Preparation method of vanadium-praseodymium-titanium composite oxide water treatment film

Abstract

The invention belongs to the field of water pollution purification materials, and particularly relates to a preparation method of a vanadium-praseodymium-titanium composite oxide water treatment film. According to the preparation method disclosed by the invention, the vanadium-praseodymium-titanium composite oxide active coating is coated on the surface of an acid-treated ceramic wafer through high-temperature spraying, and the coating is uniformly distributed on the surface of the ceramic wafer and is tightly combined with the ceramic wafer. The vanadium-praseodymium-titanium composite oxide film retains the mechanical strength of the ceramic wafer, is suitable for wide water pollution treatment processes and flows, and has strong applicability to water treatment equipment. The vanadium-praseodymium-titanium composite oxide film can degrade organic pollutants in sewage under illumination, can quickly purify the organic pollutants in water, and is suitable for a long-term stable sewage treatment process.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of water pollution purification materials, and is a preparation method of a vanadium-praseodymium-titanium composite oxide water treatment film. BACKGROUND

[0002] Organic matter is the main pollutant in industrial wastewater and domestic wastewater, which needs to be purified before discharge. Photocatalytic oxidation technology is a new pollution purification technology, which is based on materials with photocatalytic activity, and can produce substances with strong oxidizing properties under light. These oxidizing substances can oxidize and degrade organic pollutants in water, and have very strong purification ability and application potential.

[0003] The key of photocatalytic technology is the photocatalytic material used. According to the requirements of the actual application of water treatment equipment, and considering the control of the treatment process in large-scale water treatment process, the ideal photocatalytic material should have the characteristics of strong reaction activity, easy separation from water and repeated use. SUMMARY

[0004] In view of the problems existing in the prior art, the present application aims to provide a preparation method of a vanadium-praseodymium-titanium composite oxide water treatment film, which can be used to purify organic pollutants in water.

[0005] The technical scheme adopted by the present application is:

[0006] A preparation method of a vanadium-praseodymium-titanium composite oxide water treatment film, comprising the following process steps:

[0007] Step 1: acid treatment of ceramic sheet

[0008] (1) Heat 0.50 mol / L hydrochloric acid solution to 90℃ in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep warm for 90 min;

[0009] (2) Take out the ceramic sheet from the hydrochloric acid solution, wash it thoroughly with pure water, and then place it in a 120℃ electric heating drying box for 12h to obtain the acid-treated ceramic sheet;

[0010] Step 2: preparation of precursor sol

[0011] (1) Add 5.3mL~5.5mL n-butyl titanate, 1.5g~1.6g emulsifier Tween 60, 6.5g~6.8g sodium metavanadate and 3.2g~3.3g polyethylene glycol in 120mL ethanol to form solution A;

[0012] (2) Add 8.2g~8.6g praseodymium nitrate hexahydrate and 2.6g~2.8g sodium acetate in 50mL pure water to form solution B;

[0013] (3) Slowly mix solution A and solution B, heat to 50°C, and keep warm for 20 min to obtain precursor sol;

[0014] Step 3: High-temperature spraying

[0015] (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace chamber of the programmable box furnace, place the acid-treated ceramic sheet from step 1 3 cm below the nozzle, and use a constant flow pump to deliver the precursor sol from step 2 to the quartz nozzle.

[0016] (2) The temperature of the programmable box furnace is controlled at 330℃~350℃, the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed from the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly cured in the furnace to form a uniformly distributed coating.

[0017] (3) After the spraying is completed, the temperature of the programmable box furnace is controlled at 550℃~570℃ and calcined for 3 hours to obtain vanadium-praseodymium-titanium composite oxide film.

[0018] Furthermore, the ceramic sheet in step (1) is mainly composed of aluminum oxide, with an Al2O3 content of 99%, a planar size of 20cm×20cm, and a thickness of 0.8mm.

[0019] Furthermore, the polyethylene glycol in step (2) has a molecular weight of 1000~10000.

[0020] Furthermore, the vanadium-praseodymium-titanium composite oxide film uses a ceramic sheet as the substrate material, and the active coating of the vanadium-praseodymium-titanium composite oxide is coated on the surface of the ceramic sheet by high-temperature spraying; in the vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium trioxide and titanium dioxide is (4.85~5.07):(3.11~3.26):(1.24~1.29).

[0021] Furthermore, the vanadium-praseodymium-titanium composite oxide film can maintain phase and structural stability below 550°C.

[0022] The method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film of the present invention has the following advantages compared with the prior art:

[0023] This invention involves coating an acid-treated ceramic sheet with a vanadium-praseodymium-titanium composite oxide active coating via high-temperature spraying. The coating is uniformly distributed and tightly bonded to the ceramic sheet. The vanadium-praseodymium-titanium composite oxide film retains the mechanical strength of the ceramic sheet, making it suitable for a wide range of water pollution treatment processes and procedures, and highly adaptable to water treatment equipment. Under light irradiation, the vanadium-praseodymium-titanium composite oxide film can degrade organic pollutants in wastewater, rapidly purifying organic pollutants in water, and is suitable for long-term, stable wastewater treatment processes. Detailed Implementation

[0024] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0025] Example 1

[0026] A method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film includes the following process steps:

[0027] Step 1: Acid treatment of ceramic sheets

[0028] (1) Heat a 0.50 mol / L hydrochloric acid solution to 90°C in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep it warm for 90 min;

[0029] (2) Remove the ceramic sheet from the hydrochloric acid solution, wash it thoroughly with pure water, and then place it in an electric drying oven at 120°C for 12 hours to obtain the acid-treated ceramic sheet.

[0030] Step 2: Prepare precursor sol

[0031] (1) Add 5.3 mL of tetrabutyl titanate, 1.5 g of emulsifier Tween 60, 6.5 g of sodium metavanadate, and 3.2 g of polyethylene glycol (molecular weight 1000) to 120 mL of ethanol and stir to form solution A;

[0032] (2) Add 8.2g of praseodymium nitrate hexahydrate and 2.6g of sodium acetate to 50mL of pure water and stir to form solution B;

[0033] (3) Slowly mix solution A and solution B, heat to 50°C, and keep warm for 20 min to obtain precursor sol.

[0034] Step 3: High-temperature spraying

[0035] (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace chamber of the programmable box furnace, place the acid-treated ceramic sheet from step 1 3 cm below the nozzle, and use a constant flow pump to deliver the precursor sol from step 2 to the quartz nozzle.

[0036] (2) The temperature of the programmable box furnace is controlled at 330℃, the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed from the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly cured in the furnace to form a uniformly distributed coating.

[0037] (3) After the spraying is completed, the temperature of the programmable box furnace is controlled at 550℃ and calcined for another 3 hours to obtain the vanadium-praseodymium-titanium composite oxide film. In the final vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium trioxide and titanium dioxide is 4.85:3.11:1.24.

[0038] Example 2

[0039] A method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film includes the following process steps:

[0040] Step 1: Acid treatment of ceramic sheets

[0041] (1) Heat a 0.50 mol / L hydrochloric acid solution to 90°C in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep it warm for 90 min;

[0042] (2) Remove the ceramic sheet from the hydrochloric acid solution, wash it thoroughly with pure water, and then place it in an electric drying oven at 120°C for 12 hours to obtain the acid-treated ceramic sheet.

[0043] Step 2: Prepare precursor sol

[0044] (1) Add 5.35 mL of tetrabutyl titanate, 1.52 g of emulsifier Tween 60, 6.53 g of sodium metavanadate, and 3.22 g of polyethylene glycol (molecular weight 2000) to 120 mL of ethanol and stir to form solution A;

[0045] (2) Add 8.3g of praseodymium nitrate hexahydrate and 2.65g of sodium acetate to 50mL of pure water and stir to form solution B;

[0046] (3) Slowly mix solution A and solution B, heat to 50°C, and keep warm for 20 min to obtain precursor sol.

[0047] Step 3: High-temperature spraying

[0048] (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace chamber of the programmable box furnace, place the acid-treated ceramic sheet from step 1 3 cm below the nozzle, and use a constant flow pump to deliver the precursor sol from step 2 to the quartz nozzle.

[0049] (2) The temperature of the programmable box furnace is controlled at 335℃, the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed from the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly cured in the furnace to form a uniformly distributed coating.

[0050] (3) After the spraying is completed, the temperature of the programmable box furnace is controlled at 555℃ and calcined for another 3 hours to obtain the vanadium-praseodymium-titanium composite oxide film. In the final vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium trioxide and titanium dioxide is 4.87:3.15:1.26.

[0051] Example 3

[0052] A method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film includes the following process steps:

[0053] Step 1: Acid treatment of ceramic sheets

[0054] (1) Heat a 0.50 mol / L hydrochloric acid solution to 90°C in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep it warm for 90 min;

[0055] (2) Remove the ceramic sheet from the hydrochloric acid solution, wash it thoroughly with pure water, and then place it in an electric drying oven at 120°C for 12 hours to obtain the acid-treated ceramic sheet.

[0056] Step 2: Prepare precursor sol

[0057] (1) Add 5.4 mL of tetrabutyl titanate, 1.55 g of emulsifier Tween 60, 6.6 g of sodium metavanadate, and 3.25 g of polyethylene glycol (molecular weight 5000) to 120 mL of ethanol and stir to form solution A;

[0058] (2) Add 8.4g of praseodymium nitrate hexahydrate and 2.7g of sodium acetate to 50mL of pure water and stir to form solution B;

[0059] (3) Slowly mix solution A and solution B, heat to 50°C, and keep warm for 20 min to obtain precursor sol.

[0060] Step 3: High-temperature spraying

[0061] (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace chamber of the programmable box furnace, place the acid-treated ceramic sheet from step 1 3 cm below the nozzle, and use a constant flow pump to deliver the precursor sol from step 2 to the quartz nozzle.

[0062] (2) The temperature of the programmable box furnace is controlled at 340℃, the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed from the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly cured in the furnace to form a uniformly distributed coating.

[0063] (3) After the spraying is completed, the temperature of the programmable box furnace is controlled at 560℃ and calcined for another 3 hours to obtain the vanadium-praseodymium-titanium composite oxide film. In the final vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium trioxide and titanium dioxide is 4.92:3.18:1.27.

[0064] Example 4: A method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film, comprising the following process steps:

[0065] Step 1: Acid treatment of ceramic sheets

[0066] (1) Heat a 0.50 mol / L hydrochloric acid solution to 90°C in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep it warm for 90 min;

[0067] (2) Remove the ceramic sheet from the hydrochloric acid solution, wash it thoroughly with pure water, and then place it in an electric drying oven at 120°C for 12 hours to obtain the acid-treated ceramic sheet.

[0068] Step 2: Prepare precursor sol

[0069] (1) Add 5.43 mL of tetrabutyl titanate, 1.57 g of emulsifier Tween 60, 6.72 g of sodium metavanadate, and 3.27 g of polyethylene glycol (molecular weight 7000) to 120 mL of ethanol and stir to form solution A;

[0070] (2) Add 8.5g of praseodymium nitrate hexahydrate and 2.72g of sodium acetate to 50mL of pure water and stir to form solution B;

[0071] (3) Slowly mix solution A and solution B, heat to 50°C, and keep warm for 20 min to obtain precursor sol.

[0072] Step 3: High-temperature spraying

[0073] (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace chamber of the programmable box furnace, place the acid-treated ceramic sheet from step 1 3 cm below the nozzle, and use a constant flow pump to deliver the precursor sol from step 2 to the quartz nozzle.

[0074] (2) The temperature of the programmable box furnace is controlled at 345℃, the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed from the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly cured in the furnace to form a uniformly distributed coating.

[0075] (3) After the spraying is completed, the temperature of the programmable box furnace is controlled at 565℃ and calcined for another 3 hours to obtain the vanadium-praseodymium-titanium composite oxide film. In the final vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium trioxide and titanium dioxide is 5.01:3.22:1.27.

[0076] Example 5

[0077] A method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film includes the following process steps:

[0078] Step 1: Acid treatment of ceramic sheets

[0079] (1) Heat a 0.50 mol / L hydrochloric acid solution to 90°C in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep it warm for 90 min;

[0080] (2) Remove the ceramic sheet from the hydrochloric acid solution, wash it thoroughly with pure water, and then place it in an electric drying oven at 120°C for 12 hours to obtain the acid-treated ceramic sheet.

[0081] Step 2: Prepare precursor sol

[0082] (1) Add 5.5 mL of tetrabutyl titanate, 1.6 g of emulsifier Tween 60, 6.8 g of sodium metavanadate, and 3.3 g of polyethylene glycol (molecular weight 10000) to 120 mL of ethanol and stir to form solution A;

[0083] (2) Add 8.6g of praseodymium nitrate hexahydrate and 2.8g of sodium acetate to 50mL of pure water and stir to form solution B;

[0084] (3) Slowly mix solution A and solution B, heat to 50°C, and keep warm for 20 min to obtain precursor sol.

[0085] Step 3: High-temperature spraying

[0086] (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace chamber of the programmable box furnace, place the acid-treated ceramic sheet from step 1 3 cm below the nozzle, and use a constant flow pump to deliver the precursor sol from step 2 to the quartz nozzle.

[0087] (2) The temperature of the programmable box furnace is controlled at 350℃, the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed from the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly cured in the furnace to form a uniformly distributed coating.

[0088] (3) After the spraying is completed, the temperature of the programmable box furnace is controlled at 570℃ and calcined for another 3 hours to obtain the vanadium-praseodymium-titanium composite oxide film. In the final vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium trioxide and titanium dioxide is 5.07:3.26:1.29.

[0089] The above description is merely an embodiment of the present invention and does not limit the scope of the present invention. Any equivalent transformations made based on the content of this specification, or direct or indirect applications in other related technical fields, are similarly included within the protection scope of the present invention.

Claims

1. A method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film, characterized in that, The process comprises the following steps: Step 1: acid treatment of ceramic sheet (1) Heat 0.50 mol / L hydrochloric acid solution to 90°C in a beaker, immerse the ceramic sheet in the hydrochloric acid solution, and keep for 90 min; (2) Take out the ceramic sheet from the hydrochloric acid solution, wash thoroughly with pure water, and then place in a 120°C electric drying oven for 12 h to obtain the acid-treated ceramic sheet; Step 2: preparation of precursor sol (1) Add 5.3 mL to 5.5 mL of n-butyl titanate, 1.5 g to 1.6 g of emulsifier Tween 60, 6.5 g to 6.8 g of sodium metavanadate, and 3.2 g to 3.3 g of polyethylene glycol to 120 mL of ethanol, and stir to form solution A; (2) Add 8.2 g to 8.6 g of praseodymium nitrate hexahydrate and 2.6 g to 2.8 g of sodium acetate to 50 mL of pure water, and stir to form solution B; (3) Slowly mix solution A and solution B, heat to 50°C, and keep for 20 min to obtain the precursor sol; Step 3: high-temperature spraying (1) Place a quartz nozzle with an inner diameter of 1.1 mm in the middle of the furnace cavity of a program-controlled box-type electric furnace, and place the acid-treated ceramic sheet of step 1 3 cm below the nozzle, and use a constant-flow infusion pump to deliver the precursor sol of step 2 to the quartz nozzle; (2) Control the temperature of the program-controlled box-type electric furnace at 330°C to 350°C, and the delivery speed of the precursor sol is 8 mL / min, the precursor sol is sprayed out of the quartz nozzle and covers the surface of the ceramic sheet, and is rapidly solidified in the electric furnace to form a uniformly distributed coating; (3) After spraying is completed, control the temperature of the program-controlled box-type electric furnace at 550°C to 570°C, and continue calcining for 3 h to obtain the vanadium-praseodymium-titanium composite oxide film.

2. The method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film according to claim 1, characterized by, The ceramic sheet of step (1) mainly comprises alumina, the content of Al2O3 is 99%, the planar size is 20 cm x 20 cm, and the thickness is 0.8 mm.

3. The method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film according to claim 1, characterized by, The polyethylene glycol of step (2) has a molecular weight of 1000 to 10000.

4. The method for preparing a vanadium-praseodymium-titanium composite oxide water treatment thin film according to claim 1, characterized by, The vanadium-praseodymium-titanium composite oxide film takes the ceramic sheet as the base material, and the vanadium-praseodymium-titanium composite oxide active coating is coated on the surface of the ceramic sheet by high-temperature spraying; in the vanadium-praseodymium-titanium composite oxide film, the relative mass ratio of vanadium pentoxide, praseodymium sesquioxide, and titanium dioxide is (4.85 to 5.07):(3.11 to 3.26):(1.24 to 1.29).

5. The method of claim 1, wherein the vanadium-praseodymium-titanium composite oxide water treatment thin film is prepared by a method comprising: preparing a solution by dissolving a vanadium compound, a praseodymium compound, and a titanium compound in a solvent; and depositing the solution on a substrate to form a thin film. The vanadium-praseodymium-titanium composite oxide film can maintain phase and structure stability below 550°C.