducing the adverse porosity influence caused by the glass powder melting (the glass powder melting mainly influences the internal pores of the carrier material such as zeolite powder, and the large pores generated by artificial pore-forming are difficult to block).
4) Compared with the supported catalyst obtained by an impregnation method, the catalyst provided by the invention has more catalytic active sites, and the cerium dioxide catalyst promoter can cooperatively participate in promoting the generation of hydroxyl free radicals (cerium dioxide can generate photogeneration carrier electrons under the illumination condition), and especially can accelerate the reaction process under the illumination condition. Meanwhile, the catalyst has improved catalytic performance under non-illumination conditions.
Drawings
FIG. 1 is SEM topography of cerium oxide modified mesoporous iron oxide prepared in example 1
FIG. 2 is an SEM topography (without heat treatment) of the surface of the particles obtained after granulation in step 3) of example 3
FIG. 3 is an SEM micrograph of internal pores of the calcined catalyst (15K) obtained in step 6) of example 3.
Detailed Description
The present invention is described in detail below with reference to specific production examples and examples, but these examples do not limit the scope of the present invention in any way.
Example 1
Preparation of cerium oxide modified mesoporous iron oxide 1
Taking 10g of mesoporous iron oxide (ferric oxide) nanoparticles with the average particle size of about 55nm (note: the preparation method of the mesoporous iron oxide is well known in the field, and the dosage of the mesoporous iron oxide in the experimental stage is small, so the preparation method of the invention is self-made, the process refers to CN104341009A, and the mesoporous iron oxide nanoparticles can also be directly obtained commercially, the raw material is common in the field and the market, for example, Jiangsu high carbon material Co., Ltd.) is added into 24ml of n-butyl alcohol/cyclohexane (volume ratio 3: 1) composite solvent, and 0.6g of Ce (NO) is weighed simultaneously3)3·6H2Dissolving O in 10ml deionized water to prepare Ce (NO)3)3And (3) solution. The above-mentioned Ce (NO) was added dropwise simultaneously at room temperature under stirring3)3The solution and ammonia (25% mass concentration) are added into the organic composite solvent, Ce (NO)3)3And (3) continuing to dropwise add ammonia water after the dropwise addition of the solution is finished until the solution becomes yellow and the pH value of the solution is not lower than 9.5, and then placing the solution on a shaking table to shake and react for 3 hours under the oscillation condition of 100 rpm. Standing and aging at room temperature for 12h after the reaction is finished, adding 30ml of acetone, stirring and suspending, performing solid-liquid centrifugal separation, washing the obtained solid with deionized water for 3 times until the solid is neutral, then washing the solid with absolute ethyl alcohol for 3 times, performing vacuum drying at 80 ℃ for 6h, then placing the solid in a muffle furnace in a nitrogen atmosphere, and calcining at 680 ℃ for 2h to obtain cerium oxide doped modified mesoporous iron oxide nanoparticles (shown in figure 1); pulverizing and sieving (mainly sieving the self-agglomerated cerium dioxide nanoparticles whose surfaces are not successfully loaded, which is determined by the process characteristics of a precipitation method, namely, not all formed nano cerium dioxide can be attached to the surfaces of iron oxide particles) for later use. As can be seen from the morphology shown in fig. 1, the surface of the calcined particulate material exhibits doped cerium oxide nanoparticles of different particle sizes (the doping amount varies with the concentration of the added cerium salt).
Example 2
Preparation of cerium oxide modified mesoporous iron oxide 2
Weighing 10g of particles with a particle size of about 50nmAdding mesoporous ferroferric oxide nano particles (with the aperture of 5-10 nm) into 24ml of n-butanol/cyclohexane (volume ratio of 4: 1) composite solvent, and simultaneously weighing 0.5g of Ce (NO)3)3·6H2Dissolving O in 10ml deionized water to prepare Ce (NO)3)3And (3) solution. The above Ce (NO) was added dropwise simultaneously at room temperature under stirring3)3The solution and ammonia (25% mass concentration) are added into the organic composite solvent, Ce (NO)3)3And continuing to dropwise add ammonia water after the dropwise addition of the solution is finished until the solution becomes yellow and the pH value of the solution is not lower than 9.5, and then placing the solution on a shaker for oscillation reaction for 3 hours under the oscillation condition of 80 rpm. And after the reaction is finished, standing and aging at room temperature for 10 hours, adding acetone, stirring, suspending, performing centrifugal separation, washing the obtained solid with deionized water for 3 times until the solid is neutral, washing with absolute ethyl alcohol for 3 times, performing vacuum drying at 80 ℃ for 6 hours, then placing the solid in a muffle furnace in nitrogen atmosphere, calcining at 660 ℃ for 3 hours to obtain cerium oxide doped modified mesoporous iron oxide nanoparticles 2, and crushing and sieving for later use.
Example 3
Preparation of heterogeneous Fenton catalyst 1
1) Selecting clean and dry raw material powder according to the following weight parts: 100 parts of a porous carrier (composed of zeolite powder, kaolin and montmorillonite powder in a mass ratio of =6:2: 2), 10 parts of hercynite, 5 parts of cerium oxide modified mesoporous iron oxide particles prepared in example 1, 20 parts of activated alumina, 3 parts of barium azodicarboxylate particles (average particle size of 5 micrometers), 10 parts of calcium sulfate particles (particle size range of 0.1-0.5 mm), and 5 parts of low-melting glass powder (particle size of 10 micrometers, initial melting point of 500 ℃); uniformly mixing the porous carrier, the hercynite and the activated alumina in the proportion in a mixer, grinding the mixture in a grinder until the particle size is less than 0.2mm, sieving the mixture, and mixing the sieved mixture with cerium oxide modified mesoporous iron oxide particles, barium azodicarboxylate particles, calcium sulfate particles and low-melting-point glass powder to obtain about 0.46kg of solid mixed raw material;
2) under the condition of stirring, dropwise adding ammonia water into a 20wt% ferric nitrate aqueous solution to react to generate a sol solution; and after the pH value is stabilized to about 8, adding polyvinyl alcohol to enable the mass fraction of the polyvinyl alcohol to be 0.5wt%, and stirring and uniformly mixing in a water bath at the temperature of 40 ℃ to obtain the treatment solution. And cooling to room temperature after the completion to obtain the adhesive solution for later use.
3) Mixing the solid mixed raw material powder with an adhesive solution, and fully stirring and wetting to obtain slurry; the solids content of the slurry was controlled to about 60% and granulated in a pan granulator to give spherical particles with a controlled diameter of about 5 mm.
The surface topography of the resulting dried catalyst particles is shown in FIG. 2, which shows that the catalyst particles have a denser structure and a lower porosity before heat treatment.
4) Carrying out heat treatment on the obtained spherical particles in a muffle furnace, and carrying out the following steps:
firstly, heating from room temperature to 150 ℃ at the speed of 2 ℃/min, preheating for 15min, then heating to 250 ℃ at the speed of 1 ℃/min, and keeping the temperature for 30 min;
and then, heating to 550 ℃ at the speed of 3 ℃/min, calcining for 1h at the temperature, then cooling to about 100 ℃ at the cooling speed of 5 ℃/min, discharging, and removing broken incomplete particles to obtain a catalyst preform.
5) The obtained catalyst preform was immersed in 0.5M FeCl3Solution (FeCl)3·6H2O is dissolved in deionized water), and the ultrasonic dispersion is uniform; under the water bath heating condition of 60 ℃, dropwise adding ammonia water solution (15 wt%) while stirring until iron ions are fully precipitated, and then filtering and separating solid particles; putting into a drying oven with the temperature of 60 ℃ for drying for 10 hours;
6) placing the dried particles in a tubular furnace, introducing nitrogen to replace the atmosphere, heating to 660 ℃ at the heating rate of 5 ℃/min, and calcining for 1.5 h; after calcination, the mixture is cooled to room temperature, fully washed with deionized water, dried and dried, and molded products are screened to obtain about 0.4kg of complete molded particles, namely the heterogeneous Fenton catalyst 1, wherein the porosity is measured to be 78.6%, and the mechanical strength of the particles is about 28 MPa. The obtained morphology of the internal structure of the catalyst particles is shown in figure 3, and it can be seen that after the heat treatment, the catalyst has high porosity inside and can expose the catalytic component loaded on the carrier.
Example 4
Preparation of heterogeneous Fenton catalyst 2
1) Selecting clean and dry raw material powder according to the following weight parts: 100 parts of porous carrier (composed of zeolite powder and montmorillonite powder with mass ratio =6: 4), and magnetic hercynite (main component MgFe)2O4) 5 parts, 3 parts of the cerium oxide modified mesoporous iron oxide particles prepared in example 2, 10 parts of activated alumina, 2 parts of barium azodicarboxylate particles (average particle size of 5 microns), 5 parts of calcium sulfate particles (particle size range of 0.2-0.5 mm), and 2 parts of low-melting glass powder (particle size of 10 microns, initial melting point of 500 ℃); uniformly mixing the porous carrier, the hercynite and the activated alumina in the proportion in a mixer, grinding the mixture in a grinder until the particle size is less than 0.2mm, sieving the mixture, and mixing the sieved mixture with cerium oxide modified mesoporous iron oxide particles, barium azodicarboxylate particles, calcium sulfate particles and low-melting-point glass powder to obtain a solid mixed raw material;
2) under the condition of stirring, dropwise adding ammonia water into 15wt% of ferric nitrate aqueous solution to react to generate sol solution; after complete reaction, polyvinyl alcohol is added to ensure that the mass fraction of the polyvinyl alcohol is 0.5wt%, and the treatment solution is obtained by stirring and uniformly mixing the polyvinyl alcohol and the water bath at the temperature of 40 ℃. And cooling to room temperature after the completion to obtain an adhesive solution for later use.
3) Mixing the solid mixed raw material powder with a proper amount of bonding solution, fully stirring and wetting to obtain granulation slurry, and granulating in a disc granulator to obtain spherical granules with the diameter controlled to be about 3 mm.
4) Carrying out heat treatment on the obtained spherical particles in a muffle furnace, and carrying out the following steps:
firstly, heating from room temperature to 150 ℃ at the speed of 3 ℃/min, preheating for 15min, then heating to 280 ℃ at the speed of 1 ℃/min, and preserving heat for 30 min;
and then, heating to 600 ℃ at the speed of 3 ℃/min, calcining for 2h at the temperature, then cooling to about 100 ℃ at the cooling speed of 5 ℃/min, discharging, and removing broken incomplete particles to obtain a catalyst preform.
5) The obtained catalyst preform was immersed in 0.6M FeCl3In the solution, ultrasonic dispersion is uniform; heating in 60 deg.C water bathUnder the condition, dropwise adding an ammonia water solution (20 wt%) while stirring until iron ions are fully precipitated, and then filtering and separating solid particles; putting into a drying oven with the temperature of 60 ℃ for drying for 10 h;
6) placing the dried particles in a tubular furnace, introducing nitrogen to replace the atmosphere, heating to 680 ℃ at the heating rate of 5 ℃/min, and calcining for 1 h; and after the calcination is finished, cooling to room temperature, washing with deionized water, fully drying and drying to obtain heterogeneous Fenton catalyst particles 2 with the porosity of 73.4%.
Comparative example 1
1) Selecting clean and dry raw material powder according to the following weight parts: 100 parts of a porous carrier (composed of zeolite powder and montmorillonite powder with the mass ratio =6: 4), 5 parts of hercynite, 3 parts of cerium oxide modified mesoporous iron oxide particles prepared in example 2 and 10 parts of active alumina; uniformly mixing the porous carrier, hercynite and activated alumina in the proportion in a mixer, grinding the mixture in a grinder until the particle size is less than 0.2mm, sieving the mixture, and mixing the sieved mixture with cerium oxide modified mesoporous iron oxide particles to obtain a solid mixed raw material;
steps 2) -6) the conditions were the same as in example 4, and heterogeneous fenton catalyst particles D1 were prepared with a porosity of 54.9%.
Comparative example 2
1) Selecting clean and dry raw material powder according to the following weight parts: 100 parts of porous carrier (composed of zeolite powder and montmorillonite powder with the mass ratio =6: 4) and 10 parts of active alumina; uniformly mixing the porous carrier and the activated alumina in the proportion in a mixer, then grinding the mixture in a grinder until the particle size is less than 0.2mm, and sieving the mixture;
2) under the condition of stirring, dropwise adding ammonia water into 15wt% of ferric nitrate aqueous solution to react to generate a sol solution; after complete reaction, polyvinyl alcohol is added to make the mass fraction of the polyvinyl alcohol be 0.5wt%, and the mixture is stirred and uniformly mixed in a water bath at the temperature of 40 ℃ to obtain the treatment solution. And cooling to room temperature after the completion to obtain an adhesive solution for later use.
3) Mixing the solid mixed raw material powder with a proper amount of the bonding solution, fully stirring and wetting to obtain granulation slurry, and granulating in a disc granulator to obtain spherical particles with the diameter controlled to be about 3 mm. And (3) carrying out heat treatment on the obtained spherical particle muffle furnace, heating to 600 ℃ at the speed of 3 ℃/min, calcining for 2h at the temperature, cooling to about 100 ℃ at the cooling speed of 5 ℃/min, and discharging to obtain a catalyst preform.
4) The obtained catalyst preform was immersed in 0.6M FeCl3In the solution, the ultrasonic dispersion is uniform; under the water bath heating condition of 60 ℃, dropwise adding an ammonia water solution (20 wt%) while stirring until iron ions are fully precipitated, and then filtering and separating solid particles; putting into a drying oven with the temperature of 60 ℃ for drying for 10 h; placing the dried particles in a tubular furnace, introducing nitrogen to replace the atmosphere, heating to 680 ℃ at the heating rate of 5 ℃/min, and calcining for 1 h; and cooling to room temperature after calcination, washing with deionized water, fully drying and drying to obtain heterogeneous Fenton catalyst particles D2.
Effect example 1
Treatment of dye wastewater
The rhodamine is used as a model wastewater organic matter, and the operation is as follows: to 500 mL of 2mM (about 1g/L) rhodamine B solution (model wastewater), 1g of the corresponding Fenton catalyst (addition ratio: 0.2 wt%) was added, the pH of the solution was adjusted to 3, and the solution was shaken for 1 hour in the dark to reach adsorption equilibrium. Then placing the sample in a flask with a stirring device, adding hydrogen peroxide under the conditions of room temperature and visible light to enable the final concentration of the sample in the model wastewater solution to be about 50mM, reacting for 1h under the condition of magnetic stirring, adding a sample after the reaction is finished to detect the residual concentration of rhodamine B (measuring an absorbance value at 552 nm by adopting a spectrophotometry method), and calculating the decolorization rate of the rhodamine B.
Wherein the corresponding fenton catalysts are respectively selected from the catalyst particles prepared in the above examples, namely: catalyst 1, 2, D1, D2, 3 replicates per set of experiments, averaged. The corresponding rhodamine B destaining rate results are shown in table 1 below.
TABLE 1 dye decolorization ratio
| Group of | Decolorization ratio |
| Catalyst 1 | 96.3% |
| Catalyst 2 | 91.8% |
| Catalyst D1 | 78.6% |
| Catalyst D1 | 57.4% |
The result shows that the high-porosity catalyst doped with the catalytic component can effectively promote the degradation of organic pollutants in a heterogeneous Fenton system under the condition of lower hydrogen peroxide dosage.
Effect example 2
Treatment of phenol wastewater
The method comprises the following steps: 100mL of phenol pollutant solution with the concentration of 0.5g/L (the pH value is adjusted to be 4) is prepared to be used as high-concentration simulation wastewater, 1g (the dosage is 1 wt%) of heterogeneous Fenton material catalyst particles prepared in the examples 3-4 and the comparative examples 1-2 is respectively added, meanwhile, 1mL of hydrogen peroxide with the mass concentration of 30% is added, and after the reaction is carried out for 1 hour under the conditions of no illumination and oscillation at room temperature, the removal efficiency of the phenol pollutants is calculated. In the experiment, 3 replicates of each group of experiments corresponding to fenton catalysts 1, 2, D1, and D2 were averaged. The results showed that the removal rates of phenol degradation were 86.7%, 82.3%, 67.6%, and 33.7%, respectively.
Effect example 3
Stability in recycling
The heterogeneous Fenton catalyst particles 1, 2, D1 and D2 prepared in the embodiment are placed in a reaction tube with openings at two ends and connected with a circulating water pump, a hydrochloric acid water solution with the pH value of 4 is used as a simulated acid wastewater system, the catalyst is immersed and circulated at a low speed to flow through the catalyst, the operation is continued for 100 hours, and the stability of the catalytic performance of the heterogeneous Fenton catalyst particles in the long-term acid solution immersion and scouring environments is simulated and calculated.
After soaking for 100 hours according to the above conditions, taking out the catalyst particles, observing and recording appearance fragmentation conditions, screening the whole product, washing with water, drying, and testing the removal rate of the catalyst particles on phenol pollutants according to the method of the effect example 2. The catalytic performance results show that the degradation removal rates of the corresponding phenol are 78.9%, 75.1%, 43.6% and 20.3% respectively. The catalyst of the invention is proved to have higher curing effect on the catalytic component, the loss rate of the catalytic component is low, and the reduction of the catalytic effect is slowed down to a certain extent due to the slow pore-forming effect of the calcium sulfate. The undoped comparative catalyst, which mainly relies on the surface-supported catalytic component, produces a greater degree of loss of the catalytic component due to the lower mechanical strength.
The appearance results showed that the catalyst particles D1, D2 retained intact particles at a proportion of less than 30% (demonstrating insufficient mechanical strength of the combined, non-high temperature calcined catalyst after carrier pulverization), while the catalyst particles D1, D2 had intact rates of about 78%, 69%, respectively. The low-melting-point glass powder is proved to have a remarkable improvement effect on maintaining the strength of catalyst particles, and meanwhile, the higher porosity (a large number of through holes are generated by an artificial pore-forming treatment process) is more beneficial to fluid passing, the fluid water pressure is effectively slowed down, and the catalyst is also beneficial to keeping the integrity to a certain degree.
It should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; those of ordinary skill in the art will understand that: modifications and substitutions may be made to the embodiments described in the foregoing without departing from the scope of the embodiments of the present invention.
Claims (9)
1. A porous heterogeneous Fenton catalyst is characterized in that cerium oxide modified mesoporous iron oxide particles, a porous carrier, hercynite, activated alumina, barium azodicarboxylate particles, slow-release pore-forming agent particles and a high-temperature binder are used as basic raw materials, and the porous heterogeneous Fenton catalyst is prepared by bonding and granulating through a bonding solution, and then carrying out thermoforming and loading steps; wherein the basic raw materials comprise the following components in parts by weight: 3-5 parts of cerium oxide modified mesoporous iron oxide particles, 100 parts of porous carrier, 5-10 parts of hercynite, 10-20 parts of activated alumina, 1-3 parts of barium azodicarboxylate particles, 5-15 parts of slow-release pore-forming agent particles and 2-5 parts of high-temperature binder;
wherein the hercynite is selected from magnetic hercynite or hercynite;
wherein the high-temperature binder is selected from low-melting-point glass powder or polyamide wax micropowder;
wherein the slow-release pore-forming agent particles are selected from calcium sulfate particles;
wherein the ceria-modified mesoporous iron oxide particles consist of mesoporous iron oxide supported ceria; the iron oxide is selected from ferric oxide or ferroferric oxide;
wherein the porous carrier is at least one selected from zeolite powder, kaolin and montmorillonite powder;
wherein the binding solution is prepared by reacting an iron salt solution with ammonia water to generate a sol solution and adding a thermal decomposition pore-forming adhesive, and the thermal decomposition pore-forming adhesive is selected from polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone;
wherein the cerium oxide modified mesoporous iron oxide particles are prepared by the following steps: adding mesoporous iron oxide nanoparticles with the particle size of 50-100nm into a composite organic solvent containing n-butyl alcohol, and simultaneously dropwise adding Ce (NO) under the conditions of room temperature and stirring3)3Adding ammonia water and the solution into the composite organic solvent, and adding Ce (NO)3)3Continuously dripping ammonia water after the solution is dripped until the pH value is stabilized at 9-10, and then reacting for 2-3h under the condition of stirring or oscillation; standing and aging at room temperature for 10-12h after the reaction is finished, performing solid-liquid separation, then fully washing with deionized water and absolute ethyl alcohol, performing vacuum drying, and calcining at 660-680 ℃ for 2-3h in a muffle furnace in a nitrogen atmosphere to obtain the cerium oxide doped modified mesoporous iron oxide nanoparticles.
2. The porous heterogeneous Fenton's catalyst according to claim 1 where the porous support is composed of natural zeolite powder, kaolin, montmorillonite powder, where the natural zeolite powder is not less than 50% by weight.
3. A method for preparing the porous heterogeneous fenton catalyst according to claim 1, comprising the steps of:
s1) selecting the following raw materials in parts by weight: 100 parts of porous carrier, 5-10 parts of hercynite, 3-5 parts of cerium oxide modified mesoporous iron oxide particles, 10-20 parts of activated alumina, 1-3 parts of barium azodicarboxylate particles, 5-15 parts of calcium sulfate particles and 2-5 parts of high-temperature binder; uniformly mixing the porous carrier, the hercynite and the activated alumina in the proportion, grinding and sieving the mixture, and mixing the mixture with the cerium oxide modified mesoporous iron oxide particles, the barium azodicarboxylate particles, the calcium sulfate particles and the high-temperature binder to obtain a solid mixed raw material;
s2), under the stirring condition, ammonia water is dripped into 10-20wt% ferric nitrate aqueous solution for reaction to generate sol; after the precipitation is completed, adding a proper amount of thermal decomposition pore-forming adhesive, uniformly mixing to obtain a treatment solution, and cooling to room temperature to obtain an adhesive solution for later use;
mixing the solid mixed raw materials with the adhesive solution, fully wetting and uniformly stirring, and then granulating in a granulator to obtain spherical granules with the diameter of 1-5 mm;
s3) heat-treating the resultant granules in a muffle furnace, the steps being as follows:
firstly, raising the temperature from room temperature to 150 ℃ at the speed of 2-3 ℃/min, preheating for 10-15min, then raising the temperature to 250-280 ℃ at the speed of 1-1.5 ℃/min, and preserving the heat for 30-60 min;
then, heating to 550-600 ℃ at the speed of 3-5 ℃/min, calcining for 1-3h at the temperature, and then cooling at the speed of 5-6 ℃/min and discharging to obtain a catalyst preform;
s4) immersing the obtained catalyst preform in 0.5-1M FeCl3In the solution, ultrasonic dispersion is uniform; water at 60-70 deg.CUnder the heating condition of bath or oil bath, dropwise adding an ammonia water solution while stirring until iron ions are fully precipitated, then filtering and separating solid particles, and drying;
s5) placing the dried particles in a tube furnace, introducing nitrogen, heating to 660-; and cooling to room temperature after calcination, washing with deionized water, fully drying and drying to obtain the heterogeneous Fenton catalyst particles.
4. The method according to claim 3, wherein in step S1, the grinding and sieving operation controls the particle size to be less than 0.2 mm; the particle size of the barium azodicarboxylate particles is 1-10 mu m; the particle size of the calcium sulfate particles is 0.1-0.3 mm.
5. The method according to claim 3, wherein the ammonia aqueous solution concentration in step S2 is 15-25 wt%.
6. The method as claimed in claim 3, wherein the high temperature binder is selected from low melting point glass frits, and the melting onset temperature is 450-550 ℃.
7. Heterogeneous Fenton's catalyst obtainable by the process according to any one of claims 3 to 6.
8. Use of a heterogeneous Fenton's catalyst according to any of claims 1-2 in water treatment for oxidation treatment of waste water in combination with hydrogen peroxide.
9. Use according to claim 8, wherein the waste water is organic-containing waste water.
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