CN104525222B - A kind of preparation method of carbon nanotube composite ZnIn2S4 green deep water treatment agent - Google Patents

Abstract

The invention relates to a preparation method of a carbon nanotube composite ZnIn ₂ S ₄ green deep water treatment agent, comprising: (1) sequentially carboxylation, amination modification, 2,4,6-trifluoro-5 carbon nanotubes ‑Chloropyrimidine modification to prepare reactive carbon nanotubes; (2) Add nano ZnIn ₂ S ₄ , stabilizer, template agent and reactive carbon nanotubes to phosphate buffer, stir for 30-60min to form a suspension ; (3) filter and dry to get the product. The invention has the advantages of low cost, simple preparation method, low requirements on equipment, and good operability; the water treatment agent of the invention can remove high-concentration organic pollutants in water, is suitable for advanced treatment of various waste water, and is environmentally friendly without secondary pollution , and has the advantages of antibacterial, deodorizing, and can adsorb other heavy metal ions.

Description

A kind of preparation method of carbon nanotube composite ZnIn2S4 green deep water treatment agent

technical field

The invention belongs to the field of water treatment agents, in particular to a preparation method of a carbon nanotube composite ZnIn ₂ S ₄ green deep water treatment agent.

Background technique

Only about 10% of the world's water is directly used by humans. The largest share, 70%, is used in agriculture, and the remaining 20% is used in industry. China's sewage is about 20% of the world's, but it only gets 5% of the world's fresh water. Therefore, solving the pollution problem is on the agenda. In the processing of textile printing and dyeing, leather, and papermaking industries, a large number of additives that pollute the environment and are harmful to the human body are used. Most of these additives are discharged in the form of liquid and pollute the environment. They have poor biodegradability, high toxicity, and high content of free formaldehyde. The content of heavy metal ions exceeds the standard. Among them, printing and dyeing wet finishing is indisputably a major water polluter. From sizing to desizing, washing, bleaching, mercerizing, dyeing and printing, and possibly coating, each process involves washing, and each process requires 20L of water per kilogram of material. The result is up to 200 liters of water per kilogram of raw cotton added up during wet finishing. When a standard men's shirt is customized and displayed in the shop window, more than 2000L of water is used in the production and processing of it (fabric: pure cotton, 125g/m).

The methods currently used to treat wastewater mainly include: physical separation, biodegradation, and chemical decomposition, but these methods have certain limitations and are not conducive to sustainable development. Therefore, people began to devote themselves to the development of pollutant removal technology with high efficiency, low energy consumption, wide application range and deep oxidation ability. In recent years, many scholars have used ZnIn ₂ S ₄ for photocatalytic degradation of organic pollutants in water, and loading ZnIn ₂ S ₄ on carbon nanotubes to prepare efficient photocatalysts has become a current research hotspot.

Contents of the invention

The technical problem to be solved by the present invention is to provide a preparation method of carbon nanotube composite ZnIn ₂ S ₄ green deep water treatment agent, the method is simple to operate, low in cost, and has low requirements on equipment; the water treatment agent is suitable for various waste water Advanced treatment, environmental protection and no secondary pollution.

A kind of preparation method of carbon nanotube composite ZnIn ₂ S ₄ green advanced water treatment agent of the present invention, comprising:

(1) Ultrasonically react the carbon nanotubes in a mixture of H ₂ SO ₄ and HNO ₃ at room temperature for 30-60 minutes, wash with water until neutral, and dry in vacuum at room temperature to obtain carboxylated carbon nanotubes; then disperse the carboxylated carbon nanotubes Add 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate to excess diethylenetriamine, react at 40~50℃ for 5~6h , washed with ethanol, and vacuum-dried at room temperature to obtain aminated carbon nanotubes; then ultrasonically disperse the aminated carbon nanotubes into a mixture of water and acetone, adjust the pH value to 5-6, add 2,4, 6-trifluoro-5-chloropyrimidine, adjust the pH value to 6-6.5, 20-30 ℃ ultrasonic reaction 24-48h, ethanol washing, water washing, room temperature vacuum drying, irradiation (irradiation under 222nm excimer ultraviolet light source 3min) to obtain reactive carbon nanotubes;

(2) Add nano-ZnIn ₂ S ₄ , stabilizers, templates, and reactive carbon nanotubes in step (1) into phosphate buffer, stir for 30-60 minutes to form a suspension; wherein, nano-ZnIn ₂ The mass ratio of S4 to reactive carbon nanotubes is 1: ₅ to 1:20;

(3) Adjust the pH value to 5-6 with an alkaline solution, heat to 80-100° C. to reflux for 6-24 hours and filter to obtain a carbon nanotube composite ZnIn ₂ S ₄ green deep water treatment agent.

The ratio of carbon nanotubes to H ₂ SO ₄ and HNO ₃ mixture in the step (1) is 10-20g:4L; wherein, the volume ratio of H ₂ SO ₄ and HNO ₃ is 1:1-5:1 .

The mass ratio of the carboxylated carbon nanotubes in the step (1) to 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphoric acid is 5 ~8:0.1~0.6.

The ratio of the aminated carbon nanotube to the mixture of water and acetone in the step (1) is 4-4.5g:1L; wherein, the volume ratio of water and acetone is 3:1-5:1.

The mass ratio of the aminated carbon nanotubes to 2,4,6-trifluoro-5-chloropyrimidine in the step (1) is 4-4.5:4-6.

In the step (1), sodium carbonate solution is used to adjust the pH value.

The nano ZnIn ₂ S ₄ concentration in the step (2) is 0.01-0.2 mol/L.

The stabilizer in the step (2) is one of disodium edetate, tetrasodium edetate, sodium gluconate, butane tetracarboxylic acid; the concentration of stabilizer is 0.01～0.1mol/ L.

The template in the step (2) is a mixture of tri-block polyether P123 and tri-block copolymer F127 with a mass ratio of 1:3; the template concentration is 0.01-0.1 mol/L.

The phosphate buffer in the step (2) is composed of 0.025-0.05 mol/L sodium dihydrogen phosphate and 0.05-0.1 mol/L sodium hydrogen phosphate.

The alkaline solution in the step (3) is an aqueous solution of sodium hydroxide or potassium hydroxide with a concentration of 0.5mol/L˜1.5mol/L.

As a porous substance, carbon nanotubes have special interlayer characteristics, and can be loaded with nano ZnIn ₂ S ₄ particles on their surface to prepare supported catalysts. The supported photocatalyst can improve the dispersibility of the photocatalyst, which is beneficial to recycling and reuse.

The present invention combines the characteristics of carbon nanotubes such as porosity, strong adsorption capacity, and easy separation from water with the photocatalytic activity of nano-ZnIn ₂ S ₄ to successfully load nano-ZnIn ₂ S ₄ on carbon nanotubes to prepare a Visible light photocatalytic materials with high catalytic activity that are suspended in wastewater and can be successfully separated from water, and applied to the advanced treatment of wastewater, can realize the oxidation and removal of high-concentration organic pollutants in water instead of transferring them to other places. It is an environmentally friendly process technology.

Beneficial effect

(1) The present invention has low cost, simple preparation method, low requirement on equipment, and good operability;

(2) The water treatment agent of the present invention can remove high-concentration organic pollutants in water, is suitable for advanced treatment of various waste water, is environmentally friendly and has no secondary pollution, and has the advantages of antibacterial, deodorizing, and can adsorb other heavy metal ions;

(3) The water treatment agent of the present invention can overcome the deficiency of the existing bismuth-based water treatment agent, has good water treatment effect and can be recycled.

detailed description

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

(1) 10g of carbon nanotubes were ultrasonically reacted at room temperature for 30min in 4L of H ₂ SO ₄ and HNO ₄ mixed solution with a volume ratio of 1:1, washed with water until neutral, and vacuum-dried at room temperature for 48h to obtain 5g of carboxylated carbon nanotubes ; Then the above-mentioned 5g carboxylated carbon nanotubes were dispersed in excess diethylenetriamine, and 100mg 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea hexa Fluorophosphate, reacted at 40°C for 5 hours, washed with ethanol, and dried in vacuum at room temperature for 48 hours to obtain 4g of aminated carbon nanotubes; finally, 4g of aminated carbon nanotubes were ultrasonically dispersed in 1L of a mixture of water and acetone with a volume ratio of 3:1 In the solution, adjust the pH value to 5 with sodium carbonate solution, add 4 g of 2,4,6-trifluoro-5-chloropyrimidine dropwise in an ice-water bath, adjust the pH value to 6 with sodium carbonate solution, react with ultrasonic at 20°C for 24 hours, wash with ethanol , washed with water, vacuum-dried at room temperature for 48 hours, and irradiated under a 222nm excimer ultraviolet light source for 3 minutes to obtain reactive carbon nanotubes;

(2) The mixture of nano ZnIn ₂ S ₄ , disodium edetate, triblock polyether P123 and triblock copolymer F127 with a mass ratio of 1:3 and the reactive carbon in the above step (1) The nanotubes were added to the buffer solution composed of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L sodium hydrogen phosphate, and stirred for 30min to form a suspension; the concentration of nano ZnIn ₂ S ₄ was 0.01mol/L, The concentration of the stabilizer is 0.01mol/L, and the concentration of the template is 0.05mol/L.

(3) Adjust the pH value of the above-mentioned suspension to 5 with an aqueous sodium hydroxide solution with a concentration of 0.5mol/L, heat at 80° C., reflux for 6 hours, and filter to obtain a reaction product; wherein nano-ZnIn ₂ S ₄ and carbon nanotubes The mass ratio is 1:5.

Example 2

(1) 10 g of carbon nanotubes were ultrasonically reacted at room temperature for 45 min in 4 L of H ₂ SO ₄ and HNO ₄ mixed solution with a volume ratio of 3:1, washed with water until neutral, and vacuum-dried at room temperature for 54 h to obtain 6.5 g of carboxylated carbon nanotubes. tube; then the above 5g carboxylated carbon nanotubes were dispersed into excess diethylenetriamine, and 300mg 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea was added Hexafluorophosphate, reacted at 45°C for 5 hours, washed with ethanol, and dried in vacuum at room temperature for 48 hours to obtain 4.2 g of aminated carbon nanotubes; finally, ultrasonically dispersed 4.2 g of aminated carbon nanotubes in 1 L of water with a volume ratio of 4:1 and In the mixed solution of acetone, use sodium carbonate solution to adjust the pH value to 5.5, add 5g of 2,4,6-trifluoro-5-chloropyrimidine dropwise in an ice-water bath, use sodium carbonate solution to adjust the pH value to 6.2, and conduct ultrasonic reaction at 25°C for 36 hours , washed with ethanol, washed with water, dried in vacuum at room temperature for 48 hours, and irradiated for 3 minutes under a 222nm excimer ultraviolet light source to obtain reactive carbon nanotubes;

(2) The mixture of nano-ZnIn ₂ S ₄ , sodium gluconate, tri-block polyether P123 and tri-block copolymer F127 with a mass ratio of 1:3 and the reactive carbon nanotubes in the above step (1) were added to The concentration is 0.03mol/L sodium dihydrogen phosphate and 0.05mol/L sodium hydrogen phosphate in the buffer solution, stirring for 45min to form a suspension; the concentration of nano ZnIn ₂ S ₄ is 0.01mol/L, the concentration of stabilizer is 0.03mol/L, and the concentration of template agent is 0.07mol/L.

(3) Adjust the pH value of the above-mentioned suspension to 7 with an aqueous sodium hydroxide solution with a concentration of 0.5mol/L, heat at 90°C, reflux for 16h, and filter to obtain a reaction product; wherein the mass of nano ZnIn ₂ S ₄ carbon nanotubes The ratio is 1:15.

Example 3

(1) 10 g of carbon nanotubes were ultrasonically reacted at room temperature for 60 min in 4 L of H ₂ SO ₄ and HNO ₄ mixed solution with a volume ratio of 5:1, washed with water until neutral, and vacuum-dried at room temperature for 60 h to obtain 8 g of carboxylated carbon nanotubes ; Then the above-mentioned 8g carboxylated carbon nanotubes were dispersed in excess diethylenetriamine, and 600mg 2-(7-azobenzotriazole)-N,N,N',N'-tetramethylurea hexa Fluorophosphate, reacted at 50°C for 5h, washed with ethanol, and dried in vacuum at room temperature for 48h to obtain 4.5g of aminated carbon nanotubes; finally, 4.5g of aminated carbon nanotubes were ultrasonically dispersed in 1L of water and acetone with a volume ratio of 5:1 In the mixed solution, adjust the pH value to 6 with sodium carbonate solution, add 6 g of 2,4,6-trifluoro-5-chloropyrimidine dropwise in an ice-water bath, adjust the pH value to 6.5 with sodium carbonate solution, and perform ultrasonic reaction at 30°C for 48 hours. Washing with ethanol, washing with water, vacuum drying at room temperature for 48 hours, and irradiating for 3 minutes under a 222nm excimer ultraviolet light source to obtain reactive carbon nanotubes;

(2) the mixture of nanometer ZnIn ₂ S ₄ , butane tetracarboxylic acid, mass ratio 1:3 triblock polyether P123 and triblock copolymer F127 and reactive carbon nanotubes in the above step (1) Add it into the buffer solution with a concentration of 0.05mol/L sodium dihydrogen phosphate and 0.1mol/L sodium hydrogen phosphate, stir for 60min to form a suspension; wherein the concentration of nano ZnIn ₂ S ₄ is 0.15mol/L, the concentration of stabilizer The concentration is 0.05 mol/L, and the concentration of template agent is 0.1 mol/L.

(3) Adjust the pH value of the above-mentioned suspension to 9 with an aqueous potassium hydroxide solution with a concentration of 1.5mol/L, heat at 100° C., reflux for 24 hours, and filter to obtain a reaction product; wherein nano-ZnIn ₂ S ₄ and carbon nanotubes The mass ratio is 1:20.

Taking the printing and dyeing wastewater of the printing and dyeing factory sampled at the same time as the treatment object, the water treatment agents obtained in Examples 1 to 3 of different concentrations were added to the wastewater, and after 6 hours of sunlight, the decolorization rate of the water treatment agent on the printing and dyeing wastewater was as follows As shown in the table:

Decolorization rate COD removal rate Example 1 99.2% 90.5% Example 2 99.4% 92.3% Example 3 99.5% 93.1%

Claims (10)

1. a CNT is combined ZnIn₂S₄The preparation method of green deep water treatment agent, including:

(1) by CNT at H₂SO₄And HNO₃Room temperature ultrasonic reaction 30～60min in mixed liquor, washing is to neutrality, room temperature Vacuum drying, obtains carboxylic carbon nano-tube；Then carboxylic carbon nano-tube is distributed in excess diethylenetriamine, adds 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 40～50 DEG C of reactions 5～6h, washing with alcohol, room Temperature vacuum drying, obtains aminated carbon nano tube；Then by aminated carbon nano tube ultrasonic disperse to water and the mixed liquor of acetone In, regulation pH value is 5～6, and ice-water bath dropping 2,4,6-tri-fluoro-5-chloropyrimide, regulation pH value is 6～6.5,20～30 DEG C Ultrasonic reaction 24～48h, washing with alcohol, washing, room temperature in vacuo drying, irradiation obtains response type CNT；

(2) by nanometer Zn In₂S₄, stabilizer, response type CNT in template and step (1) join phosphate-buffered In liquid, stir 30～60min, form suspension；Wherein, nanometer Zn In₂S₄With the mass ratio of response type CNT it is 1:5～1:20；Wherein, stabilizer is disodiumedetate, tetrasodium ethylenediamine tetraacetate, sodium gluconate, butane One in tetrabasic carboxylic acid；Template is triblock polyether P123 and the mixing of triblock copolymer F127 of mass ratio 1:3 Thing；

(3) regulating pH value with alkaline solution is 5～6, is heated to reflux and filters, obtaining CNT and be combined ZnIn₂S₄Green deep Degree water treatment agent.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the CNT in described step (1) and H₂SO₄And HNO₃The ratio of mixed liquor is 10～20g:4L；Wherein, H₂SO₄And HNO₃Volume ratio be 1:1～5:1.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the carboxylic carbon nano-tube in described step (1) and 2-(7-azo BTA)-N, N, N', N'-tetramethylurea The mass ratio of hexafluorophosphoric acid ester is 5～8:0.1～0.6.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the aminated carbon nano tube in described step (1) is 4～4.5g:1L with the ratio of water and the mixed liquor of acetone；Its In, the volume ratio of water and acetone is 3:1～5:1.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the aminated carbon nano tube in described step (1) is 4～4.5:4～6 with the mass ratio of 2,4,6-tri-fluoro-5-chloropyrimide.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: described step (1) uses sodium carbonate liquor regulation pH value.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the stabilizer concentration in described step (2) is 0.01～0.1mol/L.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the template concentration in described step (2) is 0.01～0.1mol/L.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the phosphate buffer in described step (2) by concentration 0.025～0.05mol/L sodium dihydrogen phosphate and 0.05～0.1mol/L disodium hydrogen phosphate composition.

A kind of CNT the most according to claim 1 is combined ZnIn₂S₄The preparation method of green deep water treatment agent, it is special Levy and be: the alkaline solution in described step (3) is concentration 0.5mol/L～the sodium hydroxide of 1.5mol/L or potassium hydroxide Aqueous solution.