CN113856683B - Fenton-like catalyst of carbon-supported iron ions and preparation method and application thereof - Google Patents
Fenton-like catalyst of carbon-supported iron ions and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 42
- -1 iron ions Chemical class 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 37
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 29
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 16
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 46
- 239000002351 wastewater Substances 0.000 claims description 38
- 229920000858 Cyclodextrin Polymers 0.000 claims description 26
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical group O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 12
- 235000014633 carbohydrates Nutrition 0.000 claims description 6
- 229920002101 Chitin Polymers 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
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- 238000000926 separation method Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 239000012028 Fenton's reagent Substances 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 238000004925 denaturation Methods 0.000 description 1
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- 230000037406 food intake Effects 0.000 description 1
- 231100000753 hepatic injury Toxicity 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 208000037806 kidney injury Diseases 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
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Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- C02F2101/34—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- 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)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the technical field of advanced oxidation heterogeneous catalysts, and discloses a preparation method of a carbon-supported iron ion Fenton-like catalyst, which comprises the following steps: the mass ratio is 1:0.2 to 1 of carbohydrate and ferric chloride, grinding and uniformly mixing the carbohydrate and the ferric chloride to obtain a mixture; heating the mixture, heating to 150-350 ℃, calcining for 1-4h, and naturally cooling to obtain a solid A; and washing the solid A for multiple times, and drying to obtain the carbon-supported iron ion Fenton-like catalyst. The iron nano particles are wrapped in an amorphous carbon layer, and the separation of the iron ions can be effectively avoided under the action of the carbon layer; meanwhile, under the action of xenon lamp illumination, electron transfer occurs on the surface of the catalyst to promote Fe 3+ /Fe 2+ The mutual conversion of the catalyst is not caused by the loss of iron ions, so that the recycling efficiency is high, and the catalyst can be reused for a plurality of times.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation heterogeneous catalysts, and relates to a Fenton-like catalyst of carbon-supported iron ions, a preparation method and application thereof.
Background
In the 21 st century, along with the continuous development of industries such as chemical industry, papermaking, printing, textile, biological medicine and the like, a large amount of waste water in the production process is unreasonableEmission and water environment pollution have become one of the most important environmental problems in the current society, and effective methods for solving the problem of organic pollutants in water environment are important. Phenol is among the most toxic compounds and may be present in relatively high concentrations in some industrial waste waters. In the case of contaminated water, the phenol concentration may vary from 3ppm to 4g/L, and the maximum allowable phenol concentration is 5ppm (19 mg/m, according to the Environmental Protection Agency (EPA) regulations 3 ). Phenol is very harmful to organisms even at very low concentrations. For example, ingestion of phenol contaminated water by humans can cause damage to protein denaturation, tissue erosion, kidney and liver injury, and the like.
The advanced oxidation technology is widely applied to the treatment of organic wastewater in the production process of the industries such as chemical industry, medicine and the like due to high oxidation rate and simple operation. Fenton technology is a typical representative of advanced oxidation technology and has strong capability of oxidizing organic matters in wastewater, but the technology needs to be implemented under an acidic condition (the pH of the wastewater needs to be controlled to be 2-4), and when the pH of the wastewater is not in the range, an acidic reagent needs to be additionally added, so that certain corrosion is caused to equipment, and the treatment cost is increased. And a large amount of iron mud is generated by continuously dissolving iron ions in the reaction process, so that the pipeline is easy to be blocked, and the discharge is influenced. In addition, the traditional Fenton reagent is difficult to recover, the recycling rate is low, and the practical application of the Fenton technology in water treatment is greatly hindered.
Therefore, research on a Fenton-like catalyst with low cost, wide application range, fast reaction rate and good treatment effect is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to provide a Fenton-like catalyst of carbon-supported iron ions, and a preparation method and application thereof, and solves the problems of low reuse rate, difficult recovery, high ion dissolution rate and high treatment cost caused by the need of carrying out reaction under an acidic condition of the existing Fenton-like catalyst.
The invention is realized by the following technical scheme:
a preparation method of a carbon-supported iron ion Fenton-like catalyst comprises the following steps:
(1) The mass ratio is 1:0.2 to 1 of carbohydrate and ferric chloride, grinding and uniformly mixing the carbohydrate and the ferric chloride to obtain a mixture;
(2) Heating the mixture, heating to 150-350 ℃, calcining for 1-4h, and naturally cooling to obtain a solid A;
(3) And washing the solid A for multiple times, and drying to obtain the carbon-supported iron ion Fenton-like catalyst.
Further, the carbohydrate is cyclodextrin, starch or chitin.
Further, in the step (2), heating is performed in a muffle furnace, and the temperature is raised at a temperature raising rate of 3 ℃/min.
Further, in the step (3), washing with absolute ethanol is performed a plurality of times.
Further, in the step (3), the mixture is dried at 35 to 80 ℃ for 12 hours.
The invention also discloses the Fenton-like catalyst of the carbon-supported iron ions prepared by the preparation method.
The invention also discloses an application of the carbon-supported iron ion Fenton-like catalyst in wastewater treatment, which comprises the following steps:
adding Fenton-like catalyst and 30wt% hydrogen peroxide into phenolic wastewater with pH of 3-10, irradiating with a xenon lamp light source after reaction, and taking supernatant to measure the phenol content;
wherein, the feed liquid ratio of Fenton-like catalyst, hydrogen peroxide and phenolic wastewater is 0.2g: (0.2-0.5) mL:1L.
Further, the reaction conditions are: the reaction was carried out at 25℃for 20min.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a Fenton-like catalyst for carbon-carried iron ions, which comprises the steps of mixing carbohydrate and ferric chloride, heating to obtain a solid, washing and drying the solid to obtain the Fenton-like catalyst for carbon-carried iron ions, wherein the outer layer of the material is a carbon layer, black granular substances in the material are iron nano particles, the iron nano particles are coated in an amorphous carbon layer, and the precipitation of the iron ions can be effectively avoided under the action of the carbon layer. The system has no iron ion loss, so the recycling efficiency is high. The preparation method of the invention has the advantages of simplicity, lower cost, simple and convenient operation, easy acquisition and control of preparation conditions, solid powder form and easy preservation and transportation. The preparation method provided by the invention is simple, low in cost, simple and convenient to operate, and easy to obtain the preparation conditions, and has potential application prospects in the aspect of advanced oxidation treatment of phenolic wastewater.
The invention also discloses application of the carbon-supported iron ion Fenton-like catalyst, and when the catalyst is used for treating wastewater, a heterogeneous Fenton-like catalytic system consisting of the catalyst and hydrogen peroxide can continuously provide hydroxyl free radicals (OH) with strong oxidability for a reaction system; meanwhile, the catalyst has higher reactivity in a wider pH range (pH 3-10), the pH value of raw water is not required to be regulated, the cost is reduced, and the service life of equipment is prolonged. Under neutral pH, the degradation rate of the phenol solution with the concentration of 20mg/L can reach 98% after the reaction is carried out for 20min, and the catalytic efficiency can still reach more than 97% after the reaction is repeatedly used for five times. Meanwhile, the addition amount of hydrogen peroxide is greatly reduced, and the corrosion of the strong oxidizing property of the hydrogen peroxide to the treatment equipment is reduced to a certain extent. The iron ions in the traditional material are continuously separated out in the reaction process, and Fe is continuously separated out in the reaction process 2+ Oxidized by hydrogen peroxide to Fe 3+ ，Fe 3+ Cannot react with hydrogen peroxide to generate hydroxyl free radicals, so that no free radicals capable of degrading pollutants exist in the system, and therefore, the system cannot be reused. The catalyst prepared by the invention wraps the iron nano particles in the amorphous carbon layer, and can effectively avoid the precipitation of iron ions under the action of the carbon layer. Meanwhile, under the action of xenon lamp illumination, electron transfer occurs on the surface of the catalyst to promote Fe 3+ /Fe 2+ The interconversion of the catalyst is realized, no iron ion loss exists, so the recycling efficiency is high, the repeated utilization of the catalyst is realized, the application range of pH is widened, no special requirement is provided for the pH of raw water, and the acid adjustment is simplifiedThe steps are saved, the cost is saved, the equipment corrosion is further reduced, and the social and economic effects are obvious; in the reaction process, no iron ions are separated out, and no secondary pollution is caused by iron mud.
Drawings
FIG. 1 is a transmission electron microscope image of a carbon-supported Fe ion Fenton-like catalyst of the present invention;
fig. 2 is a graph showing the effect of the carbon-supported Fe ion Fenton-like catalyst on the degradation of phenol for 5 times.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
Example 1
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 150 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 35℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating the phenol simulated organic wastewater containing 20 mg/L.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 74%, as shown in Table 1.
Example 2
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 250 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating the phenol simulated organic wastewater containing 20 mg/L.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 98%, as shown in Table 1.
Example 3
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 250 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 60℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating the phenol simulated organic wastewater containing 20 mg/L.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 82%, as shown in Table 1.
Table 1 shows the phenol removal rates in examples 1 to 3
| Examples | Preparation temperature | Phenol removal rate |
| Example 1 | 150℃ | 74％ |
| Example 2 | 250℃ | 98 |
| Example 3 | 350℃ | 82％ |
Example 4
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0.5, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 250 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 80℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating 20mg/L of phenol simulated organic wastewater.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 100%, as shown in Table 1.
Example 5
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:1, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, heating the mixture to 250 ℃ in an air atmosphere at a heating rate of 3 ℃/min, and naturally cooling the mixture after keeping the mixture for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating 20mg/L of phenol simulated organic wastewater.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 100%, as shown in Table 1.
Example 6
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking starch and ferric chloride with the mass ratio of 1:0.2, fully grinding the starch and the ferric chloride in a mortar for 20min to uniformly mix the starch and the ferric chloride, placing the mixture in a muffle furnace, heating the mixture to 250 ℃ in an air atmosphere at a heating rate of 3 ℃/min, and naturally cooling the mixture after keeping the mixture for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating 20mg/L of phenol simulated organic wastewater.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 100%, as shown in Table 1.
Example 7
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking chitin and ferric chloride with the mass ratio of 1:0.2, fully grinding the chitin and the ferric chloride in a mortar for 20min to uniformly mix the chitin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 250 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating 20mg/L of phenol simulated organic wastewater.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 100%, as shown in Table 1.
Example 8
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 250 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating 20mg/L of phenol simulated organic wastewater.
To 50mL of phenol wastewater having pH of 3, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and as shown in Table 1, the phenol removal rate was 100%.
Example 9
The invention discloses a preparation method of a carbon-supported Fe ion Fenton-like catalyst, which specifically comprises the following steps:
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding the cyclodextrin and the ferric chloride in a mortar for 20min to uniformly mix the cyclodextrin and the ferric chloride, placing the mixture in a muffle furnace, programming the temperature to 250 ℃ at the temperature rising rate of 3 ℃/min in an air atmosphere, and naturally cooling the mixture after keeping the temperature for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating 20mg/L of phenol simulated organic wastewater.
To 50mL of phenol wastewater having a pH of 10, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, as shown in Table 1, with a phenol removal rate of 85%.
As shown in figure 1, the carbon-supported Fe ion Fenton-like catalyst prepared by the invention has a carbon layer on the outer layer and iron nanoparticles on the inner black particulate matter.
The xenon lamp mainly plays a role in separating photo-generated electrons and photo-generated holes in the catalyst, and the separated photo-generated electrons can carry out electron transfer on the surface of the catalyst, so that Fe is promoted 3+ /Fe 2+ Thereby decomposing hydrogen peroxide to generate a large amount of hydroxyl radicals, so that pollutants are degraded; in addition, the photo-generated holes generated by separation also participate in the degradation of pollutants.
Comparative example
(1) Taking cyclodextrin and ferric chloride with the mass ratio of 1:0, fully grinding for 20min in a mortar, uniformly mixing, placing in a muffle furnace, heating to 250 ℃ in an air atmosphere at a heating rate of 3 ℃/min, and naturally cooling after keeping for 2h to obtain a solid A;
(2) The solid A was washed with absolute ethanol several times and dried overnight at 40℃to complete the catalyst preparation.
The product prepared by the preparation method is used for treating the phenol simulated organic wastewater containing 20 mg/L.
To 50mL of phenol wastewater having a pH of 6.8, 0.01g of Fenton-like catalyst and 30wt% hydrogen peroxide were added at a reaction temperature of 25℃for 20 minutes, and after the reaction, the resultant was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was collected for measurement of phenol content, and the phenol removal rate was 5%, as shown in Table 1.
Table 2 shows the phenol removal rates for examples 3 to 9 and comparative example
| Examples | pH value of solution | Phenol removal rate |
| Example 3 | 6.8 | 98％ |
| Example 4 | 6.8 | 100％ |
| Example 5 | 6.8 | 100％ |
| Example 6 | 6.8 | 100％ |
| Example 7 | 6.8 | 100％ |
| Example 8 | 3 | 100％ |
| Example 9 | 10 | 85％ |
| Comparative example | 6.8 | 5％ |
Examples 1-7 illustrate that a heterogeneous Fenton-like catalytic system of the catalyst with hydrogen peroxide can continuously provide a strongly oxidizing hydroxyl radical (. OH) to the reaction system. Meanwhile, the catalyst has higher reactivity in a wider pH range (pH 3-10), the pH value of raw water is not required to be regulated, the cost is reduced, and the service life of equipment is prolonged.
From the comparative example, ferric chloride is an essential raw material. Cyclodextrin is mineralized only in the presence of ferric chloride; upon mineralization of the cyclodextrin, the ferric chloride becomes iron nanoparticles, and a portion of the Fe therein 3+ Will be reduced to Fe 2+ Uniformly wrapped by an amorphous carbon layer, and meanwhile, electron transfer occurs on the surface of the catalyst to promote Fe 3+ /Fe 2+ And Fe 2+ The hydrogen peroxide is continuously decomposed into hydroxyl radicals, so that pollutants are degraded.
The catalyst after the reaction of example 2 was taken for repeated experiments, the catalyst was washed with absolute ethanol, and after the catalyst was dried, 20mg/L of phenol-simulated organic wastewater was treated, and the experiment was repeated 4 more times under the same conditions, with the experimental results shown in FIG. 2.
Treatment conditions: 50mL of simulated wastewater, 0.01g of catalyst, 20 mu L of 30wt% hydrogen peroxide, 6.8 of simulated wastewater pH value, 25 ℃ of reaction temperature, 20min of reaction time and 300W of xenon lamp light source power.
Under neutral pH, the degradation rate of the phenol solution with the concentration of 20mg/L can reach 98% after the reaction is carried out for 20min, and the catalytic efficiency can still reach more than 97% after the reaction is repeatedly used for five times.
The preparation method provided by the invention is simple, low in cost, simple and convenient to operate, and easy to obtain the preparation conditions, and has potential application prospects in the aspect of advanced oxidation treatment of phenolic wastewater.
Description: the above embodiments are only for illustrating the present invention, and are not intended to limit the technical solution described in the present invention. Although the present invention has been described in detail with reference to the above embodiments. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the Fenton-like catalyst of the carbon-supported iron ions is characterized by comprising the following steps of:
(1) The mass ratio is 1:0.2-1 of carbohydrate and ferric chloride, grinding and uniformly mixing to obtain a mixture;
(2) Heating the mixture to 250 ℃ in an air atmosphere, calcining for 1-4h, and naturally cooling to obtain a solid A;
(3) Washing the solid A for a plurality of times, and drying to obtain the carbon-supported iron ion Fenton-like catalyst;
the prepared catalyst wraps the iron nano particles in an amorphous carbon layer, and under the action of the carbon layer, the precipitation of iron ions is avoided;
the carbohydrate is cyclodextrin, starch or chitin.
2. The method for preparing a carbon-supported iron ion Fenton-like catalyst according to claim 1, wherein in the step (2), heating is performed in a muffle furnace, and the temperature is raised at a temperature raising rate of 3 ℃/min.
3. The method for preparing a carbon-supported iron ion Fenton-like catalyst according to claim 1, wherein in the step (3), the carbon-supported iron ion Fenton-like catalyst is washed with absolute ethanol a plurality of times.
4. The method for preparing a carbon-supported iron ion Fenton-like catalyst according to claim 1, wherein in the step (3), the carbon-supported iron ion is dried at 35-80 ℃ for 12 hours.
5. The carbon-supported iron ion Fenton-like catalyst prepared by the preparation method of any one of claims 1 to 4.
6. Use of a carbon-supported iron ion Fenton-like catalyst according to claim 5 for treating wastewater, comprising the steps of:
adding Fenton-like catalyst and 30wt% hydrogen peroxide into phenolic wastewater with pH of 3-10, irradiating with xenon lamp light source after reaction, and taking supernatant to measure phenol content;
wherein, the feed liquid ratio of Fenton-like catalyst, hydrogen peroxide and phenolic wastewater is 0.2g: (0.2-0.5) mL: 1L;
the phenolic wastewater is phenol simulated organic wastewater containing 20 mg/L.
7. The use of a carbon-supported iron ion Fenton-like catalyst according to claim 6, wherein the reaction conditions are: the reaction was carried out at 25℃for 20min.
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