CN113856683A - Fenton-like catalyst with iron ions supported on carbon and preparation method and application thereof - Google Patents
Fenton-like catalyst with iron ions supported on carbon and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 35
- -1 iron ions Chemical class 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 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 15
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- 238000000034 method Methods 0.000 claims description 7
- 235000014633 carbohydrates Nutrition 0.000 claims description 5
- 229920002101 Chitin Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
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- 239000008107 starch Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
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- 230000003647 oxidation Effects 0.000 abstract description 7
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/90—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
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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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention belongs to the technical field of advanced oxidation heterogeneous catalysts, and discloses a preparation method of a Fenton-like catalyst with iron ions carried by carbon, which comprises the following steps: taking the mass ratio of 1: grinding 0.2-1 of carbohydrate and ferric chloride, and uniformly mixing to obtain a mixture; heating the mixture to 150-350 ℃, calcining for 1-4 h, and naturally cooling to obtain a solid A; and washing the solid A for many times, and drying to obtain the Fenton-like catalyst of the carbon-supported iron ions. Also discloses the Fenton-like catalyst of the carbon-supported iron ion and the application thereof, and the iron nano particles are wrapped in the coatingIn the shaped carbon layer, the separation of iron ions can be effectively avoided under the action of the carbon layer; meanwhile, under the action of illumination of a xenon lamp, electron transfer occurs on the surface of the catalyst, and Fe is promoted3+/Fe2+The mutual conversion of (2) does not have the loss of iron ions, so the recycling efficiency is high, and the repeated utilization of the catalyst is realized.
Description
Technical Field
The invention belongs to the technical field of advanced oxidation heterogeneous catalysts, and relates to a Fenton-like catalyst with iron ions supported by carbon, and a preparation method and application thereof.
Background
Since the 21 st century, with the continuous development of chemical, paper, printing, textile, and biomedical industries and the unreasonable discharge of a large amount of wastewater during the production process, water environmental pollution has become one of the most important environmental problems in the present society, and it is important to adopt an effective method to solve the problem of organic pollutants in water environment. Phenol is listed as one of the most toxic compounds and may be present in quite high concentrations in some industrial wastewaters. In the case of contaminated water, the concentration of phenol may vary from 3ppm to 4g/L, with a maximum allowable phenol concentration of 5ppm (19 mg/m) according to the Environmental Protection Agency (EPA) regulations3). Even at very low concentrations, phenol is very harmful to organisms. For example, ingestion of phenol-contaminated water by humans can result in protein denaturation, tissue erosion, kidney and liver damage, and the like.
The advanced oxidation technology is widely applied to the treatment of organic wastewater in the production process of chemical industry, medicine industry and the like due to high oxidation rate and simple operation. The Fenton technology, as a typical representative of advanced oxidation technology, has a 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 within 2-4), and when the pH of the wastewater is not within 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 in the reaction process, iron ions are continuously dissolved out to generate a large amount of iron mud, so that the pipeline is easily blocked, and the discharge is influenced. In addition, because the traditional Fenton reagent is difficult to recover and low in recycling rate, the practical application of the Fenton technology in water treatment is greatly hindered.
Therefore, the 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 by those skilled in the art.
Disclosure of Invention
The invention aims to provide a Fenton-like catalyst of iron ions carried by carbon, a preparation method and application thereof, and solves the problems that the existing Fenton-like catalyst is low in repeated utilization rate, difficult to recover and high in ion dissolution rate, and treatment cost is high due to the fact that reaction is required under an acidic condition.
The invention is realized by the following technical scheme:
a preparation method of a Fenton-like catalyst with iron ions supported on carbon comprises the following steps:
(1) taking the mass ratio of 1: grinding 0.2-1 of carbohydrate and ferric chloride, and uniformly mixing to obtain a mixture;
(2) heating the mixture to 150-350 ℃, calcining for 1-4 h, and naturally cooling to obtain a solid A;
(3) and washing the solid A for many times, and drying to obtain the Fenton-like catalyst of the carbon-supported iron ions.
Further, the carbohydrate is cyclodextrin, starch or chitin.
Further, in the step (2), heating was performed in a muffle furnace, and the temperature was increased at a rate of 3 ℃/min.
Further, in the step (3), washing is performed with absolute ethyl alcohol for a plurality of times.
Further, in the step (3), drying is carried out for 12 hours at the temperature of 35-80 ℃.
The invention also discloses a Fenton-like catalyst of the iron ions carried by the carbon, which is prepared by the preparation method.
The invention also discloses an application of the Fenton-like catalyst of the carbon-supported iron ions in wastewater treatment, which comprises the following steps:
adding a Fenton-like catalyst and 30 wt% of hydrogen peroxide into phenol wastewater with the pH of 3-10, irradiating by using a xenon lamp light source after reaction, and taking supernate to measure the content of phenol;
wherein the feed-liquid ratio of the Fenton-like catalyst, the hydrogen peroxide and the phenol wastewater is 0.2 g: (0.2-0.5) mL: 1L of the compound.
Further, the reaction conditions were: the reaction was carried out at 25 ℃ for 20 min.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a Fenton-like catalyst of iron ions supported by carbon, 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 of iron ions supported by carbon. Since there is no loss of iron ions in the system, the efficiency of reuse is also high. The preparation method is simple, the cost is lower, the operation is simple and convenient, the preparation conditions are easy to obtain and control, and the product is in a solid powder form and is easy to store and transport. The preparation method is simple, low in cost, simple and convenient to operate, easy to obtain preparation conditions, and has potential application prospects in the aspect of advanced oxidation treatment of the phenol wastewater.
The invention also discloses an application of the Fenton-like catalyst of the iron ion supported by carbon, and a heterogeneous Fenton-like catalytic system formed by the catalyst and hydrogen peroxide can continuously provide strongly-oxidized hydroxyl free radicals (. OH) for a reaction system when the catalyst is used for treating wastewater; meanwhile, the catalyst has high reaction activity in a wide pH range (pH 3-10), the pH value of raw water does not need to be adjusted, the cost is reduced, and the service life of equipment is prolonged. Under neutral pH, the degradation rate of 20mg/L phenol solution after 20min of reaction reaches 98%, and the catalytic efficiency can still reach more than 97% after repeated use for five times. Meanwhile, the adding amount of the hydrogen peroxide is greatly reduced, and the corrosion of the strong oxidizing property of the hydrogen peroxide to treatment equipment is reduced to a certain extent. The traditional material is characterized in that iron ions in the material are continuously separated out in the reaction process, and Fe is generated in the reaction process2+Oxidized by hydrogen peroxide to Fe3+，Fe3+Can not react with hydrogen peroxide to generate hydroxyl free radicals, so that the system has no free radicals capable of degrading pollutants, and can not be recycled. The catalyst prepared by the invention wraps iron nano particles in an amorphous carbon layer, and can effectively avoid the precipitation of iron ions under the action of the carbon layer. At the same timeUnder the action of xenon lamp illumination, electron transfer occurs on the surface of the catalyst to promote Fe3+/Fe2+The mutual conversion does not have the loss of iron ions, so the recycling efficiency is high, the catalyst is recycled for multiple times, the application range of pH is widened, no special requirement is made on the pH of raw water, the acid adjusting step is simplified, the cost is saved, the corrosion of equipment is further reduced, and the social and economic effects are obvious; in the reaction process, no iron ions are separated out, and no iron mud is generated to cause secondary pollution.
Drawings
FIG. 1 is a transmission electron micrograph of a carbon-supported Fe ion-like Fenton-like catalyst according to the present invention;
fig. 2 is a graph showing the effect of the carbon supported Fe ion fenton-like catalyst on phenol degradation after 5 times of repeated use.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, carrying out temperature program heating to 150 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 35 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating simulated organic wastewater containing 20mg/L phenol.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 74%.
Example 2
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, carrying out temperature program heating to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating simulated organic wastewater containing 20mg/L phenol.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 98%.
Example 3
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, carrying out temperature program heating to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 60 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating simulated organic wastewater containing 20mg/L phenol.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 82%.
Table 1 shows the removal rate of phenol 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 Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:0.5, fully grinding in a mortar for 20min to uniformly mix, placing in a muffle furnace, carrying out temperature program heating to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 80 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating 20mg/L phenol simulated organic wastewater.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 100%.
Example 5
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:1, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, carrying out temperature programming to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating 20mg/L phenol simulated organic wastewater.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 100%.
Example 6
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking starch and ferric chloride with the mass ratio of 1:0.2, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, raising the temperature to 250 ℃ in an air atmosphere at the temperature raising rate of 3 ℃/min, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating 20mg/L phenol simulated organic wastewater.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 100%.
Example 7
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking chitin and ferric chloride with the mass ratio of 1:0.2, fully grinding in a mortar for 20min to uniformly mix, placing in a muffle furnace, carrying out temperature programming to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating 20mg/L phenol simulated organic wastewater.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 100%.
Example 8
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, carrying out temperature program heating to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating 20mg/L phenol simulated organic wastewater.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 3, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 100%.
Example 9
The invention discloses a preparation method of a Fenton-like catalyst of carbon-supported Fe ions, which specifically comprises the following steps:
(1) taking cyclodextrin and ferric chloride with the mass ratio of 1:0.2, fully grinding for 20min in a mortar to uniformly mix, placing in a muffle furnace, carrying out temperature program heating to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating 20mg/L phenol simulated organic wastewater.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 10, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 85%.
As shown in fig. 1, the outer layer of the carbon-supported Fe ion-like fenton-like catalyst prepared by the present invention is a carbon layer, and the black particulate matter inside is iron nanoparticles.
The xenon lamp mainly plays a role in separating photogenerated electrons and photogenerated holes in the catalyst, and the separated photogenerated electrons can carry out electron transfer on the surface of the catalyst, so that Fe is promoted3+/Fe2+So as to decompose hydrogen peroxide to generate a large amount of hydroxyl radicals, thereby degrading pollutants; in addition, the photogenerated 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, carrying out temperature program heating to 250 ℃ at the heating rate of 3 ℃/min in the air atmosphere, keeping for 2h, and naturally cooling to obtain solid A;
(2) and washing the solid A with absolute ethyl alcohol for multiple times, and drying at 40 ℃ overnight to finish the preparation of the catalyst.
The product prepared by the preparation method is used for treating simulated organic wastewater containing 20mg/L phenol.
0.01g of Fenton-like catalyst and 20. mu.L of 30 wt% hydrogen peroxide were added to 50mL of phenol wastewater having a pH of 6.8, the reaction temperature was 25 ℃ and the reaction time was 20min, and after the reaction, the mixture was irradiated with a xenon lamp light source having a power of 300W, and the supernatant was taken to measure the phenol content, and as shown in Table 1, the phenol removal rate was 5%.
Table 2 shows the removal rate of phenol in examples 3 to 9 and comparative examples
| 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％ |
As shown in examples 1 to 7, the heterogeneous Fenton-like catalytic system of the catalyst and hydrogen peroxide can continuously provide strongly oxidative hydroxyl radical (. OH) for the reaction system. Meanwhile, the catalyst has high reaction activity in a wide pH range (pH 3-10), the pH value of raw water does not need to be adjusted, the cost is reduced, and the service life of equipment is prolonged.
As can be seen from the comparative examples, ferric chloride is an essential raw material. Cyclodextrins are mineralized only in the presence of ferric chloride; upon mineralization of cyclodextrin, ferric chloride becomes iron nanoparticles, and a portion of Fe therein3+Will be reduced into Fe2+Uniformly wrapped by an amorphous carbon layer, and simultaneously, electron transfer occurs on the surface of the catalyst to promote Fe3+/Fe2+And is Fe2+The hydrogen peroxide is continuously decomposed into hydroxyl free radicals, so that pollutants are degraded.
The catalyst obtained after the reaction in example 2 was subjected to a repeatability test, the catalyst was washed with absolute ethanol, and after the catalyst was dried, 20mg/L of phenol-simulated organic wastewater was treated and repeated 4 times under the same conditions, and the test results are shown in fig. 2.
The treatment conditions are as follows: 50mL of simulated wastewater, 0.01g of catalyst, 20 mu L of 30 wt% 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 20mg/L phenol solution after 20min of reaction reaches 98%, and the catalytic efficiency can still reach more than 97% after repeated use for five times.
The preparation method is simple, low in cost, simple and convenient to operate, easy to obtain preparation conditions, and has potential application prospects in the aspect of advanced oxidation treatment of the phenol wastewater.
Description of the drawings: the above-mentioned embodiments are only used for illustrating the present invention, and do not limit the technical solutions described in the present invention. Although the present invention has been described in detail in this specification with reference to the above-mentioned embodiments. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (8)
1. A preparation method of a Fenton-like catalyst with iron ions supported on carbon is characterized by comprising the following steps of:
(1) taking the mass ratio of 1: grinding 0.2-1 of carbohydrate and ferric chloride, and uniformly mixing to obtain a mixture;
(2) heating the mixture to 150-350 ℃, calcining for 1-4 h, and naturally cooling to obtain a solid A;
(3) and washing the solid A for many times, and drying to obtain the Fenton-like catalyst of the carbon-supported iron ions.
2. The method of claim 1, wherein the carbohydrate is cyclodextrin, starch or chitin.
3. The method according to claim 1, wherein the heating in the step (2) is performed in a muffle furnace, and the temperature is increased at a rate of 3 ℃/min.
4. The method for preparing a Fenton-like catalyst containing iron ions on carbon according to claim 1, wherein in the step (3), the catalyst is washed with absolute ethyl alcohol for a plurality of times.
5. The method for preparing a Fenton-like catalyst containing iron ions on carbon according to claim 1, wherein the drying in the step (3) is carried out at 35-80 ℃ for 12 hours.
6. A Fenton-like catalyst of iron ions on carbon prepared by the preparation method of any one of claims 1 to 5.
7. Use of the iron ion on carbon fenton-like catalyst according to claim 6 for the treatment of wastewater, comprising the steps of:
adding a Fenton-like catalyst and 30 wt% of hydrogen peroxide into phenol wastewater with the pH of 3-10, irradiating by using a xenon lamp light source after reaction, and taking supernate to measure the content of phenol;
wherein the feed-liquid ratio of the Fenton-like catalyst, the hydrogen peroxide and the phenol wastewater is 0.2 g: (0.2-0.5) mL: 1L of the compound.
8. Use of the iron ion on carbon fenton-like catalyst according to claim 7, wherein the reaction conditions are: the reaction was carried out at 25 ℃ for 20 min.
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