CN113385174B - Cobalt modified hydrated iron oxide catalyst and preparation method and application thereof - Google Patents

Cobalt modified hydrated iron oxide catalyst and preparation method and application thereof Download PDF

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CN113385174B
CN113385174B CN202110809417.2A CN202110809417A CN113385174B CN 113385174 B CN113385174 B CN 113385174B CN 202110809417 A CN202110809417 A CN 202110809417A CN 113385174 B CN113385174 B CN 113385174B
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iron oxide
cobalt
modified
hydrated
tetracycline
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CN113385174A (en
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唐俊
臧纪
潘丹丹
谢正鑫
范世锁
陈正杰
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Anhui Agricultural University AHAU
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Anhui Agricultural University AHAU
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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
    • B01J23/75—Cobalt
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention provides cobalt modified waterIron oxide containing catalyst, its preparation and use, comprises FeCl 3 ·6H 2 Dissolving O in deionized water, adjusting the pH value to 7.0 by using NaOH solution, continuously stirring the formed suspension for 1 hour, and aging for 24 hours; centrifuging, collecting precipitate, washing, freeze drying, grinding and sieving to obtain hydrated ferric oxide; putting hydrated ferric oxide into cobalt chloride hexahydrate aqueous solution, performing ultrasonic treatment for 30min, adjusting pH to 7.0, performing ultrasonic dispersion for 20min, and precipitating at room temperature for 12 h; cleaning, freeze drying, grinding and sieving to obtain the oxidant. The catalyst obtained by the invention can efficiently catalyze potassium peroxymonosulfate to degrade tetracycline in water. In experiments, CoOOH @ HFO-0.1 in the cobalt-modified hydrated iron oxide material is found to have the most use value, and the degradation rate of tetracycline in 10min is more than 99% when the tetracycline concentration is 40mg/L, the solid-to-liquid ratio is 0.2g/L, the potassium monopersulfate concentration is 80mg/L and the pH value is 9.

Description

Cobalt modified hydrated iron oxide catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a cobalt-modified hydrated iron oxide catalyst, and a preparation method and application thereof.
Background
Tetracycline is the second largest antibiotic in production and use in the world, has an inhibitory effect on various pathogenic bacteria, is often used as a feed additive and is widely applied to animal husbandry and aquaculture. However, the absorption rate of animals to tetracycline antibiotics is low, and about 30% -90% of antibiotics passing through the animal body are not absorbed by the animals and are mainly discharged out of the body along with excrement and urine in the form of original drugs and metabolites, so that the antibiotics in soil and water are polluted, and the ecological safety and the human health are threatened. In addition, tetracycline residues can enhance drug resistance and challenge antibiotic therapy, thereby posing a potential threat to human health. Therefore, the technology for efficiently removing tetracycline in wastewater becomes a research hotspot at home and abroad
At present, the treatment methods of tetracycline wastewater reported at home and abroad mainly comprise an adsorption method, a biological method, a chemical method and the like. The adsorption method is mainly used for fixing the tetracycline on the surface of the material, and the tetracycline cannot be removed fundamentally. The biological method is to degrade tetracycline by utilizing the metabolism of microorganisms, but the tetracycline has an inhibition effect on the microorganisms, so the biological treatment is difficult to popularize.
Disclosure of Invention
Aiming at the technical problems, the invention uses a chemical method to catalyze potassium peroxymonosulfate to degrade tetracycline by using cobalt modified hydrated ferric oxide. The specific technical scheme is as follows:
the preparation method of the cobalt modified hydrated iron oxide catalyst comprises the following steps
(1) Preparation of hydrated iron oxide
Under strong magnetic stirring, FeCl is added 3 ·6H 2 Dissolving O in deionized water, and then FeCl with NaOH solution 3 ·6H 2 Adjusting the pH value of the O solution to 7.0, continuously stirring the formed suspension for 1 hour, and aging for 24 hours at room temperature;
collecting precipitated hydrous iron oxide particles by centrifugation, and then washing 3 times with ultrapure water to remove residual ions;
finally, freeze drying the hydrated iron oxide, grinding in an agate mortar and sieving through a 200-mesh sieve;
the hydrated iron oxides obtained were collected and stored in brown glass bottles for future use.
(2) Preparation of cobalt-modified hydrated iron oxide
Putting hydrated ferric oxide into cobalt chloride hexahydrate aqueous solution, performing ultrasonic treatment for 30min, adding ammonia water into the solution to adjust the pH value to 7.0, performing ultrasonic dispersion for 20min, and performing precipitation for 12h at room temperature;
washing with ultrapure water for three times, freeze-drying, grinding in an agate mortar, and sieving with a 200-mesh sieve;
the catalyst obtained was collected and stored in a brown glass bottle until use.
Preferably, in the step (1) of preparing the hydrated iron oxide, the materials are used according to the following ratio: 10.0g FeCl 3 ·6H 2 O dissolved in 100mL deionizationWater;
the concentration of the NaOH solution is 1 mol/L.
Preferably, in the step (2) of preparing the cobalt modified hydrated iron oxide, the materials are used according to the following proportion: 1.0g of hydrated ferric oxide and 50mL of cobalt chloride hexahydrate aqueous solution, wherein the concentration of the cobalt chloride hexahydrate aqueous solution is 0.01-0.2 mol/L.
The cobalt modified hydrated iron oxide catalyst obtained by the invention is used for removing tetracycline in wastewater.
The invention synthesizes an efficient catalyst which can efficiently catalyze potassium monopersulfate to degrade tetracycline in water. In experiments, CoOOH @ HFO-0.1 in the cobalt-modified hydrated iron oxide material is found to have the most use value, and the degradation rate of tetracycline in 10min reaches more than 99% when the concentration of tetracycline is 40mg/L, the solid-to-liquid ratio is 0.2g/L, the concentration of potassium monopersulfate is 80mg/L, and the pH value is 9.
Drawings
FIG. 1 shows the effect of different PMS catalytic systems on TC degradation in the examples;
FIG. 2 is a graph of the effect of different cobalt loadings catalyzing PMS on tetracycline degradation in the examples;
FIG. 3 is the effect of the addition of CoOOH @ HFO-0.1 in the examples on the degradation of TC by catalytic PMS;
FIG. 4 is the effect of PMS addition on TC degradation in the examples;
FIG. 5 is a graph of the effect of initial pH on catalytic PMS degradation of TC in the examples.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
The preparation method of the cobalt modified hydrated iron oxide catalyst comprises the following steps:
(1) preparation of hydrated iron oxide
Under strong magnetic stirring, 10.0g of FeCl 3 ·6H 2 O is dissolved in 100mL of deionized water, and FeCl is then dissolved with 1mol/L NaOH solution 3 ·6H 2 Adjusting the pH value of the O solution to 7.0, continuously stirring the formed suspension for 1 hour, and aging for 24 hours at room temperature;
collecting precipitated hydrous iron oxide particles by centrifugation, and then washing 3 times with ultrapure water to remove residual ions;
finally, freeze drying the hydrated iron oxide, grinding in an agate mortar and sieving through a 200-mesh sieve;
the hydrated iron oxides obtained were collected and stored in brown glass bottles for future use.
(2) Preparation of cobalt-modified hydrated iron oxide
Respectively putting 1.0g of hydrated ferric oxide into 50mL of cobalt chloride hexahydrate with the concentration of 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.15mol/L and 0.2mol/L, performing ultrasonic treatment for 30min, adding ammonia water into the solution to adjust the pH value to 7.0, performing ultrasonic dispersion for 20min, and performing precipitation for 12h at room temperature;
washing with ultrapure water for three times, freeze-drying, grinding in an agate mortar, and sieving with a 200-mesh sieve;
collecting the obtained oxidant, and storing the oxidant in a brown glass bottle until use;
the synthesized catalysts are respectively named as CoOOH @ HFO-0.01, CoOOH @ HFO-0.05, CoOOH @ HFO-0.1, CoOOH @ HFO-0.15 and CoOOH @ HFO-0.2.
The following experiment was conducted on the degradation of tetracycline by potassium monopersulfate catalyzed by cobalt-modified hydrous iron oxide obtained in this example:
1. degradation of TC by different catalytic systems
The catalytic performance of CoOOH @ HFO was evaluated in experiments by exploring the removal efficiency of TC under different conditions (CoOOH @ HFO, CoOOH/PMS, HFO/PMS, CoOOH @ HFO/PMS). As shown in FIG. 1, when only PMS was added, the degradation rate was 30% within 20min, indicating that it was difficult to completely degrade TC using only PMS. When HFO and PMS are added into the reaction system at the same time, the degradation rate of TC is only about 60 percent within 20 min. This indicates that HFO is difficult to catalyze PMS rapidly to produce free radical degradation TC. When only CoOOH was added to the reaction system, equilibrium was reached with a removal rate of 55% by reacting only for 30min, but the removal rate of TC slightly increased with the increase in the oscillation time, which may be attributed to the fact that the reaction system only had an adsorption effect and a desorption phenomenon occurred after the adsorption equilibrium. When in a CoOOH/PMS system, the TC removal rate can reach 90 percent within 2.5min, but the removal rate is increased along with the removal rateThe removal rate of TC decreased to 86% instead with increasing reaction time, probably due to the fact that CoOOH catalyzed PMS to generate free radicals only for a short time to degrade TC molecules, but desorption occurred instead with increasing oscillation time and TC could not be completely degraded. In a CoOOH @ HFO/PMS system, TC can be degraded by more than 98% in 20 min. This may be attributed to the fact that the HFO core may enhance electron transfer, thereby promoting Co 3+ To Co 2+ The circulation of the method can greatly improve the generation of free radicals in the reaction process of a PMS system, promote the free radicals to continuously attack TC molecules and lead to the rapid degradation of TC.
2. Effect of different cobalt loadings on degradation of TC
As known from the preparation method of CoOOH @ HFO, HFO is added into cobalt chloride hexahydrate solutions with different concentrations in the preparation process so as to load Co with different contents. As can be seen from FIG. 2, the degradation rates of the tetracycline by HFO, CoOOH @ HFO-0.01, CoOOH @ HFO-0.05, CoOOH @ HFO-0.1, CoOOH @ HFO-0.15 and CoOOH @ HFO-0.2 are 61%, 85%, 93%, 98% and 98% respectively within 20min, and the degradation rates of the tetracycline are increased and then reach equilibrium with the increase of the cobalt content. This indicates that as the cobalt concentration is increased to 0.1mol/L, the cobalt loading on the surface of the hydrous iron oxide is already saturated, and the cobalt concentration is increased again, so that the cobalt loading cannot be loaded on the hydrous iron oxide, and the degradation rate of tetracycline is not increased any more. The most preferred catalyst of the present invention is CoOOH @ HFO-0.1.
3. Effect of the addition of CoOOH @ HFO-0.1 on degradation of TC
In previous research reports, it can be found that the addition amount of the catalyst in the PMS system has a significant influence on the degradation of the pollutants in the system. Thus, the effect of catalyst addition on the degradation of TC was explored in the experiments and the results are shown in FIG. 3, which shows the catalytic effect of different additive amounts of CoOOH @ HFO-0.1 on TC. It can be observed that as the addition amount of CoOOH @ HFO-0.1 is increased from 0.05g/L to 0.4g/L, the degradation rate and degradation rate of TC in the reaction system are increased continuously, and the degradation rate of TC is increased from 86% to 99% within 20 min. This may be attributed to the fact that more catalytic sites are available to the PMS as the amount of catalyst added increases, thereby promoting the production of more radicals from the catalytic PMS over the given time, thereby promoting the degradation of TC. It can be observed from FIG. 3 that the degradation rate of TC in 20min can reach more than 98% when the addition amount of CoOOH @ HFO-0.1 is 0.2g/L, and the optimal catalyst addition amount of the present invention is 0.2g/L in view of the degradation efficiency and cost effectiveness of TC.
4. Effect of PMS addition on TC degradation
As can be seen from FIG. 4, the degradation rate of TC increases continuously as the concentration of PMS increases from 20mg/L to 100mg/L, showing a good positive correlation with the concentration of PMS. As the concentration of PMS in the reaction system was increased from 20mg/L to 80mg/L, the degradation rate of TC was increased from 41% to 95%, but when the concentration of PMS was further increased to 100mg/L, the degradation rate of TC was only increased to 97%, and the reaction rate was only slightly increased. Therefore, the concentration of PMS in the present invention is preferably 80 mg/L.
5. Effect of initial pH on TC degradation
The initial pH of the solution plays an important role in the decomposition of PMS to produce sulfate radicals. As can be seen from FIG. 5, when the pH value is in the range of 3.0 to 9.0, the degradation rate of TC increases as the pH value of the solution increases. When the pH value is 9.0, the degradation rate of TC reaches more than 95 percent in 2.5 min. The degradation rate of TC was higher at initial pH 9.0 compared to initial pH 11.0. The optimum pH for the present invention is therefore 9.

Claims (5)

1. The preparation method of the cobalt-modified hydrated iron oxide catalyst is characterized by comprising the following steps
(1) Preparation of hydrated iron oxide
Under strong magnetic stirring, FeCl is added 3 ·6H 2 Dissolving O in deionized water, and then FeCl with NaOH solution 3 ·6H 2 Adjusting the pH value of the O solution to 7.0, continuously stirring the formed suspension for 1 hour, and aging at room temperature for 24 hours;
collecting precipitated hydrous iron oxide particles by centrifugation, and then washing 3 times with ultrapure water to remove residual ions;
finally, freeze drying the hydrated iron oxide, grinding in an agate mortar and sieving through a 200-mesh sieve;
collecting the obtained hydrated ferric oxide, and storing the hydrated ferric oxide in a brown glass bottle for later use;
(2) preparation of cobalt-modified hydrated iron oxide
Putting hydrated ferric oxide into a cobalt chloride hexahydrate aqueous solution, performing ultrasonic treatment for 30min, adding ammonia water into the solution to adjust the pH value to 7.0, performing ultrasonic dispersion for 20min, and performing precipitation for 12h at room temperature;
washing with ultrapure water for three times, freeze-drying, grinding in an agate mortar, and sieving with a 200-mesh sieve;
the catalyst obtained was collected and stored in a brown glass bottle until use.
2. The method for preparing a cobalt-modified hydrous iron oxide catalyst as claimed in claim 1, wherein in the step (1) of preparing hydrous iron oxide, the following raw materials are used in proportion: 10.0g FeCl 3 ·6H 2 Dissolving O in 100mL of deionized water;
the concentration of the NaOH solution is 1 mol/L.
3. The method for preparing a cobalt-modified hydrous iron oxide catalyst as claimed in claim 1, wherein in the step (2) of preparing the cobalt-modified hydrous iron oxide, the following raw materials are used in proportion: 1.0g of hydrated ferric oxide and 50mL of cobalt chloride hexahydrate aqueous solution, wherein the concentration of the cobalt chloride hexahydrate aqueous solution is 0.01-0.2 mol/L.
4. A cobalt-modified hydrous iron oxide catalyst characterized by being obtained by the production method according to any one of claims 1 to 3.
5. Use of a cobalt-modified hydrous iron oxide catalyst as claimed in claim 4 for the removal of tetracycline from wastewater.
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