Preparation method of europium porcelain sand filter material with purification function

Abstract

The application provides a preparation method of europium porcelain sand filter material with a purification function, and belongs to the field of water pollution purification materials. Main preparation steps of the method include: first, preparing europium modified porcelain sand, then, preparing a titanium precursor, and finally, hydrothermally preparing a film. Through the step of europium modified porcelain sand, part of metal elements on the surface of the porcelain sand are replaced by europium ions. Then, through the step of hydrothermally preparing a film, the titanium precursor reacts with the europium modified porcelain sand to generate an europium titanate coating. The europium porcelain sand filter material has the characteristics of rich porosity, strong filtering capacity, water flow impact resistance and the like. Meanwhile, the europium porcelain sand filter material can quickly decompose organic pollutants attached to the surface under illumination, and has the performance of continuously treating organic pollutants in wastewater.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of water pollution purification materials, and particularly relates to a preparation method of europium porcelain sand filter material with purification function. BACKGROUND

[0002] The porcelain sand is made of high-quality kaolin, binder, pore-forming agent, corrosion inhibitor and the like through high-temperature calcination, has white appearance, hard texture, uniform particles, developed micropores and high porosity. The porcelain sand filter material has the characteristics of large specific surface, strong pollution interception capacity, high water yield, stable water quality and long filtration cycle, and can meet the deep treatment of various industrial wastewater and municipal wastewater with complex components. The initial water head loss of the porcelain sand filter material is small, which is very beneficial to prolonging the working cycle of the filter tank; the final water head loss of the porcelain sand filter material is small, which can reduce the height of the filter tank and save the construction cost. The porcelain sand is uniform and regular, is convenient to load, is not easy to lose, has no secondary pollution, is suitable for ion exchange, mechanical filter, valveless filter tank and reverse osmosis treatment device as pretreatment filter material or resin supporting layer, and can be used as a cushion layer of an activated carbon adsorber.

[0003] Since the porcelain sand filter material can only intercept pollutants and cannot decompose the pollutants, organic pollutants will be enriched on the surface of the porcelain sand filter material, and the function of intercepting pollutants will be gradually lost with the prolongation of the treatment time. Therefore, the porcelain sand filter material must be regenerated after a period of use, which increases the time and cost in the continuous treatment process. SUMMARY

[0004] In view of the problems in the prior art, the present application aims to provide a preparation method of europium porcelain sand filter material with purification function, which can decompose the attached organic pollutants under light conditions and is suitable for a continuous sewage treatment process.

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

[0006] A preparation method of europium porcelain sand filter material with purification function comprises the following process steps:

[0007] Step 1: europium modified porcelain sand

[0008] (1) 5.2-7.2 g of europium nitrate and 2.1-2.3 g of dodecyltrimethylammonium bromide are added into 300 mL of 0.3 mol / L hydrochloric acid solution to form solution A after stirring;

[0009] (2) solution A and 30 g of porcelain sand are mixed and then transferred into a flask, and heated to 75 DEG C, and refluxed at this temperature for 2 h;

[0010] (3) the mixture is filtered, and the obtained solid is dried at 150 DEG C for 12 h to obtain europium modified porcelain sand;

[0011] Step 2: Preparation of titanium precursor

[0012] (1) 5-6 mL of n-butyl titanate and 3.5-3.8 g of emulsifier Tween-60 were added into 220 mL of anhydrous ethanol, and stirred to form solution B;

[0013] (2) 1.3-1.5 mL of concentrated hydrochloric acid and 2.5-2.7 g of sodium dihydrogen phosphate were added into 26 mL of pure water, and stirred to form solution C;

[0014] (3) Solution B and solution C were mixed, and stirred in a constant temperature water bath at 35°C for 15 min to obtain the titanium precursor;

[0015] Step 3: Hydrothermal film preparation

[0016] (1) The titanium precursor of step 2 and the europium modified porcelain sand of step 1 were mixed, and moved into a hydrothermal reaction kettle, and the reaction temperature was controlled at 210-220°C, the reaction kettle pressure was controlled at 2.0-2.1 MPa, and the reaction time was 36 h;

[0017] (2) After the reaction was completed, the mixture was filtered and washed with pure water;

[0018] (3) The solid material obtained by filtration was dried at 155°C for 10 h, and then calcined at 650-710°C for 150 min to obtain the europium porcelain sand filter material with purification function.

[0019] Further, the porcelain sand of step (1) is white spherical, with a diameter of 2-3 mm, a bulk density of 2.31-2.38 g / cm 3 , a compressive strength of greater than 3.5 x 10 3 Pa, and a porosity of 41%-43%.

[0020] Further, the main components of the porcelain sand of step (1) are silicon oxide and aluminum oxide, and contain a small amount of iron, magnesium, potassium and sodium oxides.

[0021] Further, the europium porcelain sand filter material has the following characteristics: a diameter of 2-3 mm, a bulk density of 2.32-2.39 g / cm 3 , and a porosity of greater than 45%.

[0022] Further, the purification active component of the europium porcelain sand filter material is a europium titanate coating layer coated on the surface of the porcelain sand, and the mass percentage of the europium titanate coating layer in the europium porcelain sand filter material is 3.3%-3.5%.

[0023] The preparation method of the europium porcelain sand filter material with purification function of the present application has the following advantages compared with the prior art:

[0024] The present application makes part of metal elements on the surface of the porcelain sand be replaced by europium ions through the step of europium modification of porcelain sand, and the europium ions are firmly combined with the surface of the porcelain sand; then the titanium precursor reacts with the europium modified porcelain sand to generate an europium titanate coating through the step of hydrothermal film preparation, the europium titanate coating is closely combined with the europium modified porcelain sand, and will not block the original pores of the porcelain sand. The europium porcelain sand filter material has the characteristics of rich pores, strong filtering capacity, water flow impact resistance and the like; at the same time, it can quickly decompose the organic pollutants attached to the surface under light, and has the performance of continuously treating organic pollutants in wastewater. DETAILED DESCRIPTION

[0025] The present application will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and are not used to limit the scope of the present application. The operation methods not specified in the following examples are usually carried out according to the conventional conditions or the conditions recommended by the manufacturers.

[0026] Example 1

[0027] A preparation method of a europium porcelain sand filter material with a purification function, comprising the following process steps:

[0028] Step 1: Europium modification of porcelain sand

[0029] (1) 5.2 g of europium nitrate and 2.1 g of dodecyltrimethylammonium bromide were added to 300 mL of 0.3 mol / L hydrochloric acid solution, and stirred to form solution A;

[0030] (2) Solution A and 30 g of porcelain sand were mixed and then moved into a flask, and heated to 75℃, and refluxed at this temperature for 2 h;

[0031] (3) The mixture was filtered, and the obtained solid was dried at 150℃ for 12 h to obtain europium modified porcelain sand.

[0032] Step 2: Preparation of titanium precursor

[0033] (1) 5 mL of n-butyl titanate and 3.5 g of emulsifier Tween-60 were added to 220 mL of anhydrous ethanol, and stirred to form solution B;

[0034] (2) 1.3 mL of concentrated hydrochloric acid and 2.5 g of sodium dihydrogen phosphate were added to 26 mL of pure water, and stirred to form solution C;

[0035] (3) Solution B and solution C were mixed, and stirred in a 35℃ constant temperature water bath for 15 min to obtain a titanium precursor.

[0036] Step 3: Hydrothermal film preparation

[0037] (1) The titanium precursor of step 2 and the europium modified ceramic sand of step 1 are mixed and moved into a hydrothermal reactor, the reaction temperature is controlled at 210℃, the reactor pressure is 2.0MPa, and the reaction time is 36h;

[0038] (2) After the reaction is completed, the mixture is filtered and washed with pure water;

[0039] (3) The solid obtained by filtration is dried at 155℃ for 10h and then calcined at 650℃ for 150min to obtain the europium ceramic sand filter material with purification function; the diameter of the europium ceramic sand filter material is 2-3mm, the bulk density is 2.32g / cm 3 , and the porosity is 46%; the purification active component of the europium ceramic sand filter material is a europium titanate coating layer coated on the surface of the ceramic sand, and the mass percentage of the europium titanate coating layer in the europium ceramic sand filter material is 3.3%.

[0040] Example 2

[0041] A preparation method of a europium ceramic sand filter material with purification function comprises the following process steps:

[0042] Step 1: Europium modified ceramic sand

[0043] (1) 5.5g of europium nitrate and 2.1g of dodecyltrimethylammonium bromide are added to 300mL of 0.3mol / L hydrochloric acid solution to form solution A;

[0044] (2) Solution A and 30g of ceramic sand are mixed and moved into a flask, heated to 75℃, and refluxed at this temperature for 2h;

[0045] (3) The mixture is filtered, and the obtained solid is dried at 150℃ for 12h to obtain the europium modified ceramic sand.

[0046] Step 2: Preparation of titanium precursor

[0047] (1) 5mL of n-butyl titanate and 3.6g of emulsifier Tween-60 are added to 220mL of anhydrous ethanol to form solution B;

[0048] (2) 1.3mL of concentrated hydrochloric acid and 2.5g of sodium dihydrogen phosphate are added to 26mL of pure water to form solution C;

[0049] (3) Solution B and solution C are mixed and stirred in a 35℃ constant temperature water bath for 15min to obtain the titanium precursor.

[0050] Step 3: Hydrothermal film preparation

[0051] (1) The titanium precursor of step 2 and the europium modified ceramic sand of step 1 are mixed and moved into a hydrothermal reactor, the reaction temperature is controlled at 210℃, the reactor pressure is 2.0MPa, and the reaction time is 36h;

[0052] (2) After the reaction is completed, the mixture is filtered and washed with pure water;

[0053] (3) The solid material obtained by filtration is dried at 155°C for 10h, and then calcined at 660°C for 150min to obtain the europium ceramic sand filter material with purification function; the diameter of the europium ceramic sand filter material is 2-3mm, the bulk density is 2.33g / cm 3 , and the porosity is 46%; the purification active component of the europium ceramic sand filter material is a europium titanate coating layer coated on the surface of the ceramic sand, and the mass percentage of the europium titanate coating layer in the europium ceramic sand filter material is 3.3%.

[0054] Example 3

[0055] A preparation method of a europium ceramic sand filter material with purification function, comprising the following process steps:

[0056] Step 1: Europium-modified ceramic sand

[0057] (1) 6.2g of europium nitrate and 2.2g of dodecyltrimethylammonium bromide are added to 300mL of 0.3mol / L hydrochloric acid solution to form solution A;

[0058] (2) Solution A and 30g of ceramic sand are mixed and then moved into a flask, and heated to 75°C and refluxed at this temperature for 2h;

[0059] (3) The mixture is filtered, and the obtained solid material is dried at 150°C for 12h to obtain europium-modified ceramic sand.

[0060] Step 2: Preparation of titanium precursor

[0061] (1) 5.5mL of n-butyl titanate and 3.6g of emulsifier Tween-60 are added to 220mL of anhydrous ethanol to form solution B;

[0062] (2) 1.4mL of concentrated hydrochloric acid and 2.6g of sodium dihydrogen phosphate are added to 26mL of pure water to form solution C;

[0063] (3) Solution B and solution C are mixed and stirred in a constant temperature water bath at 35°C for 15min to obtain the titanium precursor.

[0064] Step 3: Hydrothermal film preparation

[0065] (1) The titanium precursor of step 2 and the europium-modified ceramic sand of step 1 are mixed and moved into a hydrothermal reaction kettle, and the reaction temperature is controlled at 215°C, the reaction kettle pressure is 2.1MPa, and the reaction time is 36h;

[0066] (2) After the reaction is completed, the mixture is filtered and washed with pure water;

[0067] (3) The obtained solid substance is dried at 155℃ for 10h, and then calcined at 680℃ for 150min to obtain the europium ceramic sand filter material with purification function; the diameter of the europium ceramic sand filter material is 2-3mm, the bulk density is 2.35g / cm 3 , and the porosity is 46%; the purification active component of the europium ceramic sand filter material is a europium titanate coating layer coated on the surface of the ceramic sand, and the mass percentage of the europium titanate coating layer in the europium ceramic sand filter material is 3.4%.

[0068] Example 4

[0069] A preparation method of a europium ceramic sand filter material with purification function, comprising the following process steps:

[0070] Step 1: Europium-modified ceramic sand

[0071] (1) 6.8g of europium nitrate and 2.2g of dodecyltrimethylammonium bromide are added to 300mL of 0.3mol / L hydrochloric acid solution to form solution A;

[0072] (2) Solution A and 30g of ceramic sand are mixed and then moved into a flask, and heated to 75℃, and refluxed at this temperature for 2h;

[0073] (3) The mixture is filtered, and the obtained solid substance is dried at 150℃ for 12h to obtain europium-modified ceramic sand.

[0074] Step 2: Preparation of titanium precursor

[0075] (1) 6mL of n-butyl titanate and 3.7g of emulsifier Tween-60 are added to 220mL of anhydrous ethanol to form solution B;

[0076] (2) 1.4mL of concentrated hydrochloric acid and 2.6g of sodium dihydrogen phosphate are added to 26mL of pure water to form solution C;

[0077] (3) Solution B and solution C are mixed, and stirred in a constant-temperature water bath at 35℃ for 15min to obtain the titanium precursor.

[0078] Step 3: Hydrothermal film preparation

[0079] (1) The titanium precursor of step 2 and the europium-modified ceramic sand of step 1 are mixed and moved into a hydrothermal reaction kettle, and the reaction temperature is controlled at 220℃, the reaction kettle pressure is 2.1MPa, and the reaction time is 36h;

[0080] (2) After the reaction is completed, the mixture is filtered and washed with pure water;

[0081] (3) The obtained solid substance is dried at 155℃ for 10h, and then calcined at 700℃ for 150min to obtain the europium ceramic sand filter material with purification function; the diameter of the europium ceramic sand filter material is 2-3mm, the bulk density is 2.36g / cm 3 , and the porosity is 47%; the purification active component of the europium ceramic sand filter material is a europium titanate coating layer coated on the surface of the ceramic sand, and the mass percentage of the europium titanate coating layer in the europium ceramic sand filter material is 3.5%.

[0082] Example 5

[0083] A preparation method of a europium ceramic sand filter material with purification function, comprising the following process steps:

[0084] Step 1: Europium-modified ceramic sand

[0085] (1) 7.2g of europium nitrate and 2.3g of dodecyltrimethylammonium bromide are added into 300mL of 0.3mol / L hydrochloric acid solution to form solution A;

[0086] (2) Solution A and 30g of ceramic sand are mixed and then moved into a flask, and heated to 75℃, and refluxed at this temperature for 2h;

[0087] (3) The mixture is filtered, and the obtained solid substance is dried at 150℃ for 12h to obtain europium-modified ceramic sand.

[0088] Step 2: Preparation of titanium precursor

[0089] (1) 6mL of n-butyl titanate and 3.8g of emulsifier Tween-60 are added into 220mL of anhydrous ethanol to form solution B;

[0090] (2) 1.5mL of concentrated hydrochloric acid and 2.7g of sodium dihydrogen phosphate are added into 26mL of pure water to form solution C;

[0091] (3) Solution B and solution C are mixed, and stirred in a constant-temperature water bath at 35℃ for 15min to obtain the titanium precursor.

[0092] Step 3: Hydrothermal film preparation

[0093] (1) The titanium precursor of step 2 and the europium-modified ceramic sand of step 1 are mixed and moved into a hydrothermal reaction kettle, and the reaction temperature is controlled at 220℃, the reaction kettle pressure is 2.1MPa, and the reaction time is 36h;

[0094] (2) After the reaction is completed, the mixture is filtered and washed with pure water;

[0095] (3) drying the obtained solid substance at 155 ℃ for 10 h, and then calcining at 710 ℃ for 150 min to obtain the europium ceramic sand filter material with purification function; the europium ceramic sand filter material has a diameter of 2-3 mm, a bulk density of 2.39 g / cm 3 , and a porosity of 47%; the purification active component of the europium ceramic sand filter material is a europium titanate coating layer coated on the surface of the ceramic sand, and the europium titanate coating layer accounts for 3.5% of the mass percentage of the europium ceramic sand filter material.

Claims

1. A method for preparing europium ceramic sand filter media with purification function, characterized in that, The process includes the following steps: Step 1: Europium-modified porcelain sand (1) Add 5.2-7.2 g europium nitrate and 2.1-2.3 g dodecyltrimethylammonium bromide to 300 mL of 0.3 mol / L hydrochloric acid solution, and stir to form solution A; (2) Mix solution A with 30g of porcelain sand and transfer the mixture into a flask. Heat the mixture to 75°C and reflux at this temperature for 2 hours. (3) Filter the above mixture and dry the resulting solid at 150°C for 12 hours to obtain europium-modified porcelain sand; Step 2: Preparation of titanium precursor (1) Add 5-6 mL of tetrabutyl titanate and 3.5-3.8 g of emulsifier Tween-60 to 220 mL of anhydrous ethanol and stir to form solution B; (2) Add 1.3-1.5 mL of concentrated hydrochloric acid and 2.5-2.7 g of sodium dihydrogen phosphate to 26 mL of pure water and stir to form solution C; (3) Mix solution B and solution C and stir in a constant temperature water bath at 35℃ for 15 min to obtain titanium precursor; Step 3: Hydrothermal film formation (1) Mix the titanium precursor from step 2 and the europium-modified ceramic sand from step 1, transfer them into a hydrothermal reactor, control the reaction temperature at 210-220℃, the reactor pressure at 2.0-2.1MPa, and the reaction time at 36h. (2) After the reaction is complete, filter the mixture and wash it with pure water; (3) The solid material obtained by filtration is dried at 155℃ for 10h and then calcined at 650~710℃ for 150min to obtain europium ceramic sand filter material with purification function.

2. The method for preparing europium ceramic sand filter media with purification function according to claim 1, characterized in that, The porcelain sand mentioned in step (1) is a white sphere with a diameter of 2-3 mm and a bulk density of 2.31-2.38 g / cm³. 3 Compressive strength greater than 3.5×10 3 Pa, porosity 41%–43%.

3. The method for preparing europium ceramic sand filter media with purification function according to claim 1, characterized in that, The main components of the ceramic sand in step (1) are silicon dioxide and aluminum oxide, and contain small amounts of oxides of iron, magnesium, potassium and sodium.

4. The method for preparing europium ceramic sand filter media with purification function according to claim 1, characterized in that, The europium ceramic sand filter media has the following characteristics: diameter 2-3 mm, bulk density 2.32-2.39 g / cm³. 3 The porosity is greater than 45%.

5. The method for preparing europium ceramic sand filter media with purification function according to claim 1, characterized in that, The active purification component of the europium ceramic sand filter media is a europium titanate coating on the surface of the ceramic sand, and the europium titanate coating accounts for 3.3% to 3.5% of the mass of the europium ceramic sand filter media.