CN108993472B - Titanium dioxide carbon nanotube composite carrier catalyst, preparation and application thereof - Google Patents
Titanium dioxide carbon nanotube composite carrier catalyst, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing a titanium dioxide and carbon nano tube composite carrier catalyst by a sol-gel method. The invention takes tetrabutyl titanate as a titanium source of a titanium dioxide carrier, takes carbon nano tubes treated by sulfuric acid or nitric acid as another component of a composite carrier, and takes CeO2、Co3O4、Bi2O3One or two of the NiO and the NiO are active substances, and the high-efficiency persulfate catalyst is prepared by hydrolysis gel of tetrabutyl titanate. The preparation method has the characteristics of simple preparation method, good stability, good dispersibility of active components, high low-temperature catalytic activity, good pH universality and the like.
Description
Technical Field
The invention relates to a method for preparing a persulfate catalyst by using a composite material carrier and application thereof, which have the characteristics of high catalytic activity, good stability and low requirement on catalytic conditions and are suitable for industrial degradation of organic wastewater. Belongs to the field of water treatment technology and environmental engineering.
Technical Field
Water is an important natural resource on which human beings rely to live, and in recent years, with the rapid development of industry, the waste and pollution of water resources in production and life are greatly improved, wherein organic wastewater is one of the more serious hazards in industrial wastewater. As the industrial organic wastewater contains phenolic pollutants, pesticides, dyes, polychlorinated biphenyl and the like, most of industrial organic wastewater has the characteristics of high biotoxicity, difficult biodegradation, carcinogenesis, teratogenesis and the like.
At present, the technology for treating organic wastewater comprises a physical method, a chemical method and a biological method. The physical method mainly separates the suspended pollutants, but cannot change the chemical properties of the pollutants, so that secondary pollution is easily caused. Biological methods utilize the metabolism of microorganisms themselves to degrade organic pollutants. Because organic pollutants have high biological toxicity, the biological method has poor effect of degrading organic wastewater. At present, the main method for degrading organic wastewater is a chemical oxidation method. Among them, the advanced oxidation method is widely used due to its high efficiency and high speed.
TiO2Has the advantages of low cost, no secondary pollution, stable chemical property and the like. TiO 22Has important position in the field of photocatalysis, and TiO is often used in the traditional Fenton system2Is used as a carrier to achieve the purpose of accelerating the reaction rate. In the invention, TiO is mixed with2The carrier is used for a persulfate oxidation system, and the dispersibility of the active component in the catalyst is improved.
The carbon nano tube is a novel material which is developed rapidly in recent years, has the excellent characteristics of large specific surface area, high strength, stable chemical property, high heat resistance and the like, and has strong adsorption capacity on heavy metals and organic pollutants in the environment. Due to the excellent mechanical and thermal properties of the carbon nano tube, the carbon nano tube is prepared into a catalyst carrier, so that the stability of the catalyst can be greatly improved while the reaction rate is improved. Although carbon nanotubes have many excellent characteristics, the dispersibility of carbon nanotubes in a system is very poor due to the limitation of the physical and chemical properties of carbon nanotubes, and the carbon nanotubes are difficult to be directly applied to the preparation of a catalyst carrier. The modification of the tube wall of the carbon nanotube by using the oxidizing acid in engineering is a treatment method for modifying the carbon nanotube, and the oxidizing acid can introduce carboxyl, hydroxyl and other groups on the tube wall of the carbon nanotube, so that the hydrophilicity of the carbon nanotube is improved, and the dispersibility of the carbon nanotube in water is improved. The carbon nano tube modified by acid is prepared into a catalyst carrier, and the dispersibility of the catalyst carrier is greatly improved.
In recent years, based on SO4 -The advanced oxidation technology of (2) is rapidly developed in the aspect of organic wastewater treatment. In the classical advanced oxidation technology, OH has the disadvantages of short existence time and insufficient oxidation capability. Comparison of OH,. SO4 -Has the advantages of strong oxidation capacity, long service life and wide pH application range. At present, the domestic research and application of the persulfate advanced oxidation technology is less, and the problem of high energy consumption of an activation mode still exists in the practical application process of persulfate. Therefore, the technical key is to find a preparation method of the catalyst capable of efficiently activating the persulfate under the low catalytic condition. The invention provides a preparation method of a catalyst capable of efficiently catalyzing persulfate activation under a low-temperature condition, and hopefully, the preparation method can be popularized and applied to advanced oxidation degradation of industrial organic wastewater.
Disclosure of Invention
The invention provides a method for preparing a high-efficiency persulfate catalyst by using a composite material carrier and application thereof2、Co3O4、Bi2O3And one or two of the NiO and the NiO are active substances to prepare the high-efficiency persulfate catalyst. Can activate persulfate in persulfate oxidation reaction to generate SO4 -The degradation rate of the organic matters is improved, and the organic wastewater is efficiently and quickly removed.
The invention also provides a preparation method of the catalyst, and a preparation method of the titanium dioxide and carbon nano tube composite carrier catalyst, which comprises the following steps:
step 2, dissolving b mol of tetrabutyl titanate in c mol of anhydrous ethanol to form a solution A, and stirring the solution A in a magnetic stirrer at the rotating speed of 100-;
step 3, dissolving one or two of cerium nitrate, cobalt nitrate, bismuth nitrate and nickel nitrate in d mol of deionized water to form a solution B, and adjusting the pH value with glacial acetic acid;
step 4, slowly dripping the solution B into the solution A at a speed of 10-20mL/min (optimally 12-18mL/min) to form an AB mixed solution under the condition of continuously stirring by a magnetic stirrer;
step 5, stopping stirring, adding a g acidified carbon nanotubes into the AB mixed solution, and performing ultrasonic dispersion at 60-100kHz (optimally 70-90kHz) until the carbon nanotubes become gel;
and 6, after the gel is almost completely dried, putting the gel into a tubular furnace for roasting to obtain the titanium dioxide and carbon nano tube composite carrier high-efficiency catalyst.
With CeO2、Co3O4、Bi2O3One or two of NiO and NiO are active substances, and the loading amount of the active components is 1.0-5.0 wt% in terms of metal.
In the step 2, c/b is 20-30.
D/b in the step 3 and the step 2 is 5-10.
And in the step 3, the pH value of the mixed solution is adjusted to 3-4 by glacial acetic acid.
The a/(79.87b) in the step 2 and the step 5 is 0.5-2.5 (the molecular weight of the titanium dioxide: 79.87 g/mol).
The roasting temperature in the step 6 is 500-700 ℃ for 240-300 min.
The intermittent reaction conditions for treating the organic wastewater by the catalyst are as follows: under normal pressure, the initial pH value of the wastewater is 3-11, the reaction temperature is 20-60 ℃, the adding amount of PMS (potassium hydrogen persulfate) is 6-8g/L, the adding amount of the catalyst is 0.05-0.5g/L, and the rotating speed of a water bath constant temperature oscillator is 100-.
The catalytic wet oxidation catalyst of the invention has the following advantages:
the catalyst has very high low-temperature catalytic activity for activating persulfate;
the catalyst has good stability in the process of oxidizing and degrading organic wastewater;
the production cost of the catalyst is low;
the catalyst has good pH universality.
Drawings
FIG. 1 is a graph of the relationship between the catalyst and the degradation rate of ofloxacin oxide catalyzed by the catalyst in example 1 and time.
FIG. 2 is a graph showing the evaluation of the continuous reaction life of the high-efficiency catalyst with a titanium dioxide/carbon nanotube composite carrier in example 1.
Detailed Description
The high-efficiency persulfate catalyst prepared by the invention can efficiently and quickly oxidize organic wastewater and improve the removal rate of organic matters.
The following detailed description will be made in conjunction with embodiments and the accompanying drawings.
Example 1:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 60 percent concentrated nitric acid, and nitrifying for 30 hours. Deionized water 5
And after secondary washing, removing the carbon nano tubes floating on the surface of the deionized water, taking the lower-layer precipitated carbon nano tubes, performing suction filtration, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 100 rpm. Mixing Co (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 25, c/d is 5)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 80kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 270min at 500 ℃ to obtain a composite carrier catalyst, wherein the active component Co is calculated by metal3O4The loading was 2.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 6g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 40 ℃ for 75min, the conversion rate of ofloxacin is 99 percent, and the TOC removal rate is 77 percent.
Example 2:
firstly, taking a carbon nano tube, completely immersing the carbon nano tube in 50% concentrated sulfuric acid, and acidifying for 24 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 100 rpm. Adding Bi (NO)3)3·5H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 30, c/d is 8)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the AB mixed solution, and performing ultrasonic dispersion at 60kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 270min at 600 ℃ to obtain a composite carrier catalyst, wherein the active component Bi is calculated by metal2O3The loading was 4.0 wt.%. (wherein: a/(79.87b) ═ 1)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 120min, the conversion rate of ofloxacin is 95 percent, and the TOC removal rate is 72 percent.
Example 3:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 65% concentrated nitric acid, and acidifying for 24 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Mixing Co (NO)3)2·6H2O and Ni (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B,the pH was adjusted to 3 with glacial acetic acid. (wherein: b/c is 25, c/d is 5)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 80kHz until the carbon nano tubes become gel. After the gel is almost completely dried, putting the gel into a tubular furnace to isolate air and roasting the gel for 300min at 500 ℃ to obtain the composite carrier catalyst, wherein the load capacity of an active component NiO is 2.0 wt.% in terms of metal, and the load capacity of Co is 2.0 wt.%3O4The loading was 2.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 96 percent, and the TOC removal rate is 74 percent.
Example 4:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% concentrated nitric acid, and acidifying for 30 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Adding Ce (NO)3)3·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 4 by using glacial acetic acid. (wherein: b/c 20, c/d 7)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 100kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 270min at 700 ℃ to obtain a composite carrier catalyst, wherein the active component CeO is calculated by metal2The loading was 5.0 wt.%. (wherein: a/(79.87b) ═ 2)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 6g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 100min, the conversion rate of ofloxacin is 100 percent, and the TOC removal rate is 88 percent.
Example 5:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% concentrated sulfuric acid, and acidifying for 20 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 180 rpm. Adding Ce (NO)3)3·6H2O and Co (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 4 by using glacial acetic acid. (wherein: b/c ═ 23, c/d ═ 6)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the AB mixed solution, and performing ultrasonic dispersion at 90kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 270min at 700 ℃ to obtain a composite carrier catalyst, wherein the active component is loaded with CeO in terms of metal21.0 wt.%, Co3O4At 2.0 wt.%. (wherein: a/(79.87b) ═ 1)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 99 percent, and the TOC removal rate is 76 percent.
Example 6:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 65% concentrated nitric acid, and acidifying for 30 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Mixing Co (NO)3)2·6H2O and Bi (NO)3)3·5H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 25, c/d is 5)
Thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid treated carbon nano-tubes into the AB mixed solution, and 80kHzDispersing it into gel by ultrasonic wave. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 300min at 500 ℃ to obtain the composite carrier catalyst, wherein the active component Bi is calculated by metal2O3Loading 1.0 wt.%, Co3O4The loading was 2.0 wt.%. (wherein: a/(79.87b) ═ 2.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 97 percent, and the TOC removal rate is 76 percent.
Example 7:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 65% concentrated sulfuric acid, and acidifying for 28 hours. And washing with deionized water for many times, filtering, and drying.
② dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form solution A, and stirring with a magnetic stirrer at the rotating speed of 120 rpm. Adding Bi (NO)3)3·5H2O and Ni (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 27, c/d is 8)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the AB mixed solution, and performing ultrasonic dispersion at 80kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 270min at 550 ℃ to obtain the composite carrier catalyst, wherein the load capacity of an active component NiO is 2.0 wt.% in terms of metal, and Bi is Bi2O3The loading was 2.0 wt.%. (wherein: a/(79.87b) ═ 1.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 120min, the conversion rate of ofloxacin is 98 percent, and the TOC removal rate is 78 percent.
Example 8:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 70% concentrated sulfuric acid, and acidifying for 26 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 150 rpm. Mixing Co (NO)3)2·6H2O and Ni (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 4 by using glacial acetic acid. (wherein: b/c is 30, c/d is 5)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the AB mixed solution, and performing ultrasonic dispersion at 100kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 260min at 650 ℃ to obtain the composite carrier catalyst, wherein the load capacity of an active component NiO is 1.0 wt.% in terms of metal, and the load capacity of Co is 1.0 wt.%3O4The loading was 1.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 100min, the conversion rate of ofloxacin is 95 percent, and the TOC removal rate is 72 percent.
Example 9:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 60% concentrated nitric acid, and acidifying for 22 hours. And washing with deionized water for many times, filtering, and drying.
② dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form solution A, and stirring with a magnetic stirrer at the rotating speed of 170 rpm. Mixing Ni (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 22, c/d is 8)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 60kHz until the carbon nano tubes become gel. And after the gel is almost completely dried, putting the gel into a tubular furnace, isolating the gel from air, and roasting the gel for 300min at 650 ℃ to obtain the composite carrier catalyst, wherein the load of an active component NiO is 3.0 wt.% in terms of metal. (wherein: a/(79.87b) ═ 1)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 94% and the TOC removal rate is 74%.
Example 10:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% concentrated nitric acid, and acidifying for 20 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Mixing Ni (NO)3)2·6H2O and Ce (NO)3)3·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 25, c/d is 5)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 90kHz until the carbon nano tubes become gel. After the gel is almost completely dried, putting the gel into a tubular furnace to isolate air and roasting the gel for 300min at 500 ℃ to obtain the composite carrier catalyst, wherein the load capacity of an active component NiO is 1.0 wt.% in terms of metal, and the load capacity of CeO is 1.0 wt.%2The loading was 2.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 93 percent, and the TOC removal rate is 75 percent.
Comparative example 1:
soaking Co (NO) in titanium dioxide powder as carrier in the same volume3)2·6H2O and Ce (NO)3)3·6H2O solution, roasting at 700 deg.c for 300min to obtain titania carrier catalyst with CeO as active component in metal content2Loading amount of 2.0wt. -%)，Co3O4At 2.0 wt.%.
② experimental conditions of catalytic oxidation reaction: the adding amount of the catalyst is 0.5g/L, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts for 120min in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃, the conversion rate of the ofloxacin is 56 percent, and the TOC removal rate is 48 percent. Comparative example 2:
equal volume impregnation of Ce (NO) with carbon nanotube as carrier3)3·6H2O solution, roasting at 600 deg.c for 280min to obtain carbon nanotube carrier catalyst with CeO as active component in metal content2The loading was 3.0 wt.%.
② experimental conditions of catalytic oxidation reaction: the adding amount of the catalyst is 0.5g/L, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium hydrogen persulfate is 6g/L, and after a water bath constant temperature oscillator reacts for 120min in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃, the conversion rate of the ofloxacin is 68 percent, and the TOC removal rate is 57 percent. Comparative example 3:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% concentrated sulfuric acid, and acidifying for 20 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 150 rpm. Mixing Co (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 4 by using glacial acetic acid. (wherein: b/c is 25, c/d is 2)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the AB mixed solution, and performing ultrasonic dispersion at 80kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 240min at 500 ℃ to obtain the composite carrier catalyst, wherein the active component Co is calculated by metal3O4At 2.0 wt.%. (wherein: a/(79.87b) ═ 2)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 6g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 100min, the conversion rate of ofloxacin is 68 percent, and the TOC removal rate is 58 percent.
Comparative example 4:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% nitric acid, and acidifying for 24 hours. And washing with deionized water for many times, filtering, and drying.
② dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form solution A, and stirring with a magnetic stirrer at the rotating speed of 160 rpm. Mixing Co (NO)3)2·6H2O and Ce (NO)3)3·6H2O is dissolved in d mol of deionized water to form a solution B. (wherein: b/c is 24, c/d is 7)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 60kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 240min at 500 ℃ to obtain the composite carrier catalyst, wherein the active component Co is calculated by metal3O41.0 wt.%, CeO2At 2.0 wt.%. (wherein: a/(79.87b) ═ 0.1)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 6g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 100min, the conversion rate of ofloxacin is 65 percent, and the TOC removal rate is 59 percent.
Comparative example 5:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% sulfuric acid, and acidifying for 20 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Adding Bi (NO)3)3·5H2O and Ce (NO)3)3·6H2O is dissolved in d mol of deionized water to form a solution B. (wherein: b/c is 10, c/d is 7)
Thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the AB mixed solution, and ultrasonically dispersing the carbon nano tubes to the solution A at 70kHzIt becomes a gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 240min at 600 ℃ to obtain the composite carrier catalyst, wherein the active component Bi is calculated by metal2O3At 2.0 wt.%, CeO2At 1.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 6g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 40 ℃ for 120min, the conversion rate of ofloxacin is 70 percent, and the TOC removal rate is 62 percent.
Comparative example 6:
firstly, taking a carbon nano tube, completely immersing the carbon nano tube in 50% concentrated sulfuric acid, and acidifying for 24 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 180 rpm. D mol of deionized water is taken, and the pH value is adjusted to 4 by glacial acetic acid. (wherein: b/c ═ 23, c/d ═ 6)
And thirdly, slowly dropwise adding the mixed solution of glacial acetic acid and water into the solution A to form a mixed solution, stopping stirring, adding a g carbon nano tubes treated by sulfuric acid into the mixed solution, and performing ultrasonic dispersion at 80kHz until the carbon nano tubes become gel. And after the gel is almost completely dried, putting the gel into a tubular furnace, isolating the gel from air, and roasting the gel for 270min at 500 ℃ to obtain the composite carrier catalyst. (wherein: a/(79.87b) ═ 1)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 39% and the TOC removal rate is 25%.
Comparative example 7:
soaking carbon nanotube in deionized water for 20 hr, suction filtering and stoving.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring by using a magnetic stirrer at the rotating speed of 150 rpm. Mixing Ni (NO)3)2·6H2O and Ce (NO)3)3·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 26, c/d is 8)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 90kHz until the carbon nano tubes become gel. After the gel is almost completely dried, putting the gel into a tubular furnace to isolate air and roasting the gel for 300min at 500 ℃ to obtain the composite carrier catalyst, wherein the load capacity of an active component NiO is 1.0 wt.% in terms of metal, and the load capacity of CeO is 1.0 wt.%2The loading was 1.0 wt.%. (wherein: a/(79.87b) ═ 1)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 66 percent, and the TOC removal rate is 56 percent.
Comparative example 8:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% concentrated nitric acid, and acidifying for 20 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Adding Ce (NO)3)3·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 6 by using glacial acetic acid. (wherein: b/c is 25, c/d is 5)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 90kHz until the carbon nano tubes become gel. After the gel is almost completely dried, placing the gel into a tubular furnace to isolate air and roasting the gel for 280min at 650 ℃ to obtain a composite carrier catalyst, wherein the active component CeO is calculated by metal2The loading was 2.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 63 percent, and the TOC removal rate is 55 percent.
Comparative example 9:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 65% concentrated nitric acid, and acidifying for 22 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Mixing Ni (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 3 by using glacial acetic acid. (wherein: b/c is 24, c/d is 7)
And thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 80kHz until the carbon nano tubes become gel. And after the gel is almost completely dried, putting the gel into a tubular furnace, isolating the gel from air, and roasting the gel for 300min at 200 ℃ to obtain the composite carrier catalyst, wherein the load of the active component NiO is 1.0 wt.% in terms of metal. (wherein: a/(79.87b) ═ 1.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 55 percent, and the TOC removal rate is 48 percent.
Comparative example 10:
firstly, taking the carbon nano tube, completely immersing the carbon nano tube in 50% concentrated nitric acid, and acidifying for 22 hours. And washing with deionized water for many times, filtering, and drying.
Dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and stirring with a magnetic stirrer at the rotating speed of 200 rpm. Mixing Ni (NO)3)2·6H2O and Co (NO)3)2·6H2Dissolving O in d mol of deionized water to form a solution B, and adjusting the pH value to 4 by using glacial acetic acid. (wherein: b/c is 25, c/d is 5)
Thirdly, slowly dripping the solution B into the solution A to form an AB mixed solution, stopping stirring, adding a g nitric acid-treated carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 90kHz until the carbon nano tubes become coagulatedAnd (6) gluing. After the gel is almost completely dried, putting the gel into a tubular furnace to isolate air and roasting the gel for 60min at 500 ℃ to obtain the composite carrier catalyst, wherein the load capacity of an active component NiO is 1.0 wt.% in terms of metal, and the load capacity of Co is 1.0 wt.%3O4The loading was 3.0 wt.%. (wherein: a/(79.87b) ═ 0.5)
And fourthly, experimental conditions of catalytic oxidation reaction: the adding amount of the composite material carrier catalyst is 0.5g/L, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium hydrogen persulfate is 8g/L, and after a water bath constant temperature oscillator reacts in a water bath at the rotating speed of 150r/min and the temperature of 50 ℃ for 90min, the conversion rate of ofloxacin is 71 percent, and the TOC removal rate is 65 percent.
And (4) conclusion: as can be seen from the above examples and comparative examples
1. The catalytic activity of the composite carrier catalyst is higher than that of a single carrier catalyst.
2. The catalytic activity of the composite carrier catalyst prepared from the carbon nano tubes treated by the nitric acid and the sulfuric acid is higher than that of the composite catalyst prepared from the carbon nano tubes not treated by acidification.
3. The catalyst with the active material supported has higher catalytic activity than the catalyst without the active material supported.
4. When the catalyst preparation proportion is as follows: c/b is 20-30; d/b is 5-10; when a/(79.87b) ═ 0.5 to 2.5, the catalytic activity of the catalyst is higher. (wherein a: the mass of the acid-treated carbon nanotube, unit: g; b: the amount of tetrabutyl titanate, unit: mol; c: the amount of absolute ethyl alcohol, unit: mol)
5. When the pH value of the glacial acetic acid adjusting mixed solution in the catalyst preparation step 3 is 3-4, the catalytic activity of the catalyst is higher.
6. When the catalyst calcination temperature is 500-700 ℃ for 240-300min, the catalyst has higher catalytic activity.
Claims (3)
1. The application of the titanium dioxide carbon nanotube composite carrier catalyst in treating organic wastewater in a persulfate oxidation reaction system is characterized in that: the preparation method of the catalyst comprises the following steps:
step 1, soaking a carbon nano tube in concentrated nitric acid or concentrated sulfuric acid with the weight percentage of 50-70% until the carbon nano tube is completely immersed, and acidifying for 20-30 hours; after washing with deionized water, removing the carbon nano tubes floating on the surface of the deionized water, taking the lower-layer precipitated carbon nano tubes, performing suction filtration and drying;
step 2, dissolving b mol of tetrabutyl titanate in c mol of absolute ethyl alcohol to form a solution A, and placing the solution A in a magnetic stirrer to stir at the rotating speed of 100-200 rpm;
step 3, dissolving one or two of cerium nitrate, cobalt nitrate, bismuth nitrate and nickel nitrate in d mol of deionized water to form a solution B, and adjusting the pH of the mixed solution to 3-4 by using glacial acetic acid;
step 4, under the condition of continuously stirring by a magnetic stirrer, slowly dripping the solution B into the solution A at the speed of 10-20mL/min to form an AB mixed solution;
step 5, stopping stirring, adding the ag acidified carbon nano tubes into the AB mixed solution, and performing ultrasonic dispersion at 60-100kHz until the carbon nano tubes become gel;
step 6, after the gel is dried, putting the gel into a tubular furnace for roasting to obtain the titanium dioxide and carbon nano tube composite carrier high-efficiency catalyst; the roasting temperature in the step 6 is 500-700 ℃, and the roasting time is 240-300 min;
c/b in the step 2 is 20-30, and the ratio d/b of d in the step 3 to b in the step 2 is 5-10;
the ratio a/(79.87b) of a in the step 5 to b in the step 2 is 0.5-2.5;
the organic wastewater is antibiotic wastewater.
2. Use according to claim 1, characterized in that: with CeO2、Co3O4、Bi2O3One or two of NiO and NiO are active substances, and the loading amount of the active components is 1.0-5.0 wt% in terms of metal.
3. Use according to claim 1, characterized in that: the intermittent reaction conditions for treating the organic wastewater by the catalyst are as follows: under normal pressure, the initial pH value of the waste water is 3-11, the reaction temperature is 20-60 ℃, the adding amount of the potassium hydrogen persulfate is 6-8g/L, and the adding amount of the catalyst is 0.05-0.5 g/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101601994A (en) * | 2009-07-09 | 2009-12-16 | 上海交通大学 | Rare earth modified carbon nanotube pipe-TiO 2The preparation method of photochemical catalyst |
| CN102872868A (en) * | 2012-09-04 | 2013-01-16 | 西安工业大学 | Carbon nano tube and cuprous oxide composite visible-light-driven photocatalyst and preparation method thereof |
| CN104383930A (en) * | 2014-11-25 | 2015-03-04 | 辽宁大学 | Zinc ferrite-loaded carbon nano tube catalyst prepared by microwave-hydrothermal method and application of catalyst in degrading organic pollutants in water |
| CN107398274A (en) * | 2016-05-20 | 2017-11-28 | 香港纺织及成衣研发中心有限公司 | The catalyst and preparation method of organic pollution in a kind of degraded dyeing waste water |
| CN107442123A (en) * | 2017-08-10 | 2017-12-08 | 南京理工大学 | A kind of preparation method of cobaltosic oxide/C catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101601994A (en) * | 2009-07-09 | 2009-12-16 | 上海交通大学 | Rare earth modified carbon nanotube pipe-TiO 2The preparation method of photochemical catalyst |
| CN102872868A (en) * | 2012-09-04 | 2013-01-16 | 西安工业大学 | Carbon nano tube and cuprous oxide composite visible-light-driven photocatalyst and preparation method thereof |
| CN104383930A (en) * | 2014-11-25 | 2015-03-04 | 辽宁大学 | Zinc ferrite-loaded carbon nano tube catalyst prepared by microwave-hydrothermal method and application of catalyst in degrading organic pollutants in water |
| CN107398274A (en) * | 2016-05-20 | 2017-11-28 | 香港纺织及成衣研发中心有限公司 | The catalyst and preparation method of organic pollution in a kind of degraded dyeing waste water |
| CN107442123A (en) * | 2017-08-10 | 2017-12-08 | 南京理工大学 | A kind of preparation method of cobaltosic oxide/C catalyst |
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