CN108993510B - Activated persulfate tire carbon catalyst, preparation and application - Google Patents

Activated persulfate tire carbon catalyst, preparation and application Download PDF

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CN108993510B
CN108993510B CN201810935718.8A CN201810935718A CN108993510B CN 108993510 B CN108993510 B CN 108993510B CN 201810935718 A CN201810935718 A CN 201810935718A CN 108993510 B CN108993510 B CN 108993510B
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tire
persulfate
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metal
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于杨
刘西扬
周园柏
黄菲
何益得
张永军
乔纳森贝尔
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Nanjing Tech University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • 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
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    • B01J23/8437—Bismuth
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    • 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
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Abstract

The invention discloses a preparation method of a tire carbon catalyst capable of efficiently activating persulfate, which comprises the following steps: firstly, waste tires are subjected to crushing, magnetic separation, low-temperature pyrolysis and other processes to prepare catalyst carrier tire carbon, and then CuO and CeO are added2、Fe2O3、Bi2O3、Co2O3And then the novel high-efficiency catalyst suitable for persulfate systems is obtained through the processes of dipping, kneading, pyrolysis and the like. The catalyst prepared by the invention has the advantages of high activity, small impregnation amount of active components, simple preparation, mature technology, good stability, low cost and the like in a persulfate system, and can be applied to the fields of sewage treatment, environmental management and the like. The catalyst prepared by the method disclosed by the invention is prepared from waste tires, can change waste tires into valuables, is fully recycled, realizes the purpose of treating wastes with wastes, and has remarkable economic benefit. The invention also provides a method for degrading organic wastewater by using the catalyst, the removal rate of the organic wastewater can reach more than 95%, and the organic wastewater can meet the national first-level wastewater discharge standard.

Description

Activated persulfate tire carbon catalyst, preparation and application
Technical Field
The invention relates to a preparation method and application of a high-efficiency persulfate tire carbon activation catalyst, which is suitable for persulfate oxidation treatment of organic wastewater and belongs to the fields of water treatment technology and environmental functional materials.
Background
The chemical industry is one of the important industries in China and plays an important role in the development of China. However, the rapid development of the chemical industry brings about the problem of water environment pollution which is becoming more and more serious. A great deal of organic wastewater which is difficult to degrade and is generated in the chemical industry is a big difficulty in wastewater treatment. In recent years, antibiotic wastewater has received increasing attention. Antibiotics are widely used in the treatment of infectious diseases, as well as in the prevention of diseases and growth promotion. Although the content of antibiotics in the wastewater is lower than that of conventional pollutants, the conventional sewage treatment process cannot effectively remove the antibiotics, and the antibiotics can pose potential threats to human health after entering the environment. Among them, ofloxacin is commonly used for treating acute and chronic infection caused by bacteria, and has become one of the main clinical anti-infective drugs since research and development, and the dosage is huge at home and abroad every year. However, ofloxacin mainly exists in the form of raw drug and is difficult to degrade, so that a large amount of ofloxacin is remained in a water environment, and serious environmental hazard is caused.
The organic wastewater treatment technology studied at home and abroad is mainly an advanced oxidation technology, such as a Fenton reagent method, an ozone oxidation method, a catalytic oxidation method and the like. There is currently less research on the catalytic oxidation of organic wastewater by oxone and its influencing factors. The persulfate system is an oxidation system based on sulfate radicals, and has the advantages of strong oxidation capacity and strong selectivity. Compared with hydrogen peroxide, persulfate has a wider applicable pH range. Currently used methods for activating persulfate include heat treatment, ultraviolet radiation, electrocatalysis, transition metal ion catalysis, and the like. The transition metal activation method has the advantages of simple operation and mild reaction conditions, but the metal ions cannot be recycled and need to be removed after the reaction is finished, so that the operation cost is increased and the problem of water pollution is caused. The heterogeneous persulfate activation technology can avoid the defect of introducing a large amount of metal ions into a water body, and the catalyst can be recycled after reaction. Therefore, there is an urgent need to develop and prepare heterogeneous catalysts which can efficiently activate persulfate while being economically practical.
With the rapid development of the automobile industry, the production amount of waste tires is also rapidly increased, and a large amount of waste tires brings great pressure to environmental management. Waste tires, also known as "black pollution," have been a major problem in recycling and disposal. The method of burying or stacking is adopted, so that the floor area is large, and the fire disaster is easily caused; volatile organic pollutants can be generated in the processes of retreading waste tires, producing rubber powder and the like; the process of energy recovery by incineration also produces pollutants such as dioxins, furans and polycyclic aromatic hydrocarbons. However, the tire carbon prepared by using waste tires is researched and found to have the characteristic of large specific surface area and certain catalytic activity, and the catalyst with high catalytic activity can be obtained by adopting the catalyst preparation method disclosed by the patent. After the catalyst prepared from the waste tires is applied to practice, a new way can be provided for waste tire treatment and disposal, pollution caused by the waste tires is reduced, the waste tires are fully recycled, and the purpose of treating waste with waste is achieved, so the catalyst has a good application prospect.
In summary, tire carbon is used as the active component carrier, and then CuO and CeO are added2、Fe2O3、Bi2O3、Co2O3One or more than two of the components are used as active components to be loaded on a tire carbon carrier, and a novel high-efficiency catalyst suitable for a persulfate system is obtained after processes of dipping, kneading, pyrolysis and the like. The catalyst is used for persulfate oxidative degradation of organic wastewater, has the advantages of high degradation rate and cost, changes the waste property of tire carbon, and realizes functionalization and resource utilization of the tire carbon. Therefore, the catalyst can be widely applied.
Disclosure of Invention
The invention aims to provide a preparation method and application of a catalyst with stable structure and high activity for treating organic wastewater in a persulfate oxidation system2、Fe2O3、Bi2O3、Co2O3One or more of them as active ingredients are loaded on a tire carbon support, the active ingredients being loaded in an amount of 0.1 to 5.0 wt.% in terms of metal. And then the novel high-efficiency catalyst suitable for persulfate systems is prepared through the processes of dipping, kneading, pyrolysis and the like. And (3) carrying out catalytic oxidation treatment on the organic wastewater in a persulfate oxidation system. The specific process is that persulfate and catalyst are added into organic wastewater, and the organic wastewater containing persulfate is placed in a reaction device to decompose the wastewater under the action of microwave catalytic activation of persulfate.
In order to achieve the aim, the invention obtains the metal-loaded black tire carbon catalyst by controlling the tire carbon roasting temperature and controlling the metal type, the loading amount and the loading time. Under the condition of existence of potassium hydrogen persulfate, the catalytic efficiency is improved by controlling the adding amount and the reaction temperature of the catalyst. The novel efficient activated persulfate tire carbon catalyst prepared by the invention can efficiently and quickly remove organic pollutants in water, and is a catalyst with excellent performance and suitable for a persulfate oxidation system.
In the patent of the invention, the novel high-efficiency activated persulfate tire carbon catalyst can be used for efficiently and quickly removing organic pollutants in water under a potassium peroxydisulfate oxidation system, and is hopefully applied to the field of actual water treatment.
Specifically, the preparation method of the high-efficiency activated persulfate tire carbon catalyst comprises the following steps:
(1) drawing out steel wires in the clean tires by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4-5 cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
(2) the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be 0.005-0.045 MPa (preferably 0.015-0.030 MPa) of micro negative pressure, and the reaction temperature is 300-400 ℃ (preferably 350-400 ℃) in a closed oxygen-free environment; reacting for 8-12 h (preferably 10-12 h) to obtain pyrolytic carbon black;
(3) quenching and heat exchanging (cooling medium is circulating water) the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30-40 ℃ (preferably 30-35 ℃) by a multistage discharging system, magnetically separating out residual impurities such as steel wires and the like to obtain coarse carbon black (the particle size is 100-250 mm), and carrying out micro powder grinding and screening (sieving by 80-200 meshes) on the coarse carbon black to obtain tire carbon (the particle size is 75-180 mu m);
soaking the tire carbon in the step (3) in Cu (NO)3)2·3H2O、Ce(NO3)3·6H2O、Fe(NO3)3·9H2O、Bi(NO3)3·5H2O、Co(NO3)2·6H2One or more than two of O in the solution for 2 to 48 hours (preferably 12 to 48 hours), the active component loading amount is 0.1 to 5.0 wt.% in terms of metal, and N is used2As protective gas, roasting at 300-900 ℃ for 1-8 h, and adding N2Cooling to room temperature under the protection of (1) to obtain the metal/tire carbon catalyst.
The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: normal pressure, initial pH of wastewater: 3-7 (preferably pH: 6-7), reaction temperature 10-80 ℃ (preferably 40-80 ℃), persulfate: the amount of potassium hydrogen persulfate added is 0.1-12 g/L (preferably 3-12 g/L), and the amount of catalyst added is 0.02-1.0 g/L (preferably 0.1-0.2 g/L).
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) the raw materials are wide and easily available (the waste tires are wide and cheap), the operation is simple, convenient and safe, the impregnation amount of the active components is small, the technology is mature, and the like;
(2) the preparation method has the advantages of simple preparation process, low cost, high synthesis efficiency, low energy consumption and easy control of the reaction process.
(3) The inventor tests the catalytic effect of the novel high-efficiency persulfate tire carbon activation catalyst, and finds that the catalyst can quickly and efficiently remove organic pollutants in wastewater in a persulfate oxidation system, has wide pH range applicability, is a catalyst with excellent performance, and has a good market prospect.
The catalyst prepared by the invention has the advantages of high activity, small impregnation amount of active components, simple preparation, mature technology, good stability, low cost and the like in a persulfate system, and can be applied to the fields of sewage treatment, environmental management and the like. The catalyst prepared by the method disclosed by the invention is prepared from waste tires, can change waste tires into valuables, is fully recycled, realizes the purpose of treating wastes with wastes, and has remarkable economic benefit. The invention also provides a method for degrading organic wastewater by using the catalyst, the removal rate of the organic wastewater can reach more than 95%, and the organic wastewater can meet the national first-level wastewater discharge standard.
Drawings
FIG. 1 is a graph showing the ofloxacin removal rate as a target catalyst in example 1 as a function of reaction time.
FIG. 2 is a graph comparing the reaction effect of comparative example 3 in the absence of microwaves with that of comparative example 1 in the absence of catalyst.
FIG. 3 is a graph showing the comparison of the reaction effect at 50 ℃ in example 2 and the reaction effect at 60 ℃ in example 3.
Detailed Description
The tire carbon material catalyst disclosed by the invention can be used for efficiently activating persulfate, quickly and efficiently removing organic pollutants in wastewater and promoting the wide application of persulfate oxidation technology.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon in Cu (NO) at 20 ℃ in equal volume3)2·3H2O、Ce(NO3)3·6H2In O solution, with N2Calcining the catalyst at 500 ℃ for 4 hours as a protective gas, and cooling the catalyst to room temperature to obtain the metal/tire carbon catalyst, wherein the active component loading amounts of Cu and Ce are respectively 4.9 wt.% and 0.1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 12g/L, the microwave power is 400W, the reaction temperature is 80 ℃, and the removal rate is 99.8 percent after the reaction is carried out for 12 min.
Example 2:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon in Cu (NO) at 20 ℃ in equal volume3)2·3H2O、Ce(NO3)3·6H2In O solution, with N2Calcining the catalyst at 500 ℃ for 4 hours as a protective gas, and cooling the catalyst to room temperature to obtain the metal/tire carbon catalyst, wherein the active component loading amounts of Cu and Ce are respectively 4.9 wt.% and 0.1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 1g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 3g/L, the microwave power is 200W, the reaction temperature is 50 ℃, and after the reaction is carried out for 60min, the ofloxacin is removedThe ratio was 83.3%.
Example 3:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon in Cu (NO) at 20 ℃ in equal volume3)2·3H2O、Ce(NO3)3·6H2In O solution, with N2Calcining the catalyst at 500 ℃ for 4 hours as a protective gas, and cooling the catalyst to room temperature to obtain the metal/tire carbon catalyst, wherein the active component loading amounts of Cu and Ce are respectively 4.9 wt.% and 0.1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 1g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 3g/L, the microwave power is 200W, the reaction temperature is 60 ℃, and after the reaction is carried out for 60min, the removal rate of the ofloxacin is 89.9 percent.
Example 4:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon into Co (NO) at the temperature of 20 ℃ in equal volume3)2·6H2O、Fe(NO3)3·9H2In O solution, with N2Calcining the carbon catalyst as a protective gas at 500 ℃ for 4 hours, and cooling the carbon catalyst to room temperature to obtain the metal/tire carbon catalyst, wherein the loading amounts of Co and Fe of active components are respectively 4 wt.% and 1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 1g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 3g/L, the microwave power is 200W, the reaction temperature is 60 ℃, and the removal rate is 85.2 percent after the reaction is carried out for 60 min.
Example 5:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon in Co (NO) at 20 ℃ in equal volume3)2·6H2O、Bi(NO3)3·5H2In O solution, with N2Calcining at 500 deg.C for 4 hr as shielding gas, and cooling to room temperature to obtain metal/tireThe carbon catalyst has active component loading amounts of Co and Bi of 4 wt.% and 1 wt.%, respectively, calculated by metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 3g/L, the microwave power is 400W, the reaction temperature is 60 ℃, and the removal rate is 90.3 percent after the reaction is carried out for 60 min.
Example 6:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns); soaking the obtained tire carbon in Co (NO) at 20 ℃ in equal volume3)2·6H2O、Cu(NO3)2·3H2In O solution, with N2Calcining the carbon catalyst as a protective gas at 500 ℃ for 4 hours, and cooling the carbon catalyst to room temperature to obtain the metal/tire carbon catalyst, wherein the loading amounts of Co and Cu of the active components are respectively 4 wt.% and 1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 3g/L, the microwave power is 400W, the reaction temperature is 60 ℃, and the removal rate is 83.6 percent after the reaction is carried out for 60 min.
Comparative example 1:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
fourthly, experimental conditions of microwave persulfate reaction: no tyre carbon catalyst is added, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO5The adding amount is 3g/L, the microwave power is 400W, the reaction temperature is 50 ℃, and after the reaction is carried out for 60min, the removal rate of the ofloxacin is 23.5 percent.
Comparative example 2:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
fourthly, experimental conditions of microwave persulfate reaction: the addition amount of the tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO content is5The dosage is 3g/L, the microwave power is 200W, the reaction temperature is 30 ℃, and after the reaction is carried out for 60min, the removal rate of ofloxacin is 30.5 percent.
Comparative example 3:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
fourthly, experimental conditions of microwave persulfate reaction: the addition amount of the tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and the KHSO content is5The dosage is 3g/L, microwave conditions are avoided, the reaction temperature is 30 ℃, and after 60min of reaction, the removal rate of ofloxacin is 44.3%.
Comparative example 4:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon in Cu (NO) at 20 ℃ in equal volume3)2·3H2O、Ce(NO3)3·6H2In O solution, with N2Calcining at 500 deg.C for 4 hr as shielding gas, and coolingAnd cooling to room temperature to obtain the metal/tire carbon catalyst, wherein the active component loading amounts of Cu and Ce are respectively 4.9 wt.% and 0.1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 2, and the KHSO5The adding amount is 3g/L, the microwave power is 200W, the reaction temperature is 50 ℃, and the removal rate is 31.5 percent after the reaction is carried out for 60 min.
Comparative example 5:
firstly, drawing out steel wires in a clean tire by using a wire drawing machine, crushing the steel wires into rubber blocks (with the particle size of 4cm) by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
the heat required by the reaction of the low-temperature pyrolysis reactor is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled to be micro negative pressure of 0.030MPa, and the reaction temperature is 400 ℃ in a closed oxygen-free environment; obtaining pyrolytic carbon black after reacting for 10 hours;
thirdly, carrying out quenching heat exchange (cooling medium is circulating water) on the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor to 30 ℃ through a multi-stage discharging system, carrying out magnetic separation on residual impurities such as steel wires and the like to obtain coarse carbon black (with the particle size of 200mm), and carrying out micro-powder grinding and screening (passing through 80 meshes) on the coarse carbon black to obtain tire carbon (with the particle size of 75 microns);
soaking the obtained tire carbon in Cu (NO) at 20 ℃ in equal volume3)2·3H2O、Ce(NO3)3·6H2In O solution, with N2Calcining at 500 ℃ for 4h as shielding gas, and cooling to room temperature to obtain the metal/tire carbon catalyst with active component loading of 4.9 wt.% and 0.1 wt.% in terms of metal.
Fifthly, microwave persulfate reaction experimental conditions are as follows: the dosage of the metal/tire carbon catalyst is 0.5g/L, the initial concentration of the ofloxacin is 300mg/L, the pH value is 6, and KHSO is not added5The microwave power is 200W, the reaction temperature is 50 ℃, and the removal rate is 20.3 percent after the reaction is carried out for 60 min.
And (4) conclusion:
as can be seen from the above examples and comparative examples
(1) The tire carbon has certain catalytic activity, and the catalytic activity of the tire carbon catalyst loaded with the two metals is higher.
(2) With the increase of the reaction temperature, the reaction speed is increased, as shown in figure 1, the removal rate reaches 99.8% when the reaction is carried out at 80 ℃ for 12min, as shown in figure 3, the reaction temperature is from 30 ℃ to 60 ℃ (the other conditions are the same), and the removal rate is increased from 50.9% to 89.9%.
(3) The catalytic activity of the catalyst is higher under microwave conditions than under microwave-free conditions.
(4) The catalytic activity of the catalyst is higher at pH 6 than at pH 2. (5) The catalytic activity of the catalyst is higher when the adding amount of the potassium hydrogen persulfate is 12g/L than when the adding amount of the potassium hydrogen persulfate is 3g/L and the potassium hydrogen persulfate is not added. The invention provides a preparation method and application of a tire carbon material catalyst for efficiently activating persulfate, and belongs to the field of water treatment and environmental material functions. The invention prepares the catalyst carrier tire carbon by crushing, magnetic separation, low-temperature pyrolysis and other processes of waste tires, and CuO and CeO2、Fe2O3、Bi2O3、Co2O3One or more than two of the active components are loaded on a tire carbon carrier as active components, and the loading amount of the active components is 0.1-5.0 wt.% in terms of metal. And then the novel high-efficiency catalyst suitable for persulfate systems is obtained through the processes of dipping, kneading, pyrolysis and the like. The catalyst prepared by the invention has the advantages of high activity, small impregnation amount of active components, simple preparation, mature technology, good stability, low cost and the like in a persulfate system, is used for degrading organic wastewater, wherein the removal rate of ofloxacin can reach more than 95 percent, and can meet the national first-level wastewater discharge standard.

Claims (8)

1. A preparation method of an activated persulfate tire carbon catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) drawing out steel wires in the clean tires by using a wire drawing machine, crushing the steel wires into rubber blocks with the particle size of 4-5 cm by using a shredder, removing residual steel wires in the rubber blocks through a magnetic separation process, and adding the rubber blocks into a low-temperature pyrolysis reactor;
(2) required for the reaction in the low-temperature pyrolysis reactorThe heat is provided by high-temperature flue gas of an air heating furnace, the reaction condition is controlled at micro negative pressure of 0.005-0.045 MPa, and the reaction temperature is 300-400 DEG CoC, sealing an oxygen-free environment; obtaining pyrolytic carbon black after reacting for 8-12 h;
(3) the pyrolytic carbon black reduced by the low-temperature pyrolysis reactor is subjected to quenching heat exchange by a multistage discharging system to 30-40 DEG CoC, using a cooling medium as circulating water, magnetically separating out residual steel wire impurities to obtain coarse carbon black with the particle size of 100-250 mm, and carrying out micro-powder grinding and screening on the coarse carbon black to obtain tire carbon with the particle size of 75-180 mu m;
(4) taking the tire carbon prepared in the step (3) as a carrier, CuO and CeO2、Fe2O3、Bi2O3、Co2O3One or more than two of the metal or the metal is used as an active component, and the loading amount of the active component is 0.1-5.0 wt.% in terms of metal, so that the metal/tire carbon catalyst is obtained.
2. The method of claim 1, wherein: the preparation process of the metal/tire carbon catalyst in the step (4) comprises the following steps:
soaking the tire carbon in the step (3) in Cu (NO)3)2·3H2O、Ce(NO3)3·6H2O、 Fe(NO3)3·9H2O、Bi(NO3)3·5H2O、Co(NO3)2·6H2One or more than two of O in the salt solution for 2-48 h, the active component loading is 0.1-5.0 wt.% in terms of metal, and N is used2As a protective gas, 300-900oRoasting for 1-8 h under C, and then roasting under N2Cooling to room temperature under the protection of (1) to obtain the metal/tire carbon catalyst.
3. The method of claim 1, wherein: the tire is a waste tire.
4. A tire carbon catalyst of activated persulfate salt prepared by the method of claim 1, 2 or 3.
5. Use of the catalyst of claim 4 in the microwave persulfate oxidation treatment of organic wastewater.
6. The use according to claim 5, wherein the catalyst is used for the persulfate oxidation treatment of organic wastewater under the batch reaction conditions that: normal pressure, initial pH of wastewater: 3 to 7, and the reaction temperature is 10 to 80oC, persulfate: the dosage of the potassium hydrogen persulfate is 0.1-12 g/L, the microwave intensity is 0-1000W and is not 0W, and the dosage of the catalyst is 0.02-1.0 g/L.
7. Use according to claim 5 or 6, characterized in that: the organic wastewater is wastewater generated in the process of producing antibiotics.
8. Use according to claim 7, characterized in that: the organic wastewater is wastewater containing one or more than two substances of carbamazepine, o-chlorophenol, methylene blue, oxytetracycline and ofloxacin, which are generated in the process of producing antibiotics.
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