CN113976140A - Heterogeneous Fenton-like catalyst and preparation method thereof - Google Patents
Heterogeneous Fenton-like catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000011812 mixed powder Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 239000011280 coal tar Substances 0.000 claims abstract description 12
- 239000002734 clay mineral Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- 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 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 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 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of water treatment, in particular to a heterogeneous Fenton-like catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) uniformly mixing a clay mineral material and a pore-forming agent to obtain mixed powder; (2) dissolving a metal salt in water to form a metal salt solution, the metal salt comprising Fe (NO)3)3·9H2O and Mn (NO)3)2(ii) a (3) Uniformly mixing the mixed powder with a metal salt solution to obtain a solid; (4) uniformly mixing the obtained solid with a proper amount of coal tar to prepare particles; (5) drying the obtained granules, and roasting to obtain the final productA heterogeneous fenton-like catalyst. The heterogeneous Fenton-like catalyst is synthesized by calcining the cheap and easily-obtained iron and manganese metal salts serving as active components, the clay mineral material serving as a carrier and the coal tar serving as an adhesive, and has excellent and stable catalytic performance.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a heterogeneous Fenton-like catalyst and a preparation method thereof.
Background
Refractory wastewater generally refers to organic wastewater with poor biodegradability, such as: textile/printing and dyeing wastewater, landfill leachate, coking wastewater, pharmaceutical wastewater, chemical wastewater and the like. The organic pollutants in the wastewater have high concentration, high toxicity and high salt content. If not properly treated, the water body environment is seriously damaged, the human health is influenced, and the ecological system is damaged. The Fenton oxidation technology, which is the most common advanced oxidation technology, has very strong oxidizability, high oxidation efficiency and simple process, can obviously reduce the toxicity of wastewater and improve the biodegradability, and has obvious advantages in the aspect of treating refractory organic pollutants. But the excessive Fe in the conventional Fenton reaction process2+Iron-containing sludge which is difficult to treat can be generated, the utilization rate of hydrogen peroxide is low, the requirement on the pH value of the wastewater is strict, and the development of the technology in the field of treatment of the organic wastewater which is difficult to degrade is limited.
Scientists at home and abroad improve the Fenton technology by carrying out deep research on the technology and provide a heterogeneous Fenton method, namely, iron mineral is adopted to replace Fe2+As catalysts with H2O2Reaction to produce OH. The Huqin is prepared into magnetic nano Fe by adopting an oxidation precipitation method3O4Treating rhodamine B (RhB). Obtaining the nano Fe with different shapes and particle diameters by optimizing the test conditions3O4Particles of nano Fe with spherical and small particle size3O4Has better catalytic activity, and the decolorization rate of RhB within 3h reaches more than 80 percent. The natural hematite is adopted to degrade Methylene Blue (MB) dye wastewater, hematite and H in Zhangxiaxue2O2The constructed heterogeneous Fenton-like system has wide applicable pH range, and the MB degradation rate almost reaches 100 percent; hematite can be reused, and the removal rate of MB can still reach more than 80% after 5 times of use. Cao prepared a Fe pillared bentonite (Fe)Bent) catalyst, and degrading organic pollutants in the oil refining wastewater by adopting a heterogeneous Fenton method. After the catalyst is used for degrading the petroleum refinery wastewater for five times of cyclic utilization, the COD removal rate can still reach 76%, and good stability is shown. It can be seen that the heterogeneous fenton-like process not only can overcome the limited pH conditions of the conventional fenton-like process, but also can improve the recycling performance of the catalyst, so that the research on the heterogeneous fenton-like process has made great progress in recent years.
However, the heterogeneous fenton-like catalyst still has the problems of low loading capacity, uneven distribution of active components, easy dissolution in the reaction process and the like, and the practical application of the heterogeneous fenton-like catalyst is severely limited by the series of problems. Therefore, the research and development of the catalyst which is efficient, stable and beneficial to recycling has important significance for treating the organic wastewater difficult to degrade.
Disclosure of Invention
Aiming at the technical problems of low load capacity and easy dissolution in the reaction process of the existing heterogeneous Fenton-like catalyst, the invention provides the heterogeneous Fenton-like catalyst and a preparation method thereof.
In a first aspect, the present invention provides a method for preparing a heterogeneous fenton-like catalyst, comprising the following steps:
(1) uniformly mixing a clay mineral material and a pore-forming agent to obtain mixed powder;
(2) dissolving a metal salt in water to form a metal salt solution, the metal salt comprising Fe (NO)3)3·9H2O and Mn (NO)3)2；
(3) Uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with a proper amount of coal tar to prepare particles;
(5) and drying the obtained particles, and roasting to obtain the heterogeneous Fenton-like catalyst.
Further, the clay mineral material in the step (1) is at least one of montmorillonite, diatomite and bentonite, and is preferably montmorillonite.
Further, the pore-forming agent in the step (1) is sodium carboxymethyl cellulose.
Further, in the step (1), the mass ratio of the clay mineral material to the pore-forming agent is 70-90: 1 to 5.
Further, in the step (2), Fe (NO)3)3·9H2O、Mn(NO3)2The mass ratio of (A) to (B) is 9: 1-7: 3, preferably 4: 1.
further, in the step (3), the mass ratio of the metal salt to the mixed powder is 10: 90-25: 75.
further, in the step (4), the mass ratio of the coal tar to the mixed powder in the solid is 5-10: 75-80 parts.
Further, in the step (4), the particle size of the particles is 6-10 mm.
Further, in the step (5), the drying method comprises the steps of drying the particles at 50-60 ℃ for 30-50 min to remove most of water, and then heating to 100-120 ℃ for drying for 60-80 min to prevent the particles from drying and cracking; the roasting temperature is 600-650 ℃, and the roasting time is 60-80 min.
In a second aspect, the present invention provides a heterogeneous fenton-like catalyst prepared by the above preparation method.
The invention has the beneficial effects that the invention provides the clay mineral material, the pore-forming agent and Fe (NO)3)3·9H2O、Mn(NO3)2The heterogeneous Fenton-like catalyst is prepared by taking a clay mineral material as a carrier, wherein the clay mineral material has a large specific surface area, can provide attachment sites for metal ions, improves the electron transfer capacity in the catalysis process, and is not easy to lose active components; coal tar is used as a bonding agent, has better bonding effect, can effectively enhance the hardness of the catalyst, greatly prolongs the service life of the catalyst, increases the specific surface area after being carbonized by high-temperature calcination, and increases the reaction activityA sexual site; the iron and manganese metal salts which are cheap and easy to obtain are used as active components, so that the preparation cost is low; the heterogeneous Fenton-like catalyst is synthesized by calcination, the catalytic performance is excellent and stable, the preparation method is simple and easy to control, the threshold of industrial production is low, and the industrial popularization is easy.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, 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.
Example 1
A heterogeneous Fenton-like catalyst is prepared by the following preparation method:
(1) uniformly doping 77.0g of montmorillonite and 3g of sodium carboxymethylcellulose to obtain mixed powder;
(2) the total mass of Fe (NO) was 20.0g3)3·9H2O：Mn(NO3)2According to the following steps of 4: 1 proportion is dissolved in 50ml of water to form a metal salt solution;
(3) uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with 10g of coal tar to prepare particles with the particle size of 6 mm;
(5) and putting the obtained particles into an oven, heating to 60 ℃, drying for 30min to remove a large amount of water, then heating to 120 ℃, continuously drying for 60min to prevent the particles from being dried and cracked, and then roasting in a muffle furnace at 650 ℃ for 60min to obtain the heterogeneous Fenton-like catalyst.
Example 2
A heterogeneous Fenton-like catalyst is prepared by the following preparation method:
(1) uniformly doping 87.0g of bentonite and 3g of sodium carboxymethylcellulose to obtain mixed powder;
(2) will alwaysFe (NO) with a mass of 10.0g3)3·9H2O：Mn(NO3)2According to the following steps of 9: 1 proportion is dissolved in 50ml of water to form a metal salt solution;
(3) uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with 8g of coal tar to prepare particles with the particle size of 8 mm;
(5) and putting the obtained particles into an oven, heating to 50 ℃, drying for 50min to remove a large amount of water, then heating to 100 ℃, continuously drying for 80min to prevent the particles from being dried and cracked, and then roasting in a muffle furnace at 600 ℃ for 80min to obtain the heterogeneous Fenton-like catalyst.
Example 3
A heterogeneous Fenton-like catalyst is prepared by the following preparation method:
(1) uniformly doping 77.0g of diatomite and 3g of sodium carboxymethylcellulose to obtain mixed powder;
(2) the total mass of Fe (NO) was 20.0g3)3·9H2O：Mn(NO3)2According to the following steps: 3 proportion is dissolved in 50ml of water to form a metal salt solution;
(3) uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with 5g of coal tar to prepare particles with the particle size of 10 mm;
(5) and putting the obtained particles into an oven, heating to 60 ℃, drying for 30min to remove a large amount of water, then heating to 120 ℃, continuously drying for 60min to prevent the particles from being dried and cracked, and then roasting in a muffle furnace at 650 ℃ for 60min to obtain the heterogeneous Fenton-like catalyst.
Example 4
A heterogeneous Fenton-like catalyst is prepared by the following preparation method:
(1) uniformly doping 77.0g of montmorillonite and 3g of sodium carboxymethylcellulose to obtain mixed powder;
(2) the total mass of Fe (NO) was 20.0g3)3·9H2O：Mn(NO3)2According to the following steps of 4: 1 ratio dissolutionIn 50ml of water, a metal salt solution is formed;
(3) uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with 10g of coal tar to prepare particles with the particle size of 8 mm;
(5) and putting the obtained particles into an oven, heating to 60 ℃, drying for 30min to remove a large amount of water, then heating to 120 ℃, continuously drying for 60min to prevent the particles from being dried and cracked, and then roasting in a muffle furnace at 600 ℃ for 60min to obtain the heterogeneous Fenton-like catalyst.
Example 5
A heterogeneous Fenton-like catalyst is prepared by the following preparation method:
(1) uniformly doping 72.0g of montmorillonite and 3g of sodium carboxymethylcellulose to obtain mixed powder;
(2) the total mass of 25.0g of Fe (NO)3)3·9H2O：Mn(NO3)2According to the following steps of 4: 1 proportion is dissolved in 50ml of water to form a metal salt solution;
(3) uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with 10g of coal tar to prepare particles with the particle size of 8 mm;
(5) and putting the obtained particles into an oven, heating to 60 ℃, drying for 30min to remove a large amount of water, then heating to 120 ℃, continuously drying for 60min to prevent the particles from being dried and cracked, and then roasting in a muffle furnace at 650 ℃ for 60min to obtain the heterogeneous Fenton-like catalyst.
Test example 1
The heterogeneous Fenton-like catalyst prepared in the embodiment 1-5 is used for treating methyl orange wastewater, and the specific test method comprises the following steps:
the heterogeneous fenton-like catalyst prepared in examples 1 to 5 and 2.5ml of hydrogen peroxide with a concentration of 30% were added to 5 parts of 500ml methyl orange wastewater (COD: 132mg/L), respectively, the wastewater system was placed in a shaking stirrer, and the reaction was carried out for 180min at a water temperature of 25 ℃ and a pH of 5.5, and then the COD value of the supernatant of each wastewater system was measured.
Meanwhile, a blank control group without any catalyst is arranged, the reaction conditions are ensured to be the same as those of the 5 groups, and after the reaction, supernatant is taken to determine the COD value.
The test results are shown in table 1 below, and it can be seen that, compared to the blank control group, the heterogeneous fenton-like catalysts prepared in examples 1 to 5 have a significant effect on removing COD from the methyl orange solution, and the performance of the heterogeneous fenton-like catalysts is affected by Fe (NO)3)3·9H2O、Mn(NO3)2The mass ratio of (a) and the mass ratio of the metal salt to the mixed powder are changed, and the heterogeneous fenton-like catalyst prepared in example 1 is most superior in catalytic performance.
TABLE 1 evaluation results of heterogeneous Fenton-like catalysts
Comparative example 1
A heterogeneous Fenton-like catalyst is prepared by the following preparation method:
(1) uniformly doping 77.0g of montmorillonite and 3g of sodium carboxymethylcellulose to obtain mixed powder;
(2) the total mass of Fe (NO) was 20.0g3)3·9H2O：Mn(NO3)2According to the following steps of 4: 1 proportion is dissolved in 200ml of water to form a metal salt solution;
(3) uniformly mixing the powder with a metal salt solution to obtain a suspension, and continuously stirring for 24 hours;
(4) centrifugally separating the suspension to obtain a solid, and preparing the solid into particles with the particle size of 8 mm;
(5) and putting the obtained particles into an oven, heating to 60 ℃, drying for 30min to remove a large amount of water, then heating to 120 ℃, continuously drying for 60min to prevent the particles from being dried and cracked, and then roasting in a muffle furnace at 600 ℃ for 60min to obtain the heterogeneous Fenton-like catalyst.
Test example 2
The heterogeneous fenton-like catalysts prepared in example 4 and comparative example 1 were analyzed for their iron and manganese contents using an X-ray spectrometer, and the catalysts were characterized mainly for the following four cases: heterogeneous fenton-like catalyst prepared in example 4; ② the heterogeneous Fenton-like catalyst prepared in the example 4 is used for 50 times; ③ the heterogeneous fenton-like catalyst prepared in comparative example 1; (iv) the heterogeneous fenton-like catalyst prepared in comparative example 1 was used 50 times. The results of the main metal components after characterization are shown in the following table 2:
TABLE 2 comparison of metal components before and after use of heterogeneous Fenton-like catalysts
The test results are shown in table 2, and for the iron element, the loss rate before and after the use of the catalyst of example 4 is 1.44%, and the loss rate before and after the use of the catalyst of comparative example 1 is 13.06%; for manganese, the loss rate before and after use of the catalyst of example 4 was 6.74%, and the loss rate before and after use of the catalyst of comparative example 1 was 43.77%. The loss rate of the characteristic metal elements before and after the catalyst is used can be obviously seen, after the catalyst prepared by the method disclosed by the patent is used for multiple times, the loss rate of the iron and manganese elements is smaller compared with that of the catalyst prepared by the traditional impregnation method in the comparative example 1, and the characteristic metal element load of the catalyst is firmer.
Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.
Claims (10)
1. A preparation method of a heterogeneous Fenton-like catalyst is characterized by comprising the following steps of:
(1) uniformly mixing a clay mineral material and a pore-forming agent to obtain mixed powder;
(2) adding a metal saltDissolving in water to form a metal salt solution, the metal salt comprising Fe (NO)3)3·9H2O and Mn (NO)3)2；
(3) Uniformly mixing the mixed powder with a metal salt solution to obtain a solid;
(4) uniformly mixing the obtained solid with coal tar to prepare particles;
(5) and drying the obtained particles, and roasting to obtain the heterogeneous Fenton-like catalyst.
2. The method according to claim 1, wherein the clay mineral material of the step (1) is at least one of montmorillonite, diatomaceous earth, and bentonite.
3. The method of claim 1, wherein the pore-forming agent of step (1) is sodium carboxymethyl cellulose.
4. The preparation method of claim 1, wherein in the step (1), the mass ratio of the clay mineral material to the pore-forming agent is 70-90: 1 to 5.
5. The method according to claim 1, wherein in the step (2), Fe (NO)3)3·9H2O、Mn(NO3)2The mass ratio of (A) to (B) is 9: 1-7: 3.
6. the method according to claim 1, wherein in the step (3), the ratio of the metal salt to the mixed powder is 10: 90-25: 75.
7. the preparation method according to claim 1, wherein in the step (4), the mass ratio of the coal tar to the mixed powder in the solid is 5-10: 75-80 parts.
8. The method according to claim 1, wherein in the step (4), the particle size of the particles is 6 to 10 mm.
9. The preparation method according to claim 1, wherein in the step (5), the drying method comprises drying the particles at 50-60 ℃ for 30-50 min, and then heating to 100-120 ℃ for 60-80 min; the roasting temperature is 600-650 ℃, and the roasting time is 60-80 min.
10. A heterogeneous fenton-like catalyst prepared by the method of claim 1.
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